AsC A'92
As i anCrystall ographic
Associa tion
Inaugural Conference

Singapo reNovember 13-16, 1992

. Progr am & Abstr acts

AsCA'92
Asian
Crystallographi c
Association
Inaugural Conference

Singapore
November 13-16, 1992

Program & Abstracts

AS C A' 9 2 is the inaugural conference of
the Asian Crystallographic Association.
Its organisation has been supported financiallyand administratively by the
Crystallographic Association of Japan andSociety of Crystallographers in Australia.
Grants for young scientists attending thisconference have been possible because ofcontributions from theInternational Union of Crystallography,
Crystallographic Society of Japan andSociety of Crystallographers in Australia.
AsCA is also grateful for assistance from the
National University of Singapore.

Table of Contents

Map of Singapore .......... .. ..... ... .............................. .. ... .. .. .Inside front coverConference Committees
General Information
Registration Desk ....... ....... ......... ......... ....... .. .. ..... ... ........... ... ........... 1
Notices ....... ..................... ........... .... .. ... .... ..... .................... .. ... ... .... .. .1
Conference Badges .. ... ............... ............... .... .. ................. .. .......... .... 1
Travel Arrangements ......... .. ....... ............. .. ........ .... .. ..... ..... ..... ...... ..1
Meals and Refreshments .... .... .... ... ..... ....... ... ............. ................. ..... 2
NUS Campus Bus ............ .... ... ... .. ..... ......... ........ .. .. ... ................... .... 2
Social Events
Welcoming Reception .. .. ....... .. ............... ... .... ... ... ................... ... ..... .. 2
Evening Refreshments .. .. ............ ..... ... .. ....... ... .... .... ........ .. ....... .. ...... 2
Farewell Banquet ......... ..... .... ..... ....... ....... ... ... ............. .. .. ... ....... ...... 2
Opening Ceremony ... .... .. .. ..... .............. .. ... .... .. .. ... ..... .. .. .... .. .. ........ .... ...... ... 3Society Meetings ......... ............... ......... ............. ........................... ... .... ... .. ..3
Scientific Program Summary ...... .... ... .... ....... ... ..... .. ... ........... ... .... ..... ... .... . .4
Exhibitors .. .... .... ........ .... ............ ....... .... ....... ......... ... .. ..... ..... ... .. ... .. ... ... .... .. 4
Microsymposia Topics .................... ..... ....... .. ............. .. ..... ... ............. .. ..... .. 5
Program Schedule .. .. .. ... .. .... ..... ..... ... .. ..... .. ........ ... .. .. .... .. .. ...... .. ... ....... .... ... .6
Scientific Abstracts .. ... .... ......... .. ...... ..... .... ................ ...... .. .. .... ....... ........ ... 29
Author Index ........ ...... ... .......... ........... .... .... ........ .. .. .. At the back of the bookConference Facilities ........ ... ... ........ ... ..... .. ..... ... .......... ..... .Inside back coverInternational Organising Committee
Nobutami Kasai (Ch.)
Hans C Freeman
Sydney R Hall
Hiroo Hashizume
Jimpei Harada
Hiroshi Iwasaki
Lip Lin Koh
Fumiyuki Marumo
Fang-ming Miao
Yu Wang
John W WhiteJapan
Australia
Australia
Japan
Japan
Japan
Singapore
Japan
China
TaiwanAustralia

International Program Committee
Edward N Maslen (Ch.)
Bryan F Anderson
Tamaichi Ashida
Hans C Freeman
Siba P Sen Gupta
Jimpei Harada
Kum-fun Mok
Mei-cheng Shao
Michiyoshi Tanaka
Allan H White

Australia
New ZealandJapan
Australia
India
Japan
Singapore
China
Japan
Australia

Coordinating Committees
CrSJ

SCA

Singapore

Hiroo Hashizume (Ch.)
Jimpei Harada
Hiroyuki Horiuchi
Hiroshi Iwasaki
Nobutami Kasai
Fumiyuki Marumo
Yuji Ohashi
Kazumasa Ohsumi
Satoshi Sasaki
Michiyoshi Tanaka

Sydney R Hall (Ch.)
Hans C Freeman
Edward N Maslen
Max R Taylor
John W White
Geoff A Williams

Lip Lin Koh (Ch.)
Lawrence Chia
John 0 Hill
Kum-fun Mok

Takuyuki Uragami

General Information
Registration Desk
The AsCA'92 conference registration desk will be open from 15:00 to 21 :00 on Friday
November 13 and from 8:00 to 18:00 on Saturday November 14 to Monday November 16.
The registration deck is located on the ground floor of the Regional Language Centre, 30
Orange Grove Road (see map on inside front cover). The local phone numbers for the
conference organisers are 737 9044 and 733 6108.
The re gistration desk is responsible for all participant registration and the issuing ofconference satchels and badges. It will post notices and relay messages to participants. All
bookings of ad hoc sessions should be arranged through the registration desk.

Notices
All notices will be placed on the conference Notice Board which is located on the groundfloor of the RELC outside the auditorium. General messages and mail for conference
participants will be available from the registration desk. Notice of any changes in thescientific program will be posted on the Notice Board.

Conference Badges
The conference name badge must be worn at the Opening Ceremony, all scientific sessions,exhibitions, lunches and social events. Badges are colour-coded as foll ows:

White
Yellow
Pink

Full and student participants
Accompanying persons
Members of the Organising and Program Committees

Travel Arrangements
International flights must be reconfirmed with your airline at least 24 hours prior to
departure. The local Singapore Airlines number is 223 8888.

1

Meals and Refreshments
Morning and afternoon coffee
Morning and afternoon coffee for all full and student participants will be served from10:30 to 11:00 and from 15:15 to 15:45 in the ground floor lobby and the restaurant foyer ofthe RELC on the Saturday, Sunday and Monday, November 14-16.

Lunch
Lunch will be served free of charge to all full and student participants in the RELC
restaurant from 12:30 to 13:30 on the Saturday, Sunday and Monday, November 14-16.
Conference badges must be worn.

NUS Campus Bus
A minibus will depart from Sheares Hall for the RELC at 8:15 on the mornings of Saturday,
Sunday and Monday, November 14-16. This will be free of charge for AsCA'92 registrants.
There will be no return bus to the NUS campus but taxis in Singapore are inexpensive,
especially when shared by several participants.

Social Events
Welcoming Reception
A welcoming reception and get-together will be held in the RELC lobby from 19:00 to
22:00 on Friday November 13 for all registrants (full, student and accompanying persons).
Refreshments and snacks will be served. The reception is sponsored by Si emens.

Evening Refreshments
Soft drinks and beer will be served from 17:00 to 19:00 on the Saturday and Sunday
evenings in the restaurant foyer, courtesy of MAC Science and EnrafNonius .

Farewell Banquet
A farewell banquet for all registrants (full, student and accompanying persons) will beheld in the RELC restaurant from 19:00 to 22:30 on Monday November 16. Dress is casual.
The banquet is sponsored by Rigaku.

2

Opening Ceremony
The opening ceremony for AsCA'92 will be held in the RELC auditorium from 8:30 to
9:00 on Saturday November 14. The welcoming speakers will beProfessor Nobutami Kasai, President, Asian Crystallographic Association
Professor Andre Authier, President, International Union of Crystallography
Professor Hsing Hua Huang, Deputy Vice Chancellor, National University of Singapore
This ceremony will be followed by the opening plenary lecture from N Sakabe entitled"Biological Application of Synchrotron Radiation" .

Society Meetings
The following meetings of crystallographic societies have been scheduled.
Asian Crystallographic Association
Saturday November 14
19:00

Council meeting, Casuarina theatre

Crystallographic Society of Japan
17:00
Friday November 13
Monday November 16
18:00

Council meeting, Casuarina theatre
Annu al meeting, auditorium

Society of Crystallographers in Australia
Monday November 16
18:00

General meeting, Casuarina theatre

Commercial Sponsors
The organisers wish to thank the following companies for sponsoring various aspects ofthis conference. Their assistance has kept the registration fee for this meeting to a minimum.
Enraf Nonius
Rigaku Corporation
MAC Science
PhilipsSiemens
Singapore Airlines3

Scientific Program Summary
The scientific program schedule for each of the three days of the conference will be:
9:00-10:30
11:00-12:30
13:45-15:15

Main Lectures A in the auditorium, ground floor.
Microsymposia B in the auditorium, ground floor.
Microsymposia C in the auditorium, ground floor.

9:00-10:30
11 :00-12:30
13:45-15:15

Microsymposium X in the Casuarina theatre, second floor on Monday
Microsymposia Y in the Casuarina theatre, second floor.
Microsymposia Z in the Casuarina theatre, second floor.

11:00-17:45
11:00-17:45

Poster sessions P, Q and R in restaurant foyer, second floor.
Poster sessions S, T, U, V and W in main poster hall, second floor.

The left-hand column on each page of the Program Schedule indicates the times of theoral contributions.
The right-hand column on each page of the Program Schedule comprises the abstract
numbers in the style of the Abstracts list at the rear of the Program book.

Exhibitors
A commercial exhibition will be held on ground floor lobby, and the second floor mainposter hall, from 9:00 to 17:30 each day of scientific sessions.
The exhibitors are:Enraf Nonius BV, X-ray Diffraction, Roentgenweg 1, 2624BD Delft, The Netherlands.
Fax 31 15 698500
MAC Science, 2-25-16 Nakano Ue Machi, Hachioji, Tokyo 192, Japan. Fax: 81 426 24 2723
Rigaku International Corporation, Sanseido Shinjuku Biding. 7F, 4-15-3 Nishi-Shinjuku,
Shinjuku-ku, Tokyo 160, Japan. Fax: 81 3 3299 6364
Siemens AG, X-ray Analytical Systems, Oestliche Rheinbruckenstr. 50, D-7500 Karlesruhe
21, Germany. Fax: 49 45 2845733
Xray Research, Grosse Theatrestr. 42, D-2000 Hamburg 26, Germany. Fax: 49 40 8315916.

4

Microsymposia Topics
Saturday November 14Orals
9:00-10:30
11:00-12:30
13:45-15:15

A Synchrotron Radiation
B Organic & Organometallic Structures
C Maximum Entropy Methods

Y Powder Diffraction
Z Films & Surfaces

PostersP
R
T
V

Macromolecular Structures I
Interactions in Biological Molecules
Minerals, Inorganics & Alloys I
Phase Transitions & Solid StateQ Macromolecular Structures II
S Electron Scattering & Microscope Imaging
U Minerals, Inorganics & Alloys ll
W Crystal Growth & Preparation

Sunday November 15
Orals
9:00-10:30
11 :00-12:30
13:45-15:15

A Electron Scattering
B Biological Structures
C Minerals & Inorganic Materials

Y Theory
Z Crystal Growth

PostersP
R
T
V

Synchrotron Radiation
Techniques Other than Diffraction
Carbon & Organic Structures I
Electron Distributions

Q Diffractometry & Data Analysis
S Neutron Diffraction
U Organometallic Structures I

Monday November 16
Orals
9:00-10:30
11:00-12.·30
13:45-15:15

A Neutron Diffraction
B Interactions in Biological Structures
C Diffraction Physics

X Phase Transitions
Y Extinction
Z Crystallographic Information

Posters
P Interfaces, Films & Surfaces I
R Organic Str~ctures II
T Enzyme Structures
V Phase Transitions & Solid StateQ Interfaces, Films & Surfaces II
S Organometallic Structures II
U Small Biological Structures5Program Schedu le6

Saturday November 14
Session 14A(Auditorium)

SYNCHROmON RADIATION

9:00

Biological Application of Synchrotron Radiation
by N Sakabe, K Sakabe, T Higashi, A Nakagawa and N Watanabe

14A-1

9:30

A Multi-purpose Beam-line Facility by R F Garrett

14A-2

9:50

Design Concept of the Spring-S Undulator Beamline for Macromolecular
Crystallography
by N Kamiya, H Iwasaki, T Ueki, M Yamamoto, T Uruga and H Yamaoka

14A-3

14A-4

10:10 The Scope for Improved Insertion Devices by S Yamamoto
10:30 Coffee

Session 14B(Auditorium)

CARBON AND ORGANIC SmUCTURES and
ORGANOMETALLIC SmUcruRES

11:00 Crystal Structures of Some Substituted Ethanesby L L Koh and H H Huang

14B-1

11:25 Preparation of Carbon Nanotubes by DC ARC-Discharge Evaporation
byY Ando and S Iijirna

14B-2

11 :45 Crystal Structure and Nonlinear Optical Properties of m-Nitrobenzoic
Acid Diethanol Amine Adductby X K Yao, H G Wang, R J Wang and J M Zheng

14B-3

12:00 Structural Aspects of the Trivalent Group 15 Metal(II) (As,Sb,Bi)
Complexes with a -hydroxy Acids by G Smith, D S Sagatys and R C Bott

14B-4

12:15 Studies on Organometallic Compounds: Structure and Activity ofOrganostannyl Carboxylates
by B B Maji, S Biswas, K L Ghatak, S N Ganguly and Asok Ban erje e

14B-5

12:30 Lunch

Session 14Y

POWDER DIFFRACTION(Casuarina Theatr e)

11:00 Powder Diffraction by S P Sen Gupta

14Y-1

11 :20 aTiOSO,: Structure Determination from Powder XRD Data andRelationships to other MoXO, Structures by IE Grey and R Stranger

14Y-2

11:40 Crystallography of REA10 3 (RE=La, Ce, Pr and Nd)by M Tanaka, H Horiuchi, T Shishido and T Fukuda

14Y-3

7

Saturday November 14
12:00 Crystal Structure Analysis with High-resolution Powder Diffractometer
Data by T 0 O chiai and H Toraya

14Y-4

12:15 Structures of the Two Polymorphs of Magnesium Boron Nitride
Determined from X-ray Powder Diffraction Data by H Hashizume,
N Sud a, H Hiraguchi, 0 Fukunaga, C Gilmore and G Bricogne

14Y-5

12:30 L u n ch
Session 14C(Audi t ori um)

MAXIMUM ENTROPY METHODS

13:45 Electron Density Distributions of Crystalline Materials Obtainedb y the Maximum Entropy Method by M Sakata

14C-1

14:15 Maximum Entropy Method Analysis of Neutron Powder D iffraction
Data by M Sakata, T Uno, M Takata and C J H awar d

14C-2

14:35 Analysis of an Approximation in the Maximum Entropy Method
byS K u m a z awa and M Sakata

14C-3

14:55 Direct Investigation of Thermal Vibrations of Be Metal by the Maximum
Entropy Method Applied to Single Crystal Neutron Diffraction Databy M T aka ta, M Sakata, F K Larsen, Y Kubota and B B Iversen

14C-4

15:15 C offee
Session 14Z

INTERFACES, FILMS AND SURFACES(Cas uari n a Th eat re;

13:45 Accurate Determination of the Unit Cell for an Epitaxial Layer
of Hg,_. Cd. Te Deposited by MOCVD on GaAs
by 2hu N anchang, A W St even son and Li Runshen

142-1

14:05 Evaluation of the Roughness of Crystal Surface by X-ray Scattering Theoretical Consideration by JHarada

142 -2

14:25 Grazing Angle X-ray Standing Wave Study of As-adsorbed Si Surface
by H Ku rashina, 0 Sakata and H Hashizurne

142-3

14:40 Axial Symmetry Quasicrystal Structure in Some Thin Films, Coatings
and Vegetable Fibres - An ESR Studyby N g uy en V an Tri, Pharo The Vung and Le Hai Hung

142-4

14:55 D ou ble Crystal X-ray Characterization of 11-V Multilayered Specimens
by Selective Etching by S Swarnin athan

142 -5

15:15 C offee

8Saturday November 14
Sec tion 14P

MACROMOLECULAR STRUCTURES I(Foyer)Crystallization and Preliminary X-ray Crystallographic Study of Lysozyme
Produced by Streptomyces globisporus
by C Uemats u, H N ai toh, S Harada, Y Kai and N Kasai

14P-1

Preliminary Crystallographic Study of Cytochrome c' from Achromobact er
xylosoxidans NCIB 11015 by N Shibata, T Inoue, Y Kai, S H arada, N Kasai,
T Kohzuma, S Suzuki, H Iwasaki, and S Shidara

14P-2

Crystal Structure of Streptomyces erythraeus Trypsin at 2.7A Resolution
by T Y am ane , A Suzuki, T Ashida, Y Kawata and F Sakiyama

14P-3

Crystal structure of [2Fe-2S] Ferredoxin I from the Equisetum arvense at l. BA
14P-4
Resolution by M Ban do, Y Morimoto, T Tsukihara, S Ikemizu and K Fukuyama
Crystal Structure of the TFIID TAT A-box Binding Protein: A Novel DVA
binding Motif that Recognizes the Minor Grooveby DB Nikolov, A -H Hu, J P Lin, A Gasch, A Hoffmann, M Horikosh i,
N -H Chua, R G Roeduer and S K Burley

14P-5

Sec tion 14Q(Foyer)

MACROMOLECULAR STRUCTURES II

Crystallographic Refinement of Trichosanthin at 1.9A Resolution
by Lin Yu]u an, P an KeZhen, Fu ZhuJi and Zhou KangJing

14Q-6

Crystal Structures of Two Blue Copper Proteins by T Inou e, Y Kai,S H arada, N Kasai, S Suzuki, T Kohzuma, J Tobari, S Shidara, and H Iwasaki

14Q-7

High Resolution Electron Crystallography of an a-Helical Coiled Coil Protein
by P A Tulloch, Y Fujiyoshi andY Kimura, A W S John s on, P W Dysonand A E C Spargo

14Q-8

Crystall ographic Studies on Double Shelled Spherical Virus, Rice D warf Virus(RDV) II by Y M orimoto, T Tomizaki, T Sato, T Tsukihara, M Koizu mi,
T Omura, H Kano and H Mizuno

14Q-9

Crystal Structural Analyses of Spherical Viruses, T obacco Necrosis Virus (TNV)and Rice Dwarf Virus (RDV) by T Ts ukihara, Y Morimoto, K Fu kuyama,
M Koizumi, T O mura, K Kano and H Mizuno

14Q-10The Structure and Function of Mos Kinase by B K Sathyanarayana, W Ma tten,
R Zhou, N Kew, I Daar, T Copeland, G F Van d e Woude, J Erickson and R Rubin

14Q-119Saturday November 14
Section 14R(Foyer)

INTERACTIONS IN BIOLOGICAL STRUCTURES

Drug-Protein Interaction: Refinement and Modelling of Sulfonamide Drugs
Bound to Human Carbonic Anhydrase I Enzyme
by S Chakravarty and K K Kannan

14R-12Crystal Structure of Glutathione Synthetase with Adenosine(S')tetraphospho(5')pyridoxal by T Hibi, H Kato, T Nishioka, J Oda, K Yamaguchi andY Katsube

14R-13

Active Site Conformation of Cytoplasmic Cyclophilin of Eschrichia coli.
Sterle Hindrance and Attachment of Cyclospolin A
by M Ito, M Konno, T Hayano, M Suzuki, S Sa to and N Takahashi

14R-14

Alkaline Metal Ion Bound in Human Lysozyme
by M Mats us hima, A Piililer, K Morikami and K Inaka

14R-15Structure of P. stutzeri G4-amylase and its Complex with Maltotetraoseby Y Matsuura, Y Morishita, Y Yoshioka, M Sato, Y Katsube and M Kubota

14R-16

Study of Conformational Difference Between a Dihydropyridine Calcium
Channel Antagonist and a Non Antagonist
by S Meh d i and K Ravi Kumar

14R-17

Crystal Structure of the Complex between Porcine Pancreatic Elastase andM acrocyclic Inhibitor by T Tada, T Yasuda, S Harada, Y Kai and N Kasai

14R-1814R-19Variations on the Same Theme- Crystal Structure of L-Asparaginase
and th e Uniqueness of its Structural Foldby J K Mo h an a R ao, M Gribskov, D Housset, M Jaskolski, J Lubkow ski, M Miller,
B K Sathyanarayana, A Swain and A Wlodawer
Binding and Catalytic Roles of the Active Site Metal in Zinc Proteinases
by G S hoh a m, H M Greenblatt and H Feinberg

S ec t io n 14S

ELECTRON SCATTERING, AND MICROSCOPEIMAGING OF STRUCTURE

14R-20(Ma in Hall)

Use of Atomic Force Microscope in Determination of Space Groups
by X-ray Diffraction Analysis of Crystals by N Masaki, K Machida,
H Kado, K Yokoyama, T Tohda, Y Yoshimura and M Kitamura

14S-31

Electron Microscopy and Diffraction Study of the Direct Reaction of Iron andCarbon and the Formation of a New Iron Carbide
by S Nagakura,T Komekyu, M Ando and S Odawara

14S-32Modulation Modes of Bi2 Sr2(Ca,_.Ln,)Cu,08 +~> Crystals Studied by HighResolution Reverse Imaging by T Onozuka

14S-3310

Saturday November 14
EELS Study of the Temperature Dependence of the Volume-Plasmon Energy
in Aluminium by M Terauchi, H Abe, R Kuzuo and M Tanaka

145-34Modulated Structures in Fe-Doped Bi-Sr-Cu-0 Superconductors Studied by
High-Resolution TEM by K Yanagisawa, Y Matsui, T Koizurni and T Hasegawa

145-35

Search for Crystal Structure of Long-period Bi-Mn Alloy Phase- an Exampleof Structure Analysis by High Resolution Electron Microscopy
by K Yoshida, T Kawai and K 5himonishi

145-36

Section 14T

MINERALS, INORGANICS & ALLOYS I(Main Hall)

Crystal Structure of a New Ternary Chalcogenide Ta,Ni,()l,-Se)2 (j..L,-Se) 2 (j..L,-Se) 2
by S-X Liu, B Zhang, Z-M Wang and J-L Huang

14T-38

Crystal Structures of Iron-Containing Ternary Layered Tellurides
by Huang f in-Ling, S-X Liu and G-L Cal

14T-39Structure of Na,SrSi,O, and its Relationship to Other M '.M" (TO,), Compounds
by R P Gunawardane

14T-40Plurality of Si and Co Sites in Co-Akermanite
by K Hagiya, M Ohmasa and K Iishi

14T-41

Crystal Structure of Duftite Polymorphs by Kharisun, M R Taylor and A Pring

14T0 42

Polarization Study of Magnetic X-ray Scattering of (Ba,Sr) 2 Zn,Fe 120 22
by E Tsuji, S Kumazawa, H Katoh, N Momozawa, K Ishida, K Ohshima,
J Harada and S Kishimoto

14T-43Single Crystal X-ray Diffraction and EXAFS Studies on R,TaO, (R=Ho,Y,Yb)
by T Tanaka, N Ishizawa, M Yoshimura, K Tanaka, H Oyanagi, and F Marumo

14T-44Structure Analysis of Lead Orthovanadate Pb 3 (V0 4) 2 in the Ferroelastic
and Ferroelectric Phases by T U me k i, H Kasatani and H Terauchi

14T-45Structural Variability in y-Alumina by B K Gan, B H O'Connor and C J Howard

14T-46

A New FCC Phase of Y,O, by S K Katagiri, N Ishizawa and F Marumo

14T-47

Section 14U

MINERALS, INORGANICS & ALLOYS II

Crystal Structure and Lattice Parameters of Zn,_,Co,S, Zn,_,V,S
Diluted Magnetic Semiconductors
by D G6mez de Anderez, SA Lopez-Rivera and W Giriat

11(Main Hall)

14U-48

Saturday November 14
Structure and Symmetry of PTCR Perovskites
by N ] Calos, J S Forrester, T J White and S Myhra

14U-49Structure of Ba6 _3 ,Sm8+2x Ti,_ 60 54 by H Ohsato, T Ohhashi and T Okuda

14U-50Microcrystalline Keatite- A Fibrous Si02-Phase by B Martin

14U-51The Intersite Distribution of a Small Amount of Mn Ion in Olivine
by Y Ono, M Tokonarni, H Horiuchi, N Aikawa and S Sasaki

14U-52

Local Crystal Structures of an Ilvaite Single Crystal
by Y Takeuchi, Y Matsushita, H Sawada and H Taniguchi

14U-53

Local Structure of Intercalants in Layered Compound Cu,TiS,
by K Ohshima, R Maruta and A Makita

14U-54The Zr-N-F and Y-0-F Composite Modulated Structures
byS Schmid, R L Withers and J G Thompson

14U-55

X-ray Anomalous Dispersion Determination of PbZrO, Superstructure
by K Nagino, M Iida, Y Itoh, Y Soejima and K F Fischer

14U-56

Changes in Morphology of Periodic Antiphase Boundaries in One-Dimensional
Long Period Superstructures
by M Itakura N Kuwano, S Iwasaki, K Kajiwara, A Matsumoto and K Oki

14U-57

Diffuse Scattering in an Yttria-Stabilised Cubic Zirconia, (Zr0.61 Y0.390'"805)by T R We/berry, R L Withers, J G Thompson and B D Butler

14U-58

Section 14 V

PHASE TRANSITIONS and SOUD STATE REACTIONS(Main Hall)

X-ray Study of Phase Transition in a C60 Single Crystal
by H Kasatani, H Terauchi, Y Harnanaka and S Nakashima

14V-59Crystalline State Racemization of a Bulky Chiral Groupby Y Sakai, Y Ohashi, Y Arai, Y Ohgo, N Karniya and H Iwasaki

14V-60

X-ray Diffraction Study on the Phase Relation of BaZnGeO,

14V-61by S Takai, T Atake, N Ishizawa, F Marumo and A Harnano
Domain Distributions Around Cubic-Tetragonal Phase Transitions
by T Koga, N Aomine, Z Lu, Y Soejima and A Okazaki

14V-62Chiral-to-racemic Transformation in a Cobaloxime Crystal on Exposure
to Visible Light by TN emo to andY Ohashi

14V-6312

Saturday November 14
Photoisomerization Rates Before and After a Reversible Thermal Phase
Transition by H Tatsuki, A Sekine andY Ohashi

Section 14W

CRYSTAL GROWTH AND PREPARATION

14V-64(M ain Hall )Structural Features in Some Rapidly Solidified Aluminium Alloys
by Lecong Dzuon g, Ha Thanh Binh, Le Due Lap and Nguyen Thanh Do

14W-66Growth of Pure Cadmium Iodide Crystals and Study of Laser Induced
Cracks in Them by S K Chaudhary

14W-67

Vapour Growth and Characterization of Cadmium Chloride Doped Crystalsof Cadmium Iodide by Ritu Dhingra and G C Trigunayat

14W-68Growth and Characterization of CdBr, Doped Dendritic Single Crystals ofCdl,
by Binay K u rna r, G L Bhalla and G C Trigunayat

14W-69Epitaxial BaTiO, Crystals (I) on SrTiO, Substrates by H Terau chi, Y Yoned a,
Y Watanabe, H Kasatani, K Kamigaki, Y Yano, T Terashima andY Bando

14W-70Epitaxial BaTiO, Crystals (II) on [PUMgO] Substrate by Y Yon eda, H Yabuno,
H Kasatani, H Terauchi, Y Yano,T Terashima andY Bando

14W-71

Characterization of Barium Titanate Powder Prepared by Chemical Precipitation
by T Tunkasiri and G Rujijanagul

14W-72

Hydrothermal Synthesis and Structural Characterization of A.., VOPO,.yH,O(A=Alkali, Alkaline Earth and Transition Metals)
by K H Lii, H Y Kang and S L Wang

14W-73

Defect Substructures and Mechanical Properties of Mu1lite Prepared by
Coprecipitation by S hu -Ch eng Yu and Jiann-Shing Lee

14W -74

Method to Control Microstructure by Electron Channeling Pattern (ECP)in Presence of Suppressing Contrast Forming Mechanisms by A N Efimov

14W-75

Lattice Metric M a tch at Heteroepitaxy: Non-cubic Crystals
by AN Efimov and A 0 Lebede v

14W-7613

Sunday November 15
Session 15A(Auditorium)

ELECTRON SCATIERING, AND MICROSCOPEIMAGING OF STRUCTURE

9:00

High Resolution Electron Microscopy by K Hiraga

15A-1

9:30

X-ray and Electron Diffraction from Twisted Quartz Crystals
byM Fehlmann and A F Moodie

15A-2

9:50

Electron Microscope Study of Incommensurate Lattice Modulationin Layered Composite Crystal PbS-VS1
by N Yamamoto, K Akiyama, K Yagi, Y Gotoh andY Oosawa

15A-3

15A-4

10:10 High-Resolution EELS Study of the Electronic Structures of Semiconductors Containing Lattice Defects by M Terauchi and M Tanaka
10:30 Coffee
Session 15B(Auditorium)

BIOLOGICAL STRUCTURES

11:00 Crystal Structural Analyses of Spherical Viruses, Tobacco Necrosis
Virus (TNV) and Rice Dwarf Virus (RDV) by T Tsukihara,Y Morimoto,
K Fukuyama, M Koizumi, T Omura, K Kano and H Mizuno

15B-1

11:30 Crystal Structure of Uncomplexed NC41 Anti-neuraminidase Fabin its Uncomplexed Form by M C Lawrence, R Malby, A Kortt,
V Staton, PM Colman, and R G Webster

15B-2

11:50 Studies on the Structures of Insulin Analogues and the Bindingof Insulin Interaction with its Receptor by W R Chang and DC Liang

15B-3

12:10 Enzyme Substrate Interactions: Refined Structure of Human Carbonic
Anhydrase I (HCAI)-HCO,· Complex by Vi nay Kumar and K K Kannan

15B-4

12:30 Lunch
Session 15¥(Casuarina Theatre)

THEORY

11:00 Enhanced Phase Effect in Four-beam X-ray Diffraction -Triplet Phasesfrom Four-beam Diffraction by Y S Tsai, M T Huang and Shih- Lin Chang

15Y-1

11:20 Phase Determination and Refinement by Density Modification;
Low Density Elimination by M Shiono

15Y-2

11:35 Restoring the Original Electron Distribution of Lipid BilayersA Simulation Studyby S Yamam u ra, M Takata, M Sakata, H Takahashi and I Hatta

15Y-3

14

Sunday November 15
11:55 The Role of Anomalous Dispersion in the Comparative Refinementof Modulated Crystal Structures by A D Rae

15Y-4

12:10 Optical Transforms by T R Welberry

15Y-5

12:30 Lunch

Session 15C(Auditorium)

MINERALS, INORGANICS & ALLOY STRUCTURES

13:45 Computer Simulation of the Structural and Physical Properties ofthe MgSiO, Polymorphs by M Matsui

15C-1

14:20 Photorefractive KNSBN Crystals with A-sites Unfulfilled Tungsten
Bronze Structure by H C Chen, D L Sun and Q Z Jiang

15C-2

14:40 Modulation Wave Approach to Structural Parameterization andRietveld Refinement of the C9-cristobalite Related, Low Carnegieite
Structure by R L Withers and J G Thompson

15C-3

15:00 Low-Carnegieite - Why Previous Attempts to Study its Structure
Were Unsuccessful
by J G Thompson, R L Withers, A K Whitaker and R M Traill

15C-4

15:15 Coffee

Session 15Z

CRYSTAL GROWTH AND PREPARATION(Casuarina Theatre)

13:45 Holographic Studies of the Solid-Liquid Interface Boundary Layer in
Flux Crystal Growth by Xiling Yu, Youchen Liu and Xuefeng Yue

15Z-1

14:05 Growth and Characterization of Bi-Sr-Ca-Cu-0 Single Crystals
by Alka Jain and G C Trigunayat

15Z-2

14:25 Pressure Dependence of Cell Dimensions in NiS 1 Crystals Grown underDifferent Sulfur Vapour Pressures
by T Komori, N Ishizawa, F Marumo andY Noda

15Z-3

14:45 The Synthesis and Structure of Cu,Bi,V 10 14
by G B Deacon, B M Gatehouse and G N Ward

15Z-4

15:00 Synthesis and Characterization of Ni,S1 (Heazlewoodite) Crystals
by S M Dharmaprakash

15Z-5

15:15 Coffee

15

Sunday November 15
Section 15P

SYNCHROTRON RADIATION(Foyer)

The Australian National Beamline Facility by R F Garrett, J W Boldeman,
D J Cookson, G Foran, D C Creagh, F Johnson, S Janky and S W Wilkins

P-00

Proposed Synchrotron X-ray Study of Monolayers at the Photon Factoryby G T Barnes and C H L Kennard

lSP-2

An Instrument for X-ray Surface Studies
by G Barnes, C Kennard, DC Creagh, I Jamie and J W WhitelSP-3

X-ray Evaluation of a Lapped Si Single Crystal
by H Shiwaku, M Ando, K Hyodo, Xiao-Jing Wu and S Horiuchi

lSP-4

Intensity Enhancement in Asymmetric Diffraction with Parallel-BeamSynchrotron Radiation by H Toraya, T CHuang andY Wu

lSP-5

lSP-6
Structure Refinement of Submicrometer-Sized Twinned Domains by Laue
Method using Synchrotron Radiation
by K Ohsumi, K Hagiya, T Takase, Y Shimizugawa, M Ohmasa and M Miyamoto
Ultramicro-single-crystal Diffraction Study on Barium Titanate using SR
by M Kataoka, K Suda, N Ishizawa, F Marumo, Y Shimizugawa and K Ohsurni

lSP-7

Diffraction from Composite N~ 3Fe 46 B 41 Crystal by Synchrotron Radiation
by T Ohba, S Sasaki, M Takata and Y Komura

15P-8

Section 15Q(Foyer)

DIFFRACfOMETRY and DATA ANALYSIS

Micro-area X-ray Diffraction in Crystallographic Analyses of Mineral Textures
and Tiny Single Crystals
by H Horiuchi, M Tanaka, S Nojima, T Mitsuki, and I MinatolSQ-9

Microstructure and Crystallinity of Luminescent Porous Silicon by Diffraction
Techniques by K Takemoto, Y Nakamura and 0 Nittono

15Q-10Design of New Type Four Circle Diffractometer with Movable Rotating -Anode
X-ray Sourceby] Harada, I Takahashi, T Shimura, T Miyazaki, K Yamada and K Masuda

15Q-11

Fundamental Study of a Time-resolved Laue Method for Protein
Crystallography by N Watanabe, N Sakabe, and K Sakabe

15Q-12High Resolution Data Collection from Protein Crystals on R-axis
IIC Diffractometer by T Sa to, T Higashi and T Tada

15Q-1316

Sunday November 15
Structure Determination of Organic Compounds by a Rapid X-ray Measurement
System by F Iwasaki, M Sakuratani, M Yasui, N Kamiya and H Iwasaki

15Q-14

Fully Automatic Structure Elucidation
by K Yamaguchi, E Yasudome and G Matsumara

15Q-15XTAL 3.2: A New System Release byE Blanc, D Schwarzenbach, D M Collins,

15Q-16

D D Dexter, D A Grossie, H D Flack, S R Hall, G S D King, B G Kruger,
R Olthof-Hazekamp, J M Stewart and K D W atenpaugh
Section 15R TECHNIQUES OTHER THAN DIFFRACTION(Foyer)Electron Irradiation Defect Studies on Quartz Crystals at Constant Electron
Energy (200 kV) by B Martin

15R-17

The Polarity of Thermal Conductivity in LiNb03 and LiTa0 3 by M Tokon ami,
0 Tachikawa, Y Ono, T Suetsugu, S Kan, K Yamamoto and J Hikita

15R-18Smectic Layer Structure of Ferrocene Containing Liquid Crystals
by N Nakamura, T Hanasaki and K Onoi

15R-19Cumulative Distribution Functions of Normalized Intensity, Allowing for
Atoms at Special Positions in the Unit Cell by B Pal and G D Nigam

15R-20Section 155(Mai n Hall )NEUTRON DIFFRACTION

Refinement of the Crystal Structures of Cu.O.,InCI and Cu6 DsC~Cl by
Neutron and X-ray Powder Diffraction
by H Hayakawa, E Akiba, S Ono, H Ihara, F Izumi and H Asano

15S-32

Neutron Powder Diffraction Study of Deuterated Benzene from 4K tothe Melting Point by C J Craven, P D Hatton, G S Pawley and C J Howard

15S-33

A Neutron/X-ray Diffraction Study of Simulated Radiation-Waste Element
Substitution in Synroc by W Kalceff, E A Xuereb and D N Argyriou

15S-34S ec tion 1ST

CARBON AND ORGANIC STRUCTURES I

Influence of 13C Isotope Concentration on the Structure of DiamondbyT Yamanaka, S Morimoto, H Kansaki and S Sasaki(M ain Hall)

15T-36

Single-Crystal X-ray study on fcc and hcp C60
15T-37by T Kitam ot o, S Sasaki, H Hashizume, T Atake, T Tanaka, H Kawaji, K Kikuchi,
K Saito, S Suzuki, Y Achiba and I Ikemoto17Sunday November 15
An X-ray Study of a Twinned n-Tetracosane Crystal
by S C Nyburg and A R Gerson

1ST-38

Molecular Aggregation of Cationic Surfactants and Aromatic Compounds
by T Kitamura, H Uekusa, Y Ohashi and H Hirata

1ST-39Lattice Instability Coupled with Molecular Internal Degrees of Freedom in
Biphenyl and bis(4-chlorophenyl)sulfone
by T A take, T Tanaka, H Kawaji, K Saito, K Kikuchi and I Ikemoto

1ST-40

Directed Heteromolecular Hydrogen Bond Interactions in Carboxylic Acid
Cocrystals by DE Lynch, G Smith and C H L Kennard

1ST-41

Crystal and Molecular Structures and Thermal Properties of Mesogenic 2,5-bis(4-ethylbenzoyDoxystyrene and 2,5-bis(4-methoxybenzoyl)oxybenzaldehyde
by Yang Qingchu an, Dai Sheng, Zhou Hongbing, Zhou Qifeng and Tang YouchilST-42

Unusually Short Ethylene Bond Length and Large Amplitude Torsional
Motion of (E)-stilbenes in Crystals
by K Ogawa, S Yoshimura, Y Takeuchi, T Sano and K Toriumi

1ST-43

Unusual Structure of Pentafluoronitrosobenzene
by H GAng, W L Kwik, K KOng and W Y Leong

1ST-44

Section 15U

ORGANOMETALLIC STRUCTURES I(Main Hall)

Crystal Structure of [Isothiocyanato(l,4,8,12-tetra-azacyclopentadecane)copper(II)] Thiocyanate
by Tsong-]en Lee, C -T Tsai, Wei-Jen Lan and Chung-Sun Chung

1SU-46Structure of a Hexanuclear Bimetallic Cluster (j..l-H)Os,Cu(CO),.PPh,
by H G Ang, W L Kwik and K H N g

1SU-47Structural Studies of Complexes of Copper(I) Halides with Ethylene Thiourea
and sym-diphenylthiourea by P Thavornyutikarn, Y Wattanakanjana,
C Pakawatchai, B W Skelton and A H White

1SU-48The Role of Ncs-Ion in Structures of Cu(II) Complexes with Deformed
Diazadioximes and Tetraamines
by T H Ta hirov, Tian-Huey-Lu, Yun-Long Hseih and Chung-Sun Chung

1SU-49Magneto-Structural Correlations of Dimeric Copper(II) Trichloroacetatesby H Uek usa and S Ohba·

ISU-SOThe Structural Characterization of [(cy),PIAgpyAgiP(cy),]by Effe ndy and A H White

1SU-S118

Sunday November 15
Novel Interpenetrating Molecular Frameworks Derived from AgTCM
by S R Batten, B F Hoskins and R Robson

15U-52

Ag(I) As(III) Complexes with a.-hydroxy acids: Structures of the Isomorphous
Complexes {Ag5 As.(C4 H,O,).(H 2 0) 5(X)).,{C,H20 6 = (+)tartrate(4-)
and X=N03-,ao.-), with Ag-As Bonds byG Sm it h, R C Bott and D S Sagatys

15U-53

The Crystal Structure of Au(PPh3 ) 2(PhCS 2 ) by Ju-Chun Wang

15U-54

Crystal Structure of a Platinum(II) Complex of L-methionyl-glycine
by D Shi, T W Hambley and H C Freeman

15U-55Structure of Potassium Theobrominium Tetrak.is(thiocyanato) Palladate(II)by T Giraldi, M R Tayl or, M I Moreno-Vida, J Ruis-Sanchez,
J M Salas-Peregrin and E Colacio

15U-56

Pt, Pd and Rh Complexes with Metalapentalen e Framew ork
by M Yasui, S Yoshida and F Iwasaki

15U-57

Thallium-containing Platinum Sulphur Complexes: Crystal Structure of
15U-58
TlS,Pt,(PPh,),PF, by M S Zhou, L L Koh, Y Xu, T SA Hor, PH Leung and K F Mok
Symmetry Axis of the Vanadyl Complex in V0 2+ D oped Cd(C4 H,04 )_2H,O
Single Crystals by R S Bansal and V P Seth

15U-59Unprecedented Framework Structures: New Derivatives of Cd(CN),by B F Abrahams, M] Hardie, B F Hoskins, R Robson and G A Williams

15U-60Section 15V

ELECTRON DISTRIBUTIONS(Main Hall)

Bonding Deformation and Superposition Effects in the Electron Density
by I Olovsson, G J Mcintyre and H Ptasiewicz-Bak

15V-62Extinction Corrections from Equivalent Reflection Intensities
byE N Maslen and N Spadaccini

15V-63

Electron Density Distribution for the High Melting Substance TiN
by M] Kisono, Y Kubota, M Takata and M Sakata

15V-64

Electron Distribution in a Crystal of NiS,_,Se,by U Tanaka, N lshizawa, F Marumo and T Miyadai

15V-65The Electron Distribution in Dipotassium Tetrafluoronicke late, ~ NiF4
by S K Yeh, S Y Wu and Y u Wang

15V-66

Synchrotron Radiation Vibration Amplitudes and L'. p Maps for K,SiF,
and K,PdO, by ] R Hes ter, EN Maslen, N Spadaccini, N Ishizawa and Y Satow

15V-6719

Sunday November 15
Synchrotron X-ray Study of the Electron Density in Corundum Alp,
byE N Maslen, V A 5treltsov, N lshizawa andY SatowlSV-68Synchrotron X-ray Study of ~pin Y,BaCuO, by R M Hsu and EN Maslen

lSV-69Structure and Electron-density Studies of a 11 2 CaBa2Cu,O, Superconductor
Synchrotron X-rays by 5 Sasaki, T Mori, K Kawaguchi and M NakaolSV-70A Hydrogen Bonding Study with Charge Density Distribution andInteraction Energy by Kuan-]iuh Lin and Yu WanglSV-71

Spin and Charge Transfer through Hydrogen Bonding in[Co(NH3 ) 5(0H 2 )][Cr(CN)J by B N Figgis and E 5 Kucharski

lSV-72The Electron Distribution in Nd,Fe 14B by D d u Boulay and EN Maslen

lSV-73

Electron Density in AlN from X-ray Powder Data by the Maximum Entropy
Method by N Nakahigashi, H Ishibashi, S Minamigawa and M KogachilSV-74

Electron Density in Pure Metals by the Maximum Entropy Methodby Y Kubota, M Takata and M Sakata

lSV-75On the Reproducibility of Electron Density Maps for Ideal Perovskites
byE N Maslen and N R Streltsova

lSV-7620

Monday November 16
Session 16A(Auditorium)

NEUTRON DIFFRACTION

9:00

Neutron Sources and their Crystallographic Applications
by R Chidambaram

16A-1

9:30

Scattering Length Variations in Neutron Diffraction by J W White

16A-2

10:00 Structure of Orthorhombic Hf02 by Neutron Powder Diffraction
by 0 Ohtaka, T Yamanaka, N Hara, H Asano and F Izumi

16A-3

10:15 Bragg and Diffuse Neutron Scattering Studies of Cubic Zirconia
by D N Argyriou and M M Elcombe

16A-4

10:30 Coffee

Se ss ion 16X

SOLID STATE REACTIONS and
PHASE TRANSITIONS(Casuar ina T heatre)

9:00

Nitro-nitrito Linkage Photoisomerization in Crystals of Nitropentaamminecobalt(III) Dichloride by S Ohba

16X-1

9:20

Crystalline-state Photoisomerization of Cobaloxime Complexes
by A Sekine andY Ohashi

16X-2

9:40

Phase Transition and Crystal Structures of 1-Br-Adamantane
by H Takakura, N Ichiwa and M Shiono

16X-3

10:00 X-ray Study of Ferridistortive Phase Transition in {N(CH3 )J 2 CoBr4
byY Nishihata, A Sawada, H Kasatani and H Terauchi

16X-4

10:15 Phase Transitions of the Halogen-Bridged M(II)-X-M(IV) Mixed-Valence
Complexes. Structural Studies of High- and Low-Temperature Phase of[Pt(en),)[PtBr2 (en)J(004 ) 4
by K Torium i, M Yamashita, S Kurita, I Murase and T Ito

16X-5

10:30 Coffee

Session 16B

INTERACTIONS IN BIOLOGICAL STRUCTURES(Auditorium)

11:00 DNA Conformation in Crystals by M Sundaralingam

16B-1

11:30 Probing the Interaction Between Platinum Anti-Cancer Drugs and DNA
by T W Hambl ey, G WAllen, F R Fenton, E C H Ling and K Patser

16B-2

11:50 Electrostatic Potential in tRNA-"" Recognition by Aspartyl-tRNA
Synthetase by A Takenaka, J Cavarelli, J C Thierry and D Moras

16B-3

21

Monday November 16
16B-4

12:10 Biophysical and Crystallographic Study of DNA Recognition by a
Basic-Helix-Loop-Helix-Zipper Protein
by A R Ferre-D 'A mare, P Pognonec, R G Roeder and S K Burley
12:30 Lunch
Session 16Y

EXTINCTION and ELECTRON DISTRIBUTIONS(Casuarina Theatre)

11 :00 The Exact Solution of Dynamical Diffraction in a Distorted Crystal
and its Applications by N Kato

16Y-1

11:15 Experimental Test of the Statistical Dynamical Theory of Extinction
byT Takama and T Kihara

16Y-2

11:35 A General Theory of Extinction in Crystals by T M Sabine

16Y-3

11 :50 Neutron Diffraction Study of KCl: Test of the Sabine Extinction
Formalism by S Maheswaran and T M Sabine

16Y-4

12:10 X-ray Sd-Orbital Analysis of PtP 2 and Multiple Diffraction Free Intensity
Measurement by K Tanaka, S Kumazawa, S Maruno and I Shirotani

16Y-5

12:30 Lunch
Session 16C

DIFFRACIOMETRY AND DIFFRACTION PHYSICS(Aud itorium)

13:45 Direct Observation of Anomalous Transmission of X-rays through Thin
Natural Diamond Crystals with Varying Degrees of Crystal Perfection
by Kr ishnan Lal, S Niranjana, N Goswami and Ajit Ram Verma

16C-1

14:05 Single Crystal Diffractometer on an Open Tube X-ray Generator with
Maximum Tube Voltage 200KV
by F P Okamura, K Yukino, K Yamamoto, T Hori, S Yoshimachi,
R Yokoyama, H Kawasaki, K Tsukamoto and H Izawa

16C-2

14:25 Texture Analysis by Four Circle Goniometer in Polycrystalline Materials
by A u/Haq and A Q Khan

16C-3

14:45 A System for Analysing Thin Film Structure by Grazing Incidence
diffraction: I. Grazing Incidence Diffractometerby H Toraya and T Ochiai

16C-4

15:00 Measurement of Radii of Curvature of Slightly Bent Crystals Using a
Reticon Detector by D Gao, S W Wilkins and A W Stevenson

16C-5

15:15 Coffee

22Monday November 16
Session 16Z

CRYSTALLOGRAPHIC INFORMATION(Casuarina Theatre)

13:45 The World Directory of Crystallographers, Electronic Mail, andCommunication with Crystallographers in the Asian Regionby H Hashizume andY Epelboin

16Z-1

14:05 CIFtbx: Fortran Routines for Manipulating OF's by S R Hall

16Z-2

14:25 XAFS: Can This Important Technique Achieve Respectability?
byDCCreagh

16Z-3

14:45 SHELXL-92 A New Least-Squares Refinement Program for Use With
Single Crystal Diffraction Data by G M Sheldrick and W T Robinson

16Z-4

15:00 Integrated X-ray Measurement and Computation System for Protein
Crystallography
by N Yasuoka, Y Higuchi, S Misaki, Y Morimoto and I Fujii

16Z-5

15:15 Coffee

Section 16P

INTERFACES, FILMS & SURFACES I(Foyer)Morphological Investigation of the (0001) Surface of Ice Ih Crystal by X-ray
Crystal Truncation Rod Scattering by A Go to, K Akiya, T Shimura,
I Takahashi, J Harada, Y Furukawa and T Hondoh

16P-1

CaSrF,!GaAs and CaFjS/GaAs Interface Structures Revealed by X-ray
Standing Waves and Crystal Truncation Rods
by H Hashizume, T Niwa, M Sugiyama, 0 Sakata and S Maeyama

16P-2

X-ray Diffraction Study of the Air Oeaved NaCl(lOO) Surface
by I Takahashi, T Kakiuchi, T Shimura and J Harada

16P-3

Structures of Multilayered Ag!Cu and Ag!Pb Films by X-ray Diffraction
by K Hazama, J Kozaki, SAndo and 0 Nittono

16P-4

Epitaxial Growth of (110) Ag Thin Film on NaO in a Knudsen Gas of Ar
byiOgura

16P-5

Section 16Q(Foyer)

INTERFACES, FILMS & SURFACES II

Crystal Structure Changes in Oxygen-Deficient YBa 2 Cu30,_~Superconducting
Thin Films by J Ye, A Ishii and K Nakamura

16Q-6

Structural Characterization of Fe/X (X:Ag,Cu,Ta) Multilayer Films Preparedby DC Sputtering by Y Haga, T Sugiyama, Y Nakamura and 0 Nittono

16Q-7

23

Monday November 16
X-ray Standing Waves in 100A-Thick Epilayers Under Grazing-incidence
Diffraction Conditions by 0 Sakata, I Kawamoto and H Hashizume

16Q-8

Observation of the CfR Scattering from AlAs Molecular Layers in GaAs using
Imaging Plate Detector by T Sh im ura and J Harada

16Q-9

Misfit Accommodation of Pt/Au!buffer Ag Trilayers Grown onto Si, MgO
and NaCl Substrates by A Sugawara and 0 Nittono

16Q-10

X-ray Diffraction Analysis of RTP Processed Cu/In/Se Stacked Thin Layers
by F Camillo, M Donat, H Galindo, A B Vincent, J M Martin
and D G6mez de Anderez

16Q-llSection 16R(Foyer)ORGANIC STRUCTURES II

Crystal Structures of Adenylyl2'-5'-adenosine Trihydrate and Tetrahydrate:
Molecular Conformation Under Different Hydrations
by R Krishnan and T P Seshadri

16R-12Crystal Structures of 2,6-di(2-furyl)-3,5-dimethyl Piperidin-4-one
by N Sukumar, M N Ponnuswamy, J C Thenmozhiyal and R Jeyaraman

16R-13Structural Study of 1-octadecanol by the PSPC System
by H Kobayashi and N Nakamura

16R-14

Crystal Structures of Meso-1,1'-dicyano-1,1'-diphenylethane (1) andMeso-1,1'-dinitro-1,1'-diphenylethane (2)by L L K o h, H H Huang, K Y Sim, Y L Lam and Y Xu

16R-15

Effect of Trimethylsilyl Substituent on C-0 Bond Lengths at the Beta Position:
Some Structural Studies by J M White and G B Robertson

16R-16

Sequential Base-promoted Cleavage of C-S Bonds in a Coordinated Crown
Thioether by M A Bennett, L Y Goh and A C Willis

16R-17Structure and Properties of Bilayer-forming Amphiphiles, C"AzoCmN ' Bl'
by Guiqing Xu, K Okuyama and M Masatsugu

16R-18

Crystal Structure of 1,18-Dibromooctadecane
byTYamamoto, N Nakamura andY Yoshimura

16R-19

2D-NMR Study on the Conformation of a Dodecacyclopeptide
by L H Lai, L B Ma, Z W Miao and X J Xu

16R-2024

Monday November 16
Section 16S

ORGANOMETALLIC STRUCTURES II(Main Hall)

Metal Complexes of Benzoquinonediimine and Related Diiminesby Shie-Ming Peng165-31

Crystal Structures of Four Transition Metal Complexes
by Tian-Hu ey Lu , Tahir Tahirov, Bor-Hann Chen and Chung-Sun Chung165-32Complexes of Some First Transition Series Elements with
4,4'-dipyrazolylmethane by J A Broomhead, G Camm and M Stern s

165-33Polymorphic Structures of M(HC00),.2(NH 2) 2 CO: M=Mn,Cd,Co,Mg,Zn
by N Achi wa , M Fujlno, H Takakura, M Shiono, N Koyano, Ridwan,
I Shibuya and K Yamagata

165-34

Crystal and Molecular Structure of Zinc(II) and Cobalt(II) Complexes w ith
4,5-Diazafluoren-9-one
by N V enkat a Lakshmi, K Ravikumar, G Prasuna and M V Rajasekharan

165-35

Study of Bis{trans-[bis(diphenylphosphino)ethylene]}-tricarbonyliron(O)and cis-[bis(diphenylphosphino)-ethylene]tricarbonyliron(O)by Lung-Shiang Luh and Ling-Kang Liu

165-36Structure of lodine{[3,3'-(1,3-propanediyldinitrilo)bis(2-butanoneoximato)]N ,N'N" ,N"'} (2,2,2-trifl uoroeth yl)co balt(III)by S Geremia, Asadur Rahman, E Zangrando and L Randaccio

165-37EXAFS Studies of Monomeric/Dimeric Equilibria of Nitridotechnetium(VI)Complexes in Solution
by G A Williams, L J Martin, D M Samuels and M Nomura

165-38

X-ray Structural Studies of a Novel Delocalised Triphosphazene(CF,),P=N=P(CF,),=N=PPh, and the Triosmium Cluster Complexes
O:;,(C0) 11 [(CF,),P=N=P(CF,),=N=PPh,] by H G Ang, W L Kwik andY M Cai

165-39Structures of (CF,),As=N=PPh,,[O:;,(C0)11 ((CF,),As=N=PPh,)] and165-40[Q;,(CO),(~-H),((CF,),As=N=PPh,)] -Novel Neutral Molecules
Containing As=N=P Moiety by H GAng, W L Kwik, Y W Lee and A L Rheingold
X-ray Crystal Structure of [{WCl,(PMe,Ph),},{(~-NC,H4 N-1,4}]The First Structural Characterisation of a Binuclear Complex Containing
a 1,4-phenylene Diimido Bridgeby W Clegg, R J Errington, DC R Hockless, J M Kirk and C Redshaw

165-41

Molecular Structure of Tungsten Phenoxide
by N Kanehisa, Y Kai, N Kasai H Yasuda, Y Nakayama and A Nakamura

165-4225

Monday November 16
Stereochemistry and Crystal Structure of Diphenyltin Dichloride Complexes
with meso- or rac-Bis-(phenylsulfinyl)ethaneby H-G Wang, X K Yao, R J Wang, J X Bao and P X Shao

16S-43

Coordination of Tetramethylethylenediamine with Halogen Bridged Lead(II)by H Miyamae, Y Hatanaka, Y Iijima, G Hihara and M Nagata

16S-44

Section 16T(Ma in Hall)ENZYME STRUCTURES

Crystallisation and Preliminary X-ray Studies of Calotropin DII, a Cystein
Protease from Ca lotropis gigantea by B Das, S Ghosh, S Pain,
I Dey, G Biswas, B P Mukhopadhyay, N K Sinha and Asok Ba nerjee

16T-45

Crystallization of Protein Disulfide Isomerase from Bovine Liverby G Kurisu, C Uematsu, T Shiba, S Harada, Y Kai and N Kasai

16T-46

Crystallization and X-ray Diffraction Study of Phospholipase A2 from the
Venom of Agkistrodon halys Pallas by Gui Lul u, Niu Xiutian, Yang Jian,
Bi Ruchhang, Liu Zhengjiong, Zhou Yuanchong and Lin Nianqin

16T-47

Two Crystal Forms of Bovine Heart Cytochrome c Oxidase byE Yamashita,
Y Morimoto, T Tsukihara, Y Fukumoto, K Shinzawa-Ito and S Yoshikawa

16T-48Structure Analysis of Serratia Protease from Serratia sp. E-15
16T-49
by K Hamada, H Hiramatsu, T Fujiwara, Y Katsuya, Y Hata, M Sato andY Katsube
Structure Analysis of Neutral Protease from Streptomyces caespitosus
16T-50by A Nagara, T Kinoshita, S Harada, Y Kai, N Kasai , S Tunazawa and F Sakiyama
Three-dimensional Structure of Oligo-1,6-glucosidase at 3A Resolution
by Y Hata, H Kizakai, K Watanabe, Y Suzuki andY Katsube

16T-51Three-Dimensional Structures of Aspartate Aminotransferase from
Escherichia coli at 1.8 A Resolution by A Okamoto, K Hi rotsu and T Higuchi

16T-52

Structure of the Active-site Mutants of Escherichia coli Aspartate
Aminotransferase by I Miyahara, K Hirotsu, T Higuchi and 0 Okamoto

16T-53

X-ray Structural Analysis of Aspartic Proteinase from lrpex lacteus
by H Mizuno, N Oogami, H Kobayashi, K Kasamo, I Kasukabe and K Murakami

16T-54Structure of Chimeric 3-isopropylmalate Dehydrogenase and its Thermostable
Mutants by M Sakurai, K Onodera, H Moriyama, N Tanaka,
K Num ata, H Kirino, T Oshima, Y Katsube and M Sato

16T-55

Crystal Structure of Ribonuclease U2 at 1.8A Resolution
by S Noguc hi, Y Satow, C Sasaki, T Matsuzaki and T Uchida

16T-5626

Monday November 16
Structure Analysis of Phospholipase A2 from the Venom of Trimeresuru s
flavoviridis byE Matsueda, A Suzuki, T Yamane and T Ashida

16T-57

Crystal Structure of Chicken Gizzard G Actin•DNase I Complex at 2A
Resolution by K.Sasaki, K.Sakabe, N. Sakabe, H. Kondo and M.Shimonura

16T-58Structure of Buffalo Carbonic Anhydrase II: Comparison with Other Known
Carbonic Anyhdrase (CA) Structures by V Kumar and K K Kannan

16T-59

Metal-Protein Interaction: Binding of Mercury to Human Carbonic Anhydrase
I Enzyme by S Chakra v arty, V S Yadava and K K Kannan

16T-60SMALL BIOLOGICAL MOLECULES AND FRAGMENTS(M ain Hall)

Structure and Molecular Motion in the Alkali Metal Salts of Penicillin V
by A J Edwards, C K Prout, M Dobson, J Fattah, S J Heyes, J E Taguchi,
J M Twyman, D J Watkin and M Wendeler

16U-61

Crystal Structure of the DNA Fragment d(CCGGGCCCGG)
by M A Viswamitra, D Champion C S Kumar and N Gautham

16U-62

Molecule Structure of an RNA Duplex with Four Successive non-Watson-Crick
Base Pairs by S Fujii, Y Tanaka, T Sakata, H Hiroaki, S Uesigi, and T Tanaka,

16U-63

Crystal Structure of Boc-d-Val-Ala-Leu-Ala-OMe
by V Pattabhi, C Sadasivan, S Durani and V Bohde

16U-64

Unusual Conformational Flexibility in n'-Substituted Uncommon Purine
Nucleotides: Structures of 1-allyl-isoguanosine and !-allyl-xanthosine
by Yen-Chywan Liaw, Ji-Wan g Chern and Andrew H - J Wang

16U-65

Conformational Analyses of AC-ring Bicyclic Colchicine Analogues
by R J Greenwood and M F Mackay

16U-66

Absolute Configuration and Conformation of a Novel Antiallergic Agent
KW4099 by N Hirayama, T Sugaya, S Tomioka, E Ohshima and N Obase

16U-67Structure Determination of the Blue Flower Pigment, Commelinin,from Comm elinia communis
by A Nakagawa, K Yoshida, T Kondo, T Kawai and the late T Goto

16U-68Structural Studies on ~(1~3) Linked Oligosaccharides
by K Noguchi, K Okuyama, S Kitamura and K Takeo

16U-69Crystal Structures of Modified Nucleosides 5'-o-Tosyl Adenosine and2'-o-Tosyl Adenosine by D Prahadeeswaran and T P Seshadri

16U-70Section 16U

27

Monday November 16
Metal Ion-purine Base Interactions, Zn(ll) and Cd(II) Complexes of
8-methylthiotheophylline. X-ray Crystal Structure and Solution Structureof Bis(8-methylthiotheophyllinato)diaquazinc(II) by M H Skipworth,
M R Taylor, J C Avila-Roson, M A Hidalgo, J Suarez-Varela and E Colacio
Section 16V

PHASE TRANSITIONS and SOLID STATE REACTIONS

16U-71(Main Hall)

Molecular Libration and a Possible Structural Phase Transition in Crystalline
4,4"-Difluoro-p-Terphenyl by H Sa i toh, K Saito, Y Yamamura,
H Matsuyam a, K Kikuchi, M Iyoda and I Ikemoto

16V-72

X-ray Diffraction Study of Phase Transitions and Structures of (KBr\.,(KCN),
Mixed Crystals by Y Yoshimura , T Okazaki and K Shimaoka

16V-73

Packing Effect in Solid-State Polymerization of Diethynylbenzene Derivatives
by y-irradiation
by R Kitagawa, N Kanehisa, Y Kai, N Kasai, Y Yamamoto and S Takahashi

16V-74

Asymmetric Photosynthesis in Chiral Crystal Environment
by H Kogo, A Sekine, Y Ohashi, R Matsukawa, K Miyamoto and F Toda

16V-7528

Scientif ic Abstrac ts

29

30

14A-1BIOLOGICAL APPLICATION OF SYNCHROTRONRADIATION
N. Sakabe, K. Sakabe*, T. Higashi+, A. Nakagawa & N. Watanabe,
Photon Factory, KEK, Tsukuba 305, Japan.
* Department of Chemistry, Faculty of Science, Nagoya University,
Chikusa, Nagoya 464, Japan.
+ Rigaku Corporation, Matsubara, Akighima Tokyo 1966, Japan.
The advantages of synchrotron radiation (SR) are high brilliance,
highly parallel nature and tunability. An X-ray diffraction datacollection system for macromolecular crystallography, with a
Weissenberg camera, imaging plate and image reader BAlOO, wasconstructed using SR at the Photon Factory. The basic ideas in using a
Weissenberg camera for macromolecular crystallography are: 1) A
cylindrical film cassette provides high resolution easily 2) Backgroundnoise decreases approximately as lfr2 (r is the film cassette radius) ,whereas Bragg reflections vary less strongly with r. 3) More data will
be recorded on a film, when Weissenberg geometry is applied. 4)
Bijvoet pairs are recorded with high accuracy on the same film, as
simultaneous reflections. 5) Almost all X-ray paths should be evacuatedor filled with helium gas to reduce scattering and absorption by air.
The fundamental requirements when detecting X-ray diffraction
from protein crystals are: 1) high detection quantum efficiency, 2) wide
dynamic range, 3) linearity of response, 4) high spatial resolution, 5)
large detector area 6) uniformity of response, 7) high counting ratecapability and 8)low background noise. An imaging plate(IP), a new
type of X-ray integrated-type area detector, is most suitable forcollecting X-ray diffraction data from protein crystals. The combinationof camera, IP and SR X-ray is very powerful (N. Sakabe, Nucl. lnstr.
and Meth., 1991, A303, 448). The type 3 camera using IP was designed
for station BL6A2 at the Photon Factory. Normally, one data set aroundan axis is recorded on 10-30 IP sheets, while consuming only one or
two crystals. In 24 hours 6-10 data sets can be collected. As 43 groups
from overseas and 45 domestic groups have requested use of this datacollection system, there is a long queue to secure just two days beamtime per year. To alleviate this situation, another station is underconstruction at L18B, which will also be used for time resolved LADE
experiments. Applications of this system will be presented and futuredata collection systems will be discussed.
It is contrary to common sense that X-ray crystallography should
elucidate only the static aspects of structure, whereas synchrotron
radiation should enable us to elucidate time dependent structures ofproteins. For this purpose we have made a time-resolved Laue camera
with data processing software. Evaluation of the Laue data andapplications of this method at the Photon Factory will be presented.

14A-2A MULTI-PURPOSE BEAM LINE FACILITYR F Garrett, ANSTO, Applications of Nuclear Physics, Private Mail
Bag 1, Menai NSW 2234, Australia
A multi-purpose beam-line is being constructed at the Photon Factory,
Tsukuba, Japan to provide users with routine acces s to synchrotron
radiation in the hard X-ray region. The beam-line will deliver either
monochromatic light, in the 5-20keV range, or white light to theexperimental hutch. The main experimental instrument will be a multiconfiguration vacuum diffractometer which combines a two-circle
diffractometer with a large Weissenberg mode Imaging Plate camera.
The diffractometer is optimised for protein crystallography, highresolution powder diffraction, small angle scattering and single crystal
diffraction.
Details of the beamline, monochromator anddiffractometer design will be presented.
In addition the white or monochromatic beam can pass through thediffractometer to a secondary table-top station, allowing other whitebeam techniques to be performed. This secondary station will beavailable in late 1992 for white beam experiments.

14A-3
DESIGN CONCEPT OF SPRING-8 UNDULATOR BEAMLINEFOR MACROMOLECULAR CRYSTALLOGRAPHY

N. Kamiya, H. Iwasaki, T. Ueki, M. Yamamoto, T. Uruga and H.
Yamaoka, The Institute of Physical and Chemical Research (RIKEN),
Hirosawa 2-1, Wako, Saitama, 351-01, Japan.
SPring-8 (S_uper E.hoton, ring-8GeV), a new synchrotron radiation sourcefor basic science and advanced technology, is now being constructed by
the JAERI-RIKEN SPring-8 Project Team at Harima Science Garden Cityin Hyogo Prefecture. (Commissioning of the storage ring will start in
1997-98.) SPring-8 is characterized by low emittance and the thirty-eightstraight sections for insertion devices such as undulators and wigglers.
The storage ring energy, 8GeV, provides the undulator fundamental Xray energy of 10-20 keY, which is very useful for macromolecular
crystallography.
X-ray crystallography is a most powerful technique to determine threedimen sional structures of biological macromolecules, which havecontributed so much to recent progress in molecular biology. However,
the technique is limited now by the MIR and MAD phasing (MIR with theheavy atom derivatives of low occupancy, and MAD for themacromolecules with relatively large molecular weight such as 50,000
daltons) and by the data collection for small crystals less than lOOj..t.m or
for very large macromolecules such as ribosomal proteins. All theselimitations are imposed by the accuracy of the reflection data available.
Since diffraction intensities from macromolecular crystals are
intrinsically weak, data accuracy is determined mainly by the backgroundlevel of X-ray measurement, which depends on X-ray optics and on thedetector utilized in data collection.
From the undulator of SPring-8, very intense X-rays with energy
resolution of 10-4 could easily be obtained in a small size (<lOOj..t.m) andwith small divergence (-30j..t.rad), although the high heat load problem
must be resolved for the optical elements. High quality incident X-rays
may decrease the background scattering from the sample crystal itself,from air, etc .. For macromolecular crystallography, the Imaging Plate isone of the most suitable X-ray detectors available, with a very low noiselevel, but the spatial resolution now achieved (-150j..t.m) should be
improved to -50j..t.m for recording diffraction spots less than lOOj..t.m. The
design concept of the SPring-8 undulator beamline for macromolecular
crystallography will be discussed in terms of these considerations.

14A-4

THE SCOPE FOR IMPROVED INSERTION DEVICES
Shigeru Yamamoto, Photon Factory, National Laboratory for HighEnergy Physics (KEK), 1-1 Oho, Tsukuba, lbaraki 305, Japan.
Insertion devices have been recognized as important sources ofsynchrotron radiation for physical and chemical sciences including
crystallog raphy, due to their very high brilliance, quasimonochromaticity, tunability of wave length and polarization
characteristics. Further recent progress in accelerator science is opening
the way towards producing coherent synchrotron radiation at very shortwavelength region using insertion devices.
In the Photon Factory, we have developed various undulators andwigglers with special features, and installed them in the 2.5-GeV Photon
Factory (PF) storage ring and the 6.5-GeV TRISTAN Accumulation Ring
(AR). As a whole these insertion devices provide users with synchrotron
radiation that covers the wide spectral range from lOeV to lOOkeV, andthe degree of circular polarization from 0 to 1 for both left- and righthanded circular polarization. The brilliance of the radiation from these
insertion dev ices ranges from 1015 to 1016 photons/s/mm2fmrad2/0.1 %bandwidth, which corresponds to a region of brilliance 102-103 times thatof the bending radiation both from the PF 2.5-GeV ring and the AR.
Spectral features of each insertion device will be described in detail in thepresentation.
The above activities at the PF and AR can be regarded as "Research andDevelopment" studies towards a future project in which very long (70m)
undulators are to be constructed in the TRISTAN Main Ring (MR), whichis to be renewed to very low emittance (about 1 nm rad) after high energy
experiments using the MR are terminated in a few years. The brillianceof the radiation will exceed that of the so-called third generationsynchrotron light source by three orders of magnitude. A brief
description will also be given of the possibility of producing coherent
radiation in a 4-nm region by driving a free electron laser installed in theMR.

148-1CRYSTAL STRUCTURES OF SOME SUBSTITUTEDETHANES
L. L. Koh and H. H. Huang

Chemistry Department, National University of Singapore
Singapore 0511
Crystal structures of a number of substituted ethanes have been
determined by X-ray diffraction. The substituent groups included nitro,
cyano , phenyl, alkyl and cyclic alkyl groups The following observations
have been made.
1. The main factors that determine the conformation of the molecules
appear to be the steric and polar interactions between the substituent
groups. Bulky groups at 1 and 1' positions tend to be trans to each otherwhereas nitro groups tend to be gauche .
2. The central C-C bond length is very much affected by steric effects.
The observed length ranges from 1.488(3)Ain 1,2-dinitroethane to1.630(3) A in 1,1' -diphenyl-bicycloheptyl.
3. For diastereoisomeric meso and (±) pairs, the meso isomer tends tohave higher density than the (±) isomer. The ratio of the densities
ranges from 1.024 to 1.054.
4. Most of the crystals have monoclinic cells. The internal symmetry of
the compound is usually not fully utilized in the solid state packing.

148-2
PREPARATION OF CARBON NANOTUBES BY DC ARCDISCHARGE EVAPORATION
Y.Ando, Department of Physics, Meijo University, Tenpaku-ku, Nagoya
468, Japan, and S. Iijima, Fundamental Research Laboratories, NEC
Corporation, 34 Miyukigaoka, Tsukuba, Ibaraki 305, Japan.
Carbon fullerenes such as C6o (Kroto et al. (1985)) can be prepared by dearc-discharge evaporation between two graphite electrodes in rarefied
inert gas. Part of the positive electrode is evaporated and deposited on thenegative electrode. Carbon nanotubes with helical structure (lijima (1991 ),Iijima et al.(1992)) were found in the deposit by high resolution TEM.
In thi s experiment, carbon evaporation was carried out in three different
kinds of atmospheric gas, He, Ar and CH4. The deposit on the negativeelectrode in each gas, with different gas pressures, was sectioned by adiamond cutter. By measuring the thickness of the deposit, its growth rate
was obtained as shown in Fig. 1. There exist optimum conditions on thegrowth rate of the deposit for each gas. The existence of carbon nanotubes
in the deposit section was confirmed by SEM and TEM for every gas
within the pressure range 20-200 Torr. Coexistence of whisker-like
nanotubes and small graphitic particles was observed by SEM. In addition
to the two typical morphologies, graphitic sheets were observed by TEM.
It is also concluded that the production of carbon nanotubes has been
completed in a very short timeby arc-discharge.
c:E.se 1.0
Iijima,S. (1991). Nature 354,
56-58.
Iijima,S., Ichihashi,T. andAndo,Y. (1992). Nature 356,776-778.
Kroto,H.W., Heath,J.R.,
O'Brien,S.C., Curl,R.F. andSmalley,R.E. (1985) . Nature
318. 162-163.

·;;;
0
a.

"

0

0 .5

\\
0

10

20

so

Pressure of Atmosphere

100(Torr)

Fig.!. Growth rate of carbon deposit200148-3
CRYSTAL STRUCTURE AND NONLINEAR OPTICALPROPERTIES OF m-NITROBENZOIC ACID DIETHANOLAMINE ADDUCT
X.K.Yao, H.G.Wang, R.J.Wang and J.M. Zheng, Central Laboratory andDepartment of Chemistry, Nankai University, Tianjin, 300071, China.
Variou s molecular organic compound with one or more aromatic
systems in conjugated positions have been studied actively for the lasttwenty years (Bailey et al ., 1991; Qin et al ., 1990) . Some criteria for amolecular crystal engineering approach have been formulated ( Zyss etal. , 1990). The 1:1 adduct of m-nitrobenzoic acid and diethanol amine(m-NB A-DEA) was obtained and a bulk single crystal with dimension 15
x 45 x 20 mm was grown by slow-cooling. This crystal, when irradiatedby laser light at 1064 nm (Nd3+:Y AG) generates a second-harmonic
wave at 532 nm. The structure of m-NBA-DEA has been determined by
X-ray diffraction, monoclinic, Cc, a = 22.892(8), b = 4.61 2(2), c =14. 809(5)A, 13 = 124.77 (2) 0 , Z = 4. T = llOK. R = 0.025. The m- NBAcarboxyl group's hydrogen atom has been transferred to the aminogroup of DEA. Six hydrogen bonds make the title compound a twodimensional network structure stretching on the (010) plane and thebenzene ring planes are perpendicular to the (010) plane. Thus the dipole
moment of the molecules enhance each other and macroscopic nonlinearities may, therefore, be manifested. From molecular mechanics
calculations it is shown that the molecular dipole moment of the groundstate reduced the original 6.25D to the current 5.80D owing to the shiftof the H atom and the resulting hydrogen bond generation. The head-toend arrangement of molecules is favourable to enhancing the value of
second order nonlinear optical coefficient 13 (Ye & Fang, 1990). It is also
known that there is no obvious difference between the conformation of
the title compound in the crystal and its ideal conformation predicted bymolecular mechanics. This helps to explain why m-NBA and DEA are
good partners for a nonlinear optical material.
Bailey, R .T., Cruickshank, P.R., Pugh, D . & Sherwood, J.N. (1991)
Acta Cryst. A47, 145-155.
Qin, J.G. & Liu, D.Y. (1990) Huaxue Tongbao, No.10, 23-30.
Zyss, J. & Tsoucaris, G. (1990) Structure and Properties of Molecular
Crystals, edited by M. Pierrot, pp. 97-350, Netherlands: Elsevier
Science Publishers B.V.
Ye, Cheng & Fang, Shibi (1990) Huaxue Tongbao, No.6, 5-12.

148-4
STRUCTURAL ASPECTS OF THE TRIVALENT GROUP 15
METAL (As, Sb, Bi) COMPLEXES WITH a-HYDROXYACIDSGraham Smith, Dalius S. Sagatys and Raymond C. Bott, Centre for Instrumental andDevelopmental Chemistry, Queensland University of Technology, Brisbane, 4000,
Australia.
The Group 15 metals constitute a pharmacologically important series of elements usedprimarily for the treatment of a number of exotic diseases, eg Schistosomiasis andLeishmaneisis (tartar emetic). However, because of the acute toxicity of theseelements, current usage is mainly limited to the less toxic bismuth compounds which
are cheap and efficacious in the treatment of amoebic stomach infections and peptic
ulcer disease (Gilman et a!., 1991). The most common means of producing suitablewater soluble compounds for pharmaceutical use is with a -h ydroxy acids and despite
their historical significance, little is known about their mode of action or about theirstructural chemistry [except for the antimony tartrates of the tartar emetic type (Mu,
1966)] . A project aimed at the systematization of the structural aspects of antimony(lii)and other Group 15 metals with a-hydroxy acids has provided a number of examples
of complex species involving these metals and both citric acid and (+)-tartaric acid,stabilized by various counter cations. Structural types include monomers such as[LiSb(citrate2')z(H2 0)] · 2H2 0, [NaSb(citrate2') 2 (H2 0)J · H2 0 (Hartley et a! ., 1991) :dimers, eg [AgSb(citrate2-)J 2 (Hartley et a! . , 199 1) and polymers [A~Sb 4 (tartrate•­MH20)4]. (Sagatys eta!. , 1991). Examples also include those with metal-metal bonds{[Ag5 As4(tartrate4-) 4(H2 0) 5 X].} (X = N03-, Cl04 -) and mixed-valence citrate species{[CuSb(citrate2-)(citrate3-)(H2 0)]· 2.5H2 0 (Smith eta! ., 1992) ; [K2Sb 4(citrate•-)g (H 2 0)s(n = +1 to +3)] . Only one bismuth example is described, a polymeric species,(NH4). [Bi(tartrate4-) 2 (H2 0)]. (Sagatys eta!., 1992) .
Gilman, A.G., Rail, T.W., Nies, A.S. & Taylor, P. , in ' Pharmacological Basis of
Iherapewics', 8th Edn. (Pergamon; New York, 1991) .
Hartley, D .W., Smith, G . , Sagatys, D .S. & Kennard, C.H.L. (1991). J. Chern. Soc.
Dalton Trans. , 2735-2739.
Mu, H.-C . (1966) . K'o Hseuh T'ung Pao 17, 502 .
Sagatys, D .S., Smith, G. , Lynch, D.E. & Kennard, C.H.L. (1991) . J. Chern. Soc.
Dalton Trans., 361-264.
Sagatys, D .S. O'Reilly, E.J. , Patel, S., Bott, R.C ., Lynch, D.E., Smith , G . &Kennard, C.H.L. (1992). Polyhedron 11, 631-634 .
Smith, G., Sagatys, D.S . , Bott, R.C., Lynch, D .E. & Kennard, C.H.L. (1992).
Polyhedron 11, 631-634 .

