AsCA'95

Program and Abstracts

Thai

Thai Airways International

AsCA'95
2nd Conference of the
Asian Crystallographic Association
Chulalongkorn University

Bangkok, Thailand
22-24 November 1995

Program and Abstracts

Organising Committees
International Organising Commillee
W.T. Robinson
S. HallK. Kannan
C . Kennard
K. Nishikawa
A. H. Othman
P. Phavanantha
J. Simpson
M. Tokonami
T . Uragami

New ZealandAustralia
India
Australia
Japan
Malaysia
Thailand
New Zealand
Japan
Japan

(Chairman)

Secretariat (New Zealand)
Ward Robinson
Jim Simpson
Jan Wikaira
International Program Commillee
Y. Ohashi
S. Chang
R. Chidambaram
T. Hambley
G. Jameson
E.N. Maslen
K. Ohsumi
T. Tsukihara
Z. Zhang

Japan (Chainnan)
TaiwanIndia
Australia
New ZealandAustralia
Japan
Japan
China

Local Organising Committee
Phathana Phavanantha (Chairman)
Narongsak Chaichit
Chaisingh Poorakkiat
Tawee Tangasiri
Pongchan Thinapong
Ahpisit Ungkitchanukit
Sajec Wongchaiboon

Chaveng Pakawatchai
Achara Prichavudhi
Srinuan Thanomkul
Wimonrat Trakampruk
Siri YarothaiGeneral Information
Conference Venue and Accommodation
The map inside the front cover of the Abstract Book shows the locations of the
University Halls, Krit Thai Mansion, Novotel Siam Square, Siam Intercontinental
Hotel, Florida Hotel and the Asia Hotel in relation to the Conference Venue. The
venues for the Welcoming Reception and the Farewell Banquet are also indicated.

Registration/Information Desk
Prior to the opening of the conference, a Registrationllnfonnation Desk will belocated at Vittaya Nives Hall and will be open from 18.30 to 19.30 on both Monday
20th and Tuesday 21 November. From 08.30 on Wednesday November 22, theRegistrationllnformation Desk will be situated outside the Main Lecture Hall in theInstitute Building III and will remain open for the remainder of the Conference.

The Conference Venue
The Conference will be held in Institute buildings II and Ill shown on the map. Poster
sessions will be on the ground floor of Institute Building Ill, the main lecture hall is on
the I st floor and one other lecture room is on the 2nd floor. The trade exhibitions andthe other 2 lecture rooms will be in adjacent rooms on the 1st floor of Institutebuilding II.

Name Badges
Name badges will be issued to all registrants in their conference satchels. Participants
are kindly requested to wear their badges throughout the meeting. For the purpose ofeasy identification the following colour scheme will be used
Active participants
Accompanying Persons
Local Organising Committee
Exhibitors
International Organising Committee,
Secretariat and AsCA Council Members

Green
Yellow
Red
Blue
PurpleMail and Messages
Mail for conference participants will be available from Vittaya Nives Hall or from theRegistration Desk

Telephones
Telephones for outgoing International calls are available in the rooms at SASA
International House and the Krit Thai Mansion (an additional charge is levied forInternational calls). International card-phones are available on the University Campus

Meals and Refreshments
Momilrg and aftemoon coffee
Morning and afternoon coffee will be provided for all full and student participants atthe conference venue.

Lunch
Lunches are provided free of charge for all full and student participants at theconference venue. Conference badges must be worn.

Poster sessions
Light refreshments will be provided during the poster sessions sponsored by Mac
Science.

Social Events
Welcoming Reception
A welcoming reception and get together will be held at the Thai Pavilion from 19.30
to 21.30 on Tuesday November 21 for all registrants (full student and accompanying
persons) . Refreshments and snacks will be served. The reception is sponsored bySiemens

Farewell Banquet
A farewell banquet for all registrants (full student and accompanying persons) will beheld in Sasapata Sala on Thursday November 23; 19.30 for 20.00. Dress is informal.
The banquet is sponsored by Rigaku.

Local Tours
Participants are reminded that tours of Bangkok and district can be arranged daily at
the Registration/Information Desk. A group tour is planned for Saturday 25th
November at a cost of $US40 per person.

Opening Ceremony
The opening ceremony for AsCA '95 will be held in the main' lecture theatre in
Institute Building III from 8.30-8.45 on Wednesday November 22nd. The speakers
will be:Professor Ward T. Robinson,
Professor Philip Coppens,
Professor Dr Supachai Yavaprabhas,
Conference announcements:
Professor Phathana Phavanantha

President, Asian Crystallographic
Association
President, International Union of
Crystallography
Vice President for International Affairs,
Chulalongkorn University
Chairman, Local Organising Committee

Society Meetings
Asian Crystal/ograpllic Associatio11

Wednesday 22 November , SASA International House
18.30 International Organising Committee
19.00 Council Meeting

Sponsors of AsCA'95
The Asian Crystallographic Association wishes to thank the following professional
bodies and institutions for their contributions towards the organisation and funding of
AsCAuote 95
The International Union of Crystallography
The Crystallographic Society of JapanThe Society of Crystallographers in Australia
The Crystallography Group of the New Zealand Institute of Chemistry
Chulalongkorn University
The Thai Crystallographic Association

The Asian Crystallographic Association also wishes to gratefull y acknowledge
generous financial support from the following companies:
Enraf-Nonius (Columbia Trade Company)
Mac Science
Marresearch
RigakuSiemens
Thai Airways International
Xray Research

Scientific Programme
The overall programme is shown in the following Table. Coffee, tea and fiuit juice
will be served at the times stated in the programme. Participants giving poster
presentations are reminded that they should be at their posters for the last two hours of
the poster session

8:30-8:45
9:00-9:45
9:45-10:30
10:30- 11:00
11 :00 - 12:30

12:30- 13:45
13:45 -15:15

15:15 -15:30
15:30 -17:45

22{Wed)Official Opening(5 . Yavaprabhas)
Plenary lecture(M. Ando)
Plenary lecture(Hai-Ju Fan)
Coffee BreakMicrosymposium
A
B
C
MS02 MS17 MS01
(1Al lBl 1C1)
Lunch
Microsymposium
A
B
C
MS09 MS17 MSOl
(1A2 1B2 1C2)
Coffee Break
Poster Session(1 POl - 1 P60)

23 (Thu)

24 (Fri)

Plenary lecture(T. Matsuzaki)
Plenary lecture(G. Desiraju)
Coffee BreakMicrosymposium
A
B
C
MS06 MS05 MSOB
(2A1 2Bl 2Cl)
Lunch
Microsymposium
A
B
C
MSlO MS12 MS04
(2A2 2B2 2C2)
Coffee Break
Poster Session(2P01 - 2P60)

Plenary lecture(8. O'Connor)
Plenary lecture(Y. Wang)
Coffee BreakMicrosymposium
A
B
C
MS18 MS07Lunch
Microsymposium
A
B
C
MS11 MS14 (3A2 3B2)
Coffee Break
Poster Session(3P01 - 3P60)

Invited lecture by Prof P Coppens (3PL3) is held in MS18
Seating capacities of the rooms, A: 250; B; 40; C: 30
All of the Plenary lectures are given in room A
MS-01 Diffraction theory and phase problem (Prof 5. -L. Chang)
MS-02 Synchrotron radiation (Prof E. N. Maslen)
MS-04 Neutron diffraction (Dr. A. S. Sequeira)MS-05 Recent development of Powder diffraction (Prof T. Yamanaka)
MS-06 Methods in biological crystallography (Dr. G. Jameson)
MS-07 Crystal growth and characterisation (Prof T. Olrachz)
MS-08 New Instrumentation (Prof H. Hashizume)MS-09 Mineral and inorganic compounds (Prof K. Ohsumi)
MS-10 Organic and organometallic compounds (Prof Y. Kal)
MS-11 Structural biology (Prof. T. Tsukihara)
MS-12 Interface, films and surfaces (Prof 0. Nittono)
MS-13 Phase transformation (Prof T. R. We/berry)
MS-14 Organic crystal engineering (Prof F. Iwasaki)
MS-17 Data bases and software (Prof 5. R. Hall)
MS-18 Charge density (Prof K. Tanaka)

PrograiTI Schedule

November 22

Room A

Plenary Lecture lPLl (Prof. S. Wilkins) 9:00-9:45
lPLl

Synchrotron Radiation Science in Crystallography Ando, M.

Present and Future -byPlenary Lecture 1PL2 (Prof. T. Ashida) 9:45-10:30
1PL2

Direct Methods - New Developments Outside The Traditional Field by Fan, H.-F.

Coffee Break 10:30-11:00
MS02 Synchrotron radiation (Prof. E.N. Maslen) 11 :00-12:30
lAll
11:00
1Al2
11 :18
1Al3
11:36
1Al4
11 :54
1Al5
12:12

Single Crystal X-ray Diffraction Using SR in Material Science by lshizawa , N.
Microcrystallography by Synchrotron Radiation by Ohsumi, K., Hagiya, K. ,Miyamoto, M. & Ohmasa, M.
Multiple-Detector System for Powder Diffractometer Using Synchrotron Radiationand High-Resolution Diffraction Data Obtained with It by Toraya , H., Hibino, H.
& Ohsumi, K .
Electron Density Imaging with Synchrotron X-radiation by Maslen, E.N. & Streltsov, V.

A.
Texture Study on Synchrotron Radiation by Abovian, E.S.,
Trouni , K.G .

Grigorian, A.H. &Lunch 12:30-13:45
MS09 Mineral and inorganic compounds (Prof. K. Ohsumi) 13:45-15:15
1A21
13:45
1A22
14:05
1A23
14:25
1A24
14:45

Modulated Structures in the Nb 2 Zrr_ 2 0 2r+l and Ta2Zrr-20 2r+l (7.1 ::; x ::; 12)
Solid Solution Fields by Schmid, S., Futterer, K., Thompson , J. G., Withers, R .
L. & Ishizawa, N.
X-ray Analysis of 4f-Eiectron Density in CeB 6 crystals by Tanaka , K & Ohnuki, Y.
A Joint X-Ray and Electron Diffraction Study of MgO by Abramov, Y. A., Avilov, A.S.,
Belokoneva, E .L., Rushdi, K., Feil, D., Tsirelson , V.G . & Okamura, F.P.
Crystal Structure and Magnetic Properties of the Linear Homo or Hetero Trinuclear Metal Complexes of Bis(2-pyridyl)amide Ligand by Lin, C.-C., Yang, E.-C.,
Lee, G .-H. & Peng, S .-M.

Coffee Break 15:15-15:30
Poster Sessionl5:30-17:45

November 22

RoomB

MS17 Data bases and software I (Prof. S. R . Ha/Q 11:00-12:30
lBll
11 :00
1B12
11:30
1B13
12:00
1B14
12:15

CIF as the Common Language of Crystallography by McMahon, B.
The Brookhaven Protein Databank by Sussman, J. L.
XtaLGX: CIF-Entry Graphics for Geometry Analysis by Hall, S., Boukay, D. D.,
Hester, J . & Grossie, D.
Maximum Entropy Deconvolution in X-ray Diffraction by KalcefJ, W., Armstrong, N.
& Cline, J .P.

Lunch 12:30-13:45

MS17 Data bases and software II (Prof. S. R . Hal£) 13:45-15:45
1B21
13:45
.1B22
14:15
1B23
14:45
1B24
15:00

The Macromolecular CIF Dictionary,Version 1.0 by Bourne, P. E.
The Nucleic Acid Database Project by Berman, H. M., Clowney, L., Gelbin, A.,
Hsieh, S. H. & Westbrook, J.
-:'!TAN: A Molecular Graphics Program to Aid Structure Soktion and Refinementwith the SHELX Suite of Programs. by Hunter, K. A. & Simpson, J.
MOLDRAW: Molecular Graphics ForMS-Windows by Ugliengo, P., Chiari, G. &Viterbo, D.

Coffee Break 15:15-15:30

Poster Session15:30-17:45

November 22

Room CMSOl Diffraction theory and phase problem (Prof. S.-L . Chang) 11 :00-12:30
lCll
11 :00
1Cl2
11:20
1Cl3
11 :40
1C14
12:00

X-Ray Phase Recovery : Mapping of Two-Dimensional Crystal Lattice Strains with
Nanometre Depth Resolution by Nikulin, A . Y., Gureyev, T.E., Hashizume, H.,
Stevenson, A.W. & Wilkins, S.W.
X-ray Polarization Analysis of Allowed and Forbidden Reflections of Iron Pirite,
FeS 2 • by Yazawa, 1., Nagano, T ., Kurasawa, T., Ishida, K., Tsuji , E., Kumazawa, S., Sasaki , S., Mori, T . & Kishimoto, S.
Use of Harker sections of Patterson Function as Constraint of Density Modification
for Direct Phase Determination by Shiono, M.
Phase Extension Using X-ray Multiple Diffraction & Maximum Entropy Method
by Wang, C.-M . & Chang, S .-L.

Lunch 12:30-13:45

MS13 Phase transformation (Prof. T . R . We/berry) 13:45-15:45
1C21
13:45
1C22
14:00
1C23
14:15
1C24
14:30
1C25
14:45
1C26
15:00

Diffuse X-ray Scattering and Phase Transitions of Urea Inclusion Compounds. by
We/berry, T.R . & Mayo, S.C.
Atomic Short-Range Order in Nickel-Platinum Alloys by Saha, D.K. & Ohshima, K.
Crystallographic Studies of C60 and C1o by a Single Crystal X-ray Diffraction by
Horiuchi, H., Mitsuki, T ., Li, J., Kino, N. & Kitazawa, K.
High Pressure Polymorphs of Zr0 2 by Ohtaka, 0 ., Yamanaka, T ., Yagi, T . &Shimomura, 0 .
Isosymmetric Structural Phase Transitions and Crossovers : Phenomenology, Examples and Implications by Christy, A . G.
Nucleation and Growth Model of Martensitic Phase Transition by A"be, H. & Ohshima, K.

Coffee Break 15:15-15:30

Poster Session15:30-17:45

November 22

Poster Session 15:30-17:45

Poster Session (MS01,02,09,13,17) 15:30-17:45
lPOl..) 1P02

1P03

1P04

1P05
1P06
1P07

1P08

J 1P09v lPlO
v

lPll
1P12
1P13

v 1P14\ l tP15..Jr 1P16
V IP17

Normal Mode Analysis of Incommensurate Modulations and Its Relation to the
Atomic Debye, Waller Factors of the Normal Phase by Achiwa, N., Machida, M. &Yamauchi, Y.
Atomic Anisotropic Displacement Parameters For Silicates and Oxides: A latticeDynamical Derivation From Empirical Potentials by Pilati, T., Demartin, F. &Gramaccioli, C. M.
The Anomalous Scattering Factor Obtained from Rocking Curve Measurements of
Ge Single Crystal by Kuribayashi, M., Kanamaru, T ., Inoue, A., Katoh, H. &Ishida, K.
X-ray Study of Defects Produced by MeV Ion Implantation into Si Perfect Crystal by
Kuribayashi, M., Inoue, A., Kanamaru, T., Katoh, H., Ishida, K., Tomimitu, H., Aizawa, K. & Kazumata, Y.
Measurements of X-Ray Diffraction Intensities from Uniformly Bent Single Crystals
by Takama, T . & ltoh K.,
Observation of Defects without Directly Reflected Wave in Bragg Case by Uragami, T.,
Kobayashi, H. & Orii, D.
The Grazing Incidence Diffraction of X-Rays with Wave Front Amplitude Periodically Varying along the Crystal Entrance Surface (Symmetrical Laue Case).
by Bezirganyan, A.P. & Bezirganyan, S.E.
Density of the p3 Close Packing of Identical Ellipses by Matsumoto, T. & Tanemura, M.
The Use of The Diffractometer at the Australian National Beamline at the Photon
Factory for Unusual Experiments by Creagh, D.C.
In-situ study of structural defects in materials using Synchrotron radiation by Yeritsian, G.N., Sahakian, A.A . & Nickogosian, S.K.
Investigations on Solid State Physics and Crystallography Using Synchrotron Rafiation at Yerevan Physics Institute by Egikian, D.L.
RIKEN Contract Beamlines for Structural Biology at SPring-S by Iwasaki, H.
The Bio-Crystallography (MIR-OAS) Beamline at the SPring-S by Kamiya , N.,
Ueki, T., Iwasaki, H., Tanaka, N. & Miki, K.
Electron Density Distribution in Pyrite-Type MnS 2 by Ueki, M., lshizawa, N. &Marumo, F.
Size Dependancy of the cfa Ratio of Tetragonal Barium Titanate Micro-Crystals
Using SR by Suda, K., Kataoka, M., Ishizawa, N., Marumo, F. & Ohsumi , K.
Structure Analysis of CaYAl0 4 Small Crystal Using SR by Morita, K., Suda, I<.,
lshizawa, N., Kodama, N. & Yamaga, M.
Single Crystal X-Ray Diffraction and EXAFS Analysis of (Y 0 . 2 Zr0 . 8 )0~. 9 FluoriteType Compound by Matsushima, Y., Hayashi, M., Suda, K., lshizawa, N. &Oyanagi, H.

1Pl8
1Pl9
1P20

1P21

1P22
1P23
1P24
1P25
1P26

1P27
1P28
't!ll lP29
1P30
1P31
1P32
1P33
1P34
1P35

Structural Study on the Defect-Perovskite-Type Compounds La 1t 3M03 (M=Ta,Nb )by Tanabe, K., Suda, K., lshizawa, N., Sohn, J.-H. & ltoh, M.
X-ray Diffuse Scattering Study of Magnetite by The Valence-Difference Contrast
Method. by Toyoda, T ., Sasaki, S. & Tanaka, M.
Structural Changes of (Pb,Cu)SrLaCuOH6 on Oxygen Introduction into Block Layers by Khasanova, N .R. , Izumi, F., Shida, M., Chakomakos, B., Ohahima, E.,
Kikuchi, M. & Syono, Y.
Neutron Diffraction Study of the Improved Chemical Stability of Cation Substituted'123' Superconductor Yo .6C~. 4 Ba~. 6 Lao.4Cu307-d by Sequeira, A., Rajagopal, H.,
Ganguly, R. & Yakhmi, J .V.
The Inverse Problem in Multiple Small-angle Scattering by Mazumder, S. & Sequeira, A.
SANS from SDS Micellar Solutions in Presence of Amines and Ammonium Salts
by Kumar, S., Aswal, V.K., Goyal, P.S. & Kabir-Ud-Din ,Microphase Separation in Adsorbed Paraffin Mixtures by Gilbert, E.P., Reynolds, P.A :& White, J .W .
Vanadium and Vanadium-Bearing Micas by Bekenova, G.K.
The Crystal Structures of Dehydrated Fully Cd2+ -Exchanged Zeolite X and of its
Carbon Monoxide Sorption Complex by Jang, S., Kwon , J., Kim, U. , Kim , Y.
& Seff, K.
Structural investigation of high- and low-symmetry vesuvianite by Ohkawa, M.,
Takeno, S. & Yoshiasa, A.
Synthesis and Characterization of Alkali-Metal Tin(IV)Arsenates : ASn0As0 4 (A=K and Rb), Cs2Sn3As 6 0 22 and CsSn2As30 12 by Lin, K.-J. & Lii , K.-H .
Crystal Structure Studies of CeAl0 3 by Synchrotron Radiation by Tanaka , M.,
Horiuchi, H. , Shishido, T. & Fukuda, T.
canceled
Sodium Magnesiosilicates with the Carnegieite, or "Stuffed Cristobalite" Structure
by Lobo, C.J ., Schmid, S., Thompson , J .G., Withers , R.L. & Stranger, R .
Cation Distribution and Crystal Chemistry in Y3Al 5 _rGar0 12 (0 S x 5 5) Garnet
Solid-Solutions by Nakatsuka, A., Yoshiasa, A. & Yamanaka , T .
The Crystal Structure of Vesuvianites From Taiwan by Yu, S.C., Lee, J.S . &Wang, C.P.
Charge Density Study of Nonlinear Optical Crystals of LBO and KB5 by Sheu, H.-S.
& Wang, Y.
Structural Change of Ca2(Mg,Fe)Si 20 7 By Heat Treatment by Hagiya, K ., Kusaka, K.,
Haga, N., Ohmasa, M. & lishi, K.

V 1P36 Structure and Residual Density of CaFe03 with Fe<+ by Morimoto, S, Yamanaka, T .
1P37& Tanaka, M.
Structure and Twinning of a Small Crystal of Mawbyite PbFe 1_rZnr(As0 4 h(OH)1_r, x = 0.06. by Kharisum, Taylor, M. R. & Rae, A .D.

1P38
1P39
1P40
1P41
IP42

Comparison of Crystal Structures between Li-Doped and Undoped Superconductorof the Type Bi 2Sr 2CaCu0 8 . by Kitahama, K., Horiuchi, T . & Kawai, T .
Synthesis and crystal structures of zirconolite Polytypes by Ono, Y.
Superstructure of Ba.,_3rSIDs+2r Ti 18 0 54 (x=0.71) by Ohsato, H., Kato, H., Mizuta, M.
& Okuda, T. ·Intramolecular Interactions Observed in Four Bis(phthalocyaninate)Janthanoid(III)Complexes by Koike, N., Uekusa, H. & Ohashi, Y.
Structure Analysis of (NH 4 )JH(S0 4 }2 at 150K by Noda, Y., Fukuchi, S. & Tamura, I.

Incommensurate-Commensurate Phase Transition of Intramolecular Hydrogen-bonded
Material d-BrHPLN by Tamura, I., Noda, Y., Kuroiwa, I., Mochida, T . & Sugawara, T.
IP44 Observation of Anomalous Diffuse Rod below 200K in Ba2NaNb 5 0 15 by Shobu, T.,
Noda, Y. & Uesu, Y.
IP45 Structure Change Investigation of Perovskite-Type (Nd,Sm)Al03 by X-ray Powder
Diffraction by Yoshikawa, A., Horiuchi, H. & Tanaka, M.
IP46 Structural Phase Transitions Among Complex Metal Oxides With Perovskite Type
Structure: Studies by Precise X-Ray Powder Diffractometry by Sergey, I. & Zhurov, V.
IP47 A Single Crystal X-ray Diffraction Study of the low Temperature Phase of RbCN
by Yoshimura, Y., Shinohara, S., Tsuda, N. & Iwasaki, H.
IP481 Single-Crystal X-Ray Diffraction Study of AgGaS 2 Under High Pressures by Kitahara, H., lshizawa, N. & Noda, Y.
IP49 Structure of Pyridinium Tetrafluoroborate and Its Phase Transition Observed by a
New Diffractometer by Nemoto, T .. , Ohashi, Y., Hanaya, M. & Oguni, M.
IPSO BUNYIP: A New Approach to Detecting Errant Symmetry by Hall, S . & Hester, J.
IP43

y

\f

1P51
1P52

1P53
IP54

IP55

A Flexible Four-Circle Diffractometer Control System For BL14A at the Photon
Factory by Vaalsta, T.P. & Ishizawa, N.
Analysis of Metallic and Related Compounds Using ICDD Metals & Alloys Indexes
by Dann, J .N., Huang, T.C., McClune, W.F., Mueller, M.H., Robert, A.C. &Wallace, P.L.
TITAN : A Molecular Graphics Program to Aid Structure Solution and Refinementwith the SHELX Suite of Programs. by Hunter, K. A. & Simpson, J.
Organo-Template Control of Inorganic Structures : A Sheet Aliminophosphate of
Low Symmetry 3[NH3CHMeCH2NH3 J[AlsP 8 0 32 J[H 2 0] by Williams, I. D., Lin, Z.,
Gao, Q., Chen, J. & Xu, R .
Structural Changes in Modified Smectites: Lj+ Diffused Montmorillonite Case by
Mulaba-Bafubiandi, A., Helsen , J ., Maes, A., Langouche, G. & Prost, R.

November 23

Room A

Plenary Lecture 2PL1 (Prof. T. Baker) 9:00-9:45
2PL1

Crystallography-based Drug Design by Matsuzaki, T .

Plenary Lecture 2PL2 (Prof. W. Robinson) 9:45-10:30
2PL2Strong and Weak hydrogen bonds in Crystal Engineering by Desiraju, G. R .

Coffee Break 10:30-11:00

MS06 Structural biology I (Dr. G. Jameson) 11 :00-12:30
2All
11 :00

2A13
11:50

Crystal Structure Analysis of a Large Membrane Protein with the Molecular Weightof 400K Da at 2.8 A Resolution by Aoyama, H., Yamashita, E., Tsukihara, T .,Tomizaki, T ., Yamaguchi, H., Shinzawa-Itoh, K. , Nakajima, Y. & Yoshikawa, S.
Crystal Structure Determination of a Form of Human Apo-Lactoferrin with Both
Lobes Open by Molecular Replacement by Faber, H.R., Anderson, B.F., Baker , H.M .
& Baker, E .N.
Protein Sequence-Structure Alignment Based on Mutant Profile From Mean Force
Field Potential by Lai, L. U. & Wang, Y.

2A14
12:10

Crystal Strucutre of Bovine ,8-Lactoglobulin at 1.9A Resolution by Bewley, M . C.,
Kingston, R., Baker, H. & Baker, E.N.

2A12
11 :30Lunch 12:30-13:45

MSlO Organic and organometallic compounds (Prof. Y . Kai) 13:45-15:15
2A21
13:45
2A22
14:03
2A23
14:21
2A24
14:39
2A25
14:57

Crystalline-State trans-cis Photoisomerization of Cobaloxime Complexes by Yamada, T., Uekusa, H. & Ohashi, Y.
Crystal Structure of Bicyclomangostin : The New Acid-Catalyzed Cyclization Product from Mangostin by Pakawatchai, C., Malabusarakam , W., Wiriyachitra, P.,
Taylor , W .C. & Skelton, B.W.
The-y and 6 Structural Effects of Silicon and T in by Green, A . J . & White, J . M.
Comparison of Fe(II)-P and Fe(O)-P Lengths : Structure of [(1) 5 -C 5 H5 )Fe(CO)C(0)Me)(p-'7 1 :1) 1 -dppe)-[(1J 4 -MeC 5 H5 )Fe(COh] by Liu, L. -K . & Luh, L.-S.
Structures of Novel Metal-carbene Complexes Derived from Hypervalent Tetraazathiapentalenes by Iwasaki, F., Manabe, N., Shimamoto, S. , Yasui , M. & Matsumura, N.

Coffee Break 15:15-15:30

Poster Sessionl5:30-17:45

November 23

RoomB

MS05 Recent developemt of Powder diffraction (Prof.. T . Yamanaka) 11 :00-12:30
2811 Laue Classes of a- and ,8-Quartz and Their Patterson Functions Evaluated with
11 :00 Powder Diffraction Data by Ohmasa, M., Ohsumi, K. & Taraya, H.
2812 X-Ray Quantitative Analysis without Standards Using Rietveld Methods with High
11 :18 Accuracy by Kuo, C.-L. & Liu, H.-C .
2813 XRD Determination of the Mineral Structural State Characteristics by Slusarev, A.P.
11 :362814 Profile Analysis for Lattice Deformation and Crystallite Size under Compression
11 :54 by Yamanaka, T.
Lunch 12:30-13:45'v MS12 Interface, films and surfaces (Prof. 0 . Nittono) 13:45- 15:15
2821
13:45
·2822
14:05
y 2823
14:25\11 2824
14:45

Roughness Estimation of Polycrystal Metal Surfaces with Use of X-ray Glancing
Scattering by Fujii, Y., Yoshida, K. & Yoshida, K.
X-Ray Scattering from Microcrystallinity in the Thermally Oxidized Si0 2 Thin
Films on Si(llO) Surfaces by Shimura, T ., Kojima, R., Misaki, H. & Umeno, M.
Determination of electron density profile from x-ray reflectivity data using Distorted
Wave Born Approximation. by Sanyal, M.K. , Datta, A. & Banerjee, S.
Electron Density Maps for Clean and Adsorbed Silicon Surfaces Calculated with the
Maximum-Entropy Technique by Hashizume, H., Carvalho, C.M., Yokota, 0 .,Stevenson, A.W. & Robinson, I.K.

Coffee Break 15:15-15:30
Poster Sessionl5:30-17 :45

November 23

Roome

I MS08 New Instrumentation (Prof.

2Cll
11 :00
2Cl2
11:18
2C13
11 :36
2C14
11:54
2C15
12:12

H. Hashizume) 11:00-12:30

Development of CCD-based X-Ray Detectors with a Beryllium-windowed Image
Intensifier for Diffraction Studies. by Amemiya, Y
The Optimization of Parameters of Bragg-Fresnel Lenses by Haroutunyan , L . &Trouni, K.G .
The Theoretical and Experimental Study of X-Ray Diffraction Focusing Phenomenaon the Two-Block Crystalline System with Missorientated Blocks by Trouni, K . G.
& Grigoryan, A. H.
Recent Developments of X-Ray crystal Structure Analysis by New Diffractometerand Cooling Equipment by Uekusa, H. & Ohashi, Y.
X-ray Wiggler Beamlines at SRRC by Jean, Y.-C., Lee, C.-H., Tsang, K.- L.,
Hung, H.-H ., Chan, J.-R., Hsu, C.-H., Jang, L.-Y ., Tang, M.-T., Lee, H.-Y.,
Sheu, H.-S., Dann, T.-E., Lee, J .-F., Wang, J.P. & Chang, S.-L.

Lunch 12:30-13:45

MS04 Neutron diffraction (Dr. A .S. Sequeira) 13:45-15:15
2C21
13:45
2C22
14:00
2C23
14:15
2C24
14:30
2C25
14:45
2C26
15:00

Hydrogen in Metals: Neutron Diffraction Studies of the Crystal Structures of Zr 2NiD.,
by Elcombe, M .M., Howard, C.J. & Campbell, S.J .
Nuclear Density Distribution and Anharmonic Thermal Vibration of Sn02 by the
Maximum Entropy Method by Kumazawa, S ., Ishida, K., Takata, M., Sakata, M. ,Ishii, Y. & Morii, Y.
Recent Neutron Studies of High Tc Superconductors by Sequeira, A, Sharma, R.
& Rajagopal, H .
A New Aspect of the Reaction Mechanism of Cobaloxime Complexes by Neutron
Diffraction by Ohgo, Y., Ohashi, Y., Klooster, W.T . & Koetzle, T .F .
Neutron Diffraction Investigation of Phase Transition in LiNaGe 4 0g by Iwata , Y.,
Wada, M. & Sawada, A.
Single Crystal Neutron Study of Structural Phase Transition in (Ba/Ca)Ti03 by Sastry, P.U. M., Sequeira, A, Dasannacharya, B.A., Rajagopal, H. & Ramasamy, P.

Coffee Break 15:15-15:30

Poster Sessionl5:30-17:45

November 23

Poster Session 15:30-17:45

Poster Session (MS04,05,06,08, 10,12) 15:30-17:45
2P01
2P02
2P03
2P04
2P05

2P06
·2P07

2P08

2P09

2P10

2Pll
2P12
2P13

2P14
2P15
2P16

The Effect of Ending Angle on the Structural Parameters and Profile Agreement
Indices in Rietveld Refinement by Kuo , C.-L. & Liu, H.-C.
Crystal Structure and Data On Bi 4 (Si0 4 )a by X-ray Rietveld Analysis by Kuo, C.-L.
& Liu, H.-C.
Crystal Structure Analysis of Alkaline Protease (M-Protease) Forml Crystal. by
Shirai, T. , Suzuki , A., Yamane, T ., Asjoda, T., Kobayashi, T . & Ito, S.
Crystal Structure of an Acyl-Enzyme Intermediate of Guanidinohexanoyl-Trypsin
by Nitanai, Y., Noguchi , S., Satow , Y., Sasaki, C. & Matsuzaki, T.
Visualisation of the 3D-Structure of Calotropin DII A Plant Thiol Protease at 3A
Resolution by Ghosh, S., Mukhopadhyay, B. P., Pal, A., Seal, A., Bera, A.,
Dey, I., Sinha, N.K . & Banerjee, A.
Crystal Structure of a Complex of Wheat Germ Trypsin Inhibitor Il-5 with Bovine
Trypsin by Kibushi, E., Su zuki, A., Shirai, T . & Yamane, T .
Structure of a Kunits-type Chymotrypsin Inhibitor Protein from Winged Bean Seeds
at 2.95A Resolution by Dattagupta, J.K., Podder, A., Chakrabarti , C., Sen, U.,
Dutta, S.K. & Shingh, M.
Crystal Structure of Macrocyclic Inhibitor for Elastase and Structural Comparison
between Non-binding and Binding States by Kinoshita, T., Tada, T ., Yasuda, T .,Fujita, H. & Hatanaka, H.
Ligand-induced conformational changes of 3-isopropylmalate dehydrogenase from
Themus thermophilus by Moriyama, H., Kadono, S., Sakurai, M., Oshima, T.
& Tanaka, N.
Crystallization and Preliminary X-Ray Crystallographic Study of Streptomyces Olivaceoviridis E-86 ,8-Xylanase by Fujimoto, Z. , Mizuno , H., Kuno, A., Yoshida, S.
& Kusakabe, I.
Ability of Some Specific Natural Structures to Interact Concurently Contrary to
Dioxin. ESR Study. by Nguyen, V. T ., Vung, P. T . & Thai, D. P.
X-ray Crystallography of Methionyl-tRNA Synthetase from Thermus thermophilus
HBB by Sugiura, I., Ugaji, Y., Maeda, S., Konno, M., Nureki, 0 . & Yokoyama, S.
Crystallographic Studies of Hammerhead Ribozymes. II. by Chatake, T., Matsumoto, 0., Chen, Y., Tsunoda, M, lmaizumi, N., Takenaka, A., Ohta, A.,
Komatsu, Y. , Koizumi, M. & Ohtsuka, E.
On Refinement of Protein Structures by Means of SHELXL93 by Jameson, G.B. &Edwards, R. A.
Measurements of the Faraday effects and X-ray birefringence at Co K-edge with the
X-ray polarimeter. by A~emiya, Y
Crystal and Molecular Structure of a 1:1 Complex of Phathylyl Sulphathiazole andSalicylic Acid by Verma, A . K. & Tiwari, R.K.

2P17

2P18
2P19
2P20
2P21
2P22
2P23
2P24

2P25
2P26
2P27

2P28
2P29
2P30
2P31
2P 32
2P33
2P34
2P35

Structure Characterization of Constituents from Bridelia ovata Dense and From
Davalia So/ida Sw. by Haller, K . J., Petson, A., Roengsumran, S., Lertpratchya, P.,
Boonyaratavej, S., Thongkon, N. & Phaopongthai , J .
Syntheses and Crystal Structures of Group 6 metal Carbonyls Containing Polyphos·
phine Ligands by Ueng, C.-H., Horng, D.-N., Luo, T.-T. & Shieh, M.- H.
Aperiodic Crystal Structure in Vegetable Fibres by Nguyen, V. T ., Thang, N. V.
& Vung, P. T.
Outer-sphere Coordination of Phenanthroline in Aquachlorotri{p-chlorophenyl)Tin· 1,10-Phenanthroline Dimer by Weng, N. S. & Kumar Das, V.K.
Novel polychalcogen-pnicogen chromium compounds by Chen, W, Gob, L. Y. &Wong, R.C.S.
Structure Analysis of Unstable Crystals Using Rapid X-Ray Measurement System
by Watanabe, T., Manabe, N. , Nashiyama, H., Yasui, M. & Iwasaki , F .
Structure of {[(Ph2NCH2PPh 2 )Au]aS}Cl·H 2 0 by Wang, J.-C. & Lion, L.-S.
Crystal Structure of Binuclear 1:1 Silver{I) 2-Hydroxy-3,5-dinitrobenzoate: Triphenylphosphine Complex by Othman, A. H., Kimia, J ., White, E. & White, A.
H.
Crystal Structure of (4-(w-( cholesteryloxycarbonyl)hexyloxycarbonyl]phenyl]ferrocene
by Nakamura, N. & Takayama, T .
Solvant Influence on Crystallization of Phenyl Carbamidonitrile by Yang, Q.-C.,
Huang, D.-M., Chen, H.-Y. & Tang, Y.-Q.
Crystal Structure of cis[-5-{2-Dimethlaminoethyl)-3-hydroxy-2-{4-methoxyphenyl)-2,3-dihydro-1,5-benzothiazepine)(±) by Kumaradhas, P ., Nirmala, K.A. & Sridhar, M.A .
Crystal Structure of cis[1 ,5- Benzothiazepine-4{ 5H )-one-1-oxide-3-( acetoxy )-2,3-dihydro2-{4-methoxyphenyl)]{±) by Nirmala, K.A & Kumaradhas, P.
Crystal Structures of Tin xanthates by Mohamed-Ibrahim, A·f ./., Shawkaraly, 0 .
B., Fun, H.-K. & Sivakumar, K.
Carbon Nanotubes on the Top Surface of Cathode Deposit at DC Arc-Discharge
by Ando, Y., Zhao, X., Ohkohchi, M. & Wang, M.
Crystal Structures of Group 15 Mixed Ligand Derivertives of Ru 3 (C0)! 2 by Shawkataly, 0
B., Lee, S.-T., Parameswari, M., Fun, H.-K. & Sivakumar, K.
Structure of 1-(4,5-Dihydro-1-H-imidazol-2-y1]- imidazolidine-2-thione hydrobromide
by Wattanakanjana, Y., Pakawatchai, C., Skelton, B.W. & White, A.H.
Structural and Conformational Studies of Triterpenoids : 19-Epimers of Lupenes
by Kiyotani, T ., Masuda, K. & Ageta, H.
Syntheses, Characterisation and Crystal Structure of Triosmium Alkylidyne Carbonyl Cluster Containing Chiral Auxiliaries by Wong, W .-Y. & Wong, W .-T.
Molecular Structure of Organic Lanthanide Complexes having Ethylene Polymerization Activity by Kanehisa, N., Hashimoto, H., Yamagashira, M., Kai, Y.,
Nodono, M., Ihara, E. & Yasuda, H

2P36

2P37
2P38
2P39
2P40
2P41
2P42
2P43
2P44
2P45

2P46
2P47

2P48

2P49

2P50
2P51
2P52

Crystal Structure of 2,10-dichloro-6-(2,4-dimetbyl pbenoxy)-Dibenzo [d,g][l,3,6,2)dioxathiaphospbocin-6-sulfide by Kumar, NJ, Krisbnaiab, M., Reddy, B.S. &Reddy, C.D.
X-ray Structural Studies on Substituted Tbioures Derivatives. by Sivakumar, K .,Akilan, R., Subramanian, K. & Fun, H.-K.
'Sheet with Holes' Structure of Lead(II) Iodide - N-methyletbylenediamine(3/2),(Pbi 2)3(Me-en)2 by Miyamae, H., Ito, T . & Hihara, G.
Structures of furo and thieno derivatives of 5-amino-8-metbyl-1,2-dibydro[2,3h][l,6)Napbthyridines by Kingsford-Adaboh , R ., Kasbino, S. & Sasaki, K.
X-ray Investigation on Structural Phase Transition
in HOOC(CH2) 4 COOH by Machida, M. & Nishimoto, S.
Very Rapid Photoisomerization of 1-Cyanoethyl Group in Cobaloxime Crystals by
Inthapanya, P., Ohgo, Y. & Hashizume, D.
Crystalline-state Racemization of Chiral Methoxycarbonyletbyl Group in Cobaloxime
Complexes by Saitoh, M., J;lashizume, D., Uekusa, H. & Ohashi, Y.
A Chiral N-Methylbenzamide by Yamaguchi, K. , Azumaya, 1., Okamoto, 1.,
Kagechika, H. & Shudo, K.
Asymmetric Photoisomerization of (2-Cyanoethyl)(2-butylamine)cobaloxime Complexes in The Solid State by Koura, T. , Kogo, H. & Ohashi, Y.
Structure of A Briarein Diterpenoid :(IS*, 2S*, 5Z, 7S* , 8R*, 9S .. lOS*, llZ, 14S*,
17R*)-2,14-diacetoxy-8,17-epoxy-9-hydroxy-briara-5,11-dien-18-one++ by Lee, T.-J.,
Wang, A., Sheu, J .-H., Sung, P.-J . & Kun, F.-H .
Grazing-Induced Diffraction of X-rays on Single Crystal with Near-Surface LatticeDistortion by Haroutyunyan, V.S.
Model-Independent Determination of Electron Density Profiles for Al-C Multilayers Using Anomalous-Dispersion X-Ray Refiectometry Data by Ohkawa, T., Yamaguchi , Y., Sakata, 0 ., Hashizume, H., Datta, A. & Sanyal, M.K.
In-plane Structure of Arsenic-deposited Silicon Surfaces Studied Using Grazingangle X-ray Standing Waves by Sakata, 0., Kumano, S., Nikolaenko, A.M. &Hashizume, H.
Micromolphology of Polished Silicon Surfaces Studied by X-Ray Refiectometry by
Yamaguchi, Y., Nakanishi, M., Sakata, 0 ., Hashizume, H., Nakano, M. & Bennett, J .M.
Dislocation of Some Industrial Aluminum Alloys After Rolling by Thang, T. Q.
Structure of Microcrystalline Ag-based Amalgam Alloys by Do, M. N. , Ha, C. T .,Dzan, N. V. & Dzuong, L.
Common Features of P-type and N-type Porous Silicon Layers with Visible Photoluminescence by Nittono, 0. & Takemoto, K.

November 24

Room Ar~lenary Lecture 3PL1 (Prof T . Yamanaka) 9:00-9:45
3PL1

Advances in the Use of Rietveld Analysis for Materials Characterisation by O 'Connor, B .l

Plenary Lecture 3PL2 (Prof E .N. Maslen) 9:45-10:30
3PL2

Charge Density Studies and Characterization of Chemical Bonds by Wang, Y .

Coffee Break 10:30-11:00

Plenary Lecture 3PL3 (Prof. K. Tanaka) 11:00-11:45
3PL3

Charge Density Studies Revisited by Coppens, P.

MS18 Charge density (Prof K . Tanaka) 11 :45-12:30
3All
11:00
3A12

~:45

Topological Analysis of Experimental Electron Density of LiF Crystal by Abramov, Y.
A., Zavodnik, V.E., Feil, D. & Tsirelson, V.G.
Electron Density in YTi03 by Hester, J. R., Okamura, F .P., Tomimoto, K. &Akimitsu, J .

Lunch 12:30-13:45

MSll Structural biology II (Prof T. Tsukihara) 13:45-15:15
3A21
13:45
3A22
14:15
3A23
14:45
3A24
15:00

Crystal Structure of Chimers in B-form Show that RNA can Exist as B-RNA by
Sundaralingam, M., Chen, X. & Ramakrishnan, B.
X-ray Structure Determination of Abrin-a. by Lu, T. -H., Tahirov , T . H., Liaw, Y.C., Chen, Y.- L. & Lin, J .-Y.
Three-Dimensional Structure of the Pseudomonas BphC Enzyme Having Polychlorinated Biphenyl (PCB)- Degrading Activity by Narita, H., Sugimoto, K. , Senda, T. ,Kimbara, K. , Fukuda, M. & Mitsui, Y.
Crystal Structure of Pea-Seedling Amine Oxidase by Kumar, V., Freeman, H.C.,
Guss, J .M., Zubak, V.M ., Dooley, D.M. & McGuirl, M.A.

Coffee Break 15:15-15:30

Poster Session15:30-17:45

November 24

RoomB

MS07 Crystal growth and characterisation (Prof. T . Ohachi) 11 :00-12:30
3Bll
11 :003Bl2
11 :20
3Bl3
11 :40
3B14
12:00

The Effect of Copper Dopant on the Growth and Properties of Potassium Sodium
Strontium Barium Niobate Crystals by Chen, ll.C., Jiang, Q.Z. & Lu, X.L.
Single Crystal Growth and Growth Mechanism of YNi2B2C Superconductors by
Floating Zone Technique by Takeya , H., Kadowaki, K., Hirano, T . & Togano, K.
Anomalous Density Variation of Silicon Melt and Melt Flow in Cz Process by
Terashima, K ., Sasaki, H., Togawa, A., Kawanishi , S., Izunome, K . & Kimura, S.
Etching Studies of Solution-Grown Crystals : (100) Faces of Mixed KDP:ADP(K 1 _.,NH 4 .,H2P0 4 ) Crystals. by SenGupta, S. & SenGupta, S.P.

Lunch 12:30-13:45

MS14 Organic crystal engineering (Prof. F. Iwasaki) 13:45-15:15
3B21
13:45
3B22
14:00
3B23
14:15
3B24
14:30
3B25
14:45
3B26
15:00

The Attempt to Design Solid State Reaction by Reaction Cavity by llashizume, D.
& Ohashi, Y.
Study on Complexes of Alkylammonium Salt-Aromatic Additive by Vongbupnimit, K.,
Noguchi, K. & Okuya.ma, K.
Diverse Mode of Crystal Structures in the Host-Guest Comlexes of Diols by Kai, Y.,
Suzuki, H. , Kanehisa, N., Tanaka, K. & Toda, F.
Extended Molecular Networks lncorporationg the 1,4-Bis(imidazol-2-yl)but-2-yne
Ligand by Slizys, D. A., Hoskins, B. F . & Robson, R.
Dynamic Behavior of N-(2,4-Dinitropbenyl)-o-anisidine Crystals by Ya sui, M.,
Taguchi , K. & Iwasaki, F.
Modelling and Refinement of Disordered Structures from Single Crystal X-ray Data
by Fun, H.-K., Shivakumar , K. & Yip, B.-C.

Coffee Break 15:15-15:30

Poster Session15:30-17:45

November 24

Poster Session 15:30-17:45

Poster Session (MS07,11,14,18) 15:30-17:45
3P01
3P02
3P03
3P04
3P05
3P06

3P07

3P08

3P09

3P10

3Pll

3P12

3P13

On Cross-Sectional Transmission Electron Microscopy Study of Carbon Nanotubules
by Hu, G ., Zhang, X.F. & Zhang, Z .
Local Structure Around Magnesium in CaMgSh06 Glass by Oxygen K-Edge EXELFS Analysis by Tabira, Y., Ishizawa, N. & Matumo, F.
Optimization of Prolyl endopepidase Crystal Growth by Kagawa, Y., Kawauchi, Y.,
Sato, T., Yamashita, E., Tsukihara, T ., Sazaki, G. & Komatsu , H.
Use of DLS to Compare Crystallinities of SSB and Ribosome by Nakagawa, A.,
Kawauchi, Y., Sato, T ., Tsukihara, T., Sazaki , G. & Komatsu, H.
Single Crystal Growth of Vacancy Defect Type Sulfide Spinel Compounds Using
Bridgman Technique by Ohachi, T., Ohmuro, Y., Asahi, K. & Taniguchi, I.
Crystal Structure of the C-terminal Domain of Rabbit Serum Haemopexin at 1.8A
Resolution. by Baker, E.N., Baker, H.M., Faber, H.R., Groom, C.R., Morgan, W .T. & Smith, A.
Crystal Structure of L-2-Haloacid Dehalogenase from Pseudomonas sp. YL at
2.5A Resolution by Hisano, T., Hata, Y., Fujii, T., Kurihara, T ., Esaki , N.
& Soda, K.
Crystal Structure of 3-Isopropylmalate Dehydrogenase from Facultative Thermophile,
BACILLUS COAGULANSby Tsuchiya, D., Matsumoto, 0 ., Takenaka, A., Murakami, T ., Sekiguchi, T. & Nosoh, Y.
Structure of Substrate-Complexed G4-Amylase Inactivated by Mutation of Catalytic Residues by Hasegawa, K., Yamaguchi, H., Yoshika, Y., Matsuura, Y. &Kubota, M.
X-Ray Structural Analysis of the Five Isoleucine to Valine Mutants of Human
Lysozyme: Contribution of Hydrophobic Residues to the Stability by Fujii, S., Yamagata, Y., Kaneda, H., Takano, K. & Yutani, K.
Crystal Structure of Acidic Phospholipase. A2 from the Venom of Agkistridon Halys
Pallas at High Resolution by Wang, X .Q., Yang, J ., Gui , L.L., Lin, Z.J . &Zhou, Y.C.
Crystallization and Preliminary X-ray Studies of Phophpenolpyruvate Carboxylase from Escherichia Coli by Nagara, Y., Inoue, T ., Suzuki , Y., Ohtsuka, R.,
Fukuhara, K., Nishiura, S., Kitagawa, R., Nakanishi, H. , Hayashi, M., Inoue, M., Sugimoto, S., Kai, Y. & lzui , K.
Crystal Structure of Ferredoxin from a Thermoacidophilic Archaean by Fujii, T.,
Hata, Y., Oozeki, M., Moriyama, H., Wakagi , T ., Tanaka, 1\ . & Oshima, T.

3P14

The Refined Crystal Structure of Bence Jones Protein Pav at 2.4A and its DomainDomain Associations by Hsiao, C.D., Rose, J., Swaminathan, S., Furuen, W.
& Wang, B.-C.

3P15

Structure of Bovine Cytochrome c Oxidase at 2.8 A Resolution by Tsukihara, T .,Aoyama, H., Yamashita, E., Tomizaki, T ., Yamaguchi , H., Shinzawa-Itoh, K. ,Nakajima, R., Yaono, R. & Yoshikawa, S.

3P16
3P17
3P18
3P19
3P20
3P21
3P22
3P23
3P24
3P25
3P26
3P27
3P28
3P29
3P30

3P31

3P32
3P33
3P34

PII: The Structure of a Signal Transducing Protein by Ollis, D, Cheah, E., Carr, P.
& Suffolk. P.,
The Utility of 4-Aminobenzoic Acid in the Promotion ·of Hydrogen Bonding in Crystallization Processes by Smith, G.
MAD Analysis of Rat Liver Macrophage Migration Inhibitory Factor by Suzuki, M.,.
Sugimoto, H., Nakagawa, A., Tanaka, 1., Fujinaga, M. & Nishihira, J .
Crystal Structure of VHR, A Dual-specific Phosphatase by Yuvaniyama, J., Saper, M.A .,Denu, J.M. & Dixon, J.E.
Crystal Structure of the Active-Site Mutants of Escherichia Coli Aspartate Amino
Transferase by Miyaham, I, Okada, K. , Hosomi, K., Hirotsu, K. & Kagamiyama, H.
Unique Polymorphism and Inclusion Complex Formation of Dianilinegossypol. by
Ibmgimov, B . T., Beketov, K.M. & Talipov, S.A .
The Attempt to Design Solid State Reaction by Reaction Cavity by Hashizume, D .
& Ohashi, y_
Study on Complexes of Alkylammonium Salt-Aromatic Additive by Vongbupnimit, K.,
Noguchi, K. & Okuyama, K.
Diverse Mode of Crystal Structures in the Host-Guest Comlexes of Diols by Kai, Y.,
Suzuki, H., Kanehisa, N., Tanaka, K. & Toda, F.
Extended Molecular Networks Incorporationg the 1,4-Bis(imidazol-2-yl)but-2-yne
Ligand by S/izys, D. A ., Hoskins, B. F. & Robson, R.
Dynamic Behavior of N-(2,4-Dinitrophenyl)-o-anisidine Crystals by Yasui, M.,
Taguchi, K. & Iwasaki, F.
Modelling and Refinement of Disordered Structures from Single Crystal X-ray Data
by Fun, H.-K., Shivakuma.r, K. & Yip, B.-C.
canceled
Structure Analysis of N-(2,4-Dinitrophenyl)-o-anisidine at High Temperature by
Takada, K., Watanabe, T ., Taguchi, K., Yasui, M. & Iwasaki, F.
Crystal Structures of TEMPO Radicals Showing Ferromagnetic Interaction by Yamamoto, H., Yoshikawa, H., Mitsuda, H. , Takada, K., Yasui, M., Ishida., T.,
Nogami, T . & Iwasaki, F .
The Central C-C Bond Length in the Bi(anthracene-9,10-dimethylene) Photoisomer:
Unusual Elongation and Crystalline State Reactions by Harada, J., Ogawa, K &Tomoda, S.
Crystal Structures of Copper Complexes Showing Ferromagnetic Interaction by
Ishikawa, Y ., Yasui, M., lwsaki, F., Ishida, T . & Nogami, T .
Crystalline-state Racemization of Bulky Groups on Exposure to Visible Light by
Ohashi, Y., Sato, H. , Arai , Y. & Ohgo, Y.
Cyclic 0-H ... N/C-H ...O H-Bond Coupling in the Design of Supramolecular Assemblies by Pedireddi, V.R ., Jones, W., Cambridge, A.P. & Docherty, R.

3P35
3P36
3P37
3P38
3P39

3P40
3P41

V 3P42
3P43

Layered Structures of Antiferroelectric Mesogens by Okuyama, K ., Kawano, 1\ .,Uehori, S., Noguchi, K., Okabe, N., Suzuki, Y. & Kawamura, I.
Complex Formation of Surfactant Molecules with Aromatic Compounds in a Mortar
by Sawada, K., Ohashi , Y., Imura, N. & Hirata, H.
Generation of Asymmetry in the Crystalline State Photoisomerization of Cobaloxime
Complex by Yoshimiya, T ., Sekine, A. & Ohashi, Y.
Chemical Bond and Atomic Displacements in Bao.s7 K0 . 1aBiOa Crystal by Abramov, Y.
A ., Reznik, I.M. & Tsirelson, V.G.
HRTEM Characterization of Homologous Series of Super Conductors
GaSr2Ca.,_ 1 Cun02n+3 (n=3 and 4) by Ramirez-Castellanos, J., Matsui, Y.,
Takayama-M., E. & lsobe, M.
Analysis of Quasicrystal Structures by Use of Powder Neutron and Single Crystal
X-ray Data by Yamamoto, A ., Kajitani , T . & Morii , Y.
A New Barium Copper Oxychloride, Ba2Cua0 4 Ch ; Its Synthesis and Crystallographic Characterization by Zou,
Tachikawa, 0 . & Horiuchi, H.
Synchrotron Radiation Imaging of the Deformation Electron Density in LiNb0 3 and
LiTa0 3. by Hsu, R., Maslen, E.N ., Streltsov , V.A . & Ishizawa, N.
Topological Study On The Electron Density Distribution of Bis(diiminosuccinonitrilo)Nickel, Ni(C4 N4 H2)2 by Hwang, T .-S. & Wang, Y.

z.. ,V 3P45

Electron Density Studies of Cobalt(II) Octaaza Bis-a-diimine Macrocyclic complex [Co(CIOH20Ns)(H20)2)2+[Cl0 4 g- by Lee, J .-J., You, Y.-S. , Lee, G.-H . &Wang, Y.
Effect of Magnetic Field on Ni-Pt Alloys by Saha, D.K.

v 3P46

Atomic Radii from Electron Densities by Maslen, E.N. & Etschmann, B .

3P44

3P47

Crystal Structure Refinement of Silk Fibroin: Bombyx mori by Takahashi, Y.

3P48

Physicochemical Investigations on Natural Spinels(MgAh0 4 ) by Udawatte , C.P.,
Gunawardena, R.P. & Annersten , H.
Structural Studies on a - and /3- Forms of Poly (Tetramethylene succinate) by Noguchi, K.
Igarashi, Y., Okuyama, K., Ichikawa , Y. , Imaizumi, M. & Moteki , Y.
On the Interpretation of Small Angle Scattering Data by Sabine, T.M., Bertram, W .K.
& Aldridge, L.P.
Three-Dimensional Structure of the Pseudomonas BphC Enzyme Having Polychlorinated Biphenyl (PCB)-Degrading Activity by Narita, H., Sugimoto, K. , Senda, T .,Kimbara, K., Fukuda, M. & Mitsui, Y.
Crystal Structures of the Copper Complexes Toward the Functional Model Compound of Dopamine /3-Hydroxylase by Li, C., Kanehisa, 1\ ., Kai , Y ., Itoh , S.,
Kondo, T ., Komatsu, M., Ohshiro, Y. & Fukuzumi , S.

3P49
3P50
3P51

3P52

Scientific Abstracts

1PL1SYNCHROTRON RADIATION SCIENCE IN CRYSTALLOGRAPHY- PRESENT AND FUTUREMasami Ando, Photon Factory, KEK, Oho 1-1, Tsukuba 305, Japan
Since the advent of synchrotron x-radiation in early 1970's, mostly becauseof its quite brilliant nature, its parallelity, wavelength tune ability andselectivity of polarization, a number of its applications to crystallography
have been intensively attempted; most of their challenges have beenachieved and further some new methods are in development. Of typicalexamples are simultaneous observation of dynamic solid-state phasetransformation, crystal growth by means of high spatial resolution x-ray
topography, production of massive good quality film-based data such as inproteins and enzymes, a challenge to crystal structure analysis of nanometer scale crystals, as other major applications are XAFS which canrelatively easily bring information about first neighbour atoms and some
new tools for composite determination of complexes such as ternary alloys.
It will be important to describe about any sciences in crystallography
which could have been brought only with synchrotron radiation, such as
magnetic scattering; that had been hardly observable due to its low signal
level based on very weak interaction of synchrotron radiation withmagnetic electrons. This has brought a new tool to survey magnetic solidstate.
Also Mossbauer scattering can lead us to various applications coveringfrom solid state physics to x-ray optics which is also a part ofcrystallography. Pulse structure synchrotron radiation can reveal hyperfine
structure of condensed matters and liquid phase. Further owing to a very
very narrow bandwidth of most Mossbauer nuclei radiation with a very
long temporal coherence length from them are now routinely available.
Together with a high spatial coherence which comes from a nature of thirdgeneration light sources such as the SPring-8, APS and ESRF one canproceed more research which needs more coherence. Preparation of an
extremely brilliant third generation light source using the main ring at KEK
for some experiments in this autumn which may give us a good idea to see
what a fourth generation light source should be will be also given in a talk.
With a help of doing synchrotron radiation science using third generation
sources advent of x-ray laser light will be seen in the next century alongwith development of linear accelerators capable of extremely low
emittance and specially designed insertion devices for that purpose.

1PL2
DIRECT METI-IODS - NEW DEVELOPMENTS OUTSIDE THE
TRADITIONAL FIELD
Fan Hai-fu, Institute of Physics Chinese Academy of Sciences Beijing
100080, P.R. China
During the last ten years, the application of direct methods has been
extended from the traditional field to new areas. Important progress wasmade along the following lines:* from single crystals to polycrystalline materials;* from small molecules to biological macro-molecules;* from ordinary structures to modulated structures;* from X-ray crystallography to electron microscopy.
Details on the last three topics will be given.
1< In principle, the combination of direct methods with the informationfrom single isomorphous replacement (SIR) or one-wavelength
anomalous scattering (OAS) will simplify the process of protein structure
analysis. Significant contributions in this area were made by different
groups on the world. The method developed in our group has beensuccessfully tested with experimental data from known proteins ofmoderate size.
2. Incommensurate modulated/intergrowth structures are often found insolid state materials. They do not have three-dimensional periodicity but
can be considered as the three-dimensional hypersection of a higherdimensional periodic structure. Based on this, multi-dimensional direct
methods have been established, with which incommensurate modulated/intergrowth structures have been solved without relying on an assumed
model.
3. Many solid state materials are composed of small and imperfect
crystals . They are difficult to analysis by X-ray diffraction but aresuitable for electron microscopic observation. However an electron
micrograph needs special processing before it can reveal the true
structure image of the sample. Direct-method procedures have beendeveloped for image processing in high resolution electron microscopy
combining information from electron micrographs and the corresponding
electron diffraction pattern. The method has been used in ab-initio
structure analysis of minute crystalline samples.

1A11

SINGLE CRYSTAL X-RAY DIFFRACTION USING SR IN
MATERIALS SCIENCE
Nobuo Ishizawa, Research Laboratory of Engineering Materials, Tokyo
Institute of Technology, Nagatsuta Yokohama 226, JapanThe high brilliance and tunability of synchrotron radiation (SR), whenutilized on the four-circle diffractometer, are powerful tools for the
single crystal diffraction studies of inorganic compounds generally. It is
impossible to review all work of importance in materials sciencecomprehensively. Several topics for recent studies on the horizontal-typefour-circle diffractometer (Satow & Iitaka, 1989) at the 14A vertical
wiggler line, Photon Factory, KEK, will therefore be presented.
It is most important when measuring the electron-density in a crystal
unambiguously and precisely to reduce extinction experimentally as far as
possible. we recently succeeded in obtaining almost extinction-freediffraction data from a small rectangular CaY Al04 crystal with volume864 J..l.m3. The specimen was studied using focused 0.75 A X-rays. The
structure refinement revealed not just a slight deviation fromstoichiometric composition, but also a slight but significant shift of the Ca
position from that of the Y atom. The latter result contrasts profoundlywith earlier understanding. The crystal was previously considered to be a
mid member of the K2NiF4-type solid solution with Ca and Y atoms
replacing the crystallographically-unique K site in a disordered form .
It can be stated quite generally that the stage has been reached where
thermal and positional parameters for two different elements at the"same" structural sites can be determined independently, with reasonableaccuracy. The a spherical electron redistribution of bonding electrons andsmall compositional fluctuations can also be detected. With the help of
EXAFS analysis, slight deformation of the local structure around a solute
atom in a solid solution is detectable even though it is superimposed on
the host structure . Physical properties are often sensitive to local
deformation caused by the solute atom, which in most cases, wereundetectable previously .
Examples on the fluorite-type superionic conductors will be shown.
Satow, Y. & Iitaka, Y. (1989) Rev. Sci. Instrum. 60 [7]. 2390-93.

1A12
MICROCRYSTALLOGRAPHY
BY SYNCHROTRON RADIATION
Ohsumi.K.(Photon Factory, Natl. Lab. for High Energy Physics, KEK),
Hagiya,K.(Dept. of Life Sci., Himeji lnst. of Tech.), Miyamoto, M.
(Miner. lnst.,Univ. Tokyo) and Ohmasa, M.(Dept. of Life Sci.,HimejiInst. of Tech.)
For crystallographic studies of a submicrometer-sized crystal particle or
micrometer-sized area of larger specimen, an equipment and softwaresystem has been developed employing the Laue method withpolychromatic synchrotron radiation (Ohsumi et al.(l991) , Ohsumi etal.(1995). The micro-area Laue method(ML) may be important in thefield of material science, because crystallographic information is obtainedfnj)m the exact same area of samples as is probed by optical microscopy,
EPMA or micro Raman spectroscopy.
Due to the limited space around the bearnline, micro-beams are produced
by using micro-pinholes of which diameters are 2.4, 3.5 and 8J..Lm full
width at the half maximum. An imaging plate was employed as a twodimensional detector and covers -60 to 165 degrees in two-theta with acylindrical camera radius of 100 nun.
The software system includes (a) assignment of indices, (b) simulation ofLaue pattern, (c) refinement of crystal orientation, (d) calculation of
integrated intensities, (e) absorption correction and (f) structurerefinement based on intensities of Laue spots.
The recent application of ML to unknown carbonaceous material in a thinsection of the meteorite(ureilite) is briefly introduced in below.
Laue pattern from a crystal with dimension of 2x 1 Jlffi was obtained for
60 min. exposure. By assignment of indices and subsequent simulation of
the Laue pattern, the unknown material is determined to be diamond.
Refinement of an isotropic temperature factor gave 0.19(3) A2 based on
twelve Laue intensities.
Ohsumi,K., Hagiya,K. & Ohmasa,M.(l991 ). J.Appl.Cryst.24,340-348.
Ohsumi,K., Hagiya,K., Uchida,M., Suda,N., Miyamoto,M., Kitamura,M.
& Ohmasa,M.( 1995). Rev .Sci.Instrum.66(2),1448-l450.

1A13

Multiple-Detector System for Powder Diffractometer Using
Synchrotron Radiation and High-Resolution Diffraction Data
Obtained with It
H. Toraya and H. Hibino, Ceramics Research Laboratory, Nagoya Institute ofTechnology, Asahigaoka, Tajirni 507, Japan and K. Ohsumi, Photon Factory,
National Laboratory for High-Energy Physics, Ohho, Tsukuba 305, JapanA new powder diffractometer for synchrotron radiation with six detector arms
has been constructed. Five detector arms compose a multiple-detector system.
They are set radially at the interval of 25° on the 29-axis of goniometer. Fivescintillation counters coupled with a flat Ge crystal analyzer on respective arms
can record simultaneously the whole powder pattern divided into five segmentswith an equal29 span. The optics design is based on the flat-specimen-reflection
geometry using parallel-beam. A 29-step-scanning technique is used for datacollection in the asymmetric diffraction at a fixed incident angle. Thus a rapid
diffractometer scan at step intervals of 0.001 to 0.004° could be realized. A sixth
detector arm can be used for multi-purpose, and it can equip various kinds ofanalyzers such as long horizontal parallel slits, a flat or channel-cut crystal
analyzer, a receiving slit, a solid state detector. This arm can be operated in theconventional single-arm-scanning mode.
Test operations of diffractometer were conducted at the BL-4B experimental
station at the Photon Factory in Tsukuba. Monochromatic beam with awavelength of 1.5416 A was obtained from a water-cooled double-crystal Si(111) monochromator. The diffractometer scan, for example, of the (Ill)reflection from Si using a multiple-detector system recorded the full-width at
half-maximu of 0.022° and the peak maximum intensity of more than 40,000
counts per second. The whole powder pattern of Mg 2Si04 could be step-scanned
at a step interval of 0.004° in 29 just within 4 hours.

1A14
ELEcrRON DENSITY IMAGING wrrn SYNCHROfRON X-RADIATION
E. N. Maslen and V A. Streltsov, Crystallography Centre, University of Western
Australia, Ned lands, W A 6907, Australia
Historically electron difference densities (.O.p) were measured using X-ray diffraction withtube sources. Because of unreliable extinction corrections and high noise due to limited
intensity, the reproducibility of those experiments was often mediocre. The resulting .O.p
maps were poor representations of the electron density due to chemical bonding. Property
predictions were inaccurate. Because of its excellent qualities, the electromagnetic
radiation emitted by transversely accelerated relativistic electrons or positrons has becomea very powerful tool for exploring basic properties of materials that were previously
inaccessible. High precision diffraction using synchrotron radiation (SR) has now
overtaken X-ray tube diffraction imaging because it provides less noisy images withlower distortion by extinction errors. Here we review some recent studies of the electron
density with SR. The high accuracy .O.p images measured at the Photon Factory in Japan
allbws the reorganisation of the electron density in the atoms that form crystalline solids
to be depicted unambiguously, sometimes with surprising conclusions.
For the birefringent carbonates CaC03, MgC03 and MnC03 the .O.p density correlateswith optical anisotropy to a degree consistent with a cause and effect relationship between
electron density and refractive index. That index is large where locally antisymmetriccomponents dominate the electron density. The metal-C03 interaction has a significant
effect on the .O.p density near the C03 group, the moiety responsible for opticalanisotropy.
Electron densities are perturbed significantly by non-bonded interactions. Metal-metalinteractions strongly influence SR electron densities for a-Ah03 and for a-Fe203, atheme that continues in the orthoferrites : YFe03 and SmFe03, and the C-type
sesquioxides: Y203, Dy203 and Ho203. The cation electron densities arc deformed morestrongly by interaction with other cations than with 0 atoms except where the cation's 0coordination crystal field includes a low symmetry component. These metal-metalinteractions are beyond the normal range of chemical bonds. When spin-dependent theymust play important roles in magnetic ordering and structural transitions.
The topography of SR images indicates that valence electron density overlapping cations'closed inner subshells is repelled by exchange towards regions of lower electrostatic
potential more remote from the nuclei. The transferred density retains the cation's
symmetry. That is consistent with the observed regularity of cation arrays- which often
exceeds that of the anions.