148-5STUDIES ON ORGANOMETALLIC COMPOUNDS:STRUCTURE AND ACTIVITY OF ORGANOSTANNYLCARBOXYLATES
B.B.Maji*, S.Biswas, K.L.Ghatakt, S.N.Ganguly#, A.Banerjee,
Bose Institute, Biophysics Department, Calcutta 700054.
* Presidency College, Calcutta 700073, India.
t Durgapur Govt. College, West Bengal, India.
# Bose Institute, Calcutta 700009,India.
The synthesis, structure determination [B.C. Das et al., (1992)] andbiological activity of organo-stannyl carboxylates [Maji, Ghatak, Ganguly,
Ray (1989)] are described. Orange red crystals were obtained byinteraction of 0-arylaminoazobenzene-2'-carboxylate at 298K. A singlecrystal X-ray diffraction analysis revealed a strictly planar COOSnBun3
moiety. This unique structural feature could be correlated with thecompound's biological property, which was due to the presence of both themetal and the P-azoic nitrogen in the reactive site of the molecule. The
biological potency of these organostannyl carboxylates is associated with
the nucleophilic character of the P-azoic nitrogen. The more thenucleophilicity, the greater will be the activity.
This was explained on the basis of intercalation of the (gly-gly) dipeptide ,into two specific and properly oriented binding sites of the organotin
compound, resulting in the formation of a stable complex. Such anintercalation mechanistic approach for arresting bacterial growth was
supported by chemical as well as by spectral studies. A computer simulated
intercalated model (Silicon Graphics) nicely corroborates the experimental
resuits.

Das B.C., Biswas G ., Ghosh S., Maji B.B ., Ghatak K.L., Ganguly S.N., &Banerjee A. (1992) Acta Cryst. C (in press).
Maji B.B., Ghatak K.L., Ganguly S.N., & Ray P.G.(1989). Trans Bose
Res. lnst. 52 (4), 97-100.

14 Y-1
POWDER DIFFRACTIONS P Sen Gupta, Department of Materials Science, Indian Association for
the Cultivation of Science, Calcutta 700032, India.
[Abstract will be supplied at conference]14Y-2
aTiOS0 4 : STRUCTURE DETERMINATION FROM POWDER XRDDATA AND RELATIONSHIPS TO OTHER MOX04 STRUCTURES.
I.E. Grey, CSIRO Division of Mineral Products, Port Melbourne, Vic. 3207 ,Australia, and R. Stranger, Department of Chemistry, University of
Queensland, Q. 4072, Australia.

aTiOS0 4 forms as a leach-resistant phase during the digestion of alteredilmenite concentrates in concentrated sulphuric acid. It contains about 7 wt%
Fe 20 3 and its composition can be expressed as Ti 85 Fe 15 0 85 (0 H). 15S0 4 . It has
monoclinic symmetry , space group C2/c, with unit cell param eters a =5.1175(2), b = 13.7675(6), c = 9.5035(4) A , ~= 91.097(3)'. Its structure wasdetermined using powder X-ray diffraction data and refined using the Rietveld
method to Rwp = 0.059, Rs = 0.022, G of Fit = 1.56 for 706 reflections to 28= 140°, CuKa radiation. The structure comprises a 3-D frame work ofcomer-linked Til06 and Ti20 6 octahedra and S0 4 tetrahedra, with 6-sided
channels running parallel to both [100] and [001]. Alternating comer-sharedoctahedra and tetrahedra form 4-member rings which link together into
ribbons via the constituent octahedra. Ribbons containing Ti106 and Ti206
octahedra lie along [001] and [100] respectively, and differ in the relative
positions of the pairs of octahedral vertices that are utilised in the formationof the 4-member rings.
Variation of the acid leaching conditions in the digestion experiments led to
the formation of two other (Ti,Fe )(O,OH)S0 4 polymorphs, structurally related
to Ge(OH)P0 4 and ~NbOP0 4 respectively, as well as various double sulphates. Structural relationships between aTiOS0 4 and these other phases will
be described.

14Y-3
CRYSTALLOGRAPHY OF REAI0 3 (RE =La, Ce, Pr and Nd)
M. Tanaka, Photon Factory, National Laboratory for High Energy,
Physics, 1-1 Oho, Tsukuba, Ibaraki 305 , Japan,
H. Horiuchi, Mineralogical Institute, Facu lty of Science,
University of Tokyo, Hongo 7-3-1 , Tokyo 11 3, Japan,
T. Shishido and T. Fukuda, Institute fo r Material Research,
Tohoku University, Katahira, Sendai 980, Japan.
The crystal lattices of the title compounds were carefully investigated by
X-ray powder diffraction profile analysis. All lattices are very slightly
distorted fro m the so called 'ideal' cubic perovskite structure . The
LaAl03 and NdAl03 structures are rhombohedral, but two different
crystal systems, rhombohedral and tetragonal have been suggested for
CeAl03 and PrAl03 [1-4]. Powder samples of these four compounds were
carefully prepared, in a graphite crucible under He gas atmosphere toprevent oxidation[5] , particularly as Ce and Pr prefer valency 4+. to 3+
in air. X-ray powder diffraction data were collected in the 29 range 10 to
135 degrees, by 0.02 degree step scanning, counting for 10 seconds ateach step with multiple measurements . Cu K a radiation (35kV and
22.5mA) monochromatized by pyrolytic graphite, with Si as external
standard, on a JEOL/DX-GO-S2 di ffractometer. The 29 angles
determined precisely for each peak by profile fitting program PROFIT[6] were used to evalu ate lattice constants by least squares methods. The
results indicate that REAl03 with La, Pr and Nd crystallize in therhombohedral system, but CeAl03 has a tetragonal structure . According
to a single crystal structure analysis of CeAl03 [7], some 0 atom shapes
deviate markedly from spherical. This might be due to averaging overstatistical arrangements of very fine scale domains with symmetry
structure lower than tetragonal. The lattice distortion from an ideal cubic
perovskite type structure is smaller in LaAl03 and greater in NdAl0 3.
[1] Geller S. & Bala V.B. (1956). Acta. Cryst. 9, 1019.
[2] Margolis N.V., Toropov N.A. & Udalov Yu P (1964). Soviet Physics
Crystallography, 9, 328.
[3] Kim,Y.S. (1968). Acta Cryst., B24, 295.
[4] Zachariasen; W.H. (1949). Acta Cryst. 2, 388.
[5] Shishido T., Tanaka M., Horiuchi, H. & Fukuda T. (1992). Bull.
Chern. Soc. Japan, 6,47.
[6] Toraya, S .(1986). J. Appl. Cryst. 19, 440.
[7] Tanaka M., Shishido T., Horiuchi H., Toyota N., Shindo D. &Fukuda,T. (1992). Proceedings in 'Rare Earth 92', in print.

14Y-4

CRYSTAL STRUCTURE ANALYSIS WITH HIGHRESOLUTION POWDER DIFFRACTOMETER DATA
T. Ochiai and H. Toraya, Ceramics Research Laboratory, Nagoya
Institute of Technology, Asahigaoka, Tajimi 507, Japan
There has been growing interest in the use of high-resolution powder
diffractometer data for crystal structure analysis (Louer and Langford,
1988, Kurahashi, Honda, Goto, Inari & Katayama, 1991). In the present
paper, the quality of the data measured on a commercial-type highresolution powder diffractometer was assessed. The advantages anddisadvantages of its use in structure analysis have been studied.
The diffractometer used was a Rigaku RINT system, equipped with a
Johanson-type Ge(lll) crystal monochromator on the incident-beam side toremove the Ka.2 component. In order to compensate for loss of intensity
due to rnonochromatization, it was installed on a rotating anode generator(Cu target), which at maximum load could be operated at 18 kW. Powder
samples of a.-Si02 (!l = 96.4 cm-1) and Ce02 (!l = 2240 cm-1) were used
as reference standards for investigating the variation of profile shape with
29. Their powder patterns were analyzed by profile fitting. The pseudoVoigt function gave a better fit than the Pearson VII function in the full29 range. The minimum full-width at half maximum (FWHM) for areceiving slit (RS) width of 0.15mm of 0.068° at 29 = 33° decreased to
0.057° with loss of intensity for an RS width of 0.05mm. The profile
shape varied almost linearly from Gaussian to Lorentzian with increasing
29 as observed by Louer and Langford (1988). The shapes for the Ka.lsinglet were almost symmetric for Ce02 sample with a narrow Soller slit
(aperture = 2°). However, the profile slightly broadened and became
asymmetric for a.-Si02, possibly because of displacement-type aberration
due to specimen transparency.
In order to study the dependence of pattern decomposition on the
resolution of the data, powder patterns for monoclinic-Zr02 observed byusing diffractometers of the present high-resolution type, of normal type,
and with parallel-beam synchrotron radiation were analyzed by wholepowder-pattern fitting techniques. Two overlapping reflections at a
distance of a quarter of FWHM from each other could be decomposed
when the high-resolution type diffractometer data were used, giving muchbetter resolution than that by a normal-type diffractometer. The effect ofdata resolution on the refined positional and occupancy parameters ofseveral inorganic materials is also under investigation.
Louer D. and Langford, J. I. (1988). J. Appl. Cryst. 21, 430-437.
Kurahashi M., Honda K., Goto M., Inari Y., and Katayama C. (1990)
J . App/. Cryst. 24, 61-63

14Y-5
STRUCTURES OF THE TWO POLYMORPHS OF MAGNESIUM BORONNITRIDE DETERMINED FROM X-RAY POWDER DIFFRACTION DATA
H. Hashizume, N. Sudo, H. Hiraguchi, 0. Fukunaga (*L C. Gilmore (+)
and G. Bricogne (SL Research Laboratory of Engineering Materials,
Tokyo In stitute of Technology, Yokohama 227, Japan.
(*) Dept. of Inorganic Materials, Tokyo Institute of Technology.
(+) Dept. of Chemistry, University of Glasgow, Scotland.
($) LURE, Orsay, France and MRC, Cambridge, England.
The crystal structures of magn esium boron nitride Mg3BNJ in the lowand high-pressure forms have beerr determined ab initio from X-ray
powder data. The steps used are to decompose the powder pattern toextrac t integrated intensity data, calculate Patterson functions andbuild try-and-error structure models, followed by test powder patterncalculations and Rietveld refinements. 54 and 21 reflections observed
on a laboratory 8 -8 diffractometer were used to solve the structuresof Mg3BNJ(L) and Mg3BNJ(H) respectively. The effective data resol ution
is 0.9A for Mg3BNJ(L) .and 1.25A for Mg3BNJ(H). Low-pressure Mg3BNJ(L)
has a hexagonal cell (space group F6J/mmc, Z= 2) with a= 3.54453(4)and c = 16.0353(3)A while the high-p r essure Mg3BNJ(H) cell is orthorhombic ( Pmmm, Z = 1) with a= 3.0933(2), b = 3.1336(2) .and c =7.7005(5)A. The two structures commonly include linear N=B=N molecu lar anions, which are thought to play a role in catalyzing the reaction BN(hexagonal) -+ BN(cubic) at high pressure-temperatures.
A very similar structure has been obtained by applying standard
direct methods to the same Mg3BNJ(L) intensity data. Refinements
revealed unimportant anisotropic thermal vibrations for each of theMg, B and N atoms, which are supported by quasispherical distributionsof the atomic electrons in the density maps calculated from the phased
structure factors by entropy maximization . The maximum-entropy maps
also show significant electron densities between the N and B atoms,
sup porting the double-bond N=B=N molecules. An attempt to solve the
Mg3BNJ(L) structure from the unphased structure factors using theprocedure devised by Gull, Livesey and Sivia [Acta Cryst. A43, 112(1987)] did not work. A separate application of a multisolution methodof phase determination by combined maximization of entropy and likelihood [C. Gilmore et al., Acta Cryst. A47, 830 (1991)] yielded a clean
map which revealed the positions of all the Mg, B and N atoms for
Mg3BNJ(L). Inclusion of overlapped reflections was essential. The
same Mg3BNJ(L) structure was thus obtained by the three independent
structure determinations.

14C-1
ELECTRON DENSITY DISTRIBUTIONS OF CRYSTALLINE
MATERIALS OBTAINED BY THE MAXIMUM ENTROPY METHOD
M. Sakata, Department of Applied Physics, Nagoya University, Chikusa-ku, Nagoya,464-01, Japan.
This is a review of recent studies on electron density distributions of crystalline materials obtained by the Maximum Entropy Method ( MEM ) done by our group. T hestudies to be reviewed are limited to ones which deal with the Fourier transformationof crystal structure data in order to estimate the electron-density distribution of acrystal. The MEM provides us with t he least-biased deduction which is compatible
with certain given information . In the present case, the given and missing information corresponds to the observed and unmeasured structure factors , respectively.
Since the materials for which the electron density distributions have been obtained
by MEM analysis so far have very simple structures, it is assumed that the phase
could be determined without any significant ambiguities.
The first work to restore the precise electron density distribution by t he MEM analysis was performed for Si by Sakata & Sato r M. Sakata & M. Sato ( 1990) Acta
Cryst. A46 , 263 ]. The data used in the analysis were collected by Saka & Kato
( T. Saka & N. Kato (1986) Acta Cryst. A42 , 469]. They measured the st ructure
factors for 30 net planes by the Pendellosung method on an absolute scale. In theirdata set , however, so-called forbidden reflections were not included because of experimental difficulties. In the conventional Fourier method, the core electrons could be
easily see n in the electron density distribution bu t it was not possible to restore thecovalent bond electrons due to probably lack of forbidden reflections , which arise
from purely the contribution of bonding electrons at room temperature. On theot her h and, the electron density distribution of Si obtained by the MEM analysis
by using the same data set clearly showed the covalent bond electrons bet ween Si
atoms as well as core electrons. It was also shown that the MEM density map hadmuch higher peak height at atomic position than that of conventional Fourier map;roughly speaking twice. In other word, it could be said that the resolution of MEM
density distribution is very high. Furthermore it was revealed that unmeasured forbidden reflections could be well predicted from the MEM map of Si .
The method was extended so as to treat X-ray powder data. Modern powder diffraction has been greatly improved in various ways, particularly, profile refinement anddecomposition. It is possible to evaluate integrated intensities for each Bragg reflection unless the peak overlap is very severe. At this point, high resolution diffractometer utilizing synchrotron radiation has a great advantage. The extension wasmade to handle the severely overlapped peaks as a combined structure factor. By
this extension , the method is now having a versatility. So far about 10 compounds
have been already analyzed by the present method, such as Ce0 2 , CaF 2 , Ti0 2 , Be,
Mg, AI, Cu, ice Ih, LiF, LiH, etc and the number is increasing quite rapidly. It isnotable from the results that the structure of hcp and fcc metals in electron level arecharacteristically different; hcp metals forms electronic layer by three center bondbut fcc metals. It is also notable that the electron density distribution of hydrogenis strongly influenced by the existence of hydrogen bond.
Methodologically further extension is going on, such as trying to solve the negative
scattering problem in neutron diffraction case or trying to find out small structure change with either temperature, pressure or composition by simply subtracting
MEM density map of two states.

14C-2MAXIMUM ENTROPY METHOD ANALYSIS OF NEUTRONPOWDER DIFFRACTION DATA
M. Saka.ta, T. Uno, M. Takata, Department of Applied Physics, Nagoya University, Nagoya, Japan; and C. J. Howard, Australian Nuclear Science & Technology
Organization, Lucas Heights, NSW 2234, Australia.
It is often said that X-ray and neutron diffraction is complementary. In X-ray
powder diffraction, X-ray photons are scattered by electrons in materials, while
neutron beams are diffracted by nuclei in neutron powder diffraction case assuming that there is no magnetic interactions. What could be observed from X-ray
and neutron powder diffraction data is, therefore, the electron and nuclear density
distribution of the crystalline materials, respectively. There have been, however,not known how to restore such electron and/or nuclear density distribution directly from the observed structure factors by powder diffraction without using
any structural model.

Recently Sakata & Sato ( M. Sakata & M. Sato (1990) Acta Cryst.A46, 263] has
successfully applied the Maximum Entropy Method (MEM) to restore the precise
electron density distribution from the accurately determined structure factors by
the Pende//osung met hod. It is possible to measure the accurate Bragg intensities
free from extinction effects by a powder diffraction experiment. The success ofthe method depends on the fact that the electron density is always positive. In
order to analyze neutron diffraction data by the MEM, it is necessary to overcome
the difficulty of negative scattering length for some atoms, such as H, Ti and Mn .
Though a method to tackle this negative scattering problem was presented in the
XVIIth Meeting of the Society of Crystallographers in Australia, it was not fully
satisfactory. The reason is that it had to use the calculated structure factors
in order to reverse the contribution of negative scatterers. The results of thismethod necessarily depend on the structural model used .
In this work, the new method has developed. The new approach is based , noton scattering length densities, but on nuclear densities which are always positive. Two equations are obtained, one for atoms with nuclei of positive scattering
length and the other for atoms with negative scattering length. Using these two
equations, nuclear densities of Ti and 0 atoms can be calculated separately. This
procedure, like its X-ray counterpart , requires no structural model. MEM analysis of the rutile data by this approach has been successfully completed. As
expected, and in contrast to the electron density distribution obtained by the
MEM f Sakata, Uno, Takata, Mori. (1992) Acta Cryst . B48, in press] , the map
shows both Ti and 0 nuclear densities localized within very small regions aroundthe atomic centres. It is concluded that the MEM applied to a neutron powder
diffraction data is much superior to conventional Fourier transformation and, inspite of the longer computation time, is well worthwhile.

14C-3
AN ANALYSIS OF APPROXIMATION OF THE MAXIMUMENTROPY METHOD
Shin taro Kumazawa, Department of Physics, Science University ofTokyo, Noda, Japan, and
Makoto Sakata, Department of Applied Physics, Nagoya University,
Nagoya, Japan.
A new method has recently been developed for accurate structure
analysis, that is, the Maximum Entropy Method(MEM) [1]. The MEM is avery powerful method for visualizing detail in electron and nuclear
densities without using any structural model. In an increasing number ofexamples, such as Si[l], Ce02 [2], Ti02 [3], etc the MEM was successfully
applied. In this work, the MEM fundamental equation was solved under
the conditions; 1) to satisfy symmetry requirements, 2) to conserve thenumber of electrons, 3) to adopt 0-th order single pixel approximation[4]. The MEM solution is thus obtained iteratively, starting from the
maximum entropy state of uniform density. Among the conditions, 1) and2) are consequences of our knowledge of crystallography. Howevercondition 3) is needed to solve the equations numerically at each iteration.
It is therefore desirable to examine the validity of this approximation.
The purpose of the work is to examine the validity of the 0-th order
single pixel approximation and to analyse the MEM by simulation.
First we consider a very simple case of a !-dimensional electron densitywith a center of symmetry where only two pixels exists. In this case it ispossible to solve the MEM equation analytically at each iteration. There isvirtually no difference between the exact and approximated solutions aslong as the value of Lagrange multiplier, A, is sufficiently small. As A
increases, the discrepancy between the two solutions becomes larger.
Secondly, the MEM was examined by 1 and 2 dimensional simulation andcompared with the conventional Fourier synthesis. When all non-zerostructure factors are used, the MEM and the Fourier synthesis give thesame density distribution which is, of course, identical to the originaldensity. For a limited number of structure factors, the MEM solution
reaches the original density much faster than the Fourier synthesis as thenumber of structure factors increases. It is concluded from thesesimulations that the MEM is greatly superior to the conventional Fourier
synthesis for restoring the original electron density when the available
structure factors are limited, which is likely in practical cases.
[1] Sakata M & Sato M. (1990) Acta Cryst. A46, 263.
[2] Sakata, M. et al. (1990) J.Appl.Cryst. 23, 526.
[3] Sakata, M. et al. (1992) Acta Cryst. B48, in press.
[4] Wilkins, S.W. et al.(l983) Acta Cryst. A39, 892.

14C-4A DIRECT INVESTIGATION OF THERMAL VIBRATIONSOF Be METAL BY THE MAXIMUM ENTROPY METHODAPPLIED TO SINGLE CRYSTAL NEUTRON DIFFRACTION
DATA
M.Ta!cata. M.Sakata, F.K.Larsen*,Y.Kubota & B.B.Iversen*
Dept. of Applied Physics, Nagoya Univ., Nagoya, 464-01, JAPAN*Dept. of Chemistry, Aarhus Univ., DK-8000 Aarhus C, DENMARKA conventional approach for describing the atomic thermal vibrations is to assume that thevibrations are determined by an effective one-particle potential which is expanded
according to the atomic site symmetry. The corresponding atomic thermal smearing
function is thus temperature dependent. The Maximum Entropy Method (MEM) directly
yields the nuclear density distribution, which is equivalent to the thermal smearing
function, from even a limited number of accurate neutron diffraction datal). Therefore,
the MEM enables us to investigate thermal vibrational features directly without using amodel. The purpose of this study is to examine the capability of the MEM for the direct
investigation of thermal vibrations and Be was chosen as a test case.
Mean-square atomic displacement and antisymmetric atomic vibrations in Be at room
temperature have been determined from short-wave length neutron data by conventional
analysis. The same data have been treated by the MEM. In one analysis, the 48
reflections up to the sin() 1 J.. = 1.41A -I are used and the unit cell is divided into
120X120X120 pixels in order to get good spatial resolution. The density distribution at
the presumed nuclear site in the basal and in the (100) plane which is perpendicular to thebasal plane of the hcp structure are shown in Fig. 1 (a) and (b), respectively.
In Fig.1(a), a characteristic triangular feature is clearly visible. We interpret this as beingcaused by 3rd order anharmonic vibrations in the basal plane. 1n Fig.1(b), the nuclear
density shows significant difference from the expected oblate shape for harmonic
vibrations. We interpret this feature as being due to a significant quartic term of the oneparticle potential function. 1n the conventional approach, it is very difficult to prove theexistence of a quartic anharmonic term since there is a very high correlation between
second and fourth order parameters. So far, only inconclusive results have been provided
for the quartic anharmonicity in Be. However, in this study it seems that the MEM
density maps have revealed the existence of 3rd order as well as 4th order anharmonic
vibration. Curve fits to the MEM density proflles along different directions are being
calculated in order to derive the quantitative values for the anharmonic terms directly from
the MEM map. Results will be presented at the meeting .

•

[001]

[100]~

H

(a)

O.lA

(b)

Fig. l MEM nuclear densities (a) in the basal plane, (b) in the (100) plane.
The contour lines are drawn in logarithmic scale.
I) Sakata,M., Takata,M., Kubota,Y., Uno,T., Kumazawa,S .• & Howard,CJ., (1992)
to be published in Advances in X-ray Analysis
2) Larsen,F.K., Lehmann,M.S., & Merisalo,M.(l980) Acta CrysL,A36 ,!59

14Z-1
ACCURATE DETERMINATION OF THE UNIT CELL FOR
AN EPITAXIAL LAYER OF Hg!-xCdxTe DEPOSITED BY
MOCVD ON GaAs
Zh u Nanchang", Andrew W. Stevenson' and Li Runshen""Shanghai Insti tute of Metallurgy, Academia Sinica, 865 Chang Ning Rd. , Shanghai
200050, China' CSIRO Division of Materials Science and Technology, Locked Bag 33, Clayton,
Victoria 3168, Australia
Hg, _, Cct,Te (MCT) is a ternary alloy with the cubic zincblende structure. It iscurrently receiving considerable anention because of its applications in areas such as
infrared detection, op toelec tronic devices and solar cells. Stevenson, Gao, Pain &Wieluri ski ( 1991) reponed on strucrural aspec ts of six metal organic chemical vapour
deposition (MOCVD)-grown Hg,_,Cct,Te epitaxial layers (of order 1 to 2 pm thick)on novel GaAs su bstrates.
GaAs is chosen as a substrate because of its
inexpensiveness, excellent structural quality and the availability of large-areamateriaL There is however, a large lattice mismatch be twee n GaAs and Hg 1_,Cct, Te.
Large layer miscu ts (the angle betwee n the surface and the Bragg planes of thenominal orientation), of 4.3°, were reponed for the samples of (3 11 ) and (311)orien tation, whereas the substrate miscuts were less than 1° (0.94° and 0.84°
respectively). The substrate orientations are the same as for the corresponding
layers.
Double-crystal diffractometry has been used, employing the method
described by Li Runshen & Zhu Nanchang (1990), ro accurately determine thedisroned unit cell of the Hg, _,Cd., Te (311) layer and its orientation re lative to theunit cell of the GaAs (311) substrate . Four-circle diffractometry is used to relate
the disposition of the unit cells to the sa mple surface.
The effects of wave length dispersion and asymmetric Bragg diffraction geometry on
the double-crystal rocking curves colkcted will be discussed. The rocking curves
The composition of thealso reveal an anisotropy in the Hg,_,Cci., Te layer.
Hg,_,Cct, T e layer (i.e. the Cd x fraction) is also determined.

Stevenson, A.W., Gao, D., Pain, G.N. & Wieluriski, L.S . (1991 ). Acca Cryst. A47,
128-133.
Li Runs hen & Zhu Nanchang. (1990). Chin. J. Semiconducrors. 11, 759-767 (inChinese).

14Z-2

EVA LU ATION OF THE ROUGHNESS OF CRY STAL
SURFA CE BY X-RAY SCATTERING- THEORETICAL CONSIDERATION J.Harada , Department of Applied Physics, Nagoya University,
Chikusa-ku , Nagoya, 464-01, J apan
The relationship between the intensity di stribution of t he Crystal
Truncation Rod (CTR) scattering and the surface roughness of acrystal is discussed by developing a kinematic theory for the CTR
scattering. The intensity of the CTR scattering elonga ted from a
Bragg point is shown to be reduced by a factor [f(q)[ 2 for a surface
possessing some roughness, where f(q) is defined by a simple Fouriersummation of /p , the relative area with the same step height p ona surface, ie
00

f(q) =

L /pexp{2nip · q}

00

with

p=O

L / p=l ,p=Oq being the distance in recipro cal space from the Bragg point along
the CTR scattering. A pair correlation function between t he steps
can , therefore, be obtained by a simple Fourier integral of the Roughness Damping Factor [f(q)[ 2 •< / 0/p >= 21qmaz [f(q)[ 2 exp{2nip · q}dq
where < /O/p > is the pair correlation fun ction defined as< /0/p >=L/p'Tp'+P

p'2':0For the case where /p has a Gaussian distribution around the average
step height, [f( q) [2 is approximated by the well known De bye-Waller
like factor, exp { -4n 2 • < 6.p 2 > ·q}, where < 6.p 2 > is the meansquare deviation of step height in the units of lattice spacing.
Diffuse scattering arises also due to the existence of the irregularityof the surface. This term is given by Fourier summation of pair corrections between the steps separated by rmn latt ice on the surface.
The relationship between the diffuse scattering and above r (q) will
also be given.

14Z-3GRAZING-ANGLE X-RAY STANDING WAVE STUDY OF
As -ADSORBED SILICON SURF ACE
H. Kurashina, 0 . Sakata and H. Hashizume, Res. Laboratory of Engineering Material s, Tokyo Institute Technology, Yokohama 227, Japan
Monolayer As atoms chemisorbed to c lean silicon (111) surface are known
to remove the complex reconstruction of the silicon surface . An X- raystanding-wave study revealed the As atoms occupyin g the upper half ofthe silicon (111) double layer at a slightly increased vertical distance.
Bond considerations favor the three-fold T sites for the As atoms but
this has yet to be experimentally confirmed. We hav e attempted to use
X-ray s tanding waves at grazing angles to tackle this prob lem. The Si(111) surface was cleaned b y thermal evaporation of oxide layers at
850'C in ultrahigh vacuum. The substrate was then exposed to a beamof As molecules from an effusion cell for 25 min during which time thesample was cooled from 800 to 400'C. A sharp (1X 1) RHEED pattern
was observed after As deposition. The X-ray experiment was performedat the BL-14B workstation of the Photon Factory. Vertically polarizedsynchrotron X ray at 17.5 KeY photon energy made a small glancing
ang le to the surface and simultaneously satisfied the Bragg condition
for the bulk (220) planes. In this condition the coherent interferenceof the incident, the specular reflected and the Bragg diffracted b eams
generates X-ray standing wave field with an intensity modu lation parallel to the surface. In Fig. 1 the observ ed intensity profiles of the
specular r e flected and the Brag g diffracted beams show features of theperf ect-crystal rocking c urves with half widths 50% larger than calculation. The v alley-peak profile of AsK emission signal is characteristic of a disordered surface structure. Exposure to air for four days
destroyed the original registryof the As atoms to substrate Si
tJJ
atoms. This difficulty could be
;..>
.....
'
1.0
overcome by p lacing the sample~:lin a UHV chamber with beryllium.0)>~
windows under commissioning.
(I)
aj
X X X
xx
The sample is to be transportedIs.....::0
in a pumped vessel and trans.....,.c
X K )(X
XXX X
0ferred to the scattering chamber
0.5
0
0
Ih
......(/)
0
mounted on a high- precision
0 0.
<Irotary table at the Photon
10
arc
sec
Factory workstation.

..

.........

I(

l(

I(

0 • 0 0

DEVIATION ANGLE

14Z-4
AXIAL SYMMETRY QUASICRYSTAL STRUCTURE IN
SOME COATING THIN FILMS AND VEGETABLE FIBRES.
ESR STUDY
Nguyen Van Tri, Pham The Vung and Le Hai Hung,
Institute of Technical Physics, Hanoi University of Technology.
PCHT, Truong Dai hoc Bach khoa Hanoi, Hanoi Vietnam.
The microstructure and related properties of oxidized silicon surface,special porcelain enamel and pineapple fibre have been studied. The
normal diffraction and other methods showed that these materials can bereferred to as amorphous or polycrystalline. However, a careful ESR
study can give another result: distinct axial symmetry quasicrystal
structures persist in these systems. Numerou s exchange couple
complexes and the respective bond lengths and bond angles were revealed
and evaluated. Especially, the angular dependences of the g-values on themagnetic field direction were measured. These dependences possess avery prominent characteristic axial symmetry. In the case of the Si-Si02
system, the factor responsible for this axial symmetry is an ensemble
included in the Si-Si02 interface layer with identical Zachariasen units
whose planes are parallel to the silicon surface. In the case of special
porcelain enamel, the responsible ensemble includes plane pentagonal
units coupled by fivefold (2F-2M) complexes growing on the porcelainsurface. In the case of pineapple fibre, there is a local structure in thephysical network coupled by fivefold (2Fe-2S) rhombic complexes
diagonally bonding a macromolecule chain with five neighbouring ones.
This local structure is based on a pentagon created by five sulfur atoms
whose plane is perpendicular to the axis of the fibre. The importantroles of quasicrystal structures in specific features of these materials(such as the peculiar conductivity of the porcelain enamel and thestrength, the tensility, the torsional module of natural fibres, etc.) havebeen partly discovered.

14Z-5
DOUBLE CRYSTAL X-RAY CHARACTERIZATION OF 111-V
MULTILAYERED SPECIMENS BY SELECTIVE ETCHINGS Swaminathan, School of Electrical and Electronic Engineering,
Nanyang Technological University, Singapore 2263
Double crystal experimental rocking curves of III-V multilayer
specimens can provide valuable information about the lattice mismatch,
crystallographic quality, compositional and thickness variations of theindividual layers . Thick multilayer systems as in laser structures undergointerference effects resulting in oscillations in rocking curves (Chu &Tanner, 1986). In extreme cases, when the layers are thin, additional
peaks are predicted that do not correspond to a Bragg peak (Halliwell etal, 1984). Rocking curves from multilayer structures thus generally havecomplex shapes and extractiing relevant information from theexperimental curves is not straightforward. In order to isolate rocking
curve characteristic of each layer in a heterostructure, a selective etching
technique (Phatak & Kelner, 1979) has been used . Two specimens werechosen for this purpose, a DH laser and an edge emitting LED, grown byliquid phase epitaxy on (100) InP substrates. Each layer in the multilayer
structure was etched off in sequence. A corresponding experimental
double crystal rocking curve plotted.
The double crystal arrangement (Grasserbauer & Werner, 1991 ) wasaligned for recording a (400) reflection at 1.54 A wavelength, with ahighly polished (100) InP crystal on the first axis. From a comparison of
the different experimental rocking curves, it was possible to extract
information about peak height, peak width, and lattice mismatch ofindividual layers. The method of selective etching has therefore made it
possible to identify individual layer peaks in a multilayer structure. Thismismatch data from selective etching was effectively used as initial input
for simulating rocking curves for the multilayer specimens and an
accurate estimate of the thickness and compositional variation in theindividual layers was thus possible.
Chu, X. & Tanner, B.K. (1986). Appl. Phys. Lett., 49, 1773.
Grasserbauer, M. & Werner, H. W. (Eds) (1991). Analysis of
Microelectronic Materials, John Wiley and Sons.
Halliwell, M.A.G. et al (1984). J. Crystal Growth, 68, 523.
Phatak, S . B. & Kelner, G. (1979). J. Electrochemical Soc., 126, 287.

14 P- 01
CRYSTALLIZATION AND PRELIMINARY X-RAY
CRYSTALLOGRAPHIC STUDY OF LYSOZYME PRODUCEDBY STREPTOMYCES GLOBISPORUS
C.Uematsu, H. Naitoh, S.Harada, Y.Kai and N.Kasai
Department of Applied Chemistry, Faculty of Engineering
Osaka University, Suita, Osaka 565, Japan
Lysozyme is the enzyme which causes lysis of cell walls of bacteria byhydrolyzing the, ~-(1~4) -glycosidic bonds of the polysaccharide backboneof the peptidoglycan. On the basis of the homology of amino acidsequence, lysozymes are classified into four distinct types: (I) chikin, (2)phage, (3) goose and (4) Chalaropsis. Streptomyces globisporus produces
two kinds of lysozyme (M-1 and M-2 lysozyme) and secretes them in thecultural broth. The molecular weights are about 20,000 and 11 ,000 for
M-1 and M-2 lysozyme, respectively . Analysi s of the amino acidcompo sition of M-1 and M-2 lysozyme indicated that (1) M-1 lysozyme
belongs to the Chalaropsis type, and (2) M-2 lysozyme is similar to henegg white lysozyme but there was no cystein residue in this enzyme. M-1
lysozyme from Streptomyces globisporus has been crystallized in a form
suitable for X-ray crystallographic structure analysis. Crystallization wasachieved by hanging-drop vapour diffusion and a seeding method using
sodium citrate as a precipitant at room temperature.

Crystal data:

tetragonal, space group P4t2t2 (or P432t2)
a=b=63.09, c=121.44A

After the heavy atom derivative search, diffraction data sets werecollected for native and two kinds of Hg derivative crystals usingsynchrotron radiation at the Photon Factory. Structure analysis using the
SR data is in progress.

14P-02PRELIMINARY CRYSTALLOGRAPHIC STUDY OF
CYTOCHROME c' FROM ACHROMOBACTERXYLOSOXIDANS NCIB 11015
N. Shibata. T. Inoue, Y. Kai, S. Harada and N. Kasai, Department ofApplied Chemistry, Faculty of Engineering, Osaka University,
Suita, Osaka 565, Japan,
T. Kohzuma and S. Suzuki, Institute of Chemistry, College of General
Education, Osaka University, Toyonaka, Osaka 560, Japan,
H. Iwasaki, Nagoya University of Foreign Studies, Nisshincho, Aichi 47001, Japan and
S. Shidara, Department of Environmental Science, Faculty of Integrated
Arts and Sciences, Hiroshima University, Naka-ku, Hiroshima,
Hiroshima 730, Japan.
Cytochromes c', a class of c-type cytochrome found in photosynthetic anddenitrifying bacteria, are noted for their unusual chemical and physicalproperties. These properties are derived from the ferric heme-ion
ground state electronic configuration. The function of cytochrome c' isunknown, but cytochrome c' must contribute to denitrification, since acomplex of cytochrome c' with nitrogen monoxide was found to exist in
Achromobacter xylosoxidans NCIB 11015 by Yoshimura, Iwasaki,
Shidara, Suzuki, Nakahara & Matsubara (1988). A preliminary
crystallographic study on cytochrome c' from Ach. xylosoxidans NCIB
11015 has already been reported by Norris, Anderson, Baker & Rumball(1979), but successful structure determinations have never been reported .
Consequently, to elucidate the heme environment and the mechanism ofdenitrification, cytochrome c' crystals suitable for X-ray crystal structure
analysis have been prepared. The crystals belong to the hexagonal spacegroup P6122 (or P6s22). The unit cell dimensions are a=b=54.9 A ,c=181.3A. We have collected the native data with synchrotron radiation
at 1.0A. Data collection at the iron absorption edge and structure analysis
by molecular replacement using model of cytochrome c' from
Rhodospirillum molischianum are in progress.
Yoshimura T., Iwasaki H., Shidara S., Suzuki S., Nakahara, A. &Matsubara, T. (1988). 1. Biochem. 103, 1016-1019.
Norris, G . E., Anderson, B. F., Baker, E. N. & Rumball, S. V. (1979).
1. Mol. Bioi. 135, 309-312.

14P-03

CRYSTAL STRUCTURE OF STREPTOMYCESERYTHRAEVS TRYPSIN AT 2.7A RESOLUTION
T. YAMANE, A. SUZUKI and T. ASHIDA, School of Engineering,
Nagoya University, Nagoya 464-01, Japan, and Y KAWATA and F.
SAKIYAMA, Institute for Protein Research, Osaka University, Osaka
565,Japan
Streptomy ces erythraeus trypsin(abbr. as SET) is a trypsin-like serine
protease very similar to St. griseus trypsin (abbr. as SGT). SET consistsof 227 amino-acid residues with three disulfide bridges, and has amolecular weight of 22,300. SET is stable between pH 5 and 10, andhardly autolyzes itself at all at its active pH range. SET was crystallized
at its active pH of 7.0. The space group is P3221 and the lattice constants
are a=47.0 and c=178.9A. An asymmetric unit contains one moleculewith Vm=2.45A 3/dalton. The structure was determined by the MIR
method, using K2PtCl4, (NH4)2Hg(SCN)4, and K2Hgi4 derivatives. High
resolution X-ray data of the native protein were collected with ascreenless Weissenberg camera(Sakabe) at the BL6A2 station at the
Photon Factory. A total of 48,452 reflections were measured at 1.7 A
resolution, of which 19,912 were independent, giving the merging R
factor of 0.061. The model structure was made at 3.5A resolution. Now
the structure refinement using X-PLOR(Bruenger) is in progress.
Comparison of the molecular structures among SET, bovine trypsin and
SGT shows that: 1) the folding of the main chains of the three proteins isessentially the same though there are significant differences on themolecular surface; 2) the spatial arrangements of the catalytic triads inthe three proteins are similar to each othet
Bruenger, A. T. (1990) X-PLOR Manual, Version 2.1, Yale Univ., New
Haven, USA.
Sakabe, N. (1983) J. Appl. Cryst. 16, 542-547.

14P-04
CRYSTAL STRUCTURE OF [2Fe-2S] FERRODOXIN I FROMTHE Equisetum arvense AT 1.8A. RESOLUTION
M.Bando, Y.Morimoto, T.Tsukihara, Department of Biotechnology,
The University of Tokushima, Tokushirna, Japan,
S.Ikemizu, National Lab. for High Energy Physics, Tsukuba, Japan and
K.Fukuyama, Faculty of Science, Osaka University, Toyanaka, Japan.
The ferredoxin with two iron atoms and two inorganic sulfur atoms,[2Fe-2S] , that have been isolated from a wide range of plans and algae
have been named plant-type ferredoxin (Fd). The ferredoxin functions asredox components in photosynthetic system I and other metabolic systemwith low redox-potentials at about -400mV.
The [2Fe-2S] Fd I from Equisetum arvense consists of 95 amino acidresidues and has a relative molecular mass of 10,263. The amino acidsequence of this protein differs from that of Aphanothece sacrum Fd by
58 %. The crystal was monoclinic with space group ?21 and unit cellparameters a=30.4, b=57.4, c=47.5 A, and ~=78.7 °. It contains twomolecules per asymmetric unit with a Vm of 1.98A3JDa. The structure of
Fd I was solved by molecular replacement using the structure of the Fd I
from the blue-green alga Aphanothece sacrum. The electron density map
was so clear and unambiguous that main polypeptide chains could be
easily traced. However N-terminal residues and 4 C-terminal residues ofboth independent molecules could not be traced in the map because of thepoor electron density in these regions. An atomic model of the Fd I wasconstructed using the "FRODO" program on a Silicon Graphics IRIS
graphics system. Crystallographic refinement was performed using the
restrained least-squares refinement program of Hendrickson andKonnert. The occupancies of all atoms were fixed at 1.0. The final
refinement cycle was carried out for 1420 non-hydrogen protein atoms
and 183 water molecules, using 13,838 (>lcr) observed F 0 data between
10.0 to 1.8A spacing. The pre sent crystallographic R factor for therefined model is 16.3% at 1.8A resolution, with a root-mean-square(r.m.s.) deviation of 0.014A from the ideal bond length.
The r.m.s . deviations for equivalent Ca. atoms of two independent
molecules superposed by the least squares method average 0.26A. There
are structural differences between them in the molecular surface. For
example, Glul9 Ca. atoms of two independent molecules are more than
0.4A from each other, and the deviation was also lain on the residue of
Ser61. The structural differences are presumably caused by hydrogenbonds between carbonyl oxygen atoms and water molecules.

14P-05
CRYSTAL STRUCTURE OF THE TFIID TAT A BOX
BINDING PROTEIN:A Novel DNA binding Motif that
Recognizes the Minor Groove
D.B. Nikolovt, S.-H. Hut%, J.P. Lint %, A. Gascht, A. Hoffmannt,
M. Horikoshit N.-H. Chuat, R.G. Roedert and S.K. Burleyt%t Laboratories of The Rockefeller University and %Howard Hughes
Medical Institute, 1230 York Avenue New York, NY 10021-6399 USA
The three-dimensional structure of the TATA-box binding protein, acentral eukaryotic transcription factor, has been determined by multiple
isomorphous replacement and refined at 2.6A resolution. Eukaryoticorganisms possess three distinct RNA polymerases (forms I, II, and III)
that catalyze transcription of nuclear genes. Despite their considerable
structural complexity, these multi-subunit enzymes require sets ofauxiliary proteins known as general transcription factors to initiate
specific transcription from corresponding class I, II, and III nuclear
gene promoters. Recent studies have documented that aphylogenetically-conserved TATA-box binding protein (TBP or
TFIID't), first identified as a component of the class II initiation factor
TFIID, is required fo r transcription by all three nuclear RNA
polymerases, making it the first universal transcription factor. In class
II transcription, TBP functions by recognizing and binding DNA in thevicinity of the transcription start site (the TAT A-box) and subsequently
directing assembly of the transcription machinery prior to mRNA
synthesis. The newly determined structure of TBP is that of a highly
symmetric a/~ protein representing a novel DNA-binding fold, which
resembles a molecular "saddle" that sits astride the DNA. The DNAbinding surface is a curved, antiparallel ~ -sheet that can make specificcontacts with the minor groove of DNA. When bound to DNA, theconvex surface of the molecular "saddle" is presented for interaction
with other transcription initiation factors and regulatory proteins.

140-06
CRYSTALLOGRAPHIC REFINEMENT OF
TRICHOSANTHIN AT 1.9.A RESOLUTIONLin YuJuan, Pan KeZhen, Fu ZhuJi,and Zhou KangJing, Fujian Instituteof Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou Fujian 350002, P.R. China.
Trichosanthin is a protein extracted from a Chinese herb medicine.
Recently, it has drawn great attention because of its application in
medicine. As well as having an abortion function, it is a ribosome
inactivating protein with a single chain, which can also combine with
antibody to produce immunotoxin. A series of research studies oftrichosanthin have been reported [1,2,3,4,].
A crystal suitable for X-ray diffraction at 1.9A has been obtained. A setof data (32357 reflections with Fo > lcr (Fo)) has been collected bysynchrotron radiation with the help of researchers in EMBL. An initialmodel based on the results of refinement at 2.6 A was refined with
1.9 A data first by the molecular dynamics ( XPLOR ) in SGI stationand then by restrained least squares (PROLSQ) on a VAX785 computer.
After the initial model was refined by XPLOR, the R-factor decreased
from 0.365 to 0.299, with RMS deviations of bond lengths and angles of
0.021 A and 3.99° respectively, using 32119 reflections in the resolution
range 8 to 1.9 A with IF 0 I> lcr(F0 ).
The 2FoFc map was used to adjust the displacing protein atoms and the
FoFc map to find solvent molecules. A total of 3828 protein atoms and
105 water molecules have been refined to an R-factor of 0.239 withRMS deviations of 0.040A (1-2), 0.099 A (1-3), and 0.125 A (1-4).
The crystalline form of the protein (Mr "" 27,132 Dalton) is monoclinic,
space group C2, with unit cell parameters a = 75.60 A, b = 75.44 A,
c = 88.36 A P = 99.50°. There are two molecules in an asymmetric unit,
each molecule containing 247 amino acids and 1914 non-hydrogenatoms . The polypeptide chain folds into 8a - helices and 13p - strands,
forming two domains, the bigger one from N terminal to Pro 181, andthe smaller one from Ser 182 to C terminal. Refinement of the structureis still in progress.
We are grateful to K.S . Wilson for help with data collection.
[1] Pan Kezhen et al.,(1982). Scientia Sinica, B25 730-737.
[2] Pan Kezhen et a1.,(1985). Scientia Sinica, B29 26-32.
[3] Pan Kezhen et al.,(1987). Scientia Sinica, B30 386-394.
[4] Pan Kezhen et a1.,(1992). Scientia Sinica, B35 29-39.

140-07
CRYSTAL STRUCTURES OF TWO BLUE COPPERPROTEINS
T. Inoue, Y. Kai, S. Harada, N. Kasai, Department of Applied Chemistry,
Faculty of Engineering, Osaka University, Suita, Osaka 565, Japan,
S. Suzuki, T. Kohzuma, Institute of Chemistry, College of General
Education, Osaka University, Toyonaka, Osaka 560, Japan,
J. Tobari, Department of Chemistry, College of Science, Rikkyo
University, Nishi-ikebukuro, Tokyo 171, Japan,
S. Shidara, Department of Environmental Science, Hiroshima University,
Naka-ku, Hiroshima 730, Japan, and
H. Iwasaki, Nagoya University of Foreign Studies, Nisshin-cho, Aichi
470-01, Japan.
The proteins containing type-I copper(ll) tum deep blue in the oxidized
state and their absorption intensities are about 10 to 50 times larger thanthose of non-blue copper proteins. Both pseudoazurin fromMethylobacterium extorquens AMI and azurin from Achromobacter
xylosoxidans NCIB 11015 are blue copper proteins.
Single crystals of these blue copper proteins have been obtained by thehanging-drop vapor diffusion method using ammonium sulfate asprecipitant. Crystal data are
Pseudoazurin;
Azurin;orthorhombic, space group P21212l(No.19)
a=52.62, b=63.28, c=35.13A
tetragonal, space group P4!22 (No.91)
a=b=52.3, c=100.2A

Intensity data were collected with SR radiation at 2.5 Gev. For
pseudoazurin, native data up to 1.2A were collected with two X-ray
beams of 1.04 and 1.375A, and for azurin, data up to 2.0A with a LOA
beam. The locations of copper atom in the unit cell for each crystal wereobtained by calculating the anomalous difference Patterson function.
The structure analyses have been carried out by molecular replacement
using the copper-copper distances as translation parameters in MERLOT.
The starting structure was obtained from pseudoazurin from Alcaligenes
faecalis S-6 (homology 44%), and azurin from Alcaligenes denitrificans
NCTC 8582 (homology 73%), respectively. By using XPLOR, thecrystallographic R-factor has been reduced from 0.52 to 0.25 at 2.2A
resolution for pseudoazurin, and from 0.35 to 0.25 at 2.5 A for azurin.
The refinements including solvent molecules are now in progress.

140-08
HIGH RESOLUTION ELECTRON CRYSTALLOGRAPHY OF
AN a - HELICAL COILED-COIL PROTEINP A Tulloch, Biomolecular Research Institute, 343 Royal Parade,
Parkville, 3052, Australia,
Y Fujiyoshi & Y Kimura, Protein Engineering Research Institute,
6-2-3,Furuedai, Suita-shi, Osaka, 565, Japan,
A W S Johnson, Centre for Microscopy & Microanalysis, University ofWestern Australia, Nedlands 6009, Australia, andP W Dyson and A E C Spargo, School of Physics, University of
Melbourne, Parkville 3052, Australia.
Our aim is the 3-dimensional structure determination of a fibrous protein
at 3A. resolution, extending the poorer resolution projection analysis of
Bullough and Tulloch (1990). The success of Henderson and his coworkers in determining the major part of the structure of the membraneprotein bacteriorhodopsin in the deh ydrated state by electron
crystallographic methods , together with recent improvements in technique
has shown that the problems of radiation damage and lack of structural
stability can be overcome for a number of 2-dimensional protein crystals.
A significant experimental advance has been the development of a highly
stable super fluid helium temperature stage and cryo-transfer system in a
dedicated high resolution microscope by Fujiyoshi et al (199 1). Thismachine is used in the present study of a -helical coiled-coil protein in theform of natural micro-crystals extracted from the ootheca of the praying
mantid. Further development of the vitreous ice embedding technique has
resulted in the diffraction data being extended to 1 A. for untilted crystals
and 2 to 3 A. for tilted crystals. The phases for the diffraction data will be
determined from the FT of images to the resolution limit of the image ofaround 3 A.
Tilting methods show the micro-crystals to be 200 to 300 A. thick with arepeat distance in the electron beam direction of 18A.. These values meanthat for some orientations, considerable atomic overlap will exist and thatthe possibility of multiple scattering should be investigated. This has been
done by dynamical calculation for a poly-alanine model of the structure
based on the low resolution result of Bullough and Tulloch (1990). The
results so far, in the untilted case, show the weak phase object
approximation, upon which the phase determining method relies, will holdreasonably well for crystals of 200A. (Dyson, Spargo, Tulloch & Johnson,
1992).
Bullough, P A, & Tulloch, P A (1990). f. Mol. Bioi. 215, 161.
Dyson, P W, Spargo, A E C, Tulloch, P A, & Johnson, A W S, (1992).
Fujiyoshi, Y, et a1 (1991). Ultramicroscopy 38, 241.

14Q-Q9
CRYSTALLOGRAPHIC STUDIES ON A DOUBLE SHELLEDSPHERICAL VIRUS, RICE DWARF VIRUS (RDV) II.
Y.Morimoto, T.Tomizaki, T.Sato, T.Tsukihara, The University ofTokushima,Tokushima, Japan,
M.Koizumi, National Institute of Sericultural and Entomological Science,
Tsukuba, Japan,
T.Omura, National Agriculture Research Center, Tsukuba, Japan, and
H.Kano and H.Mizuno, National Institute of Agrobiological Resources,
Tsukuba, Japan.
Rice Dwarf Virus (RDV), a phytoreovirus, from Nephotettix species
infects systemically rice and wheat plant and causes stunting or dwarfingof plant bodies. The virus is an icosahedral double-shelled particle
approximately 700 A in diameter. The particle molecular weight of thevirus is 6.52 x 107. A total of 540 identical protein subunits are on theparticle surface, suggesting T=9 icosahedral symmetry of the capsid. Xray crystallographic analysis of the virus is a useful method for
determining the double shelled structure of the virus, and for revealing
the mechanism of symmetrical self-assembly of subunits. The virus has
been crystallized in the cubic space group 123 with a=789A. Two particles
are located on positions of Wyckoff notation "a" in the unit cell.
Diffraction experiments were carried out with a macromolecular
Weissenberg camera at BL-6A2 in the Photon Factory, Japan. The crystal
to film distance was 573mm and the wavelength was 1.488A. The incident
beam, focused by double bent mirrors, was collimated to O.lmm<j>.
Oscillation speed 0.03° /sec, oscillation range 1.5°, coupling constant
100°/mm. Diffraction data were recorded on an Imaging-Plates (IP), andread out by the Fuji BA-100 system. Program "WEIS" was used toprocess the data. As the crystals deteriorated quickly when taken from themother solution, they were kept in that solution during data collection.
Therefore, modifying "WEIS" to determine the crystal orientation of
without setting photographs, we searched <j>x, <jly, <j>z values from -45° to
45° for each angle with step size of 1o on a Personal IRIS workstation.
A total of 56096 reflections up to 10 A was collected from one crystal,and the mean Rmerge of 10.51% for 29075 independent reflections was
obtained by a scaling procedure. The self-rotation function calculatedusing the diffraction data indicated icosahedral symmetry. As very low
angle reflections are important when using molecular replacement
methods in the initial stage of structure analysis, they were observed bymeans of a small beam stopper attached just before the Imaging-Plate. We
will report a non-crystallographic symmetry or self-assembly of the virus
structure calculated from the diffraction data.

140-10CRYSTAL STRUCTURE ANALYSES OF THE SPHERICAL
VIRUSES, TOBACCO NECROSIS VIRUS (TNV) AND RICEDWARF VIRUS(RDV).
T. Tsukiharal, Y. Morimoto!, K . Fukuyama2, M. Koizumi3, T. Omura4,
K. Kano5, H. Mizuno5.
!Faculty of Engineering, The University of Tokushima.
2Faculty of Science, Osaka University
3National Institute of Sericultural and Entomological Science, Tsukuba
4National Agriculture Research Center, Tsukuba
5National Institute of Agrobiological Resources, Tsukuba, Japan.
Tobacco necrosis virus (TNV) is a typical spherical virus. Its coat protein
contains 275 amino acids. TNV crystallizes in cubic space group P4232
with a=b=c=338 A. Its 3.86x107 A3 unit cell contains two virus particles
with molecular weight 6.7x1 06, and Vm value 2.9A3/dalton. The (T=3)
symmetry of TNV capsid and subunit arrangement of 180 copies of its
coat protein were determined previously. X-ray diffraction intensities fora 0.7x0.7x0.7 mm3 TNV crystal were measured at 5 A resolution on a
Weissenberg camera with cassette radius 430 mm, at the Photon Factorysynchrotron. The merging R-factor is 0.115 for 90,251 reflections with
l>Scr(l). The 27,437 (F>3 cr (F)) and 24,127(F>5cr(F)) independent
reflections were 94% and 83% of the theoretical number. The virus
crystal's structure was determined by a 91 cycle iteration of molecularreplacement averaging. The correlation coefficient between calculated
and observed structure factors converged to 0.92, and R-factor 0.16.
Secondary structures such as a-helices and ~-structures were clearly
assigned in the 5 A resolution electron density map. The TNV viru s
resembles SBMV both in the orientation and folding of the coat protein
subunits. The ordered part of that subunit is shorter by 12 and the longer
disordered part by 27 residues than corresponding parts of SBMV.
Rice Dwarf Virus (RDV), a phytoreovirus, from N ephotettix species
infects rice and wheat systemically, causing stunting or dwarfing of plantbodies. The molecular weight of the double-shelled virus particle,
approximately 700 A in diameter, is 6.52xl07. Crystallographic analysis
helped reveal the double shelled structure of the virus, and themechanism of symmetrical self-assembly of its subunits. RDV crystallizedin cubic space group !23 with a=789A. Two particles are on Wyckoff "a"positions in the cell. For diffraction experiments on a macromolecular
Weissenberg camera at BL-6A2 in the Photon Factory, the crystal to film
distance was 573mm, and wavelength 1.488A. The incident beam,focused by double bent mirrors, was collimated to O.lmm<j>. 56096
reflections up to 10 A were collected from one crystal The mean
Rmerge for 29075 independent reflections was 10.51%. A self-rotation
function indicates icosahedral symmetry for RDV.

140-11

THE STRUCTURE AND FUNCTION OF MOS KINASE
B.K. Sathyanarayana, Wayne Matten, Renping Zhou, Nelson Yew,
Ira Daar, Terry Copeland, George F Vande Woude, John Erickson+
and Ronald Rubin
ABL-Basic Research Program, and +PRI-Dyncorp NCI-FCRDC,
Frederick, Mary land 21702.
The c-mos proto-oncogene product, pp39mos, is a cellular threonine/
serine kinase which functions during oocyte maturation and is the active
component of cytostatic factor (CSF).
Based on the three-dimensional structure of the related cyclic AMP
dependent protein kinase catalytic domain (CPK), we have modelled thestructures of the protein kinase domains of mos from several sources
including human, mouse and Xenopus. The model structures wererefined using energy minimization. Although the mos amino acidsequence fo rm these species can differ in up to 48 % of the residues, mostchanges are found on the surface of the 3D structure distal from theactive site cleft. The modelled structures consist of two distinct domains;an amino terminal ATP binding domain cons isting of residues 58-143 in
the human c-mos sequence, and a larger carboxyl terminal peptide
binding domain consisting of residues 144-346. The polypeptide chain
linking these two domains contains the conserved mos sequence GTIIME,
which is located at the initiation site for truncated form s of mos
expressed in maturing mouse oocytes and transformed cells. The
substrate binding cleft lies in a deep groove located between the twodomains . The topology of the mos kinase active site cleft was used tomodel potential substrate/inhibito r peptides which maximize theelectrostatic, hydrogen bonding and van der Waals interactions withresidues in the active site cleft.
Research sponsored in part by the National Cancer Institute, DHHS,
under contract No. N01-C0-74101 with ABL.

14 R- 12
DRUG-PROTEIN INTERACTION: REFINEMENT AND
MODELLING OF SULFONAMIDE DRUGS BOUND TO
HUMAN CARBONIC ANHYDRASE I ENZYME
S . OJakravarty and K.K. Kannan , Solid State Physics Division, 8Jabha Atmic ResearchCentre, Pari:>ay 400 085, India.
Therapeutic effects of Sulfonamide carpounds

withunsubsti tuted sulfamidogroup is believed to be strongly correlated with the specific inhibitioo of Carbonic

Anhydrase isozyrres.

Structures of three Sulfooanide drugs Ild11Ely, Acetazolamide,!1ethazolamide and 3-Acetaxy Mercuri, 4-illlino benezene sulfonamide (AmSulf) carplexed
to flunan Carbonic Anhydrase I enzyn>! have been investigated .
refined by ffiOI.5Q Package as inplar.ented by us onprocessing system.

l.hileThe structures have been

a localRIX based parallel

the R-factor for Acetazolamide

is 0. 176 using 14303

reflections the corresponding R-facton; for !1ethazolamide and AmSulf are 0 .182 and0.192 using 14201 and 13691 reflections respectively with good stereoc:hanical models.
Inspection of . the IJFo/-/Fc/1 and {2/FoJ - /Fc/J 11EpS clearly shows the drug nolecules
bound in the active site of the enzyn>!.

The Sulfamido group and the cyclic rings arelocated in approximately the sane region around Zinc in all the three croplexes.
Besides, the Nitrogen atan of the Sulfamido group displaces a zinc coordinated solvent
ITOlecule of the native et1Z)'!l>! and the 0.0 Oxygens displace 0.0 other solvent ITOleculesin the active site, one of which is a prop:>sed fifth coordination site

for

the

substrate OJ ITOlecule . Ch croparing the spherical p:>lar coordinates of the atans of2
residues in the active site with Zinc at the origin, it is seen that IBJ 199 shows the
T7l3Xinun change in both Ac:etazolanide and 11ethazolamide carplexes as carpared to thenative, while His 200 shows the largest change in Amsulf.

Eight residues in theactive site which sh<M significant changes have been identified and it is seen that
<HDngstthese,

there are systematic differences in the interactions

withheterocyclic ring (Acetazolanide and tiethazolamide) and benzene ring of AmSulf.

the

These

dlffererJCES may govern the final orientation of the sulfamido group with respect tothe Zinc ion and the binding of drug ITOlecules in the active site thereby explaining
the differences in the strer'K]th of inhibition.

sulfamido group andthecyclic ring as

Based oo the above location of the

fourdfran experinental

data,

t:\o.enty

sulfooamides containing heterocyclic and/or harocyclic rings ~;ere docked intotheactive site using IRIS-4D work station, and free energy minima determined using Xff.CII. .
ll?tailsofinteractions of these

drugs

with

the protein residues

incliXiing

intranrJlecular Hydrogen bonding show systematic trends which rray also be correlated totheir strength of inhibi tioo.

14R-13
CRYSTAL STRUCTURE OF GLUTATHIONE SYNTHETASE
WITH ADENOSINE(S')TETRAPHOSPHO(S')PYRIDOXAL
T. Hibi , H. Kato, T. Nishioka, and J. Oda, Institute for Chemical
Research, Kyoto University, and H. Yamaguchi andY. Katsube, Institutefor Protein Research, Osaka University, Japan.
Glutathione synthetase from E. coli B was specifically modified with an
ATP analog, adenosine(5')tetraphospho(5')pyridoxal (AP4 -PL). AP4 -PL
was more tightly bound to the ATP-binding site of the enzyme than ATP,and was irreversibly attached to a lysyl residue (Lys-18) by reduction. In
contrast, modification with AP 3-PL, an analog one phosphate shorter thanAP4 -PL, was less specific because of unstable binding. To elucidate such
behaviors of the reagents, the crystal structure of the enzyme complexedwith AP4 -PL has been determined at 2.55 A resolution.
The crystals of the AP4 -PL:enzyme reduced complex was isomorphous to
the unliganded enzyme crystals (P6 222), with cell dimensions of a = b =87.8 A and c = 164.8 A. The adenosine moiety of bound AP4 -PL wassandwiched between two ~-sheets, and this site corresponds to the ATPbinding site identified with D-Fourier method. Whereas , the pyridoxyl
moiety of AP 4 -PL was fixed at the entrance of the y-Glu-Cys-binding
crevice. The main body structure of the enzyme subunit was almost
unchanged as compared with that of the unliganded enzyme. In addition,
well-defined electron density was shown for a flexible loop region(residues 226-241), which is disordered in the unliganded enzyme . The
model of the flexible loop had an 0-loop-like structure and appeared toform a hydrogen bond between a -phosphate of AP 4 -PL and NH atom ofIle-236. Closure of the loop ass isted the formation of the Schiff basebetween Lys-18 of the enzyme and AP4 -PL. The resulting structure of
the complex supports the ligand-induced conformational change of theloop, which is suggested by limited proteolysis of the loop (Tanaka et al.
1992). Refinement is in progress and the detail structure of the active site
will be presented.
Tanaka, T. et al. (1992). Biochemistry 31, 2259-2265 .

14R-14ACTIVE SITE CONFORMATION OF CYTOPLASMICCYCLOPHILIN OF Eschrichia Coli IN ASPECT OF STERICHINDRANCE TO ATTACHMENT OF CYCLOSPOLIN A
M. Ito and M. Konno, Department of Chemistry, Faculty of Science,
Ochanomizu University, Bunkyo-ku, Tokyo 112
T. Hayano, M. Suzuki, S. Sato and N. Takahashi, Corporate Research andDevelopment Laboratory, Tonen K. K., Iruma-gun, Saitama 354, Japan
Cyclospolin A(CsA) inhibits signal transduction pathway toT-lymphocyte
activity, commonly available to prevent graft rejection in clinical organtransplantation. Complexes between CsA and cyclophilins from yeast tohuman are abundant, whereas in E. coli cyclophilin little affinity to CsA
was unexpectedly confirmed. The complex of CsA-cyclophilin blocks
phosphatase activity of calcineurin required for transcription ofinterleukin 2 in T-cell. The complex of FK506 and FKBP (FK506 binding
protein) (VanDuyne, et al. (1991)) also inhibits potently T-cell activity inthe same manner as the complex of CsA-cyclophilin. Drastic
conformational change of CsA follows attachment to cyclophilin(Kallen,
et al.(l991); Spitzfaden, et al.(1992)). In E. coli little affinity is attributed
to the conformational difference at the active site, where CsA will not
attach. Our structure analysis aims to clarify the structural difference
between prokaryotic and eukaryotic proteins .
Crystals of the E. Coli cyclophilin complex consisting of 164 residues
and tripeptide succinyl-Ala-Pro-Ala-p-nitoanilide have space group?212121, a=66.33(12) , b=68.23 (9), c=40.03 (5) A. Intensity data fornative and HgCb, K2PtCl4 and SmCI3 derivatives were collected with a
Weissenberg camera using 1.00 A synchrotron radiation at KEK. After
refinement, the mean figure of merit for MIR phases was 0.73 at 2.5 A
resolution. The electron density maps show the core of an eight-stranded
anti-parallel, ~-barrel as observed in hum an cyclophilin. Fourhydrophobic residues Phe-48, Met-49, Phe-99 and Leu-108 at the active
site have the same conformation as in human protein. Notable differences
apparently found are l)A hydrogen bond links Asn-102 and MeBmt-1 of
CsA in human cyclophilin. By contrast, Arg-87 in E. co li, corresponding
to Asn-102, is in no case fixed in a rigid loop. 2)£. coli has Phe-107 at theposition corresponding to a conserved Trp-121 of human cyclophilin
which hydrogen bonds to the MeLeu-9 carbonyl group of CsA. A 13
residues antiparallel p type loop is additionally inserted next to Phe-107.
We thank Prof. N. Sakabe, Dr. A. Nakagawa and Dr. S. Iwata at the
Photon Factory KEK for kind help in data collection and model building.
Kallen, J., et al., (1991). Nature, 353, 276-279.
Spitzfaden, C., eta!., (1992). FEBS Lett., 300, 286-290
VanDuyne, G. D., et al., (1991). Science, 252, 839-842.

14R-15
ALKALINE METAL ION BOUND IN HUMAN LYSOZYME
M. Matsushima, A. Pahler, K. Morikarni and K. Inaka
Protein Engineering Research Institute, Furuedai, Suita, Osaka 565, JapanThe human lysozyme crystals were soaked in N aCl, LiCl, and KCl solutions.
The x-ray diffraction intensity data were collected by use of Mo Ka radiation andan area detector. The crystal structures were refined at 1.50 A resolution and theconventional R-factors were reduced to 0.145, 0.150 , and 0.144 , respectively. Oneof the solvent molecules in the crystal soaked in the N aCl solution had a low B
factor and extensively interacted with the protein molecule. The solvent molecule
was surrounded in an octahedral geomet ry by three main- chain carbonyl oxygen
atoms of Ser 61, Cys 65 , and Val 74, two water molecules and a methyl groupof Ala 73. The distances to these oxygen atoms were 2.4 A. On the other hand ,t he electron density of the solvent molecule was not found in the crystal structure
soaked in the LiCl solution.

Therefore, the solvent molecule was identified asa sodium ion. In addition to these results, the ion was substituted by a watermolecule in the crystals soaked in the KCl solution and the peptide bond between
Val 74 and Asn 75 was rotated in the structure. The water molecule donated thehydrogen bonds to the carbonyl oxygen atoms of Ser 61 and Cys 65, and accepted
the bonds from the arnido of the rotated peptide and a water molecule.
Since neither a potassium ion, nor a divalent metal ion, such as a calcium ion
or a copper ion, was bound at the site , human lysozyme selectively bound a sodium
ion, which was octahedrally coordinated by the three carbonyl oxygen atoms ofthe main-chain and the water molecules.
Inaka, K. et al. ( 1991 ) J. Bioi. Chern. 266, 20666-20671.
Blake, C.C.F. et al . (1983) J . Mol. Bioi. 167,693-723.

14R-16
STRUCTURE OF P.STUTZERI G4-AMYLASE AND ITSCOMPLEX WITH MAL TOTETROSE
Y. Matsuura, Y. Morishita, Y. Yoshioka, M. Sato andY. Katsube ,Institute for Protein Research, Osaka University, Suita, Osaka, Japan,
and M. Kubota, Hayashibara Biochem. Lab. Inc., Amase-minami, Okayama, Japan.

Maltotetraose forming a -amylase from Pseudomonas stutzeri is an exoamylase which degrade starch from its non-reducing end. We havedetermined the crystal structure of this enzyme and its complex withmaltotetraose at 2.2A resolution.
The enzyme crystallizes in orthorhombic P2t2t2I , a=65.6, b=l70.5 andc=46.7 A. The complexed crystal was obtained by co-crystallization of the
E219Q mutant of this enzyme with maltopentaose, as orthorhombic
P2t2t2I, a=65.1, b=l38.4 and c=50.7A. Both crystals were obtained fromthe ammonium sulfate solution at pH7.5 by hanging drop vapor diffusion .
Intensity data were collected on an imaging-plate diffractometer Rigaku
RAXIS-IIc . The structure of the native enzyme was solved by MIR method
using two heavy-atom derivatives, K3U02Fs and SmCl3. The structure of
the complexed crystal was solv ed by the molecular replacement methodwith the native structure as a search model by using the program
AUTOMR 1>. The native crystal structure was refined to an R-factor 17.4%
by using the programs XPLOR and PROFFT. A Co:-backbone model of thenati ve enzyme is shown in the Figure. Two disulfide bonds and two
calcium atoms were defined. A loop (66-72th) and the C-terminal (418429th) region are not well-defined in the electron density map. A 2Fo-Fc
map of the CORELS refined complexed crystal showed clearly themaltotetraose instead of pentaose and the loop which was invisible in thenative crystal. Model building showed that the maltotetraose is boundessentially in the same manner with that proposed in Taka-amylase2>.
I) Y. Matsuura. (1991 ). J. Appl. Cryst. 24, I 063-1066.
2) Y. Matsuura et al. (1984) . J. Biochem. 95, 697-702.

14R-17
STUDY OF CONFORMATIONAL DIFFERENCE BETWEENA DIHYDROPYRIDINE CALCIUM CHANNEL ANT AGONISTAND A NON ANT AGONIST
Safia Mehdi and K. Ravi Kumar, X-ray Section, Indian Institute ofChemical Technology, Hyderabad- 500 007, AP, INDIA.
Crystal structure of 1 ,4-dihydro-2,6-dimethyl-4-(2,4-dichlorophenyl)3,5-N-methyl carbamoyl pyridine (I) and 1,4-dihydro-2,6-dimethyl-4(2,4-dichlorophenyl)-3,5-N-diethyl carbamoyl pyridine (II) have been
determined and the important structural requirements for biologicalactivity (Janis & Triggle, 1983) compared with those of twenty threeother reported ones.
Crystal data of (I) is: - M,=368.26, orthorhombic, Pca21. a=12.928 (3),b=14.506(3), c=9.740(2) A, Z=4, (Mo Ka) = 0.71069A, T=293K,
R=0.0541 and Rw=0.0582.
Crystal data of II is:- M r=470.4, monoclinic, P211n, a=14.686(5),b=7.590(2), c=23.578(6) A, ~=107.47 °(1), Z=4, (Mo Ka) = 0.71069A,
T=293K, R=0 .051 and R w=0 .055 .
The overall structure of both compounds is similar to that of the reported
analogues. But the deviation from planarity in the dihydropyridine ring(defined as the sum of the numeric values of the six intra ring torsion
angles) is 106°.15 for compound I and 75°.09 for II, it being 72°.1 fornifedipine, the most potent calcium channel antagonist (Triggle, Shefter
and Triggle, 1980). The 2,4-dichlorophenyl ring in compound I is notnormal to the DHP ring, whereas in compound II it is normal to thisring , which is the orientation preferred in all the phenyl substituted
derivatives investigated. The presence of the water molecule in II
provided a different type of hydrogen bonding pattern.
Janis, R.A. & Triggle, D.l. (1983). J Med Chern 26, 775-785.
Triggle, A.M., Shefter E. & Triggle, D.Ju (1980). J Med Chern 23,
1442-1445.

14R-18
CRYSTAL STRUCTURE OF THE COMPLEX BETWEENPORCINE PANCREATIC ELASTASE AND MACROCYCLICINHIBITOR
I. Tada and I . Yasuda, Analytical Research Laboratories, Fujisawa
Pharmaceutical Co., Ltd., Osaka, Japan, and S. Harada, Y. Kai and
N. Kasai, Department of Applied Chemistry, Faculty of Engineering,Osaka University, Osaka, Japan.
Elastase belongs to the se rine protease family of enzymes which arecapable of cleaving connective ti ssue components. Uncontrolled
proteolysis by the elastase can cause some inflammatory diseases. The
title compound was isola ted from Streptomyces resistomicificus. The
compound has a unique macrocyclic structure and exhibits potent
inhibitory activity for e lastase . To investigate the na tur e of theinteraction of this novel class of inhibitor, X-ray structure analysis of thecomplex of porcine pancreatic elastase (PPE) with the inhibitor has been
performed. Crystals of the complex were obtained using a solution of
PPE and inhibitor in 0.08M sodium sulfate and O.OSM sodium acetate at
pH 5.0 by vapor diffusion from 0.16M sodium sulfate and O.lM sodium
acetate solution over 20 days. The reflection data were collected to 1.7 A
resolution on the RIGAKU R-AXIS IIC Imaging Plate Area Detector
using Cu-Ka radiation less than 2 days. All the data were measured on
one crystal and a total of 23097 unique reflections (I(o)~o) wereobtained (R-merge: 4.44 % ). The space group is P2 12 12 1 with celldimensions a=51.67 A, b=57.84 A, and c=75 .52 A. The isomorphous
native PPE coordinates were used for initial phasing of the reflections
and calculation of a di fference Fourier map to locate the inhib itor.
Programs X-PLOR an d PROLSQ were used for the refinements and thecalculation of maps. The electron density map confirmed conclusively thelocation and orientation of the inhibitor molecule in the active site of
PPE. Details of the structural features for the interaction mode between
PPE and inhibitor will be reported.

14R-19
VARIATIONS ON THE SAME THEME - CRYSTALSTRUCTURE OF L-ASP ARAGINASE AND THE
UNIQUENESS OF ITS STRUCTURAL FOLD
J. K. Mohana Rao, Michael Gribskov, Dominique Housset,
Mariusz Jaskolski, Jacek Lubkowski, Maria Miller, B. K. Sathyanarayana,
Amy Swain and Alexander Wlodawer
ABL-BRP, NCI-FCRDC, P.O. Box B, Frederick, MD 21702, USA.
L-asparaginase (E.C.3.5.1.1), an enzyme encountered in the oxaloacetate
pathway, catalyzes the hydrolysis of L-asparagine to L-aspartate andammonia. It is used clinically in the treatment of acute lymphoblastic
leukemia. The crystal structures of the type II tetrameric L-asparaginasefrom Escherichia coli (EcA), Erwinia chrysanthemi (ErA) , andA cenetobacter glutaminasificans (AGA) have been solved in ourlaboratory using multiple isomorphous replacement and molecularreplacement techniques. At present, the R-factors for the three crystal
structures are respectively 0.14 for EcA at 2.3 A, 0.16 for ErA at 1.8 A,
and, 0.17 for AGA at 2.9 A resolution. These highly similar structures of
enzymes with different activity profiles have also been compared among
themselves. Each monomer of the tetramer (222 symmetry) has two
distinct domains with unique topological features. The larger N-terminal
domain has a mixed eight-stranded 13 sheet and four a -helices. The
parallel a/13 part of this domain has a flavodoxin-like fold. However, thisregion is characterized by a unique left-handed crossover, rarely seen inprotein structures. The C-terminal domain has a four-stranded parallel 13
sheet flanked on either side by two a helices. From the topologicalfeatures, the active site was first predicted and thereafter verified in theelectron density maps. The active site lies between theN- and C- terminal
domains belonging to different monomers. Details of various
comparisons (among themselves and with other proteins) with theresulting similarities and differences will be discussed. Based on the
crystal structure of the type liE. coli enzyme and its sequence alignment
with the type I enzyme from E. coli, the structure of the type I enzyme
has been modeled.
This research is sponsored by the National Cancer Institute (DHHS)
contract NOl-C0-74101 with ABL.

14R-20
BINDING AND CATALYTIC ROLES OF THE ACTIVE SITE
METAL IN ZINC PROTEINASES
G. Shoham. H. M. Greenblatt and H. Feinberg, Department of Inorganic
Chemistry and The Laboratory of Structural Chemistry and Biology,
The Hebrew University, Jerusalem 91904, Israel.
Several series of crystallographic studies have been performed todetermine the yet unknown general mode of action of zinc proteinases.
For detailed structural analysis we chose the digestive proteinase
Carboxypeptidase A (CPA) which is often used to represent this enzyme
family. In attempts to fully understand the role of zinc in CPA and otherzinc proteinases, and in zinc enzymes in general, several metal
derivatives have been prepared and their kinetic behaviour studied.
These metal-substituted enzymes show very interesting patterns ofactivity towards various peptide and ester substrates. The catalytic
activity changes dramatically with the particular metal substituted andwith the specific substrate chosen. Although crystallographic studies ofsuch zinc proteinase derivatives have been carried out previously, nosatisfactory explanation has been given to the kinetic deviations observed.
We have prepared apo-CPA (zinc removed) in which no trace of zincremains, and have used the resulting enzyme to prepare a series ofmetallo-CP A derivatives. These derivatives were crystallized and theircrystal structures were determined at high resolution. In addition to thedetailed structures of the metallo-derivatives themselves, we have also
analyzed structures of their complexes with a number of inhibitors andreaction coordinate analogues. The specific purpose of these studies wasto ascertain whether the observed changes in the activities of metalloderivatives of CPA (or zinc proteinases in general) are due to differencesin the way in which the metal is bound to the enzyme, due to local
changes in the conformation of the active site, or whether different
metals affect the binding of substrates in various ways. Similar studies
were also carried out on the apo-enzyme, in order to determine theeffect of the zinc ion on the so called "Michaelis-Menten" complex,
formed before any reaction takes place. We will present high resolution,refined structures of native-, apo-, and metallo-enzymes described above ,both alone and in complex with various affectors, and describe therelevance of these data to the role of zinc in biological catalytic activity.

14S-31
USE OF ATOMIC FORCE MICROSCOPE IN THE
DETERMINATION OF SPACE GROUPS BY X-RAY
DIFFRACTION ANALYSIS OF CRYSTALS
N. Masaki and K. Machida, Fac. of Pharm. Sci., Kyoto Univ., Kyoto,
H. Kado, K.Yokoyama and T. Tohda, Central Res . Labs ., Matsushita
Elec.
& Ind. Co.Ltd., Moriguchi, Osaka,
Y. Yoshimura, Fac. of Sci. & Eng., Ritsumeikan Univ ., Kyoto, andM. Kitamura, Fac. Sci., Kyoto Univ., Kyoto, Japan.
Space group determ ination is an important initial step in diffraction
studies of crystals. Systematic absences of reflections are mainly used forthis purpose. Identifying centers of symmetry, mirror planes or rotation
axes which give no systematic absences requires subsidiary means such as
intensity statistics and crystal morphology that are always not definitive.
The fi nal space group may be determined from possible ones after
completing x-ray analyses by selecting that with the lowest R-factor. Even
the proof of extinction spectra from a limited range of intensities
observed under particular experimental conditions is often unclear.
An atomic force microscope AFM revealed atomic scale images of
surfaces on (001) and (100) faces of aspirin crystals.J ,2) The (001) image
satisfied the X-ray structure3-5) but the (100) image did not. It did notrevealed the c-glide plane expected for the accepted space group(a=11.430, b=6.591, c=l 1.395A, P=95.68°, P2I/a, Z=4)Re-examination of h01 reflections from aspirin crystals in X-ray
precession photographs confirmed the presence of weak but significant
1=2n+1 reflections. In (Okl) and (hkO) photographs, OkO reflections for
k=2n+ 1 were not detected. The space group for asp irin should therefore
be P2Jim or P2I fro m the systematic absence data. Although we could not
distinguish between them from systematic absences, the AFM images of(00 1) and (100) faces clearly show absence of mirror symmetry. The
space group of aspirin crystals was uniquely determined as P2J, Z=2.
The successful re-detennination of the space group for aspirin confirms
the power of AFM for determining space groups. AFM can easily detectmirror, glide plane or two fold axis symmetry if appropriate surfaces areprepared and are not reconstructed from the internal structure.
1) Masaki,N. etal.(1991) Chem. Pharm.Bull.39,1899-1901.
2) Masaki, N. et al.(1992) Ultramicroscopy 41 , (5).
3) Nitta, I. & Watanabe,T. (1937) Sci.Papers lnst Phys. Chem.Res.(Tokyo)
31,125-128 .
4) Weatley, P.J. (1964) J.Chem.Soc . 1964, 6036-6048.
5) Kim,Y. et al.(1985) Chem.Pharm.Bull . 33, 2641-2647.

14S-32
ELECTRON MICROSCOPY AND DIFFRACTION STUDY OF
THE DIRECT REACTION OF IRON AND CARBON AND THE
FORMATION OF A NEW IRON CARBIDES. Nagakura and T. Komekyu, Department of Materials Engineering,
Waseda University, Shinjuku-ku, Tokyo 169,
M. Ando and S. Odawara, Department of Mechanical Engineering,
Nagaoka Univ. of Technology, Nagaoka, Niigata 940-21, Japan.
It has long been believed that iron and carbon do not react directly to
produce carbides. Recently, however, the authors have found that direct
reaction takes place when composite films of iron and carbon are heatedin vacuum.
On amorphous carbon films, iron and carbon were successively vacuum
deposited to produce C-Fe-C sandwich films. The deposited amounts ofiron and carbon are 10-20 nm thick. AC vacuum-arc evaporation usingiron and carbon electrodes was also applied to evaporate iron and carbon
simultaneously to make Fe-C mixed films. The films produced were
heated in a vacuum better than 2x 10-4 Pa at various temperatures and for
different periods of time.
In the as-deposited state, the sandwich films with iron thinner than 10 nm

were structureless and gave halo rings, but those with iron thicker than 20
nm were made of finely dispersed iron particles embedded in amorphous
carbon. The mixed films were always structureless giving halo rings.
When they were heated, the direct reaction between iron and carbon
occurred. No difference in the reaction products was found between the
sandwich films and the mixed films.
(1) 700°C, 1 h: The reaction product is 8-Fe3C (cementite) with particles
about 30 nm in size dispersed in the film, as occurs in tempering ofmartensitic steel. High resolution observations did not reveal any
structural defects in the particles. (2) 500°C, 3 h and 400°C, 48 h : The
reaction product is 8'-particles , as in steel tempering, where thin (001)layers of El-Fe3C and thin (100) layers of x-FesC2 are microsyntacticallyintergrown. (3) 400°C, 24 h -200°C, 336 h: The reaction product was aslarge as 1 )lm but very thin. Its diffraction pattern shows hexagonallyarranged spots giving axial length a=0.5286 nm. The axial length c could
not be measured because of crystal thinness. The products seems to be a
new higher iron carbide. High temperature in situ observations showedthat this carbide began to decompose at 400°C to form finely dispersed
El-Fe3C particles 20-30 nm in size and without orientation.

~4S-3 3

MODULATION MODES OF Bi2Sr2(Cai-xLnx)Cu208+0
CRYSTALS STUDIED BY HIGH-RESOLUTION REVERSEIMAGING
T. Onozuka
Institute for Materials Research, Tohoku University, Sendai 980, Japan.
Modulation modes of the Bi2Sr2(Ca1-xLnx)Cu208+8 (Ln=Pr, Nd)
compounds, of which the lattice is modulated by a longitudinal
displacement wave of metal atoms along the b axis*, are analyzed on thebasis of the microphotometric density distribution recorded directlyfrom the negative film of [001] high-resolution reverse image and thesimulations computed using three structure models of b=4.5bo, 5bo and4bo. A rnicrophotometric density distribution is shown in Fig.l (theupper curve) together with its image,
being equivalent to the one-dimensional
contrast modulation in the image. The
density distribution of the unit, 5bo, hasa single maximum peak at the middle.
Those joining at both sides of the unit
are that of the unit, 4.5bo, which isdistinguished from that of 5bo by thetwin peaks in the middle. The pattern ofdensity distribution is in good agreementwith the simulation.
I

5b 0

The density distributions of Fig.2 reveal
the existence of the modulation modes of(1,l)s and (1,0) in the crystal.

·'Fig 1. Microphotometric density
distribution and its image, being
compared with the simulations(the lower curve and the inset)

Fig. 2. Microphotometric density distributions obtained from specimens of x=O (theupper curve) and the praseodymium concentration of x=0.32 (the lower curve).

*ONOZUKA, T., IWABUCHI, Y., FUKASE, T., SATO, H. &MITCHELL, T. (1991). Phys. Rev . B43, 13066-13072.

14S-34

EELS STUDY OF THE TEMPERATURE
DEPENDENCE OF THE VOLUME-PLASMON
ENERGY IN ALUMINIUM
M.Terauchj , H.Abe, R.Kuzuo and M.Tanaka, Research Institute for
Scientific Measurements, Tohoku University, Katahira 2-1-1, Aobaku, Sendai 980 , Japan.
The temperature dependence of the volume-plasmon energy in aluminum had been measured using electron energy-loss spectrometers
The energy resolutions were about 2e V exby several authors.
cept for one report. 1l The temperature ranges examined were limited.
The interpretation of the temperature dependence has not
yet been clear because two different temperature dependences below
room temperature were reported. 1•2l
The present authors have measured the volume-plasmon energy ofaluminum over a wide temperature range between -175°C and 500° C
with energy resolutions of 0.10 ,. . ., 0.27eV. The high-resolution electron energy-loss spectroscopy (EELS) microscope used is equippedwith two Wien filters as the monochrometer and the analyzer. The
experimental results showed a smooth decrease of the volume-plasmonenergy with increasing temperature. The theoretical temperaturedependence was calculated based on the free-electron model, whichtakes account of the change in the density of the free electrons due tothe thermal expansion of aluminum. The experimental temperat ure
dependence agreed well with the theoretical one. Thus , it has been
revealed that the temperature dependence of the volume-plasmonenergy of aluminum is explained quantitatively by the thermal expansion of the material.
1) A.Imbusch and H.Niedrig : Phys. Lett. 3 2A(1970)375.
2) L.B.Leder and L.Marton : P hys . Rev. 11 2( 1958)341.

14S-35

MODULATED STRUCTURES IN Fe-DOPED Bi-Sr-Cu-0
SUPERCONDUCTORS STUDIED BY HIGH RESOLUTION
TRANSMISSION ELECTRON MICROSCOPY
K. YANAGISAWA 1.*, Y. MATSU11 , T. KOIZUM12 and T. HASEGAWA2,
1 National Institute for Research in Inorganic Materials 1-1 Namiki, Tsukuba
305, JAPAN, 2 Showa Electric Wire & Cable Co ., Ltd. 2-1-1 Odasakae,
Kawasaki-ku, Kawasaki 210, JAPAN, *on leave from Kobe Steel, Ltd. 1-5-5
Takatsukadai, Nishi-ku, Kobe 651-22, JAPAN.
The effects of Fe-doping on the modulated structures inBi2.sSq .sCuOy(2.5/1.5-Phase), as well as Bi2 .2Sr1 .sCuOy(2 .211.8-Phase),are examined by electron diffraction and high-resolution electron microscopy.
The Fe-free Bi2.sSr1.sCuOy[1], as well as the specimens doped with Fe up to
30% Cu in the initial ratio, crystallizes in an orthorhombic superlattice withmodulation periodicity bs=4.5b(Fig .1-a). At 30% substitution, transition of thesymmetry accompanied by a shortening of the modulation periodicity isobserved. Specimens in the range of Fe from 30% to 50% have a monoclinic
superlattice with bs=4.0b(Fig .1-b). The Fe-free Bi2.2Sr1 .sCuOy[2], on theother hand, has a monoclinic superlattice with bs=4.8b(Fig .2-a). Partial
substitution of Cu with Fe in Bi2.2Sr1 .sCuOy results in a slight decrease of themodulation periodicity down to bs=4.5b and also in a transition of the symmetry
to an orthorhombic superlattice(Fig .2-b).
[1] Y. Ikeda, et. , a/. Physica C 159 (1989) 93.

[2] Y. Matsui , et., al. Jpn. J. Appl. Phys. 27 (1 988) L1 873.

Fig.1 HATEM images of 2.5/1.5-Phase
doped with (a) 10% Fe and (b) 40% Fe .

148-36
SEARCHING FOR THE CRYSTAL STRUCTURE OF A
LONG-PERIOD TETRAGONAL Bi-Mn ALLOY
AN EXAMPLE OF STRUCTURE ANALYSIS BY HIGHRESOLUTION ELECTRON MICROSCOPY
K. Yoshida, T. Kawai and K. Shimonishi, Faculty of Engineering, Kobe
University, Rokkodai, Nada, Kobe 657, Japan.
Bi and Mn are difficult to mix atomically from the melt. However, theauthors formed several new alloy phases by low temperature heating of
their double layer composite films. Atomic arrangement of the mostremarkable, a long-period tetragonal phase, is being investigated by highresolution electron microscopy and diffraction only, since we have noother means to analyse such thin and small crystallites.
Double layer thin films, consisting of a 300 A Bi layer and a 200 A Mn
layer, were prepared by successive deposition in a vacuum of about l0-7
Torr. They were then heated for 50 to 200 hr in the same vacuum at 265°
C, just below 271 o C, the melting point of Bi. Solid state alloying
occurred at the contacting interface for both layers, permitting someatomic ordering. As their total thickness is less than 500 A, specimens
could be observed directly under a JEM-200CX electron microscope.
Single crystal electron diffraction patterns were easily obtained. Somepatterns consisted of closely spaced arrays. A three dimensional
reciprocal lattice successfully constructed gave a tetragonal direct lattice,a = 17.26 A, c = 10.21 A.l) These cell dimensions are large (evenassuming C-face-centering with a= 12.20 A,c = 10.21 A) compared with
the Sigma-phase lattice constants, in some transition-transition binary
metal alloys (e.g. a = 8.8 A, c = 4.6 A for Sigma phase Ni-Cr). However,Bi and Mn ions, were mixed in the above large unit cell with the Sigmaphase structure. Bi and Mn were assumed to have the Goldschmidt ionicradii, and the mixture assigned the arithmetic mean radius (1.82+1.12)/2= 1.47 A. The packing of these spheres in the Sigma-phase structurearranged in the above cell, is unexpectedly good. This structure was
Fourier transformed and the result compared with the diffraction pattern.
Some observed reflections satisfying the h+k=odd condition that should be
extinct for the regular Sigma-phase structure are quite distinct. Thus 740
is too strong to be due to multiple diffraction. A structure with atoms
displaced systematically from the regular structure, was Fouriertransformed . Whereas the Sigma-phase space group is P42/mnm , thederived model may have P42/n. A few spots surrounding the originallyextinct 740 reflection became relatively strong, but 740 remained weak,though not extinct. Simulated images of the structural model thus derived
are now being being compared with high resolution electron
micrographs.
1) K. Yoshida , T. Yamada andY. Taniguchi , Acta Cryst. B45(1989) 40.

14T-38
CRYSTAL STRUCTURE OF A NEW TERNARYCHALCOGENIDE: Ta2Ni2 (J13·Seh(J14·Seh(Jls-Se)
S-X Liu, B Zhang, Z-M Wang and J-L Huang, Chemistry Department,
Fuzhou University, Fuzhou, Fujian 350002, China; Fuzhou Laboratory ofStructural Chemistry, Academia Sinica, Fuzhou, Fujian 350002, China.
Ta2Ni2 (J..L3-Seh (J..L4-Se)2 (J..Ls-Se) was obtained by direct combination of
the elements at high temperature. The title compound crystallizes withfour formula units in the monoclinic space group C2/m in a cell withdimensions a=l2.821(4) A, b=3.4913(4) A, c=16.444(2) A, P=91.34(2) 0 ,V=735.9 A3. The crystal structure was solved by the heavy atom method
and refined by full matrix least square calculations . The final cycle ofrefinement included 56 variable parameters, R=0 .048, Rw=0.059 ,goodness -of-fit= l.25, w=lfcr2(F 0 ). Max. shift/e.s.d. < 0.01, and theresidual electron density was +4.02 (-9.29) eA3, no chemically significant
features.
The compound displays a new layered structure type. Every layer
contains octahedral tantalum atoms, square pyramidal tantalum atoms,
and tetrahedral nickel atoms each coordinated by selenium atoms. Thereis a van der Waals interaction between Se atoms from the neighbouring
layers. There are two kinds of Ni atoms in a formula Ta2Ni2Ses: one Ni
atom is connected with other two Ni atoms and three Ta atoms in thesame layer; the other Ni atom is connected with four Ta atoms in thesame layer. Therefore metal chains are formed along the b axis in eachlayer. The one Ta atom in the formula has a square pyramidal geometry
with Ta-Se bond lengths of 2.523-2.664 A, while the other Ta atom in theformula is octahedrally coordinated with Ta-Se bond lengths of 2.5482.661 A. All Ni atoms are tetrahedrally coordinated by four Se atoms
with Ni-Se bonds between 2.328 and 2.657 A. These polyhedra which
are distinctly irregular join via shared edges.

This search was supported by the National Natural Science Foundation ofChina.

14T-39
CRYSTAL STRUCTURES OF SOME TERNARY LAYEREDTELLURIDES CONTAINING IRON ATOM
J-L Huang, S-X Liu and G-L Cal, Chemistry Department, Fuzhou
University, Fuzhou, Fujian 350002, China; Fuzhou Laboratory ofStructural Chemistry, Academia Sinica, Fuzhou, Fujian 350002, China.
Six ternary Fe-containing tellurides were prepared by high-temeprature
reaction of the elements and characterized by the single crystal X-ray
diffraction, shown in Table 1. The layered structure of these tellurides
can be described as a series of sandwiches. Neighbouring sandwiches areheld together by weak van der Waals interaction between Te atoms. In
each sandwich, Fe atoms and Ta (or Nb) atoms are packed between layersof Te atoms. The Fe atoms in these compounds are in a distorted
tetrahedral environment, Fe-Te bond lengths being between 2.478A and2.665A. The Ta (or Nb) atoms in these tellurides have distorted
octahedral, square-pyramidal and tetrahedral geometries, respectively.
The anisotropic resistivity and some other physical properties were
measured for these layered compounds.
Table 1

Crystal Data

Compounda(A)FeTaTe3
FeNbzTe4
FeTazT~o-FezNbzT~*
m-FezNbzT~+

FeTaTe2

Space
Group

7.407 (4) 3.625 (3) 9.966 (3) 109.16 (3) nj/m
12.412 (2) 3.8173 (9) 7.295 (2)Pmmn
12.377 (3) 3.7687 (7) 7.266 (2)Pmmn
7.920 (3) 6.241 (3) 7.228 (4)Pma2
7.301 (1) 6.313 (1) 8.002 (1) 92.46 (1) n11c
7.873 (1) 7.2229 (6) 6.174 (1)
Pmna

R

0.051
0.055
0.076
0.076
0.037
0.083

*orthorhombic form of FezNbzTe4+monoclinic form of FezNbzTe4
This research was supported by the National Natural Science Foundationof China.

14T-40
STRUCTURE OF Na4SrSi309 AND ITS RELATIONSHIP TO
OTHER COMPOUNDS OF FORMULA M'4M" (T03)3
R.P. Gunawardane, Department of Chemistry, University of Peradeniya,
Peradeniya, Sri Lanka.
Single crystals of Na4SrSi309 were grown from a melt of composition 75
mol% Na2Si03: 25 mol% SrSi03 at l035°C and the unit cell was
determined using rotation and Weissenberg photographs. Crystal data:
Na4SrSi309 monoclinic, space group C2,

a= 10.706(2), b=10.866(2), c = 6.509(1) A
0~ = 144.14(2) , z = 2.
The structure was determined using 411 independent reflections
measured on a Nicolet P3 4-circle diffractometer. The atomic
coordinates were refined to R = 0.084.
Bond lengths and angles are normal, although the Si-0-Si angle is nearly
180°; this rather large value is associated with large temperature factors
for the bridging oxygen atoms.
The compound contains infinite Si03 chains of a conformation notdescribed previously. The structure is built from a new type of zig-zag
Si309 chain, parallel to (001), the conformation of which is quite
different from the chain structure of calcium silicates such aswollastonite. Conformationally it more nearly resembles the infinite
Ge03 single chain found in K4BaGe309 . The structure of Na4SrSi309 iscompared with those of the other compounds of general formula
M'4M"(T03)3 where M'=Na, K; M"=Ca,Sr, Ba and T=Si, Ge.

Gunawardane, R P and Glasser, F P (1975). Z Anorg Allg Chern 411,
163-171.

14T -41
PLURALITY OF Si AND Co SITES IN Co AKERMANITE
K. Hagiya and M. Ohmasa, Department of Life Science, Himeji Instituteof Technology, Kanaji 1479-1, Kamigori, Akogun, Hyogo 678-12,
K. Iishi, Department of Mineralogical Science and Geology, Yamaguchi
University, Yoshida, Yamaguchi 753, Japan.
An incommensurate modulation in synthetic Co-ftermanite, Ca2CoSi207,
has been determined by five-dimensional refinement of the structure. The

basic structure is tetragonal P42tm, unit-cell dimensions a=7 .8417(6),c=5.0249(3)A, Z=2, Dm=-3.307(4) g-cm-3 at 293K, Dx= 3.302 g-cm-3.
The modulated structure is also tetragonal P~~:, kt= 0.2913x(a*+b*),k2=0.2913x(-a*+b*) where kt, k2 are wave vectors and a*, b* arereciprocal lattice vectors of the basic structure. The modulation is causedby shifts of the constituent atoms and there was no evidence for anomalous
occupancy at the metal sites. When distances longer than 3A are excluded
the coordination of oxygen around a Ca atom is 6 or 4+4. Since Ca-0
distances at different sites change markedly, it is concluded that the Si04
tetrahedron does not behave as a rigid body. One of the four Si-0
distances is almost constant along a direction of the modulation, while therest vary markedly. This indicates that distortion of the Si-0 tetrahedra in
the crystal varies. The behaviour of the Co-O distances differs from thatof the Si-0 distances, since all four Co-O distances vary simultaneously ina sinusoidal manner. The distributions of the mean Si-0 and Co-O
distances evaluated from the modulation functions indicate that some mean
distances occur more frequently than others in the structure. Splittings ofpeaks for tetrahedral cations in Ca2(Mg,Fe)Si207 were observed by
Merwin, Sebald and Seifert (1989) and by Seifert, Czank, Simons andSchmahl (1987) in spectroscopic studies. The plurality of tetrahedral
bonds found in the present study may provide a reasonable interpretationof those spectra.
Merwin, L.H., Sebald, A. & Seifert, F. (1989). Phys. Chern. Minerals
16, 752-756.
Seifert, F., Czank, M., Simons, B. & Schmahl, W. (1987). Phys. Chern.
Minerals 14, 26-35.

14T-42
CRYSTAL STRUCTURE OF DUFTITE POLYMORPHS
Kharisun and M. R. Taylor, School of Physical Sciences, The Flinders Universityof South Australia, G.P.O. Box 2100, Adelaide, SA 5001, Australia, and A. Pring,South Australian Museum, Adelaide, SA 5000 , Australia.
The lead copper arsenate mineral, duftite, PbCu(As0 4 )0H is found in nature in
two polymorphs known as a-duftite and ,8-duftite. a-Duftite has the conichalcite,
CaCu(As0 4 ), structure. Both polymorphs are believed to have essentially the samechemistry, however the relationship between the two structures has not yet been
fully explored.
Single crystals of synthetic a-duftite have been prepared hydrothermally at 200 oc
and 20 atmospheres from aqueous solutions wh.ich were 10- 2 mol dm- 3 in copper(II)acetate, lead(II) acetate and disodium hydrogen arsenate. The pHs of the solutions
were adjusted to pH 3 using HC10 4 • We are attempting to establish a syntheticroute to ,8-duftite.
The crystal structures of the two polymorphs of duftite are believed to be closely
related. Both structures consist of a network of As0 4 tetrahedra, CuOs octahedra
and Ph in square antiprisms . In a-duftite the copper-centred octahedron is regular,
however, in ,8-duftite the octahedron is strongly distorted changing the space groupfrom Pnma to ?2 1 2 1 21 . A detailed comparison of the two structure types will bepresented.

14 T -43

POLARIZATION STUDY OF THE MAGNETIC X-RAY
SCATTERING OF (Ba,Sr)2Zn2Fe12022
E. Tsuji, S.Kumazawa, H.Katoh, N.Momozawa and K.Ishida, Science
University of Tokyo, Noda-shi, Chiba 278, Japan,
K.Ohshima, University of Tsukuba, Tsukuba, lbaraki 305, Japan,
J.Harada, Nagoya University, Chigusa-ku, Nagoya 464, Japan and
S.Kishimoto , Photon Factory, Oho-machi, Tsukuba, lbaraki 305, Japan
The purpose of the present work is to study X-ray magnetic scattering ofhexagonal ferrite (Bat-x,SrxhZn2Fet2022 with polarization analysis of thescattering peaks.
Single crystals of the hexagonal ferrite with x=0.748 were prepared by aflu x growth method. The magnetic structure of the crystal is a proper
helix below the Neel temperature 337K. The temperature dependence ofthe period of the helix was determined by neutron diffraction!). Since theperiod is incommensurate with the lattice, we attempt to observe weak
peaks of magnetic X-ray scattering separately from intensive charge
scattering. The X-ray experiment was carried out at BL4C in Photon
Factory of KEK using a precise 4 axis goniometer with a variabletemperature cryostat. For the polarization analysis, we chose thewavelength, A = 1.15483A. Being of incommensurate nature, magnetic
satellites such as 006+, 009+ were observed whereas 006-, 009- were not.
The observed period of the helix at 50K was in good agreement with that
determined by neutron diffraction, but the angular resolution of the X-ray
experiment is more than 20 times higher than that of the neutron
experiment.
Polarization analysis was performed with a Ge(444) reflection who se
Bragg angle is rt/4 for A = 1.15483A. The polarization planes formagnetic satellite peaks were rotated at right angle to that of the incident
beam. The polarization analysis for weak diffraction peaks at theforbidden reflection angle of the crystal structure indicated that the peaks
might be due to charge-magnetic interference scattering2).
1) N.Momozawa, (1986) J. Phys. Soc. Jpn.55, 4007-4013
2) M.Blume and D.Gibbs (1988) Phys . Rev. B37, 1779-1789

14T-44SINGLE CRYSTAL X-RAY DIFFRACTION AND EXAFSSTUDIES ON RJTa07 (R=Ho,Y,Yb)

T. Tana ka, N. Ishizawa, M.Yoshimura , Research Laboratory ofEngineering Materials , Tokyo Institute of Technology , Nagatsuta ,Midori-ku , Yokohama, 227, Japan , K. Tanaka, Nagoya Institute ofTechnology, Gokiso-cho, showa-ku, Nagoya, 466, Japan, H. Oyanagi,
Electrotechnical Laboratory , Umezono, Tsukuba, 305, J apan, andF. Marumo, College of Humanities and Science, Nihon University,
Sakurajosui, Setagaya-ku , Tokyo, 156, JapanThe structure analysis of RJTa0 7 (R=Ho,Y,Yb) have been carried out
by means of single crystal X-ray diffraction and EXAFS spectroscopy.
Although circular diffuse spots were observed in addition to thefundamenta l reflections based on the fl uorite-type s ubcell for allcompounds, the structural parameters were refined neglecting thosediffuse spots and assuming the defect-flu orite-type structure with spacegroup FmYm. Residual electron densities, which can be explained withthe assump tion of anh armonic thermal vibrations were , observed
around the respective constitu ent atoms . Actually, refinement withanharmonic thermal parameters improved coincidence of observed andca lculated structure factors significantly for HoJTa07 and YbJT a0 7.
EXAFS spectra of these crystals were measured at Photon Factory,
K .E.K, at absorption edges of Ta Lm, Ho Lm, Yb Lm and Y K ,indicating that the R-0 and Ta-O distances were generally slightly
shorter than those given by the single crystal X-ray structurerefinement.

14 T-45
STRUCTURE ANALYSIS OF LEAD ORTHOV AN ADA TE
Pb3(V04)2 IN THE FERROELASTIC AND THE
FERROELECTRIC PHASES
T. Umeki, H. Kasatani and H. Terauchi, School of Science, Kwansei-Gakuin
University, Nishinomiya 662, Japan.
Lead orthovanadate Pb3(V04)2 undergoes successive phase transitions at
TI=373K and T2=273K. The crystal in the high-temperature phase (T>TI) is
trigonal with the space group of R 3m (Z=l). The ferroelastic phasetransition occurs at T1 with decreasing temperature. The crystal in the
ferroelastic phase (T1>T>T2) is monoclinic with a space group P2t/c (Z=2).
The ferroelectric phase appears below T2, where the crystal is monoclinic.
A spontaneous polarization Ps takes place along the b-axis, the unique axisof the monoclinic system. Concerning the ferroelectric phase, there was acontradiction between the results of Salje and von Hodenberg (1977) andGarnier et al.(1984 ). The former authors reported that the ferroelectricphase belonged to P2I with the multiplications of the unit cell along the a andc axes. The latter authors, on the other hand, suggested that the space groupof the ferroelectric phase was A2 without cell multiplication.
Here we determine the space group of the ferroelectric phase by means of
X-ray diffraction using a mono-domain crystal. The space group of theferroelectric phase was A2. The structure analyses were conducted atseveral temperatures from 300K to 14K. The R-factors were less than 0.060
in the ferroelastic phase and 0.045 in the ferroelectric phase. With a simple
point-charge model, the spontaneous polarization was calculated from theatomic positions in the ferroelectric phase and compared with value s
observed u sing pyroelectric measurements by Midorikawa et al.(1980) . The
mechanism of the ferroelectric phase transition will be discussed in terms ofthe model of atomic displacements.
We wish to acknowledge Professor Y. Ishibashi of Nagoya University forsupplying the Pb3(V04)2 crystal.
Salje, E. & von Hodenberg, R. (1977). 1. Appl. Crystallogr. 10, 132.
Garnier, P., Calvarin, G., Beran, J.F. & Weigel,D. (1984). Mat. Res.
Bull. 19, 407-414.
Midorikawa, M., Kashida, H., Sawada, A. & Ishibashi, Y. (1980). J. Phys.
Soc. Jpn. 49. 1095-1097.

14T-46
STRUCTURAL VARIABILITY IN GAMMA ALUMINA
B.K. Gan and B.H. O'Connor, Department of Applied Physics, Curtin Universityof Technology, GPO Box U1987, Perth, WA 6001, Australia and C.J. Howard,
Ansto, Private Mail Bag 1, Menai, NSW 2234, Australia.
The extensive literature on ,-alumina (A! 20s) has established that the structure
approximates to the spinel (ABPJ form with either a cubic or tetragonallydistorted cell. The cubic structure for 1-alumina has the full complement of 32
close-packed oxygen ions found in spinel but only 21 lj3 A! 3 + ions, i.e. there are
2 2j3 cation sites vacant. The arrangement of A!3 + ions is uncertain. Most reported
structures describe a distribution of A! 3 + ions between the octahedral andtetrahedral sites. Zhou (1988) reported some additional Al 3 + occupation of ahighly distorted octahedral site (32e). Analysis by the authors of 1-alumina x-ray
powder patterns from three sources has indicated that the arrangement of cation
vacancies may vary wi th synthesis conditions.
Comparisons were made using the gamma samples:1. Gamma alumina, Zhou (1988), obtained by heating boehmite (A!OOH) in air at
600 •c for 8 hours;
2. G amma alumina produced by the authors from gibbsite Al(OHh by heating in
air at 700 •c for 8 hours;
3. Gamma alumina supplied by Johnson Matthey, Materials Technology,
U.K.,consisting of a mixture of gamma and alpha (5%) alumina - synthesis
procedure not known.
The measured patterns have been compared with a set of calculated patterns
covering the range of possible vacancy distributions. The results indicate that thevacancy arrangements for these three specimens are markedly different. The
differences are attribu ted to the distribution of AJ3+ ions between the octahedraland tetrahedral sites. All still maintain the cubic spinel model.

Zhou, R-S (1988). Thesis for PhD in Ceramics, A Structural Study of theTransition Aluminas, Alfred University, New York, USA.

14 T -4 7
A NEW FCC PHASE OF Y203
S. Katagiri and N. Ishizawa, Research Laboratory of Engineering
Materials, Tokyo Institute of Technology 4259, Nagatsuda-cho,
Midori-ku, Yokohama-shi, Japan and
F. Marumo, Department of Humanities and Sciences, Nihon University,
Sakurajosui, Setagaya-ku, Tokyo 156, Japan.
A new high temperature form of Y 203 has been found to be attainedwith a laser beam heating technique. The new form has a fcc structurewith a=5.2644(3)A. The lanthanide sesquioxides are known to
crystallize in either of three structures A, B and C, belonging to thehexagonal, monoclinic and cubic systems, respectively. The Y 203
crystals so far reported possess the C -type structure with the spacegroup /a3 and a=10.604A. In the present study, Y203 powder with
99.99 purity was pressed into a rod 4mm in diameter and 12mm inlength. The upper part of this rod was heated at about 2220°C for
25min by making use of two Y AG laser beams applied fromsymmetrically-placed positions. The powder diffraction pattern of thelaser-processed part indicated that the lines typical of the C-type
structure disappeared while those for the fluorite subcell remained. The

space group of this crystal was found to be Fm3 m or Fm3 from theprecession photograph of a single crystal with a grain size of
30x40x2j..Lm. The powder data are given in the Table 1. This new fcc
form of Y203 appears to have a fluorite-type structure containing
disordered oxygen vacancies.
Table 1. Powder diffraction data for Y 203
hk 1

111
200
220
311
222
400
331
240

lobs
100
24
33
24
3
2
9
3

3.03462.63181.8615
1.58701.52001.31611.20791.17713.03942.6322
1.8612
1.5872
1.51971.31611.2077
1.1772

14U-48
CRYSTAL STRUCTURE AND LATTICE PARAMETERS
OF Znl-xCoxS, Zn1-x V xS DILUTED MAGNETICSEMICONDUCTORS
D. Gomez de Anderez and S.A. Lopez-Rivera, Facultad de Ciencias,
Universidad de Los Andes, Merida, Venezuela and
W. Giriat, Centro de Fisica, IVIC, Aptdo 21827, Caracas 1020-A,
Venezuela.
Crystal structure of ternary alloys formed by substituting Co or V for thegroup II element in the AliB VI lattice, are given in this paper. X-ray
single crystal analysis of the new cobalt and vanadium diluted magnetic
semiconductors Znt-xCoxS and Znt-xVxS are discussed for concentrationsof x=0.01, 0.05, and 0.10. The diluted magnetic semiconductors retain
the crystal structure of the "parent" hexagonal wurtzite ZnS structure for
x=0.05 in Zn1-xCoxS and for x=0.10 in Znt -xVxS. For low (x=0.01) V
concentration and for high (x=O.lO) Co concentration, the structure is
cubic. A complete crystal structure analysis of the compound
Vo.lZn0.90S will be presented. This the first time that single crystal Xray analysis is reported for diluted magnetic semiconductors.

14U-49
STRUCTURE AND SYMMETRY OF PTCR PEROVSKITES
N.J. Calos ,J. S. Forrester and T . J. White, Centre for Microscopy andMicroanalysis, University of Queensland, St. Lucia , Australia, 4072 andS.

Myhra ,

Division of Science andTechnology,

Griffith University,

Nathan, Australia, 4111.
A number of perovskites show theunusual characteristic of higher

resistivity with increasing temperature.

Usually referred to as the

positive temperature co-efficient of resistivity (PTCR), this property isfinding

application

devices.

In this investigation, PTCR characteristics are correlated withinthermistors

and

other

temperaturesensitive

the crystal chemistry and microstructure for a number of titanate
perovskites of the form (Ca1 -xAx)Ti03 where A= Sr, Pb, Ba, La.
Average crystallographic features were determined by Rietveld analysis
and Raman spectroscopy,
boundary

structure

while order-disorder phenomena andwerestudiedbyconvergent

grainelectronbeam

diffraction and high resolution electron microscopy.
The series (Ca1-xPbx)Ti03 typifies the results obtained.

Using X-ray

diffraction it was confirmed that in passing from the lead to calcium
endmembers

of

the

series,thesymmetrychangesfromtetragonal(P4mm) to orthorhombic (Pnma), with the transition point occurring at
x=O. 4.

This was confirmed by Raman spectroscopy where two broad

bands between 200-500 cm-1 and 580-900cm-l were preserved throughout
thecomposition

range,

while

theoverlyingmarkedly about the symmetry transition.

fine

structurechangedThe former bands are due tovibrational modes associated with the titanium and oxygen atoms (whose
octahedral topology is essentially invariant ) while the fine detail can be
relatedtoA-0

bending

throughout the series.
complicated.

andstretching

In detail ,whichchangesmarkedly

the symmetry transition is quite

For x=0.25 superlatti.ces are observed by high resolution

electronimaging andelectron diffraction.

ordering

which

be

( <600°C )annealing.

mayenhancedbylongThese arise from
term,

low

Ca/Pb

temperature

The influence of these complex structures onelectrical resistance and other properties is now being evaluated.

14U-50
STRUCTURE OF Ba6-3xSm8+2xTiJ6054(0<x<l)
H. Ohsato, T.Ohhashi and T.Okuda, Nagoya Institute of Technology,
Gokiso-cho Showa-ku Nagoya, 466 Japan.
The compound has excellent dielectric constant, low dielectric losses andlow temperature coefficients of capacitance (Kolar et al. 1978). Recently,
such dielectric ceramics have been used for microwave resonator. Ohsato
et al.(l992) synthesized single crystals from the melts with composition
BaSm2Tis014, reported the dielectric properties and the crystal data, andfound a superlattice with doubled c-axis lattice parameter.
Crystal data offundamental lattice : Orthorhombic system, Pba2 (No.32 )or Pbam(No.55), Z=l, a=12.142(4), b=22.300(6), c=3.827(2)A.
The crystal analysis of the fundamental structure was performed based on
the structure model of Ba3 .7sPr9 .sTi1sOs4 reported by Matveeva etal.(1984 ). This compound has a tungsten bronze-like structure withperovskite-like columns, which have 2x2 perovskite unit cell dimensions.
Because the Ti06 octahedra connect with each other at apices, the atomic
ratio of Ti to 0 is 1:3. There are three kinds of large cation sites, A1, A2
and C. A1 has twelve fold coordination as in a perovskite structure. A2
contains a pentagonal channel cavity among the perovskite-like columns
as in the tungsten bronze structure. C has a triangle channel cavity which
is vacant in this compound. The structural formula is described by[(Ba2-2x, Sms+2x) Ba4-x]Tits0s4.
The authors wish to thank K.Hiraiwa, M.Fujisawa & Y.lshiguro.
This work was supported by Murata foundation for science development.
Kolar D., Stadler Z., Gaberscek S. & Suvorov, 0.(1978). Ber. Dt.
Keram. Ges. 55, 346-348.
Matveeva R.G., Varfolomeev M.B. & ll'yushchenko L.S. (1984). Zh.
Neorg. Khim . 29, 31-34, transl.: Russ. f . Inorg . Chern. 29, 17-19.
Ohsato H., Nishigaki, S. & Okuda T. (1992), flAP, in press.

14U-51
MICROCRYSTALLINE KEATITE- A FIDROUS SiOz-PHASE
B. Martin, Institute of Mineralogy, Ruhr-University, Universiti:itsstr.150,
D-W4630 Bochum, Germany.
Keatite was first synthesized by Keat, 1954, who claimed to have obtained"single crystals". Shropshire et al.,1959, determined the structure andproclaimed an "idealized keatite-model". However, under the conditions
given in Keat's paper the keatite synthesis is not reproducible.
For the first time microcrystalline. fibrous keatite, K, has been
reproducibly crystallized from high purity silica glass HERALUX(>99.99 wt.% SiOz) under hydrothermal conditions (400°C, 350 bar) in
0.01 mol NaOH/HzO solution (Martin & Roller,1990). This metastablesilica transition phase is always associated with microcrystalline strongly
stacking disordered cristobalite Co in the beginning of its occurrence andwith microcrystalline granular quartz before its fading out. The fibres areelongated parallel to <110> (P 4J2J-Setting). The optical character of
elongation is length-slow (KLS). KLS is crystallographically wellcharacterized (Martin & Roller, 1990, Martin, 1991). A few milligram ofkeatite free of Co, however, intergrown with quartz are used for X-ray
diffraction analysis on a special automatic high-resolution Guinier-X-raydiffractometer for small samples prepared without texture (method :Thringer, 1982). Structure refinement was carried out with the WYRIET
2 of Schneider (1989).
Crystal data for keatite(micro-crystalline powder): space group P4J2J2 (orP432I2) a=7.479(7) c = 8.539(2)-8.540(7)A V=477.6(9-14)A3,T = 298K
X-rays:l.5406A; 28 range:14.0-60.0°; in 0.02° steps: 15 (overlapping!)
reflections. RBragg (X-ray resolution 0.6 A-1)
15-32%
Comparison of the structural analysis of Shropshire et al. with "singlecrystals" and the data for the new fibrous, microcrystalline material gives
compatibility with the idealized keatite-model. Current investigations withneutron radiation will show whether the idealized structure model is amean structure caused by right- and left-rotating a) domains or b)
lamellae analogous to chalcedony, a natural microcrystalline fibrousquartz species (Martin,l991).
Keat, P.P.(l954). Science 120,328-330
Thringer, J.(1982)J.Appl.Cryst. 15,1-4
Martin, B. (1991)Thesis Fakultiitfiir Geowissenschaften, Ruhr-University
Martin, B. & Roller, K.(1990). N.Jb.Miner .Mh.lO, 462-466.
Schneider, J. (1989). IUCr Int. Workshop on the Rietveld method, Petten.
Shropshire, J., Keat, P.P. & Vaughan, P.A. (1959).Z.Krist.l12, 400-413.

14U-52
THE INTERSITE DISTRIBUTION OF A SMALL AMOUNTOF Mn ION IN OLIVINE.Y.....QnQ, M. Tokonami and H. Horiuchi, Mineralogical lnst., Faculty ofSci., Univ. of Tokyo, Hongo,Tokyo 113,
N. Aikawa, Dept.of Geosciences, Faculty of Sci., Osaka City Univ.,
Sugirnoto-cho, Osaka 459, and
S. Sasaki, Res. Lab. of Eng. Materials, Tokyo Inst. of Techn., Nagatsuta,
Yokohama 227, Japan.

Olivine(M2Si04) contains non-equivalent Ml and M2 sites and the intersite distributions of cations are of importance in the geoscience of theupper mantle [1]. Large Mn2+ ions prefer larger M2 sites in Mg-Mn or
Fe-Mn binary systems, but the distribution of very small amounts of Mn
in the Mg-Fe-Mn ternary system has not been investigated.
Anomalous scattering with synchrotron radiation is effective for thedetermination of cation inter-site distributions, but in the case of a: verysmall amounts of cation in ternary system, it remains very difficult. We
now introduce order(O)-disorder(D) structural models and repeated datacollection fo r statistical inspection. A new analysis of the inter-site
distribution for only 1.4 mol% of Mn ion in (Mg,Fe,Mn)2Si04 is
described.
The sample was a natural crystal, shaped into a lOOJlm ellipsoid. Twowave lengths of 1.913A and 1.903A were used for the intensity
measurements. The latter wavelength is very close to the Mn-absorption
edge (1.8964A). Accordingly the anomalous dispersion effect for the Mn
ion is significant, whereas in the former case there is much less anomalous
influence on the reflections. A set of seven reflections, which wasmeasured repeatedly, was selected from two types of calculated structure
factor. For three "standard" reflections, the difference between structure
factors for the two wave length both in 0 and D models are almost zero,
while in the other four, there are large differences only in the 0 -model.
From a comparison of the statistical coincidence factors with the 0 or D
structural models at two wave lengths, Mn ions in the ternary systems
seem to occupy the two non-equivalent sites randomly. The existence ofmany Mg2+ and Fe2+ ions, which tend to disordered distributions in theirbinary system, supposedly compensates for the energy gap between MlM2 sites for the Mn2+ ion.
[1] Aikawa N.,Kurnazawa, M. & Tokonami, M. (1985). Phys. Chern.
Minerals 12, 1-8.

14U-53
LOCAL CRYSTAL STRUCTURES OF AN ILVAITESINGLE CRYSTAL
Y. Takeuchi, Y. Matsushita, H. Sawada and H. Taniguchi, Department ofEarth Sciences, Nihon University, Tokyo 156, Japan.
Our eight structure refinements of ilvaite CaFe2+2Fe3+Si20700H fromvarious localities in Japan have revealed that specimens from theTochibora skarn, Kamioka mine, exhibit a notable feature (Takeuchi &Saga, 1990); the p versus order-parameter plots of those specimens
deviate strongly from the correlation line proposed by Takeuchi, Haga &Bunno (1983). Using a single crystal of Tochibora ilvaite, about 1.5 em
wide and 4.5 em long, we prepared X-ray specimens from three portions
along c: (1) around the bottom, (2) middle, and (3) top (termination of thegrowth). Their MnO contents are around 3 wt%. Structural studies [P21fa;
spherical specimens with radii 0.11-0.16 mm, AFC-SS, MoKa
A, = 0.71073 A, 28max = 70° - 90°, No. of reflections 1486-2460,
wt. scheme 1fcr2 , R = 0.030 - 0.035, wR = 0.041 - 0.047] gave thefollowing cell dimensions and approximate order parameters:
Specimen
(1)
(2)
(3)

a(A)

b(A)

c(A)

13.040(1)13.036(1)13.019(4)8.831(1)8.829(1)8.818(2)5.8626(4)5.8610(4)5.855(1)~( 0 )

Order
parameter(%)
90.012(7)2
90.231(6) 36
90.271(2) 47

Thus, the bottom portion, (1), is essentially orthorhombic while the otherportions are monoclinic. This result contradicts the hypothesis that natural
orthorhombic ilvaites were heated subsequent to their formation (Ghose,
1988). It thus appears to be worthwhile to consider the twinnings,
disorders, along c, of the edge-sharing octahedral chains both suggested
by Takeuchi et al. (1983) or partial oxidation to account for the natural
occurrence of orthorhombic ilvaites.
Takeuchi Y. & Saga S.(l990). Abstr. 1990 Annual Meet. Miner. Soc. Jpn
Takeuchi Y. Haga N. & Bunno,T.(1983). Z. Krist. 163, 267-283.
Ghose S.(1988). Adv. in Phys. Geochem . 7, 141-161.

14U-54

I;OCAL STRUCTURE OF INTERCALANTS IN THE
LAYERED COMPOUND CuxTiS2
K. Ohshima, R. Maruta and A. Maldta, Institute of Applied Physics,
University of Tsuk:uba, Tsukuba 305, Japan.
X-ray measurements have been performed on the structure of thelayered compound CuoJsTiJ.osS2 at room temperature. Both theintercalated copper atoms and self-intercalated titanium atoms are
positioned at the octahedral sites in the van der Waals gap's layer. Weakdiffuse scattering at 1/2 0 3/2, 0 1/2 3/2 and their equivalent positions isobserved. This reveals that the intercalants are correlated with eachother three-dimensionally and that stacking sequence a~a~ ... isdeduced. By analyzing diffuse intensity, the short-range order (SRO)
parameters were determined. 2x2 in-plane ordered structure is expected
for the low temperature phase. The estimated in-plane and interlayer
correlation lengths are about 12 A, which correspond to about 4ao and2co, respectively (ao and co are unit cell parameters for a and c axes in
the hexagonal lattice) . In a computer-simulated arrangement ofintercalants, based on the observed SRO parameters, it was noticed thatthe atoms have close to random positions with the above structuralcharacteristics.

14U-55
THE Zr-N-F AND Y-0-F COMPOSITE MODULATEDSTRUCTURES
Siegbert Schmid, Ray L. Withers and John G. Thompson, Research
School of Chemistry, The Australian National University, GPO
Box 4, Canberra, ACT 2601, Australia
In both the YOxF3-2x (0.78::; x ::; 0.87) and ZrNxF4-3x (0.906::; x ::; 0.936)

systems [1,2] there are reported to exist anion-excess, fluorite-related,
non-stoichiometric solid solution fields in which each and every
composition has its own unique (but closely related) structure. Such solid
solution fields are best characterized as composite modulated structures.
We report the results of a TEM and XRD study of the ZrNxF4-3x system.
Yttrium oxide fluoride is difficult to study in the TEM because of beam
damage. Isostructural ZrNxF4-3x, however, is 'beam-stable' and therefore
various compositions of this material were synthesized by ammonolysis of
ZrF4 for study by TEM and XRD.
Composite modulated structures consist of two (or more) in generalmutually incommensurable sub-structures each of which is characterized
by its own 3-dimensional space group. The influence of the sub-structures
upon each other leads to incommensurate modulation of the fractional
coordinates of both. Structural characterization of such systems requires
refinement of both parent sub-structures as well as of the Atomic
Modulation Functions (AMF's) describing the above modulations .
Approximations to the above parameters have been obtained via Fourier
decomposition of the reported structures of Y706F9, Y 60 sFs andZr10sN 98FI38 (obtained by using a superstructure approximation).
Fourier decomposition of these reported structures gives both underlying
sub-structures as well as the above AMF's. A modulated structure
approach provides a much simpler parameterization and shows thatsuperstructure refinements using independent atom-based parameters aregrossly over-parameterized.
[1] Bevan, D. J. M., Mohyla, J., Hoskins, B. F. & Steen, R. J. (1990). Eur.
J. Solid State Inorg . Chern. 27,451 -465.
[2] Jung, W. & Juza, R. (1973). Z. anorg. allg . Chern. 399,1 29 -147.

14U-56
X-RAY ANOMALOUS DISPERSION DETERMINATION OF
PbZr03 SUPERSTRUCTURE

K.Nagino,
Physics,

M.Iida, Y.Itoh and Y.Soelima,
Kyushu University 812,

Department ofJapan, and K.F.Fischer,

Fachrichtung Kristallographie der Universitat des Saarlandes, Saarbrucken, BRD.

The supe rstructure of PbZr03 has been investigated byu sing X- ray anomalous dispersion effect at both PbLm
ZrK absorptio n edges.

andThe method proposed by Soejima andFischer ( 1 98 8) was applied for det e rmining displacem e nts
of Pb and Zr atoms along the Z dir ec tion .

Int e nsity

measurements of s eve ral superstructur e reflections aroundboth t h e abso rption edges were made with synchrotron
radiation.

From changes in the intensity due to those inf ' a nd f" we find the displacement vectors of Pb and Zr
atoms in the superstructure.
ato ms shift along z;

The r e sults indicat e that Zr

this is in contradi ct ion with themode l given by Jona et al. (1975) .

J ona,F.,

Shirane,G., Mazzi,F. & Pepinsky,R.(l975). Phys.

Rev. 105,849 - 860 .
Soe jima, Y. & Fischer,K.F . (1988) Z.Kristallogr. 184,71-85.

14U-57
CHANGES IN MORPHOLOGY OF PERIODIC ANTIPHASE
BOUNDARIES IN ONE-DIMENSIONAL LONG PERIODSUPERSTRUCTURES
M. Itakura, N. Kuwano , S. Iwasaki, K. Kajiwara, A. Matsumoto
and K. Oki,
Department of Materials Science and Technology ,Graduate School of Engineering Sciences, Kyushu University-39, Kasuga,
Fukuoka 816, Japan.
Cu3Pt and PdsCe have one-dimensional long period superstructures(LPSs) where antiphase boundaries (APBs) are distributed periodically in
the Ll2 ordered structure. It is well known that Cu3Pt has a state of anormal Ll2 at low temperatures . Some of the present authors (Itakura etal., 1990) confirmed that in PdsCe the LPS transforms to Lb at hightemperature. In this study, the changes in morphology of periodic APBs
in the alloys during the LPS~ L 12 transition process have been
investigated by electron microscopy. On the way to the transformation, a
lot of hairpinshaped APBs are formed by linking adjacent periodic APB s.
Some of the hairpin tips have a spear-like shape. High resolution images
indicate that the order-structure is distributed in the region of the hairpintip, demonstrating that the hairpin-shaped APB recedes, dragging a small
region of a low degree of order. It is found that the hairpin-shaped APBs
tend to be arrayed to form "patchwork" of Lh- and LPS-regions. This
texture shows that formation of a pair of hairpins induces anotherformations in the neighbourhood. A computer simulation of thetransformation from LPS to Lh has been performed using a timedependent Ginzburg -Landau model to successfully reproduce theformation process of hairpins. The kinetics of annihilation of periodic
APBs have also been discussed in order to clarify the dependence of thestability of LPS on the shapes of the APBs.
Itakura, M ., Kuwano, N., Yamamoto, K . & Oki, K. (1990). J. Electron
Microsc. 39, 1-6.

14U-58

DIFFUSE SCATTERING IN AN YTTRIA-ST ABILISEDCUBIC ZIRCONIA, (Zro.6I Yo.390 1.805)
T.R .Welberry. R.L.Withers, J.G.Thompson & B.D.Butler. Research School ofChemistry, Australian National University, GPO Box 4, Canberra City, ACT
2601, Australia.
Details of the diffuse X-ray scattering distributions in a cubic yttria-stabilized
zirconia, recorded using a position-sensitive detector (PSD) system, arepresented in far greater deail than has hitherto been reported. In addition
we present the results of some investigations using Monte Carlo simulation
techniques to tr y to establish the origins of the various diffraction featuresthat are observed in the experimental patterns.
The most significant feature of the experimental patterns that is observed isa set of dark p lanes normal to each of the six (1 1 O) directions and of a
spacing equal to the reciprocal of the metal-metal interatomic vector. Thisfeature is observable in yttria-doped zirconia as a result of the fact that the
scattering factors for Y and Zr are very similar, and would probably beunobserved in systems displa ying first order scattering effects which dependon the difference in the two sca ttering factors. We consider that this feature
unequivocally demonstrates that lattice distortions due to variations of thisfundamental metal-metal distance are the basis for understanding thewhole diffraction pattern. The presence of such dark lines in this secondorder sca ttering term (i.e. due to mean-square atomic displacements), ischaracteristic of atomic size-effect distortions. In the classical 'size-effect',
local lattice relaxation results in neighbouring atoms moving in towards thesmaller atoms of a binary mixture or away from the larger atoms, the strain
field being propagated outward relatively large distances along rows of
atoms. In the present case, however, a second feature of the pattern, in theform of characteristic 'bow-tie' shaped regions of scattering, displays apolarization and azim uthal variation that can only be explained if the
distortions in two orthogonal directions (e.g. [1 1 O] and [1 -1 OJ) are out ofphase. That is to say, if an atom tends to push away a neighbour in the [1 1 0]
direction, then the corresponding neighbour in the [1 -1 O] direction is drawn
inwards, and vice-versa . We have dem onstrated with a simple 2D model
system that, with this thesis, each of the different diffraction effects noted inobserved patterns can be obtained.

14V-59
X-RAY STUDY OF PHASE TRANSITION IN C60
SINGLE CRYSTAL
H.Kasatani & H. Terauchi, School of Science, Kwansei-Gakuin
University, Nishinomiya 662, Japan, and
Y. Hamanaka & S. Nakashima, Faculty of Engineering, Osaka University,
Suita 565, Japan.
The discovery of a C60 molecule (Kroto, Heath, O'Brien, Curl &Smalley, 1985) and a method for synthesizing solid C60 [buckminsterfullerene] (Kratschmer, Lamb, Fostiropouls & Rhuffman, 1990) has
inspired many studies in the physical and chemical properties of this newform of carbon. At room temperature, the pure C60 crystal has a facecentered cubic (fcc) Bravais lattice with a high degree of rotational
disorder. With decrease in temperature, this rotation slows down. Highresolution synchrotron X-ray powder diffraction experiments conductedby Heiney et al. (1991) showed that the C60 crystal undergoes a weak
first- order phase transition at 249K, where the crystal is transformed
from the fcc structure of the orientationally disordered state of C60
molecules to a simple cubic (sc) structure of the orientationally orderedstate. The space group of the sc structure is Pa3 as commented by
Sachidanandam & Harris (1991).
Here, we carried out X-ray diffraction experiments on singlecrystal C6o at temperatures from 300K to 14K. A small jump in the lattice
parameter was observed at the transition temperature Tc=260K, implyingthat this was a first order transition. The integrated intensity of new
Bragg reflections observed below Tc, which corresponded to the orderparameter transformed from the orientationally disordered state to theorientationally ordered state, was proportional to the anomalous part ofthe lattice parameter.
We wish to thank Professor H. Shinohara for providing us withpurified C60Kroto, H. W., 'Heath, J. R., O'Brien, S. C., Curl, R. F. & Smalley, R. E.,(1985). Nature (London) 318. 162-163.
Kratschrner, W., Lamb, L. D., Fostiropouls, K. & Huffman, D. R. (1990)
Nature (London) 347. 354-358.
Heiney, P. A., Fischer, J. E., McGhie, A. R., Romanow, W. J.,
Denenstein, A. M., McCauley, Jr., J.P., Smith, ill, A. B. & Cox,
D. E. (1991) Phys. Rev. Lett. 66. 2911-2914.
Sachidanandam, R. & Harris, A. B. (1991) Phys. Rev. Lett. 67. 1467.

14V-60

CRYSTALLINE STATE RACEMIZATION OF A
BULKY CHIRAL GROUP.Y....SMru and Y. Ohashi, Deparunent of Chemistry, Tokyo Institute of Technology, 0 - ·okayarna, Meguro-ku, Tokyo 152, Japan, Y. Arai and Y. Ohgo, Niigata College of
Pharmacy, Kamishin-ei-cho, Niigata 950-21, Japan, and N. Karniya and H. Iwasaki,
The Institute of Physical and Chemical Research, Wako, Saitarna 350-01, JapanA new type of bulky chiral group, 1,2-dimethoxycarbonylethyl group,of two cobaloxime complex crystals has been found to be racemized on
exposure to a Xe lamp without degradation of the crystallinity. For thecomplex with diphenylmethylphosphine as an axial base ligand, threedimensional intensity data were rapidly collected several times
irradiating the crystal with a Xe lamp on a new diffractometer (IPDW AS). The analyzed structures clearly indicate that the racemization
occurs step-by-step and that the unstable intermediate structure appears
during the reaction (Fig.l.). For the complex with pyridine as an axial
base ligand, similar stepwise racemization was observed although thereaction rate was very slow. For the complexes with (S)-1-phenylethylamine , (R)- 1-phenylethylamine and 1-propylamine, such a crystallinestate racemization has not been observed. These crystal structures werecompared with those of the above two reactive crystals . The cooperative
motion of the two reactive groups in a crystal and enough size of thecavity for the reactive group seem to be essential for the racemization.

Fig.l. Stepwise inversion process of the chirall,2-dimethoxycarbonylethyl group

14V-61

X-RAY DIFFRACTION STUDY ON THE PHASE
RELATION OF BaZnGe04
S. Takai, T . Atake, N. Ishizawa and F . Marumo, Res. Lab. Eng. Mater. ,Tokyo lnst. Tech ., 4259 Nagatsuta-cho, Midori-ku , Yokohama, 227 Japan and
A. Hamano, Sumitomo Metal Ind. , Ltd. 1-3 Nishinagasu-Hondori, Amagasaki,
660 Japan .
Low t emperature X-ray precession photography for BaZnGe0 4 of th e cr ystal sizeof 0.2 - 0.8 mm in diameter has been carried out and a revised phase relation
is proposed as shown in Fig. 1. T he symmetry of phase VI, which app eared byholding the crystal larger than 0.2 mm in the temp erature range 100 - 160 K forseveral hours (Hamano, Atake & Saito , 1989), was det ermined to be hexagonalwith the lattice constants of a = 5.32 A. and c = 8.73 A. at 145 K. The diffraction
pattern is essentially the same as that of phase I in the a 1 *-a2 * plane, while thec-length is tripled. After holding the crystal in th e temp erature range 100 160 K for several weeks, the X- ray diffraction pattern at room temperature wasfound to be different from t hat of phase III. This new room temp erature ph ase
is considered to be hexagonal with th e space g~oup of P63 or P6a/m, a = 10.68
A. and c = 8.69 A at about 300 K. The a-length is doubled in comparison wit hphase I and the c-length is 1 % smaller than that of the sub-cell of phase III at 300
K. The new room temperature phase seems to be irrelevant to the sequence of thephases II-III-111'-IV-V, as they all have structures of tripled repetition along the(110) direction of phase I. The diffractio n pattern of this new room temp eraturephase was ret ained even at 1451< , whe:reas the crystal reversed to phase III by
an nealing at 1273 K.

100K

v

11

a=.J3a.
C =3 C .

131 K 14 3K

tw

530K

ill

m . a=.J3a.
a =.J3a . a =.J3ac -4 c. c =4c . c - 4c .

II

a=.!Ja.
c =c.

186K

l

II 0 0KVI
a =a.
c =3 c .

a.

c.

New Roo m Te mp e ra t u re Phasea =2 a .
c =0.99c .
Fig. 1 Phase relation of BaZnGe0 4.
Hamano, A., Atake, T . & Saito Y. (1989). A ppi.Phys. A49 , 91-94.

14V-62

DETERMINATION OF DOMAIN DISTRIBUTIONS AROUNDCUBIC-TETRAGONAL PHASE TRANSITIONS
T.Koga, N.Aomine, Z.Lu, Y.Soejima and A .Okazaki, Department of
Physics, Kyushu University 812, Japan.
In a single-crystal specimen of cubic crystals, three kind of domains
appear when the crystal undergoes a cubic-to-tetragonal phase transition.
Relative volumes of those domains can be determined, in principle, fromthe relative intensities at appropriate reciprocal-lattice points which areequivalent in the cubic phase. By high-resolution X-ray diffraction, we
can separately observe relevant reflections which are overlapped inconventional measurements; we can then unambiguously determine therelative volumes. The only difficulty in a technique such as high-angle
double-crystal X-ray diffractometry (HADOX) is limited freedom of
motion of a specimen crystal. The problem is now solved by introducing
into HADOX a combination of a four-circle goniometer and arefrigerator type of cryostat, and by taking advantage of the crystal
symmetry. An application has been made to the 105 K transition in
SrTi03: the reciprocal-lattice points 400, 040 and 004 in the cubic phasewere successively traced around 8 "" 82 with FeKa1 radiation. It is foundthat, when the temperature approaches the transition, the relative volumesof the domains varies so remarkably in some cases that one of the threekinds of domains nearly disappears. An anomalous variation of peak
profiles observed in the previous HADOX experiment by Ohama et al.
(1984) can be explained by the behaviour mentioned above.
Ohama, N., Sakashita, H. & Okazaki,A.(l984) Phase Transitions 4, 81-90.

14V-63

CHIRAL-TO-RACEMIC TRANSFORMATION IN A
COBALOXIME CRYSTAL ON EXPOSED TO VISIBLE LIGHT
Takashi Nemoto and Yuji Ohashi, Department of Chemistry, Tokyo
Institute of Technology, 0-okayama, Meguro-ku, Tokyo 152, JapanThe crystal of (R-1-cyanoethyl)(piperidine)cobaloxime has space group
P2J2J2J with two crystallographically independent molecules, A and B, in
the asymmetric unit.!) The racemic crystal has a structure isomorphous tothe chiral one, in which the cyanoethyl group of the B molecule (B cegroup) has the opposite configuration to the A ce group. When both
crystals, chiral and racemic, were exposed to visible light, the B ce group
was gradually changed to the disordered racemates whereas the A
molecule remained unaltered.2) This means that the racemic crystal wasconverted to the partly racemized one. In order to examine thedisordering process of the B ce group more quantitatively, crystals withdifferent R:S compositions were made.
As shown in Table 1, crystal 1 was obtained from a solution containing R
and S complexes with the ratio of 50:50. Crystals 2 to 6 were also
obtained from solutions with 56:44 to 100:0. Crystal structures of 2, 3
and 4 were determined. The ratio of R :S in each crystal differs slightly
from that in solution. Table 1 also gives the cell dimensions for the six
crystals. The a and V values of have maxima at the ratio of 75:25, whichis the final stage if the chiral and racemic crystals were exposed to visible
light. Each crystal has been exposed to a Xe lamp and crystal structure
determination after irradiation is in progress.

sample
R:S/X-ray/Solution

a!A
b/A
c/A
VJA3
R

1

2

Tab le 1.
4
3

50:50
11.682(4)30.704(6)11.395(6)4087(3)

55:45
56:44
11.708(5)30.684(5)11.401(5)4096(2)
0.057

66:34
69:31
11.733(2)30.771(9)11.412(4)4120(3)
0.073

75:25
78:22
11.745(4)30.844(4)11.390(4)4126(2)
0.077

5

6

90:10
11.733(4)30.914(3)11.340(3)4105(4)100:0
11.739(6)31.055(4)11.303(4)4120(3)

1) Osano, T.Y., Danno, M., Uchida, A., Ohashi, Y.(1991) Nature 352 ,
510-5122) Osano, T.Y., Uchida, A. , Ohashi, Y.(1991) Acta Cryst. B47, 702-707.

14V-64
PHOTOISOMERIZA TION RATES BEFORE AND AFTER
REVERSIBLE THERMAL PHASE TRANSITIONS
Hiroaki Tatsuki, Akiko Sekine and Yuji Ohashi
Department of Chemistry, Tokyo Institute of Technology , 0-okayama,
Meguro-ku, Tokyo 152, Japan
It has been found that the 2-cyanoethyl (2-ce) group bonded to the cobalt
atom is isomerized to 1-cyanoethyl (l-ee) group in some cobaloxime
complexes on exposure to visible light in the solid state. Many cobaloxime
crystals with the 2-ce group were prepared replacing the axial base ligand
with the other amines or phosphines . The isomerization rates of thecrystals were well explained by the reaction cavity for the 2-ce group.
Among the crystals, the complex with 4-methylpyridine as an axial baseligand, exhibits a reversible single crystal-to-single crystal thermal phasetransition at 343K. In order to examine whether or not the reaction rates
and the cavity volumes before and after the phase transition are different
to each other, the structure determination and measurement of theisomerization rate were performed at 341 and 346K . Table 1 shows the
crystal data at 341 and 346K. Figure 1 shows the crystal structures at thetwo temperatures. The cavity volumes are 9.58 and 12.80A3 for at 341K,
and 13.32A3 for at 346K. The measurement of the isomerization rate is
now in progress .
Table 1. Crystal data
341K
Formula C 17 N 60 4H 25 Co

F.W .

a/A
b/A

ciA
~

v;A 3

z

436.3630.18(2)9.058(5)17.16(1)124.2 1(4)4007(5)8126.23(2)2051(2)4

S.G.

P2 1/aDx!g cm·3

1.413

Figure 1. Crystal structures viewed
along b axes

14W-66

STRUCTURAL FEATURES IN SOME RAPIDLY SOLIDIFIEDALUMINIUM ALLOYS
Lecong Dzuong , Ha Thanh Binh, Le Due Lap, Nguyen Thanh Do,
Materials Science Center, Hanoi Technical University, Truong
DHBK Hanoi, Vietnam.
The influence of rapid solidification with moderate cooling rates of 102... 1Q4 K.s-1 on microstructure was studied for A -Mg and A -Cu based
alloys containing a consi derable amount of manganese.
The
microsegregation, the specific morphology of secondary phases, and thehigh density of lattice defects were important factors in as cast structureof the alloys. The precipitation process of the supersaturated solid
solution occurred in a complicated manner.

14W-67
GROWTH OF PURE CADMIUM IODIDE CRYSTALS AND
STUDY OF LASER INDUCED CRACKS IN THEM
S.K.Chaudhary,

University College, M.D . University,

Rohtak - 124001 ( I NDIA).
The single crystal cadmium iodide is characterized b y amarked polytypism i.e . the ability of a substance tocrystallize in various polytypic modifications .

The

crystal lattice of these polytypes is formed by st r uctu rally identical,

yet translationally non-equivalentla yer packets. Each layer packet forms a sandwich
structure that consists of three rnonolayers of atoms
I-Cd-I . The bonding in an I-Cd-I layer i s largel y ionicwhile that between the sandwich is predominant l y Vander Waals.
For the purification of material and growth of
Cdi 2 crystals, a zone-refining s y stem has been fabricatedin our laboratory. The process of refinement was carriedout in the atmosphere of argon which he l ped to prevent
any oxidation of the material. Complete purificationnecessitated 10 Zone-passes. The atomic absorptionspectroscopic technique was exploited t o check the
purity. Crystals measuring nearly 1 inch in length
have been grown successfully. The XRD oscillation
photographs were employed for structure identification.
A pulsed Nitrogen laser was us e d to irradiate thecrystals at room temperature. The development of crack s
when exposed to laser beam have been discussed on thebas is of s t ructural cons ideratio ns of Cdi 2 .

14W-68
VAPOUR GROWTH AND CHARACTERIZATION OF
CADMIUM CHLORIDE DOPED CRYSTALS OF CADMIUMIODIDE
Ritu Dhingra and G .C. Trigunayat, Department of Physics andAstrophysics, University of Delhi, Delhi - 110007, INDIA.
Horizontal zone refining technique has been employed for the
purification of cadmium iodide. Single crystals of cadmium chloride
doped cadmium iodide have been grown from the vapour phase. The
crystals have been characterized by X-ray diffraction methods. The
doped crystals have shown the formation of rhombohedral polytype 12R
along with the common polytype 4H of Cdl2 in about 40% of the cases.
This is in sharp contrast with the earlier findings of undoped crystals of
cadmium iodide (grown by vapour deposition) which contained the 4H
polytype exclusively. Streaking also occurs in three fourths of theoscillation photographs, with arcing in 30% of the cases. Theseobservations are explained on the basis of thermodynamic considerations
and the kinetics of crystal growth.

14W-69
GROWTH AND CHARACTERIZATION OF CdBr2 DOPEDGROWTH AND CHARACTERIZATION OF CdBr2
DENDRITIC SINGLE CRYSTALS OF Cdh
Binay Kumar and G L Bhalla, Sri Ram Institute for Industrial Research,
19 University Road, Delhi-7 andG C Trigunayat, Dept. of Physics and Astrophysics, University of Delhi,
Delhi-110007, India.
Dendritic single crystals of CdBQ doped cadium iodide have been grownin vacuum. X-ray diffraction methods have been employed tocharacterise the dendrites for their polytypism and related behaviour.
The surface growth features have been studied by optical and scanningelectron microscopy. The crystals are fairly transparent and of lateralsize up to 6*3mm. The X-ray diffraction studies have shown theoccurrence of 4H(thermodynamically stable structure of Cdl2) and 12
layered rhombohedral polytype 12R. The microtopographic studies haverevealed many interesting features on the crystal surface. It is observedthat the growth is by two dimensional nucleation and not by spiralgrowth. The observed polytypes and related phenomena like streaking
and arcing have been discussed in terms of various faults developed in thehost structure by cadmium bromide doping.

14W-70
EPITAXIAL BaTi03 CRYSTALS I
ON SrTi03 SUBSTRATESH.Terauchi, Y.Yoneda, Y.Watanabe, H.Kasatani & K.Kamigaki, Dept ofPhysics, K wansei-Gakuin University, Nishinomiya 662,
Y.Yano, Research Institute of Production Development, Kyoto 606,
T.Terashima and Y.Bando, Institute for Chemical Research,
Kyoto University, Uji 661, Japan.
The polarization of small ferroelectric particles or thin film behavesdifferently compared to that in bulk crystals. Recently the preparation ofhigh-quality thin films has been achieved (Terashima et al. 1990). Here we
report results of an X-ray study of ultra-thin BaTi03 films with thickness
ranging from 60A to 1500A. The films were grown on SrTi03 substrates
using the activated reactive evaporation method. The ultra-thin crystal
shows a large contraction along the a-direction and a large expansion
along the c-direction due to a strong epitaxial effect. The lattice parametera increases and the parameter c decreases with increasing thickness t of thethin crystal. The tetragonality, t::.=c/a-1, is found to be/:;. = 11o exp[ -t/to ],to=87.l A.

Below to, the lattice parameter a becomes too small to fit that of the
SrTi03 substrate. The mismatch between BaTi03 and SrTi03 is taken up
in the strain of thin BaTi03. The temperature dependence of the lattice
parameters was examined in order to clarify the nature of the phasetransitions in our thin crystals, but there were no evidence of phasetransitions in the temperature range 15K to 670K, where the BaTi03
lattice remained tetragonal or nearly cubic (Terauchi et al. 1992). Thisanomalous behaviour of our thin ferroelectric films will be discussed interm of a surface layer effect, as well as an effect of ionic or electric
space charge.
Terashima, T., Bando, Y., Iijima, K., Yamamoto, K., Hirata, K., Hayashi,K., Kamigaki, K. & Terauchi, H. (1990) Phys. Rev. Lett. 65, 2687-2690.
Terauchi, H ., Watanabe, Y., Kasatani, H., Kamigaki, K., Yano, Y.,
Terashima, T. & Bando, Y. (1992) f . Phys. Soc . Jpn. 61 No.7.

14W-71

EPITAXIAL BaTi03 CRYSTALS II
ON [Pt/MgO] SUBSTRATESY.Yoneda, H.Yabuno, H.Kasatani & H.Terauchi, Department of Physics,
Kwansei-Gakuin University, Nishinomiya 662 Y.Yano, Kyoto 606,
T.Terashima and Y.Bando, Institute for Chemical Research, Kyoto
University, Uji 661, Japan.
BaTi03 film will show phase transitions differing from those in the bulk.
Because of the effect of substrates interesting phase transitions will occur
in films. Thin films were grown on MgO substrates. X-ray diffraction
patterns in BaTi03 films were measured to clarify their properties such as
the temperature dependence of the lattice parameter. At room temperature
the lattice parameter a of bulk BaTi03 is 4.034A and the parameter c is3.993A, and the lattice constant of MgO is 4.211A. The mismatch is about
4 %. The epitaxial relation is MgO(l 0 0)11 BaTi03(1 0 0).
In the case of Mg0(1 0 0) substrates we use Pt (lattice constant= 3.933A)

as a buffer. Good quality BaTi03 thin films were grown on the Pt-coatedsubstrates (lijima et al. 1990). BaTi03 thin films on [Pt/MgO] wereprepared by activated reactive evaporation method with several
thicknesses from 66A to 4000A (Iijima et al.), in which we made certainthat films were grown as single crystals. From X-ray measurements oflattice parameters of BaTi03 films, it is found that BaTi03 shows thermal
expansion changes with film thickness in the temperature range room
temperature to 800K. The results indicate that thin films have some bulk
BaTi03 properties because of the effect of the Pt buffer layer. We willreport experimental results of BaTi03 single-crystal-films on [Pt/MgO(l 00)] substrates.
Iijima, K., Terashima, T., Yamamoto, K., Hirata, K. & Bando, Y. (1990)
Appl. Phys. Lett. 56. 527-529.
Iijima, K., Terashimaj T., Bando, Y., Kamigaki, K. & Terauchi, H. J.
Appl. Phys. (to be published)14W-72

CHARACTERIZATION OF BARIUM TITANATE POWDERPREPARED BY CHEMICAL PRECIPITATION
T. Tunkasiri and G. Rujijanagul., Department of Physics, Faculty of
Science Chiang Mai University, Chiang Mai. 50002. Thailand.
Barium titanate powder was prepared by chemical precipitation. A
solution of barium chloride and titanium tetrachloride in 1N hydrochloric
acid was slowly added to aqueous oxalic acid (heated to 80 - 85 C) .
Barium titanyl oxalate tetrahydrate precipitated. This was filtered, dried
and then annealed to yield barium titanate powder. Annealing was carriedout for one hour. The effects of various temperatures, from 700 C to1400 C in steps of 100 C, were examined by X-ray diffraction anddifferential thermal analysis. The ratios of lattice parameters, c/a, were
determined by least squares methods. Results showed that for annealing
temperatures less than 1100 C, the barium titanate formed in a cubic
perovskite phase . However for temperatures above 1100 C, the productformed in a tetragonal phase. Microstrain was reduced by increasing theannealing temperature. The crystallite size was found to increase with theannealing temperature.
1. Wagner, C.N.J. (1966). "Local atomic arrangements by X-ray
Diffraction" Gordon & Breach, New York.
2. Fu-Sen, Chen T. Chang, and Yen-Hwei Chang. (1990). J. Am. Cerm.
Soc., 73[11] 3422-27

14W-73

HYDROTHERMAL SYNTHESIS AND STRUCTURAL
CHARACTERIZATION OF Ao.sVOP04.yHzO (A-ALKALI,ALKALINE EARTH, AND TRANSITION METALS)
K. H. Lii, Institute of Chemistry, Academia Sinica, Taipei,
and H. Y. Kang and S. L. Wang, Department of Chemistry,
National Tsing Hua University, Hsinchu , Taiwan, Republic of
China

In 1983, Johnson and Jacobson prepared a series of compounds~VOP0 ·yH 0

42

by redox intercalation reactions of VOP0 4 ·2H 2 0with metal iodides in aqueous solution. These are the firstintercalation reactions in which the charge transfer
proceeds chemically but not electrochemically. Further·investigation on these interesting compounds appeared inseveral other r e ports. On the basis of powder X-ray
diffraction, it was reported that the basic tetragonal
structure of VOP0 4 · 2H 2 0 was essentially maintained andc ations were incorporated into the interlayer spaces.
Detailed structural information has been unavailable due tothe lack of suitable single crystals for X-ray analysis. wehave now found that crystals of A0 . 5 VOP0 4 ·yH 2 0 can be grownunder hydrothermal conditions. In this paper, we report thehydrothermal synthesis and structural characterization of
six vanadyl phosphate hydrates A0 . 5 VOP0 4 ·yH 20 {A = Na, Ca, Sr,
Co , y = 2; A = K, Ni, y = 1.5). Their structural
relationships will also be discussed.