1A15
TEXTURE STUDY ON SYNCHROTRON RADIATION
E.S.Abovian, A.H.Grigorian and K.G.Trouni Department of Solid State
Physics, Yerevan State University, A.Manoukyan 1, Yerevan, 375049,
Armenia.
A systematic study is carried out with the purpose to demonstrate thepotentialities of application of the continious spectrum of synchrotron
radiation for express study of textured state of various materials.
The experiments are carried out on the special diffractometer placed on the
Yerevan electron accelerator "Arous". The simple geometry of "direct"
exposure was realized, which enabled to register diffraction pattern on
nuclear photoplates located behind the specimen, perpendicular to theincident beam.
As the objects to be investigated the AI and Cu foils having the texture ofrolling, as well as the wires of Ag,Cu and Pt.
For quantitative analysis of obtained data there is carried out the study of
texture by the X-ray energy-dispersive diffractometry technique. Energydispersive diffractograms are obtained for Al-foil when the rolling plane isperpendicular to the incident beam.
In comparison to the classic method of texture study by monochromaticradiation with the use of special textures of goniometric heads in the given
work the necessary bulk of information is obtained in a few minutes. The
impotrant fact is the revealing of K-edge of absorption on the diffraction
pattern. Thus, the use of monochromatic synchrotron radiation together
with energy-dispersive diffractometry proves to be rather promising
thechnique in studies of textured materials.
Buras B. et al. J.Appl. Cryst.,l977, v.IO, p.431-438.

1A21
MODULATED STRUCTURES IN THE NbzZrx-202x+l AND
Ta2Zrx-202x+l (7.1 ~ x ~ 12) SOLID SOLUTION FIELDS
Siegbert Schmid, Klaus Fiitterer, John G. Thompson and Ray L. Withers,
Research School of Chemistry, The Australian National University,
Canberra ACT 0200, Australia, and Nobuo Ishizawa, Research Laboratoryof Engineering Materials, Tokyo Institute of Technology, Nagatsuta,
Midori-ku, Yokohama 226, JapanAt the Zr02-rich end of both the Zr02 . Nb205 and Zr02 . Ta205 systems,
wide range solid solutions of the type M2Zrx-202x+l (M = Nb, Ta) are ·observed. The widths of these solid solutions, when synthesized via solidstate reaction, have been reported as 7.1 ~ x ~ 10.3 (Thompson et al.,1990), however x is beyond this range when the syntheses are carried out
via a flux method. It has been shown that such systems are best describedas composite modulated structures rather than homologous series Mn02n+l(x =2n) of closely related phases.
X-ray intensity measurements from a Nb2Zrx-202x+l • x =12 single crystal
were carried out at BL14-A of the Photon Factory, Tsukuba, Japan. Data
were collected at 1458 and 8 eV below the Zr K absorption edge. The
enhanced scattering contrast between the neighbouring metals close to the
Zr K absorption edge enables refinement of potential metal atom ordering.
The displacive modulation wave amplitudes obtained from theserefinements (Fiitterer et al., 1995) are in remarkable agreement with thoseobtained from a Fourier decomposition of the previously published,
conventional superstructure refinement of the member x = 8 (Galy & Roth,
1973).
The refinements in the Nb2Zrx-202x+l system will be compared with theresults for Ta2Zrx-202x+l. x = 8, both in terms of displacive modulation
waves as well as metal atom ordering patterns!
Fiitterer, K., Schmid, S., Thompson, J. G., Withers, R. L., Ishizawa, N. &Kishimoto, S. (1995). Acta Cryst. B51 (in press).
Galy, J. & Roth, R. S. (1973). J. Solid State Chern. 7, 277-285.
Thompson, J. G. , Withers , R. L. , Sellar, J., Barlow, P.J. & Hyde, B. G.
(1990). J. Solid State Chern. 88,465-475.

1A22
X-RAY ANALYSIS OF 4f-ELECTRON DENSITY IN CeB 6 CRYSTALSK. Tanaka. Chemistry Department, Nagoya Institute ofTechnology, Gokisocho, Showa-ku, Nagoya, 466, Japan, and Y. Ohnuki, Physics Department,
Osaka University, Machikaneyama-cho, 1-1, Toyona.ka 560, Japan.
4f-electron densities have been measured by several researchers. However
they have not been analyzed quantitatively with scattering factors which take
into account the aspherical 4f-electron distribution. Ce atoms in the CeB 6
crystals locate in the oh crystal field. In the limit of the crystal field theory,the 4f-orbitals are clearly defmed in this case. Therefore CeB6 is a very goodcompound to begin the 4f-electron density analysis. Since f-electrons locates closer to the nucleus and the distinction between the 4f-electron density and the anharmonic thermal vibration of Ce was expected to be difficult ,the structure factors were measured at 100 K and 165 K. Further the ratioof the numbers off-electrons to that of the total electrons is very small, special care was taken in the measurement. First the temperature variation at the
sample position with ro and X was measured in advance and the intensity wasmeasured where the temperature of the sample position is stable. Second themultiple diffraction effect was also avoided with the \f'-scan. The deformation densities around the Ce atom reveal the sharp peaks along [ 100], indicating the existence of a f-electron on the triply degenerate fx3- x/. fy 3-y/ andfz 3-z? orbitals. For the calculation of the scattering factors of each f-orbital,
4 f atomic orbital were calculated with the Dirac-Slater method using the program HEX. 1> The refinement assuming this 4f-electron configuration reduced the peak heights by half. The following anharmonic thermal vibration
analysis further diminished peaks by half. The tendency are the same for experiments at both temperatures. These results show that the peaks around theCe atom are due to both the aspherical distribution of 4f electrons and the anharmonic thermal vibration of the Ce atom.
!)Liberman, L.A., Cromer, D.T. & Waber, J. T. (1971). Comp . Phys. Commun. , 2, 107.

1A23
THE JOINT X-RAY AND ELECTRON DIFFRACTION STUDY OF MGO
Yu.A. Abramov*, A.S. Avilov', E.L. Belokoneva&, Kitaneh Rushdi , D. Feil~.
5

V.G. Tsirelsons and F.P. Okamura** National Institute For Research in Inorganic Materials, Tsukuba, Japan# Institute of Crystallography , Moscow, Russia& Moscow State University, Moscow, Russia% University ofTwente, Enschede, the Netherlands$ Mendeleev University of Chemical Technology, Moscow, Russia
The results of study of electrostatic potential (EP) and some physical propenies of MgO
crystal by accurate electron and X-ray diffractometry are presented. The polycrystal thinfilm in the transmission electron diffraction and single crystal sample in the X-ray diffraction have been used. An agreement within 5% for the EP distributions, reconstructedfrom diffraction data, have been achieved. A good agreement of those with the results oftheoretical calculation by the Hartree-Fock method for bulk MgO crystal was observed
as well. This allows to be sure that details of EP distribution are available for the experimental study with a good degree of accuracy. The diamagnetic susceptibility and static
electronic polarizability were calculated from X-ray and electron kinematic structure amplitudes for MgO. Those are in good agreement with independent experimental values.
The analysis of the MgO X-ray electron density was given in terms of Bader's quantumtopological theory. The gradient field and Laplacian of the electron density have been
calculated by using the obtained multipole model parameters. The bond (3,-1) criticalpoint on the Mg-0 internuclear vector was found and "sizes" of atoms bonded in the
crystal were determined. The near spherical shape of bonded 0 atoms was revealed. The
corresponding average radius equals 1.27 A. This value as well as the distance from theMg atom to the bond critical point ,0.936 A, are in good agreement with Shannon andPrewitt's ionic radius values of 1.26 A and 0.86 A for o·2 and Mg•2 ions, respectively.
The Laplacian value a t the bond critical point is positive as is usual for the case of ionicbonding. A (3,+1) critical point was found at the centre of the (001) plane.
Support of this researc h by the Netherlands Organization for Scientific Research (NWO)
and International Scientific Foundation (Grant UIGOOO) is gratefully acknowledged.

1A24
Crystal Structure and Magnetic Properties of the Linear Homo or
Betero Trinuclear Metal Complexes of Bis(2-pyridyl)amido Ligand
Cheng-Chen Lin, En-Che Yang, Gene-Hsiang Lee, and Shie-Ming Peng
Department of Chemistry,
National Taiwan University
Taipe~ 10764, Taiwan ROC

Polynuclear metal chain complexes have received considerable interest because of
their spin interaction and the nature of the metal-metal bonding. The bis(2-pyridyl)amido
ligand in the syn-syn conformation allows each nitrogen atom to coordinate with aseparate metal.ions.

syn-synanti-anti

anti-synHere we report the syntheses, crystal structures and magnetic properties of a seriesof quadruply bridged trinuclear metal complexes, [M~' 1 (J1l·dpa)~].,.(PF6)., where M=Con or Niu, M' =Con, Niu, Pdu, dpa = bis(2-pyridyl)amido, L = cr, Ncs·, CH1CN etc.
The representative structure of this family is [Co~d(Jll·dpa).Cht which shown in
the Figure and a structural comparison of this series are presented. The magnetic
interaction of these trinuclear metal complexes will also be discussed.
ca

1811

CIF AS THE COMMON LANGUAGE OF CRYSTALLOGRAPHY
Brian McMahon, International Union of Crystallography, 5 Abbey Square, Chester
CHI 2HU , EnglandWithin a scientifi c discipline, the efficient interchange of experimental data andderived information relies on the existence of an established protocol for representing the concepts and measurables of that discipline. The International Unionof Crystallography has been vigorous in its sponsorship of suitable protocols , including the Standard Crystallographic File Structure (SCFS) (Brown, 1983) andits successor, the Crystallographic Information File (CIF) (Hall, Allen & Brown,
1991 ).
Although SCFS had little impact on the discipline, CIF has become established as
the working language of small-molecule crystallographers, owing to its promotion
by Acta Crystallographica as the preferred submission format to Section C of thejournal, and to the growth of a substantial number of programs for generating,an~lysing and visualising C!Fs. They offer an error-free route from refinement
package, through submission to the journal, publication and deposition in crystallographic databases .
Together with a simple syntactic structure, ClF offers a detailed glossary of crystallographic terms, formalised in the Core Dictionary for small molecules , andnew extension dictionaries for powder diffraction and macromolecular applications. Additional di ctionaries for modulated structures and general symmetry
definitions are also under development. Hence the CIF protocol offers a grammar
and vocabulary for form al data activities; and guidelines drawn up by the Acta
editorial office (IUCr, 1995), together with discussion lists and collaborative software projects undertaken by software developers, help to define the usage andidiom of what is increasingly the language of crystallography.
References
Brown, I. D. ( 1983). Acta Cryst. A39, 216-224 .
Hall , S. R., Allen , F . H. & Brown, I. D. (1991) . Acta Cryst . A47, 655-685 .
IU Cr (1995) . A Guide to CIF for Authors. Available from the Managing Editor,
IUCr , 5 Abbey Square, Chester CHI 2HU.

1812

THE BROOKHAVEN PROTEIN DATA BANK
Joel L. Sussman, Protein Data Bank, Brookhaven National Laboratory, Upton,
NY 11973, USA
The Protein Data Bank (PDB) at Brookhaven National Laboratory (BNL) is
an archive of experimentally determined three dimensional structures of biological macromolecules, serving a global community of researchers, educators, andstudents. The challenges presented by the enormous growth in data over the
past several years have been met by the PDB staff and management, which now
provides an up-to-date archive, while simultaneously expanding network access(Stampf et al., 1995) and building strong world-wide collaborations (Peitsch etal., 1995). Even larger challenges are at hand, as the deposition rate continues
to rise along with the expectations of the consumers of these data. We are enhancing the capabilities of the PDB and transforming it into a new biologicalThree-Dimensional Macromolecular Structure Database, while retaining many of
the features of the PDB, for compatibility.
Over the course of the next few years, we plan to:• Ensure that the archive remains current , correct, and relevant• Provide a rapid and painless automated deposition system, using internationally agreed-upon CIF standards• Enhance data validation tools• Build a relational database to store and provide flexible access to the information• Integrate the PDB with complementary biological and chemical databases
through semantic links and schema sharing• Provide easy access, through the Internet , to the PDB at BNL and otherdeposition and distribution sites worldwide
References
Peitsch, M . C., Stampf, D. R., Wells, T. N. C. & Sussman, J . L. (1995) . The
Swiss 3D-Image Collection and Brookhaven Protein Data Bank Browser on theWorld- Wide Web. Trends in Biochemical Sciences 20, 82-84.
Stampf, D . R., Felder, C. E. & Sussman, J . L. (1995). PDBBrowse- a Graphics
Interface to the Brookhaven Protein Data Bank. Nature 374, 572·574 .

1813

XTAL_GX: CIF-ENTRY GRAPHICS FOR GEOMETRY ANALYSIS
Syd Hall and Doug du Boulay, Crystallography Centre, U. Western Australia,
Nedlands, Australia 6009 {syd@cn;stal.uwa.edu.au], James Hester, NIRIM,
Namiki 1-1, Tsukuba, lbaraki 305, Japan [jrh@nirim .go.jp], and David Grossie,
Chemistry, Wright State University, Dayton OH, USA {dgrossie@chem .wsu.edll].
A new software package Xtai_GX has been developed to display and analyse
structural data stored in CIF format. It is supplied gratis by ftp as executable
modules for major operating systems supporting X11 graphics, and for a
PC/MS-DOS. Xtal_GX is specifically designed to process and validate CIF
data but it will handle other entry data. It was originally intended to test Acta
Cn;stallographica C submissions and is suitable for checking geometry,
additional symmetry and for preparing publication plots. It will not process
diffraction data.
The package performs the following calculations:• Read and validate, or write, data in CIF format• Display and manipulate molecular structure interactively• Generate ellipsoid plots which have been oriented with PIG• Generate Newman molecular projection plots• Search for non-space-group symmetry elements• Search for additional unit cell settings• Calculate full range of molecular geometry data
• Calculate least square plane equations and deviations• Enter non-CIF cell, symmetry and coordinate data
• Interactively adjust/insert text in ORTEP or NEWMAN plots• Output ORTEP or NEWMAN plots as PostScript or HPGL
These calculations are a small sub-set of the new Xtal 3.4 System due to bereleased in November. A WWW server may be used to obtain further Xtal
information (http://www.unige.ch/cn;stal/axtal/xtal.html).

Xtai_GX will be available in July by anonymous ftp (130.95.232 .12 in directoryfree). A README file describes the various versions. The PC version can also
be obtained by floppy from the last named author. Documentation and an
example input command file with test CIF are also supplied .

1814

MAXIMUM ENTROPY DECONVOLUTION IN X-RAY DIFFRACTIONANALYSIS.
W. Kalceff and N. Armstrong, Department of Applied Physics, University ofTechnology, Sydney, PO Box 123 , Broadway, NSW 2007, Australia, and J.P.
Cline, Ceramics Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.
The removal of instrumental contributions k from a measured profile g in thepresence of noise n to find the specimen function f is known as the "inverse
problem" and requires the solution over some range of the integral equation,g(x) =

Jk(x,~)f(~)d~ + n(x)(1) .

In this paper we discuss a C++ implementation of a maximum entropy (Max.Ent)

algorithm for solving this equation and show its application in the determinationof profile functions for size/strain broadened x-ray diffraction data from various
specimens.
The maximum entropy method can be formulated in terms of a Lagrangian function Q (Skilling and Bryan, 1984),
Q(J,A.) = S(f)- A.C(f)(2),

where S(f) is the entropy function, C(f) is the constraint statistic, f is the
profile function and A. is an unknown Lagrangian multiplier. In order to determine the profile function, S(f) must be maximised with respect to C(f) forsome A. The standard approach to solving a non-linear equation such as (2) is to
apply Newton's Method or the steepest descent method. However, this has beenfound to be unsuccessful, because (2) is not only non-linear, but it cannot be expressed as a quadratic model, as required to ensure convergence of the solution.
The Skilling-Bryan algorithm we have used determines the Max.Ent solution byforming a subspace spanned by a number of vectors. A quadratic model of theentropy and constraint functions can then be constructed and a solution determined within the subspace.
Skilling, J. and Bryan, R.K. (1984). Mon . Not. R. Astr. Soc., 221, 111-124.

1821
THE MACROMOLECULAR CIF DICTIONARY VERSION 1.0
Phil E Bourne, San Diego SuperComputing Center, PO Box 85608, San Diego
CA 92186-9784, USA.
Version 1.0 of the macromolecular Crystallographic Information File (mmCIF)
dictionary is complete and it is anticipated that it will be published close to thetime of the meeting. The dictionary represents a major reference work in describing the crystallographic experiment and the resultant structure. Moreover, since
the dictionary and the Dictionary Definition Language (DDL) used to describe it
are self defining and rigorous in their implementation, new opportunities exist fordeveloping software where the semantics are identical for all applications. Thisis possible since the semantics are described by the ONE dictionary and not the
many different programs. Details of the DDL, the contents of the dictionary, andthe emerging software tools that work with mmCIF will be described.

1B22
THE NUCLEIC ACID DATABASE PROJECT
Helen M. Berman, Lester Clowney, Anke Gelbin, ShuHsin Hsieh, and John Westbrook, Department of Chemistry, Rutgers University, Piscataway NJ 08855, USA
The Nucleic Acid Database (NDB) (I) contains information about the structuresof more than 350 nucleic acid containing crystals. In addition to the coordinates,
primary experimental information and derived features of these structures are
stored. Several methods of access are provided including a forms based interface
that is available via the World Wide Web . We will present some of the many
types of reports that can be retrieved as well as the queries that are possible using
this resource.
In addition, the standard dictionaries that have been created by the NDB for use
in validation and refinement of nucleic acids will be described .
Funding for this project is provided by an NSF grant BIR 9305135
1. "The Nucleic Acid Database: A Comprehensive Relational Database of Three
Dimensional Structures of Nucleic Acids," Helen M. Berman, Wilma K. Olson ,David Beveridge, John Westbrook, Anke Gelbin, Tamas Demeny, ShuHsin Hsieh,
A.R. Srinivasan and Bohdan Schneider, Biophysical J ., 63 :751 -759, 1992.

1823, 1 P53

TITAN: A MOLECULAR GRAPHICS PROGRAM TO AIDSTRUCTURE SOLUTION AND REFINEMENT WITH THE
SHELX SUITE OF PROGRAMS.
Keith A. Hunter and Jim Simpson, Department of Chemistry, University ofOtago, P.O. Box 56, Dunedin, NEW ZEALAND

TITAN is a Windows based molecular graphics program designed to be
used in conjWlction with SHELXS-86 1 for structure solution and
SHELXL-93 2 and/or SHELX-76 3 for structure refinement. The program. facilitates the on-screen assignment of peaks from the direct methods E-·
map or Patterson map to individual atom designations. Once these
designations are completed, a file is written that can be input directly to
the SHELXL-93 refinement program without further modification. TITAN
cab also be used in the location of additional atoms in series of leastsquares and difference Fourier cycles and as an aid to the inclusion ofhydrogen atoms into the refinement using the HFIX and/or AFIX
commands.
TITAN runs in the Windows environment and requires a 386 or preferably
486 processor with a minimum of 4Mb memory. Hard-copy plots can beobtained using any Windows compatible printer.
As TITAN was written specifically for use with the SHELXS-86/SHELXL93 suite of programs this combination is strongly recommended. TITAN
will also read all results files produced by SHELX-76 to allow display andplotting of data produced using that program. However some minor
intervention will be required to produce input files using TITAN that can beused by SHELX-7 6.
A demonstration of the operation of the TITAN program will be given as
part of this poster presentation.
Sheldrick, G .M. (1986) SHELXS-86 ' A program for the solution of
crystal structures from diffraction data.' University of Giittingen,Federal Republic of Germany
Sheldrick, G.M. (1995) SHELXL-93 J. Appl. Cryst. in preparation
Sheldrick, G.M. (1976) SHELX-76 ' Program for crystal structure
determination', University of Cambridge, England

1824
MOLDRAW: MOLECULAR GRAPHICS FOR MS-WINDOWS
P. Ugliengo+, G. Chiari* and D. Viterbo++Dipartimemto di Chimica lnorganica, Chimica Fisica e Chimica dei
Materiali, Universita, Via P. Giuria 7, 1-10125 Torino, Italy.
*Diparimento di Scienze Mineralogiche e Petrologiche, Universita, Via
Valperga Caluso 37, 1-10125 Torino, Italy
MOLDRAW [1] is a program for the graphical manipulation of moleculeson personal computers, which can be used to analyze the conformation ofmolecules resulting both from diffraction techniques or from theoretical
calculations, and to study the detailed structure of crystalline materials.
More recently we have undertaken the porting of the code under MSWINDOWS, in order to take full advantage of the facilities offered by thissystem. The "look & feel" features of all WINDOWS applications arepreserved and all operations are menu, mouse or event driven; thesefeatures make this new version of MOLDRAW very easy to learn and use.
Graphic resolution and performance are entirely determined by the
WINDOWS driver. With last generation graphic boards, molecular structures
may be rendered as on more costly graphic workstations. The resulting
images can be printed on any WINDOWS defined printer and pasted to the
clipboard or saved as bitmap files to be used by Paintbrush, Word, etc. fordesktop publishing.
The improved memory management of WINDOWS allows to overcome
the memory limits imposed by MS-DOS and the program may thus beextended to handle very large systems (biological macromolecules).
All features present in the MS-DOS version have been improved andsome new facilities have been introduced. The format of the input files has
been preserved.
We are currently involved in setting up a much easier interface to the
crystallographic data bases and programs (CSD, ICSD, SHELX, CRYSTALS.
SIR92, etc.}, to the computational chemistry packages (GAUSSIAN, AMPAC,etc.) and to other molecular graphics systems (Alchemy, Biosym, etc.).
We are also engaged in the setting up of the following new facilities:a) simulation of powder diffraction patterns;b) representation of polyhedra;c) generation of a complete unique molecule from the given coordinates andsymmetry operators.
d) animation of molecular vibrations as computed by GAUSSIAN.
(1) P. Ugliengo, D. Viterbo & G. Chiari, Z. Kristallogr., 207 (1~93),9-23

1C11
X-RAY PHASE RECOVERY: MAPPING OF TWO-DIMENSIONAL
CRYSTAL LATIICE STRAINS WITH NANOMETRE DEPTHRESOLUTION
A. Yu. Nikulin. T. E . Gureyev, School of Physics, University of Melbourne, Parkville,
Vic. 3052, Australia, H . Hashizume, Research Laboratory of Engineering Materials,
Tokyo Institute of Technology, Nagatsuta, Midori, Yokohama 226, Japan, and A. W.
Stevenson and S . W . Wilkins, CSIRO Division of Materials Science & Technology,
Private Bag 33, Rosebank MDC, Clayton, Vic. 3169, Australia.

A model-independent rrethod of mapping two-dimensional (20) strain profiles in nearsurface region of crystals has been developed for the crystals with lD periodic
superstructure modulations. The algorithm is based on an application of the solution for
the 1D inverse problem to the Fourier-components of the strain profile.
The rrethod relies on high-resolution x-ray diffractorretry. Peak intensities of 1D crystal

truncation rods (CTRs) are rreasured for the fundarrental Bragg and individual satellite
reflections. Spatial resolution is determined by the range of angles over which the data iscollected. Each CfR has a different intensity distnbution along the direction in reciprocal
space parallel to the surface normal of the crystal. A Hilbert transform formalism isapplied to retrieve the phase infonnation for the individual CfR intensities (Petrashen,1989). This procedure actually determines the phases of the Fourier harmonics of the 2D
distribution of complex dielectric susceptibility of the distorted crystal
The relative phases of the individual harmonics are indeterminate. Since all harmonics are
independent within the framework of kinematic approximation, each harmonic has an
ambiguity of constant phase shift. For laterally symrretric displacerrents it is possible toreduce the ambiguity to the choice of signs. The sign selection is made according to thesequential trial or minimum energy criteria.
The rrethod was applied to a number of silicon single crystals with a laterally periodic
surface oxide mask patterns and ion-implanted through such mask. The x-ray diffraction
experirrents were perforrred at the Photon Factory synchrotron source in Japan. The
profiles obtained show localised strains with 10 to 50 run depth and 0.2-0.3 J.lm in-plane
lateral resolutions (Nikulin et a!., 1994, 1995). Test scans demonstrated that a 1 run
depth resolution is achievable.
Petrashen, P.V. eta!., Sov.Phys.Dokl. 34, 957 (1989).

Nikulin, A.Yu. eta!., J.Appl.Cryst. 27, 338 (1994).
Nikulin, A.Yu. eta!., J.Appl.Cryst. 28, 57 (1995).

1C12
X-RAY POLARIZATION ANALYSIS OF ALLOWED AND FORBIDDENREFLECTIONS OF IRON PYRITE, FeS2.
l.Yazawa, T.Nagano, T.Kurasawa, E.Tsuji, S.Kumazawa and~. Dept. of Phys.
Science Univ. of Tokyo. Noda, Chiba 278, Japan, S.Sasaki, Research Lab. of Eng.
Mater. Tokyo Inst. of Tech . Nagatsuda, Yokohama 227, Japan and T.Mori and
S.Kishimoto, PF. KEK. Tsukuba, lbaraki 305, Japan.
Usually, X-ray susceptibility is treated as a scalar, since the anisotropy of thesusceptibility of the crystal is very small in the X-ray region. But the anisotropy might
become large at an X-ray wavelength near the absorption edge of a constituent atom.
Indeed, X-ray dichroism and birefringence were observed in several crystals at theabsorption edges.ll.2l Moreover, it should be noticed that, in the visible light region,
dichroism and birefringence are not observed in a cubic crystal but, in the X-ray region,
they are observed even in a cubic crystal. This fact indicates that X-ray dichroism andbirefringence have great posibility to study local electronic structures of the crystal atoms
and/or ions. The purpose of the present work is to elucidate the relation between thepolarization and the anisotropic tensor of the structure factor (ATS). 3) For the purpose ,we carried out polarization analysis of allowed and forbidden reflections of an iron pyrite
single crystal with linearly polarized SR. The SR measurements were carried out using
four axis diffractometes at BL-3A and 4C of PF of KEK in Tsukuba. A polarization
analyzer equipment was mounted on the counter arm of the diffractometer. BaF2(333)reflection which has Bragg angle of 46.94 • at the Fe K-absorption edge was used forthe analyzer crystal. In the arrangement of the present work, the polarization of theincident beam was cr. Because of the symmetry of iron pyrite, (002n+ I) reflections are
forbidden . For an allowed Bragg reflection, (002n), the polarization of the diffracted
beam was cr. But for a forbidden reflection, (00 I), the polarization was 1t . The
dependence of azimuthal angle on the polarized beam was also measured. The result wasin good agreement with the theory which took into account of the anisotropic tensor of thestructure factor. The off diagonal components of the tensor were also detennined.
I) David H . Templeton and Lieselotte K. Templeton. (1980) Acta Cryst.A35, 237-241
2) A.Petcov, A.Kirfel and K.Fischer. (1990) Acta Cryst.A46, 754-763
3) V. E. Dmitrienko. (1983) Acta Cryst.A39, 29-35

1C13
USE OF HARKER SECTIONS OF PATTERSONFUNCTION · AS CONSTRAINT OF DENSITY MODIFICATION FOR DIRECT PHASE DETERMINATION
M. Shiono, Department of Physics, Faculty of Science, Kyushu University, Higashi-ku, F'ukuoka, 812, Japan.
Success of direct phase determinations based on either reciprocal orreal space technique depends on the starting point. Conventionaldirect methods employ multi-solution procedure for overcoming thisproblem.
A real space direct phase determination procedure which is basedon density squareing and eliminating negative density has been developed and applied to small proteins (Shiono et al. {1992) Acta
Cryst. A48, Refaat et al. (1993) Acta Cryst. A49). This method
uses multi-solution procedure and can produce ab initio solutions ofsmall and middle size structures (IUCr XVI Congress, Beijing). The
real space method, however, is time consuming and needs some criterion for selecting good starting points in order to be competitive
with reciprocal space methods. For above reason, Harker Sectioq~ ofPatterson map are used as a filter of the electron density. This density masking considerably improves power of the procedure in earlystage of phase refinement.
The method has been applied to phase determination of Ribonuclease Ap1 (Space group P2I) . Firstly, Harker section is extracted from
Patterson function. Secondly, the Harker section is contracted to
1/4 in area and then 4 pieces of them are placed in the original sizeof plane. We thus get a section which includes 4 contracted Harker
sections. By using this section as 2-dimensional filter of electron
density map, we can get phase sets with weighted mean phase error
75° . 20 trials from random phases have been made and 16 sets areof this quality.

1C14
PHASE EXTENSION USING X-RAY MULTIPLE DIFFRACTION
AND MAXIMUM ENTROPY METHOD

C.-M. Wang and S.-L. Chang, Department of Physics, National Tsing Hua
University Hsinchu, Taiwan, 300, R.O.C.

We report the extension of the phases of the structure factors of theorganic crystal CzsHzsNOz from 77 starting individual phases using the
maximum entropy method. These starting phases were determined from90 experimental triplet phases calculated from 215 measured '!'-scan 3beam and 4-beam diffraction profiles obtained with a rotating-anode xray source, where the '!'-scans were around the reciprocal lattice vectorsof the (001), (002), and (003) reflections. The extension of the structure
factors with phase values was carried out using the maximum entropy_
method for 2040 measured 2-beam Bragg diffraction intensities with 77
starting phases and the symmetry of space group as the constraints. The
likelihood criterion was applied to the maximum entropy extrapolation todiscern the best extrapolated phase sets which can be used as the new
constraints for the next step of generating new phases. With this phaseextension procedure, more than one hundred phases were determined.

1C21

DIFFUSEX-RAY SCATTERING AND PHASE TRANSITIONS OFUREA

INCLUSION COMPOUNDS.

T.R.Welberry and S.C.Mayo, Research School of Chemistry, Australian
National University, Canberra, ACT 0200, Australia.
Diffuse X-ray scattering studies have been carried out on the long chain
alkane/urea inclusion compounds Hexadecane-Urea (HD-Urea) and1,10- Di b romo-n-decane- Urea
(DBrD-Urea). In both examples theguest species are thought to occupy
the hexagonal tunnels in the hosturea structure with the alkane
chains able to rotate about theirlong axis and switch between six
energeticallyfavourable
orientations. At room temperature
there is thought to be very little
correlation
betweentheorientation of molecules inadjacent tunnels or (in the case of
HD-urea) in their relative positions along the channels. The guests thus
form a 1D crystal and this gives rise to planes of diffuse scattering normal to
the tunnel direction. In the case of HD-Urea the 1D repeat is almost
commensurate with the c-axis repeat of the urea framework, but for DBrDUrea the diffuse planes occur with a repeat distance incommensurate withthat of the urea. As well as these sharp planes of scattering other distinctive
diffuse scattering features are observed which are associated with theorientational ordering of the alkanes and the flexing of the urea framework.
Although the diffuse scattering in these materials has been noted byother workers (see for example Harris & Thomas, 1990), the resolution of
our position-sensitive detector (PSD) X-ray system has allowed us to collecthigh quality diffuse diffraction data at a range of different temperatures, andinvestigate the changes that occur as the crystals undergo a series of phasetransitions at temperatures below 150K, which are thought to correspond tothe orientational ordering of the alkane chains(see for example Harris,1993). The highly structured diffuse scattering patterns have been modelledusing Monte Carlo methods which simulate both the orientational orderingof the alkane chains and the flexing of the urea tunnels about them .
Harris, K.D.M. and Thomas, J.M. (1990) J. Chern. Soc. Farad. Trans. 86, 2985.
Harris, K.D.M. (1993) ]. Solid State Chern. 106, 83.

1C22
ATOHXC SHORT-RANGE ORDBR XN NICKBL-PLATXHUH ALLOYS

D. K. Saba, Atomic Energy Centre, P. 0. Box - 164, Dhaka
1000, Bangladesh and K.

Ohshi!Da,Institute of Applied

Physics, University of Tsukuba, Tsukuba 305, Japan.

The electron and x-ray diffraction patterns were observed
from four different alloys of the x•0.25, 0.35, 0.44 and0.50 in1

Ni ~Pt1 to understand the existence and shape ofdiffuse intensity, which gives us the information about
structuralfluctuations.

scattering

has

been

A peculiar

observed

at

shape

100,

110

of

diffuse

and

their

equivalent positions on the patterns where the shape of
100 position diffuse intensity changes with Pt content inthealloys.

The

shape

of

diffuseintensity

at100

position for the x•0.25 alloy is a rod-like but the shapeis nearly spherical for the x•O. 50 alloy. The short-rangeorder (SRO)

diffuse intensities were measured from thex•O.SO single crystal alloy at room temperature and the
Warren-Cowley

SRO

parameters

weredetermined

after

analyzing the data. A correlation length has been deduced
to be about 19 A from estimating the inverse of the full
width at half maximum (FWHH) values of the diffuse peak.

1C23
CRYSTALLOGRAPHIC STUDIES OF C6o AND C70
BY A SiNGLE CRYSTAL X-RAY DIFFRACTION
H . Horiuchi and T . Mitsuki, Mineralogical Institute, Graduate School of
Science, University ofTokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113, Japan,
J . Li, Institute of Metallurgical Physico-Chemistry and Materials, Central
South University of Technology, Changsha, Hunan, China,
N. Kino, and K . Kitazawa, Department of Applied Chemistry, FacultyofEngineering, University ofTokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113,
Japan.
Crystallographic properties such as stacking faults, twinning, and phasetransition behaviors were investigated for C6o and C7o crystals by means of
single crystal X-ray diffraction methods. Used crystals were prepared by avapor growth which is the same technique as that reported by Li et a/. [I).
The structure of C6o is based on fcc and twinning by <Ill> axes isfrequently observed. The occurrence of these type twins is due to stacking
faults on {Ill} . Although some specimens morphologically show complex
habits, they are always twinned by <Ill> without exceptions. The
structure of C7o observed in this investigation is mainly based upon hcp.
However, stacking faults in the C7o structure are much more abundant thanC6o, and diffuse streaks along the c* are much remarkable in the X-ray
diffraction patterns. Weak diffraction maxima corresponding to· ·ABCABC · ·stacking are sometimes observed in the above diffuse streaks depending on
the specimen. In the case of C7o, a unique twinning by (-1 0 2) is also
observed after phase transition at around 340K. This twinning cangeometrically interpret by that the long principal axes of C7o molecule
ellipsoids which is parallel to the c-axis before phase transition change theirdirections into one of 2a1+a2, a1+2a2 or -a1+a2 after phase transition.
Where, OJ and a2 are lattice vectors of the parent crystal. In order to occur
this phenomenon, C7o molecule must achieve free rotation in the structure.
This can be explained not only by precessional motion of C7o molecules but
also by an anisotropic thermal vibration ofC7o molecules.
[I] J.Li et al.,Physica C, 195, 205(1992).

1C24
HIGH PRESSURE POL YMORPHS OF Zr02

0 . Ohtaka, T. Yamanaka, Earth and Space Science, Osaka
University, Toyonaka 560, Osaka Japan, T. Yagi, ISSP, University ofTokyo, Minatoku 106, Tokyo, Japan and 0. Shimomura, PF-KEK,
Tsukuba 305, lbaraki, Japan
Zr02 is one of the major components of modern ceramic materials.
Recently, phase transition of Zr02 under high pressure hasgathered much interest in both material and geophysicalresearches . Because the toughening mechanism of Zr02 ceramics
is explained by a stress induced phase transition, the phase.
transition at high pressure is to be studied from a microscopic view
point. The investigation of high pressure polymorphism of Zr02 isalso important in geophysical implications as the polymorphic
structure of Zr02 might be a possible candidate for the highpressure form of Si02. Zr02 has a monoclinic symmetry at ambientconditions and three high pressure polymorphs of orthol , ortholl andtetragonal have been reported . Because of the experimental
difficulties, these studies of Zr02 under high pressure have mainly
been made at room temperature or, at most, a few hundred degree.
The phase relation at elevated temperature is still unknown.
The present authors have performed a series of synthesis
experiments and in situ observation in order to reveal the phaserelation and the crystal structure of Zr02 high-pressure and-temperature polymorphs. Synthesis experiments were undertakenwith a cubic and a split sphere type high pressure device. Stableregion of orthol and ortholl, which are quenchable phases, were
determined. Two kinds of in situ observations were performed .
Combining a diamond anvil cell and a laser heating system, Zr02
was heated above 1OOOC under high pressures above 20GPa .
Thermally quenched samples were investigated by using x-ray
diffraction under high pressure and confirmed to have a hexagonal
symmetry . Using a cubic anvil type device and synchrotron
radiation, diffraction data in the temperature range from R.T. to
900C at 9GPa were collected. The results indicated that anotherhigh pressure phase appears under these P-T conditions.

1C25
ISOSYMMETRIC STRUCTURAL PHASE TRANSillONS AND
CROSSOVERS : PHENOMENOLOGY, EXAMPLES & IMPLICATIONSAndrew G. Christy, Research School of Chemistry, The Australian
National University, Canberra, ACT 0200, Australia.
Isosymmetric structural phase transitions are those in which significant
changes of unconstrained atomic coordinates and cell parameters occur,
while atoms remain on the same Wyckoff sites and the overall space groupsymmetry remains unchanged. A simple phenomenological model
indicates that these transitions are necessarily first-order. The transitionline extrapolates through a critical point into a 'crossover' or 'diffuse
transition' across which physical properties change fast but continuously.
The location of the crossover is precisely defined as that of a minimum in
d2G/dQ2, where G ·is the free energy and Q is the order parametercharacterising the transition. Second derivatives of free energy such as
thermal expansivity exhibit a corresponding maximum (Christy, 1995).
Examples of isosymmetric transitions and crossovers are found in systems
where the transition is driven by a change in coordination number (KN03),
framework collapse (KTiOP04), competition between different orderparameters of the same symmetry (N aAISi3 0 g), and change incompression mechanism at high pressure (MgSi03).
Anorthite (CaA12Si20&) and ferrosilite (FeSi03) are mineralogicallyimporatant systems each exhibiting several different phases. Both systems
show a transition from a lower symmetry structure with doubled unit cell atambient to a higher symmetry structure with both increasing pressure andincreasing temperature. For both systems, the high-P and bigh-T phases areformally the same structure; however, there are significant differences
between them in energetics and in structural detail, implying that they areseparated by a crossover or isosymmetric transition. It is shown that thelow symmetry phase in both systems is an ordered intergrowth of bigh-Tand high-P forms . Therefore, coupling between the non symmetrybreaking order parameter and a zone boundary order parameter is
responsible for stabilising the low-P, low-T phases in these systems(primitive anorthite and the pigeonite form of FeSi03 respectively). The
crossover in the high-symmetry phase extrapolates into the stability field of
the low-symmetry phase in these systems. Modelling of the behaviour ofthe low-symmetry phase relative to a high-symmetry reference state shouldtake into account the consequent non-monotonic variation in free energy
derivatives of the reference state (Christy & Angel, 1995).
Christy, A.G. (1995). Acta Cryst. B51, in press.
Christy, A.G. & Angel , R.J. (1995). Phys. Chem. Minerals 22, 129-135.

1C26
NUCLEATION AND GROWTH MODEL OF MARTENSITIC PHASE TRANSITION
H. Abe, National Defense Academy, Yokosuka 239, Japan, and
K. Ohshima and T. Suzuki, Institute of Applied Physics,
University of Tsukuba, Tsukuba 305, Japan.
A two-dimensional idealized nucleation and growthmodel

considered,isexperimental

inresultsorder

relating

toto(20-ING)

understandmartensitic

transition

of

In-Tl alloys (Abe et al., 1994) . It

extensionoftheprobability
theKakeshitamodel(l993)

for

model

to

an

ideal

growth

phase
is

an

nucleation

derived from a nucleation barrier .

Kakeshita

theWeextendbyprocess

introducing

the concept of a dynamic embryo andnucleus.

dynamic embryo is a "non-classical" nucleus intheA

non-equilibrium state. Domains in theafrozenlow-temperaturephase

are assumed to develop gathering frozen nuclei .

The

resultsof a computer simulation based on the above

model

show

the presence of an incubation time, which istheessential

properties

first-orderanddomainsandthe fractal distribution of theirfractaldimension

domaindistribution at 256 . 7K of In-23 at. % Tl alloy.

phase

the

the

transition,

experimental

displayofone

cooperative

is obtained to be 1 . 80

results

on the kinetics ofphaseformation

for

th e

of

of

size .

The

the

final
The

martensitic

tarnsition in In-Tl alloys have been interpretedinterms of the present simulation results .
Abe,H ., Ishibashi,M ., Ohshima,K. , Suzuki , T., Wuttig, M. &Kakurai ,K . (1994) . Phys. Rev . 950, 9020-9024 .
Kakeshita,T, Kuroiwa,K . . Shimizu.K .. Ikeda,T., Yamagishi,A.
& Date,M. (1993) . Mater. Trans . , JIM 34, 423-428 .

2PL1

CRYSTALLOGRAPHY-BASED DRUG DESIGN
Takao
Matsuzaki ,Mitsubishi
Kamoshida, Aobaku, Yokohama 227 ,Chemi~alCorporation,

Japan

Protein crystallography suggested its potential ability todirectly observe drug action from the very beginning era .
In
1965,
D.C .
Philips et al.
revealedthecomplexstructure of lysozyme vi th substrate analog i nhi bi tors.
Since the middle of 1980's, protein crystallography has
shown its power in drug design field through a great
number ofstructure
determinations of protein drug
complexes, in addition to new structures vhi ch constitutedrug targets.
In the course of anticoagulant development, we founds~veral new facts in protein-drug complex structures. MQPA
which is the first synthetic thrombin inhibitor inclinical application, binds to trypsin in a new binding
mode, despite of its structural similarity to BPTI, anaturaltrypsininhibitor.
The
X-ray
structure
revealedthemechanisms of the selective inhibition
observed with synthetic inhibitors towards trypsin-likeproteases: thrombin, factor Xa, plasmin and trypsin. X-ray
structures also clarified the role of interaction energies
in complex formation ; electrostatic vs . van der Waals
energy, and the importance of good complementarity of thesurface structures between a protein and a drug.
A new drug design method has been developed based on theknowledge obtained from X-ray structures.
We have tried
to count up all skeleton structures of potentially active
compounds.
Present
resultssuggesttheabilityofproducing new skeleton structures of 35 non-hydrogen atoms
with an rms deviation of 0.7 A.
The method will be
introduced together vi th a review on other drug design
methods.

2PL2

STRONG AND
ENGINEERINGWEAK

HYDROGEN

BONDS

IN

CRYSTAL.

Gautam R.Desiralu, School of Chemistry, University of Hyderabad,
Hydetabad 500 046, India
Crystal engineering is the understanding of intermolecular interactions in
the context of designing new solids with desired physical and chemical
properties.
Crystal engineering is concerned with the systematicarchitecture of crystal structures. Crystals are recognised as being the
supramolecular equivalents of molecules and therefore, crystal engineeringis the supramolecular equivalent of organic synthesis. The goal of crystal
engineering is to be able to manipulate intermolecular interactions in thesame way that the covalent bond is manipulated in molecular synthesis.
Ideally one would like to identify connections between molecular andcrystal structure which would make crystal structure design reliable andpractical.
The hydrogen bond has been recognised as the master-key for molecular
recognition and as such is of major importance in crystal engineering
methodologies. Surprisingly, not only strong hydrogen bonds such as
0-H ...O and N-H ... O but also weaker hydrogen bonds such as C-H ... O,
C-H ... N, O-H .. .1t and N-H ... 7t are reliable agents of crystal structure design
especially when they are incorporated into schemes involving multi-point
recogmt10n. In this context and especially because of the conceptual
similarity between crystal engineering and classical organic synthesis, it is
helpful to define supramolecular synthons as designed groups ofinteractions in which are encoded the chemical and geometrical attributesof molecular recognition. Supramolecular synthons are substructural
motifs which are of the greatest importance in developing systematic
strategies of crystal engineering.

2A11

STRUCTURE OF BOVINE CYTOCHROME C OXIDASE AT
2.8A RESOLUTION.
Hiroshi Aoyama 1, Eiki Yamashita 1, Takashi Tomizaki 1, Hiroshi
Yamaguchi 1, Tomitake Tsukihara 1, Kyoko Shinzawa-Itoh2 , Ryosuke
Nakajima2, Rieko Yaono2 and Shinya Yoshikawa2!Institute for Protein Research, Osaka University, 3-2 Yamada-oka, Suita
565, Japan, Department of Life Science, 2Himeji Institute of Technology,
Kamigohri Akoh, Hyogo 678-12, Japan.
Bovine heart cytochrome c oxidase is a membrane protein complex
with molecular weight of 200 KDa containing 13 different polypeptide
subunits, 2 hemes A, two redox active copper sites, one zinc, one
magnesium and possibly some phospholipids as the intrinsic constituents.
This enzyme is one of the most intriguing biological macromolecules in thecell, since it reduces 02 to H20 at the active site with the four redox active
transition metals coupling with proton pumping across the mitochondrial
inner membrane. This enzyme have been explored most extensively among
the enzymes involved in biological oxidation, ever since this enzyme wasdiscovered. However, in spite of these extensive efforts, lack of the crystal
structure at atomic resolution limits seriously understanding of the reaction
mechanism of this enzyme.
Electron density distribution of oxidized bovine cytochrome c oxidase
at 2.8 A resolution indicated a dinuclear copper center with a novel
structure similar to [2Fe-2S] type iron-sulfur center and the 02 bindingsite containing heme a] iron and copper atoms (CuB) with an inter-atomic
distance of 4.5 A without any detectable bridging ligand between iron andcopper atoms, in spite of a strong antiferromagnetic coupling between
them. A hydrogen bond between a hydroxyl group of the long alkyl side
chain of heme aJ and a phenol OH of a tyrosine located near an imidazole
group bonded to CuB and a phenyl alanine sandwiched between the heme
a3 and an imidazole liganded to the other heme (heme a) could either
provide intra-molecular electron transfer pathways or induce the redox
coupled conformational change.

2A12
CRYSTAL STRUCTURE DETERMINATION OF A FORM OF
HUMAN APO-LACTOFERRIN WITH BOTH LOBES OPEN BY
MOLECULAR REPLACEMENT
H.R. Faber B.F. Anderson, H.M. Baker and E.N. Baker, Department ofChemistry and Biochemistry, Massey University, Palmerston North, New
Zealand.
Lactoferrin, a protein of the transferrin family (Mr :;:: 80,000, ::::691
residues) reversibly binds two Fe3+ and two C032- ions. This process isknown to be accompanied by large changes in conformation. Previous
work (1) has shown that the protein consists of two lobes, each with an
Fe3+ and associated anion bound deep within clefts between the twodomains which form each lobe. The structure of apo-lactoferrin (2)shows the second domain of the N-Iobe has rotated open by 54· whereas
the C-lobe, although empty, remains closed, possibly due to crystal
packing interactions.
We have now analysed a second form of human apo-lactoferrin in which
both lobes are open. The crystals (a:;:: 80.8, b:;:: 116.4, c :;:: 227.0 A, SG= P2I2I2I, z :;:: 4) diffract weakly and only a 3.5 A data set could becollected with synchrotron radiation at the Photon Factory , Japan.
Molecular replacement studies using various models has positioned two
similar 3 domain fragments (N-Iobe open, Cl) satisfactorily in the cell.
A series of maps, calculated with domain C2 of molecule I rotated bydifferent amounts, and quantified by calculating the average electron
density for each lobe has placed this domain with a rotation of 15". A
similar exercise with molecule II has as yet not been successful.
Refinement is continuing and with 7 of the 8 domains now placed thecurrent R value for the 3.5 A data is 0.27.
1. Anderson, B.F., Baker, H.M ., Dodson, E.J ., Norris, G.E., Rumball ,S.V., Waters, J.M. and Baker, E.N. (1987). Proc. Nat. Acad. Sci.
USA 84, 1769-1773.
2. Anderson, B.F., Baker, H.M. , Norris, G.E., Rumball , S.V. andBaker, E.N. (1990). Nature 344, 784-787.

2A13
PROTEIN SEQUENCE-STRUCTURE ALIGNMENT BASED ON
MUTANT PROFILE FROM MEAN FORCE FIELD POTENTIAL
Luhua Lai , Yanli Wang, Department of Chemistry, Peking University,
Beijing 100871 , China
Along with the rapid development of DNA and protein sequencing
techniques , the gap between the number of known protein sequences andthree dimensional stru c tures derived by X-ray crystallography or nuclear
magnetic resonance spectroscopy is expanding quickly . The rate of·sequence determination is assumed to be at least 50-fold higher than therate of structure determination . One possible way to fill this gap is todevelop efficient protein structure prediction methods . Despite of thesuccess in homology modeling, protein structure prediction remains
challenging in case that only distant homology can be found between thesequence of the target protein and those with known structures . From theanalysis of known protein structures, it is believed that the number ofdistinct protein structural folds is relatively small , perhaps no more thnn
1,500. When all the folds are known, the task for protein structure
prediction will be turned into the problem of finding an approprinte foldfor a given sequence. We worked on the protein sequence-structure
recognition problem by mean force field potential method . A new
potential was developed by introducing main chain charac teristics into
the mean force field . Based o n this potentinl , a position-dependent
protein mutant profile was con su·ucted nnd converted into n 20xL scoring
matrix . A protein sequence-structure alignment method was developedby modifying the dynnmic programming alignment to use the 20xL
scoring matrix. Both sequence-structure recognition searc h againstsequence database and struc ture-sequence recognition process agninst nn
independent data set of known structures were carried out. The method
can not o nly pick out pro te ins with high seque nce homology , but also
can find out the similarities among protein s with sequence identity . From
the analysis on sequence- structure and structure-sequence recognition
results, strucl.ure cnndiclates for a hypothetical protein and a GTP
pyrophosphokinase were sugges ted. The possible applications of thi s
method in protein structure prediction will be discussed.

2A14

CRYSTAL STRUCTURE OF BOVINE ~-LACTOGLOBULIN AT l.9A
RESOLUTION.
M.C. Bewley, R. Kingston, H. Baker & E.N. Baker. Dept. Chern. &Biochem., Massey University, Palmerston North, New Zealand.

J3-lactoglobulin is the major protein of the whey fraction of milk. Although
its function is unclear, there is evidence to suggest that that it is atransporter of lipid-soluble molecules (lametti et al. , 1995).

J3-

lactoglobulin exists as a dimer at neutral pH and tends to dissociate intomonomers when the pH is lowered. The change in pH from a high to a low
value is thought to bring about a conformational change in the protein
which is implicated in altering the flavour of the milk during industrial
processing.

Bovine J3-lactoglobulin has been crystallised at pH 7.3 by the vapour
diffusion method. The crystals have space group C2221 with unit celldimensions a=55 .5A, b=82.8A, c=66.7 A and diffract to a resolution ofl.9A.

The structure has been determined by MIR (2 heavy atom

derivatives). The FOM for the MIR map was 0.7 to 3.0A resolution. The
phases have been improved by solvent flattening and histogram matchingand extended to 1.9A. The current model is being refined using X-PLOR.

The refined structure and its biological implications will be reported.

Iametti S . et al., (1995). J. Agric. Food. Chem . 43 , 53-58.
Papiz M.Z. et al., (1986). Nature 324, 383-385 .

2A21

CRYSTALLINE-STATE TRANS-CIS
COBALOXIME COMPLEXESPHOTOISOMERIZATIONOFTaro Yamada, Hidehiro Uekusa and Yuji Ohashi
Department of Chemistry, Tokyo Institute of Technology,
0 -okayama, Meguro-ku, Tokyol52
A new type of crystalline-state photoisomerization, trans-cis conversion of
the 2-butenyl group bonded to the cobalt atom, has been found in somecobaloxime complexes. Recently we prepared the crystals of (trans-2butenyl)cobaloxime complexes with pyridine, 1, 4-bromopyridine, 2, 3chloropyridine, 3, and dimethyl sulfide, 4. X-ray analysis of these crystals
showed that the trans-2-butenyl groups take disordered structures in thefour crystals. The crystals of 1 and 2 have essentially the same structure
and the molecules lie on crystallographic mirror planes. The crystals of 3
arid 4 have no mirror symmetry although the trans-2-butenyl groups havedisordered structures similar to those of 1 and 2. Crystals of 1 and 2changed their unit cell dimensions during the irradiation with a Xe lamp.
X-ray analysis showed trans-cis transformation of 2-butenyl group took
place with retention of the crystallinity by the irradiation. The irradiation
for two hours brought about 66% conversion for the crystal 1, on the other
hand for the crystal 2 only 48% conversion was observed after theirradiation for a day. The crystals 3 and 4 showed no reactivity on exposure
to a Xe lamp. The reaction cavities of 1 and 2 have similar shape to eachother and fairly wide void space around the trans-2-butenyl group. The cis
isomers produced occupy the void space. The reaction cavities of 3 and 4
are small and have not enough void-space. This is a reason why the
crystals 3 and 4 showed non-reactivity.
N

Q

0

Br

2

0
3

Cl

Me/8 'Me4

2A22

CRYTAL STRUCTURE OF BICYCLOMANGOSTIN : THE NEW
ACID-CATALYZED CYCLIZATION PRODUCT OF MANGOS TIN
C. Pakawatchai and W. Malabusarakam, Department of Chemistry,
Prince of Songkla University, Hat Yai 90112, Thailand, and P.
Wiriyachitra, Department of Pharmacognosy, Chiang Mai University,
Chiang Mai 50200, Thailand, and W. C. Taylor, Department of Organic
Chemistry, Sydney University, NSW 2006, Australia, and B. W. Skeltonand A. H. White, Department of Chemistry, University of Western
Australia, Nedlands 6907, Australia.
Three cyclization products, 3-isomangostin, 1-isomangostin andbicyclomangostin, were obtained from the treatment of mangos tin with ptoluenesulfonic acid. Bicyclomangostin was found to be a new
cyclization product. Its structure has been determined by single crystal Xray diffraction methods. The structure is almost planar. There is a strong
intermolecular hydrogen bond . between hydroxyl group and carbonylgroup, 0 - H ---- 0 = C, 1.4 A, tllis hydrogen atom being located in a
final difference map.

Fig 1. Bicyclomangostin.

Crystal data : C24H260 6 monoclinic, space group C2/~(No. 15)
a 15.956(7), b 14.423(17), c 18.482(7) A.p 104.92(3) 0 •2A23
THEy ,AND () STRUCTURAL EFFECTS OF SILICON AND TIN
Alison 1 Green and Jonathan M. White
Department of Chemistry, University of Melbourne, Parkville, Victoria 3052

We have been examining the effect on the length of the R-OX bond of asilicon or tin substituent four (y} and five (o) bonds away, where OX
represents a leaving group.
Silicon and tin substituents can have a profound effect on the reactivity of
the R-OX bond. eg, an ester will be solvolysed more readily if there is a
SiMe3 or SnMe3 substituent 4lor 52 bonds away. These phenomena are
known as the silicon and tin y- and o- effects respectively and are based on
the ability of silicon and tin to stabilise a carbocation at these positions. The
silicon effects have been studied more extensively, although the tin effects
are more dramatic. These effects have demonstrated a conformational
dependence, ie they require favorable overlap between the donor (Si or Sn)
and the leaving group, and are thought to be stereoelectronic in origin. Most
evidence supports the involvement -of hyperconjugation in the mechanisms.
This ought to be reflected in observable ground state effects, which can be
manifest as changes in the C-OX bond length and, less prominently, aschanges in the C-Si/Sn bond length.
A structural study was undertaken in order to examine the extent of such
effects. Several nitrobenzenesulfonate esters have been prepared, with apositions. Their structures were
SiMe3 or SnMe3 group at they- anddetermined using low temperature X-ray diffraction. The results of the study
will be presented in this paper.

o-

1: Si: V.J. Shiner Jr; M.W. Ensinger Jr; R.D. Rutkowske: J. Am. Chern. Soc. 1986, .1.0.8.. 842; Sn:
Davis, D. D. ; Black, R. H. J. Orgarwrnet. Chern. 1974, .82. C30-C34; Fischer, W.; Grob, C. A.
Helv. Chirn. Acta 1978, .6.1. 1588-1608.

2: W. Adcock; V.J. Shiner Jr; J. Coope; N. Trout: J. Org. Chern. 1990, ,i5., 1411; W. Adcock;
A.R. Kristic, P.J. Duggan, V.J. Shiner Jr; J. Coope, M.W. Ensinger: J. Am. Chern. Soc. 1990, ill.
3140-3145.

2A24
COMPARISON OF Fe(JJ)-P AND Fe(O)-P LENGTHS: STRUCTURE OF[(T\5·CsHs)Fe(CO)C(O)Me](l!·111 :T}1·dppe)[(T)4·MeCsHs)Fe(C0)2]
Ling-Kang Liu and Lung-Shiang Luh , Institute of Chemistry, Academia Sinica ,Nankang, Taipei , Taiwan 11529 and Department of Chemistry, National Taiwan
University, Taipei , Taiwan 10767, ROC
In 1:1 molar ratio, (115·CsH5)Fe(C0)2Me proceeds with a dppe-assisted (dppe =PPh2(CH2)2PPh2] methyl migratory-insertion to yield the uni-dentate complex(ll5·C5H5)Fe(CO)C(O)Me(ll1.dppe) , in addition to the bridging product [(115.
C5H5)Fe(CO)C(O)Me]2(1-1·TJ1 :111-dppe).

Since the former is an intermediate

towards the latter, the reaction of (115·C5H5)Fe(C0)2Me with dppe in 2:1 molar
ratio easily proceeds to the bridging complex. At -78·c , the 1:1 mixture of (1'\5.
C5H5)Fe(C0)21 and the uni-dentate (TJ5·CsHs)Fe(CO)C(O)Me(TJLdppe) in THF
reacts with Meli to produce a novel complex [(TJ5·C5H5)Fe(CO)C(O)Me](l!·111 :111 -dppe}[(TJ4· MeC5H5)Fe(C0)2] in which a dppe links two isomeric,methylated [(C5Hs)Fe(C0)2] units, one end being in the form of (115.
C5Hs)Fe(CO)C(O)Me and the other end (TJ4·exo-MeCsHs)Fe(C0)2. The X-ray
structure of the title complex exhibits a dppe-bridged pseudo-octahedral
Fe(ll)/pseudo-square pyramidal Fe(O) complex with no metal-metal bonding .
The embedded structural parameters of Fe(ll) and Fe(O) give evidence to asmaller Fe(ll) radius than Fe(O) , as suggested by the Fe(II)-P length of 2.178(2)Asimultaneously present with that of Fe(O)-P , 2.212(1 )A. The shortening of
0.034A is significant as it represents a difference greater than 10 esds.

~~

Fe.......- ocr-)......._

oo~- · F....._~I

J

OC"''••

oc

Me

I

dppe
THF

0

c:
,f '-.

MeI~~ PPI>, •!
, f '-.

O :;r

Me

~

I

~~ P .....-F't-..,co
~
Ph:

<(.,

M/ ~o

Meli
THF

[(TJ5·C5Hs)Fe(CO)C(O)Me](l!·111 :TJ1-dppe}[(TJ4· MeCsH5)Fe(C0)2], crystal data:
C42H4oFe204P2 , P-1 , a 11.967(2), b 12.066(1), c 14.855(4)A, a 106.51(1) , ~97.84(2), y 108.20(1)o; v 1893.1(6)A3, FW = 782 .42 , Z = 2, F(OOO) = 811 .88,
Peale = 1.373g/cm3, I! = 0.89mm· 1, Mo-Ka A. = 0.7093A, CAD-4, 29 $ 50°,transmission factors 0.935 - 0.999, 90 atoms, 451 parameters, 4052
observations [lo > 2.5cr(l 0 )], R =0.031 , Rw =0.037, GOF = 1.81 , 6Jcr =0.020.