14W-74
THE DEFECT SUBSTRUCTURES AND MECHANICALPROPERTIES OF MULLITE PREPARED BY
COPRECIPIT ATION
Shu-Cheng Yu* and Jiann-Shing Lee*** Department of Earth Sciences** Institute of Mining, Metallurgy and Materials Science National
Cheng Kung University, Tainan, Taiwan 70101 Republic of China
Mullite and Zr02-mullite were prepared using co-precipitation withZrO(N03)2, Al(N03)3 and silica sol as precursor materials. With twobeam conditions in an electron microscopy study, dislocations of Zr02mullite(15wt%Zr02) with Burgers vectors in [001] and [213] directions
were observed. The former dislocation is much more abundant in defectdensity than the latter. The prevailing dislocations with Burgers vector
parallel to the c-axis in mullite is consistent with the fact that [001] is aprominent direction for chains of Al06 octahedra and double chains of(Al,Si)04 tetrahedra in mullite structures.
Mechanical property measurements on mullite with various Zr02
concentrations were also made. The result indicates that Vickers hardness ,flexure strength and flexure toughness are all significantly improved forZr0 2-mullite. With Zr02 content in mullite increased from 0 to 30%,
Vickers hardness was found to increase from 11.1 to 13.2 GPa ; flexurestrength from 346 to 551 MPa and flexure toughness from 1.88 to 3.92
MPa-m-1.5 . In contrast, the Young's modulus was decreased from 190 to
168 GPa with increasing Zr02 content in mullite. Measurements onmechanical properties for mullite without Zr02 but with different
Al203/Si02 ratios were also carried out. The data show that both flexurestrength and flexure toughness were independent of the A 12 0 3
concentration in mullite.

14W-75

METHOD TO CONTROL MICROSTRUCTURE BY MEANS OF
THE ELECTRON CHANNELING PATTERN (ECP) IN THE
PRESENCE OF SUPPRESSING CONTRAST FORMINGMECHANISMS
A.N. Efimov, A.F. Ioffe Physical-Technical Institute, Sankt-Peterburg,
194021, Russia
Microstructural characterization of crystalline objects by ECP provides aunique possibility for obtaining information about symmetry,
crystallographic orientation and lattice parameters. High spatial resolution(10 nm) and non-destructive control of the crystallographic parameters
makes this technique extremely convenient for micro-structuralcharacterization. However, when objects with inhomogeneous structures
are investigated, contrast necessarily occurs due to effects arise other thandiffraction contrast.
In this study the diffraction component of the contrast was extracted byslightly varying the electron wavelength. The formation of the difference
signal allowed us to reduce the contribution to the final signal ofcomponents not concerned with the crystalline perfection of the structure
significantly. This is possible due to the fact that only diffraction angles
depend significantly on the electron wavelength, leading to thedisplacement of ECP. The system of registration is based on the lock-in
technique. The resulting difference signal is fed to the visual display unit.
Investigation of various objects with inhomogeneous structures showed
high efficiency of the selective diffraction contrast formation .

14W-76
LATTICE METRIC MATCH AT HETEROEPITAXY: CASE OFNON-CUBIC CRYSTALS
A.N. Efimov, A.O. Lebedev, A.F. Joffe Physical-Technical Institute,
Sankt-Petersburg, 194021, Russia
Traditionally active materials for microelectronics crystallize in the cubic
system. For a cubic substrate, strict coincidence of lattice parameters isneeded to create the transient region without defects. This should bepossible by choosing the correct substrate or by using solid solutions when
the dependence "composition - lattice parameter" is utilized. Both lattice
parameter correspondence and coincidence of thermal expansion
coefficients are possible for multi-component solid solutions.
Unfortunately, active materials used in modern functional (opto-,
acousto-, HTSC-)electronics belong to both cubic and non-cubic systems.
In the general case the modified lattice metric match is:(1)

where a,b,c,a,p,y are unit cell parameters; subscript 1 denotes epilayer,
2 denotes substrate.
It is impossible to find pairs of compounds satisfying all conditions (1) inpractice. Altering solid solution composition makes feasible only one
condition. The right choice of substrate orientation allows the inter-facial
region "layer-substrate" to be created without topological defects if thefollowing two conditions are fulfilled:

where:

1 2
1 2
1 2
A=a2-a2; B=b2-b2 C=c2-c2;

D=a1 b1 cos"rl-a2h2cosY2;E=q a1 cosP1-C2a2cosP2; F=b1 q cosaJ-h2C2COSY2
Angles and bond lengths for inter-facial atoms vary, but the changes are
small if the difference between metrics of layer and substrate is small too.
It should be pointed out that only condition (3) must be carried out
strictly. Inequality (2) is a condition that enables the number of possible
crystal combinations to be reduced.
So, if conditions (2,3) are fulfilled for a particular composition for a twocomponent solid solution, the defect-free interface can be created.
Additionally, for any given pair of crystals the probability of satisfying is(2) and (3) is much higher than that for the six conditions (1).
Recommendations on the choice of metrically-matched substrate for
HTSC-material growth based on the above statements will be presented.

15A-1
HIGH-RESOLUTION ELECTRON MICROSCOPY
K. Hiraga, Institute for Materials Research, Tohoku University,
Katahira, Aoba-ku, Sendai 980, JapanThe use of high-resolution electron microscopy has been extended
to a wide range of natural sciences with the development of theresolving power of electron microscopes in the last two decades. In thispaper, I will illustrate the capability of high-resolution electron
microscopy for crystal structure analysis using results for high-Tc
superconducting oxides (Hiraga, Shindo, Hirabayashi, Kikuchi ,Kobayashi and Syono, 1988) and for quasicrystals (Hiraga and Sun,
1992). High-resolution images of the high-Tc superconductors, takenwith an electron microscope having a resolution of 0.1 7 nm, make itpossible to determine atomic arrangements of heavy atoms directly,
atom positions to an accuracy of O.Olnm, and positions of oxygen
vacancies. Some materials with unknown structures, which are hard to
prepare as single phases and single crystals , have been studied
successfully. For quasicrystals with nonperiodic arrangements of atoms,
high-resolution images show that the structures of the quasicrystals arefo rmed by aggregation of atom clusters, enabling us to determine not
only long-range correlations of the atom clusters in wide regions, butalso the atomic arrangements in the atom clusters.
I will demonstrate that high-resolution electron micro scopy
exhibits its full power for crystal structure analysis when combined withdiffraction methods.
Hiraga, K., Shindo, D., Hirabayashi, M., Kikuchi, M., Kobayashi, N. &Syono, Y. (1988). Jpn . J. Appl. Phys. 27, L1848-Ll851 .
Hiraga, K. & Sun, W. (1992). Philo. Mag. Lett. in press.

15A-2

X-RAY AND ELECTRON DIFFRACTION FROMTWISTED QUARTZ CRYSTALS
M. Fehlmann, Institute of Crystallography, Swiss Federal Institute ofTechnology, ETH-Zentrum, CH -8092 Zurich, Switzerland, and A.F.
Moodie, Department of Applied Physics, Royal Melbourne Instituteof Technology, Melbourne, VIC 3001, Australia.
For over one hundred years, crystallographers and mineralogists
have wondered about the origin of the twisting in 'Quindelquartzes'.
It has been ascribed to twinning as well as to screw dislocations.
With conventional X-ray Laue diffraction, we have been able to confirm that the microscopic twisting corresponds to the macroscopically observed twists. White beam synchrotron radiation topography
indicates that neither dislocations nor twinning can be responsible
for the twisting. A suggestion by Kozlova & Belov (1981) that
Brazilian type micro-twinning be the cause of the twisting must be
rejected for several reasons (Laue diffraction , topography, el ectron
microscopy, optical activity).
Using electron microscopy we have inspected a number of different
samples. So far, we have observed a single twin boundary and occasionally a dislocation. But judging by the very low density of these defects we must co nclude that they are not responsible for the bending , the more so because the crystals are uniformly bent in defectfree regions . 'Selected Area Diffraction' (SAD) does not reveal any
clues as to the origin of the twists. We cannot observe any defects in'Larg e Angle Convergen t Beam' micrographs either. Conventional'Convergent Beam Electron Diffraction ' (CBED) pictures , however,show that the symmetry of the .Q.D§1al (see e.g. Johnson , 1972) is indeed trigonal. The likelihood that crystal bending will influence the
CBED patterns is less than in SAD patterns, because the volume of
specimen contributing to it is so much smaller.

Kozlova, O.G . & Belov, N.V. (1981) Sov. Phys. Dokl. 26, 805.
Johnson , A.W. (1972), Acta Cryst. A28, 89-91.

15A-3
ELECTRON MICROSCOPE STUDY OF INCOMMENSURATELATTICE MODULATION IN LAYERED COMPOSITE
CRYSTAL PbS-VS2
N. Yamamoto, K. Akiyama and K . Yagi, Tokyo Institute of Technology,
Oh-okayama, Tokyo 152, Japan, andY.Gotoh andY. Oosawa, National Chemical Lab. for Industry
Tsukuba, Ibaraki305,Japan

PbS-VS 2 is a composite crystal which is made up of alternative stacking
of NaCl-type PbS layers and Cdl2-type VS2 layers. The PbS and VS2
layers have common lattice parameters along the a and c axes , butdifferent ones along the b axis, i.e., bJ/b2=1.74. The interaction forces
between the two layers cause atomic displacements with a lattice period
in the neighbouring layer, which result in an incommensurately
modulated lattice in each layer (Onoda (1990)). From an analyses of theextinction of diffraction spots and convergent beam electron diffraction
patterns, a super-spacegroup of the crystal is determined to be Pet. In
order to avoid multiple diffraction from the fundamental reflections tothe satellite ones, a diffraction pattern in the (1 00) orientation iscompared with a calculation by the multi-slice method. We propose a
new model for the lattice modulation which gives a good fitting with theobserved intensity distribution for the satellite reflections.

Onoda, M Kato, K . Gotoh, Y . & Oosawa, Y.(l990) Acta Cryst B46,
487-492.

15A-4
HIGH- RESOLUTION EELS STUDY OF THE ELECTRONICSTRUCTURES OF SEMICONDUCTORS CONTAININGLATTICE DEFECTS

M.Terauchi and M.Tanaka, Research Institute for Scientific Measurements, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980,
Japan.
We have studied the effect of lattice defects on the electronic structures of Si and GaAS using the high-resolution electron energy-loss
spectroscopy (EELS) microscope, which is equipped with two Wien
filters as the monochrometer and the analyzer.
The energy-loss spectra were obtained from specified specimen areasof 1800A in diameter of Si containing dislocations with an energy resolution of 90me V. The spectra showed three features different fromthe spectra obtained from perfect specimen areas .
Firstly, there
exist the additional energy-loss peaks originated from dislocations
below the onset energy (band-gap energy) of perfect Si. Secondly,
high intensity was observed in an energy region between about leV(onset energy) and about 2eV , whereas the spectra of perfect Si did
not show such high intensity because the direct interband-transition
does not exist in this energy region. Thirdly, two of nine peaks dueto the interband transitions, which were observed at the shoulderof the broad volume-plasmon peak, were shifted to the lower energy
side from those of perfect Si, other peaks being not shifted. These
results clearly showed the influence of dislocations on the electronic
structure of Si.
The energy-loss spectra of as grown GaAs were obtained with anenergy resolution of 58me V. The spectra showed a lower onset
energy of the inter band transition than a band gap energy of 1.4e V
and exhibited a specific structure near the onset energy.
Thosefeatures may be due to the anti site defects of EL2.
Those spectra obtained from Si and GaAs will be discussed wit h thestrain fields and the energy-band structures .

158-1CRYSTAL STRUCTURE ANALYSES OF THE SPHERICAL
VIRUSES, TOBACCO NECROSIS VIRUS (TNV) AND RICEDWARF VIRUS(RDV).
T. Tsukiharal, Y. Morimoto!, K. Fukuyama2, M. Koizumi3, T. Omura4,
K. Kano5, H. Mizuno5.
I Faculty of Engineering, The University of Tokushima.
2Faculty of Science, Osaka University
3National Institute of Sericultural and Entomological Science, Tsukuba
4National Agriculture Research Center, Tsukuba
5National Institute of Agrobiological Resources, Tsukuba, Japan.
Tobacco necrosis virus (TNV) is a typical spherical virus. Its coat protein
contains 275 amino acids. TNV crystallizes in cubic space group P4232
with a=b=c=338 A. Its 3.86xi07 A3 unit cell contains two virus particles
with molecular weight 6.7x106, and Vm value 2.9A3/dalton. The (T=3)
symmetry of TNV capsid and subunit arrangement of 180 copies of its
coat protein were determined previously. X-ray diffraction intensities fora 0.7x0.7x0.7 mm3 TNV crystal were measured at 5 A resolution on a
Weissenberg camera with cassette radius 430 mm, at the Photon Factorysynchrotron. The merging R-factor is 0.115 for 90,251 reflections with
1>5 cr(l). The 27,437 (F>3cr(F)) and 24,127(F>5cr(F)) independent
reflections were 94% and 83% of the theoretical number. The virus
crystal' s structure was determined by a 91 cycle iteration of molecularreplacement averaging. The correlation coefficient between calculated
and observed structure factors converged to 0.92, and R-factor 0.16.
Secondary structures such as a-helices and 13-structures were clearly
assigned in the 5 A resolution electron density map. The TNV virus
resembles SBMV both in the orientation and folding of the coat protein
subunits. The ordered part of that subunit is shorter by 12 and the longer
disordered part by 27 residues than corresponding parts of SBMV.
Rice Dwarf Virus (RDV), a phytoreovirus, from Nephotettix species
infects rice and wheat systemically, causing stunting or dwarfing of plantbodies. The molecular weight of the double-shelled virus particle,
approximately 700 A in diameter, is 6.52xl07. Crystallographic analysis
helped reveal the double shelled structure of the virus, and themechanism of symmetrical self-assembly of its subunits. RDV crystallizedin cubic space group 123 with a=789A. Two particles are on Wyckoff "a"positions in the cell. For diffraction experiments on a macromolecular
Weissenberg camera at BL-6A2 in the Photon Factory, the crystal to film
distance was 573mm, and wavelength 1.488A. The incident beam,focused by double bent mirrors, was collimated to O.lmm<j> . 56096
reflections up to 10 A were collected from one crystal The mean
Rmerge for 29075 independent reflections was 10.51%. A self-rotation
function indicates icosahedral symmetry for RDV.

158-2
THE CRYSTAL STRUCTURE OF NC41 ANTINEURAMINIDASE FAB IN ITS UNCOMPLEXED FORM
M. C. Lawrence, R. Malby, A. Kortt, V. Staton and P.M. Colman, CSIRO
Division of Biomolecular Engineering I Biomolecular Research Institute,
343 Royal Parade, Parkville 3052, Victoria, Australia, and R. G. Webster,
St Judes Childrens Research Hospital, Memphis, Tennessee 38101 , USA.
The structure of the uncomplexed NC41 anti-neuraminidase Fab has beensolved by molecular replacement from diffraction data collected at the
Photon Factory, with the aim of determining what structural changes occur
in the Fab on binding antigen. This work complements structural studies of
the NC41 Fab in complex with influenza-virus neuraminidase (Colman eta/., 1987, Tulip eta/., 1992).
The structure of the uncomplexed Fab is surpnsmg in that thecomplementarity-determining regions (CDR's) of the two molecules in theasymmetric unit abut each other across a psuedo-diad. The interface iscomparable in size (ca 900A 2 ) and compleq1entarity of fit to that observedin the complex. The interface area is considerably larger than that typical of
crystal contacts, and would tend to imply dimerization and selfcomplementarity of the Fab in solution.
The earlier study of the Fab-antigen complex suggested that significant
movement of the heavy-chain variable domain with respect to the lightchain variable domain on antigen binding. Analysis of the uncomplexed
structure indicates slight differences in domain pairing compared to thecomplexed structure. However the extensive interaction between the Fab's
in the uncomplexed crystal structure could imply that this structure is not agood representation of that found in solution.
Colman, P.M., Laver, W.G., Varghese, J.N. , Baker, A.T., Air, G.M. &Webster, R.G . (1987) Nature 326, 358-363 .
Tulip, W.R., Varghese, J.N., Laver, W.G., Webster, R.G. and Colman,
P .M. (1992) J. Mol. Bioi. (in press).

158-3
STUDIES ON THE STRUCTURES OF INSULIN ANALOGUESAND THE BINDING INTERACTION OF INSULIN
MOLECULE WITH ITS RECEPTOR
W. R. Chang and D. C. Liang
National Laboratory of Biomacromolecules, Institute of Biophysics,
Chinese Academy of Sciences, Beijing, 100101 China.
Extensive conformational comparisons among the structures determinedfor different species and crystal forms of insulin and its derivatives were
performed using least-squares superimposition and graphics techniques.
The investigation showed that the structure of molecule I in 2Zn insulin
was closer to that in the natural monomer. The conformational difference
between two molecules that emerged during dimerization was further
improved and stabilized during the hexamerization and packing ofhexamers in crystals Through the hinge peptides, such as A10, B4 , B8 ,B24, B20 and B23, there was flexible relative motion among thestructural segments in the insulin molecule. The residues at the B-chain Cterminal might shift more than lOA. The mobility for each residue sidechain was very different due to the changed environment.
1l1e structures of DPI, 2Zn insulin and some other derivatives of insulin
were compared after investigation in detail. The binding interaction withthe receptor molecule should take place mainly on an amphipathic surfaceof the insulin molecule. In the middle, there is a hydrophobic surface withan area of about 150A2 consisting of many hydrophobic residues. The
polar or charged groups distributed around the hydrophobic surface
construct a hydrophilic zone. The hydrophobic surface is usually coveredby the extended B-chain C-terminal peptides with great mobility and isthus protected from the solvent molecules. The angle between theamphipathic surface and the surface of dimerization is about 20 degrees.
The detailed structural comparison of Al-(L-Trp) insulin with Al-(DTrp) insulin has provided a very good explanation for the great
difference in their biological activities, confirming our proposed binding
interaction model of the insulin molecule with its receptor.

158-4ENZYME SUBSTRATE INTERACTIONS: REFINEDSTRUCTURE OF HUMAN CARBONIC ANHYDRASE I(HCAI)-HCO) COMPLEX
Vinay Kumar and K.K. Karman, Solid State Physics Division, Bhabha
Atomic Research Centre, Bombay-400085, India.
HC03 anion, the substrate for reverse reaction catalyzed by Carbonic
anhydrase (CA) isoenzymes, inhibits the enzyme at higher pH. The single
crystal diffraction data for the complex at pH 8.7 , extending to 1.6A
resolution, was collected using synchrotron radiation at the Photon
Factory, Japan (Kannan et al., 1989) with Rmerge of 8.13%. Treating therefined HCAI model (Karman et al., 1984) without solvent molecules as
the initial model the structure of the complex was refined by alternating
PROLSQ cycles and model building against 'OMIT' Fourier maps on
IRIS -4D graphics using TOM. The data was extended during refinement
in steps from 3A to 1.6A resolution. The added solvent molecules andinhibitor were refined for occupancy in addition to positional and thermal
parameters. The R-factor for the final model with 2023 non-hydrogenprotein atoms, one HC03 anion and 279 solvent molecules, against 24967
Fobs in the resolution shell of 10-1.6A, is 17.3%. The rms shift for
positional parameters in the final PROLSQ cycle was 0.023A. In contrast
to the initial Fourier maps, the refined structure suggests [4+ 1]
coordination for the essential Zn(ll) ion. The HC03 anion binds in thevicinity of the Zn(ll) ion. In addition, the imidazole ring of the H200
residue is marginally displaced in the complex structure compared to thatin native HCAI. The Fourier maps computed with refined phases also
reveal an alternate partially occupied binding site for the HC03 anion.
The details of binding mode and interactions of the HC03 anion in theactive site of HCAI will be presented.
Karman, K.K., Ramanadham, M & Jones, T.A., (1984). Ann. N.Y. Acad.
Sci., 429, 49-60.
Kannan, K.K., Vinay Kumar., Chakravarty, S & Sathyamurthi, P. (1989).
Photon Factory Activity Report, Japan, 7, 112-113.

15Y-1ENHANCED PHASE EFFECT IN FOUR-BEAM X-RAY
DIFFRACTION - DETERMINATION OF TRIPLET PHASEFROM FOUR-BEAM DIFFRACTIONY.

s . Tsai, M. T. Huang, and S. L. Chang, Department ofPhys ics , National Tsing Hua University, Hsinchu, Taiwan,
3 00 43 , R. 0.

known as a clue to phase determination of structuremultipl ets .

factorForathree-beamdiffraction with a weak reflection G,
onit

may not be suited for phase determinationfortriplet phaseobserved for four - beam (0,In this p a per, we r e port
dependence

obs erva tion .

isG, L, M) cases in wh i c h M is
G,

L)

and

the

are employed to account for

this

Theoretically,t heories

kinematical

I( G)

of

(0,

additional reflection to the three-beamdiffracti o n.

inef fe ct

the phaseweakstrongaL)sonon-centrosymmetr ic crystals.
that

G,

(0,

multipl y d i ff racted intensity I(G) is

the

t hat

an

x- r aysinteraction in multiple diffraction of

Coherent
is

C.

the

dynamical

It is found that the intensity

variation

I(G ) due to the three-wave interference in the. weak

fou r -beam

cases

is

at

least anstronger tha n t hat in the three-beamo r i ginofmagn i tude

diffract i on.

o f this enhanced phase effect on weak

di f fra c t i ont h eory.

order

The

four-beam

will be d i scussed in the light of dynamical

15Y-2
PHASE DETERMINATION AND REFINEMENT BYDENSITY MODIFICATION - LOW DENSITYELIMINATIONM Shiono, Department of Physics, Faculty of Science, Kyushu
University, Higashi-ku, Fukuoka, 812, Japan.
A density modification technique for phase determination andrefinement, which replaces all density less than one-fifth of the averagepeak height by zero, is presented. Its effectiveness is demonstrated byapplications to small proteins. 36-amino acid A vi an Pancreatic
Polypeptide (App) which has 302 independent atoms has been solved
with this Low Density Elimination procedure (LDE) starting fromrandom phase sets. The method was successfully applied to phaserefinement for Ribonuclease Pl: A phase set with a 74° mean phase error
was refined. The final mean phase error was 50.2° after 293 cycles.
Since the procedure includes two Fourier Transforms in one cycle, it isvery expensive in computation time. In order to speed up the procedure,
we square the electron density instead of Low Density Elimination in theearly stage of phase determination. We will also discuss possiblecombinations with conventional reciprocal-space direct methods.

Shiono, M. and Woolfson M. M. (1992). Acta Cryst. A48 (In press).

15Y-3RESTORING THE ORIGINAL ELECTRON DISTRIBUTION
OF LIPID BILA YERS - A SIMULATION STUDY
S.Yamamura, M.Takata, M.Sakata, H.Takahashi and I.Hatta
Department of Applied Physics, Nagoya University, Furo-cho,
Chikusa-ku, Nagoya, 464-01, Japan
X-ray diffraction studies have identified a characteristic feature of lipid
bilayers, i.e. both sides of each bilayer are composed of high electron
density polar headgroups (PH). There are hydrocarbon chains (HC) withlow electron density inside the layer. Biomembrane structure is often
studied by Fourier reconstruction of the electron density from X-ray
diffraction data. In most cases, only a one dimensional distribution,
perpendicular to the lipid bilayer, is considered. A typic al model
structure and electron density for such a bilayer is shown in Fig. 1. The
electron density evaluated by Fourier transformation shows rather severe
termination effects because the number of measurable reflections isnormally les s than 10. It is of prime importance to establish bettermethods for recons tructing electron density di stributi ons inbiomembranes. To assist that objective, restoration of the original one
dimensional electron density shown in Fig.l from a limited number ofdiffraction measurements was simulated.
A Maximum Entropy Method (MEM) density evaluated initially wasalmost identical with that from Fourier transformation. As the map
resolution is much worse than atomic scale, an MEM constraint that thedensity is positive everywhere does not play an important role. The MEM
density improves when the method is modified to permit densities positiveor negative compared to the flat density of the hydrocarbon chain - anapproach resembling that used to cope with negative scattering density inneutron diffraction. It worked effectively, being able to restore theoriginal model density with reasonable accuracy using 10 reflections asshown in Fig.2. Practical applications are under consideration.
1110
I I
1110
PH

()11 10=I I
01110=

HC

'§

~

·~

!

1

~

~

;;;

;;;

ffi

ffi
Q

"

z

z

Q

0

~

~
o.u

0~

1.0

COORDINATE

Fig. I Model Structure and Density

0.0

0.5

1.0

COORDINATE

Fig.2 Rec onstruction of Electron Density

15Y-4

THE ROLE OF ANOMALOUS DISPERSION IN
THE COMPARATIVE REFINEMENT OF
MODULATED CRYSTAL STRUCTURES
A. Dav id Rae, School of Chemistry, University of New South Wales,
Kensin gton 2033, Australia.
A modulated crystal structure is conveniently described as a perturbation
away from an idealised parent structure. 'This idealised parent structure
may consist of more than one coexisting substructure, each with its own
unit cell and space group. The perturbations may be describedas modulation waves associated with vectors in the Brillouin zones of thesubstructures and correspond to extra observed reflections. Options forthe relative phases of modulation waves exist and these need notnecessarily correspond simply to cho ice of origin and orientation. In real
crystals some waves may be cont inu ous throughout the cry stal whileothers may not. This allows the possibility of stacking faults , twinning andintergrowths of components of different overall symmetry and this alters
the scale of some of the various symmetrised components of the observedin tensi ty . A hierarchical approac h to refinement is neces sary and anunderstanding of the distributi on of information content is essential.
Anomalous di spersion creates correlations between modulation waves andcan be used to resolve questions involving modulation wave amplitude ,disorder and twinning as well as distinguishing between Friedel related
reflections. These corre lations may be used to initiate refinement ofmodulation waves starting from a zero amplitude approximation and toaccentuate differences in comparative refinement statistics for alternative
stable refinement minima.
Appl ication to the refinement of the Aurivilliu s pha se compounds
Bi2W06 , Bi4Ti30 12 and Bi2SrTa209 will be outlined and a comparisonof the X-ray structure of Bi2W06 and the powder neutron diffraction
structure of y-B i2Mo06 will be made.

15Y-5OPTICAL TRANSFORMS
T.R. Welberry.
Research School of Chemistry, Australian National
University, GPO Box 4, Canberra City, ACT 2601, Australia.
The idea of using optical analogues (or Optical Transforms) to aid in theinterpretation of X-ray diffraction patterns originated with Sir Lawrence
Bragg round about 1938, and the method has developed considerably sincethat time. Prior to the advent of digital computers calculation of thediffraction pattern of even a fairly simple crystal structure was an enormous
task, and use of optical diffraction from a model had obvious benefits,particularly for testing trial structures. With the advent of computers thetask of obtaining a calculated diffraction pattern of an ordered crystal
structure fo r comparison with observed measurements became a ra thertrivial exercise and use of the optical method for this purpose began to fall
into disuse . On the other hand for the structural elucidation of disorderedstructures, amorphous materials and even liquids the transform method
has continued to be used even though the diffraction pattern of even themost complex structural model can in principle be calculated quite readilyw ith modern computers.
Optical Transforms are particularly useful in a teaching context where thestudent is able to verify for him/herself the relationship between a realspace object and its diffraction pattern. In this demonstration we present
examples of optical diffraction m asks, the structural details of which can beinspected with the use of an ordinary micro-fiche viewer or 35mrn slide
projector, and whose diffraction patterns can be observed using only simple
apparatus. A varied selection of masks will be available to demonstrate thediversity of diffraction effects which may be achieved by the technique.
In recent years we have sought to de velop methods to allow the routine
production of optical diffraction masks (or screens) for use as aids in theinterpretation of X-ray or electron diffraction patterns. We are now able toproduce, rapidl y and easily, an optical diffaction mask which is a good
representation of almost any real diffraction problem encountered with Xrays or electrons. Among the diverse range of problems that we havestudied with the aid of such diffraction masks are: short-range order inmolecular crystals; size-effect distortions in alloys; thermal and disorderdiffuse scattering in minerals; small-angle scattering in microemulsions;fluctuations of local order in liquids; quasi-crystals.

15C-1COMPUTER SIMULATION OF THE STRUCTURAL AND
PHYSICAL PROPERTIES OF THE MgSi03 POLYMORPHS
Masanori Matsui, Department of Earth and Planetary Sciences,
Faculty of Science, Kyushu University, Hakozaki, Fukuoka 812, Japan
There are six known MgSi03 polymorphs. Of these , both enstatite(Pbca) and clinoenstatite(P21/c) occur naturally. Protoenstatite(Pbcn)
is stable above 1273 Kat ambient pressure. The gamet(I41/a), ilmenite(R3), and perovskite(Pbnm) phases occur at high pressures. The
purpose of the present investigation is to simulate the structural andphysical properties of the six MgSi03 polymorphs using molecular
dynamics(MD) method with quantum corrections to the simulated
properties.
The potential energy of the crystal is approximated as the sum of
Coulomb, dispersion, and repulsion interactions between atoms(Matsui & Price, 1992). Energy parameters are taken from ourprevious investigation. The simulated crystal structures, bulk moduli,volume thermal expansivities, and enthalpy trends are in good
agreement with those observed. In addition, the simulation is
successfully used to reproduce the measured (or estimated) de nsity of
the MgSi03 melt at 2000 K and 0 pressure, and its temperature andpressure derivatives.
The MD technique is further applied to the inve stigation of thepossible exis tence of a post-protoenstatite phase at high temperature
and another pyroxene phase with space group C2/c at high pressure,both of which have p reviously been infe rred from experiment.

Matsui, M. & Price, G. 0.(1992). Phys. Chern. Minerals 18, 365-372.

15C-2
PHOTOREFRACTIVE KNSBN CRYSTALS WITH A-SITESUNFULFILLED TUNGSTEN-BRONZE STRUCTURE
H. C. Chen, D. L. Sun and Q. Z. Jiang, Institute of Crystal Materials,
Shandong University, Jinan 250100, P R China.

This paper describes studies of new compositions of photorefractive
crystals of potassium sodium strontium barium niobate (abbreviated
KNSBN) which have the tungsten-bronze structure. By changing the Asite occupation with lA ions of the periodic table in the structure anddoping with the ions of the first transition metal series in B-sites, theferroelectric and ph otorefractive parameters of the crystals are
considerably modified.

Cu-doped crystals are typical examples ,exhibiting excellent polarization stabilities with two-wave coupling gain
coefficients as large as 20-1 em. The PR sensitivity is in the order of
l0-3cm2fJ and the "cat" self-pumped conjugation reflectivity up to 65%with a response time of ten seconds can be reached.

15C-3
A MODULATION WAVE APPROACH TO THE STRUCTURALPARAMETERIZATION AND RIETVELD REFINEMENT OF
THE C9 - CRISTOBALITE RELATED, LOW CARNEGIEITESTRUCTURE
R.L.Withers and J.G.Thompson , Research School of Chemistry,
Australian National University, GPO Box 4, Canberra, ACT, 2601,
Australia.
Camegeite, NaA1Si0 4 , is one of a large family of materials topologicallyclosely related to the so-called C9 structure type. Its parent crystal
structure can be described as a "stuffed" derivative of the C9 structure
type in which half of the cavities in the comer-connected, tetrahedral
AlSi0 4 (ramework are filled with sodium atoms . The crystal structure of
low camegeite has not been solved. Indeed even its unit cell and spacegroup s ymmetry have proved difficult to determine owing to theextremely sluggish kinetics of formation of fully-ordered, single-phase
low camegeite from the component oxides. Powder XRD and TEM givean orthorhombic unit cell a'= 10.261 , b' = 14.030 and c' = 5.1566A withspace group symmetry of Pb2 1a.
Given this resultant space group symmetry, there are potentially (14 + 2)
x 3 = 48 displacive degrees of freedom plus 8 compositional degrees of
freedom to be refined in order to determine the structure of low
camegeite - far too many to be refined via an unconstrained Rietveld
refinement. Therefore it is essential to be able to derive a plausible
starting model for the structure before beginning a Rietveld refinement.
In this contribution, a group theoretical or modulation wave approach isused in order to parameterize the structural deviation of low camegeite
from its underlying C9 aristotype . Appropriate crystal chemical
constraints are then applied in order to provide what turns out to be two
distinct plausible starting models for subsequent Rietveld refinement. The
chemical plausibility of both starting models is checked via the use of thebond length-bond valence formalism and Rietveld refinement used to
distinguish between the two possibilities and to give a final refinedstructure.

15C-4LOW CARNEGIEITE - WHY PREVIOUS ATTEMPTS TOSOLVE ITS STRUCTURE WERE UNSUCCESSFUL

J. G. Thompson and R. L. Withers, Research School of Chemistry,
Australian National University, GPO Box 4, Canberra, ACT 2601,
Australia, A. K. Whittaker, Centre for Magnetic Resonance, University of
Queensland, QLD 4072, Australia, R. M. Traill, Department of Chemistry,
Monash University, Clayton VIC 3168, Australia.

Single crystals of low-carnegieite, NaA1Si04, have not been attainable
due primarily to a phase transition at - 940 K. Consequently it has beennecessary to study powder specimens. We have reinvestigated the crystal
structure of low-carnegieite by a combination of X-ray powder diffraction,transmission electron microscopy, solid-state 29Si and 27 AI MAS NMR
spectrosco py , and electron microprobe analysis . With sufficienthomogenisation of component oxides and annealling at 1673 K it waspossible to obtain a single crystalline phase which could be indexed to an
orthorhombic unit cell: Pb2 1a, a= 10.261(1 ), b = 14.030(2), c = 5.1566(6)A. Electron microprobe analysis confirmed the stoichiometry to be
NaA!Si04 . 29Si and 27 AI NMR spectroscopy verified the perfect Si :Alordering.
It is now clear from the present work that previous attempts to synthesize
low-carnegieite all suffered from incomplete reaction and the presence ofmultiple phases. Having for the first time synthesized low-camegieite as
the only crystalline phase it has been possible, using the constraints
provided by group theory and bond-valence requirements, to determine
the Na ordering and to refine the crystal structure using X-ray powder
diffraction data.

15Z-1HOLOGRAPHIC STUDIES OF THE SOLID-LIQUIDINTERFACE BOUNDARY LAYER IN FLUX CRYSTALGROWTH
Xiling Yu, Youchen Liu and Xuefeng Yue, National Laboratory of
Crystal Materials, Shandong University, Jinan, 250100, P R China.
As compared with low temperature solutions, high temperature solutions
have relatively large viscosity, small diffusion coefficient and lowtransparency.

Moreover, during crystal growth, flux may have thedisadvantages of being volatile, corrosive or poisonous, which brings
about experimental difficulties in research on crystal growth. Special
single crystal growth equipment designed by us not only satisfies theconditions for stable crystal growth, but is also convenient for real-timeobservation and measurement by optical methods. Potassium Titanium
Oxide Phosphate (DTP) crystal which has extensive applications, has beengrown with this equipment.

The growth temperature usually ranges

from 800 to 1000°C. We have investigated regular variations of thesolid-liquid interface boundary layer in KTP crystal growth anddissolution

bymicrophotography .

holographic

phase-c ont ra stinterferometric

The experiments demonstrate that the relation

between the thickness of the boundary layer and the supersaturation islinear under free convection conditions.

The variation of refractive

index caused by the change of solute concentration in the boundary layer
has a logarithmic relation to the distance from a crystal face.

15Z-2GROWTH AND CHARACTERIZATION OF
Bi-Sr-Ca-Cu-0 SINGLE CRYSTALS
Alka Jain and G.C. Trigunayat, Department of Physics and Astrophysics,
University of Delhi, Delhi - 110 007, India.

Single crystals of Bi2Sr2CaCu20x (2:2: 1 :2) have been grown by a flux
growth technique. The crystals prepared so far are thin and have small
lateral sizes, measuring approximately 2 mm x 1 mm x 0.1 mm.
Examination by X-ray diffraction has confirmed their single crystal
character. Their surface growth features have also been studied, boththrough optical microscopy and scanning electron microscopy.
Typically, a crystal surface displays parallel domains of different widths,
with each domain consisting of parallel steps oriented at approximately
60° with respect to the length of the domain. It is conjectured that thesurface features observed are related to the formation of polytypes in the
crystals.

15Z-3
PRESSURE DEPENDENCE OF CELL DIMENSIONSIN NiSz CRYSTALS GROWN UNDERDIFFERENT SULFUR VAPOUR PRESSURES
Takashi Komori and Nobuo Ishizawa, Research Laboratory ofEngineering Materials,Tokyo Institute of Technology, andFurniyuki
Marumo,Departmentof
Earth
Sciences,Nihon
University, and Yasutoshi Noda, Department of Materials
Science,Tohoku University, Japan
Crystals of NiS2 have a pyrite-type structure with the cubic
space group of Pa3 and are known to show insulator-metaltransition at about 46 kbar . There is no drastic structuralchanges at the phase transition pressure.
The authors havealready examined changes of the cell dimension and the x
parameter of the sulfur atom (the only positional parame te r
in the pyrite-type structure) with pressure on several NiS2
crystal~grown with different method, and found that thepressure dependence of cell dimension is not identic al in
the crystals prepared by chemical vapour transport withchlorine with those in the crystal grown by the sublimation
method. The origin of the difference was supposed to lie inthe degree of imperfections of the crystals . To verif y thisspeculation, cell-dimensi on measurements were carried out up
to 55 kbar on two types of crystals grown with thesublimation method under the sulfur vapour pressure (Ps) of
about 2.0 atm and 0 . 5 atm, respectively .
Thediffraction angles of 50 reflections ranging from 40
to 70• were measured with the single-crystal method on afour-circle diffractometer on the respective typ es ofcrystals at various pressures by making use of Ag Ka ,radiation and a diamond-anvil high-pressure device . At theambient pressure, the crystal grown under Ps=0 . 5 atm has acell dimension slightly longer (0 . 0014 A) than that grownunder Ps=2 . 0 atm. However , the cell dimension of the former
crystal decreases more slowly than that of the lattercrystalwithincreasing pressure,andthedifference
increases to 0.0086 A at 45 kbar. Both crystals undergo thephase transition at around 46 kbar, showing discontinuous
diminutions of the cell dimensions.
The discontinuity at
the transition point is larger in the former crystal than in
the latter . After the phase transition , the cell dimensionof the former crystal also decreases more slowly withincreasing pressure than that of the latter.
Since thecrystals grown under lower Ps are supposed to have higher
defect densities than the crystals grown under higher Ps,
the results of the present study indicate that an NiS2
crystal with a higher defect density decreases the celldimens i on more slowly and shows a larger jump of the celldimension at the transition point than that with a lower
defect densit y .

15Z-4
THE SYNTHESIS AND STRUCTURE OF Cu3Bi4Vz014·
Glen B. Deacon, Bryan M. Gatehouse and Gregory N. Ward.
Chemistry Department, Monash University, Clayton 3168, Victoria, Australia.
Crystals of Namibite (CuBi2Y06)l in a mineral sample2 from the lron Monarchmine in South Australia were unsuitable for single-crystal data collection . The title
compound was produced during unsuccessful attempts to synthesize Namibite bysolid state reaction.
Crystal data. Cu3Bi4 V2014, Mr = 1352.4 gmol-1, triclinic P-1 (#2), a= 5.317(2), b= 7.91 6(4), c = 8.095(5) A, a= 74.58(5) 0 .~ = 89.38(4) 0 ;y = 70.39(3)0 .
Z = 1, Dm not measured, De= 7.286 Mg m-3. U = 308.2(3) A3. R = 0.0398, Rw =0.0576 for 1382 observed reflections (F > 6.0 cr (F)). Single crystal data werecollected on a Nicolet four-circle diffractometer and solved by direct methods using
the SHELXTL-plus sofrware.
The structure consists of an infinite three-dimensional metal oxygen array in which
the rwo independent copper(II) atoms are square-planar (Cu( 1) has one, and Cu(2) has
two, longer contac ts), the two independent bismuth(lll) atoms are eight-coordinate(4,4 bicapped trigonal pyramidal3) and vanadium(V) is four-coordinate (tetrahedral).
Mean bond distances are Bi-0 2.57(3l)A, Cu-0 1.956(27)A (square planes),
2 .64(10)A for the three long contacts, and V-0 1.713(29)A; the shortest Cu-0
distance is 3.063(3)A. The Bi-0 and Cu-0 distances compare favourably with thosein Francisite (Cu3Bi(Se03)202Cl), a recently determined structure4.
Further attempts to synthesise Namibite hydrothermally, which coincidently has acell volume of 309.7 Al, or an erbium substituted compound CuEr2 V06, failed toyield crystals of suitable size for X-ray structure determination.
References.
1. Knorring, 0. V . & Sahama, Th. G. (198 1}, Schweiz. Mineral. Petrogr. Mill .. (1981}, 61, 7- 12.

2. Birch, W. D. & Pring, A. Private Communication.
3. King, R. B.(1969). J. Am. Chern. Soc., 91,7211 -7216.
4. Birch, W. D., Gatehouse, B. M. & Pring, A. (1990}, Amer. Mineralogist, 75, 1421-1425.

15Z-5SYNTHESIS AND CHARACTERIZATION OF Ni3S2(HEAZLEWOODITE) CRYSTALS
S. M. Dharmaprakash, Department of Physics, Mangalore University,
Mangalagangotri 574199 Mangalore, India.
The growth of Ni3S2 (Heazlewoodite) single crystals is described.
Heazlewoodite crystals were synthesized by chemical vapour transport,
using iodine as a transporting agent. The size and quality of the grown
crystals were influenced by the growth conditions. Optimum conditions
to grow large size and defect free single crystals were determined.
Single crystals up to 2 - 3 mm on edge were grown in 10 - 12 days
under the conditions used.
The Ni3S2 crystals were characterized utilizing chemical analysis, atomic
absorption spectral analysis, x-ray diffraction and differential thermal
analysis.
Ni3S2 crystals are rhombohedral with unit cell parameters a - 5.7522A,
c = 7.1405A, a= 89.99°. Ni3S2 crystals melt at 1043 K.

P-00
THE AUSTRALIAN NATIONAL BEAMLINE FACILITY
R.F. Garrett, J.W . Boldeman, D.J. Cookson, G. Foran, Australian Nuclearl,

PMB

Organisation,

Technology

andScience

Menai

NSW,

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D.C. Creagh, F. Johnson, University College, University

MaterialsofDepartment

ScienceCSIRO

Wilkins,W.

S.

Janky ,

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and2600 ;

Wales, Campbell ACT,Technology, Locked Mailbag 33,

andClayton VIC, 3168.

severalinvolvi ng

Au st r a li an research organisations, Universities andA multi-purpose X-ray beamline

gove rnment funding agencies.
constructed

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coop erativeaisFacility

The Australian National Beamline

PhotonTsukuba, Japan.

Factory,

project is to provide Austra lianr outinewithscientists

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being

The aim of theaccesstosynchrotron radiation in the hard X-ray region.

The

will deliver either monochromatic light, in the 5 -2 0 keV

beamline

The main experimental

range, or white ligh t to the experimental hutch.
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vacuumwhich

a two-circle goniometer with a large Weissenberg mode Ima gi n g
The diffractometer is optimised

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Detailsofthebeamline , monochromator and diffractometer design andperformance will be presented , and preliminary results fromwhite be a m experiments will be reported.

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15P-02PROPOSED SYNCHROTRON X-RAY STUDIES OF
MONO LAYERS AT THE PHOTON FACTORY
Geoffrey T. Barnes and Colin H.L. Kennard
The University of Queensland, Brisbane, Q4072, Australia
Studies of monolayers on water surfaces help in understanding
amphiphile structure and behaviour, evaporation control, modelling
biological membranes and modelling of some industrial processes.
Monolayers are formed on the water surface in a film balance,
enabling the monolayer to be compressed and expanded, much as gas iscompressed and expanded in a cylinder and piston apparatus. A verysmall amount of compound in a volatile solvent is carefully placed on acleaned water surface with a microsyringe. The balance contains atrough and movable barrier. Surface pressures are measured by a
Wilhelmy plate suspended from a strain gauge. As the barrier is moved,
molecules align in a perpendicular orientation, forming a monolayer
with hydrophilic ends of molecules pointing towards the water, andhydrophobic ends away. This is followed in the film balance bymeasuring surface pressure as a function of monolayer area. At acritical stage, the fully compressed monolayer behaves like a crystal
with regular order which may be studied by diffraction techniques. On
further reduction of area, the monolayer collapses.
A high resolution powder diffractometer is being designed byothers under Australian Government auspices for installation on an Xray beam line at the Tsukuba Photon Factory in Japan. It is proposed tomount the film balance on a second platform behind the powder
diffractometer, to study monolayers on water surfaces. A system thatshould allow users to gain experience involves phosphotungstic acid anduranyl acetate as stains in electron microscopy. At low pH use of thefilm balance indicates that there are changes in the structures of stained
animal cell wall materials, such as phospholipid monolayers. For better
understanding, it is planned to study the structure of the material by Xray reflectivity/diffraction techniques.
In specular reflectivity, the reflected beam at a low angle ofless than 0.1 of a degree is scanned directly (Qx scans) with ascintillation counter. This may be interpreted to give the density profileof the interface with the total count representing the integral of thescattered intensity along the Bragg rod. However, additional
information is obtained using grazing incidence diffraction. Thenfor a given Qx peak, Qz scans using Soller slits and a position sensitive
detector are carried out by varying the Bragg angle.
It is possible with the film balance to obtain a phase diagram. By
selecting the appropriate surface pressure at a given temperature , aparticular state may be selected. Analysing the results , it is possible toget an idea of the structure of this monolayer.

15P-03
AN INSTRUMENT FOR X-RAY SURFACE STUDIES
G. Barnes and C. Kennard, Department of Chemistry, University of Queensland, St
Lucia, Qld, 4072, D . Creagh and I. Jamie, Department of Physics, University College,
University of New South Wales, Campbell, ACf, 2600 and J. White, Research Schoolof Chemistry, Australian National University, Canberra, ACf, 2601
While traditionally the bulk properties and structure of materials have received an
overwhelming proportion of attention in materials studies, it is becoming increasingly
obvious that an understanding of the surface science is very importan t. The main barrier
to investigatio n of surfaces in standard X-ray tec hniques has been the lack of sufficient
intensity to produce measureable scattering from the very small proportion of material in
the surface reg ion, compared to th at in the bulk volume. Synchrotron radiation has
provided the required intensity and there has been an increasing number of surface studies
undertaken in recen t years.

Thi s paper will present an overview of the Australian National Beamline Facility. It will
also discuss in more detail a refractometer that is currently under construction, which will
be used for hig h resolution surface studies at th e ANBF. The reflectometer will allow thesurfaces to be studied through Critical Extern al Re flection, Grazin g Angle Diffraction,
Total Reflec ti o n X-Ray Fluorescence and Surface Extended X-ray Ab sorption Fine
Structure spec troscopy. Some of the initial ex periments to be undertaken will be theinves tigation o f the structure of Langmuir films of phospholipids and cho lesterol (Barnes(1986), Barnes e1. a/ ( 1980), Gorwyn and Barnes (1989)), and the in ves tigation ofphase transition s in crys ta lline fatty acids (Kenn e1. a/ (1990)) and polymer (Dai et. a/(1989)) monolayers.
Barnes, G., (1 9 86) Adv. Colloid Interface Sci., 25, 89
Barnes, G., Bacon, K. and Ash, J., (1980), J. Colloid Interface Sci., 76, 263
Gorwyn, D, and Barnes, G ., (1 990), Langmuir, 27 , 113
Kenn, R.M., Bilbo, A.M., Peterson , I.R ., Mohwa ld, H., Kjaer, K. , and Als-N ielsen ,J., (1990), Physics Department Annu al Pro gre ss Report, I Jan - 31 Dec, 1990, Ris!ilNational Laboratory. Ris!il-R-582
Dai, L., White, J.W., Kerr, J., Thomas, B.K., Penfold, P. and Ald issi, M., (1989),

Synth . Metals , 28, D69- D89

1 SP-04
X-RAY EVALUATION OF A LAPPED Si SINGLE CRYSTAL
Hideaki Shiwakul, Masami Ando2, Kazuyuki Hyodo2,Xiao-Jing Wu3
and Shigeo Horiuchi4
1. Japan Atomic Energy Research Institute, Tokai, Naka, Ibaraki, 319-11, JAPAN
2. Photon Factory, KEK, Ohol-1, Tsukuba, Ibarak.i, 305, JAPAN3. Mitsubishi Gas Chemical Co. Ltd., Tsukuba Ibarak.i, 30s, JAPAN4. National Institute Research in Inorganic Materials, Tsukuba, Ibaraki, 30s, JAPANDevelopment of a K-edge subtraction imaging system with synchrotron
radiation, for non-invasive coronary angiography is under way at the
Photon Factory, KEK. It needs a large monochromatic x-ray beam withhigh integrated intensity, and energy resolution better than 150 eV. Single
crystals lapped by abrasives were characterized by their integrated
intensity , reflectivity and full-width at half maximum (FWHM). The
effect of abrasives was studied for a range of abrasive particle sizes andfor some semiconductor materials via the shape of the rocking curve. The
effect of Bragg plane asymmetry relative to the crystal surface was alsostudied. For example, at photon energy 33 .17 keY a Si 311 single crystal
with an asymmetry angle a. of 5° has good (70%) reflectivity in spite oflapping of the surfaces by lO!J.m abrasive particles. This photon energy
corresponds to the K absorption edge of iodine, a commonly used contrast
material in angiography. Its FWHM becomes 10 to 15 times that of amechanochemically polished crystal, implying that the integrated intensity
becomes 15 to 20 times larger. This confirms that a lapped asymmetrical
Si single crystal can be used as a monochromator for coronary imaging
with synchrotron radiation.(1 ,2)Fitting of rocking curve, by a mixture of Gaussian and Cauchy functionsof the form f(x)= A e-Px 2 + B/(l+qx2) , where x is the deviation angle
from the Bragg angle and A, B, p, q are constants, has been attempted .
The Figure 1 example shows FWHMs of resolved Gaussian and Cauchy
components for Si 311 with a. =5 ° lapped by abrasives. The Gaussian and
Cauchy components from the fitted curves were found from this analysis.
The FWHMs and integrated intensities'0 ;-====;-----=---,
were then related to the abrasive material's -~ 10 l/I' - -~ ~::·~/--'--'
particle size. Cross-sectional observations ~ . 5 " 11 a-s'
by transmission electron microscopy shows " •o .
many cracks and grains generated on the i - [__c;surface by the lapping process . ( 3) ~ 10 o._.
0Construction of a diffraction model to::-o= --::-:------__J
0
1
0 1
10
100
elucidate these data is under discussion.
o.o· Pmic!c ~<ze ()Unl~IIl) H Shiwaku eta!, Jpn J. Appl. Phys. 30(12A) L2065 (1991)
2) H Shiwaku eta!, Rev. Sci. Instrum. 63 1201 ( 1992)
3) X.-J.Wu et al, Jpn J. Appl. Phys. 31(6B) L803 (1992)

jj.lfuV15P-05
INTENSITY ENHANCEMENT IN ASYMMETRICDIFFRACTION WITH PARALLEL-BEAM SYNCHROTRONRADIATION
H. Toraya, Ceramics Research Laboratory, Nagoya Institute ofTechnology, Asahigaoka, Tajimi 507, JAPANT.C. Huang and Y. Wu, IBM Research Division, Almaden ResearchCenter, 650 Harry Road, San Jose, CA95120-6099, USA
Recently, there has been considerable interest in the use of parallel-beam
X-ray optics in powder diffraction. In this paper, intensity enhancement
in asymmetric diffraction with a fixed incident angle a was studied using
parallel-beam synchrotron radiation. Vertical-scan powder
diffractometers having horizontal parallel-slits with an aperture of 0.05 °and parallel-beam synchrotron radiation with A, of 1.54A and a of SO and10° were used to collect the diffraction patterns of Si, Ce02, and Zr02
powders. Experiments were conducted for Si and Ce02 at the Photon
Factory (PF) in Tsukuba and for Zr02 at both PF and Stanford
Synchrotron Radiation Laboratory. The experimental data for Si andCe02 were analyzed by the individual profile fitting technique and thoseof Zr02 by the whole-powder-pattern fitting technique. Experimental
intensities were corrected for the incident beam decay by using monitor
counts collected between the monochromator and specimen. As expected,
significantly higher intensities were obtained from the asymmetricdiffraction. Intensity enhancement in asymmetric diffraction wasmeasured as a ratio R of the integrated intensity obtained in asymmetric
28 scanning to that of the corresponding reflection in symmetric 8-28
scanning. The observed ratios R had values between 1 and 2 in the range
28 > 2a, and its variation with 28 was well in accord with that expectedfrom the intensity formula derived in the case of asymmetric diffraction.
The change in profile shape was very small between the two cases
obtained by 28 (a fixed) and 8-28 scannings, as expected from theprevious experiment I) The shift in peak maximum position was also verysmall for a sufficiently large incident angle as in the present experiment.
These results showed that the diffracted intensity from a stationary sample
could be enhanced without degrading the profile shape in asymmetricdiffraction.
1) H. Toraya, T.C. Huang, and Y. Wu, Denver X-ray Conference, Aug.
1992, Colorado Springs, Colorado.

15P-06

STRUCTURE REFINEMENT OF SUBMICROMETER-SIZEDTWINNED DOMAINS BY USING SYNCHROTRONRADIATION WITH THE LAUE METHOD

K Ohsumi, PF-KEK, K Hagiya, HIT, T Takase, Univ Tokyo,
Y Shimizugawa, NIRIM, M Ohmasa, HIT and M Miyamoto, Univ Tokyo
It is essential to analyze the structure and/or texture of submicrometersized specimens to understand the phase compositions of these materials
more completely. A system developed for this purpose has been applied tosome inorganic materials at the Photon Factory(PF), KEK , usingsynchrotron radiation(SR) with the Lai.ie method.
In analyzing submicrometer-sized specimens, it is important to reduce
background to the lowest possible level. Use of a strong X-ray sourcesuch as SR is essential for such an experiment. To reduce the time needed
to colleci: diffracted intensities from such small samples, it was decided touse the Lai.ie method with an imaging plate (Fuji Co, Ltd) - a storage
phosphor detector. A new optical system has been developed and installedin the Laue camera to reduce the background caused by interaction of thepolychromatic SR beam with the slit systems . Software for Lai.ie
reflection data reduction and for structure refinement has been developed
at the PF to support this new experimental program.
This has been applied to study a twinned molybdenum sphere 0.8 )lm indiameter, and a truncated icosahedral chemical vapour deposited(CVD)diamond, 5 )l.m in diameter.
Molybdenum Sphere
The Mo sphere was found to be twinned. The volume ratio of thetwinned domains was determined from 14 Lai.ie reflections. The isotroJ.lic
temperature factor (B) of 0.08(6)A2 compares with a value of 0.04A2
obtained by the same method for another Mo sphere of the same size andwith 0 .07(4)A2 determined for the same powdered chemical by powder
diffraction. The refined volume of the smaller domain, 0.02mm3, isbeyond the resolution limit of an optical microscope. The estimatednumber of molybdenum atoms within that domain is around 5x108.
Icosahedral CVD Diamond
A truncated icosahedral CVD diamond was found to consist of 17
domains. The presence of a spinel twin type was confirmed in sixteen of
those domains. The isotropic temperature factor (B) was determined to be
0.2(1)A2 by analysing a twin-free domain with an 0.08mm3 volume.
These results demonstrate that crystal structure refinement of twinned
samples can succeed even under these extremely difficult conditions.

15P-07
UL TRAMICRO-SINGLE-CRYSTAL DIFFRACTION STUDYON BARIUM TITANATE USING SR

M. Kataoka, K. Suda, N. Ishizawa, Research Laboratory of Engineering
Materials, Tokyo Institute of Technology, Nagatsuta, Midori-ku,
Yokohama 227, Japan, F. Marurno, College of Humanities and Science,
Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156, Japan, Y.
Shimizugawa, National Institute for Research in Inorganic Materials,
Namiki, Tsukuba 305, Japan, and K. Ohsumi, National Laboratory forHigh Energy Physics, Oho, Tsukuba 305, JapanThe effect of crystal size on the tetragonal-cubic phase transition of
barium titanate, BaTi0 3 , has been studied by means of ultramicrosingle-crystal diffraction using SR .

Crystals of BaTi03

weresynthesized by the flux method. Laue photographs were taken at thebeam line 4B of the Photon Factory, KEK, on crystals with dimensions
ranging from 10 !-lm to 0.25 1-lm. The imaging plate was used as an Xray detector. The exposure time was varied from 1 s to 4 h dependingon the size of specimen. The crystal to film distance was fixed at
66.5mm. Splitting of diffraction spots due to the twinning of thetetragonal form was clearly observed for crystals with dimensions of
10!-lm-0.56 1-lm. The splitting seemed to become smaller as the crystal
size decreases, and the crystal with dimension of 0.25 !-lm gave no clear
splitting. This crystal has the least volume among the crystals fromwhich Laue photographs have ever been taken. A detailed analysis on
the change of c/a ratio with crystal size is now in progress and will
provide a clearer understanding on the critical size of the tetragonalcubic phase transition of BaTi03.

15P - 08
DIFFRACTION FROM COMPOSITE CRYSTAL Nd13Fe46B41BY SYNCHROTRON RADIATION

L.. Ohba, Department of Materials Science and Engineering, Teikyo
Un iversity, Utsunomiya 320, JAPAN, S. Sasaki, Tok yo Institute ofTechnology, Naga tsuda, Yokohama 227, JAPAN , ~1. Takat a, De par tmen t ofApplied Physics, Un iversity of Nagoya , Furoucho, Nagoya 464-01,
JAPAN , and Y. Komura, Hiroshima Institute of Technology, Saeki-ku,
Hiroshima 730-51, JAPAN.
Nd 13 Fe 46 o41 is a composite crystal which is constructed by two subsystems interpenetrating each other in a crystal, i. e. Nd and Fe
subsystems . We observed electron diffraction patterns using several
kinds of heat treated samples to examine a correlation betwee n aperiodicity of the composite crystal and th ose of Nd and Fe subsystems. Recently, a structural study of the composite crystal has been
done by multi-dimensional analysis by man~ authors.
lloweve r , it is
not easy to understand the structure for this method. Structural
st~dy of the com posite crystal using a synchrotron radiation was madefor examining a contribution of each subsys tem . X- r ay diffraction
pr ofiles along 20 .e line was measured with Nd and Fe absorption edges
by synchrotron radiation at OL-lOA at Photon Factory in KEK.
A ratio of intensity I(Nd )/I(Fe) along 202 was shown in Fig. 1 . The
ratio a t 2=18 becomes stronger than the back ground and that of 2=20
is weaker than the back ground. It is obvious that an effect of two
subsystems contribute differently.
3 5" [ (Nd) /[(Fe)

Fig.

2.:.

0.5

17

li.S

18

IS . 5

I~

13 .5

21

150-09
MICRO-AREA X-RAY DIFFRACTION: ITS APPLICATIONTO CRYSTALLOGRAPHIC ANALYSES OF MINERALTEXTURES AND TINY SINGLE CRYSTALS
H. Horiuchi. M. Tanaka*, S. Nojima, T. Mitsuki, Mineralogical Institute,
University of Tokyo, Hongo, Bunkyo Tokyo 113, Japan and
I.Minato, JEOL Ltd., Application Laboratory Musashino, Akishima,
Tokyo 196, Japan.
A new method was developed in order to analyze lattice constants andlattice orientation relationships among the crystalline substances which
comprise textured minerals or inorganic materials. Analysis can proceedwithout special sample separation, using conventional X-ray sources suchas CuKa radiation from a shielded tube operating at 35KV, 25mA. Whena crystalline fragment of synthetic rare-earth aluminate with diameteraround 30j.Ull was examined, it was found that the fragment was composedof several individual crystals. We succeeded in analyzing lattice constantsfor each crystal. It was finally deduced that some of these crystals wererelated to each other by twinning. In the case of a single crystal specimenof synthetic CaNiSi206 of about I03J..Lm3 volume, a data set of integrated
intensities strong enough for structure analysis was obtained. Thus, in thecase of analyzing lattice constants and lattice orientations for crystalline
phases in mineral textures, the minimum size of a crystal which can bestudied individually is I03J..Lm3 or less.
Equipment originally developed by JEOL as a micro-area powder X-ray
diffraction apparatus (DX-MAP2), was utilized as a single crystal
diffractometer for this work. A curved one dimensional position sensitive
proportional counter was used as a detector and this provides an effective
record of the intensities of the diffracted beams. The distance from the Xray source through the specimen to the detector is 220mm. The X-ray
beam is collimated by holes of 10, 30, 50 or lOOJ..Lm<J>. Specimenorientations can be controlled by three axes 8 , X and <1> as for a 4-circle
goniometer. Software systems for data collection and for analyses oflattices and their orientations were developed in this investigation.
*)Present address: Photon Factory, National Laboratory for HighEnergy Physics, Tsukuba, Ibaraki 305 , Japan.

150-10
MICROSTRUCTURE AND CRYSTALLINITY OF
LUMINESCENT POROUS SILICON STUDIED BYDIFFRACTION TECHNIQUES
Kuniko Takemoto, Yoshio Nakamura and Osamu Nittono
Department of Metallurgical Engineering, Tokyo Institute of Technology,
2-12-1, Oh-okayama, Meguro-ku, Tokyo 152, Japan.
Porous Silicon (PS) layer is obtained by anodic oxidation of a monocrystal silicon wafer in concentrated hydrofluoric acid (HF) solution. It
consists of a great number of micro pores and fine silicon parts. The
silicon parts have intricate 3-dimensional micro systems and a huge
specific surface area depending on the wafer type and formation
conditions . Using these characteristics, applications of PS layer toelectronic materials were expected and have actually been achieved.
In 1990,· Canham reported a demonstration of visible photo-luminescence(PL) from highly porosity PS layer. Silicon normally emits only
extremely weak infrared PL because of the relatively small and indirect
band gap. Then this phenomenon was explained by quantum size effects insilicon parts such as quantum wires. Now red, orange, yellow and green
visible light emissions have been reported. Many studies of luminescentcharacteristic of PS layer have been performed, but few studies discuss
the possibility of quantum size effect from the view points of
microstructure, size and morphology , and the crystallinity of siliconparts.
In this study, we investigated microstructure and crystallinity of PS layers
produced on p- and n-type degenerate silicon (100) wafers by highresolution SEM (HRSEM) observations and by X-ray multi-crys tal
diffractometry. Anodization was carried out with current densities
ranging from 10 to 300 mA/cm2 in a constant electrolyte solution of HF:
C2HsOH: H20 = 1: 2: 1. In addition, visible light emission excited by HeCd laser was confirmed for several PS layers.
The main results are: 1) p-type silicon: When a PS layer was anodized
below 200mA/cm2, the lattice distortion of the PS layer increased,
depending on the forming current density. Its crystallinity was as good asthat of the substrate. Above 250mA/cm2, the lattice distortion decreased
and the crystallinity was considerably worse than that of the substrate.
2) n-type silicon: The lattice distortion decreased depending on theforming current density. Especially at low current densities, its variation
was remarkable.
The relationship between crystallinity and the visible light emi ssion will
be discussed on the basis of experimental results.

150-11

DESIGN OF NEW TYPE FOUR CIRCLE DIFFRACTOMETER
WITH MOVABLE ROT ATING ANODE X-RAY SOURCE~ Harada.

1. Takahashi, T. Shimura, T. Miyazaki,
K Yamada, and K Masuda•
Department of Applied Physics, Nagoya University, Chikusa-ku,
Nagoya 464, Japan. • Department of Product Development, Rigaku
Co., 3-9-12, Matsubara -cho, Akishima-shi, Tokyo 196, Japan .

A new type of multi-purpose four circle diffractometer system has
been constructed by developing a movab le rotating anode X-ray
source . It en abl es us to collect X-ray scattering data from a single
crystal or liquid surface by keeping the sample stage horizontal. It
provides rotation around the <p axis normal to the horizontal plane .
The mechanism of th is goniometer is such that, with the sample
stage fixed horizontall y, a rotating anode X-ray generator(18kW:
40kV, 450 mA for a Cu target) is driven to change the grazing
incidence angle a.. A conventional scintillatio n counter can be set
to any scatte ring angle by rotating it through an angle n around the<p axis and by a tilting angle x from the horizontal plane. The
gon iometer movements , shown schematically in the figure, aredriven by computer controlled stepping motors.
The goniometer proves to be effective, especially for measurementof surface scattering with the grazing incidence in vacuum , andal so for solutions or for samples which dissolve or melt at highte mperature. It would be the we ll suited to measurement of thecritical scatterin g for phase transitions from solid to liqu id, usingsi ngle crystals.
Rotating
Anode

\\

/

q,

:I)t

~
"-

(J

Detector

0\

SamplePlane.

,

150-12FUNDAMENTAL STUDY OF A TIME-RESOLVED LAUEMETHOD FOR PROTEIN CRYSTALLOGRAPHY
N.Watanabe and N.Sakabe, Photon Factory, KEK, Tsukuba, Ibaraki 305,
T.Higashi, Rigaku Corporation, Akishimashi, Tokyo 196, and K.Sakabe,
Nagoya University, Nagoya 305, Japan.
White synchrotron X ray can be used to obtain the integrated intensityfrom a single crystal in Laue geometry. In spite of many inherent
limitations, the use of the technique is believed to have a great potential intime-resolved structural studies on macromolecules within the time scaleof milliseconds or less. We have constructed a Laue camera to investigate
the dynamical change of molecular structure in a single crystal. The
camera system combines a multi-slit rotation shutter with a linearlystreakable Imaging Plate (IP) cassette. It can record the diffraction
pattern after the reaction initiation into continual spots as a function oftime . Eight IF's can be put on the largest cassette with a total size of
800mmx800mm . A large area is required in order to record thecontinual spots without spatial overlap . The shortest width of the X ray
pulse achieved by the shutter is 125~ sec. The preliminary test of thecamera was performed at a bending magnet beamline BL-6A2 and at thevertical wiggler beamline BL-14C of the Photon Factory with protein
crystals of w-amino acid:pyruvate aminotran sfera se (w-AP T ),myoglobin, hemoglobin, actin, and L-lactate dehydrogenase. A bent planefused quartz focus sing mirror was installed at 6A2 and no focu ss ing
optics were used at l4C. A typical one-shot exposure time using an IPwith a crystal of w-APT (the size of crys tals are about 0.7 x 0.8 x
2.0mm) was lOmsec at 6A2 and lOOmsec at 14C, when the storage ring
was operated with 2.5Ge V 350mA. The quali ty of the Laue data wascompared with the monochromatic (Weissenberg) data using crystals of
w-APT. Time-resolved experiments on w-APT crystal and some organic
crystals were performed using a Q-switched Nd:YAG laser as a trigger.
Intensity variations of reflection spots were observed with a time
resolution of submilliseconds to milliseconds. Results of this work will bepresented.

150-13

HIGH RESOLUTION DATA COLLECTION FROM PROTEIN
CRYSTALS ON R-AXIS IIC DIFFRACTOMETER
T.

Sato

and

T.

Matsubara-cho,Tada,

Higashi,Akishima-shi,

Rigaku Corporation,

3-9-12

Tokyo 196,

Japan,and T.

Co.

2-1-6 Kashima,

Fujisawa Pharmaceutical

Ltd.,

Yodogawa-ku, Osaka 532, JapanThe

RigakuR-AXIS

automatic data

IIC

diffractometercollection fromFuji Imaging Plate (IP)the flat-plate

was designed

forprotein crystals using theas an x-ray detector.
The size of2and the minimum crystal to

IP is 200x200mm

IP distance is 55mm,

hence the maximum resolution limit isca. 1.6A for CuKa radiation .
Elastase-inhibitor

complexcrystals(o rt ho rhombic,

P2 2 2 ,a=57.8,b=74.5,c=51 . 7A)
d iffract up to 1.3A
1 1 1
resolution and were used forthe present test of highresolution data collection on the R-AXIS IIC.
Using

CuKa radiation,

diffraction data were collected up

to theresolution limit

lOOmA,

crystal tohand,similar2°/frame,

data

data

collection was(50KV

of 3.4%completeness)

is obtainablemachine.

90mA,

for Cuto theto160mm,

IP

The

completeness)wasof rather

7.5%,

due

to crystal

partlyintensities (averaged
present

resolution
IIC.

(1.3A

shows

decay and
the

data

collection fromA

detailed comparison

will be presented.

limit ofresolution

poor quality,

intensity was

experiment

resolution andthat reasonable data quality

mechanical resolution
datasetR-AXIS

total
obtainperformed to

crystaldataset (1.6A

indicates

Mo

The

30min/ 2°,

Using MoKa radiation, on the other

40min/ 2°, total oscillation range 80°).

The R-merge
75%

2° / frame,

IP 59mm,oscillation angle 86°).
higher-angleof 1.6A in a routine manner (40KV

and

the
77%

with R-merge
inevitably weak

only 22% of Cu case).
capability

forprotein crystals

highon theof Cu and Mo datasets

150-14
STRUCTURE DETERMINATION OF ORGANICCOMPOUNDS BY A RAPID X-RAY MEASUREMENTSYSTEM
F Iwasaki, M. Sak:uratani and M. Yasui, Dept. of Applied Physics andChemistry, The Univ . of Electro-Communications, Chofu-shi , Tokyo
182, Japan and N. Kamiya and H. Iwasaki, The Institute of Physical andChemical Research (RlKEN), Wako-shi, Saitama 351-01 , Japan.
Rapid collection of X-ray intensity data is especially important fo r
determining structures of unstable compounds. In order to get structural
information from a single crystal within several hours, a new type of Xray diffractometer has been developed (Iwasaki & Kamiya, 1992). Thisequipm.e nt is a Weissenberg camera type with multi-screens, two
cylindrical imaging plates (IP; the two IP's are used alternately to reduce
effective readout time) and rotating laser optics designed for the readoutof the cylindrical IP. Diffraction intensities of two stable compounds (Iand II) and two unstable compounds (III and IV) were measured using
this equipment with MoKa radiation (50kV, 200mA, 28rnax=45" ). Total
time for measurement is 2 or 3 hours for each compound. The structures
were solved successfully by conventional direct methods and the Patterson
method. For I and II intensities were also measured with a 4-circle
diffractometer using the same specimens.
The agreement between thetwo sets of structural geometry, obtained from the IP and the 4-circle
diffr atometers , was quite satisfactory .
Accurate intensities of theunstable III and IV could not been obtained by the 4-circ lediffractometer.

sII
sII,c......__,c,
Ar
;:,
Ar

t-Bu

t-Bu

Me* MeAr : 2,4,6-tri-Me-Ph

Ac
Ac
Ac: COOMe

I

II

I

Sp. gr.
P2j/C

m

II

P2y:
C2c

N

P21p

a/ A
8.52fX2)
10.855(1)15.4298.7XX1)(Me-Ph)3BiCI2

b/A
12.434(2)10.169(1)19.7298.789(2)

Ill

v;A.3
c/ A
~r
18.71XX:3) 100.91(2) 1954.7(6)17.597(2) 104.82(1) 1883.1(3)16.036121.364123.649.298(8) 93.83(2) 3770;))

Iwasaki, H. and Karniya, N. (1992). to be published.

z
4
4
8
4

Refs.
1995
236)

2502
3667

R
0.054
0.050
0.067

0.063

150-15
FULLY AUTOMATIC STRUCTURE ELUCIDATION
Kentaro Yamaguchi. Emi Yasudome and Go Matsumura,

Schoolof Pharmaceutical

Sciences ,Showa

University,

1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142, Japan.
A fully automatic procedure for solving crystal structuresof organic small molecules has been devised.

Automatic

deci sions at each critical point of the analysis in which theuser intervention used to be required are provided, based
The procedure named FASE

on empirical considerations.

(Fully Automatic Structure Elucidation) has been mainly
implemented into the packages RCRYSTAN and SAP/85.

It

is able to solve structures without any user intervention.
The us er simply inputs "FASE" to carry out this procedure.
Th e comp lete structure is solved and di splayed in mostcases .

This procedure has been applied to 137 crystaline

org anic

com pounds

structures

were

was

throughout

848

capability

andderived.

112

chemicallysignificant

The highest molecular· weightthese

analyses ,indicatingits

to be applied to organic structures generally.

The shortest computing time of 3 minutes for the wholecalculation
withouts uggests

missing

quick

atoms

analysis.

usingnormally in the range 0 .1 5-0 .30.
procedure will be shown.

Risotropic

valuesrefinedrefinem e nt

areSome results using this150-16XTAL 3.2: A NEW SYSTEM RELEASE.

E. Blanc, U. Lausanne, D.M. Collins, N.R.L. Washington DC, D.D.
Dexter, Middlebury College, D.A. Grossie, Wright State U., H .D .Flack,
U. Geneva, S.R. Hall, U. Western Australia, G.S.D. King, U. Leuven,
B.G. Kruger, Rand Africaans U., R. Olthof-Hazekamp, U. Utrecht, D.
Schwarzenbach, U. Lausanne, J.M. Stewart, U. Maryland and K.D.
Watenpaugh, Upjohn Co. Kalamazoo.
Version 3.2 of the Xtal System was released in September 1992. The
prime difference with version 3.0 is the inclusion of the new programs
summarised below. Other system changes simplify implementation: theseinclude macro switches to specify f77 compilers types and an automatic
implementation script for Unix OS's. The ability to process CIF's is an
important aspect of Xtal. and these may be generated for archiving andsubmission to Acta Crystallographica and the Cambridge Data Centre.
New programs in Xtal3.2 are: (a) ADDPAT to input powder intensity
patterns into Xtal; (b) CREDUC is an adaption of the Le Page cell
reduction approach augmented with the calculation of (psuedo)-merohedral twin laws; (c) LSABS applies absorption corrections which leadto refi neable crystal dimensions; (d) LSLS is a SF least-squares
refinement with restraints dealing with raw observed intensities andinnovative error calculation; (e) LSRES is a restraint loader; (f) MIND
generates site data for the graphics program MindTool (Tirado-Rives &Blake); (g) MOLVU generates site data for the graphics program
MolView (Cense); (h) NEWCEL transforms cell data; (i) R EFCAL

reduces and analyses raw data intensities; U) R!ETVD refines structuresfrom multi-phase powder samples by the Rietveld method; and (k)XTINCT estimates an extinction coefficient from measured intensities.

15R- 17
ELECTRON IRRADIATION DEFECT STUDIES ON QUARTZ
CRYSTALS AT CONSTANT ELECTRON ENERGY (200kV)
B . Martin, Institute of Mineralogy
Ruhr-University, UniversitiHsstr. 150, D-W4630 Bochum, Germany.
Electron irradiation damage in quartz single crystals and the induced
transformation of crystalline areas to non-crystalline were studied by
McLaren & Phakey, 1965 . Later Gopal Das & Mitchell,1974, Hobbs &Pascussi,1980, Pascussi et al. ,1983, Haliburton,1985, Vance et al. ,1986
and Inui et al.,1990 examined particular aspects of this phenomenon.
Because electron irradiation has a complex action we studied only wellcharacterized, homogeneous areas of synthetic single crystals with fewer
structural defects than those in natural quartz. In view of results by
McLaren & Phakey, 1965, we examined samples with different
concentrations of Li, Al, K, Fe, H only in two growth sectors (<c>, <z>).
The proton concentration and defect types were influenced by heat pretreatment.
We used crystallographically oriented cantilever thin sections (30 11m) for
parallel light-microscope, REM, TEM and FTIR-, Ramanspectrometerstudies. The electron irradiation defect, in a circular isotropic volume
area (IV A) with damage decreasing from the inner to outer zones , wascarried out in TEM at constant electron energy and varying temperatures(Florke et al.,l990).
Damaged areas, when characterized by the methods cited above , showthat the electron irradiation defects are independent of ion etching method
and nearly independent of proton concentration for a given sample
orientation. The damage induced depends on thin section orientation andtemperature pre-treatment. This is evident in light-microscope, brightfield mode in TEM, REM after slight HF-etching of the sample,
diffraction mode in TEM and in Raman spectra.
Electron diffraction patterns show variable streaking for certain Braggreflections, dependent on the volume studied in the IV A which means ameasuring point in the structurally disordered IV A. These observations
can also be verified by studying the strong quartz Raman signals scanning
the sample from the non-damaged outer crystalline zones representing
structural ordered quartz to the inner non-crystalline center of IV A.
McLaren, A . C. & Phakey, P . P ., Aust . J. Phys . ( 1965 ) 18, 135.
Gopal Das & Mitchel, T. E ., Radiation Effects ( 1974) 23, 49.
Hobbs, L. W. & Pascussi, M.R.,J.Phys.,C6 No.7,Tome (1980) 41,237 .
Pascussi, M.R., Hutchison, J.L. & Hobbs, L.W.,Radiation Effects (1983)74,219.
Halliburton, L.E.,Cryst.Latt.Def. and Amorph . Mat. (1985)12, 163.
Vance, E.R., Cann, C.D. & Richardson, P.G. ,Radiation Effects (1986)98,71.
Florke, O.W., Martin, B., Roller, K. & Wirth, R. ,15th General Meeting of the Int.
Min. ASS. (1990), Abstracts Vol.I,425 .
Florke, O.W., Martin, B. , Roller, K. & Wirth, R. , Proc. of the XII th Int. Congress forElectron Microscopy ,Material Sciences, (1990), VOL. IV ,826.