2A25
STRUCTURES OF NOVEL MET AL-CARBENE COMPLEXESDERIVED FROM HYPERVALENT TETRAAZATHIAPENTALENES
F. Iwasaki, N. Manabe, S. Shimamoto, H. Nishiyama and M. Yasui, Dept.
of Applied Phys. and Chern ., The Univ. of Electro-Comm., Chofu-shi,
Tokyo 182, Japan, and N. Matsumura, Dept. of Applied Chern., College
of Eng ., Univ . of Osaka Prefecture, Sakai-shi, Osaka 591 , Japan
6a-Thiatetraazapentalene derivatives (I) (Iwasaki, et a!. , 1991;
Matsumura, et al., 1986) which contain the hypervalent sulfur atom havebeen found to give novel metal-carbene complexes by reaction with
Pt(PPh3)4, Pd(PPh3)4 and RhCl(PPh3)3 (Matsumura, et al. , 1995). In
the case of Ia, X-ray investigations revealed that the central sulfur atom
in Ia was substituted by a metal atom and that thiocarbonyl groups on
one or both sides were rotated to form metal-sulfur bonds in the resulted
metallapentalene framework (2, 3, 4) . In the case of lb the carbonylgroup remained without coordinating metal atom (5 , 6). The reaction ofRhCl(PPh3)3 with lc gave a Rh complex (7) of a different type.
Frontier electron densities were calculated on these tetraazathiapentalenes
using MO calculations in order to investigate the difference of reactivity
among Ia, lb , and lc . In this paper, structures of these novel calbene
complexes with metallapentalene frameworks and the effects of the sidegroups will be reported . From the results of the structures of complexes
and MO calculations the mechanism of the formation of these metalcarbene complexes will also be discussed .
(1
(1
r1

~~~y

A

.

.

la X~, Y=S
lb X =S,Y=O

A

AN~1XA ~~~~A
I/I'

PPh3 Cl PPh3
PPh3
J A=P·Cl ·Ph
2 M=Pt.Pd
A:Me. Et. p·CI·Ph

lc X=O,Y=O

Iwasaki, F. , Murakami , H ., Yamazaki, N ., Yasui, M., Tomura, M. & Matsumura, N .
(l991) .Acta Crysr. , C47, 998-1003.
Matsumura, N ., Kawano , J. , Fukunishi , N ., Inoue, H. , Yasui, M. & Iwasaki , F.
(1995). J. Am. Chem. Soc., 117, 3623-3624.
Matsumura, N ., Tomura, M., Yoncda, S. & Toriumi, K . (1986). Ch em. Lett. , 1047-

1050.

2B11

LAUE CLASSES OF a- AND ~-QUARTZ AND THEIRPATTERSON FUNCTIONS EVALUATED WITH POWDERDIFFRACTION DATA
M. Ohmasa, Department of Life Science, Himeji Institute of Technology,
Kanaji 1479-1, Kamigori, Akogun, Hyogo 678-12, Japan, K. Ohsumi,
Photon Factory, National Laboratory for High Energy Physics, Oho 1,
Tsukuba, lbaraki 305, Japan, and H. Toraya, Ceramics ResearchLaboratory, Nagoya Institute of Technology, Asahigaoka, Tajimi 507,
Japan

There are two possible Laue classes, holohedral and hemihedral ones, forthe crystal systems with trigonal symmetry or symmetries higher than
trigonal. Recently Ohmasa & Ohsumi (1995) indicated that the available
informations obtained from powder diffraction data can be regarded as acomposite reciprocal lattice when the data are demonstrated in the three
dimensional reciprocal space, and the Patterson function obtained by
Fourier transform of the composite diffraction pattern represents a set ofvectors corresponding to a composite vector set. Hemihedral Laueclasses can then be distinguished from holohedral ones based on theconcentration of Patterson peaks. The present studies have been carriedout to apply the method to the powder X-ray diffraction data of the aand ~-quartz and to demonstrate how the difference of the Patterson
functions of both phases is. The sample crystal used for the present
studies was grown by the Toyotushinki Ltd. The profiles of a- and Pquartz were measured with conventional diffractometers at 293K and
893K respectively. The profiles were analysed with the program WPPF
(Toraya, 1986). The lattice parameters are a=4.91296(2), c=5.40442(3)A for a-quartz and a=4.9947(2), c= 5.4585(2)A for ~-quartz .
Significant difference of heights of the peaks in both P(uOw)'s wasobserved and ascertained to be consistent with their Laue symmetries.
Ohmasa, M. and Ohsumi, K. (1995). Acta Cryst. ASl, 87-91.
Toraya, H. (1986). J. Appl. Cryst. 19, 440-447.

2812

X-RAY, QUANTITATIVE ANALYSIS WITHOUT STANDARDSUSING RIETVELD METHODS WITH HIGH ACCURACY
Changlin KUO and Hongchao LIU, Shanghai Institute of Ceramics, Chinese
Academy of Sciences, Shanghai 200050, P . R. China

In quantitative phase analysis using the Rietveld method , weight fractions ofcrystalline phases can be calculated directly from scale factors . Various corrections
were introduced in the Rietveld method to get correct intensities data. However, lessattention was paid to the microabsorption effect. This leads the quantitative analysis
give unreliable results. The diffraction data can be corrected for microabsorption
effect in

two ways. For the linear correction of microabsorption by Sparks that

represents an empirical statement for strong absorption, the following function is
used
S,=P, +2eC, (P, and C, adjustable parameters)(2)

For the use of Hermanns model ,(3)

S,= l-P0 -C ,/sine (l - 1/sine )where P0 , C and 1 are adjustable parameters . This model is valid exactly for weakabsorption and low surface roughness degree.
Expressions (2) and (3) can be incorporated into DBWS 9600-PC Rietveld program .
Equation (4) is used to calculated the relative abundance of phase A.
(4)

Where, M are the number and mass of unit cell ; V is the volume of unit cell . The
summation is over all t crystalline and identified components. If an internal standard
phase s has been added to the mi xture prior to data collection, then the amount ofamorphous and minor phases may be estimated using the follow equation .
W •morph •nd m;nor phm s = 1- 'f.W r(5)

Where Wr is determined by equation (6) .
W,=W,S,(ZMY),IS,(ZMV),(6)

The subsc ript s and r refer to standard phase and each phase in the mixture.
Prac ti cal analysis proved th at new correction can give more precise results .

2813
XRD DETERMINATION OF THE MINERAL STRUCTURAL STATE
CHARACTERISTICS

A.P.Slusarev, Institute of Geological Sciences NAS RK, Almaty,
Kazakhstan

Investigations of the XRD structural criterions reveal relationships between
structural features and alteration of minerals during geological process
their evolution in sediment rocks or weathering complexes. The numerous
quantitative and statistical criterions: index of crystallinity, coefficient ofvariation of basal spacing, integral half height breadth of diffraction reflex,
crystallochemical properties of clay minerals, content of dispersive
subamorphous components, total iron content were used as probableindicators for evatuating of forming conditions, direction and degree of
diagenesis and rate of weathering of rocks and minerals. Numericalestimations of characteristics, describing clay minerals structural state wereobtained: type of interlayer cation, degree of hydration, layer charge,
expandable layers content, tetrahedral and octahedral cation substitutions,type of layers, their nature and contents, order of stacking mixed-layered
minerals. The XRD criterions determined from diffraction pattern of
powder, randomly and preferentially oriented samples, treated samples, orby results of special X-ray diffraction measurements were used forstructural state of mineral description.

2814

PROFILE ANALYSIS FOR LATriCE DEFORMATION AND CRYSTALLITE SIZEUNDER COMPRESSION
Takamitsu YAMANAKA
Osaka University

Department of Earth and Space Science, Faculty of Sciencel-I6 Machikaneyama

Toyonaka Osaka 560 Japan

In the last two decades structural investigations by X-ray diffraction studies under non
ambient condition have been interested in order to comprehend their elastic properties andpressure-induced polymorphic transition. It has been known that the lattice deformationand lessening of the grain size under static compression bring about the line broadeningof diffraction profile and that the peak position is directly related to the compressibility
or bulk modulus.
Profile analysis has been made using energy dispersive diffraction spectra of NaCI,
which were taken under hydrostatic pressures up to 12GPa with high pressure apparatus
MAX90 in Photon Factory, Tsukuba. Pseudo- Voigt function, linear equation ofGaussian and Lorentzian function, is applied for the profile fitting concerning strainenergy and grain size, which are changed with increasing pressure. The full width at
half maximum (FWHM) rL of the Lorentzian profile continuously increases withpressure in comparison with ra of Gaussian. The Lorentzian component 11 parameter ofpseudo-Voigt function is raised with pressure. Integrated half width ~(hkl) is basically
expressed by ~=B+b, where B is related to the lattice deformation and size effect and b is
instrumental broadening. Mean crystallite size <Da> and mean squares-strain <e2> arederived from the observed ~(hkl). A smaller crystallite size makes a larger ~L . On theother hand the dislocation density and intrinsic strain in the lattice enhance ~ Pressure-induced amorphization of hydrates Ca(OH)2 has been observed using
diamond anvil pressure cell at pressures higher than 6.5GPa. With increasing pressure
the peak profile becomes gradually broadened and finally no peaks are observed. The
amorphous state is reversibly changed to the original hydrate structure without
dehydration reaction in the course off depression. The amorphization corresponds not tothe size effect but to the lattice deformation. Crystallite size estimated from B of hkl
peaks is a little change with press ure but a significant change of the strain energy . The
individual hkl diffraction peaks show the anisotropic lattice defonnation underhydrostatic-pressure. Peak shift assigned to 0 -H bond of the Raman speclra observed atvarious pressur6S indicates the increase in hydrogen bond character. The trend of thepeak shift is continued even in the amorphous state.

2821
ROUGHNESS ESTIMATION OF POLYCRYSTAL METALSURFACES WITH USE OF X-RAY GLANCING SCATTERING
Yoshikazu FUJII, Kenji YOSHIDA and Kentaroh YOSHIDA,
Department of Mechanical Engineering, Kobe University, Rokkodai, Nada,
Kobe 657, JapanAt glancing angle incidence of x-ray beam on a solid surface, most of the
x-ray are scattered at only shallow region near the surface. For suitablychosen geometries, the scattered x-ray intensity is sensitive to surface
morphology . Using these nature of x-ray glancing scattering we triedroughness estimation of polycrystal metal surfaces. The experiments were
performed with use of Cu-Ka characteristic x-ray with .l..=l.54A from
18kW rotating-anode x-ray source. At several glancing angle incidence ofthe x-ray beam on a polycrystal silver surface, angular distributions of thescattered x-ray intensity were measured. This angular distributions reveal
the surface roughness. Unlike electron diffraction, for x rays multiple
scattering is negligible except very close to a bulk Bragg peak, then theobserved intensity of the scattered x-ray can be computed by use of
kinematical theory. The angular distributions of the scattered x-ray intensity
were simulated with use of simple model of rumpled surface. Based onthese result we propose new method of roughness estimation of surface.

2822
X-RAY SCAITERING FROM MICROCRYSTALLINITY IN THE
THERMALLY OXIDIZEDSi0 2 THIN FILMS ON Si(llO) SURFACES
T.Shimura, R.Kojima, H.Misaki, and M.Umeno, Deparonent of Materialand Life Science, Osaka University, 2-1 Yamadaoka, Suita, Japan
Very weak peaks were observed in the X-ray diffraction from the thermally oxidized
thin films on Si(OOI) surfaces by Iida et al. (1991) . They claimed that these peaks were
Bragg peaks originated from small crystallites which coexisted with the amorphous
phase having some epitaxial relationship with the Si substrate. A pseudo-cristobalite
structure was proposed as a possible model, in which the atomic arrangement is similar
to that of the cristobalite structure, while the unit cell is tetragonal so as to match thelateral lattice spacing with that of the Si substrate. Takahashi it et al. (1993) extended
this study so that the crystallites were found to locate not only at the interface between
the Si substrate and the amorphous layer, but also widely in the amorphous layer,
preserving the epitaxial relation with the substrate. The volume fraction of such
crystallites was estimated to be a few percent of the whole volume of the amorphouslayer.
In this paper we show that similar Bragg peaks are observed from the oxide layers on
Si(llO) surfaces, indicating the existence of crystallites having epitaxial relationshipwith the Si substrate. The samples were prepared by oxidizing Si wafers at 950°C in a
dry oxygen atmosphere. The thicknesses of the oxide layers were 760A and 230A. In
the X-ray diffraction patterns from these samples, similar peaks were observed just on
the lower angle side of the CTR (crystal truncation rod) scattering around the Ill Bragg
point, of which position is approximately 0.45 0.45 0.00 in reciprocal space. The peakintensity depends on the thickness of the oxide layer, while the peak is not observed in
the etched sample. A high resolution measurement of the profile of the peak using a
synchrotron radiation source revealed that the profile had Laue-function-like oscillation
fringe pattern, of which period corresponded to the inverse of the film thickness.
From these results it was concluded that these peaks were Bragg peaks originated fromthe crystallites which coexisted in amorphous Si0 2 having some epitaxial relationshipwith the Si substrate.
The authors thank to Prof. J.Harada of The University of Electro-communications and
Dr. I. Takahashi of Nagoya university for discussions and encouragement.
Iida, Y., Shimura, T., Harada, J., Samata, S., & Matsushita, Y. (1991) Surf. Sci . 258 ,
235-238.
Takahashi, 1., Shimura. T., & Harada, J., (1993) J.Phys. : Condens. Matter 5, 65256536.

2823
DETERMINATION OF ELECTRON DENSITY PROFILE FORM XRAY REFLECTIVITY DATA USING DISTORTED WAVE BORNAPPROXIMATION

Milan K. Sanyal, Alokmay Datta, and Sangam Banerjee Saha Institute of
Nuclear Physics, 1/AF Bidhannagar, Calcutta 700 064, INDIA.

X-ray reflectivity measurement of a multilayer system in principle provides
us an independent determination of thicknesses, electron densities andinterfacial roughnesses of different sublayers of the film . But, due to thewell-known "phase problem", determination of the electron density profile
from the x-ray reflectivity data is not trivial [1) . We present here a scheme
to extract electron density profiles from x-ray reflectivity data using
Distorted Wave Born Approximation (DWBA). We illustrate the scheme
using both simulated and measured data.
In this scheme,the electron density profile across a multilayered thin film isapproximated by thin slices of fixed electron densities.

Difference

amplitudes of the electron densities of these slices from an average electron
density of the film are determined by fitting them to x-ray reflectivity datausing a DWBA formalism [ 1)[ 1). M. K. Sanyal et. al., Europhys. Lett, vol. 21, pp. 691, (1993)

2824
Electron Density Maps for Clean and Adsorbed Silicon
Surfaces ·calculated with the Maximum-Entropy Technique
H. Hashizume, C.M. Carvalho!, 0. Yokota, A.W. Stevenson 2
and I.K. Robinson3

Res. Lab. Eng. Mater., Tokyo Institute of Technology,
Nagatsuta, Yokohama 226, Japan. 1) Inst. de Fisica, Univ.
de Sao Paulo, Brazil, 2) CSIRO Div. of Mater. Sci. & Tec h.,Australia, 3) Dept. of Phys., Univ. of Illinois, USA.
Maximum-entropy (ME) electron density maps have been calculated for two-dimensional reconstructed surface structuresusing X-ray and electron diffraction data.
Clean Si( 111)
7 X 7 and arsenic-adsorbed Si(001) 1 X 2 surfaces are studied.
Experimentally determined structure-factor magnitudes forin-plane reflections from these surfaces are assigned phasesfrom refined models and then used as a constraint in a maximization of Shannon-Jaynes entropy.
Surface diffraction
data feature missing integer-order reflections which overlap
the bulk reflections and are experimentally inseparable fromthem. The maps calculated for the Si(lll) 7 X 7 surface
using 84 fractional-order X-ray refle c tions with a maximum
1.135 A resolution
clearly
resolve
all the 102 atoms of
Takayanagi's dimer-adatom-stacking fault model.
Electrons
are concentrated on the atomic sites, showing peaks at theadatom locations more than twice as high as the mean of theother atomic peaks, where third-layer atoms exist immediately below. The a tomic coordinates determined from the map
are in good agreement with those from a least-squares refinement [ 1], confirming the p6mm symmetry assumed in th elatter refinement.
The electron diffraction (ED) data offered by R. Twesten include 193 reflections, whose inten si ties are evaluated by averaging symmetry-equivalent reflections to minimize dynamical effects [2].
Higher-orde r reflections contained in the ED data give more round shapes tothe atomic peaks and more clearly show bonding electrons for
the Si( 111) 7 X 7 surface atoms in ME maps.
We will a lso
discuss ME maps calculated for the Si(001 ):As 1 X 2 surface,which are believed to show nonspherical electron distributions around the non-reconstructed surface atoms .
The ME technique h as a tendency to underfit large stru c ture factors, often associated with low-angle reflections.
To avoid adverse effects o n bonding e lec tron densities [ 3 ],we do not stop iteration calculations at
X 2 = 1.0,
but goto x 2 ~ 1 for several sets of I F(obs) I data obta ined byrandomly fluctuating individual I F{obs) I data within theexpe rime ntal variances. Features common to the flu c tuatedmaps are real ones and others are attributed to noise .
[1] I.K. Robinson e t a l., Phys. Rev. B 37, 4325 (1988).
[2] R.D. Twesten and J.M. Gibson, Ultramicroscop. 53, 223(1994).
[ 3] G. Jauch, Acta Cryst. Acta. Cryst. A 50, 650 (1994).

2C11

DEVELOPMENT OF CCD-BASED X-RAY DETECTORS WITH A
BERYLLIUM-WINDOWED IMAGE INTENSIFIER FOR
DIFFRACTION STUDIES
Y. Amemiya, K. Ito, PF, KEK, Oho, Tsukuba, Ibaraki 305, Japan,
N. Yagi, Tohoku Univ. , Y . Asano, JAERI, K. Wakabayashi, Osaka
Univ . T. Ueki, Riken, and T. Endo, Hamamatsu Photonics K.K .
We have developed a large area-sized CCD-based x-ray detector for
diffraction studies especially for real-time and time-resolved
measurements (Amemiya et al., 1995). The detector consists of i) an xray image intensifier, ii) an optical lens, iii) a CCD image sensor, andiv) a data acquisition system. An x-ray image is converted to intensified
and de-magnified visible-light image by the x-ray image intensifier.
Then the visible-light image is viewed by a cooled CCD (TC-215, 1000
x 1018 pixels) or a TV-rate (30 frames/s) CCD (SONY XC-77) throughthe optical lens. The signal from the CCD is digitized and stored in thedata acquisition system. The x-ray image intensifier uses a I mm thickberyllium plate which serves as both an entrance window and a substrate
for the phosphor. .The Csi:Na phosphor of 150 11m thickness is attacheddirectly on the inner surface of the beryllium window . The Csi:Na
crystals are made in a columnar shape along the direction normal to thephosphor surface so that the undesired light scattering within thephosphor in the lateral direction is minimized. A hi -alkali (RbCsSb)
photo-cathode is evaporated onto the inner surface of the Csi:Na
phosphor. Owing to the photon gain of the image intensifier, as manyas 550 visible photons per 8 keY photon are incident to the CCD. Thisvalue is large enough to employ a TV-rate CCD with its noise quantumlimited. The image intensifier responds to x-ray intensity range ofmore than 6 orders of magnitude . The detective quantum efficiency ofthe detector is 60 % . Because of the convex shape of the beryllium
window, the detector has the image di stortion and the consequent nonuniformity of response to be corrected by software . Detailed
performance of the detector will be described together with its
applications to x-ray diffraction experiments with synchrotron
radiation.
Amemiya, Y., Ito, K., Yagi, N., Asano, Y., Wakabayashi K., Ueki,
T., Endo, T. (1995). Rev. Sci. lnstrum . 66, 2290-2294.

2C12
THE OPTIMIZATION OF PARAMETERS OF BRAGG-FRESNELLENSES
L. A. Haroutunyan and K. G. Trouni, Department of Solid State Physics,

Yerevan State University, A.Manoukyan 1, Yerevan, 375049, Armenia
One of techniques for hard X-rays focusing is the utilization of zonal platewith incident spherical (or plane) X-ray wave. The phase modulation of Xrays reflected by monocrystal, causing the beam focusing in vacuo, is
accomplished by a step-like variation of plate thickness at the Fresnel's
zones edges because of the plate exit surface relief. The purpose of ourstudy was to select optimized parameters for experimental set-up. The
problem was formulated as follows: what should be a step-like profile ofplate thickness for the reflected beam phase shift, associated with thepresence of zones, being 180 degree. Both approximate analytical
calculations by means of the above-mentioned phase shift series expansion
as well as more accurate computer ones are carried out. As a result, in thecase of incident spherical wave, for optimized focusing the crystal
thickness jump has to be some varying quantity, as a dependence from thezones numbers, and this functional dependence is determined from theconcrete experimental conditions.
Aristov V.V., Kuznetsov S.M., Kouyumchyan A.V. & Snigirev A.A.
(1991). phys.stat.sol.(a)125, 57-66.
Aristov V.V., Basov Yu.A., Snigirev A.A., Yunkin V.A.
Ishikawa T. & Kikuta S. (1991). Nucl. Instr. and Meth. A308, 413-415.

2C13
THE THEORETICAL AND EXPERil\1ENTAL STliDY OF X-RAY
DIFFRACTION FOCllSIKG PHE~01\1E!'\A ON THE T\\"0-BLOCKCRYSTALLINE SYSTEi'"1 \\'ITH MISSORIENTATED BLOCKS

K. G. Trouni and A . H. Grigoryan. Department of Solid State Physics.
Yerevan State University. A.l\1anoukyan I . Yere\·an. 375049. Armenia.

Theoretically and experimentally the problem of th e diffraction focu sing in
LL - interferometer with missorientated plates is ill\estigated . The
asymptotic solution for the double reflected beam amplitude is obtained in
the approximation of the saddle-point method for the case of small angularmissorientations of the blocks. This solution points at the oscillatory
behavior of beam intensity in the center of the diffraction patterndepending on small misso1ientation s of the order 0.01 angular seconds. The
solution explains as we ll the phenomenon of the central peak splitting at
the same missori entations of plates. The high sensitivity of the diffraction
focusing phenomenon to small mi ssorientations is experimentally shown .
After preparation of the interferometer it was splitted up into two
independent plates orientated on the two goniometric heads. The plates
rotation was realized by piezocrystals. There are registered the oscillations
and spatial splitting of the peak stimulated by the missorientation s of theorder 0.0 I - 0.1 angular seconds. The correspondence between theory andexperiment is fairly we ll.

lndenhom.\' .L.. Slohodetski.I.Sh. & Trouni.K.G. (1974). JETP. 66. 111011::!0

2C14
RECENT DEVELOPMENTS OF X-RAY CRYSTAL STRUCTURE
ANALYSIS BY NEW DIFFRACTOMETER AND COOLING
EQUIPMENT
Hidehiro UEKUSA and Yuji OHASHI, Department of Chemistry, Tokyo
Institute of Technology, Ookayama, Tokyo 152, Japan
Recently we have designed and made a new type of diffractometer for
rapid data collection. The purpose of this development is to collect thedata of unstable crystals and to determine the structures of reaction
intermediates.
The new diffractometer has a Weissenberg camera type mechanism with a _feature of a K-type goniometer, two imaging plates, and spiral motion
reading mechanism. It is also equipped with a new type of nitrogen gas
stream equipment to adjust the temperature of crystal specimen.
This type of equipment requires no liquid nitrogen, instead, it extracts dry
nitrogen gas from the air and cool the gas with a cooling system using
closed circle He gas. The cold nitrogen stream is surrounded with dry
sheath gas stream to prevent the formation of ice around the specimen.
This equipment covers a temperature range of 80 K to room temperature in
low temperature mode and up to 420 K in high temperature mode.
Successful structure determinations of the crystals that are sensitive to Xray exposure, loses the solvent molecules easily, and have weak diffraction
intensity also demonstrate the ability of this diffractometer. For example,
the initial molecular structure of syn-tricyclooctane derivative has been
determined by 140 minutes measurement, which has not been analyzed,
because the bond cleavage easily occurs under X-ray irradiation.
Although some cobaloxime and cobalt complex with sugar ligands crystals
easily decomposed by loss of the solvent molecules, we have successfully
determined the structure without sealing the crystal in a capillary.
All the results of the crystal structure analysis indicate that the total
accuracy of the new diffractometer is comparable to that of a four circle
diffractometer despite a very short measurement time.

2C15

X-ray

Wiggler

Beamlines

at

SRRC

Y.-C. Jean , C.-H. Lee, K.-L. Tsang, H.-H. Hung, J.-R. Chen,
C.-H. Hsu, L.-Y. Jang, M.-T. Tang, H.-Y. Lee, H.-S.Sheu,
T.-E. Dann, J.-F. Lee, J.P. Wang, S.-L. Chang, SRRC &National Tsing Hua University, Hsinchu, Taiwan, R.O.C.

Synchrotron Radiation Research Center (SRRC) is a third generationsynchrotron radiation facility being setup in Taiwan for basic science
research and advanced technology development. In order to increase theusable X-ray photons up to 15 KeV, a 1.8 T wiggler insertion device has
been installed with the 1.3 GeV storage ring. Three X-ray beamlines
sharing the 13 mrad horizontal radiation fan from the wiggler have been
specially designed to cover various kinds of X-ray experiments including
macromolecular crystallography, surface sciences, high resolution powder
diffraction, small-angle X-ray scattering, elastic diffuse scattering nonambient crystallography, and X-ray absorption spectroscopy. The
construction of thease three beamlines is nearly completed, however, due
to the significant delay in the delivery of mirrors, a temporary back-up
bearnline has been constructed and under commissioning now. The
construction of these three bearnlines and the characterization of the backup bearnline will be described in detail.

2C21
HYDROGEN IN METALS: NEUTRON DIFFRACTION STUDIESOF THE CRYSTAL STRUCTURES OF Zr2NiDx
M.M. Elcombe and C.J. Howard, Australian Nuclear Science andTechnology Organisation, Lucas Heights, NSW 2234, Australia, and S.J .
Campbell, Depa rtment of Physics, Australian Defence Force Academy,
Canberra, ACT 2600, Australia.

Zirconium and zirconium alloys are known to absorb large quantities ofhydrogen . This study concerns Zr2Ni (tetragonal CuAh structure, spacegroup I 4/mcm) which is found to absorb as much as 5 hydrogen(deuterium) atoms per formula unit. The objectives have been to determine
how the hydrogen (deuterium) is accommodated, and what expansion or
distortion is associated with the incorporation of hydrogen into the crystal
structure.
An advance has been made through the recent unambiguous determinationfrom neutron powder diffraction (Elcombe, Campbell, Howard, Buttner
and Aubertin, 1995) of the room temperature crystal structure of Zr2 NiD4
[monoclinic, space group 12/c, a 6.7887(1) , b 6.7584(1), c 5.6748(l)A, ~91.039(1 rJ. The deuterium occupies the tetrahedral interstices, subject tothe restriction that two tetrahedra sharing a common face cannot both beoccupied.
The room temperature structure of Zr2NiD 5 has been shown to be triclinic,
the triclinic distortion being indicated in the high resolution neutron
powder diffraction pattern, and confirmed using synchrotron X-rays. The
lattice parameters have been determined, and progress towards the solutionof the crystal structure from the neutron powder data is encouraging.

Elcombe, M.M., Campbell, S.J., Howard, C.J., BUttner, H.G. and Aubertin,F. ( 1995). Submitted to Journal of Alloys and Compounds.

2C22
NUCLEAR DENSITY DISTRIBUTION AND ANHARMONIC THERMALVIBRATION OF Sn02 OBTAINED BY THE MAXIMUM ENTROPY METHOD
S.Kumazawa & K.Ishida, Department of Physics, Science University of Tokyo, Japanand M.Takata & M .Sakata, Department of Applied Physics, Nagoya University, Japanand Y.Ishii & Y.Morii, Japan Atomic Energy Research Institute, Japan .
From non-magnetic neutron powder diffraction data, the Maximum Entropy Method(MEM) can provide a high resolution nuclear density distribution . The density
distribution describes thermal motion of atoms regardless harmonic or anharmonic. It is,therefore, possible to determine potential parameters of corresponding atoms by the leastsquares refinement of nuclear density distribution. The purpose of this paper is tocalculate the nuclear density distribution of Sn02 at room temperature by the MEM and to
determine the potential parameters from this density distribution
The nuetron powder diffraction experiment was carried out by HRPD ( High Resolution
Powder Diffractometer ) at JAERI-3M. The HRPD has 64 detectors for the efficientcollection of a powder pattern. In order to obtain an accurate intensity for the MEM
analysis, the measurement was performed by overlapped scanning along 29 angle with64 detectors and then the overlapped data were averaged on each step. By comparing thereliability factors of Rietveld Analysis between the new and the conventional
measurements, the significant change of accuracy is recognized. The powder pattern isrecorded at the wave length 1.823A and 34 reflections up to sin9/A.=0.538A-t are
obtained.
The MEM calculation was done by using the super computer, Fujitsu VP2600 at Nagoya
University Computation Center. In the calculation, the unit cell was divided into 128xl28
x l28 pixels. The total CPU time took 30 sec for 524 iterations. As shown in the obtained
MEM map, the densities of tin and oxygen atoms are deformed into rectangle and triangle
shapes, respectively. This is due to an effect of anharmonic thermal vibration of theatoms. The anharmonic potential parameters are analyzed by the least squares refinement
using One Particle Potential (OPP) model. For tin atom, 9 OPP parameters are
determined with reliability factor R=0.50%. For oxygen atom, 12 OPP parameters are
determined with R=5.29%. The comparison with previous study of Ti02. which havesame structure, is now in progress.

2C23SUPERCONDUCTORSRECENT NEUTRON STUDIES OF HIGH-Tc

A.Segueira, Rajni Sharma and H.Rajagopal, Solid State
Physics Division, B. A.R.C, Trombay, Bombay 400085, India .

has been extensively used tocharacterise

and substituted [124]-type compounds ,(d) Thallium[1212] and [2212] structures.

with [1201],

cuprates(c) Bismuth cuprates

structures,[2223]

and[2212]

pure(b)[123]-type compounds,(a) pure and substituted

with [2201],

These includeof HTSC.

a numberofstructural features

theinvestigatedhave

Trombay, we

years . At

structurethesuperconductors (HTSC)

and properties of high temperaturein recentpowder neutron datatechnique using

refinement

Rietveld

The recent findings of our studies include (i) observationinterstitialoflayersCu02(iii) anomalous

by

and

oxygendimers in [2212]-Bismuth cuprates,[2201] - and
for

Redox

of

Tl(Ba/Sr)La cuprate system.
thesestudies

will

be

hole

superconductor,ofpresenceoxygen(iv) oxygen disorder in[2223]- Bismuth cuprates,
mechanismfor direct oxidation

Ca in [123]-(Lu/Ca)

excess[123]-(Ca/Co)of

Y-layers(ii) evidence

substituted compounds,ofinoxygenandgeneration

Some of the newhighlighted.

(v)inevidence[1201] -findingsof2C24
A NEW ASPECT OF THE REACTION MECHANISM OF
COBALOXIME COMPLEXES BY NEUTRON DIFFRACTION
Y. Ohgo 0 ,Y. Ohashi a, W. T. I<looster6 and T . F . Koetzle6 ,a Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo
152, Japan, 6Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000
It has been found that the chiral alkyl groups bonded to the cobalt
atom in some cobaloxime complexes are racemized on exposure tovisible light in the solid-state. The reaction process of the crystallinestate reaction have been observed directly from the structures analyzed by X-rays at any intermediate stages. To make it sure of themechanism of crystalline-state racemization we prepared cobaloxime
complexes that 01 carbon of which in the cyanoethyl group labeledwith deuterium. And we attempted neutron diffraction experimentto observe about racemization process. The molecular structure isshown in Fig.1. Although this labeled complex was not racemized
because of its large crystal size, some interesting results were obtained. The 01 deuterium and one of hydrogen atom of the neighboring methyl group, both are hatched in the Fig.1, exchanged with eachother. This may suggest quite a new mechanism of the racemization,
which will be discussed in detail.
Table 1. Crystal Data.

a/A 8.686(2}b/ A 13.516(5)cf A 9.618(3)
afo

fJ;o

96.92(2)'Yrv; A 1120.9(5)
3

z

2

Space
Group

P2 1
Fig. I2C25
NEUTRON DIFFRACTION INVESTIGATION OF PHASE
TRANSITION IN UNaGe409
Y. Iwata. Research Reactor Institute, Kyoto University, Kumatori, Osaka 590-04,
Japan, M. Machida , Department of Physics, Kyushu University, Fukuoka 812, Japan,
M. Wada, Faculty of Liberal Arts, Shinshu University, Matsumoto 390, Japan, and
A. Sawada, Department of Physics, Okayama University, Okayama 700, Japan.

LiNaGe409 crystal (abbrev. as LNG) undergoes ferroelectric phase transition at 112 K.I) Single crystal neutron diffraction was undertaken toinvestigate the transition. Neutron data collection was made at temperatures above and below the transition point using 4-circle neutron diffractometer at Kyoto University Reactor (KUR). The crystal structure
previously determined by X-ray method (corresponding to the paraelectric one) is an orthorhombic system (a=9.31, b=4.68, c=l5.88 A,
Z=4) with a space group Pcca-D8zh.2) It is reported that Li atom in thevacant space of the puckered structure is statistically distributed over thetwo sites with half occupancy. Dielectric dispersion study by Wada eta/.
suggests an order-disorder type phase transition)) Present structurerefinement disclosed that in the paraelectric phase not only the Li atom
but also the Na atom is split into two sites. Extinction rules in the ferroelectric phase proved that the space group is P2 1ca-CS2v (Z=4), and thestructure was determined based on this symmetry with R-value 0.065
using 870 reflections. A transition mechanism derived is as follows ;The disordered Li and Na atoms in the high temperature phase become
gradually ordered in one of the two split sites as the temperature goes
through the transition point. The x - components of displacement ofalkali metals at the polarity reversal are estimated as 0.32 A for the Li
atom and -0.28 A for the Na atom. These values enable appearance of
spontaneous polarization along the a-direction. While atomic shifts in
the germanate polyhedra are smaller ones (less than 0.15 A) . .This implies germanate network in LNG is much rigidly connected comparedwith that of structurally similar ferroelectrics LizGe"JOis which contains
twice of germanate tetrahedra in the structure unit and shows both anorder-disorder and softening of the optical phonon at its phase transition.
1) M. Wada et al., J. Phys. Soc. Jpn. 52 (1983) 2981.
2) H. Vollenkle eta!., Mh. Chern. 100 (1969) 79.
3) M. Wada et al. , J. Phys. Soc. Jpn. 62(1993) 4503.

2C26
SINGLE CRYSTAL NBUTRON STUDY OF STRUCTURAL PHASB TRANSITION
IN ( Ba/Ca) TiOa
P.U.M. Sastry,
A. Sequeira,
B.A. Dasannacharya and R.
Rajagopal, Solid State Physics Division, B.A.R.C, Trombay,
Bombay 400085 and P. Ramasamy, Crystal Growth Centre, Anna
University, Madras 600025, India
Tetragonaltransition
ferroelectric
to
cubic
in
(BCT)
studied
using
has
been
singleBa 0 • 1 • Ca 0 • 0 1 Ti0 3
crystal neutron diffraction technique. The Bragg profiles .
exhibit anomalous temperature variations of intensities,
which initially increase with temperature and then drop
sharply before
reachingthetransition
temperature(T 0 ) . The intensity variations as well as T0 depend on thesample heating rate, with T0 =145°C and the intensities
peaking around T=120°C at slow heating rate of l0°C/hr.
Structural refinements indicate that the observed intensity
variations are essentially due to changes in extinction
effects brought about by changes in the domain sizes.
The refined thermal parameters exhibit anomalous changes
with temperature, particularly for the Ti-ion,whichexhibits significant positional disorder at around 120°C
indicating a non-zero value for the soft-mode frequency
below T0 • The size of the domains is highly anisotropic
with the average equivalent isotropic
domainradiusdecreasing from about 250A 0 at ~oom temperature to about
100A 0 just below T0
in the tetragonal phase and thenincreasing dramatically to over 1000A 0 in the cubic phase
above T0 • The line widths of the diffraction profiles are
influenced by contributions from the anisotropic domain
sizes as well as from the internal strains . There is noevidence for the presence of mixed phases upto 120°C.
However,the profile widths at 130°C
indicatesome
add~tional
contributions arising from the coexistance oftetragonal and cubic phases. The results suggest that thesmall
domainsizes
and the concomitant composition
fluctuations
mayberesponsibleforthediffuseferroelectric transition reported for BCT.

3PL1

ADVANCES IN THE USE OF RIETVELD ANALYSISFORMATERIALS CHARACTERISATION
Brian H O'Connor, Materials Research Group, Department of Applied
Physics, Curtin ·university ofTeclmology, GPO Box Ul987, Perth, W A
6001, Australia.
The advent of the Rietveld method for diffraction analysis of crystalline
materials offers exciting prospects for a multiplicity of materials
characterisation applications. The author and colleagues now use Rietveld
refinement of laboratory x-ray source diffraction data in both research andcommercial service work to provide the following information •phase composition analysis•

density determinations•

solid solution characterisation•

texture analysis•

residual strain analysis•

crystallite size determination

The paper will examine the capacity and limitations of Rietveld analysis
with particular reference to (i) the processing of alumina-matrix ceramics
and (ii) gibbsite-corundum transformations including the crystal chemistryof intermediate aluminas.
Bias caused by instrumental factors (optical aberrations, specimen off-set,etc) and specimen-related effects (high backgrounds, micro- and macroabsorption, preferred orientation, extinction, etc) will be reviewed. The
value of using synchrotron radiation diffraction and neutron diffraction
data, as alternatives to laboratory-source x-ray data, will be discussed.
Questions to be considered will include What are the strengths andweaknesses of Rietveld analysis ? Is it the method of choice for materials
characterisation under all circumstances? Ifnot, what are the alternatives?

3PL2
CHARGE DENSITY STUDIESCHARACTERIZATIONANDCHEMICAL

BOND

Yu Wang, Department of Chemistry, National Taiwan University, Taipei,
Taiwan, R.O.C.
Charge density studies have been investigated both by X -ray diffraction
experimentally and by molecular orbital calculation theoretically. The
combined study can provide useful information on the characterization ofchemical bond. Examples on the bond characterization on a series · ofcompounds, which contain a Cr-L multiple bond, will be given. Cr-nitrido, imido, -oxo and -carbyne bonds are all isoelectronic, the Cr-L bond (L=N, 0,
C) is essentially a triple bond with one cr bond and two 7t-bonds. However the
7t-density distribution show different polarization along the bond in thesecompounds. Detail chemical bond characterization is applied to a Ni-complex,
Ni(s-disnh It is a planar molecule with a fully 7t-delocalized ligand. All themetal-ligand bonds as well as the 7t-delocalization of the ligand are expressedin terms of molecular orbital wave functions and in some cases, the localizedatomic hybrid orbitals. In addition, the bond characterization is also studied by
a topological approach. Atom domain, bond path and bond critical points will
be presented.
In all the transition metal complexes, the asphericity on electron density aroundmetal atom are clearly seen and the d orbital populations can be derived fromthe multipole model. The agreement on the deformation density distribution as
well as the topological properties between experiment and theory is very good.

3PL3

CHARGE DENSITY STUDIES REVISITED
Philip Coppens, Department of Chemistry, State University of New Yorkat Buffalo, Buffalo, New York 14260-3000 USA.

Recent developments in hardware and soft ware are increasing theaccuracy and the speed with which charge density studies can be
performed.
corresponding

This talk will review some of these advances andresults,

anddiscussthepossibilities

developments with emphasis on transition metal complexes.

forfuture3A11
TOPOLOGICAL ANALYSIS OF EXPERIMENTAL ELECTRON DENSITY
OF LiF CRYSTAL
Yu. A. Abramov* , V.E. Zavodnik", D. Feil% and V.G. Tsirelsons* National Institute For Research in Inorganic Materials, Tsukuba, Japan# Karpov Institute of Physical Chemistry, Moscow, Russia%University ofTwente, Enschede, the Netherlands$ Mendeleev University of Chemical Technology, Moscow, Russia
A parameters of the multi pole Hansen & Coppens model of the LiF crystal has been evaluated from an X-ray diffraction experiment (Mo Ko:, CAD-4, T=298 K, (sin9/l..)rnu = 1.291
A', 632 measured and 52 unique reflections, Fm3m, a=4.024(1) A, R=0.0068, wR=

0.0082, S==0.99). The atomic valence shell populations obtained revealed almost pure ionic
Li-F bond in crystal. A detaijed analysis of the electron density distribution has been performed in terms of Bader's quantum-topologicaltheory using the obtained multipole model
parameters. The calculation of the Laplacian and critical points of the electron density has
been done using a version of the LSPROP program (Howard & Mallinson). The bond
(3,-1) critical point ("saddle") on the Li-F internuclear vector was found and the "sizes" ofatoms bonded in the crystal were determined. The corresponding evaluated average radii ofF(- 1) and Li(+l) ions, 1.24 A and 0.77 A, appear to be rather close to Shannon and Prewin's ionic radii 1.19 A and 0.90 A, respectively. The Laplacian value at the bond criticalpoint is positive as expected in the case of an ionic bond. At the centre of the (001) plane
another (3,- 1) critical point was found, reflecting the F-F interaction in the LiF crystal. The(3,+1) critical points ("cycle") are found on the Li-Li vec-tor in the (001) plane at a distance of 0.68 A from each Li ion. This overall picture of the critical points and basins ofions is in good correspondence with theoretical investigations of the bulk LiF crystal(Tsirelson, Zou & Bader. Acta Cryst. AS!. 143-153).
Support of this research by the Netherlands Organization for Scientific Research (NWO)
is gratefully acknowledged.

3A12
ELECTRON DENSITY IN YTi03 • J. R. Hester, F. P. Okamura (National Institute for
Research in Inorganic Materials, Japan), K. Tomimoto, J. Akimitsu (Aoyama Gakuin
University, Japan).
Accurate electron density experiments have been performed on the title compound. Threehigh resolution room temperature experiments were performed, two using AgKcr radiation (sin 0I A < 1.5) and one using W Kcr radiation (sin 0I A < 1.3). The space group,
cell dimensions and refinement parameters agree with those reported by MacLean, Ng
and Greedan (J. Solid State Chem.,l979, 30, 35-44).
Despite a noticeable degree of random fluctuation in regions far from the atomic nuclei,
the difference density map topographies agree reasonably well for all three data collections, allowing tentative conclusions to be drawn about d electron redistribution. Fourdifference density peaks, perhaps corresponding to Ti ! 29 d orbitals, are located about
0 .6A from the Ti nucleus (see figure). It appears that electron redistribution around Ti
is influenced by the long range symmetry as well as the local octahedral symmetry.
There is a fairly complex arrangement of difference density peaks around the Y atomwhich appear unrelated to the nearest-neighbour symmetry.

Figure 1: Difference electron density around Ti in YTi03 . Contour interval 0.4eA- 3 • borders 3.0A.
Dashed lines-negative. solid lines-positive difference density

3A21

CRYSTAL STRUCTURE OF CHIMERS IN 8-FORM SHOW THAT RNA CANEXIST AS 8-RNA
M. Sundaralingam, Xin Chen and B. Ramakrishnan, Laboratory of
Macromolecular Structure, Departments of Chemistry & Biochemistry, The
Ohio State University, 1060 Carmack Road, Columbus, OH 4321 0
RNA adopts the A-form and has not been so far observed in the B-form. Xray fiber diffraction 1, solution C02 and NMR spectroscopf have implicated that
DNA-RNA chimers could exist in the 8-form. Theoretical studies have shown
the possible existence of 8-RNA with C2'-endo sugar puckering•. In searchof crystal structure of B-form RNA, we undertook the study on the structure ofchimeric octamers (lciCICIC) and (lclciCIC) (lower case letters represent RNA
residues) and their complexes with the DNA minor groove binding drug
distamycin. This drug was chosen because it is known to bind to only 8-formof DNA. The native crystals of these octamers could not be obtained ;however, the structures of the complexes with distamycin have been
determined at 1.73 and 1.70A resolution respectively. Crystals of thesechimeric octamer drug complexes are isomorphous with their all-deoxy
counterpart d(ICICICIC)2 with two drugs bound side-by-side in the minor
groove5 • Surprisingly, the DNA-RNA octamers are in the B-form in contrast to
the A-form for all the known free chimer oligomers in crystals. The ribose
sugars, like the deoxy sugars, are in the S-type puckering and the 2'-hydroxyl
groups are in the major groove and form a direct hydrogen bond to the N7
atom of the succeeding 3'-side inosine residue. Modeling studies indicate that
B-form is possible for the all-ribose (ICICICIC) octamer and alternating RNA.
In the B-form RNA duplexes, the 2'-hydroxyl groups can be hydrogen bonded
to N7 of the 3'-side purines and the backbone phosphates of the 3'-side
pyrimidines.
In RNA uracil is present instead of thymine, the 5-methyl group would havesteric conflict with the 2' -hydroxyl group in the major groove. This could be thereason why RNA contains "U" instead of "T", enabling it to assume the B-formin stretches when involved in interactions with drugs/protein factors.
1.
2.
3.
4.
5.

Zimmerman, S. B. & PheiHer, B. H. (1981) Proc. Nat/. Acad. Sci. USA 78, 78-82.
Jayasena, S. D. & Behe. M. J. (1987) Nucleic Acids Res. 15(9), 3907-3916 .
Reid, D. G. et al. (1983) Eur. J. Biochem. 135, 307-314.
Rao, S. N. & Kollman , P. A. (1986) J. Am. Chern. Soc. 108, 3048-3053.
Chen, X., Ramakrishnan , B., Rao, S. T. & Sundaralingam, M. (1994) Nature Structural
Biology 1, 169-175.

Supported by NIH grant GM-17378

3A22

X-Ray Structure Determination of A b r in - a
Tian-Huey Lul, Tahir H. Tahirovl, Yen -Chywan Liaw2, Yung-Liang
Chen3 and Jung-Yaw Lin3.
1 Department of Physics , National Tsing Hua University, Hsinchu, Taiwan.
2 Institute of Molecular Biology, Academia Sinica, Nankang, Taipei, Taiwan .
3 Institute of Biochemistry , College of Medicine, National Taiwan
University, Taipei, R. 0 . C.
The crystal structure of abrin-a, a type II ribosome-inactivating
protein from the seeds of Abrus precatorius has been determined from anovel crystal form (Tahirov, Lu, Liaw, Chu & Lin , 1994) by molecularreplacement method using the coordinates of ricin (Montfort et al., 1987).
The cell dimensions determined by area multiwire detector are a=84.58,
b=73 .07 , c=48 .23 A, and B=96.20o in a monoclinic crystal system withspace group P2 1.The structure has been refined at 2.14 A to a R- factor of
18.9% by using X-PLOR program (BrUnger, 1990). The r.m.s. deviations ofbond lengths and angles from the standard values are 0.013 A and 1 .82°
respectively . The overall protein folding is similar to ricin but there aredifferences in secondary structure, mostly of A-chain . Several parts ofthe molecule surface differ sign ificantly and some of the differences arequite near the active site cleft and might influence the ribosome
recognition . The positions of invariant active site residues are remained
except the position of Tyr74, which is more mobile or partially disorderedin abrin-a. Three water molecules have been located in active site cleft .
B-chain is a glycoprotein and the positions of two sugar chain si tes were
determined. One of the sugar chains is a bridge between two neighboring
molecules since one of its mannose residue have been aff iliated bygalactose binding site of neighbor molecule. Another sugar chain wraps up
the surface of B-chain . Various colourful models of abrin-a will bepresented to illustrate the crystal structure of abrin- a.
This work was supported by National Science Council , ROC, under grant
NSC84-2311-B007-015 .
References :BrUnger, A. T. (1990). Acta Cryst. A46, 46-57 .
Montfort, W., Villafranca , J. E., Monjingo, A. F., Ernst, S. R., Katzin , B. ,Rutenber, E., Xuong, N.H., Hamlin , R. & Robertus, J. D. (1987). J. Bioi.
Chern. 2 62, 5398- 5403 .
Tahirov, T. H., Lu, T. H., Liaw, Y. C., Chu, S.C., & Lin, J. Y. (1994). J. Mol. Bioi.
235,1152 - 1153.

3A23

TIIREE-DIMENSIONAL STRUCIURE OF TIIE PSEUDOMONAS
BphC ENZYME HAVINGPOLYCHLORINATED BIPHENYL(PCB)-DEGRADING ACTIVITY
H.Narita, K.Sugimoto, T.Senda, K.Kimbara,M.Fukuda and Y .Mitsui.
Department of BioEngineering, Nagaoka University of Technology,
Nagaoka, Niigata 940-21, Japan.
Polychlorinated biphenyls (PCBs) are widely distributed environmental pollutants which are recalcitrant to biodegradation.
Pseudomonas sp. strain K.KS102 is one of the PCB-degrading microorganisms and the " BphC"
enzyme (2,3-dihydroxybiphenyl <lioxygenase) is a key enzyme in the relevant PCB --degrading pathway. The
BphC enzyme is an extra<liol type <lioxygenase having one ferrous
iron in the active site.
To gain insight into the catalytic
mechanism of the BphC enzyme, we undertook a de oovo X-ray
crystallographic analysis by MIR method. The enzyme (M.W. ca.250
kDa) is made up of eight identical subunits each of 292 aminoacid residues.
The BphC enzyme turned out to be a thick-walled cylinder which
has a 422 point group symmetry in the molecule. A barrel-shaped
central cavity penetrates the molecule. The subunit of the BphC
enzyme is composed of four repetitions of a folding motif consisting of ca. 55 amino acid residues. The repetitive motif hasa " ~(3(3(]' topology (Sugiyama et al.,1995). In the active site,
we found an Fe ion which was coordinated by side chains of threeamino acid residues, His 145, His 209 and Glu 260.
Crystallogrpahic analysis of the BphC enzyme complexed with 2,3<lihydroxybiphenyl (2,3-DHBP) showed that the two hydroxyl groups
of 2,3-DHBP are coordinated to the Fe ion resulting in a trigonal
bipyramidal form. With the structure of the BphC enzyme-substratecomplex at hand, we can identify a putative binding cavity forthe oxygen molecule required for the enzymatic reaction .
Sugiyama,K. ,Senda,T. ,Narita,H.,Yamamoto, T. ,Kimbara,K. ,Fukuda,M.,
the late Yano,K. & Mitsui,Y.(1995) Proc.Japan Acad. 71B, 32 - 35.

3A24

CRYSTAL STRUCTURE OF PEA-SEEDLING AMINEOXIDASE
Vinay Kumar, H.C. Freeman, J.M. Guss and V.M. Zubak, School ofChemistry and Department of Biochemistry, University of Sydney, NSW
2006, Australia and D.M. Dooley and M.A. McGuirl, Department ofChemistry and Biochemistry, Montana State University, Bozeman, USA.
Copper-containing amine oxidases (AO) catalyse the oxidative deaminationof primary amines to the corresponding aldehyde. An important
subcategory found in higher organisms, diamine oxidases, participate in
the catabolism of di- and poly- arnines which are important agents in many
fundamental cellular processes.
Diamine oxidase from pea seedlings is a glycosylated protein consisting of
two identical subunits with a total molecular weight -145 kDa. The
protein crystallises in space group P2 12 12 1 with one dimer per asymmetricunit. The positions of the individual tungsten atoms in a phosphotungstate[PW 12 0 40 3 -] derivative were fitted to a difference map which had beenobtained by molecular replacement. The molecular replacement
calculations used the structure of E. coli AO (communicated prior to
publication by Professor S.E.V. Phillips) as a search model. An electron
density map for the protein was calculated using phases obtained from thephosphotungstate derivative using single isomorphous replacement andoptimised anomalous scattering phases. The map, improved by solvent
flattening and non-crystallographic symmetry averaging. was readilyinterpretable.

3811
THE EFFECT OF COPPER DOPANT ON THE GROWTH AND PROPERTIES OFPOTASSIUM SODIUM STRONTIUM BARIUM NIOBATE CRYSTALS
H. C. Chen, Q. Z. Jiang, X. L. Lu and L. Chen. Institute of Crystal Materials, Shandong
University, Jinan, 250100. P. R. China

Potassium sodium strontium barium niobate ( KNSBN) crystals doped with CuO weregrown by pulling method using the MCGS-3 system. The starting materials we used are
4N K2C03, Na2C03, SrC03, BaC03, Nb205, and CuO. They were mixed according
to the fonnula of(KxNaJ-x)0.2 (SryBaJ-y)0.9 Nb2)6 ,where 0.3< X< 0.7, 0.25 < Y <.
0.75 . A very small amount of CuO ,0.03%-0.07%, was added to the mixture. The,growth conditions are pulling rate 3-5 mmlh and rotation rate 15 r.p.m. The as-grown
KNSBN :Cu crystals were annealed at 1050 •c for 24 h and then cut into samples withsize of 5 x 6 x 6 mm3 along the a, b and c axes. The samples were polished and poled at
100 •c under a 6 kv/cm ofC.D . electrical field
From the transmission curves we can see that the Cu ions have caused two absorption
peaks at 475 and 495 nm. Because the positions of the peaks are not affected by thedoping level of CuO, it means that these two peaks correspond to the intrinsic energy
levels of Cu ions, 2 .61 ev and 2.50 ev in KNSBN. These two deep energy levels in theband gap can increase the effective charge-combination-center concentration
The two-wave coupling gain and the response time of KNSBN crystals are increased
while the photoconductivity and the effects of a de field on the photorefractive
properties are reduced. Self-pumped phase conjugation experiments have rev~aled thatthe effect of Cu ions on the photorefractive properties have a wavelength dependence.
The SPPC response time can be shortened to 200 ms.

3812
SINGLE CRYSTAL GROWTH AND GROWTH MECHANISM OF
YNi2B2C SUPERCONDUCI'ORS BY FLOATING ZONE TECHNIQUE
H Takeya, K. Kadowaki, K. Hirata, T. Hirano and K. Togano
National Research Institute for Metals, 1-2-1 Sengen, Tsukuba, Ibaraki
305, Japan
Since the discovery of a new family of borocarbide intermetallic
superconductors, a great deal of studies have been performed on the arcmelted polycrystalline samples which contain many micro cracks and a
trace of the second phase. In this study, we have succeeded in growing thesingle crystals of YNi2B2C by floating zone technique.
Czochralski method using a tetra-arc furnace or a skull melting furnace
was preliminarily applied, but the grown crystals contained dense lamellar
structure which consisted of YNi2B2C, YB2C2 and Ni-rich phase.
Metallurgical studies and composition analyses on the grown crystals
suggest that YNi2B2C is an incongruent material and decomposes to
YB2C2 and Ni-rich phase. In such a case, YNi2B2C is precipitated fromthe solution of the Ni-rich phase. However, no improvement was observedin the crystals grown out of a Ni2B flux by the Czochralski method.
On the contrary, the considerable improvement has been performed by
the floating zone technique without any solvent. No second phase wasobserved in the grown single crystal. The as-grown crystal showed thesuperconductivity at 15.6 K (onset) with the transition width of 0.7 K by
the SQUID magnetometer, which is compared to 14.8 K (onset) with thetransition width of 2.3 K for the arc-melted polycrystalline samples. deHaas-van Alphen effect was also successfully observed on the single
crystal. These results suggest the high quality of the grown crystal.
Since the successful result by the floating zone technique without solvent
is inconsistent with the preliminary study that YNi2B2C is an incongruent
material, the further investigation on the growth mechanism has been
made by the back-scattered electron micro-analysis and X-ray diffraction.
According to the analyses, a considerable amount of YB2C2 was seen at
the tip of a feed rod just above the molten zone and the molten zone wasrich in Ni. This suggests that YNi2B2C decomposes to YB2C2 and the Nirich solution at the tip of the feed rod . Though any solvent is not preparedat the beginning, the Ni-rich solution forms the molten zone and the single
crystal of YNi2B2C is precipitated from the solution.

3813
ANOMALOUS DENSITY VARIATION OF SILICON
MELT AND MELT FLOW IN CZ PROCESSK.Terashima.Department
Ceramic

Materialso(Technology, Shonan

lnst

Science

tute

o f

and

Technology,

1- 1- 25

Tsuj i d o - N i s h i k a i g a n , Fuj isawa, kanagawa 25 1, Japan ,

and

H.

Sa sa k i,

S . Togawa , S. Kawan ish i.

S. Kimura, KimuraR e s e a r c h

I b a r a k i

MetamelCo n s o rttemperaturewa s

determinedt

Ar c himedianrang ewasterm sofAnobserved
vo lumewa s

ju s tThi s

f i r s t,

the

o n
the

of

The

impurity

mentioned
changesu et hemelting

point .

A

thermaabout

1.

OXI0 -4"C - l

range

r om

about

14 3 0"C

wid e l y

varid

n ext

regionpulingvi s co s

t y

and
and

region
soft

w as

me
the

proces s.
surfacecry s t a l

si l i co nc rucibl eThebasical yrand omc hang ed

These

o f
by

anomaly

the

i n

will

and

it

s p ec ies

abovestrongly(density ,variation,

un i f o rmity

the

flow

c ru ci ble

pr o p e r t i e s

ten s i o n)meltRayl e i g h -phe nom ena

s t r u c tur es
M e ltunder

measured .

d e n s ity

flow

the

v ariation .

turbulence "

t.

t o
on

in

f l u c t u a t io n s

structure

the

melt

d epen dings tudi e d

we r einvolumethermao fdens i ty

th eregion s

th e

was

anomalous

flow

in

in

of

a b o u t

the

We

th i

densityabout

thr eecienttemperaturedurings tructures

va
o I

into

coef fgrowthsuggestthedividedCzochralski

interface

melt

I rom

impr ove d

th e

th e

clarified

Benard .

ol

for

range

temperature

coefficientanomalysi l i c on

the

for

be

ab ove

o{

in

Th e

ous

species.

structure
was

anoma

duringgrowthe - 2, 5- 5- 9T o k o d a i , T u k u b a ,t e chniqu ecoefficiet

dep e ndingAttoexpansion

impurity
flow

and

JRDC, Tukuba

measurement .

temperature

ob t a i n e d

I 54 O't .

u s i n gound

expansiont

dep e ndenc e

densitythed e n s i t y.

i u m, S a t e I i

accurate l y

I 6 5 O'to

I z unome

Ja p a n

300-26,The

I 4 2 O'tK.

P r o j e c t , ERATO,

t

be

melt

l o w

di sc ussed .

3814

ETCHING STUD!ES Of' SOLUTION-CROWN Cl~ YST/\LS : (I 00) F /\CES
Suparna Sen
NH H PO ) CRYSTALS.
OF MIXED KDP:ADP (K1Gupta and S. P. Sen Gupta~x De~~rfmen~ of Matenals Sctence, lndtan
Assoctatl()n for the Culttvatton of Sctence, Jadavpur, Calcutta - 700
032, INDIA.
The

study

of

mtxed

crystals of

attracted constderable attenttonm

KDP:ADP (K ·- xNH xH Po J has
42
41
years as they present a newrecentclass of matenals wtth mtrmstc mterests due to thetr potential appltcatJons 1n opto-electronics. However, 1n the past very Jew work have beenthts.. system.

reported on

Mtxed c rystals of KDP-ADP have been grownby the method of slow evaporation over the enure r<mRe of co rnpos1t1on.
lhe growth condrt1ons to obtarn tran ~ purcnt ulld lloodl·ru·le son!{ll: cry~tuh
have been cnucally examtned byseveraltests.

to understandIn orderthcn· defect co nf1gnratJons, we have undertuk en chCIIIICill etch tc:c :luuquc
details.

wt th

greaterwtth

varymg etch

Dtfferent

etchants

mcludmgt1me have been employedalcohols

and

ac1ds

to reveal dtslocattOn sttes

m these crystals. Growth hillocks, ptts of dtfferent mclmauon, low angle
tilt

and

boundary

many

other

surface. It 1s also observed thatexhtbttAn

werefeaturesobservedtheetchedfew stmllar features like pure KDP and pure ADP respecttvely .

mterestmg

patterne.g.

atrtsec uon

ofboundarieSof c losely spao'd etch p"11s (F1g . l(a,b)) were c learly see nsurfa ceon

KDP-nch and ADP - nch mtxed crystals

or

and

brandung

011

the e tched

IIIJXcd nystuls. The se etch patterns hilve i>cell ob~t-rvcd ;uodphol<'!;!r;~ph"dllll(I Cr Ull uptle<ll llll <: ro sco pt• ;uod uho

111.' iEM. Tlw dt't ;llh

will be pre se nted through opllcal and clc c tro11 IIIICrogruphs.

Fig. I (a) tri section of bound:J.ries.

Fig. I (b) hranching of dislocations

3821,3P22
THE ATTEMPT TO DESIGN SOLID STATE REACTION
BY REACTION CAVITY
D. Hashizume andY. Ohashi, Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, JapanThe 2-cyanoethyl group bonded to the cobalt atom in cobaloxime
complexes is isomerized to 1-cyanoethyl group on exposure to visible
light in the solid state. The reaction cavity for the cyanoethyl groupis an important factor determining the rate and selectivity of thereaction. We report the attempted to control the reaction rate andthe reactivity.
The ( 2-cyanoethyl) (3-hydroxypyridine )co baloxime complex crystallizes into a triclinic system from a methanol solution. There are two
crystallographically independent molecules in the asymmetric unit
and the structures of these two molecules are almost the same andone of them is shown in Fig. 1. The cyanoethyl group are well packed
with neighboring molecules.
The monoclinic system crystal was obtained from a chloroform solution , contains chloroform molecules which are placed around the
cyanoethyl group. As a result, the reaction cavity around the cyanoethyl group is expanded, and therefore the rate of the isomerization of cyanoethyl group different from triclinic one.
NS

Table 1. Crystal Data.
a/A 12.367(2) 9.230(2)bf A 15.207(3) 23.985(3)cf A 11.356(1) 11.450(2)at/ 0 104.45(1)f3;o 93.69(1) 93.15(2)'Y /73 .77(2)Vf A3 1985.6(6) 2531.0(8)
z
4
4
Space
PI
P2Ifn
Group
0

1

3822,3P23
STUDY ON COMPLEXES OF ALKYLAMMONIUM SALTSAROMATIC ADDITIVE
Kulthida Vongbupnimit, Keiichi Noguchi and Kenji Okuyama, Faculty ofTechnology, Tokyo University of Agriculture and Technology, Koganei,
Tokyo 184, Japan

Recently, some amphiphiles such as ammonium salts, phosphonium salts
and other onium salts without any intramolecular cavities have beenfound to form complexes with organic guest molecules. In some cases,
formation of complexes can also be prepared simply by mixing bothpowders of host amphiphiles and small guest molecules. In the present
work, we will present the complex crystal structures of the hostamphiphilic molecule; dodecyltrimethylammonium chloride (DTAC)
with various kinds of guest aromatic molecules, i.e., hydroquinone(HQN), catechol (CTC) and p-iodophenol (p-IoPh).
Crystal dnta :monoclinic
DTAC/HQN; CH3(CH2h1N+(CH3)3Cl-/p-C6i1602·2H20,
P21/n, a= 7.212(2), b = 45 .099(5), c = 8.208(2) A, {3 = 108.96(2r.
monoclinic
CH3(CH2h 1N+(CH3)3Cl-/o-C611602· 2H20,
DTAC!CTC;
P21/n, a= 7.084(4), b = 44.271(6), c = 8.415(2) A, f3 = 108.98(3r.
DTAC/p-IoPh; CH3(CH2)nN+(CH3)3Cl-/p-C6HsiO, monoclinic P21/n, a= 9.840(7), b = 9.976(3), c = 26.357(10) A, f3 = 1oo.43(4r.
The complex crystal structures and the amphiphile aggregation systemdepended on the kinds of guest molecules have been discovered. The
packing structures of complexes, DTAC/HQN and DT AC!CTC are
similar to each other, but they are quite different from that of DTAC/pIoPh. In addition to the complex crystal structures, to get better
understanding about behaviors of these complexes, the phase transitions
and thermal behaviors of host molecule and complex molecules will be
discussed by differential thermal analysis (DTA) and X-ray powder
diffraction patterns too.

3823, 3P24
Diverse Mode of Crystal Structures in the Host-Guest Complexes of Diols

Yasushi Kai. Hiroshi Suzuki, Nobuko Kanehisa, Koichi Tanaka,t and Fumio Toda t
Department of Applied Chemistry, Faculry of Engineering, Osaka University, Suita,
Osaka 565, Japan
toepartment of Chemistry, Faculty of Engineering, Ehime University, Matsuyama,
Ehime 790, Japancis-1,4-Diphenylcyclohexane-1 ,4-diol forms the crystaUine Host-Guest complexes
with methanol (1 :1) (complex 1), cis-2-butene-1 ,4-diol (1 :1) (complex 2), and trans-2butene-1,4-diol together with water (1 :1:1) (complex 3). The crystal structures were
determined by X-Ray diffraction method. Crystal data and final R values are; for complex
1, monoclinic, P21, a=7.589(2), b=10.057(2), c=11.033(2)A, .8=93 .81(1)',V=840.2(3)A3, Dc=l.187gcm-3, Z=2, and R=0.039 for 1341 observed reflections, forcomplex 2 , monoclinic, P21/n, a=9.565(1), b=9.371(1), c=21.633(1)A, .8=98.27(1)',
V=1918.8(2)A3, Dc=l.234gcm-3, Z=4, and R=0.055 for 3059 observed reflections, andforcomplex 3, monoclinic, P21/a, a=7.479(2), b=35 .328(2) , c=7.801(1)A,,8=100.58(1)', V=2026.0(5)A3, Dc=l.228gcm-3, Z=4, andR=0.045 for 3087 observedreflections. In spite of the common mode stacking of 21 symmetry for host molecules inall the crystals, the packing structures are quite different from each other. Guest molecules
are arranged separately in the channel of host molecules in 1, while guest molecules form

strings through the hydrogen bonds with host molecules in 2 . In complex 3 , guest
molecules arrange in layer sandwiched by the hydrophilic part of the host molecules.

1

2

3

Scheme 1. Schematic presentation of the crystal packing of complexes 1 to 3 .

3824,3P25
EXTENDED MOLECULAR NETWORKS INCORPORATING THE 1,4lliS(IMIDAZOL~2- Y L)llUT -2- YNE LIGAND
Damian A. Slizys, Bernard F. Hoskins and Richard Robson

School of Ch emistry. University of Melbourne, Parkville, Victoria 3052,
AUSTRALIA
Extended molecular networks can be constructed from metal centres linked bybridging ligands. Examples of ligands used to construct such networks include
cyanide, 4.4' -bipyridine and pyrazine.
Our research has focused on using bridging ligands incorporating nitrogen-based
heterocycles as the binding functions. In particular the imidazole moiety has been
the preferred binding function because of its relatively high affinity for metal ionsand its small size when compared to other nitrogen-based heterocycles such as
pyridines . One novel ligand of this type that we have developed is I ,4-bis(imidazol1-yl)but-2-yne.
Molecular networks incorporating this ligand have been prepared from CdSiF6 and
ZnSiF6. In both cases crystals separated from an aqueous solution of I ,4bis(irnidazol-1-yl)but-2-yne and the appropriate metal salt. The crystals wereinsensitive to solvent loss.
l11e two structures are very closely related. X-ray diffraction studies show them tobe composed of sheets of metal atoms each linked by four molecules of I ,4bis(irnidazol-1 -yl)but-2-yne to four other metal atoms. These sheets in turn werelinked vertically by SiF6 anions coordinating to the metal atoms above and below .
Overall the topology was equivalent to <X-polonium.
The crystal structure of these networks will be presented .

3825,3P26
DYNAMIC BEHAVIOR OF N-(2,4-DINITROPHENYL)-o-ANISIDINECRYSTALS
M. Yasui. K. Taguchi and F. Iwasaki, Dept. of Applied Physics andChemistry, The Univ. of Electro-Communications, Chofu, Tokyo 182,
Japan.
N-(2,4-Dinitrophenyl)-o-anisidine crystallizes in two modifications, orange
and red fonns. The condition to crystallize each form is very subtle, sothat it is by chance which form can be obtained. The coexistence of thesefonns is often observed. In the wide temperature range from II 0 to
158°C depending on specimen, orange crystals begin to transform to red
crystals in the solid state, which have been found to be identical to the redform recrystallized from the solution by mean of the powder diffraction.
This transformation is irreversible since the red crystals do not return tothe orange fonn by the cooling. However some orange crystals directly
melt without this transformation. The molecular structure of the red form
is a rotational isomer of the orange form. In the red form, the NH groupis hydrogen-bonded to nitro and methoxy groups bifurcately, while in theorange form the hydrogen-bond between NH and OMe groups is notformed. Oscillation photographs of the partially transformed orange
crystal were taken on a rapid X-ray measurement system using the
Imaging Plate. At the orange form the crystallographic b axis is parallel tothe needle axis of the crystal. The diffraction patterns from thetransformed region, a red form, are concentric circles with many sharp
spots. These spots show that the single crystal of a red form coexists inthe polycrystalline and that the crystallographic b axis of a red fom1 iscoincident with that of the unchanged orange crystal. The relationship ofb axis between the orange and the transformed red crystals was kept in
the several specimens. From these results, we conclude the mechanismof the transformation from an orange to a red form as follows. The
conversion may be performed by twisting of the molecule as well as theintra-molecular rotation. As a result of twisting, the crystal structure may
be changed to the red form. However, such motion needs a large space,so that this rearrangement may occur at defects in a crystal and destroy
the orientation of whole molecule to be a polycrystalline.

3B26,3P27
MODELLING

AND

REFINEMENTOFDISORDERED

MOLECULAR

STRUCTURES FROM SINGLE CRYSTAL X-RAY OATA

Fun Hoang Kun , K. Sivakumar and Yip Boon Chuan, X-Ray Crystallography
Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang,
Malaysia.
Crystal structure refinement becomes a routine work with the high speed
computers and software packages available to us. Even then it is not a routine
work in the scientific sense that, many problems are faced in individual cases
particularly when the structure has any form of disorder. Hence one has to becareful in analysing the intermediate results of the refinement procedure andcarry out the next step with reasoning . Analysis of the mode of disorder andsuitably carrying out the refinement with constrains and restraints comes withexperience. In our laboratory, we have come across many such occasions withdifferent types of disorder present in the molecular structures. There areexamples of rotation of a group of atoms with respect to a bond, disorders dueto the conformational flexibility of certain rings, mixture of two isomorphous
structures and many more. A detailed survey of all such disordered cases andhow the structures were refined to give a good model will be discussed. The
presentation will also include how to identify the minor conformational
components present in the structure and model them to get better structural
informations.

Poster Presentatio n

1P01NORMAL MODE ANALYSIS OF INCOMMENSURATE
MODULATIONS AND ITS RELATION TO THE ATOMICDEBYE- WALLER FACTORS OF THE NORMAL PHASE
By N .Achiwa*, M. Machida andY. Yamauchi, Department of Physics,
Kyushu University, Fukuoka 812, Japan.
We have developed a geometrical method to analyse molecular modulation modes in incommensurate crystal structures. From the three dimensional locus of each modulated atom which is pulled back ~o the original unit cell,that of a special mode, for example translational or rotational external molecular displacement is subtracted. Then,the remainder figure suggests the next main mode, for example, internal molecular mode. So we can find successively miner modes orthogonal to the subtracted modes by