15R-18

POLARITY OF THERMAL CONDUCTIVITY IN
LiNb03 AND LiTa03
M.Tokonami, O .Tachikwa, Y.Ono and T.Suetsugu, Mineralogical Inst.,
Faculty of & i., Univ. of Tokyo, Hongo,Tokyo 113, Japan,
S.Kan, Daiso Co.,Ltd., Otakasu-cho, Amagasaki 660, Japan
K.Yamamoto and J.Hikita, R&D Center
Toshiba Ceramics Co. Ltd., Soya, Hadano 257, Japan .
Thermal conductivity is believed to be a second-rank symmetricaltensor property , showing no difference for any given direction andthe reverse. To study the hypothe sis that conductivity may reflect
the polarity of materials, we measured thermal diffu sivity of polar
crystals by a laser flash method, observing significant differe nces
between (+) and (-) directions along a polar c-axis .
LiNb03 and LiTa03 were selected for study from a variety of polar
crystals, since their polarity is hard to reverse at room temperature,and homogeneous synthetic crystals are readily obtained.
Preparation of oriented specimens: Single crystals were grown by CZ
techniques taking care with poling procedures. Disc s, 3 .5mm thickand 9.5mm in diameter, were cutperpendicular to the e-axis fr om
single domain samples of LiNb03 and LiTa03.
Thermal diffusivities were measured with an UL V AC TC-3000
flas h-type thermal constant analyzer. Data measurement in a di sc
was repeated 10 times for each direction along the c axis. The tableshows sample number, average value(mm2Js), standard deviationand temperature ( 0 C) for three LiNb03 (N) and one LiTa03 ( T)samples.
No.
Temp.
<ct>
s
The diffusivity with the (+)
Nl+
1.65
.18
2I
direction is significantly larger
Nl1.51. 12
20than one with the (-) direction in
N2+
I. 70
. 10
21
all five data sets. The differenceN21.59. 10
21of the diffusivity in LiTa0 3 is
1.63
.07
20
N3+
larger than that for LiNb03. It is
N319
. 11
I. 53
Nl22
1.65
.05
concluded
that
thermal
22
Nl+
1.70
.05
conductivity, which is product of
TlI. 81.05
22
diffusivity, spec ific heat and the
Tl+
1.95
.08
23
density, is also a polar property.

15R-19
SMECTIC LAYER STRUCTURE OF FERROCENECONTAINING LIQUID CRYSTALSN. Nakamura, T. Hanasaki, and H. Onoi, Department of Chemistry,
Faculty of Science and Engineering, Ritsumeikan University,
Kita-ku, Kyoto 603, Japan.
The liquid crystallinity of the ferrocene derivatives, [4- [rocholesteryloxycarbonyl)alkoxy carbonyl]phenyl]ferrocene, was studied byNakamura, Hanasaki, and Onoi(1992) using a polarizing microscope anddifferential scanning calorimeter. Liquid crystallinity was observed in the
ferrocene derivatives containing 2, 4, 6, 10 and 11 carbon atoms in theflexible alkyl spacer. Small angle X-ray measurements on thesecompounds were carried out using a position sensitive proportionalcounter(PSPC). The temperature of the samples was controlleci by anitrogen gas blow system. Results obtained in the liquid crystal phase forthese samples are listed in Table 1.
Table 1 .. long spacing
n

(A)

2

61.3
62.0
64.4
38.0
37.4
50.6

4

6
10
11

n is the carbon atom number in the flexible alkyl spacer
The results suggest that the ferrocene derivatives containing 2, 4, 6
carbon atoms in the flexible alkyl spacer have double-layer structures andthe others are mono-layer structures. The derivative with 11 carbon
atoms is intermediate between the double-layer and the mono-layer
structures.
Nakamura, N., Hanasaki, T. & Onoi, H. (1992). Mol. Cryst. Liq. Cryst.,
in press.

15R-20
CUMULATIVE DISTRIBUTION FUNCTIONS OFNORMALIZED INTENSITY, ALLOWING FOR ATOMS IN
SPECIAL POSITIONS IN THE UNIT CELL
B. Pal and G. D. Nigam. Department of Physics, Indian Institute ofTechnology, Kharagpur 721 302, India.
The effect of atoms, located in fixed and variable special positions, on the
cumulative distribution function of the normalized intensity has been
investigated, under the assumption that the heavy atoms are surrounded
by inaccessible volumes (parallel strips surrounding the mirror planes
and cylinders surrounding the axis of symmetry), which exclude lightatoms occupying general Wyckoff positions in the unit cell. The shapetransform of the inaccessible volume modulates the intensity in thereciprocal space, which changes the cumulative distribution function of
intensity significantly from the usual Wilson type for Pl and PI. A
detailed numerical study has been made. It is noted that the effect ofheavy scatterers, located in special positions in triclinic, monoclinic andorthorhombic space groups investigated, is very marked and should beconsidered in cases of space-group ambiguity.
The theoretical results have been tested on sets of diffraction data
available for a few compounds. It was observed that the theory is capableof resolving space group ambiguities in such cases.

15S-32

REFINEMENT OF THE CRYSTAL STRUCTURES OF
Cu609InCl AND Cu609Cu2Cl BY NEUTRON AND X-RAY
POWDER DIFFRACTION
H. Hayakawa, E. Akiba and S. Ono, National Chemical Laboratory for
Industry, Tsukuba, Ibaraki 305, Japan,
H. Thara, Electrotechnical Laboratory, Tsukuba, Ibaraki 305, Japan,
F. Izumi, National Institute for Research in Inorganic Materials, Tsukuba,
Ibaraki 305, Japan and
H. Asano, University of Tsukuba, Tsukuba, Ibaraki 305, Japan.
A new group of Cu oxide compounds Cu60sMmX (M=Cu,In,Y,Ln,Pb
etc.; X=halogen, N03 etc.) are electrical conductors. Two typicalcompounds with different structures have been synthesized and theircrystal structures refined by the Rietveld method using neutron (NPD)A Rigaku RAX
and X-ray powder diffraction (XRD) data .
diffractometer was used for XRD measurements. NPD measurements
were carried out using a time-of-flight diffractometer, HRP, at KENS ,KEK. A Rietveld program, RIETAN, was used for both XRD and NPD
analyses.
Cu60slnCl is stoichiometric, with a murdochite-like structure (Dubler,1983). Crystallographic data are space group: Fm1m, a =9.1555(2)A ,d 0 =5.69 g/cm3, Z=4. Rwp =4.74%. [Cu608] blocks form a 3-dimensional

network of 26 polyhedra composed of [Cu04] planes sharing oxygen
atoms (Cu-0 :1.908A). Another block is a network of [InOs] cubes
sharing oxygens with the 26 polyhedra at the comers (In-0 :2.257 A). The
centers of each block are occupied by Cl and In, respectively. The 0 andCl sites (32f and 4b) are fully occupied. It is concluded that the compoundhas the ordered structure Cu60slnCl.
The Cl sites for Cu60sCu2Cl were partly substituted by N03.
Crystallographic data are space group: Fm'Jm, a =9.3806(4)A, d 0 =4.95
g/cm3, Z=4. Rwp 4.09 %. The Cu60sCu2Cl unit cell is larger than thatof Cu60slnCl, as the former contains large N03 anions instead of Cl
atoms. The crystal structure is essentially the same as that of Cu60sinCl
except for Cu sites corresponding to In sites. The Cu atoms are located,
not at the In sites (2b), but distributed among 6 equivalent sites (24e)around the center of the oxygen cubes with occupation factor about 29%.
A Cu atom from the cubes is coordinated with 4 oxygens forming a
distorted [Cu04) plane (Cu-0:1.916A). The cubes and the 26 polyhedra
share the [Cu04] planes and form the 3-dimensional network. This typeof compound can therefore be expressed as Cu6-m0s•Cu2-nClo.7(N03)0.3
where m+n = 0.4. For the sample in this work, m was 0.1.

15S-33
A NEUTRON DIFFRACTION STUDY OF DEUTERA TEDBENZENE FROM 4K TO THE MELTING POINT
C.J.

Craven,University

P . O. Hatton, and G.S.

of Edinburgh, Scotland

Paw l ey ,DepartmentofPhysic s,

and C.J. Howard, Austra l ian Nucle a r

Science and Technology Organisatio n , Australia.

Benzene (C H ) is one of the basic c ompounds of organic chemistry,
this

and

6

6

for

reason there have been numerous experimental and theor et ical

investigations
molecule

is

of

this

now

very

material.

reports of unusual behaviour
theincludeparameterssuggestion

with

In

well understood.

many

respects,

There

of

benzeneadiscontinuous

of

in

the

benz ene

are, however , several

its

solid

form.

These

variationofl atticet emperature below 140 K and reports of anomali es n ea r

the melting point (280 K) in nmr determined rotation rates and i n X- rayintensities and lattice parameters.

Ue

have

completed

deuterated

benzeneaneutron(C D )
6

6

powderfromdiffraction

were refined to provide estimates of latticetheorientation

The

latticeinvestigat io n

4 K to the melting poi n t
parameters1

andda t aonof the benzene molecule as a function of te mperature .

parameters obtained are in excellent agreement with tho s erecorded (at a l imited number of temperatures) in previous work on
deuteratedof

The d a ta

compound,

and

they

variedsmooth l yacrossthet he
wh o l etemperature range. The most spectacular " anomaly" was the occurrence of
crystalgrowthafew degrees below melting; we believe this ha s been

responsible for th e effects seen, for example, in the X- ray work

The r eremained an increase in the expansion

so meanomalouschangesinorientation

of

the

b

parameterandof the benzene molecule j us t below

melting. These are thought to be the f ir st indications of aphase transition which is, however, preceded by melting

2

stru c tural.

References
1

C.J. Craven, P.O. Hatton, C.J. Howard and G.S. Pawley. To a ppe ar i n J .
Chern. Phys.

2

C.J. Craven, P . O. Hatton and G.S. Pawle y. Submitted to J. Chern . Phys .

158-34
A NEUTRON X-RAY/DIFFRACTION STUDY OF
SIMULATED RADIATION-WASTE ELEMENTSUBSTITUTION IN SYNROC
W. Kalceff, E.A. Xuereb and D.N. Argyriou, Department of Applied
Physics, University of Technology, Sydney, P.O. Box 123, Broadway,
N.S .W. 2007, Australia.

This paper decribes a study aimed at revealing the mechanism ofincorporation of waste elements into the various phases of SYNROC.
Seven SYNROC samples, with simulated-waste loadings ranging fro m 0%
(SYNROC-B) to 30% (SYNROC-C) at increments of 5% were fabricatedusing the alkoxide route and Pw-4b-D waste. Preliminary characterisation
studies were carried out on each sample, including density and open
porosity measurements, scanning electron microscopy studies and leachrate and chemical analyses. The x-ray and neutron TOF diffraction data
was then simultaneously refined using the GSAS program (Larsen andVondreele, 1986).
The hollandite phase was found to exist in two forms, monoclinic andtetragonal, depending on the waste loading. There is conclusive evidence
for the substitution of Cs into Ba sites in the tetragonal material. It is also
clear that Sr substitutes for Ca in the perovskite phase. However,substitutions into other phases could not be determined as reliably, due tothe complexity of the data.

Larsen, A.C. and Von Dreele, R.B . (1986), GSAS, General Structure

Analysis System, LAUR 86-748, Los Alamos National Laboratory.

15T -36

INFLUENCE OF 13C CONCENTRATION ON THE
STRUCTURE OF DIAMOND
T.Yamanakal), S.Morimotol), H.Kanzaki2) and S.Sasaki3)!)College of General Education, Osaka University, 1-1 Machikaneyama
Toyonaka, Osaka 560
2)Nat. Inst. Res. Inorganic Materials, 1-1 Namiki Tsukuba Ibaraki 305
3) Res. Lab. Engineering Mater. Tokyo Inst. Tech. 4259 Nagatsuda
Midoriku Yokohama 227, Japan
Differences in lattice constant between 3He and 4He, 20Ne and 22Ne, 12C
and 13C, 74Ge and 72.6Ge have been reported. The thermal conductivityof diamond is extremely sensitive to 13C isotope concentration. The
influence of 13C concentration on the structure of diamond was therefore
investigated by X-ray diffraction. Diamond single-crystals with various
13C concentrations were synthesized using a flat-belt high pressure
apparatus. The 13C concentration for all synthesized specimens, verified
by secondary ion mass spectroscopy (SIMS) was 18.3±1.1, 48 .1±1.0,
67 .3±1.1 and 98.5± 0.4wt%. Specimens about 20 J.Lm in diameter wereused for diffraction studies.
Lattice constants of these and a natural sample were determined from25-30 independent 28 values measured at 26±0.5°C on a four-circle
diffractometer using positron synchrotron radiation at the Photon
Factory, Tsukuba. The wavelength A. for the incident X-ray beam, finely
monochromated by a Si (111) plate, was 0.697148±0.000028A, confirmedby reference to a silicon crystal with lattice constanta =5.430940±0.000003A. Diffraction intensities were measured in ro-28
scan mode with scan speed 0.01 o /sec in 29.
The influence of 13C concentration on the diamond lattice constant can be
expressed by the binary equation a(A) = 3.56712- 0.00155X + 0.00066X2
where X=1 3C/(12C+13C). The difference of the lattice constant ~abetween natural diamond and 13C diamond aO.Ol - a0.99 is 0.00086A.
Ho lloway et al (1991) previously reported the linear equationa(A) = 3.56715 - 0.00053X for isotope dependency. The linear functionis, however, puzzling in view of the effect of lattice vibrations.
Thermal parameters for natural (1 %) and 13C diamond (99%) wererefined to elucidate the isotope dependence of the anharmonic thermal
vibrations. Anharmonic temperature factors for 12C and 13C were
evaluated by the cumulant expansion (Johnson, 1969). The one-particle
potential V(u) (Wills, 1969) was also calculated. Raman peak shifts showthat the lattice vibration varies with the atomic mass difference between
12C and 13C. Thus the lattice vibrations affects the atomic displacements.
H. Holloway, K.C. Hass and M.A. Tamor Phys. Rev. B. 44, 7133 (1991)
C. K. Johnson Acta Cryst. A25, 187 (1969)
B.T.M. Willis Acta Cryst. A25, 277 (1969)

1ST -37

SINGLE-CRYSTAL X-RAY STUDY ON fcc and hcp C6o
T. Kitamoto, S. Sasaki, H. Hashizume, T. Atake, T. Tanaka, and H.
Kawaji, Research Laboratory of Engineering Materials, Tokyo Instituteof Technology, 4259 Nagatsuta, Midori-ku, Yokohama 227, Japan and
K. Kikuchi, K. Saito, S. Suzuki, Y. Achiba, and I. Ikemoto, Departmentof Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo 192-03.
The crystal structure of pure C6o has been determined using singlecrystal x-ray diffraction methods. Some crystals examined in this study
gave single-crystal diffraction patterns, but the intensities were very
weak at a laboratory source. Precession photographs and synchrotron
x-ray measurements showed for the first time that face -centered cubic(jcc) and hexagonal close-packed (h cp) crystals coexist in a single
sample.
The samples of C6o were prepared by arc-heating of graphite rod in ahelium atmosphere and purified using the liquid chromatography withbenzene solvent. The benzene residue in the crystal, determined bythermogravimetry, was less than 1 wt % . Single crystals of planar
shape, 0.1 x 0.1 x 0.01-0.03 mm, were selected from the polycrystalline
aggregate.
Unit cells and space groups of the two phases were
determined from precession photographs and synchrotron x-ray
measurements with a vertical-type four-circle diffractometer (A = 0.7
A; BL-lOA, Photon Factory). The maximum observed peak intensity
was 2 kcps. The fcc phase at 267 K has a cell with a = 14.13(2) A; thespace group is Fm3m.
The crystal structure was refined with 13
independent reflections of 57 measured up to 28 = 20°, where afullerene form factor of the molecular radius 3.55 A was assumed (R =0.06, wR = 0.04).
The isotropic temperature factor of the C6ofullerene is 10(2) Az. The cell dimensions of the hcp phase at 299 K
are a= 9.98(2) and c = 16.30(5) A; the space group is ?63/mmc. The
intensity data up to 28 = 40° were measured but no significant peak was
observed at 28's higher than 20° because of strong thermal vibration.
Fifteen independent reflections of 934 measured are being used inrefinements of the hcp phase. Low-temperature studies within 100 260 K are in progress.

15T -38

AN X-RAY STUDY
OF A TWINNED n-TETRACOSANE CRYSTAL
S.C. Nyburg & A. R. Gerson ,Department of Chemistry, King 's College, London
University, Strand, London WC2R 2LS, England.

n- Tetracosane ( n-C 24 Hso) crystals appear commonly to be twinned. The method forstructure analysis of a twinned n-C 24 H50 crystal is described. The crystal consisted ofa number of crystallites related by a 180° rotation about c·. On recording diffraction
data (28 scans ) a high degree of overlap between the two x-ray diffraction sets wasobserved as manifested by extremely uneven background measurements. In order
to correct the two sets of diffraction intensities for overlap and perform an ab-initio
structure determination an iterative ro utine was devised. From the orientation rnatrices of the twins and a model of the reflection intensity profile it is possible t oapproximate the degree of overlap between reflections. Analysis of each data set
corrected for overlap is carried out to give rise to a new structural model which isin turn used to calculate a new set of diffraction intensities and a more accurate
definition of the overlap between neighbouring reflections.

Crystal data: n-C2 4Hs 0 , triclinic, Z=1, space group PI (No. 2) a 4.282(6), b 4.828(6),c 32 .56(2)A, et 86.20(8), /3 68.83(9), 1 72.3(1) 0

From this analysis it was possible to show that n-C24Hso is isostructural with theshorter even n-alkanes (eg C2oH 42 , Nyburg & Gerson , 1992, C1 aHJa , Nybur g & Potworowski, 1973).

Gerson, A. R. & Nyburg, S. C. (1992). Acta. Cryst. B48 , 103-106.
Nyburg, S. C. & Potworowski, J. A. (1973) . Acta. Cryst. B29 , 347-352.

15T -39
MOLECULAR AGGREGATION OF CATIONICSURF ACT ANTS AND AROMA TIC COMPOUNDS
Tarsuo Kitamura, Hidehiro Ue kusa, and Yuji Ohashi, Department of Chemistry, Tokyo
Institute of Technology, 2- 12-1, 0 -okayama, Meguro-ku, Tokyo 152, Japan, andHirotaka Hira ta, Niigata College of Pharmacy, 2-13-5 Kamishin' eicho, Niigata, 9502J,Japan

It has been found that some cationic surfactants such as cethyl-, myristyland decyltrimethylammoniumbromide (CTAB, MTAB and DTAB, respectively) exhibit very high viscoelasticity even in very dilute solutions
when some aromatic compounds are added to the solution. The electron
microscopic study revealed that such high viscoelasticity is caused by theentanglement of enormously elongated rod-like micelles . Recently single
crystals were obtained from the solution containing the surfactant andaromatic compound . The obtained crystals are CTAB only[I] , CTAB/mcyanopheno l[ll], CTAB/p-cresol[III], CT AB/acridine[IV], CT AB/o-iodophenol[ V], MT AB/o-iodophenol[VI] and DTAB/o-iodophenol[VII] . In
order to analyse the rod-like micelles, the crystal structures of the above
crystals were determined.
Crystal data are summarized in Table 1. In all the crystals the surfactant
molecules are packed to form a head-to-tail ribbon. The ribbons arealigned in an antiparallel fashion to form a layer.The aromatic molecules
are situate d between the surfactant cati ons and bromide ions. Such acharacteristic structure seems to be closely related to the structure of themicelles.
Table 1. Crystal data*; 238K
I
II
III
IV

v
V*
VI*
VII*

a!A

b!A

c!A

~1 0

5.638( 1)

7.260(2)52.072(7)93.78( 1)V/A32128 .8(8)33.767 (3)7.470(1)5.575( 1)

107 .076(7)32.303(3)7.4737(5)5.5743(5)32.066(2)17.482(4)17.23 1(2)7.4014(7)8.409(3)8.51 32(6)z41344.2(6)P2 tfcP2 1

2

92. 19(1)1344.8(3)P2 1

2

5.5898(4)9 1.602(8)1326.1(2)P2 1

240.052(5)39.167(4)

90.0
90.0

5888(2)5745( 1)

Pna2 1
Pna2 1

8
8

Pca2 18

17.288 (3)8.292(6)37.34( 1)90.05351(1 )

17.21

8.271

35.3 19

90.0

5027

15T-40LATTICE INSTABILITY COUPLED WITH MOLECULAR
INTERNAL DEGREES OF FREEDOM IN BIPHENYL AND
BIS( 4-CHLOROPHENYL)SULFONE
T. Atake, T. Tanaka and H. Kawaji,
Institute

of

K.

and

Kikuchi

Science,Technol ogy,
Ikemoto,I.

Res. Lab. Eng. Mater.,

Yokohama,

227

Department

J apan ,andof Chemistry,

Tokyo

K.

Saito,

FacultyofTokyo Metropolitan University, Tokyo, 192-03 Japan.

Biphenyl and bis(4-chlorophenyl)sulfone(BCPS) are typical examples
of a group of crystals which undergo a structural phase transition
closely related to the molecular flexibility.

The

heat capacityof BCPS was measure d by adiabatic calorimetry between 10 and 300
K, and an anomaly caused by the normal-incommensurate transition
was found at 148 K.

No anomal y was detected concerning a possible

l ock-in transition at a bout 115 K.

The role of internal twistingsof phenyl groups in BCPS was studied through a calculation of
simple lattice dynamics.

Only three internal degrees of freedom,

i.e., two internal rotations of chlo roph enyl rings around the C-Saxes and

the

L.

e-s-c

bending. were taken in to account for the

calculation.
The internal rotation of the B species of th emolecular point g roup C2 strongly couples with acoustic phononmodes.
phaseThe

coupli ngtransition

probably

associatedinduces

with

a

a

soft

normal-incommensurate
mode.

The

detailed

co mparis on between the present result of the calculation and thatonbiphenyldiffer encein

(Plakida

eI

a/.,

1983)

a

of

the

molecular

structural phas elatticerole

reveals

anint erest ing

fl exibility

transition in biphenyl and BCPS .

in

the

Although themodulation in the low temperature phase of biphenylisessentially due to the molecular twisting, the flexibilit y of BCPS
molecule merely enhances the intrinsic lattice instability a nd thelatticemodulationincrystalline

BCPS

is

probablyacomplexcombination of all the possible deg r ees of freedom allowed by thesymmetry properties.

In this r espect , biphenyl and BCPS should be

regarded as two limiting examples that show two types of couplingof molecular int e rnal degrees of freedom with lattice prope rties.
Plakida,(1983).

N.M.,

Belushkin,

Phys . Status

SolidiA.V.,

Natkaniec,

b 118,

129-138.

I.

&

Wasiutynski,T.

i5T-4i
DIRECTED HETEROMOLECULAR HYDROGEN BOND
INTERACTIONS IN CARBOXYLIC ACID COCRYST ALS
Daniel E. Lynch and Graham Smith, Centre for Instrumental andDevelopmental Chemistry, School of Chemistry, Queensland Universityof Technology, Brisbane, and Colin H . L. Kennard, Department ofChemistry, The University of Queensland, Brisbane.
Directed hydrogen bonding has recently been used as a means to designacentric organic materials for non-linear optical purposes . Formation
occurs between chemically different carboxylic acids as the result of adifference in pKa values . Important biological interactions between anacid and a base occur, more often than not, because of zwitterion
formation. A series of simple model compounds that demonstratedifferent modes of directed hydrogen bonding have been prepared andcharacterized using X-ray diffraction. The series shows eight examples
ranging from an 0-H···O dimer (Fig.l) to an O·· ·H-N dimer (Fig.2). The
different modes of interaction are also detectable in the infrared spectra.
Some of the molecules used have important herbicidal properties.

O·······H-N

0-H: ····· ··O~

~C-R'

R-C/

~O·········H-0/
Fig.1

R-C

"'
/

"'

O······H-N /

Fig.2

C-R

I

1 5T -42
CRYSTAL AND MOLECULAR STRUCTURESAND THERMAL PROPERTIES OFMESOGENIC 2,5-BIS(4-ETHYLBENZOYL)OXYSTYRENE
AND 2,5-BIS(4-METHOXYBENZOYL)OXYBENZALDEHYD E
Yang Qingchuan

Dai Sheng
Zhou Hongbing
Zhou Qifeng Tang Youqi(Department of Chemistry , Peking University, Beijing 100871, China)

The crystal and molecular structures of the mesogenic 2,5-bis(4-ethylbenzoyl)oxystyrene (I) and 2,5-bis(4-methoxybenzoyl)oxybenzaldehyde (II) have been determined by single crystal X-ray diffraction
methods. Both compound I and compound II are liquid cr ys t alline .
Crystal data:
Compound I,
C2Ho · C.,H. · COO · C.,H,(CH:CH 2) . OOC. C.,H • . C2H 0 ,triclinic, ~pace group P 1(No . 2). a=9 .356(6). b=9.842(6). c=13.357(8 ) A,
a =108 .68(5) 0 , S =105.67(5) 0 , Y =96 . 36(5) 0 , Z=2;
Compound II,
H.CO · C.,H. · COO· C.,H 3 (CHO) . OOC . C.,H • . OCH 3 ,monoclinic, space group P n(No . 7), a=9 .109(2), b=9 .187(3), c=23.166(8) A,
S =93 . 93(2) 0 , Z=4 .
In both crystals, the molecules take fully extended form with the longmolecular ax es of 22 . 7 A for compound I and of 22 .2 A for compound II .
The molecules of these two compounds are not plate-like but rather rod-like.
The middle phenyl rings of the molecules rotate from the other two phen yl
rings by 86.3° and 135.8° for compound I; and by 84 . 9° and 84 .7° forcompound II. All molecules are arranged parallel along their long axes in
the crystals.
Compound I is a polymerizable monomer , it easily forms high molecularweight polymer upon heati ng without any initiators at about 140°C . Its
high polymerizability might be explained b y the fact that the molecules
are packed such that the lateral vinyl groups of neighbouring molecules
are closely correlated with a distance of only 4 . 7-5.6 A and the energyfavorable parallel moleculararrangement , which is similar to thearrangement of the mesogens in its po l ymer.

(1] Zhou, Q. F., L i, H. M . , Feng, X. D., Macromolecules , 1987, 20, 233.
(2 ] Zhu, X. 1. , Yang, Q . C., Zhou, Q. F., Chinese J . of Polymer Science,
1992, 10, 187.

15T-43

UNUSUALLY SHORT ETHYLENE BOND LENGTH AND
LARGE AMPLITUDE TORSIONAL MOTION OF(E)-STILBENES IN CRYSTALS
K. Ogawa, S. Yoshimura, andY. Takeuchi, Department of Chemistry,
The College of Arts and Sciences, The University of Tokyo, Komaba,
Meguro-ku, Tokyo, 153, Japan T. Sano, Mitsubishi Oil Co. Ltd.,
Ohgimachi, Kawasaki-ku, Kawasaki, 210 Japan and K. Toriumi, Dept.
of Material Science, Faculty of Science, Himeji Institute of Technology,
Harima Science Park City, Kamigori, Hyogo, 678-12 Japan.
This paper answers a long standing problem on the X-ray structures of(£)-stilbene (Ogawa, Sano, Yoshimura, Takeuchi & Toriumi, 1992).
X-ray diffraction analyses of (£)-stilbene s 1 - 6 revealed that the X-ray
structures of these compounds commonly show an unusually short bondlength for the ethylene bond and strong temperature dependence of themolecular structure. No confirmation of these anomalies could be
detected in solution NMR or UV spectroscopy. It is concluded that the
short ethylene bond is an artifact of dynamic averaging originating inlarge amplitude torsional vibration of the C-Ph bonds during which the
movements of the benzene rings are restrained minima. The observed
temperature dependence of the molecular structure is ascribed to theslight energy difference between conformers that are interconverted by
the torsional vibration.

R4

R3

R1

R2 R3 R4H
H
2 Me H
3 Me H

H H
H H
Me H

4 Me H H Me
5 Me H Me Me
6 Me Me H H

R2
R3

Reference
Ogawa, K., Sano, T., Yoshimura, S. , Takeuchi, Y. & Toriumi, K.
(1992). J. Am. Chern. Soc. 114,1041-1051.

15T-44

UNUSUAL STRUCTURE OFPENTAFLUORONITROSOBENZENE
H.G. Ang, W.L. Kwik, K.K. Ong and W.Y. Leong, Department of Chemistry,
National University of Singapore, Lower Kent Ridge Road, Singapore 0511 .

The title compound was prepared from oxidation of pentafluoroaniline (28 mmole)by 90% hydrogen peroxide (5 ml) and 90% formic acid (20 ml) in dichloromethane(125 ml) under reflux. The product was purified by vacuum fractionation to afford
a volatile blue fraction in dichloromethane and a less volatile brownish green
fraction . Blue and green variations of C 6F5NO crystallised out from the respective
fractions. Interestingly, structure determination of blue pentafluoronitrosobenzene(I) at 218K by single-crystal X-ray diffraction methods revealed the co-packing of

hexafluorobenzene molecules and cis-dimeric units of C6F5N O.
Crystal data: [C 6F5NOh[C 6F6] monoclinic, space group P21 / c
a 9.132(2), b 16.993(5), c 11.387(3) A, (3 110.96(3) 0 •
The

N-N

distance[1.335(7)

Al

in

the

cis-dimer[ cis-

azo(pentafluorob enzene)dioxide] does not differ significantly from those in theanalogous nitrosobenzene cis-dimer and nitrosomethane cis-dimer, but is 0.09 A
longer than the N-N distances in trans-azobenzene and trans-p-azotoluene.
The pentafluorophenyl rings are essentially planar. As with nitrosobenzene and anitrosonaphthalene, no trans-dimer has been detected in the solid state for I.

15U-46
THE CRYSTAL STRUCTURE OF[ISOTHIOCY AN A T0(1,4,8,12TETRAAZACYCLOPENT ADECANE)COPPER(II)]THIOCYANATE
1Tsong-Jen Lee, 1c.-T. Tsai, 2wei-Jen Lan & 2chung -Sun Chung
1 oepartment of Physics, 2oepartment of Chemistry, National
Tsing Hua University[Cu(C 11 H26 N4 ) (NCS)] (SCN), Mr = 394.06, Monoclinic P2 1 /c, a=
9.058(1),b = 14.729(1), c = 14.443~2) A, p = 107.24(1)•, u =.l..(Moka)= 0.71073 A,
1840.4 A3 , Z=4, Dx = 1.41 Mg·m-,~=1 . 41mm- 1 , F(OOO) = 828, room temperature (300±5 k), final
R=0.056, WR =0.055 for 2085 observed reflections. The coordination about Cu(II) is a distorted square pyramid withtetraamine equatorial and the N atom of the isothiocyanato
group axial. The four donor N atoms of the macrocyclic ligand
lie almost in a plane with maximum displacement of 0 . 038 A.
The copper(!!) atom is 0.207 A out of the basal plane of thefour nitrogens toward the isothiocyanato group. The axial
Cu(II)-N bond distance 2 .201(5)A is significantly longer thanthe equatorial Cu(II)-N bond distances, 2.035(6)-2.062(6) A.
The isothiocyanato ion is almost in a straight line, ( angle
N(5)-C(12)-S(1)= 179.1°). This bond angle and the bondlengths suggest that the resonance structure M-N=C=S ispredominant in this crystal. The configuration of the fourchiral nitrogen centers is (1RS, 4RS, 8SR, 12RS) .The figure
with theperspective view of the molecule,ashowsdisplacements of Cu and N atoms indicated.

*This work is supported by the NSC Grant, ROC, under thecontract number NSC81-0228-M-007-44 and NSC-81-208-M007-86 ·15 U-47
STRUCTURE OF A HEXANUCLEAR BIMETALLIC
CLUSTER (J.1-H)OssCu(C0)18PPh3
H.G. Ang, W.L. Kwik, K.H. Ng, Department of Chemistry, National University ofSingapore, Lower Kent Ridge Road, Singapore 0511, Republic of Singapore.

The hexanuclear bimetallic cluster ().l-H)Os 5 Cu(C0) 18PPh 3 (1), was prepared fromthe reaction of ().l-H) 2 0s 3(C0) 10 and (CF 3 COOCu)PPh 3 . (I) was shown by X-ray
analysis to consist of a pentaosmium framework with a copper atom bridging fourof the osmium atoms to form a puckered "ladder-like" arrangement based on four
triangular units. The dihedral angles are: Os(1 )0s(2)0s(3) and Os(2)0s(3)Cu(1),20.7°;

Os(2)0s(3)Cu(l)andOs(3)0s(4)Cu(1 ),26.5°; 0s(3 )0s(4)Cu(1)and

Os(4)0s(5)Cu(1), 25.1 °. It is interesting to note that the bond distances between
Cu(1) and the four Os atoms are almost equal, being 2.589(2), 2.673(2), 2.663(2)and 2.663(2) A. The three longer Cu-bridged Os-Os bonds are also of similar
length, being 3.000(1), 3.041(1), 3.069(1) A. A bridging hydride was detected to beeither bridging Os(4)-0s(5), Os(5)-Cu(l) or Os(4)-0s(5)-Cu(l).

Crystal data

: ().l-H)Os 5Cu(C0) 18 PPh 3 (I), monoclinic, space group P2 1 /n,

a = 16.072(4), b = 14.834(2), c = 18.032(4)A, ~ = 100.97(2)z = 8.

0and15U-48
STRUCTURAL STUDIES OF THE COMPLEXES OF
COPPER(!) HALIDES WITH ETHYLENE THIOUREA AND
sym-DIPHENYL THIOUREA
P. Thavornyutikarn, Department of Chemistry, Chiangmai University,
Chiangmai 50002, Thailand, and Y. Wattanakanjana and C.Pakawatchai,
Department of Chemistry, Prince of Songkla University, Hat Yai 90112,
Thailand, and B. W. Skelton and A. H. White, School of Chemistry,
University of Western Australia, Nedlands, WA 6009, Australia.
Complexes of ethylene thiourea(etu) and sym- diphenylthiourea (s- dptu)
with copper(!) halides (X=Cl,Br,I) were synthesized by varying the molerati.o of copper halides and ligands in appropriate solvents; water, ethanolor acetone. Qualitative elementary analysis was performed using X -rayfluorescence spectrometry. The percentage of copper and of sulphur ofthese complexes were determined by titrimetric methods. These
complexes form different stoichiometries and geometries which are
expectedtobe[(etu)2CuC1]2, (etu)3C u Br,[(etu)2Cul]2,(s- dptu)2CuCLH20, (s- dptu)2CuBr and (s- dptu)2Cul. Crystal structuresof the complexes [(etu)2CuC1]2 and (s- dptu)2CuCLH20 determined bysingle crystal X-ray diffraction methods revealed the former complex to
be dimeric with two different geometries of Cu(I) and the latter complex
to be monomeric solvated by a water molecule with tri gonal Cu(I)geometry . In both complexes the ligands coordinate to Cu atoms via S
atoms.
Crystal data : [(etu)2CuClh monoclinic, space group P2i/c (No. 14)
a 7.516(4), b 18.686(6), c 16.376(6) A, p 94.73(4t(s- dptu)2CuCLH20 triclinic, space group PI (No. 2)
a 12.747(8), b 12.118(7), c 9.609(6) A, a 68.96(5),13 73.28(5), y 88.46(5) 0 .

15U-49

THE ROLE OF Ncs- ION IN Cu(II) COMPLEXES WITH
DEPROTONATED DIAZADIOXIMES AND TETRAAMINES
Tahir H.Tahirov, Tian-Huey Lu, Yun-Long Hsieh & Chung-Sun Chung
National Tsing Hua University, Hsinchu, Taiwan 300, ROC
How can the linear Ncs- ion enter into the coordination sphere of thenamed type of Cu(II) complexes, with N or S, or both atoms
simultaneously? To solve this question we studied the structures of(A) Thiocyanato[3,9-dimethyl-4,8-diaza-3,8undecadiene-2,10-dione
dioximato(l-)]copper(II), Cu(NCS) (02N4CuH19), triclinic, a=7.275(3),b=7.7110(7), c=14.293(1) A, a=90.152(7), ~=98.77(1), y=100.49(2) 0 ,sp. gr. PI, Z=2, 4193 refl., R=0.062;(B) Isothiocyanato[3,10-diethyl-4,9-diaza-3,9-dodecadiene-2, 11-dione dioximato(l-)]copper(II)(Tahirov, Lu, Luh & Chung, ACA meeting, 1992); (C) Isothiocyanato{uthiocyanato-di -[N ,N'-bis(3-aminopropyl-ethylenediamine )] }copper(II)dithiocyanate hydrate, [Cu(NCS)(N4CsH22)]2 (SCN)2•H20, monoclinic,
a=9.932(3), b=l3.934(7), c=1 2.137(2) A, ~=98.35(2) 0 , sp. gr. Pn , Z=2,
2120 refl. , R=0.031.
The number n of CH2 links in the poly-ethylene N,N' bridge in complexes(A) and (B) essentially influences the Cu coordination with the Ncsgroup. The geometry about the Cu atom in both (A) and (B) is distorted
square-pyramidal with four N atoms of the diazadioxime equatorial, bu t
the axial positions in (A) and (B) involve different atoms of the Ncsgroup . In (A) with n=3 the axial position is occupied by the thiocyanate S
atom, the Cu-S distance being 2.520(2)A. In (B) with n=4 the axial
position is occupied by the isothiocyanate N atom with Cu-N distance
2.147(4)A. Unlike (A) and (B), the crystal structure of (C) consists of not
one but two crystallographically independent molecules (Cl) and (C2)bonded with the interaction Cu ... S 3.059(3)A. The coordination geometry
about Cu in (Cl) is square-pyramidal with the tetraamine N atom s
equatorial and the isothiocyanate N atom axial. But in (C2) the S atomfrom the bridging Ncs- group in another axial position has squarebipyramidal geometry. The axial distances Cu-N for (Cl) and (C2) are
2.261(8) and 2.372(9)A respectively.
This work was supported by the National Science Council, ROC, under
grants NSC81-0208-M007-110 and NSC81-0208-M007-86.

15U-50MAGNETO-STRUCTURAL CORRELATIONS OF DIMERIC
COPPER(In TRICHLOROACETATES

Hidehiro Uekusa, Department of Chemistry, Tokyo Institute of Technology, Tokyo 152, Japan, Shigeru Ohba, Department of Chemistry,
Keio University, Yokohama 223.
The structures of sixteen copper(II) trichloroacetate dimers havebeen determined by single-crystal X-ray diffraction in order to establish the correlations between the - 2J values, a singlet-triplet
energy separation due to anti-ferromagnetic spin-exchange interaction, and the deformations of the cage structure.• In the crystals of
the compounds which have small -2J values, less than 200 cm- 1 ,the coordination geometry around the Cu atom is deformed fromsquare-pyramidal (SP) to trigonal-bipyrarnidal (TBP)(Fig. 1) , andthe Cu · · ·Cu interatomic distance is elongated (3.112(3) - 3.261(1)A). The tendency that the longer is the Cu· · ·Cu distance, the smaller
is the - 2J value is observed (Fig. 2). This indicates that the spin
super-exchange interaction is weaker in the TBP than in the SP
structure. The reason may be as follows ; The magnetic orbitals in
the TBP structure mainly consist of the copper d,, orbitals, which
are directed perpendicularly to each other at the two Cu atoms, andoverlap only slightly with each other on the bridging carboxylate ligands. Therefore the spin-super exchange interactions are suppressedby the TBP deformation.

....---------,
SP

TBP
50
2.7

Fig.l (Cu(ClaCCOO), 2,3-Me,-py),
Chlorine atoms are omitted for clarity

2.8

2 .9

3.0

3.1

3.2

3.3

Cu ... Cu (AlFig.2·uekusa, H., Ohba, S., Tokii, T., Muto, Y., Kato, M., Husebye, S., Steward , 0. W., Chang,
S.-C. , Rose , J. P., Pletcher , J . F. & Suzuki, I. (1992) .Ac ta Cryst. 848 , in press.

15U-51
THE STRUCTURAL CHARACTERIZATION OF[(cy)3PIAgpy AgiP( cy)3]
Effendy, and Allan H. White, Department of Physical and Inorganic
Chemistry, University of Western Australia, Nedlands, W. A. 6009.
l : l Complexes of silver (I) chloride and bromide with the bulky
phosphine ligand L = P(cy)3 (cy = cyclohexyl) have been structurally
characterized as centrosymmetric dimers, LAgX2AgL, suitable crystals
being obtained from acetonitrile or pyridine.l The iodide complex was
obtained in a satisfactorily crystalline form only from pyridine, as ahemisolvate. Surprisingly, this complex provides an example of "crevice"coordination of pyridine ligand, a previously recorded example being[(MoO )2( C3H9P S2)4(0S)zpy] .2 Crystal data monoclinic, C 2/c,
a= 9.313(7)A, b = 17.03(3)A, c = 28.23(1)A, ~ = 93.17(5) 0 , Z = 4 . Two
projections of the molecule are shown, a two-fold axis passing through thepyridine.

ab[(cy)3PIAgpyAgiP(cy)3],
projected (a) down the two-fold axis; (b) normal to the two-fold axis

Interatomic distances and angles
Primed atom lies at (1-x, y, 1/2-z)
Atoms
Ag-I
Ag-I'
Ag-P
Ag- N(l)Ag .. Ag'I.. I'

distance( A)
2.822(1)2.857(2)2.415(3)2.76(1)2.977(2)4.548(3)Atoms
I- Ag- I'
I- Ag- P
I'- Ag- p
I- Ag- N(l)I'- Ag- N(l)P- Ag- N(l)Ag- I - Ag'
Ag-N(1)- Ag'

106.43(5)128.56(8)122.43(8)88.1(1)
87 .4(1)107.9(2)63.24(4)65.3(3)

1. Effendy and A. H. White, Unpublished work.
2. M. G . B. Drew, P. C. H. Mitchell and A. R. Read, J. Chern. Soc. ,Chern. Commun., 1982, 239.

15U-52
NOVEL INTERPENETRATING MOLECULAR
FRAMEWORKS DERIVED FROM AgTCM
Stuart R. Batten, Bernard F. Hoskins, and Richard Robson.
Inorganic Section , School of Chemistry, Unive rsity of Melbourne ,Parkville, Vic 3052, Australia.

The construction of large, open frameworks with unusual structuralprope rti es has been the foc us of recent research. One consequence ofassembl ing such structures is the interpenetration of two or more identicalframewo rks.
The recrystallisation of AgTCM (TCM = tricyanomethanide , C(CN)3-)
from acetonitrile, yields the compo:md AgTCM(MeCN). The structure ofthis compound is very similar to AgTCM. AgTCM consists of layers of two
infinite, corrugated , interwoven hexagonal "chicken-wire" sheets stacked
one on top of the other. The corrugation of the sheets, which allows theinterpenetrating, is produced by the Ag havin g a distorted trigonal
geometry. In AgTCM(MeCN), thi s is re placed by a tetrahedral Ag, whichis also three-coordinate with respect to the sheets, but has a fourth bond toacetonitrile, which projects into the space between the layers.
Reaction of AgTCM in acetonitril e with a number of linear bridg ing
ligands gives a new type of structure possessing a five coordinate sil ver.
fhis time the fra mework consists of layers of planar infinite, hexagonal"chicken-wire " sheets linked to each other by the bridges connected to theax ial pos itions of the tri gonal bipyramidal si lver. The structure thenconsists of two of these frameworks interpenetrating each other, such thatthe bridges of one framewo rk pass through the cen tre of the hexagonalrings in the sheets of the other.
While this structure is found for the pyrazine and dabco bridges, the 4,4'bipyridine (bipy) bridge is found to behave slightly differentl y. In thisstructure the bridge connects the layers at an angle of about 70°.

15U-53

Ag(l) AS(lli) COMPLEXES WITH a-HYDROXY ACIDS:STRUCTURES OF ISOMORPHOUS COMPLEXES{AgsAs4(C4H206)4(H20)s(X)}n{C4H206 = (+)TARTRATE(4-) AND X=N03-,CI04-} WITH
Ag-As BONDS
Graham Smith, Raymond C. Bott and Dalius S. Sagatys, Centre for Instrumental andDevelopmental Chemistry, School of Chemistry, Queensland University of Technology,
Brisbane, 4000, Australia.
Silver(!) has proved to be a considerable utility in the stabilization of crystalline
complexes of antimony(III) with hydroxy acids (Sagatys et al. , 1991: Hartley et al.,1991) . As an extension of this project in our laboratories, to include complexes ofother Group 15 metal ions with carboxylic acids, the isomorphous silver(!) arsenic(III)complexes with tartaric acid, having formula {Ag5 As4 (C4H2 0 6)illzO)s(X)}., [(C4HzOJ= tartrate(4-); X = N0 3• (1) and Cl04• (2)] have been prepared and characterized by
X-ray diffraction . Crystals are monoclinic, space group P2 1 with Z = 2 in cells ofdimensions a= 12.057(3), b = 10.651(1), c = 12.496(3), (3 = 93 .37(2)0 , (I) and a= 12.170(5) , b = 10.570(1), c = 12.634(4)A, (3 = 92.74(2)

0

,

(2) .

The twocomplexes have polymer framework structures based upon two configurationallyidentical [ASz(C 4H2 0 6) 2f· dimer anions , analogous to these in the tartar emetic structure[As-O(hydroxyl): 1.790(7)- 1.804(8)A (1); 1.767(4)- 1.818(4)A (2). As-O(carboxyl):
1.966(8) - 2.118(8)A(1); 1.940(5) -2.127(5)A (2)]. However, an arsenic of one of the
dimers forms a short bond to a silver atom [As-Ag , 2. 729(2)A (1) and 2. 728(1)A (2)],completing a trigonal bipyramidal coordination about arsenic. The arsenic dimers arein tum linked by a chain of five silver cation centres via both carboxyl and hydroxyl
oxygens which also form intra-chain links.

All five water molecules are bonded tosilver ions, with three of them bridging silver centres. The main difference between
the two structures arises from the isomorphous replacement of the nitrate group in
structure ( 1) by a perchlorate in structure (2) .

Sagatys, D.S., Smith, G., Lynch, D.E. & Kennard , C.H.L., (1991), J. Chern. Soc.

Dalton Trans., 361-364.
Hartley, D.W., Smith , G. , Sagatys , D.S. & Kennard, C.H. L., (1991), J. Chern. Soc.

Dalton Trans. , 2735-2739.

15U -54
THE CRYSTAL STRUCTURE OF Au(PPh3)z(PhCSz)
Ju-Chun Wang, Department of Chemistry, Soochow University, Taipei, Taiwan
11102, REP OF CHINA
The title compound have been synthesized by reacting Au(PhCS 2 ) with excess
triphenylphosphine in DCM solution. The dark reddish brown crystals suitablefor X-ray analysis were grown from DCM/Et20 mixed solvent system. The
crystal structure has been determined at room temperature. The Au-P distances
are 2.328(2) and 2.317(2),6., respectively. The Au-S distances are 2.627(2) and2.859(2),6., which are slightly longer than the sum of the covalent radii, 2.37,6., ofthese two atoms. The bonding interaction in between the dithiobenzoate ligand
and the Au atoms is significant. This significant bonding interaction is also
reflected on the non-linear angle of P1-Au-P2, which is 136.66(6)0. Thus, thecoordination number about Au center is 4, and the coordination geometry about
Au center is distorted tetrahedron.
Crystal Data: Au(PPh 3h(PhCS0 is monoclinic, a=9.190(2), b=19.561(6),c=20.734(3)A, {J=98.54(1)o, V=3685.7(15)A.3, Z=4, spacegroup P2Jn (NO 14). Final R values are R=0.044,
Rw = 0.057 and S = 1.607 for 4359 observed reflections and223 parameters.

15U-55
THE CRYSTAL STRUCTURE OF A PLATINUM(II)COMPLEX OF L-METHIONYL-GLYCINE
IL.S.hi.. T.W. Hambley & H.C. Freeman, School of Chemi stry, University of Sydney ,Sydney, NSW 2006, Australia.
The investigation of the interactions of platinumcm with ami no acids, peptides and related
ligands is interesting for two reasons. (i) It conUibutes to a better understanding of thevarious reactio ns that platinum(II) undergoes in the body including those which conUibute to
the toxic side effects of cisplatin and to its deactivation. (ii) Pl atinum(II) has been used
extensively to prepare isomorphous heavy-atom deri vatives for protein structure analysis. The
present re searc~ is aimed at providing models for the interaction of pl atinu m(II) withproteins .
The discovery that the [PtC1 4 ]2· complex ion binds preferentiall y to the methio nine (Met)residues in proteins, especial ly when these are located at the surface of the protei n molecule,aroused an interest in the platinum(m -methi onine compound. It has also been reported thatmethionine and its metallic complexes show some antiviral and carci nostatic properties.
Here the complex dichloro-L-methionyl-glycineplatinum (II) monohydrate [Pt(L-MetGly)Cl2].H20 has been prepared by the direct interaction of PtC14 2- with the free li gand inaqueous soluti on, followed by recrystalli zation from dilute HCL.

Crystal Data: [Pt(L-Met-Gl y)Cl 2].H20, orthorhombic, space group P2 12 12 1, Z 4, a 5.004(2),b 6. 761 (2) , c 39. 159(7) A. The crystal s tructure has been determined bysingle-crystal X-ray diffraction methods and refined to a conventional
residual ,R of 0.037.
The structure of the complex may bedescribed
asa platinumatom
surroundedinasquare-planar
configuration by two chlorine aloms
and a L-methionyl-glycine ligand. The
latter is coordinated to platinum(II)atom via the N(amino) and S(thioether)atoms to form a six-membered chelate
ring. The protonated peptide N, thepeptide 0 and protonated carboxylgroup are not coordinated. The
conformation of the six-memberedchelate ring is a 'chair' conformation
with the peptide group and the S-CH 3
in equatorial positions.

15U-56
CRYSTAL STRUCTURE OF POTASSIUM THEOBROMINIUMTETRAKIS(THIOCY ANATO)P ALLADATE(II)T . Giraldi and M. R. Taylor, School of Physical Sciences, The Flinders Universityof South Australia, G.P.O. Box 2100, Adelaide 5001, Australia, and M. I. MorenoVida, J . Ruiz-Sanchez, J . M. Salas-Peregrin and E. Colacio, Departmento de Quimica Inorganica, Facultad de Ciencias, Universidad de Granada, 18071 Granada,
Spain.
In the course of attempting to prepare palladium complexes of xanthine derivatives,
red crystals were obtained from a mixture of (10 ml) K 2PdCl 4 (0.33 g, 1 mmol),
KSCN (0 .97 g, 10 mmol) and a suspension of 2 mmol of theobromine refluxed in
100 ml ethanol. X-ray crystal structure analysis has shown that the solid is thepotassi um theobrominium salt of tetrakisthiocyanatopalladate(II) . Theobromine isprotonated at Nl. The tetrakisthiocyanatopalladate( II ) ion is very nearly planarwith thiocyanate groups making a swastika pattern around the palladium .
A search of the Camb ridge Structural Database has shown that this is the firstexample of the tetrakisthiocyanatopalladate(II) anion whose structure has been
determined, at least in structures containing organic carbon. The planar anions
and the theo brominium cations lie parallel to each other in the structure and arestacked alternately. Potassium ions have a distorted 7-fold co-ordination.
Crystal Data: KC 7 H8 N4 0 2Pd(SCN)4.H20 monoclinic, spacegroup P2J/c (No.14)
a 15.1 72 (2), b 7.173(1), c 18.619(2) A, f3 = 95.98(1) 0 .

The Pd-S distances do not differ significantly and average 2.338(2) A. The anion
has very close to c4h symmetry although this is not required crystallographically.
The anion and base cation will be compared with similar species in other structures.

,,

15U-57'PLATI_NUM, PALLADIUM AND RHODIUM COMPLEXESWITH MET ALAPENT ALENE FRAMEWORK
M. Yasui, S. Yoshida and F. Iwasaki, Dept. of Applied Physics andChemistry , The Univ. of Electro-Communications, Chofu, Tokyo 182,
Japan
6a-Thiatetraazapentalene derivative (1) which contains the hypervalentsulfur atom (Iwasaki et al.) was found to give novel carbene compl exes
treating with Pt(PPh3)4, Pd(PPh3)4 and Rh(PPh3)3CL X-ray investigations
have revealed that the central sulfur atom in 1 was substituted by a me tal
atom and the thioamide group on one or both sides was rotated to have themetal-sul fur bond in the resulted meta lapental e ne framework . The
molecular structures of platinum (2) and palladium (3) complexes werevery similar. Each metal atom is coordinated by S, S, C and P atoms in asquare planar geometry . The M-S (2.28-2.29 A), M-C distances (2 .01 A)
and S- M-S (169°), P-M-C angles (177) in 2 agree well with those in 3.
The rhodium complex (4) h as S -Rh-N bond s in contr as t to Pt or Pd
complexes that have S-M-S bon ds. The Rh atom is coordinated by six
a toms in th e di storte d oc tahedron wi th Cl, N, S, and C ato ms in an
equatorial plane and two triphenylphosphine groups in apical posi tions. A
pseudo mirror relating two PPh3 groups is lying on the metalapentaleneplane. Rh-S 2.34, Rh-C 1.94A and P-Rh-P 174, Cl-Rh-C 174 and S-Rh-N
162° were fo und. The s teri c hindr a nce due to two PPh 3 led th isasym metric S-Rh-N bond. On the other hand, Pt and Pd compl exes w ith
S-M-N bond s were found in solution, which transformed graduall y to SM-S structure.
Crysta l data:
space gro up abc /A~( No of observed R
2
P21/a 16.419(4) 10.415(2) 16.748(4) 112.72(2) 4114
0.043
3
P21/a 17.667(5) 11.001(2) 15.658(4) 112.26(2) 5005
0.068
4P21/n 10.302(2) 36.241(5) 11.958(2) 101.04(2) 6175
0.074

(I

(I

(I

sloYols MeNioloiNMe sloYoiNMe
Me./N- S Me S-M - S M
e./N -Rh-S/i "-..,_-N...._

I

P(Ph)31

2 M=Pt;3 M=Pd

P(Ph)3 Cl

P(Ph) 3

4

Iwasaki, F., Murakami, H., Yamazaki, N., Yasui , M., Tom ura, M. and Matsumura, N.

(199l)Acta Cryst. C47, 998-1003

15U-58
THALLIUM-CONTAINING PLATINUM SULPHUR
COMPLEXES: CRYSTAL STRUCTURE OF
TISzPtz(PPh3)4PF 6
M S Zhou, L L Koh, Y Xu*, T SA Hor, PH Leung and K F Mok
Dept of Chemistry, National University of Singapore, S(0511)
A main group element, thallium(TI+) was, for the first time, successfully
introduced into platinum-sulphur complexes. The resulting compound
forms yellowish, diamond-shape crystalS. The structure has been
determined using X-ray diffraction.
Crystal data: TIS2Pt2(PPh3)4PF6, Monoclinic, Space group ?2/n, Z=2
c=l8.348(5)A
b= 10.544(3 l A
a=l8.128(2)A,~=107.37(4)a=y=90.ooo
R=0.0470 for 3634 observed reflections
0

The crystal structure (Fig 1) shows that the TIS2Pt2(PPh3)4PF6 moiety
has a hat-like geometry. TI+ sits on top of the 2-fold axis passing throughthe complex. Tl+ is strongly bound to two, 2-fold axis related, S atoms
with Tl-S=2.764A and S-Tl-S=68.9°. There is secondary interaction
between Tl+ and two 2-fold axis related Pt atoms with Tl-Pt=3 .379A and
Pt-Tl-Pt=58.3°, suggesting substantial covalency in the Tl-Pt bonding.
The geometry of the Tl, Pt and S cluster allows stabilization of this one
centre(Tl+) platinum-sulphur complexe, differentiating it from transition
metal analogues, through electron delocalization. It is interesting to notethat the PF 6 counter ions are far from the positive charge centre Tl+,
which again supports the delocalization function of the cluster. Pt,
coordinating with two S and two P, forms a plane with average PtP=2.304A, Pt-S=2.380A, P-Pt-P=97.0°, P-Pt-S=87.4°, S-Pt-S=82° and SPt-P=920.

15U-59

STUDY OF SYMMETRY AXIS OF THE VANADYLCOMPLEX IN V02+ DOPED Cd(C4H204).2H20 SINGLECRYSTALSR S Bansal and V P Seth, Dept of Physics, M.D. University Rohtak,
Hryana, India.
Single crystals of Cd(C4H204) doped with V02+ were grown at room
temperature (300K).
The tran sparent crystals grew as prisms
approximately rectangular in shape and slightly elongated along the aaxis with the (011) faces well developed, Cd(C4H204 ) .2H20 ismonoclinic with space group P2uc[l]. the EPR spectra were recorded
along a-axis and c*-axis of the crystal at RT and LNT. Angular variationof the hyperfine lines recorded at RT in different planes indicate that
VQ2+ ion occupies a single site in the lattice. The hyperfine tensor A andthe g-tensor are found to be axially symmetric and co-axial for the V02+
complex. The V -0 bond direction determined from angular variation is
8=85° and ~=46° which shows the distorted octahedron around v+ (SeeFi gure). It is evident that this octahedron is quite distorted and thehigher symmetry (axial, C4v) of the vanadyl complex as indicated by the
EPR results demands a local relaxation around the impurity metal ion tocreate the observed axial symmetry of the vanadyl complex.
"

0(121

(
Q(2)

0(4)~7SJ ~ .

~~...,.;"';'-''<'«) M -27s1n,-,<O.S,05JG.S) --() 0( )
4

:(1

Ot2)
~
<:

f

oom'>
Reference: 1. M L Post and J Trotter, J Chern Soc (Dalton) (1974) 674.

15U-60
UNPRECEDENTED FRAMEWORK STRUCTURES: NEW
DERIVATIVES OF Cd(CN)2
Brendan F. Abrahams; Michaele L. Hardie: Bernard F. Hoskins andRichard Robson, School of Chemistry, University of Melbourne,
Parkville, Victoria, 3052, Australia, and Geoffrey A. Williams ,Australian Radiation Laboratory, Lower Plenty Road, Yallambie,
Victoria, 3085, Australia.
Cadmium cyanide and its derivatives have provided a diverse range of
3D -polymeric framework structures, which may lead to prototypicalstructures important for industrial processes such as heterogeneous
catalysis and molecular sieving. Although the structure of the parent
Cd(CN)2 involves two independent interpenetrating diamond-related
frameworks, newly discovered geometrical arrangements involving
Cd(CN)2 frameworks are based on either a single diamond-like lattice,linked 2D grids or a honeycomb-like arrangement.
Crystal structures of new cadmium cyanide derivatives obtained by thereacting Cd(CN)2 with N-donor ligands will be presented. The different
coordination numbers available to cadmium and the flexibility shown by
the usually rigid M-cyanide-M linkages have resulted in novel variationsof the known structural types of Cd(CN)z. The framework structure of
crystals of Cd(CN)z.l/2[4,4'-bipyridine] , for instance, consists of an
approximately trigonal bipyramidal Cd environment with bridging
cyanides bent so that the Cd(CN)2 framework forms a distorted diamondlike arrangement. Each rod-like bipyridine links two Cd centres in two
adjacent adamantane-shaped cavities of the diamond-like framework andpasses through the shared cyclohexane-like window. The Cd(CN)2
pyrazine structure consists of a single framework of pyrazine linked
andself- ca tenation ,exhibits
andgrids
Cd(CN)2
Cd(CN)2.2/3CH30H .l/3tetramethylpyrazine has a deformed honeycomblike Cd(CN)2 arrangement.
Solvated species of Cd(CN)2 exist as either diamond or honeycomb
related systems. The study of vapour-phase solvent exchange within such
crystals will also be presented. This study has demonstrated that solvent
exchange can be accompanied by an extensive topological reorganizationof the Cd(CN)2 framework where crystallinity, and even the single natureof the crystals involved, is preserved.

15V-62
BONDING DEFORMATION AND SUPERPOSITION EFFECTS
IN THE ELECTRON DENSITY
I. Oloysson, G.J . Mcintyre * & H. Ptasiewicz-Bak**

Institute of Chemistry, University of Uppsala, Box 531,
S-75121 Uppsala, Sweden* Permanent address: Institut Laue-Langevin,
156X, 380 42 Grenoble CEDEX, France.
** P ermanen t address: Institut e of Nuclear Chemistry and Technology,
Dor odna 16, 03-195 Warsaw, Poland
There appears to be conflicting experimental evidence on the redistributionof the electron density in the lone-pair and other regions of a molecule dueto the interaction with its nearest neigbours. In some experimental as wellas theoretical deformation density maps a decrease in the lone-pair density
has been reported, whereas in other cases an increase has been found. It
appear s that two major, counteracting factors are responsible for thesedifferences (apart from experimental errors in the diffraction studies andlimited accuracy in the theoretical calculations): an increase in the lone-pairdensity is expected due to the polarizing influence of the neighbours,
wher eas simple superposition of the isolated monomer deformation densities will lead to an apparent decrease due to the overlap with the negative
contours of the neighbouring atom. Depending on which of these factors isthe dominant one, an increase or decrease may thus be observed.
These facts will be illustrated by recent results on nickel sulfate hexahydrate and some other hydrogen-bonded compounds. The electron density
in NiSO, · 6 H 20 has been determined at room temperature and 25K bymultipole refinement against single-crystal X-ray intensity data. The
electron density based on the fitted deformation functions of all atoms inthe structure is compared with the individual densities calculated fromdeformation functions of only Ni or the separate water molecules. In thisway the effects of simple superposition of the individual densities werestudied, and a partitioning ofthe electrostatic and polarization contributions
to the hydrogen bonds and relatively weak Ni ··· 0 bonds attempted. Whenthe effects of superposition are removed the deformation density around Ni
shows just the features expected for Ni in a weak ideally-octahedral ligand
field. The individual deformation of the three crystallographically independent water molecules show that their interaction with the environmentis largely electrostatic. However, some polarization of the lone-pair densities
according to the coordination of the water molecules is clearly evident.
The spin density ofNiSO, · 6H2 0 has also recently been studied at 1.5K anda comparison is made with the charge deformation density.

15V-63
CORRECTIONS FOR EXTINCTION FROM EQUIVALENTREFLECTION INTENSITIES
E.N. Maslen & N. Spadaccini, Crystallography Centre, University ofWestern Australia, Nedlands, WA 6009, Australia.
Alternative procedures for correcting diffraction intensities for extinction
are b ased on different models of crystal micro-structure. Reliablecorrections require a correct theory of extinction, accurate intensity
measurements, and valid statistical procedures when deriving parametervalues. The widely known Zachariasen (1967) theory contains parameters
defining a mosaic distribution of micro-domains, which determine theextinction corrections. Such parameters can minimize a weighted sum ofsquares of differences between observed and calculated structure factors,
but if a modest change to the weight of a strong reflection changes
extinction corrections by amounts which standard tests indicate to besignificant when correcting for extinction as part of a structurerefinement, the validity conditions for least squares processes are unlikely
to be satisfied. Extinction corrections evaluated from diffraction
intensities for equivalent reflections with different path lengths provide an
independent check on values which minimize differences between
observed and calculated structure factors. The former techniqueeliminates correlation between extinction corrections and bonding electron
contributions to X-ray structure factors. The principles are not restricted
to any particular form of extinction formula. For X-ray studies on several
small ionic crystals corrections with the Zachariasen theory fromcomparison of equivalent reflections are markedly less than those which
minimize differences between observed and calculated structure factors.
Discrepancies originating in extinction parameter bias are exacerbated by
the unfavourable statistical distribution function of the residuals whenminimizing differences between observed and calculated structure factors.
Analysis of intensities for equivalent reflections, although moredemanding experimentally, provides least squares residuals closer to thenormal distribution required for reliable non-linear least squares
processes.
Zachariasen, W. H. (1967). Acta Cryst. A23, 558-564.

1 5 v- 64
ELECTRON DENSITY DISTRIBUTION OF A HIGHMELTING SUBSTANCE, TiN.
M. L. Kisono, Y. Kubota, M. Takata, and M. Sakata
Department of Applied Physics,Nagoya University, Nagoya, Japan
Titanium nitride TiN, has a NaCl type crystal structure, a high melting
temperature(-3200°C) , great hardness(l770kg/mm2), and high electric
conductivity (22-30J.!Qcm). It would be reasonable to expect very strong
chemical bonding in this substance. There have been several investigationsof the bonding in TiN, by both experimental and theoretical approaches .
It is often considered that chemical bonding in TiN combines ionic,
covalent, and metallic contributions in a rather complicated bonding state.
The purpose of thi s paper is to study bonding in thi s hi gh melting
substance via a precise electron density distribution which should beobtained by the Maximum Entropy Method(MEM).
MEM provides an electron density distribution, consistent with theobserved structure factors, which has least bias with respect tounmeasured structure factors. For a simple structure like TiN it is now
possible to derive a high resolution distribution from X-ray powder
diffraction data. The sample for this work was prepared b y gas
evaporation. Before measuring integrated intensities, the sample waschecked by co-scan observations and by electron microscopy, to ensure its
suitability for X-ray powder diffraction. The micrograph showed that theTiN particles are about O.lJ.lm cubed, and the co-scan profile was verysmooth, indicating that the sample was suitable for intensity measurementsby powder diffraction.
Intensities were measured with CuK a radiation, and using synchrotron
radiation with A.=0.9A at the Photon Factory. Line profiles werebroadened slightly, because of the small particle size. Only 10 structure
factors were measured from the CuK a experiment, and 22 with thesynchrotron. The resultant MEM density maps show no covalent bondelectrons between Ti and N atoms. The electron distributions around both
atoms are slightly non-spherical. In order to estimate ionic bonding
contributions, charges for Ti and N were calculated by integrating theelectron density within a sphere around the Ti and N sites. The resultsshows that both ions are positively charged, by about +2 for Ti andslightly for N. The electron density between Ti and N is rather high, i.e.
0.56(efA3) at the mid-point along the [100] direction. This strongly
suggests that metallic bonding predominates in TiN. The result ispreliminary because the limited number of reflections measured andcoarse pixel size (32x32x32 pixels per cell) may not justify final
conclusions. In order to improve the MEM map, an experiment using
MoKa radiation is in progress. Results will be presented at the meeting.

15V-65

ELECTRON DISTRIBUTION IN A CRYSTAL OF NiSz-xSex!.L. Tanaka. N. Ishizawa, Research Laboratory of Engineering Materials,
Tokyo Inst. of Technology, Nagatsuta, Midori-ku, Yokohama 227
F. Marumo, Department of Earth Sciences, Nihon University,
Sakurajosui, Setagaya-ku, Tokyo 156, andT. Miyadai, Faculty of Science, Hokkaido University, Kita-ku, Sapporo
060, Japan.
Crystals of NiS2 are known to show the insulator-metal transition on
replacing S with Se or applying pressure. The transition occurs aroundx:c=0.55 in the NiSz-xSe x solid solution!). In order to investigate thechanges of the electron density distribution in this solid solution system,
structure refinement was carried out on an NiS2-xSex single crystal with
x:c=0.37.
Crystals were grown by the chemical vapour transport method using Clz
carrier gas. Intensities were measured on a 4-circle diffractometer with
MoK a radiation monochromatized with pyrolytic graphite. On theresidual electron density maps, eight positive peaks corresponding to thefilled de orbitals of the Ni atom were found on the threefold axis and on
three pseudo-threefold axes of the NiS6 octahedron. Among them, six
peaks on the latter axes are located further from the two on the former
axis. This is slightly different from the electron distribution observed in
NiS22), where the eight positive peaks around Ni atom were located at
almost equal distances. The structural distortion of NiSz-xSex (x"'0.37) issimilar to that for NiS2 under high pressures3). Therefore, replacementof S with Se in NiS2 will have an effect similar to that of increasingpressure.
I) Bouchard. R. J. et al., Mat.Res.Bull. 8, 489-496 (1973).

2) Sato. S & Noda. Y., Abstract of the 38th Annual Meeting of Phys. Soc .
Jpn., 164 (1983).
3) T. Tsuchida, T. Komori & F. Marumo, unpublished work.

15V-66
ELECTRON DENSITY DISTRmUTION IN CRYSTAL OFDIPOTASSIUM TETRAFLUORONICKELATE, K2NiF 4
S.K. Yeh, S.Y. Wu andY!! Wang, Department of Chemistry, National
Taiwan University, Taipei, Taiwan, R.O.C.
Dipotassium tetrafluoronickelate(II), Mr=212.90 tetragonal, I~m, Z=2,
a =4.0130(6), c= 13.088(2)A,V=210.78(4) A3, T=300K, Dx=3.36 Mg.m3, MoKa, 'A =0.7107A, 11 = 6.56cm-i, F(000)=204, final R=0.018 for 698
unique reflections. The charge asphericity around the Ni atom caused by
the splitting of 3d orbitals is clearly observed in the deformation density.
Although the Ni site symmetry is D4h, the geometry around Ni ispractically 0 h, with Ni-F distances of 2.0065(3), 2.0062(8)A. The
d-orbital occupancies derived from the multipole coefficients are inaccord with the prediction of simple crystal field theory. The splitting of
the d -orbitals in D4h is eg, bzg (from t2g orbitals in Oh ), and big, a 1g
(from eg in 0 h) . The occupancies of all these orbitals are nearly equalwith eg the largest (1.57), big, and bzg the second (1.54), and a1 g thesmallest (1.51). Although the differences in occupancies are minimal, theasphericity around M can still be observed in the deformation density
distribution: Positive deformation density corresponding to eg (dxz, dyz)
orbitals, negative troughs corresponding to aig (d2 2) orbitals and slightly
negative density corresponding to big (dx2 -y2) and bzg (dxy) orbitals are
manifested around the Ni atom. The effect of extinction on the
deformation density will be discussed.

15V-67
SYNCHROTRON RADIATION VIBRATION AMPLITUDES
AND ap MAPS FOR K2SiF6 AND K2PdCI4
J. R. Hester, E.N. Maslen & N. Spadaccini, Crystallography Centre,
University of Western Australia, Nedlands, WA 6009, Australia
N. Ishizawa, Research Lab. of Engineering Materials, Tokyo Institute ofTechnology, 4259 Nagatsuta, Midori-Ku, Yokohama 227, Japanand Y. Satow, Faculty of Pharmaceutical Sciences,
University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113, Japan.
The value of synchrotron radiation in accurate electron density studies
is confirmed by the agreement between ~p maps measured with
'A = 0.9A and 0.7 A. High angle Fourier coefficients contribute lessstrongly to synchrotron maps than to maps for Mo Ka radiation.
Low noise in the 0.9A ~p maps for K2SiF6 justifies confidence thatphysical properties predicted from the one-electron density should be
reliable. Atomic charges for K, Si and F from all three data sets areclose to zero. The redistribution of electrons indicated by the ~p maps
mainly reflects exchange interactions, and does not support simple ionicand orbital models for the bonding in K2PdCl4.
Vibration parameters from least squares refinements on the three
K2PdCl4 data sets agree closely. The ~p maps for the synchrotron data
are consistent, and agree approximately with the Mo Ka map awayfrom the Pd nucleus. There is marked depletion of electrons near the
Pd core, and substantial movement of electron density near the
structural cavities. Whereas the Pd charge approximates +2, the K
charge is significantly negative. These charges reflect transfers ofelectron density from tightly packed to open regions of the structure,
which do not necessarily reflect atomic electronegativities.
Potassium hexafluorosilicate, K2SiF6, Fm 3m, cubic, M r= 220 .27,
= 539.73(3)A.3, Z = 4, Dx = 2.711Mg m-3, J.I.0.9 = 39.19,
ll0.7 = 19.09, J.I.Mo Ka = 20.07 cm-1 , F(OOO) = 424; T = 293 K, R = 0.021,
wR = 0.018, S = 4.519 for 155 unique reflections measured with 0.9A data.
Potassium tetrachloropalladate, K2PdCI4, P4/mmm, tetragonal M ,= 326.4,
a= 7.0750(5), c = 4.1158(5)A, V = 206.02(4)A3,Z=1, Dx= 2.631Mg m-3,
J.I.0.7 =41.874, J..L0.9 =86.075cm-1, F(000)=152, T= 293K, R = 0.021, wR = 0.020, S= 3.96 for 710 unique reflections measured with 0.7 A data.
a = 8.1419(3)A, V

15V-68SYNCHROTRON X-RAY STUDY OF THE ELECTRONDENSITY IN CORUNDUM a-Alz03
E. N. Maslen and V. A. Streltsov, Crystallography Centre, University ofWestern Australia, Nedlands, 6009, Australia, and N. Ishizawa,Research Laboratory of Engineering Materials, Tokyo Institute ofTechnology, 4259 Nagatsuta, Midori-Ku, Yokohama 227 , Japan, andY.
Satow, Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo
7-3-1, Bunkyo-ku, Tokyo 113, Japan.
The corundum a-Al203 structure can be classified as defining anarchetypal special class within the important perovskite ABX3 series. A
detailed understanding of its structural properties and electron density isan essential prerequisite to any classification of the physicalproperty/structure relationships for the perovskite series as a whole.
Over the past decade the electron density in single crystals of o:-A1203
has been measured in X-ray diffraction analyses several times using a
range of experimental techniques and crystal specimens. While thesestudies have much in common, there are significant discrepancies
between the deformation density maps reported. This motivated us tocarry out further independent studies, aimed at identifying the source ofthe differences between the published analyses.
The problem may originate in the common practice of determining
extinction corrections as part of the least squares minimizing ofdifferences between observed and calculated structure factors.
Deformation electron densities for corundum a-Al203 have beenmeasured using 0.7A and 0.9A synchrotron radiation as well as Mo Ka(1..=0.71069A) radiation. Two small specimens with natural faces anddimensions 20 x 38 x 38 x 38 !liD for crystal I and 20 x 44 x 44 x 44 !liDfor crystal 2 were prepared by flux growth methods. Structure factors
from two sets of synchrotron and three sets of Mo Ka tube data for thetwo crystals are remarkably consistent. An isotropic extinction
parameter refinement was compared with results from the method of
Maslen and Spadaccini (1992). The difference electron densities exhibit
approximate symmetry related more closely to the Al-Al contacts than
to the nearest neighbour Al-0 interactions.
Maslen, E.N. & Spadaccini, N. (1992). Acta Cryst. Submitted.

15V-69A SYNCHROTRON X-RAY STUDY OF ~pIN YzBaCuOs

R. M. Hsu and E. N. Maslen, Crystallography Centre, The Universityof Western Australia, Nedlands, WA 6009, Australia.
Diyttrium barium copper (II) pentox.ide, Y2J3aCu05, Mr = 458 .7, Pnma,
orthorhombic , Z = 4, a= 12.1793 (7), b = 5.6591 (5), c = 7.1323 (4) A,V = 491.58 (6) A3, Dx = 6.197 Mg m-3, A. = 0.9 A, J1= 28.893 mm-1,

F(OOO) = 812, T = 295 K. R = 0.020, mR = 0.022 for 16154 uniquereflections measured at the Tsukuba Photon Factory. Seven 0 atoms
are bonded to each Y atom. Each Ba atom is surrounded by eleven 0
atoms. Five 0 atoms coordinate pyramidally to the Cu atom. · Bond
lengths: Y-0 2.275(2)-2.379(1), Ba-0 2.611(2)-2.8312(3) and Cu-0
1.974(1 )- 2.016(1). The t.p map in (010) plane, y/b = 0.25, on which
two Y, one Ba and one 0 atoms are packed tightly is strongly depleted
near the metal nuclei. This reflects the depleting effect of exchange on
closed sub-shell density. The depleted region around each metal atom
has two hollous symmetrically dispersed along the a-axis as shown. The
depletion of electron density is reflected in charges of 2.8(1), 2.1(1),1.6(1), 2.4(1 ), and -1.6(1), -1.8(1) -1.8(1) e for Y1, Y2, Ba, Cu and 01,
0 2, 03 determined by projecting the t.p function onto atomic density
basis functions. The orientation of thedepleted regions provides significant
evidencefor

secondnearestneighbours interactions between Y, Ba
and Cu atoms, because the density isstrongly depleted along the line of themetal-metal vectors.