the trial and error method. The atomic De bye-Waller factors{ADWF) in a normal phase is tightly related to themode amplitude of the incommensurate phase, because thelowest frequency normal mode contributes most strongly
to the ADWF in the normal phase. Then, we have estimated contributions of the external and the internal modes
to the ADWF in the normal phase. The family compounds(C3H1NH3)2MCl4 {M=Cu, Mn, Cd) shows the following
phase sequence: a --+ f3 --+ r -+ {j --+ f --+ ( ' with the two
incommensurate e and r-phases. These incommensurate
structures were extensively studied using superspace symmetry. We have applied the new geometrical method tofind the displacive modulation modes in the r and e phases
and its application to analyse the ADWF in the normal
8 phase by the external and internal modes. The main
normal modes of modulated r (superspace group, Pbca:(
aOO}ssO, Doudin Chapuis, 1990 B46 180. ) and e (superspace group, BP2t/b11 : (0,0. 5,~}1l, Ikeda and Achiwa) phasesof (C3H 7 NH3)2CuC~ are a translational modulation along
the c-axis and a twisted intra-molecule mode of propyl ammonium base, respectively, though in both phases each orbit
of atomic modulation consists of multi-molecular modes.

1P02
ATOMIC ANISOTROPIC DISPLACEMENT PARAMETERS FORSILICATES AND OXIDES: A LATIICE-DYNAMICAL DERIVATIONFROM EMPIRICAL POTENTIALS
Tullio Pilati, Centro del C.N.R. per lo Studio delle Relazioni, fra Strutturae Reattivita Chirnica, Via Golgi 19, 1-20133 Milano, Italy, Francesco
Demartin, Dipartirnento di Chirnica Strutturale e Stereochimica lnorganica,
Universita degli Studi di Milano, Via Venezian, 21, 1-20133 Milano, Italy,
and Carlo Maria Gramaccioli, Dipartirnento di Scienze della Terra,
Universita degli Studi di Milano, Via Bottitelli 23, 1-20133 Milano, Italy.
Using empirical potentials derived from fitting the vibrational frequencies
of a group of neso-silicates and oxides, a Born-von Karman rigid ion
lattice-dynamical model extended to the whole Brillouin zone has been
applied to a series of oxides and silicates, such as quartz, bromellite (BeO),
corundum (a-AI 20 3), chrysoberyl (Al 2Be04 ) , forsterite (a-Mg 2Si04 ),monticellite (CaMgSi04),
andradite(Ca3 Al2Si 30 12),
(Ca 3 F~Si 3 0 12 ), almandine (Fe 3 A~Sip 12 ), pyrope (Mg 3 Al 2Si 30 12), andfayalite(Fe 2 Si04 ),andalusite

tephroite(Al 20Si04),(Mn2Si04 ),grossular

diopside (CaMgSi20 6 ) to obtain estimates of anisotropic atomic
displacement parameters (A.D.P.'s); as by-products, a consistentinterpretation of the vibrational spectra of all these minerals and of their
thermodynamic behaviour at different temperatures have also been derived.
The agreement with the corresponding experimental data is quitesatisfactory, even for substances such as diopside and grossular, whose
spectra and physical properties in general were not included in the processof fitting the potentials. For garnets, in particular, the problem of theanomalous behaviour of thermodynamic properties of pyrope andalmandine (especially with respect to the specific heat Cp and entropy S asa function of temperature) can be very reasonably explained on grounds ofan order-disorder transition occurring at low temperature, involving the Mg
or the Fe atom, respectively: such an anomalous behaviour is reflected very
well also in the atomic displacement parameters, especially when theobserved values are compared with the corresponding lattice-dynamical
estimates.

1P03

THE ANOMALOUS SCATTERING FACTOR OBTAINED FROM ROCKING CURVEMEASUREMENTS OF Ge SINGLE CRYSTAL

M. Kuribayashi, T . Kanamaru, A. Inoue, H. Katoh and K. Ishida, Dept. of Phys .
Science Univ. of Tokyo, Noda, Chiba 278, JapanWe derived a new formula 1) based on the Takagi equation 2) for a rocking curve of aperfect single crystal. It is well known that the traditional formul a 3) for a rocking curve is
not applied when the real pan of the structure factor is very small . To avoid the difficulty,
Fukamachi and Kawamura proposed an improved formula 4) which can be applied for thecase. However, they used the anomalous scattering factors to define the "W" parameter,
so that the formula is not suitable to obtain the anomalous scattering factor. On the other
hand, the present formula does not use the anomalous scattering factors to define the "W"parameter. Therefore, the formula is suitable to determine the real and imaginary parts of
the anomalous scattering factor, f' and f'', from rocking curve measurements near theabsorption edge. The SR measurement was carried out at BL-14B of the KEK Photon
Factory in Tukuba. Radiations at BL-14B were well monochromatized with a series ofthree monochromators, Si(lll) double crystals, a Si(440) grooved crystal and a Si(660)
grooved crystal. The wavelength was selected by a little rocking of the third
monochromator and the energy resolution was about O. le V. Ge( Ill ) rocking curves witha symmetrical Bragg case were measured at 124 energy points below and above theabsorption edge. The total range of the measurement was 220eV . The f' and f" wereobtained by fitting the measurement rocking curve to the present formula . The obtained
values below the edge are in good agreement with the calculated ones for a free atom.
But, above the edge, the XANES effect is clearly observed for both f' and f'' .
I) to be published in J.Phys.Soc.Japan2) S.Takagi, (1969) J. Phys. Soc. Jpn. 26, 1239-1253.
3)W.H.Zachariasen, ( 1945) Theory of X-ray Diffraction in crystals (Dover,New York)
4)T.Fukamachi and T.Kawamura. (1993) Acta Cryst. A49 , 384-388.

1P04

X-RAY STUDY OF DEFECfS PRODUCED BY MeV ION IMPLANTATION INTO SiPERFECT CRYSTALS
M. Kuribayashi, A. Inoue, T. Kanamaru, H. Katoh and K. Ishida, Dept. of Phys.
Science Univ. of Tokyo, Noda, Chiba 278 , Japan, H. Tomimitu , K. Aizawa andY.
Kazumata, Japan Atomic Energy Research Institute, Tokai, Ibaraki 305, Japan

Ion implantation in the energy range of several l 0-1 OOKe V into Si crystals is a wellestablished technique for fabrication of semiconductors. The damage produced by the
implantation is also well studied. In the present work, the defects caused by MeV ion
implantation is investigated by X-ray measurements using the diffraction theory in
distorted crystals 1). Implantations of Ni,Cu and Au ions into Si( Ill) wafers were carriedout using the tandem Van de Graff accelerator at JAERI in Tokai with the energy range of
80-230MeV. X-ray rocldng curves were measured with multi-crystal diffractometer at
BL- 14B in Photon Factory at KEK in Tukuba. The monochromator system used wasSi(lll) double crystals and a Si(220) grooved crystal with ( +, -, -,+)setting. A sample
wafer was mounted on a precise diffractometer.The measured rocldng curves had atypical profile which consist of a main peak and many subsidiary maxima. The strain
distribution could be determined by fitting the measured rocldng curves to calculate ones.
The strain profiles obtained by the simulations were compared with distributions of loss
energy and stopping-atoms calculated with Aruga 's prograrn2> which is an expanded codeof EDEP-1 for high energy region. It was found that the main profiles of strain
distribution were nearly equal to those of the distributions of stopping ions regardless of
the ion species. In the region near the crystal surface, the magnitude of strain,6.d/d, has anegative sign. The decrease of lattice spacing near the surface can be interpreted thatcrystal atoms are scattered by the collision of implanted ions . The magnitude and therange of the decreased layer depend on ion species.The annealing effect is also studied.

l)

S.Takagi, (1969) J.Phys.Soc . Jpn .. 26, 1239-1253.

2)

T.Aruga, K.Nakata and S.Takamura, (1988) Nuch.lnstr. and Meth.
B33 ,748

1P05
MEASUREMENTS OF X-RAY DIFFRACTION INTENSITIES FROMUNIFORMLY BENT SINGLE CRYSTALS
T. Takama and K. ltoh, Department of Applied Physics, Faculty ofEngineering, Hokkaido University, Sapporo 060, Japan.
Diffraction phenomena in uniformly bent single crystals were studied bymeasuring the integrated intensities as a function of X-ray wavelength.
Two kinds of isosceles triangular specimens with different orientation were
cut from Fz silicon wafers of about 0.55 mm in thickness. One specimen
has the (111) surface orientation with [0 1-1] direction parallel to the baseand the other has the (001) with [1 -10] parallel to the base. Bending wasintroduced by keeping the base of the triangle fixed and using a differential
micrometer screw to push the apex . The integrated intens1t1es were
measured for the X-ray wavelength range from 0.2 to 0.6-0.9A by theenergy-dispersive diffraction method.
As the curvature increases, the following changes were observed in mostcases. The diffracted intensities increased especially for the shortwavelength side. The positions of the Pendellosung beats shifted to theshort wavelength side. In addition, the amplitude of the beat decreased andfinally smeared out. The magnitude of the changes was dependent not only
on the induced curvature but also on the index and the sign of the reflection
plane, and the geometrical arrangement of the plane. The following
phenomena were noticed as exceptions. The (220) and the reverse
reflections in the symmetrical Laue case for the latter specimen did notshow any change in the profiles. On the other hand, when the (2-20)
reflection for the former specimen showed stronger intensities incomparison with those from a perfect crystal, the reverse reflection showed
weaker intensities for the wavelengths longer than about 0.6A.
The diffracted powers obtained were compared with the Kato theory(1976) for distorted crystals. A fairly good agreement was drawn between
the experiment and the theory if the elastic anisotropy is taken into accountfor the calculation of displacement fields due to the bending.
Kato, N. (1964). J. Phys. Soc. Japan, 19,971-985.

1P06

Observation of Defects Without Directly Reflected
Wave in Bragg Case
T.S. Uragami, H. Kobayashi and D. Orii, Faculty of Engineering, Okayama
University of Science, Okayama, 700 Japan.
By using X-ray diffraction with an incident wave of finite width, thedefects in a Silicon single crystal was oberved in Bragg case. At the point
where X-ray enters on the surface of the crystal, the strong diffracted wave
is created at that entrance point in the Bragg case. This directly reflectedwave contains information at the vicinity of the surface in the X-ray fan,since the wave has not penetrated so deep inside of the crystal to create thedirect reflection. When the transmitted wave encounters a defect in the Xray fan on the other hand, the Pendelloesung fringes are disturbed and the
disturbed diffracted wave propagates in the direction parallel to thediffracted wave vector toward the entr~nce surface again. This diffracted
wave, which may be said to be proportionally as strong as the diffracted
wave at the location of defect, can be oberved without disturbance of thedirectly reflected wave when the width of the entrance wave is adjusted as
to eliminate the overlapping of the directly reflected and the image earring
diffracted waves at the exit point because the directly reflected wave,
which does not contain information inside of the crystal gives rise to thebackground to the really requested wave from the inside. Silicon (220) net
plane was used for diffraction with the entrance slit of O.Olrnm wide toobserve defects just outside of the direct reflection. There could be seen
defects in the range of 3 extincion distances if expressed in terms ofthickness of crystal.

The receiving slit was arranged as it stopped the

direct reflection falling on the photographic plate.

1P07
THE GRAZING INCIDENCE DIFfRACTION OF X-RAYS WITH
WAVE FRONT AMPLITUDE PERIODICALLY VARYING ALONGTHE CRYSTAL ENTRANCE SURFACE (SYMMETRICAL LAUE
CASE)
A.P.Bezirganyan and S.E.Bezirganyan, Dep. of Solid State Physics,
Faculty of Physics, Yerevan State University, 375049 Yerevan-49,
Armenia.
The modem technology based on use of thin-layered materials with layer
thicknesses in nanometre ranges, e.g. in integrated circuits, X-ray mirrors
etc. Interfacial regions extending over a few monolayers can strongly
degrade device performance (see Forster et al.), especially as the thicknesses of performing elements become rather thin with fur therminiaturization of devices. If the device performing elements are deposited
periodically on the substrate, such layer is like a diffraction grating (DG).
The reflection (or transmission) function of DG may be used for the control
and monitoring of device surface elements quality.
With that end in view the following scheme is investigated: reflected from
DG X-ray wave field falls at grazing angles onto a single crystal (SC). The
reflecting net planes of SC are normal to entrance surface (symmetrical
Laue case).
DG has the following reflection (or transmission) function :g(x) = t(x) * u(x),where t(x) is rectangle unit impulse function with length L same as for DG;
u(x) is an arbitrary periodic normalized function with the period D; L=ND;
N is an integer; l<<KD; K is the wave number of incident X-ray planewave. The des cription of reflected from DG wave field is given by thequasi-optics approximation. The incident wave field may be presented by
the plane wave with wave front amplitude peri odically varying along theSC surface. The surface waves' origin conditions are also obtained for thisproblem.
Forster, A., Lange, J., Gerthsen, D., Dieker, C. & Luth, H. (1994). J. Phys.
D27, 175-180.

1P08
DENSITY OF THE p3 CLOSE PACKING OF IDENTICAL ELLIPSES
Takeo Matsumoto, Dept. of Earth Sciences, Faculty of Science, Kanazawa
University, Kakuma-machi, Kanazawa 920-11, Japan and Masaharu
Tanemura, The Institute of Statistical Mathematics, 4-6-7 Minami-Azabu,
Minato-ku, Tokyo 106, Japan
Concerning the systems of the densest packing of ellipses, Nowacki(1948) considered four plane groups: p2, c2mm, p2gg and p3lm. In allof these packings, every ellipse is in contact with 6 neighbour ellipses.
Matsumoto (1968) and Matsumoto and Nowacki (1966) have shown thatthe first two of the above densest packings of ellipses, p2 and c2mm,
always attain the maximum density, p=7t/2--13, which are derived from thedensest packing of circles, p6mm, by affine transformation. That of third ,p2gg, cannot exceed this maximum density. Tanemura and Matsumoto(1992) have shown that the density of p31m packing of ellipses, thefourth one of the above list, never exceeds the above maximum density p.
Griinbaum and Shephard (1987) showed four new types of periodic
patterns of ellipses, three of them, p3 and two p2gg, have 6 contacting
neighbours. We investigate the density of p3 packings of ellipses p(k, 8),
through numerical calculations and series expansions depending on k
(axial ratio of ellipses) and 8(tilt angle of ellipses). We obtain thefollowing equation as expanding form in terms of e=k-1 and e:p(k, 8) = rt/2--13 ( 1-3/32£2+ 1/128(17 -90sin28+ 240sin4e -160sin68)e3-3/4096( 411-1440sin28+ 3840sin48-2560sin68)e4} + 0(e5).
The following relations are obtained:p(k, 8) =p(k, -9) =p{k, 9+nrt/3) [n: an integer) andp(k, 9) =p{l/k, 9+rr/6).
For the tilt angle 9=nrr/3, the p3 packing coincides with the p31 m
packing, and if k=1, this corresponds to the densest p6mm packing of
circles. For values of k not equal to 1, the density of p3 packing of
ellipses is always smaller than p=7t/2-./3.
Reference:
Matsumoto, T. & Tanemura, M. (1995) Z. Krist. , 210, (in print).

1P09

THE USE OF THE DIFFRACTOMETER AT THE
AUSTRALIAN NATIONAL BEAMLINE AT THE PHOTON
FACTORY FOR UNUSUAL EXPERIMENTS
D.C. Creagh, Department of Physics, University College UNSW,Northcott Drive, Canberra ACT 2600, Australia
The Australian National Beamline at the Photon Factory was designed(Creagh (1992)) for operation on a bending magnet port, and can be usedeither with a Hart-type channel-cut monochromator with harmonic
rejection, or a Matsushita-type monochromator in which the first crystal
is of the Hart type and the second is capable of being bent sagittally toprovide typically, a gain of 20 in flux. Its range of operation is 5.5 to20 keV .
The diffractometer (BIGDIFF) was designed (Creagh and Wilkins(1989)) to be a versatile diffractometer capable of vacuum or helium
operation, with a choice of mode of operation ranging from powder
diffraction using imaging plates (camera mode) to triple axis counting
geometry. In its camera mode a Weissenberg screen can be fitted, andthe IP cassette can be moved in synchronism with the e-motion of thediffractometer. Because the Weissenberg motion exists a number of
unusual experiments, not possible in conventional diffractometer systems,
can be performed.
Experiments performed so far include a Diffraction Anomalous Fine
Structure (OAFS) (Creagh and Cookson (1995)) and the dynamical tensilestressing of polymer fibres. In its DAFS mode the motion of the IP
cassette is synchronized to the monochromator as it is scanned throughthe absorption edge of a particular element. The entire range ofdiffraction from the crystal, are recorded at the same time. As well the
fluorescent background can be analysed to give Fluorescent XAFS
information to complement the DAFS data. In situ electrochemistry
experiments, synchronizing the applied cell potential to the motion of the
IP cassette, are also planned in 1995.
This paper will describe progress made in the development of these newtechniques.
Cookson, D.J., Garrett, R.F., Foran, G.J., Creagh, D.C., and Wilkins, S.W.(l992)
Japanese Journal of Synchrotron Radiation, 6;1, 127·130.
Bamea, Z., Clapp, R., Creagh, D.C., Harada, J., Hashizume, H., Stephenson, A.
and Wilkins, S.W. (1989): Rev.Sci.lnstrum . 60, 2537-2540.
Creagh, D.C. and Cookson, D.J . (1995) Photon Factory Activity Repon, submitted.

1 P10IN- SITU STUDY OF STRUCTURAL DEFECTS IN MATERIALS USINGSVNCHROTRQN .RADIATION

G.N.Yeritsian. A.A.Sahakian, S.K.Nickogosian, Yerevan Physics Institute,
2 Alikhanian Brothers St., 375036, Yerevan, Armenia
The possibility of direct measurements is suggested by use of synchrotron
radiation with related experiments to study the atom displacement
phenomena in materials.
The displacement of an atom plays important role in the defect formationof materials. That's why several mechanisms of defect production are
discussed. The classic one is the elastic collision when energy of an atom
is greater than threshold for adiabatic displacement of the lattice host or
impurity atom.
Under certain conditions, the electronic excitation mechanism is more
efficient during subthreshold and even superthreshold processes. The
subthreshold defect formation probably is analyzed on the basis ofKlinger's impurity ionization theory.
This mechanism may be efficient:
1. when energy of Coulumb repulsion between the host and impurity atoms
is greater than threshold for adiabatic displacement
2. the time of the positive charge localization is greater than the atom
displacement time.
Some experimental results in this field were fairly optimistic. The
estimations showed high probability of this effect when using synchrotron
radiation: high intensity; sufficient time of positive charge localization ofionized host atoms; required energy for inner shell ionization of hostmaterial atom.
To our opinion the most sensitive experiment shall be applied to measurein - situ with high accuracy the displacement of an atom and thus point out
simple defects and clusters of desordered regions.
In other words the synchrotron radiation should be used as defectproduction source and measurement beam at the same time.

1P11

INVESTIGATIONS ON SOLID STATE PHYSICS AND
CRYSTALLOGRAPHY USING SYNCHROTRON RADIATION AT YEREVAN PHYSICS INSTITUTE
D.L. Egikian, Yerevan Physics Institute , Yerevan 375036, Armenia
At Yerevan Physics Institute the investigations on solid state physics
and crystallography using synchrotron radiation (SR) beams fromthe 6 Ge V electron accelerator are carried out. For these investigations Si, Ge, GaP, InP and other single crystals are used as the
samples. The following important results were obtained. The integral coefficient of reflection and other parameters for Si, Ge, GaP
single crystals were measured in wide range of wave-length including K-edge of Ge and Ga. The main diffractometrical parameters of"forbidden" (222) reflex for Si, Ge and their dependence on structural perfection of the samples were investigated. The method of thesingle crystal structural defect investigation with the depth variationof the layer from several up to few tens micrometers by monochromatic topography in different orders of reflection was developed. The
method for determination of surface and volume perfection degree ofcrystalline samples by means of measuring the widenning of collimeting slit image in SR beams diffracted by (n'+n) spectrometer wasdeveloped and studied in experiment. Several investigations werecarried out to develop the apparatus and measurement technique ofthe SR beams. All these results are observed in the paper.

1P12
RUffiN CONTRACT BEAMLINESBIOLOGY AT SPring-S

FOR

STRUCTURAL

H Iwasaki and RIKEN SR Structural Biology Research Group,

The

Institute of Physical and Chemical Research (RIKEN), Wako-shi , Saitama
351-01 , JAPANSPring-8 ~uper ~hoton ring-8GeV) is one of the largest high-brilliancesynchrotron radiation source placed at Harima in Hyogo Prefecture, about

IOOkm west of Osaka. The construction is in progress by JAERI-RIKEN
SPring-8 Project Team, and the first beam is foreseen in 1997. It has 61
beamlines in all, of which more than 30 will be "public" open to all
domestic and foreign scientists. At our Institute RIKEN, structural biology
is considered as one of the most important research fields, and two contract
beamlines for structural biology are now being designed and developed.
The first one is for protein crystallography (PX) and small-angle solution
scattering (SAXS). The X-ray sources are two undulators arranged
serially. The dichromatic SR, with energy from 6 to 14 keV, is branchedby a diamond beam splitter. It acts also as a first monochromator for the
SAXS experimental station, and the beam which goes through thebeamsplitter is guided to the PX station. The optical system for PX has
been optimized for multiwavelength anomalous diffraction (MAD) method
and includes a newly developed "trichromator" which enables us to collectthree kinds of data sets at three wavelengths quasisimultaneously for thesame protein crystal without changing the setting. The second one is fortime-resolved PX using Laue methods and for XAFS. The X-ray source isa bending magnet, and both white and monochromatic beam will be used.
The operation of these RIKEN contract beamlines will be started at theinitial stage of SPring-8.

1P13
THE RIO-CRYSTALLOGRAPHY (MIR-OAS) BEAMLINE AT THE
SPRING-8
N. Kamiya, T. Ueki, H. Iwasaki, The Institute of Physical and Chemical
Research (RIKEN), Hirosawa 2-1, Wako 351 -01, Japan, N. Tanaka,
Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology,
Nagatsuda, Midori-ku, Yokohama 226, Japan, and K. Miki, Departmentof Chemistry, Faculty of Science, Kyoto University, Sakyo-ku, Kyoto
606-01, Japan.
SPring-8 (Super Photon ring-8GeV) is a third-generation synchrotron
radiation facility of Japan, which is under construction by the JAERIRIKEN SPring-8 Project Team. The storage ring commissioning will bestarted early at 1997 . The Rio-Crystallography beamlinel) is constructed
for routine analyses of macromolecular crystallography by the multiple
isomorphous replacement method with optimized anomalous scattering(MIR-OAS). The beamline also focuses on data collections for small
crystals less than 100 Jlm or those for very large macromolecules such as
ribosomal particles and viruses. The light source of this beamline is an invacuum type undulator of magnetic periodicity of 3.2 em, which emits
highly brilliant X-rays in an energy range between 9 and 38 keY . The
highest power and power density of the undulator are 5 kW and 300
kW/mrad2 , respectively. To handle the tremendous power density, arotated-inclined double-crystal monochromator will be used. To focus thehigh energy X-rays up to 38 ke V, two super mirrors (Ovonic Synthetic
Materials Co.) will be installed to get quasi-isotropic and small beamprofile of about 100 Jlm at focal position. For recording the diffraction
patterns of sample crystals, a K-type goniostat and an imaging plate online detector will be used in the experimental station. The station further
includes an XAFS apparatus, which determines suitable values of X-ray
energy for the data collections with the heavy atom derivatives near its
L3 absorption edges, a cooling system for specimen and a softwaresystem dedicated to the MIR-OAS routine analysis.
1) N. Kamiya et al. (1995), Rev. Sci. /nstrum . 66, 1703-1705.

1 P14
ELECTRON DENSITY DISTRIBUTION IN PYRITE-TYPE MnS2
USINGSR
M. Ueki, N. lshizawa, Research Labpratory of Engineering Materials,
Tokyo Institute of Technology, Nagatsuta Yokohama 227, Japan, and F.
Marumo, Department of Earth Sciences, Nihon University , Setagaya
Tokyo 156, Japan
Pyrite-type structure consists of octahedrally coordinated M atoms and X2
dumbbell molecules. Stevens et al. (1979) carried out the population
analysis of low-spin Fe2+ in pyrite-type FeS2, stating that the calculated
excess electrons in dy orbital were possibly due to the interaction between
Fe and S. The low-spin transition elements such as Fe2+ show ananisotropic electron density distribution due to the enriched electrons in
dE orbital, which obscures the observation of the weak metal-ligand
interaction along the bond by the conventional Fourier method. The
present study has been carried out to detect such interaction on MnS2
containing Mn2+ cations of d5 electron configuration in the high-spinstate. The three-dimensional X-ray diffraction data of natural MnS2 wereobtained using the horizontal-type four-circle diffractometer at KEK
BL14A with SR of the 0.75 A wavelength. The least-squares refinement
employing atomic scattering factors of neutral atoms yielded the final
R!Rw value of 0.0119/0.0122 for
539 independent reflections in therange 28 <138°. The difference
Fourier map on the section including
Mn and S-S dumbbell is shown in the
figure with contour intervals of 0.1
eA -3. The positive residual peaks
with heights of 0.49 eA-3 around Mn
is supposed to be due to the bonding
interaction between dy orbital of Mn
and n:g* orbital of S22-, which has
been predicted from the bandcalculation in previous studies.

Stevens, E. D., Delucia, M. L. & Coppens, P.
(1980) Inorg. Chem. 19 813-820 .

Mn

1P15
SIZE DEPENDENCY OF THE c/a RATIO OF TETRAGONALBARIUM TITANATE MICRO-CRYSTALS USING SR
K. Suda, M. Kataoka, N. lshizawa, Research Laboratory of Engineering
Materials, Tokyo Institute of Technology. 4259, Nagatsuta, Midori-Ku,
Yokohama 226, and F. Marumo, Department of Earth Sciences, Nihon
University, 3-25-40 Sakurajosui, Setagaya-Ku, Tokyo 156, and K.
Ohsumi, National Laboratory for High Energy Physics (KEK), 1-1 Oho,
Tsukuba 305, JapanThe tetragonality of submicrometer-sized crystals of barium titanate,
BaTi03, has been investigated by the ultra-micro single-crystal X-ray
diffraction technique using synchrotron radiation at the beam line 4B of
the Photon Factory, KEK. Laue photographs were taken using the
Imaging Plate and processed on the DIP310SOR system. Size of thecrystal was measured using a scanning electron microscope after the SR
experiment. Conversion diameter of the crystal with anisotropic shape
was calculated assuming a sphere with the same volume. The c/a ratios
have been determined using the splitting of Laue spots due to the presenceof 90° domains of tetragonal form. They are 1.0072(2), 1.0098(3) and
1.0106(6) for crystals with conversion diameters of 0.56, 1.32 and 10!J.m, respectively. The c/a ratios of the 1.32 and 10 IJ.m crystals areapproximately the same as that of the bulk crystal, while it is significantly
small for the 0.56 IJ.m crystal. The rapid decrease of the c/a ratio can be
explained based on the effect of depolarization. No clear splitting wasobserved for the crystal with conversion diameters of 0.32 and 0.25 !J.m .
The disappearance of splitting can be interpreted in several ways; one isthat the crystal becomes mono-domain with cubic or tetragonal symmetry.
and the other is that the crystal is still composed of 180° domains oftetragonal form. The structure analysis using the integral intensities
measured for the 0.32 1-1m crystal will contribute to solve this problem.

1 P16
STRUCTURE ANALYSIS OF CaYAI04 SMALL CRYSTALUSING SRK. Morita , K . Suda, N. Ishizawa, Research Laboratory of Engineering
Materials, Tokyo Institute of Technology , Nagatsuta Yokohama 227,
Japan, and N. Kodama, Tosoh Cooperation, Hayakawa, Ayase 252, andM. Yamaga, Department of Physics, Gifu University, Gifu 501-11 , Japan
Chromium-doped CaY Al04 is expected to exhibit a spectral hole-burning
at low temperatures. The present study has been undertaken to obtain adetailed knowledge about the host structure of the K2NiF4-type CaY Al04.
Single crystals were grown by the Czochralski technique in an inert atmosphere. Three dimensional diffraction data were collected from a crystal
with dimensions of 12xl2x6 J,Am3 using a vertical-type four-circle diffractometer at the beam line 14A of the Photon Factory, KEK. The wavelength of 0.75 A, which is 508 eV below the Y K edge, was selected to
avoid the contamination due to the fluorescence of Yttrium in the com. pound and to reduce the absorption effect. X-rays were focused using a
toroidal mirror. Crystal data are; tetragonal 14/mmm, a=3 .6437(1) A,
c=ll.8682(3) A, Z=2, J.A=53.6 cm-1. In all 426 independent reflections
with IFl ~ 3a{IF]) were obtained from 2648 measured reflections in therange 28 ~ 138° . The least-squares refinement gave a final R value of
0.011 employing anisotropic temperature factors for all atoms. No improvement in the R factor, nor any significant alteration in the residual
electron density distribution was observed when the secondary extinction
correction was applied in the least-squares procedure. The minimum yvalue was 0.994 for the 200 strongest reflection when the correction was
included. It was concluded that the secondary extinction was negligibly
reduced in this experiment. Presence of excess Ca and deficient Y atoms
from the nominal composition were detected, generating a small amountof oxygen vacancies at the apical 0(2) site of the Al06 octahedron. The
AI and Ca atoms adjacent to the 0(2) vacancy are supposed to be displaced along the c axis from their ideal positions. A strong anisotropy of
the thermal parameters of oxygen atoms indicated a conspicuous librationa! vibration of Al06 octahedra around axes in the basal plane, or akind of disordering accompanying the presence of oxygen vacancy. All
these features provide a clue for understanding the unusual behavior of
Cr3+ in CaY AI04 observed by the electron paramagnetic resonance study.

1P17
SINGLE CRYSTAL X-RAY DIFFRACTION AND EXAFSANALYSISOF(Yo.2Zro.s)Ot.9
FLUORITE-TYPE
COMPOUND
Y. Matsushima, M. Hayashi, K. Suda, N. Ishizawa, Research Laboratoryof Engineering Materials, Tokyo Institute of Technology, Nagatsuta,
Midori, Yokohama 226, Japan, and H. Oyanagi, ElectrotechnicalLaboratory, Umezono, Tsukuba 305, Japan
Determination of the local structure awund a solute atom in a hoststructure provides important information on the understanding of thephysical properties of the solid solution. Positional disorder of constituent
atoms in (Y 0.2Zro.s)01.9, a member of the fluorite-type Zr02-Y 203
solid solution, has been investigated by the single crystal X-ray
diffraction technique and by the EXAFS analysis. Crystals were grown bymelting a calcined rod made of Y203 and Zr02 powders, using the
focused Y AG laser beam. A transparent part of the melt-quench productwas ground into a sphere of 35 f.1m in diameter for the diffraction
experiment using SR. Intensity data were measured with the four-circle
diffractometer at the beam line 14A, KEK-PF.
The wavelengths
employed were 0.75 and 0.7281 A (10 eV below the Y Kedge). EXAFS
spectra of the powdered sample were measured near the Y K and Zr K
A provisionaledges employing the transmission mode at 14A.
refinement using 83 independent reflections out of 2278 measured
reflections for the 0.75 A data set converged with R/Rw factors of
0.0277/0.0263 assuming the ideal fluorite model which consists of Y andZr atoms at origin and oxygens at 1/4,1/4,1/4. The R/Rw factors became
0.0137/0.0172 assuming a more complicated structural model similar tothat adopted for Y3Ta07 fluorite-type compound by Tanaka et al (1995).
This model consists of Zr atoms at origin and Y atoms at x,x,x with
x=0.030(1) and half of the 0 atoms at 1/4,1/4,1/4, and the rest at
1/4,1/4,z with z:0.320(2). The mean Y-0 and Zr-0 distances calculated
from this model agreed well with the EXAFS results.
Tanaka, T ., Ishizawa, N., Yoshimura, M., Marumo, F. & Oyanagi, F.
(1995) J. Solid State Chern., 114, 79-87.

1P18

STRUCTURAL STUDY ON THE DEFECT-PEROVSKITETYPE COMPOUNDS Lat 13MOJ (M=Ta,Nb)
K. Tanabe, K. Suda, N. Ishizawa, J-H. Sohn and M. Itoh, ReseachLaboratory of Engineering Materials, Tokyo Institute of Technology,
4259, Nagatsuta, Midori-ku, Yokohama 226, Japan
Double-layered defect-perovskite-type compounds La 113 M0 3 (M::Ta,Nb)
have ordered vacancies at every other A sites along the c axis of AB03
perovskite. From the view of material science, they are promising host
crystals for the Li ion intercalation. Single crystal diffraction study has
been carried out to verify the structural details relating to their physicalproperties. Crystals were grown by the floating zone method. Crystal dataof La 113 Ta0 3 are a::b::3.9163(1) A, c::7.9138(4) A, Z::2, SG::P4/mmm.
Three dimensional diffraction data were collected using the horizontaltype four-circle diffractometer at the beam line 14A of KEK PF with).. ::0.7 A. The specimen has a spherical shape with diameter of 45 fl. m.
The SR data were compared with those taken by the rotating anode fourcircle diffractometer using AgKa . The specimen used for the Ag
experiment was also spherical with diameter of 93 fl. m. The conventional
least-squares refinement gave a converged R value for the SR data of
0.026 using 800 independent reflections in the range sine 1).. <1.35 while
0.015 for the Ag data set using 249 reflections in the range sine/).. <0.90.
The split atom models for 0(2) and 0(3) were employed after Iyer et a!
(1967). No evidence was found for the presence of La atoms at the vacantsites at z::O.S, which might take place at higher temperatures. A
superstructure with doubled a and b dimensions was observed forLav 3 Nb0 3 from the SR experiment. The superstructure was hardly
detectable from the Ag experiment. The cell dimensions are a::7.8199(3),b::7.8394(3) and c::7.9119(3) A. The deviation from the tetragonal
symmetry was obvious.

lyer, P. N. & Smith, A. J. (1967). Acta Cryst. 23 , 740-746.

1P19
X-RAY DIFFUSE SCATTERING STUDY OF MAGNETITE BY
THE VALENCE-DIFFERENCE CONTRAST METHOD
Tal<eshi Toyoda and Satoshi Sasaki, Research Laboratory of Engineering
Materials, Tokyo Instirute of Technology, Nagatsuta, Midori-ku Yokohama, 226, Japan,
and Masahiko Tanaka, Photon Factory, National Laboratory for High Energy
Physics, Oho, Tsukuba 305, Japan.
Magnetite is a mixed valence compound of an inverse-spinel type,[Fe3+)A[Fe2+Fe3+)BQ4 . The high electronic conductivity suggests thecontinuous interchange of the electrons between Fe2+ and Fe3+ at the Bsites above the Verwey transition (T.