:......·

15V-70
STRUCTURE AND ELECTRON-DENSITY STUDIES OF A
TI2CaBa2Cu20s SUPERCONDUCTORBY SYNCHROTRON X-RAYS
Satoshi Sasaki, Res. Lab. Engineering Materials, Tokyo Institute ofTechnology, Nagatsuta, Midori-ku, Yokohama 227, and Takeharu Mori,
Photon Factory, Nat'l Lab. High Energy Physics, Oho, Tsukuba 305,
and Kenichi Kawaguchi and Masao Nakao, Sanyo Tsukuba Res . Center,
Koyadai, Tsukuba 305, Japan.
We have examined a high-Tc oxide superconductor of a ThCaBa2Cu20 sphase, based on the accurate X-ray intensity data above and below thecritical temperature Tc. The SQUID magnetometer measurement for the
single crystal showed diamagnetism below 108 K.
Single crystals were grown from an oxide melt by a slow-coolingmethod from 1233 K. Using spherical single crystals of 80 and 120!J.m cj> , integrated intensity data up to sin9/A. = 1.37 were collected at
296 K (Mo Ka) and 104 K (A. = 0.6 A; BL-lOA, Photon Factory).
Final R and wR values in the least-squares refinements (RAD Y) are
0.015 and 0.014 at 296 K and 0.014 and 0.016 at 104 K, respectively.
Cell dimensions and isotropic thermal Table I, Structu rnl parameters of 1l2CaBalCu10s
with anharmonic thermal parameters (xl 06).
parameters become smaller at lower
296 K
104 K
temperature, but little structural changes
3.8471(6)3.814(1)were observed (Table 1). Refinements
29.397(5)29.06( 1)
43 5.1(1 )422.7
wi th anharmonic Gram -Charlier
0.213209(5) 0.21324(2)thermal parameters showed large C113 Tl
1.342(2)0.896(9)0.547(6)0.272(5 )and diiii for both Tl and Ba atoms, CaBa 411!:liJ .
0.1208 18(6) 0.12075(2)0.671(2)0.307 (6)suggesting dominant anharmonicity in Cu 4e
0.05345(1)0.05338(2)0.514(2)0.227(4)the <110> and <111> directions, and 0(1) 8g
0.05263(6)0.05246(6)0.73(3)0.41(5)different values for dill! and d1133 at 0(2) 4<
0.14l08(9)0.1455(1)0.42(2)
1.02(4)
two temperatures.
Because the 0< 3> ,,0.2823(3)0.2822(2)4.9(2)
5.4(2)
existence of electron-pairing is strongly
2.2(1)
2.20(9)T1
suggested for high-Tc oxides and Cu2+
-0.006(3)0.004(1)0.27(1)2.01 (8)duu-0.00 1(3)0.027(2)ions have partially filled 3d orbitals,
0.0001 1(2)-0.0001 6(3)dnn
0.15(7)0.5( 1)electron density distributions around Cu s.
cu1
0.006(1)0.006(2)-0.11(7)atoms are discussed based on the
0.2l(3)du11-0.0 12(3)0.012(2)dun
0.00004(5)difference-Fourier maps obtained from
0.00012(3)dm1intensity data at two temperatures.
4~

CUJ

C)))

d l l )]C}J)

15V - 71

A HYDROGEN BONDING STUDY WITH CHARGE DENSITY
DISTRIBUTION AND INTERACTION ENERGY
Kuan-Jiuh Lin and Yu Wang*,
Department of Chemistry, National Taiwan University, Taipei, Taiwan,
R.O.C.
Dimethy lammonium hydrobi s(hydro gen squarate), (H2NMe2)+[H(HC404)2]-, was chosen for a hydrogen bonding study since it contains
both a symmetric (O···H ···0 distance 2.4320(6)A) and an asymmetric(O·· ·H···O distance 2.5646(6)A) H-bond in the crystal structure. The
compound crystallizes in the orthorhombic space group Peen. The cellparameters are a =l5 .614(3), b=6.0537(7), e=ll.691 (2)A , and Z=4 at
136K. Accurate X-ray diffraction data were measured with the Mo Ka
radiation up to 29 of 100°.
Deformation density distributions are illustrated in terms of f.Px-x,
f.PM- A and f.Ptheo; the former two are calculated from experimental datawith the spherical and multipole atomic model respectively, and the latter
one derived from ab initio calculation using a 3-210+ basis set with thegeometry obtained from the crystal structure. All these deformation
density distributions give consistent agreement. The ring strain of the
four-membered squarate ring is nicely demonstrated in the deformation
density map with the bonding electron density maximum directed
outwards from the C-C interatomic axis (exocyclic). The bonding electron
density maximum gives an angle of 110°, which is much larger than the
C-C-C angle of 90.80(4t.
The H-bonds of both symmetric and asymmetric types are illustrated in
the deformation density map. Their difference are quite obvious, with thedeformation density much more evenly distributed around the symmetricH-bond. In addition, the calculated interaction energies of the hydrogenbonding after BSSE(basis set superposition error) correction are -58.22
and -6.62 kcaVmole for the symmetric and asymmetric types respectively.
According to the energy decomposition analysis, the charge transfer andthe mutual polarization play important roles in stabilizing the linearhydrogen bonding system.

15V-72
SPIN AND CHARGE TRANSFER THROUGH HYDROGEN
BONDING IN [Co(NH3)s(0Hz)][Cr(CN6)]
Brian N. Figgis, Department of Chemistry, University of Western
Australia, Nedlands, WA 6009, Australia, Edward S. Kucharski, CSIRO
Division of Geomechanics, 39 Fairway, Nedlands, WA 6009, Australia,
and Mary Vrtis, Institut Laue-Langevin, Grenoble 38042, France.
The results of a polarised neutron diffraction (pnd) experiment on[Co(NH 3)5 (0H 2 )][Cr(CN)6 ] carried out at 1.5 Kanda magnetic field of 4.6
T with two crystal orientations are reported. Surprisingly, the experimentshows the presence of substantial amounts of spin in the cation, located on
both the cobalt atom and the ammine protons. The net spin population of
the cation is about one third of the total of the 3.0 unpaired electrons whicharise from the S=3t2 d3 system of the Cr3+ ion. As well as the net spintransfer to the cation, there is strong spin polarisation, so that regions ofnegative spin, where the direction is opposite to that of the majority spin,
are seen, including the cobalt atom. The [Cr(CN) 6]3- ion is strongly
perturbed, relative to that in the salt Cs 2 KCr(CN) 6 (Figgis, Forsyth &Reynolds (1987)).
Crystal data : [Co(NH 3) 5 (0H 2)][Cr(CN)6 ] rhombohedral , space group R3
a= 7.282(2)A, a= 97 .7 1(2), V = 374.6(2)N, Z = 1.

Local density functional (ldf) calculations on models contammg the[Co(NH 3) 6 ]3+ cation and one or two [Cr(CN) 6]3- anions show broad
agreement with the pnd results in giving considerable spin transfer to the
cation, with a strong involvement of the protons in the hydrogen bonds,
and large spin polarisation effects. These models contain the major
features of the hydrogen bonding interactions in the crystal. However,there are many points of disagreement in detail, at least partly due to thefact that a simple model to reproduce the complex hydrogen bonding
arrangements of the crystal is not possible.
Figgis, B.N., Forsyth, J.B . & Reynolds, P.A. (1987) Inorg . Chern. , 26, 101 105.

15V-73

THE ELECTRON DISTRIBUTION IN Nd2Fe14B
D. du Boulay and E. N. Maslen, Department of Physics,
University of Western Australia, Nedlands, WA, 6009, Australia.
Nd2Fe14B is ferromagnetic with a tetragonal structure, P421mnm, Z = 4,
a=8.816(5) and c=l2.229(6) at 295 K, R=.044, roR= .032 from 2936
unique reflections. The locally antisymmetric distribution of density near
the B atom in the x-ray difference density is consistent with sp2 bondingof B to the Nd atoms. The 4/ and 3d electrons for Nd and Fe atoms areextensively redistributed. The topography indicates that the Nd and Fe
sublattices are in parallel alignment. The densities near the two
crystallographically independent Nd atoms show evidence of uniaxial
anisotropy (see fig 1. below). The asymmetry is related to the structuralgeometry and the vibrational motion. Although the principal axes for the

t1p maps near the crystallographically independent Nd(l) and Nd(2)maps are parallel the magnitudes of the t1p

map features differ

significantly. That presumably reflects differing contributions to theintensity of magnetization in the material by those atoms.

(i) z = 0 plane(ii) Section perpendicular to (i)Fig 1. t.p near Nd(l). Map borders 2.0 x 2.0 A2, contour interval 1.0 e/A3

15V-74
ELECTRON DISTRIBUTION IN AIN FROM POWDER X-RAy
DATA BY THE MAXIMUM ENTROPY METHOD
K. Nakahigashi. H. Ishibashi. S. Minamigawa and M. Kogachi, Departmentof Materials Science, University of Osaka Prefecture, Gakuen-ch o,
Sakai 593, Japan.
AlN is a tetrahedrally coordinated m-v compound, forming a hexagonal wurtzi t e str uctur e which is regarded as partially io nic
and partially covalent. Gabe et a!. (1981) determined the valence
electron density in AlN by single crystal X-ray diffraction anddeduced that the bo ndi ng was probably more i onic than covalent.
In th e present stu dy,
two kin ds of AlN powder were used f or powder X-ray diffraction analysis. One was ultr afine particles prepared by a "nitroge n plasma-metal" reaction method and the otherwas powder with an average particle size of 1. 21J. m offered by
Tokuyama Soda Co .. Ltd. The former conta in s about 70% a l uminum .
Integrated intensities were estimated from profile fits by thecomputer program WPPD with split Pearson Vli func.tion.
The scalefactor was determined by an ordinary least - squares analysis using
th e POWLS computer program . Adoption of this refinement methodmeans that the phase prob l em can be so l ved by thi s process. Sakata
et a!. (1990) hav e report ed that the maximum - entr opy-method (MEM)
has advantages for evaluating high-quality electron-density maps
from X-ray powder data.
As a last step,
the MEM was used toobtain an electron-density-distri(11 0) PLA NE, SINGLE UNIT CELL
bution for AlN. The maps for thetwo kinds of the powder agree wellwith results from single crystal
X-ray diffraction which in dicat e
the lack of a distinct bond charge .
An example of the maps at the lower
electro n density regions for th e(110) plane of AlN obtained by MEM
is shown in the fig ure.

i

"'x
<

0
0

lA

RANGE=

0.000-

4.000,eA- 'Gabe, E., Page, Y. L & Mair, S. L. (1981) . Phys. Rev. 24.5634-5641.
Sakata , M. ,Mori,R.,Kumazawa,S . . Takata,M. & Toraya,H. (1990).J.Appl.
Phys. 23,526-534.
STEP = 0.4000

15V-75
ELECTRON DISTRIBUTIONS IN PURE METALS BY THE
MAXIMUM ENTROPY METHOD
Y. Kubota, M. Takata and M. Sakata. Department of Applied Physics, Nagoya
University, Chikusa-ku, Nagoya, 464-01, Japan.
We have already reported electron density distributions for FCC and HCP metals,
such as AI, Cu and Be , Mg and Zn in the annual meetings of CSJ l) • 2 ) andot her meeting 3) • 4l . It was found that HCP metals have characteristic electron
densities, with excess electrons around T sites, while there was no such features
for FCC metals. FCC metals can therefore be described as metals having nearly
free electrons. On the other hand , it was understood that HCP metals form
electronic layers by these excess and core electrons . The structure of electronic
layers in the basal plane was honeycomb shaped . These conclusions were obtained
directly from the electron density distri butions drawn by the Maximum Entropy
Method (MEM) which could be obtained by analyzing X-ray powder diffraction
data using no stru ctural models. The purpose here is to extend this work to theelectron density distributions of BCC metals, such as, W and Mo as part of aseries of studies on the structure of pure me tals at the electron level. Bot h Wand
Mo have rather high melting points whi ch may reflect strong chemical bonding.
Because of the short lattice parameters of the specimens, e.g. 3.1 650A for W
a nd 3.1470A for Mo, a very limited number of structure factors , less than 10,
could be measured if CuKa radiation was used. This is not sufficient to provide
reliable electron density maps by the MEM. The whole powder pattern of W was
therefore collected by MoKa radiation wi th 0.01 • steps in 28. The collection timewas 20 sec. Preliminary results show that there is no particular chemical bonding
in the BCC metals, W, which is similar to FCC metals. The remarkable difference
between FCC and BCC metals is that the electron densities between atomic sites
is much higher in the BCC metal than that in the FCC metal. Such high electron
densities around non-atomi c sites could be regarded as non-directional bonding
and seem to be consistent with the high melting points.
In the meeting, the results for W and Mo from much higher counting statistics
data will be presented.
References
1) Y . Kubota, M. Takata, & M. Sakata. (1990) Annual meeting of CSJ.
2) M. Takata, Y. Kubota, & M. Sakata. (1991) Annual meeting of CSJ.
3) M. Takata, M. Yamada, Y . Kubota, & M. Sakata.
to be published in Advances in X-ray Analysis, Vol. 35 , (1991).
4) M. Sakata, M. Takata, Y . Kubota, T . Uno, S. Kumazawa, & C.J . Howard.
to be published in Advances in X-ray Analysis, Vol.35, {1991).

15V-76
ON THE REPRODUCIBILITY OF ELECTRON DENSITYMAPS FOR IDEAL PEROVSKITES
E. N. Maslen and N. R. Streltsova, Crystallography Centre, Universityof Western Australia, Nedlands, 6009, Australia
Assessment of the significance of differences between theoretical andexperimental measurements becomes increasingly more difficult as theprecision that is claimed improves . It becomes correspondingly more
important to check the reproducibility of theory and of the experiments.
The IUCr's Commission on Charge,Spin and Momentum Density isundertaking an international project to assess the reproducibility bycomparing results obtained in different laboratories . In the case ofexperimental measurements reliable corrections for extinction areespecially important if a quantitative comparison is required.
The use of small crystals can reduce the severity of extinction as afactor limiting the precision of the measurements. However,small crystal
size limits statistical precision if a conventional tube source is used forthe measurements. This difficulty can be alleviated by using synchrotron
radiation. Measurements at two wavelengths provide additional
information on extinction, while simultaneously providing a check on the
reproducibility of the measured electron densities.
The compounds selected for the study are perovskites with the generalformula ABX3, with the ideal cubic KZnf3 used as a standard , forcalibrational purposes . KCoF3 has a closely similar structure. Single
crystals of KZnF3 and KCoF3 grown by slow diffusion from aqueous
solution exhibited mainly {100} and {111} faces. The dimensions ofspecimens selected for investigation, with sizes ranging from 15 to 75).l.rn were measured using an Philips 505 electron microscope . In apreliminary investigation to check their suitability for the project, data
sets for KZnF3 and KCoF3 crystals with maximum dimensions 49 and
66 ).l.m were measured on a Syntex P21 diffractometer. After correcting
the intensities for Lorentz factor, polarization and absorbtion analytically,
an isotropic extinction parameter was determined by comp aring
intensities of equivalent reflections with different path lengths. The
results are broadly consistent with earlier studies, but differ in details ofelectron density studies.

1 6A-1

NEUTRON SOURCES AND THEIR CRYSTALLOGRAPHICAPPLICATIONS
R. Chidambaram, Solid State Physics Division, Bhabha Atomic ResearchCentre, Trombay, Bombay- 400 085, India.
Most of the current research in neutron diffraction is being done withresearch reactors having thermal neutron fluxes in the range of 1014-1015
neutrons/cm2fsec. Some intense pulsed neutron source with higher fluxes
are also available. Several medium flux reactors incorporating improved
design features have recently become available in the Asian countries . For
example, the new indigenously developed 100 MW Dhruva reactor at
Trombay, India, has several new design features like tangential beamtubes, through-tubes , neutron guides, etc. There are also state-of-the-art
instruments like computer controlled single crystal diffractometers andpowder diffractometers using position sensitive detectors relating tocrystallographic investigations.
The applications range from structure refinements based on profile
analys is of powder patterns, studies of molecules of biological interest
using single crystals and low resolution studies using small angle
scattering. The scope of neutron powder diffraction studies has been
considerably enhanced by recent advances in the application of the
Rietveld profile refinement technique. It is now fairly straightforward torefine structures having more than 10 atoms/basis using medium
res olution instruments at medium flux reactors. For example, thestructures of a large number of high-T c superconductors have been
investigated at Trombay in the last few years. Some results of these studies
will be highlighted.
The visualisation and interpretation of the H-bond interaction in protein
structures deduced by X-ray diffraction can be assisted to a large extent
by neutron diffraction studies of small biomolecules . An analysis
specifically addressing experimentally observed H-bond populations
associated with individual donor and acceptor groups in terms of bondlength - bond strength correlations will be presented.

16A-2SCATTERING LENGTH VARIATION IN NEUTRONDIFFRACTION
J.W. White, Research School of Chemistry, Australian National
University, Canberra, Australia.
The variation of scattering contrast in neutron diffraction by substitutionof one isotope for another, particularly deuterium for hydrogen 1 but
also, for example, in the study of the structure of solutions by the use ofnickel isotopes,2 has had a major impact on structural studies ofpolymers, biological molecules and colloids and ionic solutions.
Examples will be drawn from:1. The structure of virus and ribosome.
2. Template induced nucleation of zeolite crystallisation from gels.3
3. Neutron reflectivity and the structure of thin films.
The growing interest in the use of neutron spin polarisation and polarised
nuclei 4,5 for scattering length variation and the induction of contrast in
crystals and biological systems with it will also be discussed.

IJ.W. White The Continuing Promise of Neutron Scattering in Chemistry,
Physics and Biology, Trans Amer. Cryst. Assoc., 23, 1-16 (1987).
2J. E. Enderby In "Neutron Scattering in Biology, Chemistry andPhysics", Eds. R. Mason, E.W.J.Mitchell and J.W. White, Royal Society,London, 1980. Also Phil. Trans. R. Soc. Lond. B, 290, 553-566 (1980).
3T.O. Brun, J.E. Epperson, S.J. Henderson, L.E. Iton, F. Trouw and J.W.
White Small-Angle Neutron Scattering Studies of the Template-Mediated
Crystallization of ZSM-S Type Zeolite. Langmuir, (1992).
4J.B. Hayter, G.T. Jenkin and J.W. White
Polarized Neutron Diffraction from Spin Polarized Protons : A Tool in
Structure Determination? Phys. Rev. Lett. , 33, 696-699 (1974).

ss. Cox, J.B. Hayter, G.T. Jenkin, M. Leslie, G. Warner and J.W. White
Precise Location of Hydrogen Atoms in Complicated Structures byDiffraction of Polarised Neutrons from Dynamically Polarized Nuclei.
Phil. Trans. R. Soc . Lond. B, 290, 497-503(1980).

1 6A-3

STRUCTURAL ANALYSIS OF ORTHORHOMBIC Hf0 2
BY NEUTRON POWDER DIFFRACTION
0. Ohtaka, T. Yamanaka,College of General Education, Osaka
University, Toyonaka, 560 Japan, N. Hara, H. Aso.no, Institute ofMaterials Science, University of Tsukuba, Tsukuba, Ibaraki 305 Japan,
and F. Izumi, National Institute for Research in Inorganic Material
Tsukuba, Ibaraki 305 Japan
A time-of-flight neutron diffraction experiment was undertaken on a
powder sample of orthorhombic Hf02 synthesized at 6 GPa and 600 oC
for 30 min. The Rietveld analysis for the diffraction data shows that the
space group of this phase is Pbca and that the crystal structure is the sameas that of orthorhombic Zr02. The refined lattice parameters are
a=l.00177, b=0.52276, and c=0.50599 nm. The feature of the structure isderived from a distorted fluorite (CaF2) structure by the b-glide parallelto the a axis. The hafnium atom is in seven-fold coordination, with Hf-0
distances ranging from 0.20496 to 0.22020nm. The oxygen-1 atom iscoordinated by three hafnium atoms in an approximately coplanar
configuration, whereas the oxygen-2 atom has a nearly tetrahedral
coordination.
By means of neutron diffraction, controversy on the crystal structure oforthorhombic Hf02 and Zr02 (high pressure form) has been terminated.
Orthorhombic Hf02 Space group: Pbca
B(nm2)b
Atom Position ga
x
y
z
Hf
8e
1.0 0.3845(l)C 0.0338(2) 0.2439(4) 2.0(2)* 10-3018e
1.0 0.2902(2) 0.3716(4) 0.3720(4) 5.4(3)*10-3028e
1.0 0.0227(1) 0.2431(6) 0.0004(5) 3.5(2)*10-3
Rwp=4.77 Rp=3.57 RE=4.24 RI=3.44 RF=l.68
a Site occupanciesb Isotropic thermal parametersc The figures in parentheses indicate estimated standard deviations of
the last significant digit.
Ohtaka,O., Yamanaka,T., Kume S., HaraN., Asano H. and Izumi,
F.(1990) Proc. Jpn. Acad. 66 Ser.B 193-196
Ohtaka,O., Yamanaka,T., and Kume, S.(1991) J. Ceram. Soc. Jpn. 99
826-827.

16A-4
BRAGG AND DIFFUSE NEUTRON SCATTERING STUDIESOF CUBIC ZIRCONIA
D .N. Argyriou. and M.M. Elcombe, Australian Nuclear Science andTechnology Organisation, Private Mail Bag 1, Menai 2234, Australia
A number of models have been proposed for the defect structure of cubic
zirconia (typically a fluorite structure), which include displacements of
the 0 atom either along [100] or [111], or positioning the 0 atoms on a
combination of sites. It has also been suggested that the Zr atom isdisplaced along [110] (1-4). In Zro.stYo.t901.905, Zro.87sCao.l250t.s75
and Zro.6toYo.39001.805 we have measured acoustic phonon dispersion
curves, as well as neutron elastic diffuse scattering, and we are in theprocess of collecting single crystal TOF neutron diffraction data.
Measurements of diffuse intensity in the 110 plane of these crystals showsa gradual shift of intensity from diffuse peaks at 112, 114, 116 and 332(forbidden reflection for fluorite, but allowed for tetragonal zirconia) todiffuse features on the zone boundary faces, perpendicular to the [111]direction, with increasing vacancy concentration. Measured acoustic
phonons in Zro.s tYO.t901.905 and Zro.87sCao.I250J.875 crystals areanomalously broad, so measurement as the zone boundary is approachedis difficult. In contrast in the Zro.610 Yo.39Q0t.805 crystal, phonons are
better defined and both the T A and LA modes are significantly higher
than in the previous two crystals. Results of the single crystal studies will
be discussed with reference to current studies of diffuse and inelastic
neutron scattering, as well as proposed models for the defect structure of
cubic zirconia (5,6).
1. D. Steele and B.E.F. Fender, 1974. J.Phys. C, 7, 1.
2. J.Jr. Faber, M.H. Mueller, B.R. Cooper 1978. Phys. Rev. B, 17, 4884.
3. M. Morinaga, J.B. Cohen, J.Jr Faber 1979. Acta Cryst. A35, 789.
4. H. Horiuchi, A.J. Schultz, P.C.W. Leung, and J.M. Williams, Acta
Cryst. B40 , 372.
5. R.B.Nader, F.Frey, and H.Schulz, 1990. Acta Cryst., A46, 799.
6. J.G. Allpress and H.J. Rossel, 1975. J.Sol.St.Chem., 15, 68.

16X-1NITRO-NITRITO LINKAGE PHOTOISOMERIZA TION IN
CRYSTAL OF NITROPENTAAMINECOBALT (IIn
DICHLORIDE
S . Ohba. Department of Chemistry, Faculty of Science and Technology,
Keio University, Hiyoshi 3, Kohoku-ku , Yokohama 223, Japan.
Crystals of linkage isomers, [Co(NH3)5 N02] Cl2 (I ; monoclinic C2/c.
Z=4) and [Co(NH3)5 ONO]Ch (II; orthorhombic P2Inb , Z=4) can beobtained. The nitro coordination (Co - N02) is thermodynamicallyfavoured and nitrito(Co-ONO) to nitro isomerization occurs in (II) and aphase transition follows . On the other hand, nitro to nitrito isomerization
occu rs in (I) as a result of irradiation by light. Because the crystals
gradually cracked during irradiation, the initial stage of the reaction wasinvestigated(Kubota &Ohba, 1992). Crystal of (I) was cooled by a cold
nitrogen stream in order to protect it against degradation by heat during
irradiation and to prevent the thermodynamical nitrito to nitro backreaction. Crystal structures before illumination with a Xe-larnp, (Ia),
after illumination for 40 min, (lb), and for 150 min, (lc), have been
analyzed. Nitrito coordination, caused by photochemical reaction, wasdetected on electron density maps and the populations were refined to (lb)
8.9(5) % and (lc) 14.5(8) %. Thermodynamical linkage isomerization in(II) was reinvestigated based on the X-ray intensity data measured byGrenthe and Nordin(l979). Linkage isomerization occurs in the originalplane of N02 in (1) . However, the nitro plane is inclined during theisomerization of (II) because of steric hindrance to rotation of N0 2 in theoriginal plane.
Kubota, M. & Ohba, S. (1992). Acta Cryst. B48. In the press.
Grenthe, I. & Nordin, E. (1979). Inorg . Chern. 18,1869-1874.

16X-2CRYSTALLINE-STATE PHOTOISOMERIZA TION OF .
COBALOXIME COMPLEXES
Akiko SEKINE and Yuji OHASHI , Department of Chemistry, Tokyo
Institute of Technology, 0 -okayama, Meguro-ku, Tokyo 152, Japan
It has been found that the p-cyanoethyl (p-ee) group in cobaloxime
complexes is transformed to o:-cyanoethyl (o: -ce) group when thecomplex is exposed to visible light in the solid state. Among thecomplexes with various base ligands, (p-ce)(3-methylpyridine)cobaloxime forms mixed crystals with the photoproduct o:-ce complex
in any composition. A crystal of the P-ee complex was mounted on a
Rigaku AFC-5R diffractometer and was irradiated with aXe lamp . The
lattice constants, measured by the diffractometer at a constant interval,
showed gradual change. After about 75h exposure, the threedimensional intensity data were collected. The analysed structure
revealed the disordered form of the cyanoethyl group with the p-eegroup and the o:-ce ones. This clearly indicates that the p-ee group isisomerized to the o:-ce group keeping a single crystal form on exposure
to visible light. Such a crystalline-state photoisomerization has been
observed for the crystals of the p-ee complexes with 3-chloropyridine
and 3-bromopyridine as axial base ligands.

16X-3

PHASE TRANSITION AND CRYSTAL STRUCTURES IN
1-Br-ADAMANT ANE

H.Takakura, N.Achiwa and M.Shiono, Department of Physics,
Faculty of Science Kyushu University, Higashi-ku, Fukuoka, 812,
Japan.
Structures of the plastic disordered, semi-ordered and ordered phasesof 1-Br-adamantane (C 10 H15 Br) were studied by X-ray diffraction
and diffuse scattering analyses. The plastic phase crystallizes in the
cubic space group (Fm"Jm, a= 10.079(l)A, at 340K). Its structure
was well interpreted by random populated orientations of the BrC molecular principal axis parallel to the six equivalent < 100 >directions. Diffuse scattering analyses, however, suggest that themolecule has comparatively large and nearly isotropic motion. The
ordered phase crystallizes in the monoclinic space group (P21 /c,a=10.134(1)A, b= 6.868(1)A, c= 13.315(2)A, ,8=90.05(1t, at 244K)
and the Br-C axis orients alternatively in (011) and (Oil) directions
propagating along the c-axis. The semi-ordered phase crystallizes in
the orthorombic space group (Pmcn, a= 10.120(2)A, b= 6.902(l)A,c= 13.626(2)A , at 297K) where tumbling motion of molecules aroundthe molecular principal axis is expected to occur. In all cases there
are 4 molecules per unit cell. The temperature dependence of lattice
parameters in three phases is described. Remarkable anomalies wereseen at two transition points. We will also report structural refinements for the plastic disorderd and the semi-ordered phases basedon the rigid molecular model.

16X-4X-RAY STUDY OF THE FERRIDISTORTIVE
PHASE TRANSITION IN {N(CH3)4}zCoBq
Y. Nishihata and A. Sawada, Faculty of Science, Okayama University,
Okayama 700, Japan, and H. Kasatani and H. Terauchi, School of Science,
Kwansei Gakuin University, Nishinomiya 662, Japan.
Tetramethylammonium tetrabromocobaltate, {N(CH3)4} 2 CoB r4,
undergoes a second order phase transition at about 287 K from Pmcn inthe normal phase to P121/c1 in the ferroelastic phase. The deviation t.~of the monoclinic angle from 90° behaves anomalously as reported by
Hasebe et al. The behaviour suggests that it does not represent the
primary order parameter of the phase transition. Ferridistortive crystals
are defined by Sawada as crystals whose spontaneous strains consist of
two kinds of sublattice strains with opposite signs and different
magnitudes. The purpose of the present work is to clarify the
microscopic origin of sublattice strains in this crystal.
A fou r-circle automatic diffractometer with a large x-cradle, Rigaku
AFC off-center type, was used with Mo-Ka radiation. The specimen
temperature was changed by using a closed-cycle He-gas refrigerator.
Structure determination of {N(CH3)4}2CoBr4 at 300 K by single-crystal
X-ray diffraction methods revealed a disordered array of tetrahedral
molecules . The unit cell contains three kinds of sublattices ; tw ononequivalent for N(CH3)4 molecules and one for CoBq molecules.
Electron density contour maps represent the disorder character as mirror
reflection for all C atoms. In the low temperature phase, the crystal
structure was studied at 175, 126, 76 and 46 K. Tentative results showthat the occupation probability for the two configurations of CoBr 4molecules tends to be saturated faster than that of N(CH3)4 moleculeswith decreasing temperature. The three kinds of tetrahedral molecule
rotate with different temperature dependences.

Hasebe, K., Mashiyama, H., Tanisaki, S. & Gesi, K. (1984). J. Phys. Soc.
Jpn. 53, 1866-1868.
Sawada, A. (1991). J. Phys. Soc. Jpn. 60, 3593-3595.

16X-5

PHASE TRANSITIONS OF THE HALOGEN BRIDGED
M(II)-X-M(IV) MIXED-VALENCE COMPLEXES.
STRUCTURAL STUDIES OF HIGH- AND LOWTEMPERATURE PHASES OF [Pt(en)z][PtBrz(en)z](Cl04)4
K. Toriumi , Dept of Material Science, Himeji In st of Tech, Harima
Science Park City , Hyogo 678-12, Jpn, M. Yamashita, Dept of Chern,College of General Edu, Nagoya Univ, Nagoya 464, Jpn, S. Kurita, Lab
of Applied Phys, Yokohama National Univ, Yokohama 240, Jpn ,I. Murase, College of General Edu, Kyushu Univ, Fukuoka 810, Jpn, and
T. Ito, Dept of Chern , Tohoku Univ, Sendai 980, Jpn
Halogen-bridged MILX -MIY mixed-valence complexes of [M(en)z)[MXz(en)z](C l04)4 (M=Pt, Pd; X=Cl, Br; en=ethylenediamine) withlinear-chain structures exh ibit first-order phase transitions at temperature
range of -4 oc - 25°C. Crystal structures of the orthorhombic 1 (hightemperature) and monoclinic 2 (low-temperature) phases of [Pt(en)z)[PtBrz(en)2](Cl04)4 have been determined by X-ray diffraction method
at room temperature. Both the structures consist of in fin ite linear chainswith repeating unit of (•••Ptii••• Br-PtiY_Br... ) along the b axes. It has
been revealed that conformatio ns of the ethylenediamine chelate rings ofPt(en)2 moieties are changed from "A."A. (88) in 1 to 8"A. ("A.8) in 2 . Achange of the molecular symmetry owing to the conformational change isjust corresponding to the change of site sy mmetry at the Pt complex from222 to I . Structural differences can be we ll expressed by sequences of
the chelate ring conformations in the chains with repeating units of[("A."A.)(88)] for 1 and [(8"A.)("A.8)] for 2 , the conformations being coupledwith each other through intra- and inter-chain hydrogen bond of
NHoooO(perchlorate)•••HN. The hydrogen bond network is also changed
due to the conformational change from three-dimen sional 1 to twodimensional 2. X-ray structure analyses have also revealed that both the
PtlY -Br and Ptll ... Br distances in 2 are significantly elongated ascompared with those in 1, which correspond to the negative thermal
expansion phenomena observed at the tran sition temperatures.
Crystal data: for 1, orthorhombic, lema, a=l3 .563(2) , b=l0.939(3),c=9.664(2) A, Z=2, at 25 °C; for 2 , monoclinic , P2J/m , a=8.544(l),b=l0.973(1), c=7.972(1) A, ~=109.39(1 ) 0 , Z=l, at 25°C.

168-1DNA CONFORMATION IN CRYSTALS
M. Sundaralingam. Department of Chemistry and Biotechnology Center,
Laboratory of Biological Macromolecular Structure, The Ohio State
University, 012 Rightmire Hall, 1060 Carmack Road, Columbus, Ohio
43210-1002 U.S.A.
The number of deoxyoligonucleotide crystal structures available isexpanding. The main reason for X-ray structural studies of DNA
crystals is to understand the structural and conformational properties of
the DNA governed by their base sequences. There is new information
indicating that the conformation of the DNA is determined by the basesequence. The order of the bases determines the binding characteristicsof the DNA segments for the recognition enzymes. Unfortunately, in the
crystal lattice, the intermolecular interactions between symmetry-related
molecules seem to impart significant perturbations, not only on the DNA
structure but also on the types of association between the constituent
nucleotides . From the X-ray structural studies conducted in mylaboratory on DNA octamers, decamers and dodecamers, I will show
various instances where changes in the DNA structures have been
induced by the close packing contacts. This packing effect complicatesthe interpretation and understanding of base sequence on DNA structure.
Research supported by NIH grant GM17378.

168-2PROBING THE INTERACTION BETWEEN PLATINUM
ANTI-CANCER DRUGS AND DNA
T W Hambley, G.W. Allen, R.R. Fenton, E. C. H. Ling & K Patser, School of Chemistry,
University of Sydney, Sydney, NSW 2006, Australia.
Platinum based anti-cancer drugs such as cisplarin (cis-[Pt(NH3 hC1 2]) bind tightly to DNA
and interfere with replication. It is generally accepted that these events are responsible for cell
death, however, it is yet to be unequivocally established which of the adducts cisplarin forms
with DNA are responsible for the cytotoxic action (Pinto & Lippard, 1985). The inactivity ofcompounds only able to form monofunctional adducts has been taken to mean that one ormore of the bifunctional adducts are responsible (Lippard, Ushay, Merkel & Poirier, 1983).
The major bifunctional adducts fall into two classes; (i) intrastrand, i.e. GpG (60%), ApG(25%) and GNG (<10%) and (ii) interstrand linking two guanines (<10%) (Eastman, 1983 }.
Our approach to establishing which of these adducts effects the cytotoxic activity is to designcompounds which should have a strong preference for forming only one class of adduct. We
use the techniques of molecular mechanics and computer graphics to construct andinvestigate models of each of the cisplarin!DNA adducts and to design compounds which
will bind stereospecifically. These compounds are then prepared, structurally characterised,
their interactions with DNA measured and their in vi rro and in vivo anti-tumour activities are
determined.
Cl

For example we have designed a series of compounds
to bind to GpA sequences of DNA in preference to c,,......iTr-"9~:-~l:CJI-(TJGpO or ApG sequences (cispla rin does not bind to
GpA sequences (Eastman, 1983 }). An ORTEP plot
and a schematic diagram of
one of these compounds,
2S, SS-dichloro- methionine-methylester-sulfoxide-platinum(Il) are
shown here. The basis of the design is our hypothesis that cisplarin
does not bind to GpA sequences because of repulsions between an
NH 3 ligand and the exocyclic NH2 group of the adenine (Hambley,1991). The compound shown here has a sulfoxide group in place of
one NH 3 ligand and the 0 atom of the sulfoxide is correctly oriented
to H-bond to the adenine NH2 group.
Results will also be presented for compounds designed to bind enantiospecifically to GpG or
ApG sequences and for compounds designed to bind interstrand in preference to intrastrand.
Eastman, A. (1983) Biochemisrry 22,3120.
Hambley, T.W. (1991) Inorg. ChenL 30, 937.
Lippard, S.J., Ushay, H.M., Merkel, C.M. & Poirier, M.C. (1983) Biochemisrry 22,5165.
Pinto, A.L. & Lippard, S.J. (1985) Biochim. Biophys. Acra 780, 167.

168-3
ELECTROSTATIC POTENTIAL IN tRNAAsp RECOGNITIO N
BY ASPARTYL-tRNA SYNTHETASE
A. Takenaka, Faculty of Bioscience and Biotechnology,Tokyo Institute ofTechnology, Yokohama 227, Japan, andJean Cavarelli, Jean Craude Thierry and Dino Moras , Institut de Biologie
Moleculaire et Cellulaire du CNRS, 67084 Strasbourg, France.
For high fidelity transfer of genetic information, aminoacyl-tRNA
synthetases recognize tRNA anticodon bases, catalyzing specific aminoacid attachment to a tRNA's CCA terminus . Althou gh diverse in size,
sequence, and quarternary structure, they form only two classes with aconsensus sequence motif corresponding to the aminoacylation site. X-ray
structures are available for two aminoacyl-tRNA synthetase complexes (indifferent classes) with their cognate tRNA's[Rould, Perona, SoU & Steitz(1989) , Rould, Perona & Steitz (1991), Ruff, et al. (1991 )]. To help help
understand recognition specificity we calculated electrostatic potentials of
aspartyl-tRNA synthetase (yeast) with tRNAASp (yeast) and its mutants.
Us ing recently refined atomic coordinates(R=0.25 at 2.8A
resolution), nine point-mutant tRNA's were derived by replacing one baseat the anticodon, assuming a conformation as in the wild type. Net charges
from a CND0/2 calculation for every amino acid and nucleotide residue
were assigned to all the atoms. Electrostatic potentials were computed bysolving the Poisson-Boltzmann equation with a finite differential method,using a modified program DELPHI (B . Honig et al.).
There is reasonable electrostatic complementarity of the phosphategroup of tRNA with the protein's basic amino acid residues. The freetRNA molecule is surrounded by an extened negative potential that drives
its approach to the synthetase molecule. There are negative minima at the
0 atoms in each phosphate, unless the group charge is positive. The basepairs form negative columns at the central parts in the stems . The positive
potential localized on H atoms attached to C and N atoms extruding
laterally from the bases compensates the negative sites on the synthetase.
The nine point-mutants show how crucial local adaptation of electrostaticinteraction is to specific recognition. Mis-matching of electrostatic fields
occurs in any substitution replacing the anticodon base. Although theanticodon loop is flexibile , it is hard to fine tune interactions by moving
the mutated base after overall matching between the two molecules isaccomplished. Mis-matching at the anticodon binding site causes anunfavourable situation at the reaction site or binding itself is weakened.
The next question is "how is small mis-matching transduced to andmagnified in the distant reaction site of the other domain?"
Rould, M .A. , Perona, J.J., Soli, D. & Steitz, T.A. (1989). Sci. 246, 1135-1141.
Rould, M.A., Perona, J.J. & Steitz, T.A. ( 1991). Nature 352, 213-218.
Ruff, M., Krishnaswamy, S., Boeglin, M., Poterszman, A., Mitschler, A.,
Podjarny, A., Rees, B., Thierry, J.C. & Moras, D. ( 1991 ). Sci. 252, 1682- 1689.

168-4

BIOPHYSICAL AND CRYSTALLOGRAPHIC STUDY OF DNA
RECOGNITION BY A BASIC-HELIX-LOOP-HELIX ZIPPERPROTEIN
A.R. Fern~- D 'A m a re+, P. Pognonec@, R. G. Roe der@ & S.K . Burley+%+ Laboratories of Molecular Biophysics,@Laboratory of Biochemistry and Molecular Biology and%Howard Hughes Medical Insti tute
The Rockefeller University, 1230 York Avenue, New York, NY 10021
USA
Upstream Stimulatory Factor (USF) is an eukaryotic transcription fac torthat belongs to a family of DNA binding proteins containing a basic
region (B), thought directly to contact the DNA, and two putative
dimerization motifs: the helix- loop-helix (HLH) and the leucine zipper(Z) . In addi tion to full -s ize USF, constructs compri sing the full DNA
binding domain (BHLHZ) or the DNA binding domain minus the leucine
zipper (BHLH) were overexpressed, purified to homogeneity, and shownto bind DNA specifically. Circu lar dichroism spectroscopy indicatedthat all three proteins undergo a similar coil-to-helix folding transition
upon spe ci fi c DNA binding, the increase in helical con tent being
consistent with the basic region becoming fully ex-helical when theproteins are bound to DNA.
Photon co rrela tio n spectroscopic
measurements of the hydrodynamic masses of the protein-DNA
complexes at physiologic concentration showed that while the BHLHD NA complex consists of a protein dimer bound to a single piece ofDNA, the leucine zipper containing BHLHZ-DNA complex is a protein
tetramer simultaneously bound to two pieces of DNA. Co-crystals of
BHLH bound to an oligonucleotide containing its cognate recognition site
have been obtained and structure determination is underway . Recent
results will be presented.

16Y -1

THE EXACT SOLUTION OF DYNAMICAL DIFFRACTION IN
A DISTORTED CRYSTAL AND ITS APPLICATIONSNorio Kato, Department of Physics,
Faculty of Science and Technology, Meijo University, Nagoya, JapanThe exact solution of the dynamical diffraction was obtained (Kato, 1990)
for a one-dimensional lattice expansion, in which the reflection vector isgiven in the form [g(x) = g + D 0 tanh(x!H)] , x being the coordinate
normal to the crystal surface. One can represent various forms of strain
by choosing suitable parameters D 0 , H and Xe (e: the suffix denoting theentrance surface). This paper presents the following two applications
based on this solution.
(1) Darwin-Prins rocking curves: The expression is given by
F(iv+q, 1 - iv :+- q; 1 + p + q; ~(1 + ~e))l
R(E) = 1Ca12
1F( -iv+q,l+iv+q;l+p+q; 2;(l+~e))I2where 1Ca12 is the reflectivity for the perfect crystal, F is hypergeometricfunction and the parameters involved are determined by D 0 , H, E (thedeviation from the Bragg condition), A (absorption parameter) and~e = tanh(xe/H) etc. In cases of no absorption (neutron diffraction), R(E)
has a singular behaviour -- total reflection for any distortion. The higher
angular side of the main Bragg peak, under a special condition, shows an
oscillation which can be interpreted by a simple theory as an interferenceof modified Bloch waves propagating in ± x directions. Various
numerical examples will be presented systematically .
(2) Standing waves: In surface crystallography, the standing wave method
is widely used. In most of the literature it has been assumed that the base
crystal is ideally perfect. It can be shown that, if the crystal is deformed,
an extra phase is introduced to each 0 and G waves in a different manner,so that the spatial positions of the standing wave are somehow different
from those expected for the perfect crystal. Therefore, erroneou s
conclusions could be drawn about the atomic positions in unfortunate
cases. Some numerical examples will be presented, demonstrating thiseffect.
Kato, N. (1990). Acta Cryst. A46, 672-681.

16Y-2
EXPERIMENTAL TEST OF THE DYNAMICAL THEORY OF
DIFFRACTION
T. Takama and T. Kihara, Department of Applied Physics, Faculty ofEngineering, Hokkaido University, Kita-ku, Sapporo 060, Japan.

Kato has developed an extinction theory (1980,1991) in which the local
displacement field within a crystal is treated as variable. It is free from thetraditional treatment of the mosaic idea. The theory is expected to cover thefull range of diffraction from perfect to imperfect crystals. Few
experiments, however, have been made to verify the theory. In our previous
test (1990), we studied the influence of randomly distributed small defects
on the Pendell6sung beats of X-ray on the wavelength scale. The results
showed good agreement with the theory on the assumption that thecorrelation length r of the amplitude of the wave-field is constant for areflection of sample. In the present work, a similar study was performed fora crystal with a higher degree of distortion.
The samples used were three wafers 485 Jlm thick of Si single crystal withdislocation density p of 1x 1o4 to 2x 105fcm2 and one 588 pm with
5xl02/cm2 The integrated intensities on the symmetrical Laue case were
measured by a solid state detector in an X-ray wavelength range from 0.2 to
0.8 A. It was shown that the diffracted intensities increased with dislocation
density. The degree of increase was dependent on the wavelength and theindices of the reflection plane. The Pendellosung beats were observed only
for the sample with p=Sx 102/cm2. The period of the beat somewhat
expanded as predicted by the theory. The experimental results except for thelowest dislocation density were compared with Kato's theory(1980) . The
comparison was made for two functional forms of r ; one is proportional tothe extinction distance and the other is constant for a reflection. The R
factors obtained were 1% for the (220), 2% for the (422) and 4% for the(440). In contrast to the previous study, there was no significant difference
between two functional forms. The increase of the R factor with index ofreflection indicates that diffuse scattering is important to describe thediffraction from heavily distorted crystals.
Kato,N. (1980)Acta Cryst.A36,763-769 ,770-778.
Kato,N. (199l)Acta Cryst.A47,1-11.
Takama,T., Harima,H. & Sato,S.(l990)Acta Cryst.A46,C412.

i 6Y-3
A GENERAL THEORY OF EXTINCTION IN CRYSTALS
T. M. Sabine, Advanced Materials Program, ANSTO, Menai, NSW 2234, Australia.
The starting point for crystal structure analysis is a set of relative structure factor
magnitudes for Bragg reflections from a crystal. The structure factor magnitudes (I FH I ) arefound from measurements of the integrated intensities (I0 of scattered radiation as the
crystal is rotated through the Bragg position.A knowledge of the exact relationship between
IFH I and IH for each reflection is essential for the accurate determination of IFH 1.
Theories of extinction are designed to provide this relationship.
In the earliest theory of X-ray diffraction from crystals, which is called the kinematictheory,the result IH proportional to IFHI 2 is obtained for all reflections. The dynamical
theory, which takes into account interactions between the incident and diffracted beams
during their passage through the crystal,leads to IH proportional to IFH I for strong
reflections in large crystals and to a power between 1 and 2 for weaker reflections or
smaller crystals.
By convention departure from agreement with the kinematic theory is called extinction,
and an extinction factor is defined by the equation IHoba = E IHitin in which rHobs is theobserved intensity and IHitin is the intensity expected for the reflection from the kinematictheory .The factor E is a function of the mosaic block size, the relative orientations of themosaic blocks in the crystal, the strength of the reflection and the degree of absorption.
A theory has been proposed (Sabine, 1992) from which a single extinction factor
incorporating all these quantities can be calculated. The expressions are rapidly
convergent for use in least squares refinement methods, and apply at all angles ofscattering . It is further shown (Sabine and Blair, 1992) that the theoretical methods used,
namely the Hamilton-Darwin energy transfer equations (Darwin,1922 ;Hamilton,1957),
lead to the exact Ewald and Darwin limits of the dynamical theory.
The application of this theory to practical cases will be discussed.

Darwin,C .G.(1922) Philos. Mag. 11_800-829
Harnilton,W .C .(1957) Acta Cryst. 10 629-634
Sabine, T.M. (1992) Int. Tables for Crystallography Vol C.
Sabine, T.M. and Blair, D . G. (1992) Acta Cryst. ~ 98-103.

16Y-4
A NEUTRON DIFFRACTION STUDY OF KCl: A TEST OF
THE SABINE EXTINCTION FORMALISM
S . Maheswaran and T. M. Sabine, Advanced Materials Program,Australian Nuclear Science and Technology Organization, Private
Mail Bag 1, Menai, NSW 2234, Australia andH. Klapper, Mineralogisches Institut, University of Bonn, W-5300
Bonn 1, Germany

Integrated intensities have been collected for the Bragg reflections ofneutrons by a single crystal of KCl at room temperature. Measurements
were made at a single neutron wavelength, 1.235 A 0 • The experimental
data were analysed in terms of extinction formalism given by Sabine(1992). Good agreement was obtained between observed and calculated
structure factors. Values obtained for the harmonic thermal parametersagree closely with previously published values. The results werecompared with an analysis of the same data using the extinction formalismof Becker and Coppens (1974a, b) which is now commonly used by
crystallographers. Correlations among the refined parameters are smallerwith the Sabine extinction formalism compared to that of Becker andCoppens, otherwise the results (including the R -factor) are essentially
identical.
Earlier, the crystal was characterised by Lang topography andmeasurements of rocking curves. The results predicted that the crystal isalmost ideally imperfect. The refined values of mosaic block size (1) andmosaic spread parameter (g) obtained with both the extinction formalisms
supports this prediction.

Sabine, T. M. (1992) Int. Tables for Crystallography, Vol. C, pp 530533. Kluwer Academic publishers.
Becker, P. J. and Coppens, P. (1974a). Acta Cryst. A30, 129-147.
Becker, P. J. and Coppens, P. (1974b). Acta Cryst. A30, 148-153.

16Y-5X-RAY Sd-ORBITAL ANALYSIS OF PtP2 AND MULTIPLE
DIFFRACTION FREE INTENSITY MEASUREMENT
K. Tanaka. S. Kurnazawa* and S. Maruno*, Departments of Chemistry
and Electrical and Computer Engineering*, Nagoya Institute ofTechnology, Nagoya, Japan, andIchimin Shirotani, Department of Electronic Engineering, MuroranInstitute of Technology, Mizurnoto-cho 27-1, Muroran Hokkaido
050, Japan.
Multiple diffraction(MD) free measurement was carried out for PtP2
crystals with very high absorption (Jl=780.8cm-l). Two reflections are
rarely located on the reflection sphere exactly at the same time, but MD
occurs frequently if a little time lag between the two reflections ispermitted. The R-factors were 0.0131 for 985 reflections and 0.165 for
936 reflections measured with and without avoiding MD, respectively.
The deformation density calculated from the MD-free reflection datashows clear 5d-electron peaks, while the other one has additional large
peaks which cannot be explained by further analysis.
In general d-orbitals are expressed in terms of the five real basis function s<)>(r) as,~(Ki r)=~Cim<jlm(Kir),
i=1 ,2, .. 5
where Ki allows expansion(Ki<O) and contraction(Ki>O) of the d-orbitals
calculated by the Hartree-Fock SCF method. The Pt d-orbitals in theligand field C3i-3 in Table 1 were obtained by X-ray d-orbital analysis(Tanaka, 1988). The deformation density from the spherical model andthat calculated with these 5d-orbitals agreed well.
Table 1. 5d-orbitals of Pt in PtP2
njKid;?--y2
dz2
dyz
dzx
dxy
1 1.24(7) 1.18(3)0.78(4) 0.0-0.63(5) -0.06(3) 0.0
2 1.24(7) 1.18(3)0.0
0.0-0.06(3) 0.63(5) -0.78(4)-0.06(3) 0.0
0.0-0.78(4) -0.63(5)3 1.95(15) 0.94(6)4 1.95(15) 0.94(6)0.63(5) 0.0
0.78(4) 0.0-0.06(3 )5 2.00.85(13) 0.0
1.0
0.0
0.0
0.0
ni is number of electrons on the i-th orbital.

Tanaka, K. (1988). Acta Cryst. A44, 1002-1008

16C-1
DIRECT OBSERVATION OF ANOMALOUS TRANSMISSION
OF X-RAYS · THROUGH THIN NATURAL DIAMOND
CRYSTALS HAVING VARYING DEGREES OF CRYSTALPERFECTION
Krishan Lal, S. Niranjana N. Goswami and Ajit Ram Ve rma , National
Physical Laboratory, Dr.

K.S . Krishnan Road, New Delhi -110012,

India.

We

have

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werequit einof X-rays

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thin

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study

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evenwhen theseand rather imperf ect. Specimen diamondc rystals were ( 111) platelets of Type I as well as Type II variety
withthicknesses

varying

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A highly monochromated and collimated MoK o(beam with very1small width in the plane of diffraction was the exploring beam.
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These

dynamical theory of16C-2A SINGLE CRYSTAL DIFFRACTOMETER ON AN OPEN
TUBE X-RAY GENERATOR WITH MAXIMUM TUBE
VOLTAGE 200KV
F.P. Okamura and K. Yukino, National Institute for Research in
Inorganic Materials, 1-1 Namiki , Tsukuba, Ibaraki 305,
K. Yamamoto, Institute of Applied Physics, University of Tsukuba,
Tsukuba, lbaraki 305,
T. Hori, S. Yoshimachi, R. Yokoyama, H. Kawasaki, K. Tsukamoto and
H. Izawa, Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima, Tokyo
196, Japan.
An X-ray single crystal diffraction system suitable for high resolution
electron distribution analysis has been designed and manufactured. The
system is equipped with an open tube type X-ray generator which can be
operated at a maximum tube voltage of 200kV. Detailed specifications fo r
the system are as follows:
Generator
tube voltage:
20-200kV
tube current:
2-lSmApower:
2kW
target/filter:
Cu/Ni, Mo/Zr, Ag/Rh, W /Yb
Goniometer:
off-centered four circle(Huber 512)
Collimator:
inner diameter = 0.2, 0.5, 1.0, 2.0 mm
Detector:
T1-doped Nal scintillation counter
Specimen Temperature: R.T.-lOK(cryostat=Cryogenics Inc.,DE202)
Reflection data for a spherical Si crystal were collected using Mo, Ag andW K a radiation, respectively After correction for the Lorentz factor,
polarization, absorption and extinction, they were used for electron
distribution analysis. The final residual R is 0.01.

16C-3TEXTURE ANALYSISFOR POLY-CRYSTALLINE MATERIALS ON
A FOUR CIRCLE GONIOMETER
A.ull:I.liq and A.Q. Khan, Metallurgy Division, Dr. A.Q. Khan ResearchLaboratories, Kahuta, P.O. Box 502, Rawalpindi, Pakistan

Texture, i.e. non-random orientation of crystallites, is the main, if not
exclusive, cause of anisotropy of the physical properties of polycrystalline
materials. If a material consists of several phases the knowledge of texture
becomes still more important as each phase has its own texture, which inturn leads to different anisotropy.
The texture can be determined by pole figure measurements. In this case amathematical pole fig ure inversion is necessary, for which four methods
have been published. Symmetry elements with inversion character in the
crystal as well as in the sample lead to partial extinction of the orientation
distribution function. In special cases the extinguished part can ,nevertheless, be determined. In polycrystalline materials non-conventional
sample symmetrie s, which require black-white symmetry groups forcomplete description, can occur. Textures may also be inhomogeneous.
Experimental texture determination is characterized by the developmentof step-motor operated and computerized four circle texture goniometers .
Besides X-ray diffraction, neutron diffraction and electron diffraction are
increasingly used . Angular dispersive methods are supplemented b yenergy dispersive ones . Position sensitive counters provide increased
angular resolving power as well as short time measurements in order tostudy the kinetics of texture format ion. In special cases on-linemeasurements are used to control technological production processes.
Some actual applications of textures and texture measurements , especiallyin duplex steels, are to be presented.

16C-4A SYSTEM FOR ANALYZING THIN FILM STRUCTURE BYGRAZING INCIDENCE DIFFRACTION: I. GRAZINGINCIDENCE DIFFRACTOMETER
H. Toraya and T. Ochiai, Ceramics Research Laboratory,

Nagoya Institute of Technology, Asahigaoka, Tajimi 507 , Japan.
There has been growing interest in the use of grazing incidence
diffraction for analyzing thin single- and multi- film structures. This
paper describes a study of part of a total system for thin-film structure
analysis, consisting of a grazing incidence diffractometer and computer
software for analyzing specular reflection patterns.
The hardware has been constructed from a Rigaku RINT system. Its
optical system is based on the parallel-beam geometry proposed by the
Parrish group for the study by reflectometry of thin-films 1). A Si (111)channel monochromator was mounted on the incident beam side at a
distance of 150mm from the X-ray source, to remove the Ka2 component
and to collimate the beam. In the present study, a slit system with doublesliding mechanism was specially designed , and used after the
monochromator for easy cutting of the Ka2 component and alignment of
the optical system. The thin film specimen, placed 220mm from the centerof the monochromator, can be rotated in the plane of specimen surface tothe desired angle by a pulse-driven motor. On the diffracted beam side, aSi (111) channel-cut crystal, mounted as an analyzer crystal 185mm fromthe specimen, can be removed when higher resolution is not required.
A scintillation counter was used as a detector. In order to compensate forloss of intensity due to monochromatization, the goniometer was installed
on a (Cu target) rotating anode generator, which could be operated at a
maximum load of 18 kW. The 111 reflection from anSi wafer was used
to test the hardware system. It gave a virtually symmetric profile ofnearly Gaussian shape, with a very narrow full-width at half-maximum of
0.02° and a high count rate of more than 7xi04 cps, demonstrating highperformance of the optical system as a grazing incidence diffractometer.
Several thin film samples are now under investigation using this system.
This work is supported by a Japanese Government Grant-in-Aid forGeneral Scientific Research No. 03452293 .
1) W . Parrish, C. Erickson, T.C. Huang, M. Hart, B. Gilles, and H.
Toraya, Mat. Res. Soc. Symp. Proc.,208, 327-337 (1991).

16C-5
MEASUREMENT OF RADII OF CURVATURE OF SLIGHTLY
BENT CRYSTALS USING A RETICON DETECTOR
Dachao Gao, Stephen W. Wilkins and Andrew W. Stevenson
CSIRO Division of Materials Science and Technology, Locked Bag 33, Clayton, Victoria
3168, Australia
A new experimental geometry for simultaneously mapping the rocking curves of a sample
over a one- or two- dimensional array of points on the sample has been developed by Gao,
Davis and Wilkins (1992). A monolithic channel-cut Si monochromator has been used. The
calculated angular spread of the resulting (out-going) beam is of the order of 0.1" and the
expansion factor of the monochromator is 144. A cryogenically cooled Reticon linear
photodiode array with 25 11m spatial resolution was used for the one-dimensional detector.
When a wide incident beam in the form of pseudo-plane waves (such as is used here)
irradiates a bent specimen, the Bragg diffraction conditions cannot be simultaneously satisfied
at each point on the sample. However, by rotating the sample in incremental steps, the Bragg
diffraction conditions could be satisfied point by point, for misorientation in the plane ofdiffraction. Then, the Rericon detector collects X-ray diffraction rocking curve data from ahorizontal (plane of diffraction) linear segment of the sample. Due to the extremely parallel
incident X-ray beam, there is a one-to-one correspondence between a point in the crosssection of the diffracted-beam and a point on the sample giving rise to it. Therefore, theradius of the curvature of the sample is precisely determined from the contour map of X-ray
rocking curves. This method is much more sensitive than the commonly used double-crystal
diffractometry (Ka doublet) method (Cohen & Focht, 1970).
The measurements of radii of curvature of several samples (CdTe/GaAs, AlGaAs/GaAs,
GaAs/Si, InSb and GaAs) have been obtained using this method. The results for the radii ofcurvature vary from 11 .3 to 554 m., including both concave and convex cases. The detectable
limit of radius of curvature could be greater than 1000 m. The uniformity and the local
variation of the radii of curvature over the sample is easily revealed and precisely determinedfrom the contour map.
Gao, D., Davis, T.J. & Wilkins, S.W. (1992). 1st European Symposium on X-ray Topography
and High Resolution Diffraction, 8-10 July, 1992, Marseilles, France.
Cohen, B.G. & Focht, M.W. (1970). Solid State E/ec. 13, 105-112.

16Z-1
THE WORLD DIRECTORY OF CRYSTALLOGRAPHERS,ELECTRONIC MAIL, AND COMMUNICATION WITH
CRYSTALLOGRAPHERS IN THE ASIAN REGION
H. Hashizume· Res. Laboratory of Engineering Materials, Tokyo
Institute Technology, Yokohama 227, Japan, and
Y. Epelboin· Lab. Miner. Crist., Univ. P-M Curie and CNRS, Paris
75252, France
During the organization of this conference the organizers wereparticularly sensitive to the need for good, fast communication in our
region. This motivated them to propose AsCA ComNet, acommunication network which collects current fax numbers andelectronic mail addresses for Asian crystallographers[ll. Syd Hallcollaborated in defining an information format which is simple andbrief to expedite the collection task and future updating. Fifteen subeditors were nominated in the Asia-Pacific region and data collection
work started in April 1992.
Independently of the AsCA ComNet project, the International
Union of Crystallography decided to create a database of
crystallographers and other relevant information. The idea is tomaintain that database at Chester, allowing crystallographers all over
the world to enter and retrieve information, accessing it throughcomputer networks. The database will be used to produce the 9th editionof World Directory of Crystallographers, and for other purposes likeestablishing mail lists of information exchange in special fields ofcrystallography. The stored information will be in STAR formad2]
using only ASCII letters. It will include name, title, institution, postal
address, year of birth, qualification, position, telephone and fax
numbers, e-mail address and keywords[3]. The database will be
regularly updated by national and regional sub-editors who are given
the right to do so. An official invitation was issued to the sub-editors togather the information in July 1992. A first demonstration is planned at
the next IUCr meeting at Beijing, August 1993.
E-mail addresses of crystallographers can be found in the Boston
database, compiled and maintained by Martha Teeter of Boston College.
On request, the whole body of the database is sent to the user by e-mail.
This database includes, however, only e-mail addresses and institution
names. There are very few entries from Asian countries. It will
eventually be integrated into the IUCr database together with AsCA
ComNet, to produce a more complete database.
[!]H. Hashizurne (1992) J. Cryst. Soc. Japan 34, No.2.

[2] S.R. Hall (1991) J. Chern. Info. Comp. Sci., 31, 326-333.
[3] Y. Epelboin (1992) Acta Cryst. A48, 5, 785.

16Z-2
CIFtbx: FORTRAN ROUTINES FOR MANIPULATING CIF's
S.R. Hall, Crystallography Centre, University of Western Australia,
Nedlands 6009, Australia.

C!Ftbx is a subroutine library which provides fo r simple commands toread and write a Crystallographic Information File (CIF: Hall, Allen &Brown, 1991). The CIF (software) tool box routines may be added to
any Fortran application manipulating CIF data. C!Ftbx is public domain
software which may be implemented on any computer.
C!Ftbx was developed to assist programmers developing software foraccessing and generating CIF's. It is proposed that this software makes
access to data stored in CIF format easier than fo r any other format.
Some important attributes of these tools are as follows :their application requires only a rudimentary knowledge of the
CIF syntax.
provides for automatic checking of the input and output CIF data
structure.
single commands are used to put and get CIF data to and fromassigned Fortran variables. No knowledge is required of where
the passed data item is in the CIF.
the processing of repeated data or text lines or looped text
packets is completely under the control of the programmer.
data may be validated against one or more CIF dictionaries. Thisis convenient for checking global definitions (using standard
dictionaries such as cifdic. C 91) or for local customised
applications such as CIFIO (Hall, 1992).
Hall, S.R. (1992) CIF/0: Xta/3 .2 System. Ed.s Hall and Stewart.
University of Western Australia and University of Maryland.
Hall, S. R., Allen, F .H., and Brown, I.D. (1991) Acta Cryst. A47,
655-685 .

16Z-3
XAFS: CAN THIS IMPORTANT TECHNIQUE ACHIEVERESPECT ABILITY?
D.C. Creagh, Department of Physics, University College, The University of
New South Wales, Northcott Drive, Campbell, ACT 2603, Australia.
Extended X ray Absorption Fine Structure (XAFS) is a technique w h ich has
the potential to elucidate facets of atomic environments in m aterials notobservable using other techniques. It is, however, a technique which has
been both improperly applied and imperfectly understood for at least the past
two decades.
In the X ray Attenuation Project conducted under the auspices of the IUCr
(Creagh & Hubbell (1987, 1990)) several thousand XAFS experiments wereeval uated . Of these only a few hundred were not open to severe criticism,
because of experimental deficiencies, incorrect analyses, or both.
Because of concerns about the ill-repute into which the study of materials
using XAFS had fallen a committee was created at the XAFS V Conference inSeattle to discover how best to raise the standard of XAFS papers submitted
to scientific journals.
The "Standards and Criteria Committee" has had three major workshops
since its creation. Details concerning developments in the theory, apparatus,
experimental proced ures, data reduction, experimental and data anal ysis
were addressed, and the results were reported (Lytle et al (1989), Bunker et al(1991)). Further, an XAFS data base, accessible b y all XAFS users, wasestablished at the National N uclear Data Centre at the Brookhaven National
Laboratory.
The response of XAFS users to these initiatives has been slow . Because ofthis a recent workshop addressed the problem of user education. A shortcourse of XAFS instruction has been created with a view to making an XAFS
education package available to all synchrotron radiation sources, and indeed
to all interested parties.
This paper will describe the "Short Course in XAFS" and discuss its
applicability to th e solution of problems faced in the use of XAFS by
crystallogr aphers.
Creagh, D.C. & Hubbell, J.H. (1987), Acta Cryst . A43, 102-112.
Creagh, D.C. & Hubbell, J.H. (1990), Acta Cryst. A46, 402-408.
Lytle, F.W., Sayers, D.E. & Stern, E.A. (1989), Physics B, 158, 701-722.
Bunker, G. , Hasnain, S. & Sayers, D.E. (1991), in X ray Absorption Fine
Structure, eds S. Samar Hasnain & Ellis Horwood, (London), 751-771 .

"1 6Z-4

SHELXL-92 A NEW LEAST-SQUARES REFINEMENTPROGRAM FOR USE WITH SINGLE CRYSTALDIFFRACTION DATA
George M. Sheldrick, lnstitut fOr Anorganische Chemie, der Universitat,
Gottingen, Germany, and Ward T. Robinson, Department of Chemistry,
University of Canterbury, Christchurch, New Zealand.
SHELXL-92 is a FORTRAN-77 program for the refinement of crystal structuresfrom X-ray or neutron diffraction data, and is primarily designed for single
crystal data from small structures (1-1 000 unique atoms) at atomic resolution .
It is intended to be easy to install and use on a wide variety of computers, andreplaces the structure-refining part of SHELX-76.
SHELXL-92 is general and efficient for all space groups in all settings andthere are no arbitrary limits to the size of problems which can be handled,
except for the total memory available to the program. All instructions are inmachine independent free format, with extensive use of default settings tominimize the amount of input required from the user. Instructions and data aretaken from two standard (ASCII) text files, so that input files can easily betransferred between different computers. SHELXL-92 is a PUBLIC DOMAIN
progam; it is provided in source form, also as a precompiled version which has
been optimized for Pc's . There are no restrictions on its use or distribution
anywhere in the world for non-commercial purposes.
The program produces all tile information required for efficient development of
a complete structural model from a partially correct one derived using
separate direct or vector methods programs such as SHELXS86. It contains
many options for fully automatic handling of constraints on positional andthermal parameters and for placement of hydrogen atoms. Structural models
can also be restrained to conform with chemically reasonable expectations forinteratomic distances and thermal displacement parameters . These similarity
restraints can be particularly useful in refinements of macromolecular
structure.

The atom designation rules, which accommodate standardpractices, help minimize the instructions required to invoke constraints andrestraints.

All tables necessary for electronic mail submission to both Acta

Cryst. (C) and the CSD are provided in CIF format and a companion program
CIFT AB can produce hard copy in formats suitable for other journals.

16Z-5AN INTEGRA TED X-RAY MEASUREMENT AND
COMPUTATION SYSTEM FOR PROTEIN
CRYSTALLOGRAPHY
N. Yasuoka, Y. Higuchi, S. Misaki , Y. Morimoto* and I. Fujii**,
Department of Life Science, Himeji Institute of Technology, Kanaji 14791, Hyogo 678-12, *Department of Bio-technology, Tokushima University,**Department of Biological Science and Technology, Tokai University
As workstations have become more popular in crystallographylaboratories, powerful X-ray analysis systems can now be operated via
local area networks. Here we describe an integrated system for measuring
X-ray intensities, transferring the diffraction data to workstations,computing for structure analysis and displaying the molecular structure.
For the X-ray measurements, we have a four-circle diffractometer and an
oscillation camera equipped with an imaging-plate. The machines arecontrolled with a personal computer, and measured data can betransferred via Ethernet to workstations. A block diagram of the system is
illustrated in the Figure. The older graphics workstation is a TIT AN with
2CPU (16MIPS x 2) and 64 megabytes of memory. A new one recently
installed is a Silicon Graphics IRIS Indigo Elan. A DIP100 imaging plate
X-ray diffraction apparatus is a kind of area detector. It has a disk 20cm
in diameter. X-ray intensities are measured in 125 x 125 micrometer
pixels, and the data are transferred to the TIT AN by Ethernet to giveobserved structure factors. A four-circle diffractometer is also connectedto the local area network and measured structure factors can betransferred to any workstation. Structure analysis packages such as
XTAL, PROTEIN, XPLOR, PROLSQ and so on, are installed on theseworkstations. The performance of this system will be reported.

1 6 P-0 1
MORPHOLOGIC AL INVESTIGATION OF THE (0001)
SURFACE OF ICE Ih CRYSTAL BY X-RAY CRYSTALTRUNCATION ROD SCATTERING
A.Goto and K.Akiya,
University,

Sapp oro 06 0 ,Nagoya 464 -01 ,Low

J a p an,

T . Sh i mur a, I.Takahashi a n d

Department of Applied Physics,

J.Harada,

Hokkai do

Departme n t of App l ied Physics,

Japan,

Nagoya University,

Y.Fu r ukawa and T.Hondoh, In s titute ofTemperature · Science,

Hokkaido Un i versity ,Sapporo 060,

Japan.

An

attempt

singlea

was made to characte r ize the surface state ofc rystal of ice Ih o n a molec u lar level bytherod (CTR) scattering technique 1 ).

crystaltruncation

result,it was found that very well-defined CTR

X-ray
a

As

scattering,from t he 0002 Bragg point along the surface normal

elon ga ted

direct i on of [0001], can be observed at 7°C be low the melting
when the surface was sublimated for app r oximately 1 hpoint,

i n a co ld room after making the surface me chanically flat
using a Japanese plan e .
CTRscatte r i n g ,

t he

ice

sand

dune.

Estimated fro m the divergence of the

it is suggested that th e (0001) surface

of

like

a

we investigated is ve ry smoothly undulat e dTher esult

was compared withthethe growth kin etics of ice surfac e
2
va pour phase , discussed by Kuroda and Lacmann ).
prediction

onbytheoretical
fro m

the

1) Goto,A., Akiya,K., Hondoh,T., Furukawa,Y., Shimura,T.,
Takahashi,I . and Harada , J . (1992) ,J.Crystal Gr owth, in press.
2) Kuroda.T. and Racmann.R. ( 1982 ) .J.Crystal Growth,56,189-205.

16P-02

CaSrF2/GaAs AND CaF2/S/GaAs INTERFACE STRUCTURESREVEALED BY X-RAY STANDING WAVES AND CRYSTALTRUNCATION RODS
H. Hashizume, T. Niwa, M. Sugiyama (*), 0. Sakata and S. Maeyama (*),
Res. Laboratory of Engineering Materials, Tokyo Institute Technology,
Yo k ohama 227, Japan. (*) NTT Interdisciplinary Laboratories.
Fluoride epilayers on GaAs substrates are useful materials for insulator/semiconductor stru ctures. Their electronic properties are affectedb y the stoichiometry and structure at the epilayer-s ubstrate interface,which has been studied here using X-ray standing wave s (XSW) andcrystal truncation rods (CTR) at synchrotron radiation site Photon
Factory, KEK Japan. Lattice-matcheq CaSrF2 thin films were grown on
the As-terminated (111) surface of GaAs b y molecular beam epitaxy. XSWdata collected using the (111) planes show a 0.7% expanded fluoride
epilayer spacing relative to the bulk GaAs (111) planes and the first(Ca, Sr) layer l ying at 2.38A (= du) above the top substrate (111)plane. The CTR d ata near the 111 Bragg point support the observed
very short vertical distanc e dJF , suggesting one or both of a F and As
layer missin g at the CaSrFz/GaAs interface. Emission data obtainedusing the 220 and 113 reflections locate the Sr atoms midway between
the T and T4 sites o n GaAs(111) surface [1]. This puzzling Sr position
is studied by recording CTR intensity distribution s near the 331 Bragg
point. The obse rv ed oscillation profile is far from that expected fromthe (Ca, Sr) atoms occupying the T4 s ites but close to the one calculated for the (Ca, Sr) at the T sites . Mixed-site mod e ls can only explain
the data with a marginal fraction of the metal atoms at the T4 sites.
Least-squares fits assuming the (Ca, Sr) atoms at th e T sites favor
missing top substrate As atoms over shifted As atoms at the H3 sites .
We also studied CaFz epilayers grown on S-passivated GaAs (111)
surface at 440"C using XSW and CTR. Our previous study suggest thaton the As-terminated GaAs(ll1) surface the top layer As atoms are substituted by S atoms [2]. The present XSW data confirm this result withmuch more neatly fitted data. Well co ntrasted oscillations of the CTR
profile near the 111 Bragg peak indicate ordered CaFz layers. Leastsquares fits show a 1% contracted layer spacing relative to bulk CaFz .
The first Ca layer lies 2.4A above the top substrate (111) plane,suggesting a missing F layer at the CaFz/S inte rface either.
[1] H. Hashizume et al. (1991) Rev. Sci. Instr. 63, 1142 .
[2] M. Sugiyama et al. ( 1991 ) App/. Phys. Letter in press.

16P-03

X-RAY DIFFRACTION STUDY OF
THE AIR CLEAVED NaCI(OOl) SURF ACE
I. Takahashi. T. Kakiuchi , T. Shimura, and J. Harada
Department of Applied Physics, Nagoya University,
Chikusa-ku, 464 , Nagoya, Japan .
In an attempt to study the morphology of a real crystal
surface and the microscopic mechanism for sublimation ,an air cleaved NaCI(001) surface was investigated by
X-ray CTR scattering at several different temperatures .
Samples cleaved with a razor blade were put in a vacuum
chamber installed on a diffractometer. The temperature
was controlled to within 2K from room temperature to
900K. The degree of vacuum, 1 o-s torr, was maintained
th roughout the experiment.
The CTR scattering around the (000) and (002) points atroom temperature and at 400K was almost identical ,while differing from data obtained from a surface cleavedin vacuum*. However, after the sample was heated to570K, the CTR scattering changed and became similar tothat from the vacuum-cleaved surface. This suggests thatthe surface cleaved in air is covered with absorbed
molecules, such as water, that remain on the substrate
until the temperature is increased to 570K.
Damping of CTR scattering is observed at 670K,
indicating that the dynamical surface roughening due tosublimation occurs when the sample is heated further.
Subsequent
least squares
fitting
confirms
thisinterpretation, and also indicates that CTR scattering is
one of the powerful methods available for the study ofadsorption and desorption on crystal surfaces.
* Y. Kashihara, S. Kimura, and J. Harada: Surface Science.
214, (1989) 477-492 .

16P-04
STRUCTURAL ANALYSIS OF Ag/Cu AND Ag/Pb
MULTILAYERED FILMS BY X-RAY DIFFRACTION
K. Hazama, J. Kozaki, S. Ando and 0. Nittono
Department of Metallurgical Engineering, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152, Japan.
In most cases, the structures of metallic multilayered films are analyzed
by comparing observed X-ray diffraction profiles with calculated profiles
based on models of layer stacking. This procedure, however, istroublesome when a real layer stacking deviates markedly from a model
based on an ideally designed superlattice structure. Furthermore, metallic
multilayered films have been prepared by various methods. In previous
studies films constructed with the same constituent metals have not been
investigated in detail by the same analytical technique.
In this study, we seek a practical and reliable procedure for precise
structural analysis of metallic multilayered films. First, in order to see if
a film's structure depends on the preparation method, we prepared Ag/Cu
films by evaporation and by sputtering, and characterized their natures.
Secondly, we developed a method for evaluating X-ray profiles using ananalytical model modified by both interface roughness and fluctuation oflayer thickness. This model was used to characterize the structures of
Ag/Pb multilayered films.
The results are: (1) X-ray diffraction profiles from Ag/Cu films showed
artificial layer periods, realized by both methods. Therefore, we first
adopted an ideal model: compositional modulation is expressed in terms ofa periodic rectangular concentration of the constituent element. It was
shown that, as a result, the interplanar lattice spacing of each element was
not the same as that of the bulk material, especially for small layer
periods. The deviation of interplanar spacing appears slightly larger forde-sputtering than for evaporation. (2) Our analytical procedure isessentially based on a model that a multilayered film is composed of manygrains with large dimension parallel to the substrate. Fluctuations in thenumber of atomic planes and their relative positions were introduced todetermine the layer period. Features of observed X-ray profiles were well
explained by these parameters. The present model and the introduction ofsuch parameters will be applicable to the analysis of the structural featuresfor various kinds of metallic multilayered films.

16P- 05

EPITAXIAL GROWTH OF (110) Ag THIN FILMS ON
CLEAVED NaCI CRYSTAL IN A KNUDSEN GAS OF Ar
I. Ogura, College of Engineering, Nihon University, Koriyarna 963, Japan

Since 1985, it has been reported that Ag thin films of (001) and/or(100) orientation are formed on (001) NaCI crystal at room temperature
if the Ag atoms and clusters are deposited onto the substrate in a Knudsen
gas of Ar. [1] Recently, the Ag flow in the Argas was calculated to obtain
deposition parameters. In this case, the free path length l of the Ag atom
is postulated to be distributed as dn/dl=exp (-e/i.)/f.. [2] The calculated
temperature T of the Ar gas is -900 K during deposition, and the mean
free path l=-2 .6mm. The deposition rate d8/dt of -0.3nm/s agrees withthe experimental values. The number density n2 of the Ag-Ag dimer is
3xl0-2nl, where n1 is that of the Ag monomer.
The growth of (110) Ag thin films on cold NaCl in the atmosphereof Ar is explained in this report. The substrate is maintained at room
temperature. [3] The surface 2-dimensional gas of Ag monomers anddimers is more active than that in the case of vacuum deposition, because
the high temperature Ar gas stimulates them by collision of Ar moleculeswith the surface-migrating Ag monomers and dimers. Ag deposits growepitaxially on cold NaCl substrates. A cleaved NaCl substrate has acomplicated structure, as shown by surface topographs. In some regions
deformed by multiple slip, {110} planes tilted by 45° from the (001)cleaved surface are widely exposed, although the mean surface plane tilts
within a few degrees. In these regions of multiple slip, the (110)orientation of the Ag deposits appears to grow.
[1] Hoshi, I. & Ogura, I. (1985). Jpn. J. Appl. L297-298.
[2] Ogura, I., Suzuki, S. & Nagashima, S. (1992) in print.
[3] Ogura, I., Hayashi, S. & Yomogita, K. (1986), J. Surf. Sci. Soc. Jpn.
8, 192-196.

160-06
CRYSTAL STRUCTURE CHANGES IN OXYGEN-DEFICIENTYBa2Cu301-Ii SUPER CONDUCTING THIN FILMS
J. Ye, A. Ishii and K. Nakamura

Surface and Interface Division, National Research Institute for Metals,
1-2-1, Sengen, Tsukuba-shi, lbaraki 305, JapanThe structural properties of high-Tc YBa2Cu30?-o; thin films withdifferent oxygen contents have been analyzed using X-ray diffraction. It is
well known that the superconducting properties of YBa2Cu307 -8 depend
strongly on the oxygen deficiency 8, and for bulk YBCO the c lattice
parameter increases linearly from 11 .68 to 11.82 A with 8 increasingfrom 0.1 to 0.9. In thin films, however, no such a correspondence has
been found, because even under different growth conditions the c lattice
parameter varies in a wide range from 11.7 to 12 A. Moreover, since
a-values are usually subject to large uncertainties, a quantitative study ofstructural changes due to oxygen deficiency remains difficult.
Recently, we have succeeded in controlling oxygen deficiency in epitaxial
YBCO films grown on MgO or SrTi03 substrates by equilibrating theoxygen potential of the thin films with that of bulk YBCO pellets ofknown oxygen deficiency. The X-ray diffraction experiments revealed
that both the c lattice parameters and the 00! intensities change
dramatically with the oxygen deficiency. After a systematic analysis, arelationship between the value of /(005)//(006) and the oxygen deficiency
has been established. Therefore, the oxygen deficiency of the films can be
determined accurately, in spite of the significant variation of c lattice
parameters depending on the growth conditions. Furthermore, structure
analyses from the measured DO/integrated intensity data show that the
Cu-0 and Ba-0 bond lengths increase with increasing oxygen deficiency.
This observation is consistent with that reported by Jorgensen et al. in aneutron powder diffraction (1990), supporting a "charge-transfer" model
which accounting for the decrease ofTc with oxygen deficiency.
Jorgensen, J.D., et al. (1990). Phys. Rev. B41, 1863-1877.

160-07
STRUCTURAL CHARACTERIZATION OF Fe/X (X:Ag,Cu,Ta)
MULTILAYER FILMS PREPARED BY DC SPUTTERING
Y.Haga. T.Sugiyama, Y.Nakamura and O.Nittono
Department of Metallurgical Engineering, Tokyo Institute of Technology,
2-12-1 Oh-okayama, Meguroku, Tokyo, 152, Japan
Microstructures influence the magnetic properties, mechanical properties,
conductivities and other properties of metallic multilayer films . The
investigation of microstructures of multilayer films is therefore
important. Generally, X-ray diffraction (XRD) is used for structure
analysis of multilayer films . In that method, we assess crystal structures in
the films by comparing observed diffraction profiles with the calculated
ones. Many reports about the effects of interface roughness, compositional
gradient or layer thickness fluctuations on XRD profiles of superlattices
have been published. However quantitative estimation of these factors formetallic multilayer films is especially difficult. Combination of XRD
methods with other techniques such as transmission electron microscopy(TEM) and scanning electron microscopy (SEM) is often necessary.
In our work, we characterize structural features of Fe/X (X: Ag,Cu,Ta)multilayer films prepared by double-facing-target-type DC sputtering on
Si(111 ) at room temperature. The deposition rate for Fe was 0.02nm/s.
That needed to prepare multilayer films for other elements with various
layer thickness ratios ranged from 0.02nm/s to 0.2nm/s. The perfection offilm periods and crystallinity were investigated by X-ray diffraction(8-28 measurement). To observe detailed structure in the films and to
estimate the film parameters used to calculate XRD profiles, we alsostudied the film structures with cross-sectional TEM (XTEM), fieldemission SEM (FE SEM), and scanning tunneling microscopy (STM).
Fe/Ag multilayer films were polycrystalline. Strictly speaking, those films
consisted of many columns and each column contained small linked
particle-like grains. Most Fe grains were bee with a <110> preferredorientation relative to the film normal. Ag grains were fcc and had a<111> preferred orientation to the film normal, with some stacking
faults . The orientations of these grains were irregular in the film plane,
but it seemed that the grains had orientation relationships to each other at
the inter/grain interfaces. The interface roughness gradually increased
with film thickness. In particular some multilayer films containing thick
Ag layers had very rough interfaces. We will report similar results forother multilayer films. In addition, we will report magnetic properties ofmultilayer films measured by a vibrating sample magnetometer(VSM).

160-08
X-RAY STANDING WAVES IN lOOA-THICK EPILAYERSUNDER GRAZING-INCIDENCE DIFFRACTION
CONDITIONS
0. Sakata, I. Kawamoto and H. Hashizume, Res . Laboratory of Engineering
Materials, Tokyo Institute Technology, Yoko hama 227, Japan
Jach and Bedzyk (1990) demonstrated the feasibility of the grazingincidence X-ray standing wave (GIXSW) method to determine the inplane position of monolayer Iodine atoms adsorbed on Ge surface. The
emission data were well fitted by a simple theory assuming excitationof the I atoms by GIXSW's produced from the substrate Ge crystal . Thisapproximation is no longer valid for epilayers as thin as 100A. Th e
extre me l y shallow penetration of X-rays under the grazing-incidence
condition demands dynamical diffraction in the epilayer crystal to betaken into account. Figure 1 shows Sr K e mission data observed from
100A -thick CaSrF2 epilayers on GaAs( 111) substrate diffractin g 17.5
KeV synchrotron X-rays with the (220) planes at a glancing in cidence
angle slightly larger than the critical ang le of total external reflection for GaAs . The observed emissio n profile is far from the prediction of the simple theory (dotted curve) but close to the solid curve
calc ulated including the epilayer diffraction for Sr atoms lying on thediffracting (220) planes (Z = 0) . If the fluorescing lattice Sr atoms
were located midway (Z= 0.5) , we would observe the broken profile
whic h is q u ite different from the one for Z = 0. The present theory
ass umes perfect-crystal epilayers interfacing to a perfect substrate.
Attempts to include lattice distortion in the theory would provide acloser fit to the data whereby structure parameters at the heteroepitaxial interface would be more precisely characterized .

Q

..J
~

~ 1.5

~ GLANCING ANGLE
1
1. 9 mrad
Z=O. 5} I
1

I

:z:

0
.....

I
/

Cl:l
Cl:l

s 1.0
~

::.::

Z=O

c...

Cl:l

0. 5
100 JL rad

DEVIATION ANGLE FROM THE EXACT BRAGG ANGLE
Jach, T . and Bedzyk, M.J . (1990) Phys. Rev. B42, 5399-5402 .

160-09

OBSER VATION OF CTR SC ATTERING FROM AlAs
MOLECULAR LAYERS IN GaAS USING AN IMAGE PLATE
DETECTOR
T.Shimura and J.Harada, Department of Applied Physics,
Nagoya University, Chikusa-ku, Nagoya, 46401 , Japan
The interference fringe between two crystal trun cation rod (CTR)
scatterings from AlAs molecular layers in GaAs was observed with an
Imaging Plate (IP). The rod-shaped X-ray CTR scattering emanates along
the surface normal direction from each Bragg point. Analysis of thatscattering provides difference information about crystal surfaces andinterfaces . The IP X-ray area detector combines the advantages ofdynamic range from 1 to 105, high sensitivity and unlimited count-rate
capacity. Its use in conjunction with synchrotron radiation is very
effective for studying the crystallography not only of proteins as shownby Sakabe l) but also of surfacesl),2). In this paper we demonstrate a mostinteresting observation with CTR scattering . Our GaAs/AlAs/GaAs
sample was grown on a GaAs(001) substrate by the MBE method. The
nominal numbers of molecular layers of GaAs, AlAs and GaAs were
1240, 125 and 1240 respectively. Oscillation photographs were taken at
the BL-6A2 of Photon Factory, KEK. The intensity distribution of the
CTR scattering around the 002 Bragg point is represented in Fig.l Eachdot is obtained by integrating the intensities across the CTR scatteringwith background subtracted. It is possible to interpret the Laue-function
like distribution as an interference fringe between two CTR scatterings
from the interfaces . The solid line indicates model calculations in which
numbers of molecular layers, lattice spacings and roughnes ses of the
AlAs interfaces are adjusted. Careful investigation showed that the latticespacing and the number of molecular layers of AlAs can be obtained towithin ±0.002A and ±1 molecular layer, respectively. Estimatedroughnesses of the AlAs interfaces were less than 4 molecular layers.
[1] N.Sakabe; Nucl.Instr. and Meth. A303 (1991) 448[2] T.Shimura and J.Harada; Acta Cryst. A46 (1990) suppl. C-374[3] J.Harada, T.Shimura, M.Takata, K.Yakushiji and K.Hoshi;
J.Cryst.Growth 104 1990 773

160-10MISFIT ACCOMMODATION OF Pt/ Au/BUFFER Ag
TRILA YERS GROWN ONTO Si, MgO AND NaCl
SUBSTRATES
Akira Sugawara and Osamu Nittono
Department of Metallurgy, Tokyo Institute of Technology,
2-12-1 Oh-okayama, Meguro ku, Tokyo, 152, Japan
In recent years, interface structures of metallic superlattice films grownon single crystal substrates(e.g. Si, GaAs, MgO et al.) have been
extensively studied in connection with their physical properties . In
general, lattice misfits between two metals are large, so misfit
accommodation may be important to their growth and properties.
However, most specimens were grown at low temperature and containedlarge stacking fault densities. This might affect the misfit accommodation.
In this study, we have demonstrated differences in misfit accommodation
at Pt/Au interfaces grown onto thick and annealed Ag buffer layers on
Si(001), Mg0(001) and NaCl(OOl). The lattice misfit is about 3.8%
between Au and Pt and 0.2% between Au and Ag, respectively.
All the Pt(0.5-l0nm)/Au(30nm)/buffer Ag(about 200nm) films were
deposited onto Si(OOl), MgO(OOl) and NaC1(001) single crystal substrates
at 563K by Xe+ ion beam sputtering. First an Ag buffer layer was
deposited, and then annealed above 620K for several hours. The Pt/Au
bilayer was deposited later. After dissolving the Ag buffer layer in nitricacid, a Pt/Au bilayer film was mounted on a grid and investigated bytransmission electron microscopy (JEM-200CX) at room temperature.
In all cases, parallel epitaxy was observed among the buffer Ag, Au andPt layers. Since Au layers were thin, no misfit dislocations wereintroduced at Au/Ag interfaces . At an early stage of Pt growth on an Au
layer, ps eudomorphism was observed. However, following misfit
accommodation, the Pt/Au interface features alter. For NaCl substrate,
the stacking fault density was relatively large. Two stages of introductionof misfit dislocations were observed. First mixed dislocations wereintroduced by a slip mechanism. Edge-type dislocations were introduced
by a climb mechanism in the next stage. By contrast, for Si and MgOsubstrates, stacking fault density was low and slipped dislocations were
scarce. The results suggest that misfit accommodation is greatly affectedby internal defects and by the surface flatness of the Ag buffer layer.

160-11
X-RAY DIFFRACTION ANALYSIS OF RTP PROCESSEDCu/In/Se STACKED THIN LAYERS
F. Camillo and M. Donat, Dpto de Tecnologia de Materiales, Institute
Universitario Technologico Dr F.R.P., Aptdo Postal40347,
Caracas - Venezuela, and
H. Galindo, A.B. Vincent, J.M. Martin and D. Gomez de Anderez,
Facultad de Ciencias, Universidad de Los Andes, Merida Venezuela.

Stacked layers of Cu/ln/Se have been processed by rapid thermal
processing (RTP) via strong incoherent light. Films of 250 nm thickness
were formed by evaporation, in a chamber at IQ-6 torr, of copper,
indium and selenium layers in stoichiometric proportions 1:1:2 onComing 7059 glass substrates. The films obtained were subsequently
treated on an apparatus which simulates the effect of a commercial rapid
thermal processor (RTP) controlled with a PC microcomputer. We wereable to refine the process and could obtain better films in the 260 to
290°C range . The corresponding X-ray diffraction analysis shows thepresence of a phase having chalcopyrite structure in the processed films
with a particular set of the RTP parameters. An investigation of theinfluence of these parameters showed that these must be well controlled
in order to avoid unwanted secondary phase or strong segregations.
Synthesis of ternary CulnSe2 by this technique is also discussed.

16R-12CRYSTAL STRUCTURES OF ADENYLYL-2'-5'ADENOSINE TRIHYDRA TE AND TETRAHYDRA TE:
A study of molecular conformation under different hydrations
R Krishnan and T P Seshadri, Department of Physics, Indian Institute of
Science, Bangalore 560 012, India.
Water mediated structural transformations play an important role inbiological molecules. A well known example is the polymorphism of
DNA double helix caused at different hydrations. However, there are notmany examples of nucleic acid fragmetns studied under different
hydrations by single crystal methods. Only two mononucleotides
5'd-dCMP.Na2 and 5'-IMP.Na have been reported. Interestingly the
deoxynucleotide showed conformational changes while the ribo
nucleotide did not. This study was undertaken to study the effect ofhydration on the molecular conformation of A2'p5'A.
The crystals of both the hydrated forms of A2'p5'A were grown using
vapour diffusion techniques. Cu K a intensity data were collected on a
CAD-4 machine. The structures were solved using direct methods andwere refined toR factors of 0.108 and 0.129 for the tetrahydrate (I) andtrihydrate (ll) forms respectively.
Our analysis showed that the 2'5' sugar phosphate backbone inA2'p5'A(II) is remarkably similar to that in A2'p5'A{I). All
the conformational features of A2'p5'A(I) namely, synlanti geometry forthe adenine bases, C2' endo!C3' endo mixed sugar puckering andintramolecular base- 04' stacking are also found in A2'p5'A(ll). The
two hydrated forms of A2'p5'A can be superposed with an R.M.S
deviation of less than 0.53 A in their coordinates. Though the two
hydrated forms have totally different unit cell parameters, their volumes
are very nearly the same because their cell content differs by only twosolvent molecules per asymmetric unit. But the packing of the A2'p5'A
molecules in their respective unit cells are significantly different.
Consequently, the intermolecular interactions are very different in boththe forms. However, their water nucleotide interactions are not very
different as the conformations of A2'p5'A in both the hydrated forms
are very similar.
Crystal data for A2'pS'A(I) & A2'pS'A(II)Formulaa=C2oH24N I00IOP.4H20Nl4
7.956(3)AC2QH24NI00toP.3H20
9 .284(3)Ab=

12.212(3)A

15.360(3)Ac=

36.654(3)A21.610(3)ASpace group

P2t2t2I

P2t2t2IV=

3561.3A3

3081.6A3

16R-13

CRYSTAL STRUCTURE OF
2,6-DI (2-FURYL)-3,5-DIMETHYL PIPERIDIN-4-0NE
N Sukumar and M. N. Ponnuswamy, Department of Crystallography andBiophysics, University of Madras, Guindy Campus, Madras
600 025, India, andJ. C. Thenmozhiyal and R Jeyaraman, Department of Chemistry,
Bharathidasan University, Tiruchirapalli 620 024, India.

Most nitrosamines are known to exhibit carcinogenic properties. It has
also been observed that by blocking the a position of the ring nitrogen
atom by methyl groups in cyclic nitrosamines, carcinogenic activity is
reduced. Some of the N-nitroso ureas are used as antitumor agents or
antibiotics. In view of the general interest in their utility and reactivity,
several N-nitrosopiperidines and N-nitrosopyrrolidines have beensynthesized and their conformations studied. The aim is to understand thestereodynamics of N -nitrosopiperi dines and to correlate thestereochemistry with their Cancer/anticancer properties.
Crystal Data:

CtsHnN03, Triclinic, PT,
a=8.915(1), b=11.4790(9), c=7.0986(4)A,
a= 103.83(6), ~= 98.317(6), y= 93 .644(8),V= 694.27A3, Z=2.

The piperdin ring is in a slightly "distorted chair" conformation. One of
the furyl rings assumes "half-chair" conformation whereas other furyl
ring exists in "twisted" conformation. The dihedral angle between thefuryl rings is 12.0(5) 0 • The packing of the molecules are governed by
N-H ...O hydrogen bonding and Vander Waals interaction.

16R-14

STRUCTURAL STUDY OF 1-0CTADECANOLBY PSPC SYSTEM
H.Kobayashi and N.Nakamura, Department of Chemistry,
Ritsumeikan University, Kita-ku, Kyoto, 603, Japan.
1-0ctadecanol was recrystallized several times from n-hexane. The sample
was judged to be thoroughly pure by gas chromatograph equipped with aglass capillary column. It is known that 1-octadecanol exhibi ts phasetransition behaviour on cooling process from the molten state. In thisstudy, a sample temperature control apparatus was newly designed, andconstructed by a gas furnace system equipped with a proportional
integrated differential (PID) controller. Moreover, a position sensitive
proportional counter (PSPC) system was used as a detector in order tomake quick measurements. The cooling rate from the molten state was
0.1 °C/min.

~

l'\:

'

.A

iL

'

~~.

'
'
'

~J\

1\.~

.

,\..

2 8

I· l

"

Figure 1 SA.XS patterns of 1-octadecanol

Small angle X-ray scattering (SAXS) patterns are shown in Figure 1.
From 57 to 52°C, the peak was observed at 28=1. 8°. The intensity of thepeak increased with decreasing temperature till 55°C, but after that it
decreased gradually. The peak vanished at 51 oc. From 52°C, another peak
appeared at 28=2.1 o . The intensity of this peak increased with decreasing
temperature till 50°C. In the temperature range 57 to 52°C, that is thehigh temperature phase, the long spacing is 48.7A. Below 52°C, the longspacing is 41.7 A. These values are consistent with long spacings reported
by Seto (1962). Detailed structural analysis results will be presented.
Seta, T. (1962). Mem. College Sci. Univ. Kyoto, A30, 89-107.

16R-15

CRYSTAL STRUCTURES OF
MES0-1,1'-DICYAN0-1,1'-DIPHENYL-ETHANE (1) AND
MES0-1,1 '-DINITR0-1,1 I -DIPHENYLETHANE (2)L. L. Koh , H. H. Huang, K. Y. Sim, Y. L. Lam andY. Xu
Chemistry Department, National University of Singapore
Singapore 0511
crystal structures of
x-ray Diffraction.

1

and

2

have been determined by

Cr ysta l data:(1)c 6 H5 -CH(CN)-CH(CN )-C 6 H5
Z=4
monoclinic, C2jc,
a=l9.044, b=5.794, c=12.494 ~ ' ~=115.28°
R=0.046 for 710 observed reflections(2)c 6 H5 -CH(N0 2 )-CH(N0 2 )-C 6 H5
Z=2
monocl inic, P2 1 / n,a=5.597, b=8.1 85 , c=14.389, ~=90.51°
R=0.051 for 604 observed reflections

The crystal
Compound 1 exists in the trans conformation.
The cen~ral C atom and part ofstructure is disorder ed .
the phenyl ring bonded to the central C atom aredisordered over two sets of sites each with s.o.f. of
The CN group, the outermost C atom of the phenyl
0.50.
ring and the H bonded to the central c atom are ordered.
The crystal
Compound 2 exists in the trans conformation.
structure is also disordered. However, in this case, only
The disorder is best
the central C atom is disordered.
described by a four-site disordered model with s.o.f. of
0.45,

0.25,

0.20 and 0.15.

Interesting features of the structures will be discussed
in the presentation.

16R-16

EFFECT OF THE TRIMETHYL SUBSTITUTENT ON C-0
BOND LENGTHS AT THE BETA POSITION:
SOME STRUCTURAL STUDIESJonathan M. White* and Glen Robertson, Research School of Chemistry,
Australian National University, G.P.O Box 4, Canberra, ACT 2601
*Present Address: Chemistry Department, University of Melbourne
Parkville, Victoria 3052
Results of low temperature (130 K) crystal structure analyses for sevenP-trimethylsilyl substituted cyclohexylnitrobenzoate esters are presented.
For those molecules (three) with the Si-C and C-0 bonds antiperiplanar
the C-0 bond lengths are increased by 0.014 A av. [D./cr min = 2.9]
compared with that in the silicon free analogue. For those molecules(four) with the Si-C and C-0 gauche no such systematic lengthening of theC-0 bonds is observed. The result is in qualitative agreement with that[.!11 a cos2(Si-C-C-0)] predicted from ab initio MO calculations on asimple model complex, and is attributed to the effects of interactions
between the Si-C cr and C-0 cr* orbitals. It is suggested that that existenceof the observed ground state effect constitutes compelling, if
circumstantial, evidence that the major kinetic effects known to result
from the presence of a P-silicon substituent also have their genesis in thesame cr-cr* interactions.

~6R-~7

SEQUENTIAL BASE-PROMOTED CLEAVAGE OF C-S
BONDS IN A COORDINATED CROWN THIOETHER
M.A. Bennett, L.Y. Goh* and A.C. Willis, Research School of Chemistry,
Australian National University, Canberra, A.C .T., Australia. (* on leavefrom Department of Chemistry, University of Malaya, Kuala Lumpur.)Treatment of the arene -rutheni um(II) salt [Ru(ll6-C6Me6 )(1,4,7trithiacyclononane)](PF6h (1) with one equivalent of KOH reversibly
cleaves one C-S bond to give the mono-cationic chelate tridentate vinyl
thioether complex 2 . Treatment of 2 with more KOH or KO-t- B u
irreversibly cleaves a second C-S bond to give the neutral complex 3 ,which contains vinyl mercaptan and a bidentate vinyl thioether thiolate
ligand. Finally , in the presence of an excess of KO-t-Bu , the vinyl groupof 3 couples with one of the methyl carbon atoms on the 116-C6Me6 ringto give complex 4; this process is thought to involve a Michael addition to
the vinyl group of a carbanion formed by deprotonation of coordinated
116-C6Me6. Complexes 2, 3 and 4 have been characterized by X-ray
crystallography, and their structures will be compared.

l1+

*

l+

*

s,Riu's
rl.vs ~

*
dt

3

4

s~~s

CsvJ
1

(PF 6)2

rs~u'sL.ysyJ2

l.vS~(PF 6 )

16R-18

STRUCTURES AND PROPERTIES OF BILAYER-FORMINGAMPIDPHILES CnAzoCmN+BrGuiqing. Xu, Kenji Okuyama, and Masatsugu Shimomura
Fac ulty of Technology, Tokyo University of Agriculture andTechnology, Koganei , Tokyo 184, Japan .
Totally synthetic bilayer-forming amphiphiles, CnAzoCmN+Br-, show
two typical aggregation states depending on the number of carbon
atoms in the spacer (m) and tail (n) parts. These are the side-by-sidearrangement (H-aggregate) and the head- to-tail arrangement (Jaggregate) of azobenzene chromophores. The form er arrangement wasobserved for compounds with the relation of m-n=2, and the latter wasobserved for CnAzoCsN+Br- (n=6-1 2).
By heating, the H-aggregate changes to the J'-aggregate which is very
simil ar to the J-aggregate. Interestingly , the odd-even effect ontransition temperatures from the H- to the J'-aggregate was observed.
That is , transiti on temperatures for compounds with odd number of mand n were higher than those fo r the even number co mpounds, by
about 400C. Acco rdin g to the X-ray structural anal yses , both
structures of the J' -aggregates for odd and even compounds weresimilar to each other, but tho se of the H-aggregates were different. In
the case of the H-aggregates, the detailed structures in the hydrophilic
region were different between the odd and even number compounds(for example, chain conformation, hydrogen bond distance, and ionicinteraction). These structural differences of the H-aggregates seem tobe caused a big odd-even effect on the transition temperatures from the
H- to the J'-aggregate.

16R-19

CRYSTAL STRUCTURE OF 1,18-DIBROMOOCTADECANE
T.Yamamoto and N.Nakamura, Department of Chemistry,
Ritsumeikan

Engineering

University,

Faculty of Science andKita-ku,

Kyoto

and Y.Yoshimura, Department of Mathematics and Physics,

603,

Faculty ofJapan,
Scienceand Engineering , Ritsumeikan University , Kita-ku, Kyoto 603 , Japan.

The sample used here, 1,18-Dibromooctadecane , was recrystallized from ethanol.
Single crystal was grown from xylene solution.
carried out on a crystal with size about

Crystal structure analysis was

t0.2X0.1X0.01mm);

intensity datafrom Rigaku-Denki AFC-5 automated four-circle diffractmeter eq uipped with CuKa rad iation from a rotating anode;of 25 reflections wi th 20°( -6~h~6. O~k~3 8,

unit-cell parameters from angular values~28~40°,-6~1~6)2703 unique reflections with 28<120°were measured by w-scan mode with scan speed

5° min -' . and scan ranges (1.2+0.5tan 8 )o for reflection withbe low sin40° /A.,

606

reflections withoo

~28~ 1 20°;I F l >3a( I F,, I ) were used in

the refinement ; no significant intensity variation for three standard reflections; no absorption correction . The initial coordinate of the C atoms
atom set with reference

and Brto the peak on least-squares plane by direct methods

with MULTAN84 (G.Germain ~M . M.Woolfson,1984) ; all other atoms located after
several least-squares cycles and Fourier calculations; block-diagonalsquaresrefinement , 1: w ( I Fe I -I F, I ) 2

parameters forall

non-H atoms;

minimized,

18H atoms

anisotropic

refinedthermalisotropically;parameters, R=0.0962, wR=0 . 1164.

G.Germain, P.Main and M.M.Woolfson, (1970).

least-

Acta Cryst .B2 6, 274

158

16R-20
2D-NMR STUDY ON THE CONFORMATION OF A
DODECACYCLOPEPTIDE
L. H. Lai 1 , L. B. Ma 1 ' 2 , Z. W. Miao 1 , X. J. Xu 1 , 1: Department ofChemistry, Peking University, Beijing 100871,China; 2:

Beijing

Institute of Microchemistry, Beijing 100091, China
Cyclopeptide is a useful template for

de

novo

designingfour-helix-bundle proteins by acting as a supportingofscaffold

for the he I ix. As a part of our study on de novo prate in design,
we have synthesized a series of cyclopeptides andstudied thesolution conformation of one dodecacyclopeptide by 2D-NMR:
Phe-->Lys-->Pr~>Gly-->Lys-->Glyt
Gly<--Lys<--Gly<--Pro<--Lys<--Phe
2D-NMR spetra were recorded on a Bruker AM SOOMHz spectrometer.
Complete assignment was

obtainedbyanalysis

of

COSY

and

NOESY spectra. DIANA distance geometry

calculations

then carried

constraints . 10 top

outwith 62

NOE

distance

structures with lowest target function values among
obtained were

the

100

considered as final results . The backbone root-

mean-squares between these ten

structures was 0. 29± 0. 06A andall heavy atoms was 1. H±O.l9A. Structurethat this cyclopeptide
All the side

werecontains two

chains of thethe same side of the ring,

analysis~-turns

showedand two y-turns .

four lysine residues face towards
providing goodanchorfor the assembly of synthesized helix elements .

positions16S-31

METAL COMPLEXES OF BENZOQUINONEDIIMINE AND
RELATED DIIMINES
Shie-Ming Peng, Department of Chemistry, National Taiwan University
Benzoquinonediimine has a low lying rt* orbital which can form rt-bonds
with metal dn orbitals. The energy of d7t relative to that of rt* will affectthe electron population on the rt* orbital, altering the bonding type andthe oxidation states of the ligand, namely, opdi, s-bqdi, bqdi.

opda

opdi
(a)

s-bqdi
(b)

bqdi
(c)

We have synthesized dozens of new complexes of (a), (b), (c) types anddetermined their single crystal structures. We can assign the oxidation
states according to the bonding geometries of the ligands and further
identify the oxidation states of the metal.
The results are summarized as follows:
1) Mono-ligand metal complexes: A series of Ru complexes,
RuCi2(P(C6Hs)3)2L ( L= bqdi and related diimines ) has been synthesized.
Bonding of (a), (b), (c) types can be obtained by slightly tuning rt* energy
levels from various diimine ligands.
2) Bis-ligand metal complexes: Two s-bqdi ligands are coordinated to themetal ion in a planar geometry. Two bqdi ligands are coordinated to themetal ion in a tetrahedral geometry.
3) Tris -ligand metal complexes: Three s-bqdi ligands are coordinated tometal ion in a trigonal prismatic geometry. Three bqdi ligands arecoordinated to metal ion in a octahedral geometry.
Recently, we have applied 15N NMR to identify the oxidation states ofligands according to chemical shifts. The results are consistent with thosefrom X-ray diffraction.

1 6S - 32
CRYSTAL STRUCTURES OF FOUR TRANSITION METALCOMPLEXES
T ian-Huey Lu , Tahir Tahirov, Bor-Hann Chen and Chung-Sun Chung
National Tsing Hua University, Hsinchu, Taiwan 300, R.O .C.
Crystal Structures of four transition metal complexes have been investigated.
They are (1) nickel(II) complex of the deprotonated anion of 3,6,6,9-tetramethyl-4,8-diaza- 3,8- undecadiene--2,10--dione dioxime, (Ni(N 4 0 2c 13H23 )](Cl0 4);(2) isothiocyanato( 3,1 0--dimethyl-4 ,9-diaza- 3,9-dodecadiene--2, 11-dione
dioximato(1-)]copper(II),(Cu(NCS)(N 4 o2c 12 H21)];(3)trans-dichloro( C-meso-3,5, 7, 7,1 0, 12,14,14-<Jctamethyl-1 ,4,8, 11-tetraaza--{;yclotetradeca-4,11-diene) cobalt(III) perchlorate. (CoCl (N c H )](Cl0 ), and (4)2 4 18 36
4carbona to ( C-rac- 5,7 ,7 ,12 ,14,14-hexamethyl-1 ,4,8,11-tetraazacyclotetradecane)
cobalt(III) perchlorate, (Co(C0 )(N C H )](Cl0 ). Their crystal data are (1)3
4 16 36
4
P2 /c,
1

monoclinic,

Z==4,

a==7.161(3),b== 18.945(3) ,c==13.949(4)1\,0/3==103.472(1) , Rr0 .039, Rw==0.04; (2) orthorhombic, Pn2 1a, Z==4,
a==7.5322(7), b== 12.652(4), c==17.985(4) 1\, Rr0 .034, Rw==0.036; (3) triclinic,
P1, Z==1 , a=6.974(4), b==8.530(1), c==11.061(2)r-=93 .02(3) 0 , Rr0.072,

1\, a=98.47 (1), /3==106.56(3),Rw=0.085 , and (4) orthorhombic, P22 12 1 , Z==2,

a==7. 185(5), b=9.552(3) , c==l6 .742(3) 1\, Rr0 .064, Rw==O.OSS.

(1) The Ni( II )atom is four coordinated in a distorted square plane formed by the four donor N
atoms. The six-membered ring is in chair form . (2) The Cu(II) ion is fivecoo rdinat ed in a distorted square-pyramidal geometry with the four N atoms
equatorial and aN- bound isothiocyanate axial. The Cu(II) ion deviates 0.298(2)!\ from the best plane formed by the four N atoms towards the fifth coordinatedN atom.
(3) Aside from the perchlorate group, the molecule has anon-{;rystallographic inversion center at the Co(III) ion. The Co(III) ion is in
the tetragonally distorted octahedral geometry with four N atoms equatorial andtwo chlorine atoms axial. The two five-membered rings are in gauche form.
One six-membered ring is in boat form, the other in twist conformation. ( 4) A
two-fold axis passes through the Co(III) ion and the carbon atom of the
carbonate gro up , and thus only half a molecule needs to be located. The Co(III)ion is six coordinated. The macrocyclic ligand is in a folded structure. The two
six-membered rings are in chair form and the two five-membered rings ingauche form. This work was supported by the National Science Council, ROC ,under grants NSCSl-0208-MOOi- 110 and NSC81-0208-M007-86 .

168-33COMPLEXES OF SOME FIRST TRANSITION SERIESELEMENTS WITH 4,4'-DIPYRAZOLYLMETHANEJohn A. Broomhead, Gaye Camm and Meta Sterns
Chemistry Department, Faculty of Science,
Australian National University , Canberra, ACT 2601 , Australia.
The ligand 4,4' -dipyrazolylmethane (dpzm) reacts with chlorides
MCl 2 (M=Mn , Fe, Co, Ni, Cu), in aqueous or ethanolic solutions, togive complexes of composition MCl2(dpzm)z, insoluble in waterand ethanol , sparingly soluble in N,N-dimethylformamide (dmf)and, with the exception of the nickel complex, soluble indimeth ylsulphoxide. The five complexes , which could only be
prepared as microcrystalline precipitates , were found, by X-ray
powder diffraction , to be isomorphous. Recrystallization of thecopper complex from dmf yielded deep blue crystals of a solv ate[CuCl2(dpzm)z] .2dmf, the structure of which was determined bysingle crystal X-ray structure analysis . Attempts to cry stallize theother complexes were unsuccessful.
Crystal data :CuCI2C14HI6Ns .2C3H7NO ; monoclinic, ?21/c (No . l4)
8.673(1), b 17.572(2), c 8.535(l)A, ~ 97.34(2) 0 , Z 2.

a

The structure comprises polymeric chains [CuCI2(dpzm)2]oo , withcopper atoms linked by double dipyrazolylmethane bridges.
Copper is in a distorted octahedral environment , with axial
chlorine atoms at 2.799(2)A and four coplanar equatorial nitrogenatoms at 2 .007(5)-2.030(5)A .
The dimethylformamide molecules
are accommodated in channels between the [CuClz(dpzm)z]oo
chains and are easily lost on exposure of the crystals to air, withresulting breakdown of the crystal structure. The X -ray powder
diffraction pattern of the decomposition product shows it to havethe same structure as the unsolvated precipitates MCl2(dpzm)2.

1 68-34
POLYMORPHIC STRUCTURES OF M(HCOO)z.2(NHz)zCO:
M=Mn,Cd,Co,Mg,Zn
N.Achiwa, M. Fujino, H. Takakura, M. Shiono, Department of Physics,
Faculty of Science Kyushu University, Higashi-ku, Fukuoka, 812, Japan .,N. Koyano , Ridwan , I. Shibuya, Research Reactor Institute , Kyoto University, Kurnatori, Osaka-fu 590-04, Japan, and K. Yamagata, College of Science and Engineering, Iwaki Meisei University, Chuodai,Iwaki,Fukushimaken 970, JapanNew family compounds M his-formate bis-urea (abbreviated as MFoUr)
belong to two kinds of space group , ?41 21 2 (M=Mn, Cd and Co) or C2/c
(Mg , Zn and Co) as we have reported previously 1•2 . Among them MnFoUr
and Co FoUr show a characteristic two dimensional magnetism. The structurerefinements show very similar features in both types of structures;( I) a layerof two dimensional squared network of (metal-formate) 4 is stacked layer bylayer along the c-a.x.is, (2) metal ions are surrounded octahedrally by the foursquare-planar oxygen atoms belonging to different formate ions and by theot her two oxygen atoms of urea molecules, and (3) urea molecules connectedwith metal ions which belong to the upper and lower layers are reversely
coupled by two O· ·H-N hydrogen bonds, therefore the urea molecules act
as supporters between these layers . The essential difference between thetetragonal and the monoclinic structures is attributed to the ordering of thetwo asymmetric mol ec ular units A and B. In the monoclinic structure , thesquared network plane of (metal-formate) 4 consists of A-B-A-B quasi-squarerings where A ( B ) is the inversion of the A (B). While in the tetragonal
structure the squared network consists of A-A'-B'-B rings where the A (B)is ·coupled with A' (B') along the 2 1 axis. In both compounds the layers
are connected only by hydrogen bonds through urea molecules. For the
tetragonal compounds, two kinds of chirality are expected, ?41 21 2 or ?4 3 21 2 .
Here we also report the absolute structure for CdFoUr.
1) Fujino M., Achiwa N., Koyano N., Shibuya I., Ridwan & Yamagata K.,
J. Magn. Magn. Mater. 104/107 (1992) 851-852.
2) Yamagata K., Achiwa N., Hashimoto M. , Koyano N., Ridwan, Iwata Y.,& Shibuya I. , Acta. Cryst. (1992). C48 793-795.

168-35
CRYSTAL AND MOLECULAR STRUCTURE OF
ZINC(II) AND COBAL T(II) COMPLEXES WITH
4,5-DIAZAFLUOREN-9-0NE
N Venkata Lakshmi and K. Ravikumar, Laboratory of Crystallography,
Indian Inst. of Chemical Technology, Hyderabad 500 007, India,
G Prasuna and M V Rajasekharan, School of Chemistry, University ofHyderabad, Hyderabad, India
4,5-diazafluoren-9-one (dafone) was prepared by known procedures(Henderson, Jr., 1984). Solutions of Zinc(ll) (and Cobalt(ll)) chlorides
are treated with dafone solution in molar ratio in acid medium. Upon
evaporation these gave good single crystals of the respective complexes(MCI4(dafone H)2.2H20, M=Co, Zn). The Zinc complex solution was
yellow in colour throughout whereas the Cobalt complex solution was
pale pink to start with and turned dark green just before crystallization.
Crystal data : A.(Mo Ka)=0.71069A

ZnC14(dafoneH)2. 2H20, monoclinic, C2/c, a=l6.783(3), b=l2.087(2),c=l3.912(2)A, and /3=116.51(2) 0 • Z=4, R=0.043 and Rw=0.047.
CoCI4(dafoneH)2 .2H20, monoclinic, C2/c, Z=4, R=0.045 and
Rw=0.048.
The crystallographic data revealed that both structures are isomorphous.
The unit cell consists of protonated dafone as cation, (CJ4)2- anions andwater molecules of hydration. The metal atom lies on a crystallographic
two fold axis such that only half the molecule comprises the asymmetricunit. The water molecule connects the dafone ring and the (MC4)2- via
hydrogen bonding.

Henderson, Jr. L.J., Fonezek, P.R. & Cherry R (1984). JAm Chern Soc
106, 5876-5879.

16S-36

STUDY ON
BIS{trans-[BIS(DIPHENYLPHOSPHINO)ETHYLENE ]}TRICARBONYLIRON(O) AND
cis-[BIS(DIPHENYLPHOSPHINO)ETHYLENE]TRICARBONYLIRON(O)
Lung-Shiang Luh and Ling-Kang Liu Institute of Chemistry, Academia Sinica,
Taipei, Taiwan 11529, R. 0 . C.

Two routes have been employed in the synthesis of (transPh2PCH=CHPPh2)2-Fe(C0)3, 1, and (cis-Ph2PCH=CHPPh2)Fe(C0)3 , 2.
Method A proceeds with the Me3NO oxidative decarbonylation of (maleicacid)Fe(C0)4, followed by a precipitation of maleate salt in the presence ofeither trans-Ph2PCH=CHPPh2 or cis-Ph2PCH=CHPPh2. Method B is a lowtemperature quenching of (cis-cyclooctene)2Fe(C0)3 with either transPh2PCH=CHPPh2 or cis-Ph2PCH =CHPPh2 . Complexes 1 and 2 have be en
characterized with spectroscopic methods and X-ray diffraction. X-ray
crystallographic data for the title compounds : 1, monoclinic, space group
P2 1/c, a= 11 .532(2} A, b = 20.454(2} A, c = 22.652{6} A, ~ = 104 .49(2} , v =05173(2) A3, Z = 4; 2547 data with lo > 2.5cr(lo) were refined to R = 0.049 , Rw =0.051. 2, monoclinic, space group P21 /c, a= 10.064(1) A, b = 15.164{2} A, c =17.379{2) A, ~ = 101 .136(7) , V = 2602.2(5) A3, Z = 4; 2274 data with 10 >02.5cr{lo) were refined to R = 0.035 , Rw = 0.037. Comp lex 1 has a trigonalpyramidal Fe{O} center with two diaxi ally-coordinated, unidentate transPh2PCH=CHPP h2. Compound 2 has a tri gonal-pyramidal Fe(O) center with
one chelating cis- Ph2PCH=CHPPh2 occu pying one axi al and one equatorialsites, conforming to the cis-form .

16S-37
STRUCTURE OF IODINE{[3,3'-(1,3-PROPANEDIYLDINITRILO)BIS(2-BUTANONE OXIMATO)]-N,N'N" ,N"'}(2,2,2-TRIFL UOROETHYL)COBAL T(III)Silvano Geremia, Asadur Rahman*, Ennio Zangrando and Lucio
Randaccio, Dipartimento di Scienze Chimiche, Universita di Trieste,
34127 Trieste, Italy.
*Permanent address: Department of Physics, University of Dhaka,
Dhaka-1000, Bangladesh.
The compound is a coenzyme B 1 2 model of the type
L[Co(DO)(DOH)pn]R. Deep brown crystals of the compound were usedin collecting intensity data with an Enraf-Nonius CAD-4 diffractometer.
The total number of reflexions measured was 4107 with 2948 uniquereflexions (1>3cr(l)). The structure was solved by Patterson methods andsubsequent Fourier syntheses.
Crystal data:
Co(CnH19N402)(C2H2F3)I, FW 508.17, F(OOO) 250, monoclinic,
space group C2/c, a 28.928(7), b 7.558(1), c 17.142(4)A, f3 104.92(1)V 3621.53(2)A3, T 293K, deale 1.864 gms/cc, 1.1.26.74 cm-1, A. 0.7107A,
R 0.027.
0

The Co atom forms a distorted octahedral polyhedron with axial Co-l and
Co-C distances 2.6505(8) and 2.034(7)A respectively. The average Co-N
distance of 1.896A compares well with those reported by Geremia et al,
1992, and by Randaccio et al, 1989. The fluorine atoms in C2H2F3 arepartially disordered.
Silvano Geremia, Asadur Rahman and Ennio Zangrando, (1992) Acta
Cryst C48, (in press).
L Randaccio , N Bresciani Pahor, E Zangrando and L G Marzilli (1989)
Chern Soc Rev 18, 225-250.

1 6S-38

EXAFS STUDIES OF MONOMERIC/DIMERIC EQUILIBRIAOF NITRIDO-TECHNETIUM(VI) COMPLEXES INSOLUTION
G.A .

Williams,

Laboratory,

L.J.

Martin~allambie,

and

D.L.

Samuels,

Australian Radiation

Victoria 3085, Australia; andM. Nomura, KEK Photon Factory, Tsukuba-Shi, Japan .

The behaviour of Csz[TcNClsl in various concentrations of hydrochlori cacid and in non-coordinating acids such as p-toluenesulfonic acid h as
beenstudied

by

the

EXAFS

technique.

complex; previously salts of [TcNC1 4 ]-,have been isolated and evidence forThesolutionchemistryis[TcNCls] 2- and [TcNCl4(0Hz)]the

presence[TcNC1 4 -o-of

2[TcNClz(~-O)zTcNClz] - and [TcN(OHz) 3 (~-0)zTcN(OHz) 3 ] 2 + h as

TcNC14]4-.

been obtained by a variety of techniques.

The EXAFS spe c tra e na bl e a

study

presentoftheequilibria

andspeciesinhydrochloric

andsulphuricCsz [TcNCls]

inacids,

s o lutionsofp- toluene sulfon i cacid, trifluoromethanesulfonic acid, Na(OH) and water.

Of particularinterest is

the structural identification of the aqua cation and of
the [TczN 2 o2 (0H) 4 ] 2- anion in solution.

In

order

solutions,tomeasurespecialmanufactured,
and

EXAFS

spectraleak-proof

fromsampletheradioactiv etechne tium

had

designed ,

cells

to

be

filled with the aqueous solutions at ARL , leak-tested ,transported

independently ofinappropriate

packaging

the experimentalists .

At

to

the

PhotonFactory

the Photon Factory ,twomeasurement periods each of about 24 hours were available on the EXAFS
facilityon beam-line

transported to Japan .

BL-10.

In

all,

19

cells

were

successfully

In most cases the EXAFS spectra obtained wereof a high quality.

The Japanesesoftwarefor EXAFS analysis was provided and has bee ncommissioned at ARL .

Qualitative Fourier analyses and quantitativeevaluations of the spectra are presented which show the monomeric anddimeric structures of species present in the various solutions,the equilibria among monomeric,dime ric

~-oxo

and

and dime ric di (~-oxo)

species have been quantified from the measured EXAFS spectra .

16S-39
X-RAY STRUCTURAL STUDIES OF A NOVELDELOCALISED TRIPHOSPHAZENE(CF3hP=N=P(CF3)2=N=PPh3 AND THE TRIOSMIUM
CLUSTER COMPLEXESO s3 (C 0) u[ (CF3)2P=N =P( CF3h=N =PPh3]
H.G. Ang, W .L. Kwik and Y.M. Cai,

Department of Chemistry,

National

University of Singapore, Lower Kent Ridge Road, Singapore 0511.
The molecular structures of the title compounds were determined by single crystal
x-ray diffraction methods. The most significant and unusual fea ture is that thefour phosphorus-nitrogen bond lengths within free ligand and the complex are
nearly equidistant. Furthermore, all these lie wi thin the range of 1.518-1.584 A
expected fo r a P=N double bond. In addition, the two P-N-P segments within theP(IV)=N=P(Vl)=N=P(V) moiety approach near linear structures, with theP(IV)=N=P(V1) and P(Vl)=N=P(V) angles being 153.1° and 148.18° in L, and 162.4°
and 154.1° in C, respectively. The central phosphorus atom is four-coordinatedand hexavelent. This would suggest that the unsymrnetical PNPNP segment ishighly delocalised presumable due to the strong electron withdrawing CF3 moiety.
Crystal dataL:

[C 21 5 H 15F115N 2P 3] Monoclinic, Space Group P2 1 /n,~=

11.94(2) A, .Q = 14.368 A,£ = 15.576(3) A, ~ = 92.1 7(3) .
0C:[C 33 H 15N 2 0 11 F 12 Pp~] Triclinic, Space Group PI, .!1 = 9.154(2)A, .Q = 12.208(2) A£= 21.478(4) A, a = 73. 10(3) 0 , ~ = 78.90(3) 0 ,y = 68.92(4) 0 .

Ang H .G., Cai Y.M., Kwik W.L. and Rhein gold A.L., J.C.S. Chern. Commun., (1990)
1580.
Ang H.G., Cai Y.M., Kwik W.L., E.C. Morrison and D.A. Tocher., J. Organometal.
Chern., 403(1991)383.
Ang H .G., Cai Y.M., Kwik W.L., Leong W.K. and D.A. Tocher, Polyhedron10(1991)881 .
Ang H.G., Cai Y.M., Koh L.L., Kwik W .L., J.C.S. Chern. Commun., (1991)850.

165-40NOVEL NEUTRAL MOLECULES CONTAINING THE
As=N=P MOIETY. THE X-RAY STRUCTURES OF(CF3)2As=N=PPh3, [0SJ(CO)u((CFJhAs=N=PPhJ)] AND[0sJ(C0)9(Jl-H)2((CFJ)2As=N=PPhJ)]
H.G. Ang, W.L. Kwik and Y.W. Lee, Department of Chemistry, National
University of Singapore, Lower Kent Ridge Road, Singapore 0511, and
A.L. Rheingold, Department of Chemistry and Biochemistry, Universityof Delaware, Newark, Delaware 19716, USA.
The first perfluoro-alkyl arsinous azide (CF3)2A sN 3 undergoes
Staudinger reaction with PPh3 to give the novel perfluoro-alkyl arsino
phosphinirnine (CF3)2As=N=PPh3 1 with a short As-N bond length of
1.783(10) A . In complexation of 1 with triosmium clusters to give[Os3(CO)I 1((CF3)2As=N=PPh3)] 2 and [Os3(C0)9(Jl-H)2((CF3)2
As=N =PPh3)] 3 it has been shown from X-ray crystallography that 1
assumes a highly delocalized electronic structure over the unsymmetrical
As=N=P segment with a significantly short As-N bond. Enhanced
delocalisation upon complexation of 1 is reflected in the increase in As-Np angles from 126.6(6) 0 in 1 to 135.4(9t and 133.0(8) 0 in the complexes
2 and 3, resulting in a further shortening of the As -N bond fro m
1.783(10) A in 1 to 1.716(13) A and 1.739(16) A in 2 and 3 respectively.
These molecules represent the first examples of neutral compounds
containing a highly delocalized As=N=P non-linear heterocummulene
moiety with quadrivalent arsenic center.
Crystal data:
1CF3)2As=N=PPh3, orthorhombic, space group Fdd2,
a= 19.114(5), b = 42.918(8), c = 10.378(3) A, u = 8513(3) A3 , z = 16.
2
0 s3( CO )I 1[ (CF3)2As =N = PPh 3], monoclinic, spacegroup P2Jin , a= 10.849(6) , b = 24.117(9), c = 14.618(8) A,
p = 102.76(4) u = 3730.2(34)A3 , z = 4.
3
Os3(C0)9(Jl-H)2((CF3 )2As =N=PPh3), monoclinic, spacegroup P2Jin , a= 13.7457(16), b = 15.0939(17), c = 18.3746(23) ,p = 109.935C9t, u = 3583 .8(7)A3, z = 4.
0,

1 6S-41
X-RAY CRYSTAL STRUCTURE OF[ {WCIJ(PMe2Ph)2h{(J.L-NC6H4N-1,4} ].
THE FIRST STRUCTURAL CHARACTERISATION OF A
BINUCLEAR COMPLEX CONTAINING A 1,4-PHENYLENEDIIMIDO BRIDGE.
W . Clegg, R. J. Errington, D C R Hockless. J. M. Kirk, and C. Redshaw. Departmentof Chemistry, The University of Newcastle Upon Tyne, Newcastle Upon Tyne. NEl
7RU. UK.
The do-do phenylenediimido bridge complex [(WC4h{IJ.-NC6H4N-1,4}) may beobtained by treatment of WOC1 4 with C6H4(NC0)2-1,4 1 or, alternatively, from thereaction between WC1 4 and the diazide C6~(N3h-1,4.2 This polymeric compound ispresumably chlorine bridged by analogy with the structurally characterized[{W(NC6~Me- 4 )C4hl ? and reacts with PMe2Ph to give the binuclear dLdl rungsten(\/)complex [(WC13(PMe2Ph)2}2{1J. -N C6H~-1,4}). Single crystal X-ray structural
analysis shows the two mer, rrans-WCl3(PMe2Ph) fragments to be linked in an eclipsed
conformation by a linear, 7t-bonded 1,4-phenylenediimido bridge.

Crystal data: [(WCh(PMe2Phhh{1J.- NC6~N-1,4}] monoclinic, space group P2Jfc (No14). a=25 .262(3), b=10.781(1) , c=20.655(2) A, ~=96.79(13) 0 •The adoption of ar. eclipsed conformation, rather than a less sterically demanding
staggered conformation of phosphine ligands suggests that electronic factors may beplaying a part, although the two unique molecules of the title complex have significantly
different torsion angles. It is also interesting to note that the phenyl rings of thephosphines are all directed into the region between the metal atoms, which would seem tosuggest that the chlorine trans to the imido group is more sterically active than thephenylenediimido bridge.

1. R. J. Errington, C. Redshaw. Unpublished results.
2. D. Antonello, R. J. Errington. Unpublished results.
3. W. Clegg, R. J. Errington. (1987) Acta Cryst. C43, 2223.

; 68-42

MOLECULAR STRUCTURE OF TUNGSTEN-PHENOXIDEN. Kanehisa. Y. Kai and N. Kasai, Department of Applied Chemistry, Facultyof Engineering, Osaka University, Suita, 565, Japan, and H. Yasuda, Department
of Applied Chemistry, Faculty of Engineering, Hiroshima University, HigashiHiroshima, 724, Japan, andY. Nakayama, and A. Nakamura, Department ofMacromolecular Science, Faculty of Science, Osaka University, Toyonaka, 560,
Japan.
The use of bulky aryloxy or alkoxy metal compounds of group 4-6 as analternative to the cyclopentadienyl compounds is of current interest inorganometallic chemistry. We have reported a facile method for synthesizing a
new series of pure mono- and bis-(phenoxy)metal halides. In a series ofstructural studies on early transition metal phenoxides we have isolated andcrystallized the bis-(phenoxy)tungsten halide, WC14[2,6-(i-Pr)2C6H30h (1), as
dark red crystal. The molecular structures of tris-phenoxy tungsten halide,WCl3[2 ,6-(i-Pr)2C6H30J3 (2), and bis-phenoxy derivative, WC14[ 2, 6 (C6HshC6H3)lz(3), have been reported by Quignard et. al.(l987), and also themolecular structure of tungsten his-phenoxy derivative, WC14[2,6-(CH3hC6H30h (4) have been determined by us.
In order to elucidate the structural characteristics of the series of early transition
metal-phenoxides, the X-ray structure analysis of Complex 1 has been carriedout. The integrated intensity data were measured on a Rigaku four-circl e
diffractometer with graphite monochromatized MoKa. (1.=0 .71069 A). The
determination and refinement of the crystal structure of 1 was carried out by
using the TEXSAN software system. R and Rw are 0.086 and 0.063,
respectively without the hydrogen atoms .
Crystal data: WCl40zCz4H2s. Formula Weight 674.2, Crystal System
Monoclinic, Space Group P211n (No.14), a=9 .697(2), b=l7 . 115(2)c=16 .799(2)A, ~= 91.80(1) 0 Z=4, Dc=l.607 g/cm3.
Molecular Structure of 1 has six-coordinated geometry for the central tungsten
atom, and octahedral coordination sphere as well as 2, 3 and 4. In complex 2,
three phenoxy groups occupy the meridional sites. In complex 1, two phenoxy
groups occupy the cis position as same as in complex 3, while in complex 4trans.
Quignard F., Leconte M., Basset J-M., Hsu L-Y., Alexander J.J. & ShoreS. G .
(1987). Inorg. Chern. 26,4272

168-43
STEREOCHEMISTRY AND CRYSTAL STRUCTURE OF
DIPHENYLTIN DICHLORIDE COMPLEXES WITH
meso- OR rac-BIS(PHENYLSULFINYL)ETHANE
H G Wang, X K Yao, R J Wang, J X Bao and P X Shao, Central Lab. andDepartment of Chemistry, Nankai University, Tianjin, 300071,
China.
The bidentate ligands, RS(O)C2H4S(O)R, exist as diastereoisomeric rae
and meso forms which have different melting points X-ray crystal
structure analyses proved that the higher melting isomer is of the mesoform when R groups are methyl (Svinning et al. , 1976) and phenyl(Cattalini et al., 1979 ; Pelizzi et al., 1976). In a previous paper (Zlm et al,1990), X-ray diffraction results revealed that triphenyltin chloride(TPTC) reacts with either meso- or rac-bis -(phenylsulfinyl)ethane (BPSE)
to give the same crystal in which the ratio of TPTC:BPSE is 2:1 and theligand, BPSE, is the meso-isomer. In this work, 1: 1 complexes ofdiphenyltin d ichloride (DPTC) with meso- or rac-BPSE were preparedand their crystal structures were determined by X-ray diffraction
methods. DPT C•meso-BPSE (I) is monoclinic P211a , with a = 18.549(5),b = 12.672(4), c = 22.401 (3) A, ~ = 90.15(2) 0 , z = 8; R = 0.049.
DPTC•rac-B PSE (II) is monoclinic C2/c with a = 20.584(4) ,b = 12.726(1), c = 20.230(5) A, ~ = 96.91(3) 0 , z = 8; R = 0.036. Ineach complex, the tin atom has a distorted octahedral coordination with
two oxygen and two chlorine atoms occupying the equatorial positions,and the bidentate BPSE bridges between two Sn atoms to give a onedimensional chain After the complexing reaction, meso-BPSE retains its
configuration in crystal I, but one of the S atoms of rac-BPSE in crystal II
is dipositional disordered Reasonable thermal parameters for S atoms
were obtaine d when the occupancies of 0.5 were assigned to these
positions. Although both environments of the positions can meet thedemands of tetrahedral geometry for the S atoms, their chirals are inverse
to each other, which means that about half the rac-BPSE l ~g and s invert
their configurations in the complexing reaction with DPTC.
Cattalini, L , Michelon, G , Marangoni, G & Pelizzi, G (1979) J Chern.
Soc., Dalton Trans, 96-101
Pelizzi, G , Michelon, G- Bonivento, M (1976) Cryst Struct Commun, 5,
617-620
Svinning, T , Mo F & Bruun, T (1976) Acta Cryst, B32, 759-764
Zhu, F C, Shao, P X, Yao, X K, Wang, R J & Wang, H G (1990) 1norg
Chim . Acta, 171, 85-88

16S-44
COORDINATION OF TETRAMETHYLETHYLENEDIAMINEWITH HALOGEN BRIDGED LEAD(II)H. Miyamae. Y. Hatanaka, Y. Iijima, G. Hihara and M. Nagata,
Department of Chemistry, Josai University, Keyakidai, Sakado-shi,
Saitama 350-02, Japan.
Structure determinations of 1:1 adducts of 'Me4en' (N, N, N', N' tetramethylethylenediamine) with lead(II) halides (PbX2, X=Cl, Br, I) aredescribed. Colourless PbX2.Me4en crystals obtained by slow evaporationof appropriately stoichiometric solutions in ethanol at room temperature.
were used for single crystal X-ray studies at 295 - 298 K.
Crystal data:

PbCb.Me4en. Orthorhombic, space group P2lnb (No. 33),
a 8.102(19), b 15.096(34), c 9.258(29)AV 1132(5)A3. Dx 2.313 g.cm-3. IJ.Mo 15.44 mm-1.
PbBf2.Me4en. Monoclinic, space group P2IIn (No. 14),
a 18.370(5), b 8.213(3), c 18.734(5)A, p 117 .95(2) 0V 2497(1)A3. Dx 2.442 g.cm-3. IJ.Mo 19.91 mm-1.
Pbl2.Me4en. Monoclinic, space group P211n (No. 14),

a 17.295(3), b 9.226(2), c 8.499(1)A, p 88.93(1) 0
V 1355.9(4)A3. Dx 2.709 g.cm-3. IJ.Mo 17.01 mm-1.

The results show the lead atoms to be in six-coordinate, highly distorted
octahedral environments. In the chloride complex, the environment offour chloride and two nitrogen atoms is almost trigonal prismatic, withthe suggestion that any stereochemically active lone pair at the lead atom
might be accumulated at the centre of a Cl4 square face, the four Pb-Cl
distances ranging from 2.88 to 3.00(1) A. In the iodide complex, the1-Pb-I bond angle trans to the chelating ligand is considerably enlarged,
again possibly suggestive of a sterically active lone pair in a quasitrigonal bipyramidal array. In this description, the axial Pb-1 bondlengths (< > 3.223(2) A) are shorter than the equatorial values(< > 3.323(2) A). The bromide is still under investigation.

16T -45

CRYSTALLIZATION AND PRELIMINARY X-RAY STUDIESOF CALOTROPIN DII, A CYSTEIN PROTEASE FROM
Calotropis gigantea
Bankim Das, Sreya Ghosh, Sampa Pain, Indrani Dey, Goutam Biswas,
Bishnu P Mukhopadhyay, N K Sinha and Asok Banerjee, Biophysics
Department, Bose Institute, P1/12 C.I.T. Scheme VIIM, Calcutta 700054, India.
Rectangular needle shaped crystals of Calotropin DII, a single chain
polypeptide of Mr 24163, have been obtained by a microdialysis. The
enzyme crystallised in a monoclinic structure with space group ?21. The
unit cell dimensions are a=48.689(1)A, b=31.972(1)A, c=131.597(1)A,/3=97.735(3)0•The density measurement indicated the presence of four polypeptide
molecules in the unit cell. The VM & Vs values are 2.1A 3JD and 43 %respectively. The crystals are stable at room temperature (293K) and alsowith irradiation by X-rays, diffracting diffracts to at least 1.8A
resolution. Among the possible 22296 reflections, 11219 independentunique reflections have been collected using an area detector. A three
dimensional structure solution by the molecular replacement method is inprogress.

16T -46

CRYSTALLIZATION OF PROTEIN DISULFIDE ISOMERASEFROM BOVINE LIVER
G.Kurisu, C.Uematsu, T.Shiba, S.Harada, Y.Kai and N.Kasai,
Department of Applied Chemistry, Faculty of Engineering,Osaka University, Suita, Osaka 565, Japan.
Protein disulfide isomerase (PDI) is an abundant protein which is loosely
attached to the luminal side of the ER membrane. It catalyzes theformation of correct disulfide bonds of newly synthesized proteins in the
ER lumen. PDI exists as a dimeric molecule which consists of chemically
identical polypeptide chains of 57,000 molecular weight. In order tostudy its biological function based on its three-dimensional structure,
PDI has been crystallized. PDI was isolated from bovine liver according
to the procedure described by Lanbert & Freedmann. The purity of the
enzyme was checked using SDS-PAGE analysis and reverse-phase
chromatography. Crystallization was attempted using salts, polyethylene
glycol and organic solvents as precipitants. The screening of
crystallization conditions was performed by the batch method. Although
crystals of PDI appeared in a wide variety of conditions, the best crystal
was obtained from 20-30% polyethylene glycol 8000. (pHS.0-8.0) The
shape of the crystals was tetragonal bipyramidal. We are searching for
optimum conditions to grow the tetragonal bipyramidal crystals using thehanging drop vapor diffusion method.

16T -4 7

CRYSTALLIZATION AND X-RAY DIFFRACTION STUDY
OF PHOSPIDOLIPIDASE A2 FROM THE VENOM OF
Agkistrodon halys PALL AS
Gui Lulu, Niu Xiutian, yang Jian, Bi Ruchang,Liu Zhengjiong, Instituteof Biophysics, Academia Sinica, Beij ing 100101, China, andZhou Yuanchong, Lin Nianqin, Shanghai Institute of Biochemistry,
Academia Sinica, Shanghai, China.
The acidic phospholipase A2 from Agkistrodon halys Pallas consisting of
124 residues belongs to a class of phospholipase A2 which possesses afunction of inhibiting platelet aggregation.The enzyme was purified bypreviously described techniques (Acta Biochemica et Biophysica Sinica
16,664(1984)) and crystall ized by a vapour diffusion method. The
crystals were obtained from aliquots, containing 2,5Hexandiol, O.lmg/LNa20s-HCl and 15mg/ml protein, which were equilibrated against 65%
2,5Hexandiol solution. The crystals grow as long hexagonal prisms anddiffract to a resolution better than 2.5A. Some crystal data were
determined on a CAD 4 diffractometer. The space group is P61 with celldimensions a=b=8 3.2A and c=32.6A. There is only one molecule per
asymmetric unit. Diffraction data have been collected to 2.65A resolution
using an area detector. The orientation and position of the PLA2 moleculein the unit cell have been determined by a molecular replacement method
usi ng the known stru cture of C .atrox PLA2 as search structure.
Preliminary structure analysis has shown that the overall folding of thismolecule is similar to that of C.atrox PLA2. Structure refinement is inprogress.

16T -48
TWO CRYSTAL FORMS OF BOVINE HEART CYTOCHROMEc OXIDASE
E. Yamashita. Y. Morimoto, T. Tsukihara, Faculty of Engineering, The
University of Tokushima,Tokushima 770, andY. Fukumoto, Faculty of Engineering, Tottori University, Tottori 680,
K. Shinzawa-Ito, S. Yoshikawa, Faculty of Science, Himeji Institute ofTechnology, Kamigouri Akou, Hyougo 678-12, Japan.
Cytochrome c oxidase is a key enzyme of the respiratory chain in the
mitochondria. It catalyzes the oxidation of cytochromes by molecularoxygen and couples this reaction to translocation of protons across the
mitochondrial inner membrane. The proton gradient produced by thisreaction is utilized for A TP synthesis. Our aim is to determine thestructure in order to clarify the mechanism of the enzyme reaction. Two
different crystal forms were obtained: a hexagonal form crystallized fromsolution with a low salt concentration, and a tetragonal form crystallizedby salting-out with ammonium sulfate. The space group of the hexagonal
form was P62 or P64 with unit cell constants a=b=208.7A, c=282.3A. The
tetragonal crystal space group was 14t with a=b=253.2A, c=507.1A.
Intensity data for both crystals were collected using a Weissenberg
camera for macromolecular crystals with synchrotron radiation at the
Photon Factory, Tsukuba. A total of7,000 reflections with F>3cr(F) at 7A
resolution were obtained by the use of six hexagonal crystals. The
R -factor and correlation function for each pair of data sets of hexagonal
crystals show that the quality of the intensity data decreased steeply overlOA resolution.
Intensity data for the tetragonal crystal were collected by using several
crystals . Part of the data has been processed. By some criteria thetetragonal crystals are of higher quality than the hexagonal form.

1 6T -49

STRUCTURE ANALYSIS OF SERRATIA PROTEASE FROMSERRATIA SP.E-15
K. Hamada. H. Hiramatsu and T. Fujiwara, Faculty of Science, Shimane
University, Matsue 690, Japan , Y. Katsuya, Hyogo Prefecture Institute ofIndustrial Technology, Kobe 654 , Japan, Y. Hata, Institute for Chemical
Research, Kyoto University, Uji 611, Japan, and M. Sato andY. Katsube,
Institute for Protein Research, Osaka University, Osaka 565 , Japan.
Serratia protease, isolated from culture media of Serratia sp. E-15, is a

Zn-requiring metalloprotease consisting of a single polypeptide chain of
470 amino acid residues (Mr 50,600). The function and the substitutespecificity of this enzyme are similar to those of thermolysin, but themolecular weight of serratia protease is larger than that of thermolysin(Mr 34,600) and also the homology of the amino acid sequence between
both enzymes is quite low. Crystals were obtained from 28% saturated
ammonium s ulfate by a microdialysi s method. The crystals were space0group P2I2 I2I with cell dimensions a= 109.2, b = 150.9 , c = 42.6 A and Z= 4. The intensity data from the native and Sm-derivative crystals werecollected on an IP-diffractometer (R-AXIS Ila). Initial protein phases at
0

5.0 A resolution were obtained by single isomorphous replacement
supplemented anomalous-scattering information from Sm-derivative data
0

(SIRAS), and then the phases were gradually extended to 3.0 A resolution
using solvent-flattening procedure (Wang, 1985). A total of 6 phaseextension steps were required . After each phase-extension, phaserefinement was carried out at constant resolution . An electron density0
map at 3.0 A resolution shows a polypeptide folding, although there aresome ambiguous positions. The molecule has an ellipsoidal shape withapproximate 95x40x4o A.. The analysis of the detailed structure is inprogress.
Wang, B. C. (1985). Methods Enzymol. 115,90-112.

16T -50
X-RAY STRUCTURE ANALYSIS OF NEUTRAL PROTEASEFROM STREPTOMYCES CAESPITOSUS
A. Nagara. T. Kinoshita, S. Harada, Y. Kai and N. Kasai, Department ofApplied Chemistry, Faculty of Engineering, Osaka University,
Suita, Osaka 565, Japan and
S. Tunazawa and F.Sakiyarna, Institute for Protein Research, Osaka
University, Suita, Osaka 565, JapanA neutral protease, i.e., a zinc-containing metalloendoprotease from
Streptomyces caespitosus, has been crystallized. The crystals diffract tobetter than l.5A resolution with a rotating anode X-ray generator. Protein
phase angles were calculated by the multiple isomorphous replacement
method using two heavy-atom derivatives (HgCl2 and CH3HgCl). A 6A
resolution electron density map clearly showed molecular boundaries andthe folding pattern of the polypeptide chain could be traced on a 2.5A
resolution electron density map. A large cleft, located on the molecularsurface , was proved to be the active site of the enzyme by structure
analyses of inhibitor-complex crystals. A catalytically essential zinc atom
was also identified in the active site cleft as the highest electron density
peak. Model building of the protease is in progress based on the aminoacid sequence of 132 amino acid residues which has been determinedrecently by the authors.
Crystal data:

orthorhombic, space group P2J2I2I
a= 55.21, b = 55.27, c = 37.60A

S.Harada, K.Kitadokoro, T.Kinoshita, Y.Kai & N.Kasai (1991).
J .Biochem. 110, 46-49

16T-51
THREE-DIMENSIONAL STRUCTURE OF
OLIG0-1,6-GLUCOSIDASE AT 3 A RESOLUTION'f. Hata. I nstit ut e for Ch emic a l Re sea r ch, Kyoto Univ er si ty, Uj i, Kyo t o
611,

Japan,

H.

Agric ultu ra l
Sakyo- ku,

Kizakl. K.

Cbero l st r y,

Kyoto 606,

Wata nabe andY.

Kyot oJa pan,andcoroparat i ve st udies

on f i ve

Departroe nt

Uni versity,

Y. Kats ube,

Re searc h, Osaka Uni ver si t y, Suit a, Osaka 565,
Froro

Su zuk i ,Pre f ec tural

Inst i tute f orProteinJapan.

o l igo- 1, 6- g l ucosidases ofBaci 1Jus spec! es wi tb diffe r en t ra ngesofShi ro ogaroo,

variousof growt h teroperat ur e , it has

be en proposed that the en hanc ed therroostabl lity o f these enzymes wou l dbegaine d8- turns.

byIn

increasing
order

to

th e freque ncy

elucidate

theofprolinemechanis ms

occurrenc eatfunction

andofthermo stabi I i ty of the enzymes from their structur es , we have analysedth ec r ysta l

st ructure

of

the

enzymea cereus.

froro

Hexagonal

p i I Jar-sh aped crysta l s were obtained by a hanging drop va por diffusion
method(Watana be,

Ki taroura,

crystals be long to t he
a=b= l06 . 0 A,

Kat sube, &Suzuki,hy aun i t. Th e

Hg- , U- andsoaking method .

synch rotr onradia tion 0 =1. 04Al

Di [fraction

patter ns

were

Th e

558 re sidues)

Sm-derivative c ry sta l s werelnt ensi ty data

were co l l ected

at BL6A, stat ionr eco rded1991).

P6 , with cel l constants

c=L2 0. 0 A and wi th one molecule (Mr=66 , 000,in the asymmetricpr epared

Hat a,

hexago na l space group

on

Fuj i

in KEK-PF,
imagingusingJapan.

platesandpro cessed by the program pa ckage WEIS . Th e structure wa s det ermin ed by
MIR method using 12319 r eflections
molecu l e of the(81. 6%) up

to 3 A reso l utio n. Th ecom po sed of thr eestru ctu r a l domai ns. Th ea (a/8),-structure withan additional a-helix.

enzy me is

N-term in al domain ha s

The sub-dom ain and the C-t erminal

doma in hav e 8-sheet structures. The

active s it e of th e present enzyme i s expected to I ie in the C-terminalside of th e parall el 8-sheet
in

t he

primaryof theN-t ermi na l domai n froro comparison

and t er tiary structures

glucosidase of B. th ermog/ucosidasius

withamy l ases.

Oligo-l, 6-ba s 14 extra

pro I ines wh i ch roay

be res pons i b l e for the i ncr ease in thermosta b i I i ty,

com par ed wi tb thatof B. cere us.

Th e pr ese n t

st ru ct ure oft he B. cereus

enzyme suggeststhat most of t he prolines are loca t ed in the seco nd si t es of 8-turns.
Wata nab e, K. , Kitam ur a, K. , Ha t a, Y., Kats ub e,

FEBS /..ett. 290, 221-223.

Y. & Suzuk i , Y.

(199 1) .

16T -52
THREE-DIMENSIONAL STRUCTURES OF ASP ART ATE
AMINOTRANSFERASE FROM ESCHERICHIA COLI
AT 1.8 A RESOLUTION
A. Okamoto, Faculty of Science, Osaka University, Toyonaka, Osaka 560,
K. Hirotsu. and T. Higuchi, Faculty of Science, Osaka City University,
Sumiyoshi, Osaka 558, Japan.
Aspartate aminotransferase (AspA T) catalyzes the reversible
transamination of a-amino group from L-aspartate to a-ketoglutarate andis essential in nitrogen and carbon metabolism in the cell. In eukaryotic
cells, two genetically distinct isoenzymes of AspAT (the cytosolic enzyme
and the mitochondrial one) occur, whereas only a single form of AspAT
has been found in prokaryotic cells. The overall sequence homology
between E. coli and vertebrate enzymes is about 25%, and all theimportant residues for catalysis are conserved. However, the activity of E.
coli AspAT is lower than those of the enzyme from higher animals , andthe E. coli AspAT shows a broad substrate specificity.
The enzyme is in a2 dimeric form with a subunit molecular weight about
45000 . Each subunit has one pyridoxal phosphate (PLP) forming Schiffbase with a lysine residue at the active site. The E. coli Asp AT was
overproduced in the cell. Crystals of wild type Asp AT and wild type
AspAT 2-methylaspartate (2-MeAsp) were grown from Na2S04 solution
at pH 7.0 by hanging drop vapour diffusion. X-Ray data for these crystals
were collected to a resolution of 1.8A on a screenless Weissenberg typecamera using synchrotron radiation at the Photon Factory (6A2 station),
KEK. Refinements were performed using the coordinates of the Asp AT2MeAsp (2.5 A resolution) as starting models, by the program XPLOR.
The R-values reduced to 0.21 and 0.22 for AspAT and AspAT-2-MeAsp,
respectively.
AspAT consists of two identical subunits related by the crystallographic
two-fold axes. The subunit was divided into a small domain (from Nterminus to T47 and from M326 to C-terminus) and a large domain(theremaining amino acid residues). The overall structures of AspAT and
AspAT·2-MeAsp in E. coli were similar to those in higher animals in the'open' form and 'closed' form, respectively. The conformational change
from 'open' to 'closed' found in higher animals also occurred in E. coli
AspAT. This movement is explained by a rotation of the small domain
toward the large domain to close the active site. However, this rotation is
5° in E. coli AspAT, compared to 13° found in chicken mitochondrial
AspAT.
In the present study, we present the high-resolution X-ray structures of E.
coli AspAT in 'open' and 'closed' forms.

1 6T -53

STRUCTURE OF THE ACTIVE-SITE MUTANTS OFESCHERICHIA COLI ASPARTATE AMINOTRANSFERASE

1. Miyahara, K. Hirotsu and T. Higuchi, Faculty of Science, Osaka City
University, Surniyoshi, Osaka 558, Japan andA. Okamoto, Faculty of Science, Osaka University, Toyonaka, Osaka
560, Japan
Aspartate aminotransferase (Asp AT) has a coenzyme, pyridoxal
5'-phosphate (PLP) in the active site and catalyzes the reversible
transamination reaction
L-aspartate + 2-oxoglutarate = oxaloacetate + L-glutamate
via the 'ping-pong bi-bi mechanism' . The enzyme is in a2 dimeric form
with a subunit molecular weight 45000. Each subunit has one PLP
fo rming Schiff base with a lysine residue at the active site, and is divided
into a small and large domain. Our recent X-ray study confirmed that thegross conformation of E. coli AspAT and spatial arrangement of theactive site residues are essentially identical to those of pig cytosolic andchicken mitochondrial AspATs. The substantial movement of the small
domain from 'open to 'closed', depending on the binding of substrates
found in higher animals' AspATs, also occurred in E. coli AspAT.
X-Ray structures of the active-site mutants will be very informative inassigning functional roles to the active site residues in the catalytic
process. Crystals of R292V (the mutant enzyme with Val in place ofArg292), Y70W·2-methylaspartate (2MeAsp), and H143N-succinate weregrown from (NH4)2S04 or PEG4000 solution at pH 7.0 by hanging drop
vapor diffusion. X-ray data for these crystals were collected to resolution
2.1-2.2A on a screenless Weissenberg type camera using synchrotron
radiation at the Photon Factory, KEK, Japan. Refinements, performed
using the coordinates of the wild type Asp AT or the wild type Asp AT
2MeAsp by the program XPLOR, reduced the R-Values to 0.21, 0.19 and0.22 for R292V, Y70W·2-MeAsp, and H143N succinate, respectively.
The conformations of R292V and H143N succinate were quite similar to
those of AspAT in 'open' form and of AspAT·2-MeAsp in 'closed' form,
respectively. The conformation of Y70W·2-MeAsp is between open andclosed' forms. R292V shows a striking change in substrate specificity,
increasing reactivity toward aromatic amino acid substrates.The structureof Y70W shows that 2-MeAsp binds the active site of this mutant enzyme,
but does not form a Schiff base with PLP, which is always found in
AspATs. The activity of H143N was reduced by only 30%, probably
indicating that His143 is not obligatory for catalysis. The roles of R292,
Y70, and H143 will be presented on the basis of the detailed structures ofthe mutant enzymes.

1 6T - 5 4
X-RAY STRUCTURE ANALYSIS OF
ASPARTIC PROTEINASE FROM Irpex lacteus
H.Mizuno and N.Oogami,National Institute of Agrobiological
Resources,Tsukuba,Ibaraki 305,Japan,H.Kobayashi,K.Ka samo,
National Food Research Institute,Tsukuba,Ibaraki 305,Japan,
and I.Kusakabe and K.Murakami,Institute of Applied Biochemistry, University of Tsukuba,Tsukuba,Ibaraki 305,Japan.
Aspartic proteinase from Irpex lacteus has milk -clo tting
activity. This enzyme is the first example to have nodisulfide bonds in the family of aspartic proteinase . The
sequence identity is 28.2% with pensillopepsin,28.5% withrhizopuspepsin , 27.9% with bovin e chymosin ,and 27.1% withporcine pepsin.
Crystals have recently been obtained by the hanging drop
method using ammonium sulfate,and belong to the space gro up
P2 ,cell dimensions a=54.5,b=79.6,c=37 . 5A,B=96.8° ( Kobayashi
1
et al. ,J.Mo l.Biol(1992) in press ) .
Diffraction data set to 2 . 5A resolution was measure d on afour-circle diffractometer using one crystal.
A preliminary structure analysis was examined by molecula l'replacement (program XPLOR ) using a superpos i t io n of f o ur
known structures of aspartic proteinases as the sear c hmodel. The R- factor for the translation functi o n solution
was 0 . 516 for all data 8 . 0 - 3 .5A. The simulated anneal ing
and model fitting are in progress .

16T -55
STRUCTURE OF CHIMERIC 3-ISOPROPYLMALATEDEHYDROGENASE AND ITS THERMOSTABLE MUTANTS
M. Saku rai, K. Onodera, H . Moriyama. N. Tanaka, K. Numata, H .
Kirino, T. Oshima, Y. Katsubel), M. Satol), Faculty of Bioscience andBiotechnology, Tokyo Institute ofTechnology Midori-ku, Yokohama
227, Japan. !)Institute for Protein Research, Osaka University, Suita,
Osaka 565, Japan.
Several kinds of chimeric 3-isopropylmalate dehydrogenase have been
produ ce d by hybrid genes between Thermus thermophilus
HB 8(thermophile, T) and Bacillus subtilis (mesophile, M). Theirthermostability is intermediate between that of the parent compounds. We
report here the three dimensional structures of 4M6T, 2T2M6T and its
mutants, 2T2M6T-193L and 2T2M6TS82R. Here, 4M6T is composed of
the 40% mesophile region and 60% thermophile region, and 2T2M6T isconstructed by replacing the first 20% of 4M6T to the corresponding
thermophile.
Crystallizations were achieved by the hanging drop vapor diffusion
method using 1.0 - 2.0 M ammonium sulfate. We found that the request
on match salting out reagent for 2T2M6T may be a consequence of theincrease of e xposed polar residues and decrease of exposed hydrophobic
residues.
Crystals of all enzymes were isomorphous with that of the intact
thermophilic enzyme(lOT) which has space group P3221, a=b=78.6A,
c=1 58.1A . The structures were solved by molecular replacement andrefined by PROLSQ. The R-factor was 0.20 for 4M6T within 2.2A
resolution and 0.19 for the others within 2.1A, respectively.
Few differences were observed between all the structures lOT, chimeric
enzymes and its mutants . The deviations of the Ca positions from lOT
were correlated with their temperature factors, except for res idues
between 110 and 112, which were shifted more than expected from thetemperature factors. The uncorrelated movement may bring stress on themolecule and depress its thermostability from that of lOT. In the case of
2T2M6T-S82R, an extra hydrogen bond was found between R82 and E87
via a water molecule, which may cause the mutant to recover its
thermostabili ty.
Onodera, K. et al ( 1991). J. Biochem. 109, 1-2.
Imada, K. et al (199 1). J. Mol. Bioi. 222, 725-738.

16T -56
CRYSTAL STRUCTURE OF RIBONUCLEASE U2 AT 1.8 A
RESOLUTION
S. Noguchi andY. Satow, Faculty of Pharmaceutical Sciences, Universityof Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan,
C. Sasaki and T. Matsuzaki, Research Center, Mitsubishi Kasei Corp.,
Midori-ku, Yokohama, Kanagawa 227, Japan andT. Uchida, Mitsubishi Kasei Institute for Life Sciences, Minamiooya,
Machida, Tokyo 195, Japan.
Ribonuclease(RNase) U2 of Ustilago sphaerogena is a purine specific
RNase consisting of 114 amino-acid residues and preferentiallyhydrolyses 3'-5' phosphodiester bonds of adenine. The structure of a typeII crystal (P2t2!2t, a=49 .32A, b=61.27 A, c=34.95A) was determined by amolecular replacement method using the structure of RNase Tt, which has
a 32% sequence identity to RNase U2, as a search model. The model was
subjected to extensive model building and refinement cycles with
programs X-PLOR and PROLSQ. The present model has been refined toan R-factor of 0.166 for 9807 reflections from 8 A to 1.8 A spacing, withrms deviations from ideal bond lengths and from ideal bond angles being
0.012 A and 1.5° respectively. Fourier syntheses with Bijvoet anomalous
differences phased by the model without sulfur atoms confirmed three
disulfide bond positions as obvious peaks.
As compared with RNase Tt, RNase U2 has an outward protruding betahairpin with a type I tum at residues 73-76, and an alpha helix at residues
16-32 inclined about 10°. The inclination can be ascribed to a two-residue
shortening at the RNase U2 loop region which follows the helix. The
arrangement of Glu62, Arg85, and HislOl side chains at the catalytic site
is similar to that of RNase Tt. These side chains are hydrogen-bonded to asulfate ion which marks a phosphate binding site. Part of the presumed
base-recognition site is covered with Tyr78 and Ser80 residues of aneighbouring molecule. The side chain of Glu46, which is widelyconserved in microbial RNases and plays an important role in guanine
recognition in the case of RNase Tt, extends away from the baserecognition site.

1 6T -57

STRUCTURE ANALYSIS OF PHOSPHOLIPASE A2FROMTHE VENOM OF TRIMERESURUS FLAVOVIRIDIS
E. MATSUEDA, A. SUZUKI, T. YAMANE and T. ASHIDA,
School of Engineering, Nagoya University, Nagoya 464-01, Japan
Phospholipase A2 (PLA2) from the venom of snake, Trimeresurusflavoviridis, is a homo-dimeric enzyme which hydrolyzes the ~-ester
linkage of phosphatidylcholine. A subunit is composed of 122 residues
with MW 14,000. Crystals of PLA2 were obtained using polyethylene
glycol 6,000 as a precipitant at pH 4.9, but these crystals were heavily
twinned. To obtain non-twinned crystals, repeated seeding was performed
using the crushed twinned-crystals as seeds (Shinoda et al. , 1990). The
crystals belong to space group P21 with a=44.1, b=55.7, c=48.8A, and~=92.4°. An asymmetric unit contains one dimer. The structure analysis
proceeded with the molecular replacement method. All diffraction data
for this method were collected on a four-circle diffractometer. Self- andcross-rotation searches were performed using the fast rotation function
with 8.0-4.0A data. The integration radius was 23A. Self-rotation search
resulted in an almost unique set of peaks (40% height of origin), from
whose positions, two subunits in the asymmetric unit are related by anon-crystallographic 2-fold(or 21) axis. Cross-rotation searches were
performed using different two subunits of venom dimeric PLA2 from theWestern Diamondback rattlesnake (68% sequence homology) as a searchmodel. In both cases of the search model, the two highest peaks indicate
the same two orientations of the target subunit. These orientations lead tothe same non-crystallographic diad symmetry found in the self-rotation
search. Thus the orientation of the protein is uniquely determined. A
translation search is in progress using both the Crowther & Blow method
and the R-factor minimization procedure.
Shinoda, Y., Shouji, A., Yamane, T., Suzuki, A., Ashida, T., Kihara, H.
& Ohno, M. (1990). J. Biochem. 107, 84-86.

16T -58
CRYSTAL STRUCTURE OF CHICKEN GIZZARD
G-ACTIN•DNASE I COMPLEX AT 2 A RESOLUTION
K. Sasaki, K. Sakabe*, N. Sakabe#, H. Kondo+, and M. Shimonurat,
Coll. of Medical Technology, Nagoya University, Higashi, Nagoya 461.
* Department of Chemistry, Faculty of Science, Nagoya
University, Chikusa, Nagoya 464.
# National Lab. for High Energy Physics, Tsukuba, Ibaraki 305.
+ Department of Biology, Faculty of Science, Nagoya Univ.
Chikusa, Nagoya 464.
t Faculty of Education, Tokohagakuen University, Sena 1000,
Shizuoka 220, Japan.
Although the homology between skeletal muscle actin and smooth muscle
actin is high, the super-structure of skeletal muscle and differ from thatof smooth muscle. For instance there is no troponin in smooth muscle. It
would be interesting to understand the structural differences between bothactins, at atomic level. We started an atomic level crystal structure
analysis of smooth muscle actin; chicken gizzard G actin•DNase I
complex in 1977. Crystals of the complex were prepared from a mixtureof 2mM ATP, 2mM MgCh, 0.1mM CaCh, 1mM NaN, 8 %(W/V)
polyethylene glycol and 0.05M imidazole buffer at pH 6.6. The crystal
system is orthorhombic with space group P212121 . The cell dimensions
a=42.02, b=225.3 and c=77 .4A, differ from those of skeletal muscle actin(Suck et al, Proc. Natl. Acad. Sci., 1981, 78, 4319). Intensity data werecollected on the Weissenberg camera for macromolecular crystallography
at BL6A2 combined with imaging plate and image reader BAlOO. The
data were processed using Program "WEIS". Initial phases were
calculated with five heavy atom derivatives (YB , PCMB, MMA, FMA,
and BrATF) using the MIRA method. The figure of merit was 0.69 at
2.5A resolution. Chain tracing was carried out on a mini-map. Each atom
was then assigned by PS390 using "FRO DO". Coordinates thus obtained
were refined using the "XPLOR" program. The R value is 0.194 with arestrained B value, including 100 water molecules, for 10-2 A resolution
data. The chain is very similar to that of skeletal muscle G-actin (Kabschet al, Nature 1990, 347 37) except for 4 N-terminal and 10 C-terminal
residues. The position of 373 cystein was confirmed by biochemical
analysis with crystals of a Cl4PCMB derivative prepared by soaking(H. Hayashi and H. Kondo, Private communication). Their actin used forcrystallization was treated by protease and 3 terminal residues are cut
from the original. One has a residue at the N-terminal end additional
tothat in chicken gizzard actin. The different structure at both terminals
might be caused by primary structure differences from each other. The
relation of structure to function will be discussed.

16T-59
STRUCTURE OF CARBONIC ANHYDRASE II: REFINEMENT
AND COMPARISON WITH OTHER KNOWN CARBONIC
ANHYDRASE (CA) STRUCTURES.
Vinay Kumar and K.K . Kannan, Solid State Physics Di v ision,
Bha bha Atomic Research Centre, Bombay-400085 , India .
The crysta l
structure of Buffalo Car bonic anhydrase (II)enzyme (BCAII) (Vinay et al., 1989) ha s been refined against
2 . 1A resolution data collected u sing synchrotro n radiation at
Photon Factory,
Japan.
Refinement of the structure wasca rr ied out using PROLSQ suite of programs and man u al modelbuilding against Fourier maps on IRIS-4D graphics using TOM.
Except for two residues on - NH 2 ter min us and two residues
e l sewhere , all the residues cou ld be located and fitted in
the Fo u rie r maps. The stereoc h e mi stry of the fina lmodel isgood with rms displacement of 0. 016A for bond distance-s a nd
22° for staggered torsion angles. The R-factor for the final
model wit h 2040 non-hydrogen protein ato ms and 230 solvent
mole c ules is 19.1% . The rms shift for postitional pa ra metersin the final PROLSQ cyc le was 0 . 020A. The refined structu r eo f BCAI I was co mpared with ot h er known CA structures viz. ,HCAI and HCAII.
The three structures were observed to be
h ighly homologous with the maximum rms displacement of about
1A for 1024 main chain atoms, in contrast to the sequences imilarity of 60%. The maximum deviation of about 5A in the
po lypeptide chains is observe d in a n external loop region.
Alignment of sequences of six CA isoenzymes (Okuyama et al .,1992)
reveals abo ut 16% identity (40 AA residues). Thec omparison of the 3D structures helps
in elucidating thevital role of many invariant residues. It is being proposedthat the invariant Glu117 residue, which is buried and not in
the active site, may be essential for the catalysis by CA
enzymes.
Similarily, invariant Pro30 a nd Arg254 may be vita lfor the structural integrity of CA enzymes. The details will
be presented.
(1989). Current
Vinay Kumar., Kannan,
K.K & Chidambarm, R .
Science, 58 , 344 - 348 .
Okuyama,T.,
Sato , S.,
Zhu,
L.X.,
Waheed, A & Sly , S.W.
( 19 92) . Proc. Natl. Acad. Sci. USA, 89 , 1315-139.

1 6T -60

METAL-PROTEIN INTERACTION: BINDING OF MERCURY
TO CARBONIC ANHYDRASE I ENZYME
5. OJakravarty, V.S. Yadava and K.K. Kannan, Solid State Physics Divisi011, BhatiJa
Atanic Research Centre, BariJay 400 085, India.
It is well knol.n that Ire tal ions play an inportant role in the stability andfunctioningof enzymes.

1l.o structures, an organo-rretallic sulfonamide, lld/rely,

3-acetoxy H=Iolry, 4- anino benezene sulfonamide, carplexed to the Zn2+ containing(bolo) - Hl.m3n Carbonic Anhydrase I etJZY7!E and an inorganic salt f.l](CI~ carplexed tothe apcrenzyrre (Zn2+-free l£AI) have been refined using ffiOLSO pack<lge.

are 0.192 and 0.197 respectively.

The R-factors

The refined structures sJ:x:M that the H=Io1ry ion

does not ranain bonded to the benzene ring wtlich binds in the active site of thealZJII7Ie in the foiTIEr carplex.

212 nearlymInstead, it coordinates to the sulfhydryl group of CYS
2
In the 1>] ++ apo - l£AI structure H}+

away fran the active site.

binds to CYS 212, and replaces Zn

2+

at the active site as~.ell.

Although thephenarenon of sulfhydryl group coorr:l:inating to M=:ury is well kna.n and has beenreported earlier by Kannan et al for Carbonic Anhydrase enzyme, the present refinarent
shows for the first tiire llllltiple occupancy sites of H=Io1ry near CYS 212.

n.o Mercury

sites w.ith occupancies 0.59 and 0.20 have been located in this region and there is astatic disorder of residue 212 wnere

the sulfhydryl

confonnations arourr:i one of the H=Io1ry sites.
sites

have

group shows 0..0 possible:n.o partial occupancy Mercury bindin;Jalso been identified upon refinEment

for

the

first

tiire

in

the

organaretallic cmplex structure but not in the inorganic salt carplex . Che of theseis in the vicinity of the 182-186 tum and the other is near U1J 189.

The protein

structure in the region of residue 189 shows a drastic change of confonnation as
carparedto the native enzyme in both the cases.

Mercurials cmplexed to /£All

isozyme reported in literature, hol..ever, do not induce the changes Irentioned above inthe structure probably because Cys 205 of /£Ali is located oo the surface of theprotein and cys 212 of /£AI is buried in the structure.

Also mercury ion is not /xJund

to His 64 or any of the other active site residues of the l£AI holo enzyme unlike thatreported for lD.II.

The details of these stiJd.ies and a thorough cmparison w.i11 bepresented.

K&lnan, K.K. , Vaara, I., /lbtstrand, B., Lovgren, 5., Borell, A., Fridborg, K. & Petef,M.

(1977). Drug Action at the 11:Jlecular Level, edited by G.C.K. Roberts, pp. 73-91.

Londoo, U.K.

16U-61

STRUCTURE AND MOLECULAR MOTION IN
THE ALKALI METAL SALTS OF PENICILLIN V
Alison J. Edwards, Keith Prout, Christopher
M. Dobson, Jarnila Fattah, Stephen J. Reyes, Jocelyn E. Taguchi, J. Mark
Twyman, David J. Watkin and Michaela Wendeler. Chemical
Crystallography and Inorganic Chemistry Laboratories, Oxford University,
Parks Road, Oxford OXl 3PD, U . K.
NMR studies suggest that there is a substantial motion of side chains within
the lipophilic interior of globular proteins. Specifically, the phenyl side
chains undergo 180' flips with a rotational barrier of less than 100 kJ mol-l.
Although this has been interpreted as evidence of a fluid structure forproteins there is scattered evidence that similar motions occur in molecular
crystals.
We have systematically examined a series of organic molecular crystals, thefree acid and the Li+, Na+, K+ (above and below the second order phasechange at about 80'C) and cs+ salts of Penicillin V (phenoxypenicillin) by
X-ray crystallography and solid state MAS-NMR to determine whether
similar side chain rotations can occur in the crystal and to relate any side
chain motion to structure.
Phenyl ring flips have been characterized in all the Pen V derivatives studied
to date and a wide range of rates and activation energies for the process in thevarious environments has been determined. In addition a second type ofmolecular motion has been observed in the KPenV system. At room
temperature the structure consists of four formula units per asymmetric unit,
whilst above the phase change at 305 K this is reduced to two.

Carefulconsideration of the X-Ray diffraction and solid state nmr evidence leads tothe conclusion that the structure existing above the phase change is an
example of dynamic disorder occuring in the crystalline state.

16U-62
CRYSTAL STRUCTURE OF THE DNA FRAGMENT
d(CCGGGCCCGG)
M.A. Viswamitra and D.Ch ampion Christdoss Selvakumar, Department of Pl~ysics,Indian Institute of science, Banga lore and J awahar la l
Nehru Centre for Advanced Scientific research, Indian Institute of Science campus, Bangalore - 560 012, India.
N.Ga utham, Departme nt of Biophysics a nd crystallography, Madras
university, Madras - 600025, India.
Single crys tal X-ray diffraction studies h ave thrown significant lighton the fine structural details of the double h elix a nd its several polymorphic forms. In our laboratory we have r ecently crystallised andsolved the structure of the DNA fr agment d(CCGGGCCCGG ) a self
complementary decamer duplex.
Crystals suitable for data collection (0 .5 mm x 0.3mm x 0.2mm) weregrown in a period of two to three weeks from a dro plet containing
0.1 ml\1 DNA, 0.3 mM MgC1 2 , 0 .5 ml\1 sodium cacodylate, 0.1mM
spermine tetrachloride with 15%(v/v) l\1PD (2-methyl 2,4 pentanedial) against 80%(v jv) MPD in the rese rvoir. Precession photographs· confirmed the space group to be P2 1 2 1 2 1 w ith the cell dimens ionsa24.592, b
43.535 and c ·= 46.689 A . Intensi ty dat a was collectedon the Enraf Nonius CAD4 Diffractometer to 2.5 A resolution provi ding 1659 unique reflections .

==Structure solution attempted with MERLOT (Paula Fitzgerald, 1988)
with the coordinates of an homologous B-DNA decamer sequenced(CCAGGCCTGG) (Heinemann and Ailings, 1989) did not yield any
solutions . The multidimensional search procedure ULTIMA (Dov Rabinovich and Zippora shakked, 1984) provided strong peaks for the
input A-DNA model generated using the fibre diffraction coordinates
given by Amott and Hukins (Arnott.S and D.W.L. Hu~kins,1972).
Preliminary refinement shows the fragment to adopt the A-DNA conformation. Further refinement is in progress and the full structure will
be reported elsewhere.
Amott and Hukins, Biochem. Biophy. Res. Comm.,47,1504 - 1509
(1972).
Dov Rabionvich and Zippora shakked, Acta cryst,A40, 195- 200 (1984).
Heinemann. U and Ailings . C, J. Mol. Biol.,210, 369 - 381 (1989).
· Paula Fitzgerld, J. Appl. Cryst. ,21, 273 - 278 (1988)

1 6U-63

MOLECULAR STRUCTURE OF AN RNA DUPLEX WITH
FOUR SUCCESSIVE NON-WATSON-CRICK BASE PAIRS
S. Fujii, Y. Tanaka, T. Sakata and H. Hiroaki, Faculty of Pharmaceutical
Sciences, Osaka University, Suita, Osaka 565,
S. Uesugi, Faculty of Engineering, Yokohama National University,
Kanagawa 240 and
T. Tanaka, Protein Engineering Research Institute, Suita, Osaka 565,
Japan
Thermal denaturation and NMR studies show that a tridecaribonucleotide,r(UGACWCGGCUC) forms a stable intramolecular hairpin structure inaqueous solution. Crystals of this RNA oligomer belong to space group C2
with a=38.49A, b=32.30A, c=38.76A and (3=117,56° with one molecule
per asymmetric unit. Diffraction data were collected to a Bragg spacingof about 1.8A, and the molecular replacement method was applied. The
stem region of the molecule is considered to adopt the A-form. To
detem1ine the precise position of the stem region , rotation, PC andtrans lation functions were calculated. The remainder of the structure
including 39 solvent water molecules was found by iterative phasing andrefinement. The current R factor is 17% for 2654 reflections (~1cr). In
the crys tal lattice, two base-paired RNA strands, related by acrystallographic 2-fold axis, constitute the A-form double helix structure.
Standard Watson-Crick (W&C) pairings are formed in the terminal fourbase pairs on either end, whereas non-W&C base pairs are found as a four
successive base pair array (U=G, U=C, C=U and G=U) in the middle ofthe duplex formation. 5'-End base, U is not involved in base pairing of
this duplex formation, and connects the duplexes by U-U base pairing.
Several of the water molecules that were observed provide morestabilization of non-W &C base pairing by hydrogen bonding with baseatoms and the 2'-hydroxy group of ribose .
Sakata, T. , et al. (1990). Nucleic Acids Res. 18, 3831-3839.

16U-64
CRYSTAL STRUCTURE OF
BOC-D- V AL-ALA-LEU-ALA-OME
Vasantha Pattabhi and C. Sadasivan, Department of Crystallography andBiophysics, University of Madras, Guindy Campus, Madras-600
025, India, and
S. Durani and V. Bobde, Department of Chemistry, ndian Institute ofTechnology Powai, Bombay-76, India.
Several tetrapeptides with D-residues introduced at different positions
have been synthesised. The aim of this project is to systematically study
the change in conformation of the short peptides in the presence of
D-residues. One such peptide viz Boc-D-val-ala-leu-ala-OMe has been
crystallised from aqueou s butanol and its crystal structure has been
determined. The compound crystallises in the orthorhombic system,
space group P21212, a=9.464(5)A, b=35.615(5)A, c=9 .703(2)A ,V=3270(3)A3. The structure has been refined using bond length
constraints for the leu, val side chains and the solvent molecule.
R=0.091 , Rw=0.127 for 1324 observed reflections with l>2.5.cr(I). The
molecule is in the extended ~ conformation with deviations at the leu
residue. The molecules are extended along the longest axis, viz b andpacked in an anti parallel ~ sheet with four N-H ...O hydrogen bonds oflength ranging from 2.89 to 3.08A. The so lvent molecule has been
located. Energy calculations on this and other related molecules indicatethat the crystallographically observed conformation is not the lowest
energy conformer but is one among a few other possibilities. Obviously
packing forces may be the deciding factor.

16U-65
UNUSUAL CONFORMATIONAL FLEXIBILITY IN NlSUBSTITUTED UNCOMMON PURINE NUCLEOTIDES:
CRYSTAL STRUCTURE OF
1-ALLYL-ISOGUANINE and I-ALLYL-XANTHOSINE
Yen-Chywan Liaw+, Ji-Wang Chern# and Andrew H.-J. Wang++Laboratory of Structural Biology, Institute of Molecular Biology, Academia Sinica,
Taipei, Taiwan, ROC. #institute of Pharmaceutical Research, National Defense Medical
Center, Taipei, Taiwan, ROC.
Several new NLsubstituted uncommon purine nucleosides, including doridosine (1methyl-isoguan osi ne; m-iG), 1-allyl-isoguanosine (a-iG) and !-allyl-xanthosine (a-X),
have been sy nthesized and tested as agonists for the adenosine receptors. Some havesmooth muscle relaxant or negative chronotropic activities. The x-ray crystal structure ofthese co mpounds has been determined at atomic resolution in order to understand thestructure-activity relationship. The structures were solved by direct me thods and refinedby full-matrix least-squares refinement procedure. The crystallographic parameters are :a-iG, space group P2J, a=10.573 (1) A, b=21.955 (2) A, c=14.360 (1) A, b=l10.65(l)O , no. of 3cr Fo's=4585, R=0.047 ; a-X, space group ?212121 . a=l6.015 (2) A,
b=16.239 (I) A, c=5.3723 (5) A, no. of 3cr Fo's= 1169, R=0.031. In the a-iG crystal,
there are jour independent molecules (wi th different conformation) per asymmetric unit.
While all four molecules adopt anti ccN glycosyl torsion angle, their riboses have three
distinct puckers (C2'-exo, c2'-endo and ci '-exo). In contrast, the a-X structure adopts
a syn ccN glycosyl torsion angle, which is stabilized by an intramolecular hydrogenbond between the N3 of purine base and the o5' of the ribose (in c2'-endo pucker).
Both purine bases (1-allyl-isoguanine and !-allyl-xanthine) are mainly in the ketotautomer form . For the isoguanine base, the averaged NLc2 bond distance (1.42 A) is
significantly longer than that (1.375 A) of the guanine base. For the xanthine base, N3
nitrogen has an imino proton attached which is unambiguously located in the electron
density map. The surprising flexibility in the ribose ring of these NLsubstituted
uncommon purine nucleosides suggests that the ribose moiety may not participate in thebinding of nucleoside to the adenosine receptors.

16U-66

CONFORMATIONAL ANALYSES OF AC-RING BICYCLIC
COLCHICINE ANALOGUES
of
Department
andMackay,Greenwood
M.F.
R. J.
Chemistry, La Trobe University, Bundoora, Victoria
3083, Australia.
The alkaloid colchicine ( 1) is a potent antimitotic
agent (Brossi, M. et a.l., J. Ned. Res. Rev., 1988,
8 ( 1), 77) which exerts its effect by binding to thecyctoskeletal protein tubulin, and thus inhibits its
The existence of twopolymerization to microtubules .
partial binding sites on tubulin has been established,
one for the A-ring and one for the C-ring. In view ofthis , and the potent antimitotic properties of the ACring analogues, structure-activity studies of colchicine
analogues lacking the central B-ring c ould provide
insights into the mode of the colchicine-tubulininteraction. We have used molecular mechani c s to
calcu l ate the low energy conformations of six bicyclic
analogues ( 3)- ( 8) whose X-ray structures are known.
good agreement between the
There is in generalminimized and X-ray structures, all of which mimic the
structure of isocolchicine (2), the inactive isomer ofcolchicine. However , the magnitudes of the barriers torotation about the central C-C bond indicate that theanalogues could assume the colchicine structure insolution and so achieve the configuration necessary forbinding to tubulin.
0

X

CCI-b
(1)

(2)

R"
(3) R - R' c R"- OCH3, X c H(4) R = R' c R"- OCH3, X = Cl
(5) R- R' ~ OCH 3 , R" s X = H(6) R' - R" = OCH3, R s X m H(7) R = R" c OCH3 , R' = X = H(8) A" = OCH:J, R = R' = X = H

1 6U-67

ABSOLUTE CONFIGURATION AND CONFORMATION OF ANOVEL ANTIALLERGIC AGENT KW4099
N.Hirayama, Department of Biological Science and Technology,
Tokai University, 317 Nishino, Numazu, Shizuoka 410-03 , Japan
T.Sugaya, S. Tomioka, Sakai Research Labs., Kyowa Hakko Kogyo
Co.Ltd. , 1-1-53 Takasu-cho, Sakai, Osaka 590, Japan,
E.Ohshima and N.Obase, Pharmaceutical Research Labs.,
Kyowa Hakko Kogyo Co.Ltd., Nagaizumi, Shizuoka 411, Japan.
The title compound is a novel antiallergic agent and also possesses
thromboxane A2 antagonist activity. X-ray analysis of the methyl ester of
the title compound has been undertaken to determine its absoluteconfiguration. Optical resolution has been successfully accomplished byuse of ( + )- or (-)-BNPPA(2,2'-( 1,1 '-binaphthyl)phosphoric acid).
Crystallization of the (+)-BNPPA salt from a methanol solution gavewell-formed colourless prisms. The results indicate that BNPPA acts as
an excellent crystallization agent because many attempts at crystallizationof KW4099 and its methyl ester have failed. BNPPA may be quite usefulfor crystallization of natural products.
Crystal data: C3oN34N03S.C2oH100 4P.CH40 orthorhombic. P2r2r2 r,
Z=4, a=l6.465(2), b=30.163(3), c=9.06 1(1) A, J..l (Cu Ka)=14.0 mm-1
The absolute configuration of an asymmetric carbon is determined to be R
by agr~em ent with the (+) -BNPPA with the known chirality. The
6, 11 -dihydrodibenz[b,e ]oxepin skeleton adopts a fo lded conformation.
The conformation of theskeleton is considered to beimportant for biologicalactivity. The dihedral angle
between the two phenyl rings
is 43.3°. The angle is 34.2° in
the methyl ester of isoxepac(Matsuzawa, E.S ., Hirayama,
COO MeN., Ohshima, E. & Obase, H.
Acta Cryst. in the press).

16U-68
STRUCTURE DETERMINATION OF THE BLUE FLOWER PIGMENT,COMMELININ, FROM Commelina communis
A Nakagawa*, K.Yoshida§, T.Kondot, T.Kawai1 and the late T.Goto,*Photon Factory, KEK, 1-1 Oho, Tsukuba, Ibaraki, 305, Japan§School of Life Studies, Sugiyama Jogakuen University, Chikusa, Nagoya, 464, JapanI Chemical Instrument Center, Nagoya University, Chikusa, Nagoya, 464-01, Japan~Laboratory of Organic Chemistry, Faculty of Agriculture, Nagoya University, Chikusa,
Nagoya, 464-01, Japan
Co=elinin is a blue pigment from blue-flower, Commelina communis (Japanesename:Tsuyukusa). It is a metalloanthocyanin consisting of six malonylawobanins, six
flavoco=elinins and two magnesium ions. Its molecular weight is about 9000. We
have solved the crystal structure of Cd-co=elinin, in which the complexation metal
Mg2+ is replaced with Cd2+, elucidating the mechanism of flower coloration.
Cd-commelinin crystals, obtained from aqueous-ethanol solution. have space group P321
with cell dimensions a=b=31.329A and c=33.590A. As there are two commelinin
molecules in a crystallographic unit cell, there is one-third of a molecule in the asymmetricunit (containing a total of 210 non-hydrogen atoms and about 60 solvent atoms).
Diffraction data for Cd-commelinin was collected using the Weissenberg camera for
macromolecular crystallography (Sakabe, 1991) with imaging plates (Miyahara eta/.,1986) on BL-6A2 at the Photon Factory, KEK, using an X-ray wavelength 1.04A to a
resolution of 0.75A. For a total of 19588 independent reflections the merging R-factor
based on f2 was 6.66%.
One direct method solution using SHELXS-86 (Sheldrick, 1990) showed two verystrong peaks at positions corresponding to Cd ion positions determined from Patterson
maps. Interpretation of electron density peaks calculated from this solution using
SHELXS-86 was carried out on a computer graphics system using FRODO (Jones,
1978). A t the initial stage of model building, a total of 63 peaks were assumed as parts ofmolecule; the R-factor calculated for these positions was 39.8% at LOA resolution. Cycles
of model building into different Fourier maps, and refinement of the atomic parameters
using the XTAL program system(Hall and Stewart, 1990) finally revealed the entire
atomic structure of Cd-co=elinin. The present atomic parameters, refined to an R-factorof 13.2% at LOA resolution (10164 reflections), include 30 water molecules. Anisotropic
thermal parameters are applied to 207 atoms where the isotropic thermal factors, U, are--·--·-----··--·---- ··-·-----····- ··smaller than 0.2.
Cd-commelinin is a novel type supramolecule
whic h has several kinds of association that
include self-association, co-pigmentation andan intramolecular sandwich type association.
Once a molecule is formed, not only
coordination of metal ions, but also strong ·hydrophobic stacki ng and hydrophilicinteraction make a quite stable molecule.
Hall, S.R . & Stewart, J.M. (1990) Eds .
Xta/3.0 Reference Manual. Univ. Western
Australia and Maryland
Jones, T.A. J. Appl. Cryst., II, 268 (1978)
Miyahara, J. et al. (1986) Nucl. Inst. l
Methods ,A246, 572~abe, N . (1991) Nucl. Inst. Method, A303, _. · ·· - -·-..- - · ----·---· - ..·- ·J

Sheldrick, G.M. (1990) Acta Cryst. A46, 467

16U-69
STRUCTURAL STUDIES ON
LINKED OLIGOSACCHARIDES

13-(1~3)

K. Noguchi and K. Okuyama, Faculty of Technology, Tokyo Universityof Agriculture and Technology, Koganei, Tokyo 184, Japan and
S. Kitamura and K. Takeo, Department of Agricultural Chemistry, Kyoto
Prefectural University, Shimogamo, Kyoto 606, JAPAN.
Recently, much attention is being denoted to 13-(1~3) glucan for their
physical properties and physiological functions, such as gel formation
properties, antitumor effects, and various immunological activities. These
functions are known to be closely related to their molecularconformations. For better understanding of the conformation of 13-(1~3)
linked polysaccharides, crystal structures of two oligosaccharides were
determined by X-ray diffraction methods.
Crystal data: methyl 3-o-13-D-glucopyranosyl-13-D-glucopyranoside(l),C13H240 11. orthorhombic, P21212, a=14.548(2), b=24.252(7) ,c=4. 938( 1)A, Z=4;o-(2,3 ,4,6-tetra -o-acety 1-13-D-glucopyranosy1)-(l ~ 3)o-[2,3,4,6-tetra-o-acetyl-13-D-glucopyranosyl -(1~6)]-o-(2,4-di-o-acetyl-13-

D-glucopyranosy l)-(1~ 3)-1 ,2,4,6-tetra-o-acetyl-13-D-glucopyranose(2),Cs2H7o035, monoclinic, P2J, a=12.709(4), b=27.767(9), c=9.567(4)A,
13=105.07(2) 0 , and Z=2.
The 13- ( 1 ~ 3) linkage conformation of 1 is similar to that of
13-D-laminarabiose (Takeda, Yasuoka, & Kasai, 1977). The
intramolecular hydrogen bond between Os and 04' [2.77(1)A] almost
equals that in 13-D-laminarabiose. The conformations of two 13-(1~3)
linkages observed in 2. resemble to each other, but differ from that in 1.
These two linkages' conformation are also similar to those in otheracetylated 13-(1 ~3) linked disaccharides (Takeda, Kaiya, Yasuoka, &Kasai, 1978; Perez, Vergelati, & Tran, 1985). The existence of (1~6)
branched glucose residue from the central residue in 2. does not affect13-(1~3) linkage conformation. The dihedral angles around C1-01 bonds
depend on the exo-anomeric effect. As a result, linkage conformations are
influenced by intramolecular hydrogen bonding, the size of substituents,
and the exo-anomeric effect. The dihedral angle around the C1-06 bond isalso influenced by the exo-anomeric effect. The orientation of 06 at the13-(1 ~6) linkage has a gauche-trans conformation. The conformation
around the C6-06 bond is trans.
Perez, S., Vergelati, C. & Tran, V. H. (1985). Acta Cryst. B41, 262-267.
Takeda, H., Kaiya, T., Yasuoka, N. & Kasai, N. (1977). Carbohydr. Res.
62, 27-37.
Takeda, H., Yasuoka,N. & Kasai,N. (1977). Carbohydr. Res. 53,137-152.

16U-70
CRYSTAL STRUCTURES OF MODIFIED NUCLEOSIDES
5'-0-TOSYL ADENOSINE AND 2'-0-TOSYL ADENOSINE.
D .Prahadeeswaran and T.P. Seshadri, Department of Physics, Indian
Institute of Science, Bangalore 560 012, INDIA.
Crystal structure analyses of the title compounds were undertaken as apart of our program to understand the conformational flexibility of the
2'-5' and 3'-5' nucleic acid fragments . In the modified nucleoside
5'-0-tosyladenosine, instead of a phosphate group, a sulphonyl group witha bulky phenyl ring is attached in its 5'-position. In 2'-tosyladenosine thesame group is attached in its 2'-position. Crystals of 2'-0-tosyladenosine(compound I) were grown by slow diffusion of water into DMS O
solution. Weissenberg photograph confirmed the space group to be P2I
with the cell dimension a= 7.359(3), b = 7.873(3), c = 16.098(5) A and
13 = 96.0(2) 0 • The structure was solved by direct methods using SHELX86. The R-factor converged to 0.059 for 1936 unique reflections. An intra
molecular stacking between the adenine base and the phenyl ring wasobserved in this structure. The glycosidic torsion angle about theC(l')-N(9) bond is 62.3(4t which falls in the range associated with synconformation and the sugar puckering is C2'-endo. The syn conformationof the adenine base is stabilised by a N3···05' intramolecular hydrogenbond as in A2'p5'C and A2'p5'A.
The 5' -0-tosyladenosine (compound II) crystals were grown by slow
evaporation of acetone solution. The Weissenberg photograph confirmed
the space group to be P2I2I2I with cell dimension a= 8 .045(1) ,b = 8.937(1), c = 26.773(2) A. The Cu Ka intensity data consisting of1472 reflections with F(obs) ~ 3cr(Fobs) were collected on a CAD-4
diffractometer. The structure was solved by MULTAN 82 and refined byfull matrix least square and difference fourier methods to an R-factor of
0.044. The glycosidic torsion angle about the bond C(l')-N(9) is 166.2(4) 0 which falls in the anti conformation and the sugar puckering isC3'-endo. The torsion angle about C5'-05' is -142.8(4) 0 •Unlike compound I the phenyl ring of compound II assumes a folded
shape with respect to the adenine base.

16U-71
METAL ION-PURINE BASE INTERACTIONS:ZINC(II) AND CADMIUM(II) COMPLEXES OF
8-METHYL THIOTHEOPHYLLINE.
X-RAY CRYSTAL STRUCTURE AND
SOLUTION STRUCTURE OF

BI S( 8- METHYLTHIOTHEOPHYLLI~ATO)DIAQU~~INC(II)M. H. Skipworth and M. R. Taylor, School of Physical Sciences, The Flinders University of South Australia, G.P.O . Box 2100, Adelaide, SA 5001, Australia, andJ. C. Avila-Roson, M. A. Hidalgo, J. Suarez-Varela and E. Colacio, Facultad deCiencias, Universidad de Granada, 18071 Granada, Spain.
The complexes [M(H 20)2L2], (where M= Zn2+ or Cd2+ and Lis the 8-methylthiotheophyUinato anion) have been prepared and characterised by means of I.R. 1 H
and 13 C-NMR spectral studies. Structure determination of [Zn(H 20)2L 2] at 293 K
by single crys tal X-ray diffraction methods revealed that the zinc( II ) ion is coordinated at the N7 of the two monodentate L anions and the two water molecules.
This gives rise to a Zn N2 0 2 environment with local C 2v symmetry. Co-ordinationof the zinc ion is app roximately tetrahedral wi th small deviations from the ideal
angles due to large steric factors and crystal packing.
The molecules of the complex are held together by intermolecular hydrogen bonds
and base-base stacking interactions where the interbase stacking distance is 3.40 'A.
These interactions link the molecules in extended chains which run through thestructure. Bond lengths and angles in this compound do not significantl y differ
from those reported for free theophylline and its N7 complexes [1,2].
Crystal Data:[Zn(H20 h L2] monoclinic, spacegroup C2/c (No.15), Z 4
a 14.6615(6), b 8.6664(3), c 17.253(1) A, (3 94.22(1) 0 •l.

Colacio, E., Romerosa, A., Ruiz , J. , Roman, P. , Gutierrez-Zorrilla, J . M. &Mart inez-Ripoll, M. (1989). J. Chem. Soc.

Dalton Trans. 2323 and refe rences

therein .
2. Cozak, D., Marhy, A., Olivier, M. J. & Beauchamp, A.L. (1986 ). Inorg . Chem.
25 , 2600 and references therein.

16V-72
MOLECULAR LIBRA TION AND A POSSIBLE STRUCTURAL
PHASE TRANSITION IN CRYSTALLINE
4,4" -DIFLUORO-p-TERPHENYL
H..~ K. Saito, Y. Yamamura, H. Matsuyama, K. Kikuchi, M. Iyoda

and I. Ikemoto, Department of Chemistry, Faculty of Science, Tokyo
Metropolitan University, Hachioji, Tokyo 192-03, Japan.
Crystals of a molecule having (a) soft internal degree(s) of freedom often
show an interesting phase transition associated with a change in themolecular conformation. The first three members of so-called
p-polyphenyls shows a "twist" phase transition at a low temperature andstudies have been made in detail for a long time. Study on the analogous
compounds has a crucial importance for getting a unified understandingof the mechanism of the "twist" transitions. We have chosen
4,4"-difluoro-p-terphenyl (DFTPH) as a sample compound taking into
account of the results of the study on 4,4'-difluorobiphenyl. The moleculeof DFTPH was synthesized by the coupling reaction of p-fluorophenylzinc
chloride and p-diiodobenzene using Ni[P(C6Hsb]4 as a catalyst. The
crystal structure of DFTPH was determined at room temperature bysingle-crystal X-ray diffraction.
Crystal data: F-(C6H4)3-F monoclinic, space group P21fa
a 7.868(2), b 5.741(1), c 14.129(3)A, f3 93.27(2) 0 ,v 637.2(2)A3

The structure is iso-structural with that of p-terphenyl and a molecule lies
on an inversion center. The molecular geometry assuming an orderedsingle central ring is planar within 0.03 A, and the apparent squared
amplitude amounts to 250(10) deg2 of libration of the central ring aroundthe long molecular axis. The large amplitude implies the disordered
nature of the structure. When the carbon atoms on the central ring are
split, two central rings, which have opposing conformation with respect tothe outer rings, remain planar within 0.04 A. The dihedral angle between
two conformations is 22.1(1) 0 , and the amplitudes of libration of eachcentral ring shrinks to 90(10) deg2. The potential barrier height V(O) at
the planar conformation is estimated as about 1 kJ·mol-1 in the crystal
using the method by Baudour (1991). The height is much smaller than
4.57 kJ·mol-1 for p-terphenyl and, consequently, the possible "twist"
transition of DFTPH will occur at a lower temperature.
Baudour, J. L. (1991). Acta Cryst. B47, 935-949.

16V - 73
X-RAY DIFFRACTION STUDY OF PHASE TRANSITIONSAND STRUCTURES OF (KBrh-x(KCN)x MIXED CRYSTALSY.Yoshimura, T.Okazaki and K.Shimaoka, Sci. Eng. Ritsumeikan U.,
56- I Tojiin-Kitamachi, Kita- ku, Kyoto 603, Japan.
Crystal structures and phase transitions of (KCN) 1 - x(KBr )x(x=0.9, 0.8) mixed
crystals were studied by X-ray diffraction (pr ecession) method.

The crystal

stn.:cture of the mixed crystals at room t e mperature has a NaCI type cubics tructure, with linear CN - ions achieving the required symmetry by rapid
r eorientation in the site of octahedral symmetry. The mixed crystals undergo phase transit ions associated mainly with the c hange in the orientation of
the CN - ions, which is the same mechanism in the case of the phasetransitions of alkali cyanides; NaCN, KCN and RbCN.

A crystal structureo f the mixed crystals in a low t e mperature phase [L.T.P.] is cons idered to
be isostructural with the m etastable phase of KCN _crystal in the temperature range from I 65 to I 58 K, if the crystal has been once s ubjected tot he phase transition at I 68K before cooling.
Precession photos of the mixed cryst als were taken at the temperature
range between room temperature and 8 3 K. A struc tural change was observed from cubic to a L. T .P. at about I 38 K fo r x=O. 9 and I 06 K for x=0.8.
A variety of diffraction photographs indicating a cOexistence of various

forms were obtained below the phase transitio n t e mperature.

Paying at-

t ention to the presence of splitting and superlatt ice reflections, a triclinic and a monoclinic forms were found in the L.T.P. of (KCN) 0 . 9 (KBr) 0 . 1
crystal.
are

Triclinic fo rm: The space groupa T=9.4-5(J), b T=fl..fi.J(I), C T=fi..59(J) _A,

and r T=90.0( I)" at 85 K.

PI. and t he lattice = nstants
a T=l2 J.0( 5)00{3 T: l 19.0(5)"Monoclinic form: The space group

A 2/m andthe latt ice constants: a .,=4-.61(1), b .,=4-.59(1),- c .,=7.55(1)A and{3 M=l22.5 (5)" at 85 K.

In the L.T.P. of the (KCN) 0 . 8 (KBr) 0 . 2 crystal a

new triclinic form was found.

The latt ice =nstants of the triclinic !at-tice are a T=6.4-6(1), b T=6.4-5(1), c T=6.4-5(1)_A,
f3T=87.10(10)" and rT=92.8(5)" at 85 K.

a T=90.1(5)",Crystallographic relationships

between these fonns and the cubic lattice will be presented.

16V-74
PACKING EFFECT IN SOLID-STATE POLYMERIZATIONOF DIETHYNYLBENZENE DERIVATIVESBY y-IRRADIATION
R. Kitagawa, N. Kanehisa, Y. Kai and N. Kasai, Department of Applied
Chemistry, Faculty of Engineering, Osaka University, Suita 565, Japan,
Y. Yamamoto, and S. Takahashi, Institute of Scientific and Industrial
Research, Osaka University, Ibaraki 567, Japan
Investigation of solid-state polymerization of crystalline monomers has
attracted increasing attention during last three decades . From theviewpoint of crystal engineering, structural studies on the correlation
between crystal structures and their reactivities are interesting. This
paper is concerned with the inherent reactivities of a series ofcrystalline diethynylbenzene derivatives (I-IV) in solid-statepolymerization, which is initiated by radicals generated upon irradiation
with y rays. Effects of the molecular packing in the crystals on thereactivities are discussed.

Ill

IV

0
CH1 C•CCH lO ( CH l

0

CH 10

9

Ca CC H10 CCHl

In a series of studies on the correlation between crystal structures andsolid state polymerization of diethynylbenzene derivatives, many
variation of molecular packings were revealed by X-ray crystal
structure analyses. One of the important structural factors fordetermining molecular packings is the position of two ethynyl
substituents in the benzene ring, ortho, meta, and para. The second
substituent in the benzene ring is also important in deciding themolecular packing. Only the replacement of methyl group by methoxy
causes definite differences in their crystal structures. The interatomic
distances between the acetylene carbons of neighbouring molecules
correlates well with the solid state polymerization activities of themonomer crystals. The monomer IV shows a unique dimerization
reaction in a chain mode. The mechanism of the initial stage ofdimerization reaction was simulated by energy optimization based on its
crystal structure .

16V-75

ASYMMETRIC PHOTOSYNTHESIS IN A CHIRAL CRYSTALENVIRONMENT
Hidenori Kogo, Akiko Sekine, Yuji Ohashi, Rikiya Matsukawa*,
Kyuichi Miyamoto* and Fumio Toda*.
Department of Chemistry, Tokyo Institute of Technology, 0okayama, Meguro-ku, Tokyo 152, Japan and *Department ofIndustrial Chemistry, Ehime University, Matsuyama 790, Japan.
It has been found that the a-oxo amide (1) is transformed to Plactam (2) on exposure to visible light in the solid state as shown in
Fig. 1.
0
0 X~
OH
0
II

II

/Me
cH-Me

c-c

hv

'-.N/

x-

,

~

Me~ I

I

·c · - cMe'e-N 'cH
1

CH-Me

Me/

'~

(1)

V•... /\
(2)

Me

Fig. 1

When the substituents (X) bonded to the phenyl ring are m - Cl(1 b), o- Me (1 d) and m- Me (1 e) groups, the corresponding chiralproducts (2b,d,e) were obtained with about 100 % enantiomeric
excess. On the other hand, the a-oxo amides with X= o- Cl (1 a) , p Cl (1 c) and p - Me (1 f) did not reveal such an asymmetricsynthesis. In order to clarify the factors which influence on theabove difference, the crystal structures of (1 a) - (1 f) were
determined. Moreover, the absolute structures of (1 b) and the Plactam (X= m -CI, 2b) were determined using anomalous
dispersion technique, in order to elucidate the mechanism ofcyclization . The crystals revealing the asymmetric induction, (1 b),(1d) and (1e) have a chiral space group , P2 1 2 1 2 1 ,whereas (1a),(1 c) and (1 f), which gave racemic P-lactam, have thecentrosymmetric space group, P2 1/n, Pbca and Pbca, respectively .
The asymmetric synthesis clearly depends on whether themolecular packing in the reactant crystals is chiral or not. The
molecular structures of the six crystals have very similar
conformation to each other . The absolute structures of thereactant and product crystals clearly suggest that the process ofthe cyclization is controlled topochemically, that is, a new bond isformed between the two carbon atoms with very short contacts ( C... C = 2.85 A) and then a four- membered ring is made.

Author IndexAbeH
Abrahams B F
Achiba Y
Achiwa N
Aikawa N
Akiba E
Akiya K
Akiyama K
Allen G W
AndoM
AndoM
Ando S
Ando Y
AngHG
AngHG
AngHG
AngHG
Aomine N
Arai Y
Argyriou D N
Argyriou DN
Asano HAsano H
Ashida T
Ashida T
Atake T
Atake T
A take T
Avila-Roson J C
BandoM
Bando M
Sando Y
Banerjee Asok
Banerjee Asok
Bansal R S
8aoJ X
Barnes G
Barnes G T
BattenS R
Bennett M A
Bhalla G L
8i Ruchhang
Biswas G
Biswas S
Blanc E
Bohde V
Boldeman J W

145-34
15U-60
15T-37165-34
14U-52
155-32
16P-1
15A-3
168-2
145-32
15P-4
16P-4
148-2
15T-44
15U-47165-39165-40
14V-62
14V-60155-34
16A-4
155-32
16A-3
14P-3
16T-57
14V-61
15T-37
15T-40
16U-71
14P-4
14W-71
14W-70
14B-5
16T-45
15U-59165-4315P-3
15P-2
15U-52
16R-17
14W-6916T-47
16T-45148-5
15Q-16
16U-64
P-00

Bott RC
Bott RC
Bricogne G
Broomhead J A
Burley S K
Burley S K
Butler B D
CaiYM
CalG-L
Calos N J
Camillo F
CammG
Cavarelli J
Chakravarty S
Chakravarty S
Chang Shih- Lin
Chang W R
Chaudhary S K
Chen Bor-Hann
ChenHC
Chern Ji-Wang
Chidambaram R
ChuaN -H
Chung Chung-Sun
Chung Chung-Sun
Chung Chung-Sun
CleggW
Colacio E
Colacio E
Collins D M
Colman PM
Cookson D J
Copeland T
Craven C J
Creagh DC
Creagh DC
Creagh DC
Daar IDai Sheng
DasB
DeaconG B
Dexter D D
Dey I
Dharmaprakash S M
Dhingra Ritu
DobsonCM
DonatM

148-4
15U-53
14Y-5
165-33
14P-5
168-4
14U-58165-3914T-3914U-4916Q-11
165-33
168-3
14R-12
16T-60
15Y-1
158-3
14W-67165-32
15C-2
16U-65
16A-1
14P-5
15U-46
15U-49165-32
165-41
15U-56
16U-71
15Q-16
158-2
P-00
14Q-11
155-33
15P-3
16Z-3
P-00
14Q-11
15T-42
16T-45
15Z-4
15Q-16
16T-45
15Z-5
14W-68
16U-61
16Q-11

d u Bou lay D
Du rani 5
Dyson P W
Edwards A J
Effe ndy
Efimo vA N
Efimov AN
Elcom b e M M
Epelboin Y
Erickson J
Errington R J
Fattah J
FehlmannM
Feinberg H
Fenton F R
Ferre- D 'Amare A R
Figgis B N
Fischer K F
Flack H D
Foran G
Forres ter J 5
Freem a n H C
Fu ZhuJi
Fujii I
Fujii S
Fujino M
Fujiwara T
Fujiyo shi Y
Fukuda T
Fu kumo to Y
Fukunaga 0
Fukuy ama K
Fukuyam a K
Fukuyam a K
Furukawa Y
Galindo H
Can B K
Ganguly 5N
GaoD
Garrett R F
Garrett R F
Gasch A
Gatehouse B M
Gautham N
Geremia 5
Gerson A R
Ghatak K L

15V-73
16U-64
14Q-8
16U-61
15U-51
14W-75
14W -76
16A-4
16Z-1
14Q-11
165-41
16U-61
15A-2
14R-20
16B-2
16B-4
15V-72
14U-56
15Q-16P-00
14U-4915U-55
14Q-6
16Z-5
16U-63
165-3416T-4914Q-8
14Y-3
16T-48
14Y-5
14P-4
14Q-10
158-1
16P-1
16Q-11
14T-46
14B-5
16C-5
14A-2
P-00
14P-5
15Z-4
16U-62
165-37
15T-3814B-5

Ghosh 5
16T-45Gilmore C
14Y-5
Giraldi T
15U-56GohL Y
16R-17G6m ez d e Ander ez D 14U-48
G6mez de Anderez D 16Q-11
Goswarni N
16C-1
GotoA
16P-1
Goto T
16U-68Gotoh Y
15A-3
Greenbla tt H M
14R-20
Greenwood R J
16U-66Grey IE
14Y-2
Gribskov M
14R-19Grossie D A
15Q-16
Cu i Lulu
16T-47
Gun awardane R P
14T-40
H a Thanh Binh
14W-66
Haga Y
16Q-7
Hagiya K
14T-41HagiyaK
15P-6
HallS R
15Q-16
HallS R
16Z-2
Hama d a K
16T-49Harnanaka Y
14V-59Harnano A
14V-61
Hambley T W
15U -55
Hambl ey T W
168-2
Hanasaki T
15R-19HaqA ul
16C-3
HaraN
16A-3
HaradaJ
14T-43Harada J
14Z-2
Harada J
I SQ-11
HaradaJ
16P-1
HaradaJ
16P-3
HaradaJ
16Q-9
Harada 5
14P-1
Harada 5
14P-2
Harada 5
14Q-7
Harada 5
14R-18Harada 5
16T-46
Harada 5
16T-50HardieMJ
15U-60Hasegawa T
145-35
Hashizume H
14Y-5
Hashizume H
14Z-3

Hashizume H
HashizumeH
Hashizume H
HashizumeH
Hata Y
HataY
Hatanaka Y
Hatta I
HattonP D
HayakawaH
Hayano T
Hazama K
Hester J R
Heyes SJ
HibiT
Hidalgo M A
Higashi T
Higashi T
Higuchi T
Higuchi T
Higuchi yHihara G
Hikita J
Hiraga K
Hiraguchi H
Hiramatsu H
Hirata H
Hirayama N
Hiroaki H
Hirotsu K
Hirotsu K
Hockless DC R
Hoffmann A
Hondoh T
Hor T SA
Hori T
Horikoshi M
Horiuchi H
Horiuchi H
Hori uchi H
Horiuchi S
Hoskins B F
Hoskins B F
Housset D
HowardC]
HowardCJ
Howard C j

15T-37
16P-2
16Q-8
16Z-1
16T-4916T-51
165-44
15Y-3
155-33
155-32
14R-14
16P-4
15V-67
16U-61
14R-13
16U-71
14A-1
15Q-13
16T-52
16T-53
16Z-5
165-4415R-18
15A-1
14Y-5
16T-4915T-39
16U-67
16U-63
16T-52
16T-53
165-41
14P-5
16P-1
15U-58
16C-2
14P-5
14U-52
14Y-3
15Q-9
15P-4
15U-52
15U-60
14R-19
14C-2
14T-46155-33

Hseih Yun-Long
HsuR M
H uS -H
H uangHH
H uangHH
H uang J -L
Huang ]in -Ling
HuangMT
HuangTC
HyodoK
IchiwaN
IharaH
IidaM
Iijima S
Iijima Y
Iishi K
Ikemizu S
Ikemoto I
Ikemoto I
Ikemoto I
Inaka K
Inoue T
Inoue T
Ishibashi H
Ishida K
Ishii A
Ishizawa N
lshizawa N
Ish izawa N
Ishizawa N
Ishizawa N
Ishizawa N
Ishizawa N
lshizawa N
Itakura M
ItoM
Ito T
ltoh YIversen B B
Iwasaki F
Iwasaki F
Iwasaki H
Iwasaki H
Iwasaki H
Iwasaki H
Iwasaki H
Iwasaki S

15U-4915V-6914P-5
14B-1
16R-15
14T-38
14T-39
15Y-1
15P-5
15P-4
16X-3
155-32
14U-5614B-2
165-44
14T-41
14P-4
15T-37
15T-40
16V-72
14R-15
14P-2
14Q-7
15V-74
14T-43
16Q-6
14T-44
14T-47
14V-61
15P-7
15V-65
15V-67
15V-68
15Z-3
14U-57
14R-14
16X-5
14U-56
14C-4
15Q-14
15U-57
14A-3
14P-2
14Q-7
14V-60lSQ-14
14U-57

IyodaM
IzawaH
Izumi F
Izumi F

Jain Alka]amielJanky 5
Jaskolski M
Jeyaraman R
Jiang Q Z
johnson A W S
Johnson F

K Tanaka
KadoH
KaiY
KaiY
Kai Y
KaiY
KaiY
KaiY
KaiY
KaiY
Kajiwara K
Kakiuchi T

KalceffW
Kamigaki K

KamiyaN
Kamiya N
Kamiya N
Kan 5

Kan ehisa N
Kanehisa N
KangH Y
Kannan KK
Kannan K K
Kannan K K
Kannan K K
KanoH
KanaK
KanaK
Kansaki H
Kasai N
Kasai N
Kasai NKas ai N
Kasai N
Kasai N

16V-72
16C-2
155-32
16A-3
15Z-2
15P-3
P-00
14R-1916R-13
15C-2
14Q-8
P-00
16Y-5
145-31
14P-1
14P-2
14Q-7
14R-18165-42
16T-46
16T-50
16V-74
14U-57
16P-3
155-34
14W-70
14A-3
14V-60
15Q-1415R-18165-42
16V-74
14W-73
14R-12
158-4
16T-5916T-60
14Q-9
14Q-10
15B-1
15T-36
14P-1
14P-2
14Q-7
14R-18165-42
16T-46

Kasai N
Kasai N
Kasamo K
Kasatani H

Kasatani H
Kasatani H
Kasatani H
Kasatani H
Kasukabe I

Katagiri S K
Kataoka M
KatoH

KatoN
Katoh H
Katsube Y
Katsube Y
Katsube Y
Katsube Y
Katsube Y
Katsuya Y
Kawaguchi K
Kawai T
Kawai T
Kawaji H
Kawaji H
Kawamoto I
Kawasaki H
Kawata Y
Kennard C
Kennard C H L
Kennard C HL
KewN
KhanAQ

Kharisun
Kihara T
Kikuchi K
Kikuchi K
Kikuchi K
Kimura V
KingG 5 D
Kinoshita T
Kirino H
Kirk J M
Kishimoto 5

Kison o M]
Kitagawa R
Kitamoto T

16T-50
16V-74
16T-54
14T-45
14V-5914W-70
14W-71
16X-4
16T-54
14T-4715P-7
14R-13
16Y-1
14T-43
14R-13
14R-16
16T-4916T-51
16T-55
16T-4915V-70145-36
16U-68
15T-37
15T-40
16Q-8
16C-2
14P-3
15P-3
15P-2
15T-41
14Q-11
16C-3
14T-42
16Y-2
15T-37
15T-40
16V-72
14Q-8
15Q-16
16T-50
16T-55
165-41
14T-4315V-6416V-7415T-37

Kitamura M
Kitamura 5
Ki tam ura T
Kizakai H
Ko ba yas hi H
Kobayash i H
Kog aT
Koga chi M
Kog oHK ohLLKohLL
K ohLL
Kohzurna T
Kohzuma T
Koizumi M
Koizumi M
Koiz umi M
Koizumi T
Komekyu T
Komori T
Komura Y
Kondo H
Kondo T
Konno M
Kortt A
Koyano N
Kozaki J
Krishnan R
Kruger B G
Kubota M
Kubota Y
Kubota Y
Kubota Y
Kucharski E S
Kumar Binay
Kumar D Champion
KumarV
Kumar Vinay
Kumazawa S
Kumazawa 5
Kumazawa 5
Kurashina H
Kurisu G
Kurita 5
Kuwano N
Kuzuo R
KwikWL

145-31
16U-6915T-3916T-51
16R-14
16T-54
14V-62
15V-7416V-75
14B-1
15U-5816R-15
14P-2
14Q-7
14Q-9
14Q-1015B-1
145-35145-32
15Z-3
15P-8
16T-58
16U-6814R-1415B-2
165-3416P-4
16R-12
15Q-16
14R-16
14C-4
15V-6415V-75
15V-72
14W-69
16U-62
16T-5915B-4
14C-3
14T-43
16Y-5
14Z-3
16T-46
16X-5
14U-57145-3415T-44

KwikWL
KwikWL
Kwik W L
LaiLH
Lakshmi N V e nkata
Lal Kri shnan
Lam Y L
Lan Wei-Jen
Larsen F K
Lawrence M C
Le Due Lap
Le Hai HungLe bedevA 0
Lecong Dzuong
Lee Jiann-5hing
Le e T song -Jen
LeeY W
Leong W Y
Leung PH
Li Runshen
Liang DC
Liaw Yen-Chywan
Lii K H
LinJP
Lin Kuan-Jiuh
Lin Nianqin
Lin Yufuan
LingECH
Liu Ling-Kang
Liu 5-X
Liu 5-X
Liu Youchen
Liu Zhengjiong
L6pez-Rivera 5 A
Lu Tian-Huey
Lu Tian-Huey
LuZ
Lubkowski
Luh Lung-5hiang
Lynch DE
M Miller J
MaLB
Machida K
MackayM F
Maeyama 5
Maheswaran S
Maji B B

15U-47165-39165-40
16R-20165-35
16C-1
16R-15
15U-46
14C-4
15B-2
14W-66
14Z-4
14W-76
14W-66
14W-74
15U-46
165-40
15T-44
15U-58
14Z-1
15B-3
16U-65
14W-73
14P-5
15V-71
16T-4714Q-6
16B-2
165-36
14T-38
14T-39
15Z-1
16T-47
14U-48
15U-49165-32
14V-62
14R-19165-36
15T-41
14R-1916R-20145-31
16U-66
16P-2
16Y-4
14B-5

Makita A
Malby R
Martin B
Martin B
Martin J M
Martin L J
Marumo F
Marumo F
Marumo F
Marumo F
Marumo F
MarumoF
Maruno 5
Maruta R
Masaki N
Masatsugu M
Masl en EN
Maslen EN
Maslen EN
Maslen EN
Maslen EN
Maslen EN
Masuda K
Matsueda E
Matsui M
Matsui Y
Matsukawa R
Matsumara G
Matsumoto A
Matsushima M
Matsushita Y
Matsuura Y
Matsuyarna H
Matsuzaki T
Matten W
Mcintyre G J
Mehdi S
MiaoZW
Minamigawa 5
Minato I
Misaki 5
Mitsuki T
Miyadai T
Miyahara I
MiyamaeH
Miyamoto K
Miyamoto M

14U-54
158-2
14U-51
15R-17
16Q-11
165-38
14T-44
14T-47
14V-61
15P-7
15V-65
152-3
16Y-5
14U-54145-31
16R-18
15V-6315V-67
15V-68
15V-6915V-7315V-76
15Q-11
16T-57
15C-1
145-35
16V-75
15Q-15
14U-57
14R-15
14U-53
14R-16
16V-72
16T-56
14Q-11
15V-62
14R-17
16R-20
15V-74
15Q-9
162-5
15Q-9
15V-65
16T-53
165-4416V-7515P-6Miyazaki T
Mizuno H
Mizuno H
Mizuno H
Mi zu noH
Mohana Rao J K
MokKF
Momozawa N
Moodie A F
Moras D
Moreno-Vida M I
Mori T
Morikami K
Morimoto 5
Morimoto Y
Morimoto Y
Morimoto Y
Morimoto Y
Morimoto Y
Morimoto Y
Morishita Y
MoriyamaH
Mukhopadhyay 8 P
Murakami K
Murase I
Myhra5
Nagakura S
NagaraA
NagataM
Nagino K
Naitoh H
Nakagawa A
Nakagawa A
Nakahigashi N
Nakamura A
Nakamura K
NakamuraN
Nakamura N
Nakamura N
Nakamura Y
Nakamura Y
Nakao M
Nakashima 5
Nakayama Y
NemotoT
NgKH
Nguyen Thanh Do

15Q-11
14Q-9
14Q-10
158-1
16T-5414R-1915U-58
14T-43
15A-2
168-3
15U-56
15V-70
14R-15
15T-3614P-4
14Q-9
14Q-10
158-1
16T-48162-5
14R-16
16T-55
16T-45
16T-54
16X-5
14U-49145-32
16T-50165-44
14U-56
14P-1
14A-1
16U-68
15V-74
165-42
16Q-6
15R-1916R-1416R-1915Q-10
16Q-7
15V-70
14V-59165-42
14V-63
15U-47
14W-66Nguyen Van Tri
Nigam CD
Nikolov DB
Niranjana 5
Nishihata Y
Nishioka T
Nittono 0
Nittono 0
Nittono 0
Nittono 0
Niu Xiutian
NiwaT
Noda Y
Noguchi K
Noguchi S
Nojima 5
Nomura M
Numata K
Nyburg5C
O'Connor B H
ObaseN
Ochiai T
Ochiai T 0
OdaJ
Odawara5
Ogawa K
Ogura I
Ohashi Y
Ohashi Y
Ohashi Y
Ohashi Y
Ohashi Y
Ohashi Y
Ohba5
Ohba S
Ohba T
OhgoY
Ohhashi T
Ohmasa M
Ohmasa M
OhsatoH
Ohshima E
Ohshima K
Ohshima K
Ohsumi K
Ohsumi K
Ohtaka 0

14Z-4
15R-20
14P-5
16C-1
16X-4
14R-13
15Q-10
16P-4
16Q-7
16Q-10
16T-47
16P-2
15Z-3
16U-6916T-5615Q-9165-38
16T-55
15T-38
14T-46
16U-67
16C-4
14Y-4
14R-13145-32
15T-43
16P-5
14V-60
14V-63
14V-6415T-3916V-75
16X-2
15U-50
16X-1
15P-8
14V-60
14U-50
14T-41
15P-6
14U-50
16U-67
14T-43
14U-54
15P-6
15P-7
16A-3

Okamoto A
Okamoto 0
OkamuraF P
Okazaki A
Okazaki T
OkiKOkuda T
OkuyamaKOkuyamaK
Olovsson I
Olthof-Hazekamp R
Omura T
Omura T
Omura T
OngKK
Ono5
OnoY
OnoY
Onodera K
Onoi K
Onozuka T
Oogami N
Oosawa Y
Oshima T
OyanagiH
Pahler A
Pain 5
Pakawatchai C
Pal B
Pan KeZhen
Patser K
Pattabhi V
PawleyG5
Peng Shie-Ming
Pham The Vung
Pognonec P
Ponnuswamy M N
Prahadeeswaran D
Prasuna G
Pring A
Prout C K
Ptasiewicz-Bak H
Rae AD
Rahman Asadur
Rajasekharan M V
Randaccio L
Ravi Kumar K

16T-52
16T-53
16C-2
14V-62
16V-73
14U-57
14U-50
16R-18
16U-6915V-62
15Q-16
14Q-9
14Q-10
15B-1
15T-44155-32
14U-52
15R-18
16T-55
15R-19145-33
16T-54
15A-3
16T-55
14T-4414R-15
16T-45
15U-4815R-20
14Q-6
16B-2
16U-64155-33
165-31
14Z-4
168-4
16R-13
16U-70165-35
14T-42
16U-61
15V-62
15Y-4
165-37165-35
165-37
14R-17

Ravikumar K
RedshawC
Rheingold A L
Rid wanRobertson G B
Robinson W T
Robson R
Robson R
RoederRG
Roeder RG
Rubin R
Ruis-Sanchez J

Rujijanagul G
Sabine T M
Sabine T M
Sadasivan C
Sagatys D S
Sagatys DS
Saito K
Saito K
Saito K

Saitoh H
Sakabe K
Sakabe K
Sakabe K

Sakabe N
Sakabe N
Sakabe N

Sakai Y
Sakata M
Sakata M
Sakata M
Sakata M
Sakata M
Sakata M
Sakata M
Sakata 0
Sakata 0
Sakata 0
Sakata T
Sakiyarna F
Sakiyarna F
Sakurai M
Saknratani M
Salas-Peregrfn J M
Samuels D M
Sano T

16S-35
16S-41
165-40
16S-3416R-16
16Z-4
15U-52
15U-6014P-5
16B-4
14Q-11
15U-56
14W-72
16Y-3
16Y-4
16U-6414B-4
15U-53
15T-37
15T-40
16V-72
16V-72
14A-1
15Q-12
16T-58
14A-1
15Q-12
16T-58
14V-60
14C-1
14C-2
14C-3
14C-4
15V-6415V-75
15Y-3
14Z-3
16P-2
16Q-8
16U-63
14P-3
16T-50
16T-55
15Q-14
15U-56
16S-38
15T-43

Sasaki c

Sasaki K
Sasaki S
Sasaki S
Sasaki S
Sasaki S
Sasaki S

Sathyanarayana B K
Sathyanarayana B K
Sato M
Sato M
Sato M
Sato S
Sato T

SatoT
Satow Y
Satow Y
Satow Y
Sawada A
SawadaH
Schmid S
Schwarzenbach D
Sekine A
Sekine A

Sekine A
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Seshadri T P
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ShiD
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Shibata N
Shibuya I
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Shimizugawa Y
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Shimonishi K
Shimonura M
Shimura T
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Shimura T
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16T-56
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14R-1914R-16
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16X-2
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ShionoM
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Shirotani I
Sh ish ido T
ShiwakuH
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SimKY
Sinha N K
Skelton B W
Skipworth M H
Smith G
Smith G
Smith G
Soejima Y
Soejima Y
Spadaccini N
Spadaccini N
Spargo A E C
Staton V
Sterns M
Stevenson A W
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Stewart J M
Stranger R
Streltsov VA
Streltsova N R
Su arez-Varela J
SudaK
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Suetsu gu T
Sugawara A
Sugaya T
Su giyama M
Sugiyama T
Sukuma r N
Sun DL
Sundaralingam M
Suzu ki A
Suzuki A
Suzu ki M
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Su zuki S
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Suzuki Y
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15Y-2
16S-34
16X-3
16Y-5
14Y-3
15P-4
14R-20
16R-15
16T-45
15U-48
16U-71
14B-4
15T-41
15U-53
14U-56
14V-62
15V-6315V-6714Q-8
15B-2
16S-33
14Z-1
16C-5
15Q-16
14Y-2
15V-68
15V-76
16U-71
15P-7
14Y-5
15R-1816Q-10
16U-6716P-2
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15C-2
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15T-37
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14R-1914Z-5

Tachikawa 0
Tada T
Tada T
Taguchi J E
T,a hirov T H
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Takahashi H
Takahashi I
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Takah ashi N
Takahash i S
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Takama T
Takase T
Takata M
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Takemoto K
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Tanaka K
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Tanaka N
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15V-6415V-75
15Y-3
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16U-69
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15T-43
14T-4414S-34
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15A-4
15Q-9
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16U-6315V-65
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14V-64
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15U-56
16U-71
14W-70Terashima T
Terauchi H
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Thompson J G
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Tokonarni M
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Toraya H
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Toriumi K
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Tsukihara T
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14Q-7
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Yamamura S
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Yamanaka T
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Yanagisawa K
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Yoshida K
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Yoshida 5
Yoshikawa 5
Yoshimachi 5
Yoshimura M
Yoshimura 5
Yoshimura Y
Yoshimura Y
Yoshimura Y
Yoshioka Y
Yu Shu-Chen gYu Xiling
Yue Xuefeng
Yukino K
Zangrando E
Zhang B
Zheng J M
Zhou Hongbing
Zhou KangJing
Zhou M 5
Zhou Qifeng
Zhou R
Zhou Yuanchong
Zhu Nanchang

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14W-71
145-36
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16C-2
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14R-16
14W-74
15Z-1
15Z-1
16C-2
165-37
14T-38
14B-3
15T-42
14Q-6
15U-58
15T-42
14Q-11
16T-47
14Z-1

SIEMENS
Area Detector Systems for
Macromolecular Data Collection
When you need a system with the performance to match yourdemanding applications , choose the world leader in area detector
technology .
• Complete systems,
factory-tested assystems.
• Windowing menu
environment for datacollection .
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Eulerian cradle
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• High power rotating
anode X-ray generator.
The Siemens area detector system is now the most widely used
two-dimensional real-time electronic detector for collection of datafrom macromolecules. Using a sealed area detector, noted for its
reliability and advanced user-friendly data collection software ,Siemens has forged ahead of the competition by offering thefeatures you need in an instrument for macromolecular datacollection.

Siemens is the Solution
In USA and Canada contact Siemens Analytical X-Ray Instruments. Inc. • 6300 Enterprise Lane •Madison. Wl537t9 • (608) 276-3000 • FAX (608) 276-3006
Worldwide, contact : Siemens AG Automation Group • Measurement . Test & Process Control Division. AUT V353 •Postfach 2t t2 62. D-7500 Karlsruhe 21 • Federal Republic of Germany • (0721) 596-4295 • FAX (0721) 595-6777

I Rigalc:11.11

EXCELLENCE!
IN X-RAY INSTRUMENTATION!
Supported by
Over 40 years of engineering andmanufacturing experience.
Rigaku is the world leader in scientific X-ray instruments, offering highperformance X-ray diffractometers and X-ray imaging systems alongwith excellent software packages to satisfy your needs in single crystal
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Rigaku offers:•Rigaku AFC-7 :The ultimate four circle single crystale
diffractometer.
•Rigku R-AXIS II :High resolution Automated X-Ray
Imaging System based on the Fuji * 1
imaging plate.
•AFC control software package contains fully automatic data collection
procedure.
• MSC's new "teXsan" *2 software package, comprehensive program set for
the analysis and determination ofsmall molecular structures.

PHOTO:AFC- 7R

PHOTO :R- AXIS- DC*1 : The imaging plate is a product of Fuji Photo Film Co ., Ltd .

* 2 : teXsan is the trade mark of Molecular structure Corporation (MSC).
Rigak ...

Rigaku lnternaional Corporation
4-15-3 Ni shi-Shinjyuku, Shinjyuku-ku , Tokyo 160, Japan
Tel : 81-3-3299-3821, Fax : 81-3-3299-6364

The JEM-201 0, a 200 KV ultrahigh resolution analytical electron
microscope applies existing technologies to combine our best
dedicated high resolution TEM with our finest dedicated analytical
instruments. The result is a microscope, the JEM-2010, whichsurpasses the capabilities of any previous system .

JEM-2010
Ultrahigh Resolution Analytical

Electron Microscope•UitraDuo condenser objective lens IUD lens)• Five-axis motorized side entry goniometer•Optimized CPU operation•Ultra clean specimen environment• Electron optical system best suited forhigh-sensitivity EDS analysis.
Configuration

Resolution

Spherical
aberration
coefficient

Chromatic
aberration
coefficient

UD-UHR

0.194nm

0.5mm

1.0mm

UD-HT

0.23nm

1.0mm

1.4mm

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L1~

Material
Analysis andCharacterization

The

Paradigm of New X-ray Generators

SRA M18XHF(18kW Self-rotating anode X-ray generator with Highcuit)solved problems offrequency power cirgenerators and offers
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MAC Science Co., Ltd.

Head Office:Nakano-Kamicho 2-25-16
Hachioji-shi, Tokyo 192
Tel. 0426-24-2201 Fax. 0426-24-2723

~H~-------------------DHZU SEIKI CD., LTD.

KOHZU SEIKI-Exploring the future with
its technology and determination
For experiments using synchrotron radiation ,]contact KOHZU SEIKI Co. Ltd. , a highly-reliable
sc ientific preci sion in st ruments manufact urer withnumerous sa les.

IDOUBLE CRYSTAL CAM MONOCHROMATOR
I Features• Beam emission from fixed position• Easy wavelength change• Sagittal beam focusing• Cooling way for first crystal is
flexible•Incident and exit beam can bechanged• Sales history
K.E.K. 13 sets
N.T.T. 1 set
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I Other products• Ultra-high vacuum XY stage • Large 4-axis diffractometer • High-precision
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KOHZU SEIKI CO., LTD.
Head Office:<awasaki Factory:

2-27-37 Mishuku, Setagaya-ku, Tokyo, 154 Japan
TEL:03-3413-2131
FAX:03-3413-5768
857 Maginu, Miyamae-ku, Kawasaki, 213 Japan
TEL:044-877 -2550

RECIRCULATING WATER CHILLERS
86 Kcal/h THROUGH

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Our Highly Efficient compact System

Cooling Crystal Monocrometor
Model 3072B
Type Air- Cooled
Cooling Capacity 86Kcal/hDimensions : 47.5W X 450 X ISH em
Voltage, Standard : 100/IISV I ¢ 50/60Hz
Cooling Medium : Room Air
Shipping Weight, Approx : 7kg

Cooling X- Ray Spectrometers..

T ypesCooling
Capacity

Air-Cooled

Water- Cooled Kca l/Hr

TCA-2000C-AW

TCW-2000C

2.000

TCA-4000C-AW

TCW-4000C

4.000

TCA-12000C-AW

TCW- 12000C

12. 000

TCA-20000C-AW

TCW-20000C

20.000

Water Flow
Temp.
('C)

Press
(kg/cm2)

X- Ra yEquip.
Max Power
2kw

15-25
± ! 'C

4kw
1.5 -312kw
18kw

San - Ei Giken Co., Ltd.
1-28-25 Kizawa, Toda City,

Phone 048- 443- 4003

Saitama 335, Japan

FAX

048 - 443- 9052

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