125 K), while the hopping isfrozen as charge ordering below Tv· Even above Tv. anomalous diffuse
streaks were observed in electron and neutron scattering [1,2] .
It is recognized that a chemical shift of XANES spectrum occurs
among different valence states. The anomalous scattering effect related
to the chemical shift promises the possibility of distinguishing different
ions of the same elements in a mixed valence crystal by selecting awavelength to give the different f' values [3]. In this study to use
synchrotron X-rays, valence fluctuations of ferrous and ferric ions in theB site are examined in terms of diffuse scattering just above Tv .
X-ray experiments were performed on synthetic, and partly natural,
single crystals with vertical-type four-circle diffractometer at PF-BLlOA. The synthetic crystals were kindly provided by H. Kawata and S.
Todo.
Intensity measurements in various 2-D reciprocal planes weremade around the 400, 800, 440, 221, and 444-type reflections at 130,200, and 300 K. The wavelength A. = 1.7421 A was chosen with the f'difference of 1.6 between Fe2+ and Fe3+. Weak diffuse streaks wereobserved in the disk-like or cross-like shape except 221, having somedifference from the neutron scattering results at 130K. The diffuse
streaks are possibly occurred by local charge ordering or local lattice
distortion. Modeling and further experiments are in progress.

=[I) Chiba, K., Suzuki, K. & Chikazumi, S. (1975) J. Phys. Soc. Jpn 39, 839-840.

[2) Shapiro, S.M., lizumi, M. & Shirane, G. (1976) Phys . Rev. B 14, 200-207.
[3) Sasaki, S. (1995) Rev. Sci. Instrum . 66, 1573-1576.

1P20
Structural changes of (Pb,Cu)SrLaCuOs+b on oxygen introduction into block layers
N.R. Khasanova•, F. Izumi•, M. Shidab, B. Chakoumakos<, E . Ohshimab, M. Kikuchib
andY . Syonob• National Institute for Research in Inorganic Materials, 1-1 Namiki, Tsukuba 305, Japanb Institute for Materials Research, Tohoku University, Katahira, Aoba-ku, Sendai 980-77 ,Japan
c Solid State Division, Oak Ridge National Laboratory, Oak, Ridge , TN 378311-6393,

USA

The crystal structures of superconducting (Pb,Cu)SrLaCuOs+o with different oxygen
contents (8 = 0.03 and 0.13) have been studied by neutron powder diffraction. The fully
oxidized sample with 8 = 0.13 was prepared by calcinating a starting mixture at 800°C in
air, cooling slowly and heating at !0!0°C in 02.

Removing extra oxygen in. an

atmosphere of N2 and subsequent quenching raised the superconducting transition
temperature from 27 K (8 = 0.03) to 36 K (8 = 0.13). The neutron diffraction data of thetwo samples were measured on the HB-4 powder diffractometer at HFIR and analyzed by
the Rietveld method using space group P4/mmm (K wei et at., 1991 ). Oxygen atoms inthe (Pb,Cu)O layer at z = 0 were split into four pieces at a 4n site (x, 1/2, 0 ; x = 0.31). In
the fully oxidized sample, the 2f site (0, 1/2, 0) in the (Pb,Cu)O layer was slightly
occupied by excess oxygen.

On the other hand, this site proved to be vacant in thedeoxidized sample. Possible models of atomic arrangements in the (Pb,Cu)O layer wereconsidered in our structure refinements .

The resulting values of isotropic thermal

parameters, B, indicate that atoms in the (Pb,Cu)O layer and apical oxygen are
disordered to a greater extent in the fully oxidized sample than in the deoxidized sample.
The oxidation-reduction behavior of Pb and Cu in this system and its effect on Tc will be
discussed on the basis of crystal data obtained in this study.

Kwei, G.H., Canfield, P.C. , Fisk , Z, Thompson, J.D, & Yon Dreele, R.B. (1991 ).
Physica C 176, 57-63 .

1 P21
NEUTRON DIFFRACTION STUDY OF THE IMPROVED CHEMICALSTABILITY OF CATION SUBSTITUTED '123 1 SUPERCONDUCTOR
Yo.6Cao.4Ba1.6La0.4cu3°7-d
A. Sequeira and H. Rajagopal, Solid State Physics
Division, and R. Ganguly and J. v. Yakhmi, Chemistry
Division, Bhabha Atomic Research Centre, BOMBAY - 400085,
India
It has been shown recently that appropriate cation
substitutions such as Y 1 _yC~yBa 2 ~yLaycu 3 o 7 _d not only
help to keep the Tc abov~ B"OK, ~ut also relieve thetensile stresses wh1ch exist in the parent YBa 2 cu 3 o 7compound in the Ba-0 and cu ( 2) o 2 layers due to bondIn fact, an othorhombic to tetragonallength mismatch.
transition occurs at y :::: 0. 4 and this particularcomposition (title compound) has been demonstrated to beremarkably corrosion resistant and stable against
reaction with water for upto 150 days as against
decomposition of the unsubstituted sample within 2 days
We have,of soaking in water (Zhou et al, 1994).
therefore, carried out a comparative structure analysesof the tetragonal (P4jmmmJ Yo 6 ca 0 . 4 Bal. 6 La 0 . 4 cu 3o7-dand orthorhomb1c YBa 2 cu 3 o 7 _d (Tc=93K) by
C~c=79K)
R1etveld analyses of powder neutron data recorded at room
The composition of the title
temperature ("A= 1.216 A).
is ·refinement
after
estimatedcompoundMajor diffe:ences
Yo. 59 ca 0 . 41 Ba 1 . 68 La 0 . 32 cu 3 o 6 . 95 .
observed between the two samples are: a sl1ghtly
shortened apical Cu(1)-0(4) bond(l.B9BA) and an elongatedCu(2)-0(4) bond(2.25BA) plus a slightly reduced puckeringof the Cu(2)-0(2) planes for the title compound,indicating a reduced stress in the perovskite latticewhich is likely to make the cation-substituted compound
more stable chemically . The results will be discussed indetail.
Zhou et al (1994) Jour.Am.Chem.Soc . 116, preprint.

1P22
THE INVERSE PROBLEM IN MULTIPLE SMALL-ANGLE SCATTERING
S. Mazumder and ~ •. .. St;!qUt;li~-~' Solid State Physics Division,
Bhabha Atomic Researcn centre, Trombay, Bombay-400085
Small Angle Scattering data from many materials are affectedby multiple scattering more often than it is normallyconceived.
The presence of multiple scattering is indicatedby the invalidity of the functional invariance property ofthe observed scattering profile with variation of any of theexperimental parameters like thickness of the sample, wave
length of the probing radiation and contrast of theinhomogeneities in the sample.
The inverse problem in
multiple scattering involves extraction of single scatteringprofile from scatt.ering data affected by multiple scattering.
The inverse problem in conventional small-angle scattering
deals with extraction of real space structural information
like particle size distribution (PSD) of the inhomogeneities
from scattering profiles.
Recently, we have developed an algorithm to extract single
scattering profile from scattering data affected by multiple
scattering. The algorithm is based on the theory on multiple
small angle scattering as outlined in the review article(Mazumder & Sequeira, 1992).
It uses the findings that functionality of multiple
scattering profile depends on thickness, wave length,
contrast etc., while the functionality of single scatteringprofile is independent of all these factors.
The algorithm
is based on the extraction of scattering mean free path fromat least two sets of scattering data recorded either byvarying the sample thickness or by changing the wavelength.
The input data sets can be used both in the absolute as wellas in relative scale but the output single scattering profile
can be obtained in absolute scale.
In the limiting case when the thickness of the sample is verylarge in comparison to the scattering mean free path, it ispossible to extract information like
PSD
from multiple
scattering profile itself, without going for extraction of
single scattering profile, either
by invoking variational
technique like maximum entropy or assumingthat particle
size distributio~ has some well-defined functionality like
log-normal, Gaussian etc.
The algorithm has been applied for analysis of scattering
data from some alumina based system and some cements.
Mazumder, S.
159.

& Sequeira, A.(l992). Pramana, J.Phys.

38, 95-

1P23

8AIB :fzoa 8116 llloellar Solut.icma in Pze-oeof Aai.Des mad ~iaa Salta

Sanjeev Kuaar+, V.K.Aawal*, P.S.Goyal* and Kabir-ud-Din++ Department of Cheaiatey, AHU, Alisarh 202 002, India
Solid State Physics Division, BARC, Boabay 408 085, India*

This paper reports the effect of addition of amines
6, 6, 7) and .-oniua halides (1184][; ll =( CB3CB2 >a-NB2; 111
Cl, Br, I) on ~ powt.h of aodlu. clocleoFl aalpbate (SD6)aioe11ee ae studied uai~ . . .11 ~1e neutron scatterins
surfactant
The
aeasureaents.
viscosity
and(SANS)
concentration was kept fixed <= 0.3H) and the additive
0.0 to 0.1H for amines and x
concentration was varied ( x= 0.0 to 1.6H for amoniua halides). The SANS experiaenta
were carried out uains SANS apectroaeter at Cirua reactor,
Trombay and the viscosity aeaaureaenta were aade usins a
Brookfield cone/plate viscoaeter.

==

SANS experiments on SDS/AIIIinea solutions show thatmicellar sizes are quite sensitive to addition of n-aaines.
For example, we find that the c/a for ellipsoidal aioellea
in pure SDS solution increases fro•b- 18A, c- 36A)(a7) concentration ia
2.0 to 5.0 aa the n-octylamine (aincreased from 0.0 to 0.085H [1]. We further find that thestructures of iaoviscoua SDB/Aaines solutions, aa obtainedby addinl different amounts of the three aminea are not
identical .

==The viscosity of SDS solutions is leas sensitive toaddition of aamoniUIII halides as coapared to that for
addition of amines. SANS experiments on (0.3H SDS + 0.1H
NH4X) solution show that there is only a aaall increase inmicellar aize on addition of amaonium halide. It ia aeenthat the SANS distribution for the above solutions are
independent of the halide ion .
[1]. Sanjeev Kumar, V.K.Aswal, B.N.Sinsh, P.S.Goyal andKabir-ud-Din, LaD~auir 1994, 10, 4069

1P24

MICROPHASE SEPARATION IN ADSORBED PARAFFINMIXTURES
E.P. Gilbert, P.A. Reynolds and J.W. White
Research School of Chemistry
The Australian National University
Canberra. ACT 0200. AUSTRALIA.
When equimolar mixtures of normal C3 o and C3 6paraffin hydrocarbons are quenched from the melt toroom temperature, the mixed system undergoes solidstate phase separation into lamellar phases . In this'bulk' system the microphase separation is essentiallylongitudinal, the molecules slipping along their longaxes to separate into lamellar components which
neutron scattering can easily detect when isotopic
substitution of one of the components is employed.
Our STM studies have shown that when the same
unlabelled hydrocarbons are spread onto a clean
graphite surface from a non-polar solvent, only thelonger chain is imaged. This indicates a strong demixing
enthalpy in the two-dimensional layer.
We have investigated the microphase separation process
in which the two-component protonated/deuterated meltis quenched inside the gallery structures present in
exfoliated graphite. In this system, it is possible forphase separation not only to occur in the longitudinal
direction, as in the 'bulk' , but also in a transverse
direction due to the graphite surface forces. We report
here results for the modified system.

1P25

VANADIUM AND VANADIUM-BEARING MICAS
G.K.Bekenova, Institute of Geological Sciences NAS RK, Almaty,
480100, Kazakhstan

The all-round mineralogical study of vanadium-bearing di-octahedral
micas from the Cambrian carbonaceous-cherty formation of the Bolshoi
Karatau Range (South Kazakhstan) allows to establish 4 basic groups:
chernykhite (V 2 0 3+V20 4 - 23-26% ), Ba-roscoelite (V 20 3+V20 5 - 1225%), vanadium-bearing muscovite and phengite (V 20 3 to 5%) andsecondary mica-V4+-Ba-phengite (V 20 3 << V20 4 - 6-8%). In the lastmentioned group the tetravalent vanadium locates within tetrahedral
positions in the crystal structure. The mineralogical description, physicalproperties, chemical compositions and structural data of studied micas arepresented. The comparison of the chemical compositions, optical properties
and structural data of the micas from South Kazakhstan and also ones ofother V -micas from different regions throughout the world is given. The
diagram of the dependence of the unit cell parameter

b (A)

from

vanadium content is shown. The value of b (A) increases with increasing
vanadium content in the structure.

1P26

THE CRYSTAL STRUCTURES OF DEHYDRATED FUU.Y Cd''-EXCHANGED ZEOLITE X AND OFITS CARBON MONOXIDE SORPTION COMPLEX
Se Bok Jang, Jeong Hwa Kwon, Un Sik Kim, and Y.aruLJiim, Department of Chemistry, Pusan National
University, Pusan 609-735, Korea, and Karl Seff, Department of Chemistry, University of Hawaii, Honolulu,
Hawaii 96822, U. S. A.

Large single crystals (s!Dichiometry Na<nSiunAiszO,..) of sodium zeolite X used in this work wereprepared in St. Petersburg, Russia.' Each of two single crystals, a colorless octahedron about 0.2
rrun in cross-section was lodged in a fine Pyrex capillary and exchanged by flow methods using
an exchange solution of Cci(NO,)z and Cd(O,CCH.,)z in the mole ratio of 1 : I with !Dtal
concenlration of 0.05 M. Each crystal was dehydrated at 450 •c under a constant pressure of 2 x
10-6 Torr for 48 h. To prepare the carbon monoxide complex, one crystal (crystal 2) was treatedwith 100 Torr of zeolitically dried carbon monoxide gas for 1 h at 21(1) •c. Diffraction data werecollected with an au!Dmated Enraf-Nonius four-circle computer controlled CAD-4 diffrac!Dmeterusing Mo Ka radiation. Their structures were refined to the fmal error indiecs, R1 = 0.055
and Rw = O.Cf17 with 546 reflections and R, = 0.063 and Rw = 0.065 with 523 reflections,
respectively, for which I > 3 <1 (!).
Crystal Datn: (1) ect..Si,ooAI<n(),.., cubic, space group Fd 3 (No. 221)a 24.935(1) A.
(2) Cd.;SiunAJ.,0,...28CO, cubic, space group Fd 3 (No. 221)a 24.905(1) A.
In the crystal structure of dehydrated Cd.;-X, Cd2' ions are located at the two different sites of2high occupancy. The Cd2 ' ions at Cd(l) lie at site I, the center of the double six-oxygen ring.
This sixteen-fold position is fully occupied (Cd(l)-0(3) = 2.35(1) A , 0(3)-Cd(2)-0(3) = 90.4(4)0 ).
The Cd(2) position is at site IJ in the supercage. Thirty Cd'' ions at Cd(2) nearly fill thethirty-twofold site II. The Cd(2)-0(2) distance, 2.16(1) A, is shorter than the sum of the radii of
Cd2 ' and 0 2 - , 0.97 A + 1.32 A = 2.29 A 3, a consequence of the low coordination number, three, at
this site. In the structure of a carbon monoxide sorption complex of dehydrated Cd .. - X,
twenty-eight carbon monoxide molecules are found per unit cell. Cd2 ' ions are found at threedifferent crystallographic sites. Thirteen Cd2 ' ions at Cd(l) occupy the sixteenfold site I in thecenters of a double six-oxygen rings and each coordinates tD three framework oxygens at 2.37(1)
A. The Cd(2) position is on a threefold axis in the sodalite unit opposite the double six- ring atsite ( This thirty-twofold position is occupied by only five Cd2' ions. Each coordinates at 2.500)
A tD three 0(3) framework oxygens, and is recessed ca. 1.60(1) A in!D the sodalite caviL)' fromtheir plane. To coordinate tD carbon monoxide, each of twenty-eight Cd2 ' ions at Cd(3) has moved
0.14 A along its threefold axis toward the center of the supercage and away from their triads of2three 0(2) oxygen tD a more tetrahedral coordination environment. Each Cd ' ion coordinates tD
2three framework 0(2) oxygens at 2.16(1) A. The 0(2)-Cd ' -0(2) bond angle changed from thenear trigonal planar value of 119.2(5)" in dehydrated ecto.- X tD 117.7(4)" in the carbon monoxide
complex. The C-0 distance is 1.36(4) A and the Cd-C-0 angle is 180(3)".
I. Bogomolov, V. N., Petranovski, V. P. (1986). Zeolites, 6, 418-419.
2. Kim, Y.; Han, Y. W., Seff, K. (1993). ]. Phys. Olem. 97, 1:1$3-126&1.
3. Handbook c( Olemistry and Physics, 70th ed. The Chemical Rubber Co.
Cleveland, Ohio, 1989/ 1990, p. F-187.

1P27

Structural investigation of high- and low-symmetry
vesuvianite
Makjo Ohkawa and Setsuo Takeno, Department of Earth and Planetary
Systems Science, Faculty of Science, Hiroshima University, HigashiHiroshima 724, Japan, and Akira Yoshiasa, Department of Earth andSpace Science, Faculty of Science, Osaka University, 1-16
Machikaneyama, Toyonaka, Osaka 560, Japan

Vesuvianite (idocrase) is a well-known rock-forming mineral withcomplex crystal chemistry and structure. The crystal structure ofvesuvianite is related to that of grossular garnet. In fact, the two minerals
often coexist intimately in nature. High-syrrunetry (P4/nnc) vesuvianite
occurs in metamorphic calc-silicate rocks mostly in skarn, and formed athigh temperatures. Low-symmetry (non-P4/nnc) vesuvianite occurs inrodingites, in veins found in mafic rocks and serpentinites and rarely inmetamorphic calc-silicate rocks in which it formed at relatively low
temperatures during retrogressive metamorphism.
The crystal structures of six high- and four low-symmetry vesuvianites
were determined by single-crystal X-ray diffraction method. The
structure refinements were carried out in the space group P4/nnc, P4/n
and P4nc, respectively. 3.1-8.2% of R indices were obtained.
Two types of possible ordered arrangements (P41n and P4nc) aredetermined. The satisfaction of the local charge balance on 0( 10) anions
requires alternate occupancy of oxygen and hydroxyl with an associatedhydrogen bond and ordering sequences of cations.
The high-symmetry vesuvianite can contain cr ions preferentiallyoccupying the 0(10) site that is split into two sites; one is occupied by cr
and the other by F .
Non Cl-bearing high-symmetry one indicate an additional tetrahedrally
coordinated cation site probably be occupied by AJ 3+.

1P28
SYNTHESIS AND CHARACTERIZATION OF ALKALI-METAL TIN(IV)
ARSENATES: ASnOAs04 (A = K and Rb), CszSn3As6022 and CsSn 2 As30 12

Kuan-Jiuh Lin

andKwang-Hwa Lii,

Institute of Chemistry, Academia

Sinica, Taipei, Taiwan, R.O.C.

Materials containing octahedral MIV06 and tetrahedral xvo4 groups are ofinterest because of their potentially useful physical properties. For examples,
KTiOP04 has been recognized as an outstanding nonlinear optical crystal for
frequency conversion; NaTh(P04 ) 3 belongs to the NASICON family ofcompounds which exhibit fast ion conduction and low thermal expansion. In viewof the technological interest in these compounds, we are currently making efforts
to synthesize other new phases in the A1-M1v-Xv-O (X= P, As) systems. To ourknowledge, very few compounds are known in the ternary tin arsenate phasespace. This poster reports the results of our exploratory synthesis using a flux
method and single-crystal X-ray structures of four arsenates, KSnOAs04 ,RbSnOAs04, Cs2Sn3As6022 and CsSn2As3012·
Both KSn0As04 and RbSn0As04 are isostructural with KTiOP04. The
oxygen framework for both tin compounds approximate very closely to acentrosymmetric arrangement, as indicated from the . analysis of atomic
coordinates. RbSnOAs04 has a powder SHG signal about the same magnitude asthat of quartz. Cs2Sn3As 60 22 adopts a new structure. Its three-dimensionalframework consists of comer-sharing Sn06 octahedra, As04 terahedra and As201
groups, forming 12-sided tunnels in which the cs· cations are located.
CsSn2As 30 12 has a monoclinically distorted NASICON-type structure.
Crystal data: KSn0As04, Pnah a= 13406(3) A, b = 6.678(1) A, c = 10.921(2)A, Z = 8, R = 0.034; RbSnOAs04, Pna2 1 , a= 13.567(3) A, b = 6.791(1) A c =10.891(2) A, Z = 8, R = 0.035; Cs2Sn 3AS60 22 , Pi1l n, a= 10.465(1) A, b = 13 .198(2)A, c = 15.623(2) A, p = 94.80(1) Z = 8, R = 0.028; CsSn2As3012 , P2/c, a=
10.733(4) A, b = 10.275(3) A, c = 9!267(4) A, p = 93 .09(4) Z = 4, R =-0 .031 .
0

,

0

,

1P29
CRYSTAL STRUCTURE STUDIES OF CeAI03 BY SYNCHROTRON RADIATION
Masahiko TANAKA'>, Hiroyuki HORIUCHI 2>, Toetsu SHISHID01>and Tsuguo FUKUDAl>I) Photon Factory, National Laboratory for High Energy Physics. Oho, Tsukuba, Ibaraki 305,2) Mineralogical Institute, Graduate School of Science, University of Tokyo,7-3-l
Japan.
Hongo, Bunkyo-ku, Tokyo 113, Japan. 3) Institute for Materials Research, Tohoku University,
Katahira, Aoba-ku, Sendai, Miyagi 980, Japan.

CeAJ03 crystallizes in perovskite-type structure, and its crystal system has
been reported to be tetragonal or trigonal. Tanaka et a!. [I] recently reported
the crystal structure with tetragonal lattice of atol=ato2=3 .7669(9) andcto=3. 7967(7)A. The electron distribution of oxygen atoms in its structure
was remarkably deviated from spherical distribution, and they discussed that
it would be the result of an averaged electron distribution over multiplied
unit cells. Since the superlattice reflections have not been observed bymeans of single-crystal and powder X-ray diffractometers with shield tube
X-ray sources, diffraction intensities caused by the multiplied unit cellshould be very weak if they exist. So we performed single crystal X-ray
diffraction experiments applying synchrotron radiation X-ray sources using
crystals which are the same samples as those used by Tanaka et a!. [I] .
Experiments were done using a vertical type 4-circle diffractometer at BL. 1OA, Photon Factory, National Laboratory for High Energy Physics. Since
we could observe superlattice reflections corresponding to the unit cell with
2 x atol, 2 x ato2 and 2 x cto by peak hunting on a single crystal
diffractometer, we asswned a new lattice with the above unit cell andmeasured all reflection intensities in the range of -7<h, k, 1<7, 0< 2 e<26.
Where atol, ato2 and cto are lattice vectors for original tetragonal lattice
vectors by Tanaka et a!.. As a result, the crystal was found to be tetragonalwith lattice of atl=atol-ato2, at2=atol+ato2 and ct=2 x cto. Where,
atl=at2=5 .3757 and ct=7 .6672A. Laue symmetry is tetragonal, 4/mmm,
with systematic absences of h+k+l=2n+ 1. By assuming the space group
14/mcm, the magnitude of the structure factors for weak reflections with
1=2n+ 1 could successfully explain by the displacement of oxygen atoms.
However, on the difference-Fourier map, weak but residual electron
distributions which were caused by the deviation from the ideal positions of
Ce were observed around the Ce atoms. As a conclusion, the actual unit cellof CeA10 3 is a multiplied lattice of original tetragonal lattice, and it might
have still some problems for the structure analysis due to twinning in which
reciprocal lattice points corresponding to each domain are superposed eachother.
[1] Tan~a et al.,Jour.AJ!oys and Compounds, 192, 87-89(1993)

1P31

SODIUM MAGNESIOSILICATES WITH TilE CARNEGIEITE,
OR "STUFFED CRISTOBALITE", STRUCTURE
C. J. Lobo, S. Schmid, J. G. Thompson and R. L. Withers, Research
School of Chelnistry, The Australian National University, Canberra ACT
0200, Australia, and R. Stranger, Department of Chemistry, The
Faculties, The Australian National University, Canberra ACT 0200,
Australia.

Alkali aluminosilicates and alkali magnes~osilicates with structures related
to the mineral camegieite, which has the "stuffed cristobalite" structure(Buerger, 1954), are of interest because of their property of ionic
conductivity at elevated temperatures. Previous !ltudies on sodium
magnesiosilicates with this structure-type reported various andcontradictory compositions, unit cells and space group symmetries for thephases they produced.
A systematic study of the pseudo-binary system Si0z-NaMgo.sSio.s02
using various reactive reagents as starting materials, including
magnesiosilicate minerals, has identified two crystalline phases with the"stuffed cristobalite" structure type. At high temperatures, i.e. ~ 800°C,
the stable phase has a stoichiometry close to Nao.9Mgo.45Sio.ss02 with an
orthorhombic unit cell, a= 7.067(3), b = 10.855(6), c = 5.286(3) A. At
lower temperatures, i.e. between about 500 and 800°C, a higher
symmetry disordered phase occurs as a narrow solid solution with atetragonal unit cell of typical dimensions a= 10.497(2), c = 14.334(5) A.
The crystal structures of these two phases have been refined from X-ray
powder diffraction data using the Rietveld method. The number ofdegrees of freedom required in each case was minimised by using a
modulated structure approach to the structural model refinement (seeWithers and Thompson, 1993).

Buerger, M.J. (1954) A mer. Mineral. 39, 600-614.
Withers, R.L. & Thompson, J.G . (1993) Acta Cryst. B49, 614-626.

1P32

CATION DISTRIBUTION AND CRYSTAL CHEMISTRY IN
Y3Ais-xGax012 (O~xs:S) GARNET SOLID-SOLUTIONS
A.Nakatsuka, A.Yoshiasa and T.Yamanaka, Faculty of Science,
Osaka University, Toyonaka, Osaka 560, JapanThe large single crystals of garnet solid-solutions (x=O.O, 1.0, 2.0,
3.0, 4.0 and 5.0) were grown using PbF2 flux . These crystal
structures were refined by single-crystal X-ray diffraction analyses
using high power X-ray source. Cation distributions and anisotropic
thermal parameters in the crystal structure were examined in detail.
The larger Ga3+ ions occupy preferentially the 4-coordinated site in
the all composition range , whereas the smaller Al3+ ions occupy 6coordinated site. The tendency of site preference of Ga3+ ions ismost probably caused by the covalency of the ions and geometricrestriction . The precise examination of polyhedral distribution andatomic thermal motion also revealed the enhancement of the cationcation interaction is caused by both the geometric restriction due tothe symmetry and the properties of chemical bonding. Moreover,the lattice constants are smaller than those calculated based on
Vegard's law. The deviation from the Vegard's law is also reported in
the system of Grosular and Hydro-grosular.

Obtained crystal data: cubic, space group la3d (No.230)
at x=O.O

a=12.0062(5)A

at x=2.0

a=12.0926(9)A

at x=3.0

a=12.1552(6)A

at x=4.0

a=12.2123(8)A

at x=5.0

a=12.2730(1 O)A1P33
TilE CRYSTAL STRUCTURE OF VESUVIANITES FROM TAIWAN
S. C. Yu, J. S. Lee and C. P. Wang, Department of Earth Sciences,
National Cheng Kung University, Tainan, Taiwan 70101, R.O.C.
The crystal structure of two vesuvianites in rodingite from theChinshuichi area, Yuli, Taiwan, were determined from data collected on a
Nonius CAD-4 four-circle diffractometer. Two samples are brown andgreen in color, respectively.
Electron-microprobe analysis ofvesuvianites used in this study were carried out on a Jeol instrument
equipped with EDS and WDS attachments.
The results indicate that the brown vesuvianites have high Ti content andthat the increase in Ti is fairly well correlated with the decrease in Al. In
contrast, the green ones are characterized by very low Ti concentration.
Very low fluorine and boron content in these two samples were also
found.
The two samples belong to the space group of P4/nnc and have similar
chemistry and cell parameters (a=15.548, 15.508; c=ll.833, 11.815 A).
Full-matrix least squares refinement of the structure, including
anisotropic temperature factors, gave conventional and weighted R valuesof 6.73, 4.47 and 6.67, 4.59 %, respectively for these two specimens.
The structures are virtually identical, and very similar to that proposedby Coda el al. (1970). The refinement results show the position for the Hatom at the distance of about 0.6 A from 011. According to the analysis
of a difference Fourier synthesis, the bond-valence calculations andrelationship between B-010 and 010-010 distance, it demonstrates that
another H atom should bond to 010.
Cations in vesuvianites are mainly confined to the 6-fold AlFe-sites (Al,Fe, Mg, Ti) and 5-fold B-sites (Fe, AI, Mg). The 4-fold sites are filledwith Si, the 8-fold sites with Ca (minor Na), and the 6-fold A-sites with
Al. Furthermore, along the 4-fold axis of the structure, adjacent B-sites(tetrahedral pyramid) imd C-sites (square antiprism) are half occupied
because of the Close cation-cation distance of about 1.4 A.

1P34
Charge Density Study of Nonlinear Optical Crystals of LBO and KBS
Hwo-shuenn Sheu and Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan &Synchrotron Radiation Research Center, Hsinchu, Taiwan, R. 0. C.
Borate compounds have attracted great attention recently because of its excellent
UV NLO(nonlinear optical) property. KB5(KB 50 10H 4·2H 20) is the first developed
borate NLO crystal and LBO(LiB 30 5) is the best one so far. LBO crystallized in anoncentric orthorhombic space group Pna2 1, with cell parameters a = 8.450(2), b =7.380(2), c = 5.1381(9) A, Z = 4, R = 0.017, wR = 0.023 for 5902 observedreflections ( I > 2.0 a (I)). KBS crystallized in a noncentric orthorhombic space group
Aba2, with cell parameters a = 11 .034(2), b = 11 .179(2), c = 8.961 (2) A, Z = 4, R =0.032, wR = 0.034 for 6230 observed reflections ( I > 2.0 a (I) ). Accurate single
crystal X-ray diffraction data were measured at room temperature and 125K using Mo
Ka radiation for LBO and KBS respectively. The data resolution is up to sin (B) I A.=
1.32 and 1.22 A- 1 for LBO and KBS respectively. Charge density distribution studies
were made in order to investigate the correlation between the electron density
distribution and the NLO property.
The NLO property of LBO and KBS are believed to be mainly contributed fromtheir anionic group, (8 30 7) 5· & [B 50 6 (0H)4 ] 1·. The former one is a six membered ringwith three alternate B and 0 atoms. Two B atoms are coordinated by three 0 atoms ina sp 2 fashion but the other B atom is coordinated by four 0 atoms with sp3
hybridization. The anionic group is also connected to four other anion groups throughoxygen bridges forming an infinite polymeric anionic chain. The latter one can be taken
as a dimer of the six member ring with four OH group on the side chain; the anionicgroups are connected by hydrogen bonds. Deformation density maps of LBO & KBS
are derived using the multipole model. They appear that asymmetric and symetriccharge distribution of the six membered ring for LBO and KBS respectively. Certainly,
there is difference between the 4-coordinated and 3-coordinated B-atoms. A slightdifference between the two 3-coordinated B is detected, however, a pseudo mirror
symmetry through the 4-coordinated B and the oxygen atom at para-position ispossible from the geometric data. Such model is also tried, the comparison of twomodels will be given.

1P35
STRUCTURAL CHANGE OF Caz(Mg,Fe)Siz07 BY HEATTREATMENT.
K.Ha~iya. K.Kusaka, N.Haga and M.Ohmasa, Department of Life Science,
Himeji Institute of Technology, Kanaji 1479-1, Kamigori, Akogun,
Hyogo 678-12, Japan, and K.lishi, Department of Mineralogical Scienceand Geology, Yamaguchi University, Yoshida, Yamaguchi 753, Japan.
Incommensurate phases of synthetic Akermanite solid solution were foundby Hemingway et al.[1] and Seifert et al.[2] independently. They foundthat Akermanite undergoes a reversible phase transition from the hightemperature normal phase to the low-temperature inconunensurate phase.
The modulated structures of the Co end member [3] andCaz(Mg,Fe)Si207 were determined by us based on the five-dimensionaldescription. Since a comparison of the structure of the incommensurate
phase to that of the normal phase was expected to be informative to
elucidate causes of the modulation, the present studies on effects of heat
treatment of the material have been carried out.
The specimen of the single crystal Caz(Mg,Fe)Siz07 was synthesized by
one of the authors (K.I.). On the precession photograph taken at room
temperature, the satellite reflections caused by two-dimensional
modulation were observed. The diffraction pattern at 2oo·c was taken bya high temperature precession camera, and the satellite reflections weredisappeared. After this heat treatment, however, no satellites werereappeared in the diffraction pattern at room temperature. Since thisphenomenon was not reversible, a new structure different from thenormal phase should be formed and the structure was analyzed to detect
the structure change. The cell parameters and the intensities were
determined on an Enref-Nonius CAD-4 diffractometer with MoK a
The cell parameters
radiation monochromatized by graphite.
a=7.8304(5)A, c=5.0009(2)A with a tetragonal symmetry are shorter thanthose of the basic structure of the incommensurate phase (a=7 .8668(7)A,
c=5.0138(4)A). The positional and thermal parameters were refined to
R=0.096 for 710 unique reflections.
[I] Hemingway et al. (1986). Can. Mineral. 24, 425-434.
[2] Seifert et al. (1987). Phys. Chern. Minerals 14, 26-35.
[3] Hagiya et al. (1993). Acta Cryst. B49, 172-179.

1P36

STRUCTURE AND RESIDUAL DENSITY OF CaFe03 WITH Fe 4 +S.Morimoto, Faculty of Engineering Science, Osaka University,
Toyonaka, 560, Japan., T.Yamanaka, Faculty of Science, Osaka
University, Toyonaka, 560, Japan., M.Tanaka, Photon Factory, National
Laboratory for High Energy Physics, Tsukuba, 305, Japan.

Fe4 + in CaFe0 3 shows "charge disproportionation reaction" into twovalence states of Fe3+ and Fe 5+ at low temperature (Takano et al. (1977),
Nasu et al. (1992)) and the structure analysis on CaFe03 is of greatinterst.
The crystal structures of CaFe0 3 at 293K and 113K are investigated bymeans of single crystal diffractometry.
Data collections were performed at BL-lOA in the Photon Factory with aradiaton of A.=0.69848(3)A .
Crystal data:CaFe0 3 (at 293K), Pbnm, Z=4, a=5.3480(3), c=7 .5730(5)A:(at 113K), Pbnm, Z=4, a=5 .3409(3), c=7.5585(13)A.
CaFe0 3 was revealed to have an "orthorombic perovskite structure" evenat 113K at which "chrage disproportionation" has been confirmed. The
smaller angle (ca. 160° of Fe-0-Fe in CaFe03 than that in SrFe0 3 with no"disproportionation" leads the weaker 180° interaction, which causes"disproportionation" . The very small elongation of the Fe06 octahedronin CaFe03 observed at 293K is comparable to that in GdFe0 3 (Marezio etal. (1970)) and suggests little contribution of the Jahn-Teller effect.
Residual charge density of CaFe03 was revealed by difference Fourier
map at 293K and 113K. Large residual density peaks with 1.2e/A3 as a
maxima are confirmed clearly at the center of Fe-0 bond. These are froma covalent contribution on the account of a overlapping of Fe 4 + 3d leveland 0 2p.

1P37

STRUCTURE AND TWINNING OF A SMALL CRYSTAL OF MA WBYITE,
PbFe 1_xZnx(As04 ) 2(0H) 1_x' x =0.06.

Kharisun, Max R. Taylor, School of Physical Sciences, Flinders University, GPO
Box 2100, Adelaide, 5001, Allan Pring, South Australian Museum, Adelaide, 5000,
A. Davjd Rae, Research School of Chemistry, Australian National University,
Canberra, ACT 0200, Australia.
Reflection data were collected from a very small <:rystal ofMawbyite, a 9.066(4),b 6.286(3), c 7.564(3) A, fJ 114.86(3) 0 , C2/m , Z = 2, using a sealed tube Mo X-ray
source and a SIEMENS SMART CCD detector system, courtesy of Dr C. F. Campana,
Siemens Industrial Automation Inc. Reflections indexed according to a primitive unit
cell with extra weak reflections for h+k odd, l odd but not h+k odd, l even. An initialstructure solution and refinement was obtained in C2/m using only h+k even reflections.
The angle between c and 2a +cis 89.98(1) 0 and allows the use of a twin rule to createa second unit cell orientation with a' =-(a+ c), b' = -b, c' = c, [2a' + c' = -(2a +c)]
and observations (I -a) IF(hk/)12 +a IF(h'k'l')i2 where h' =-h-1, k' =-k, l' = l.
Only the twin components of reflections with I even overlap. A value of a = 0.109(2)was obtained using 361 reflections with I> 3o(l). Values for R1 =I IMI/llFobsl were0.035 (127 h+k even, I even), 0.037 (132 h+k even, I odd), 0.091 (103 h+k odd, I odd),
0.043 (overall). A twin plane at x = 114 may be constructed using a 2 fold rotation axis
·parallel to c, i.e. 112~x. 1/2-y, 114-x+z relative to the cell a, b, c. On the twin plane, theoctahedrally coordinated Fe(lll) atoms at 1/4, N±l/4, 112 (usually T sites) and thecoordinated OH are replaced by 4 coordinated Zn(II) atoms on local rotation axes.
Apparent valence and tetrahedral coordination requirements of the Zn can be met bymoving the twin plane to x = 1/4+8with the 2 fold rotation axis, now described by theoperation 112+28-x, 112-y, 114+8-x+z, passing through a Zn atom at 114+8, 1/4, 1/2+£.

1P38
COMPARISON OF CRYSTAL STRUCTURES BETWEEN Li-DOPEDAND UNDOPED SUPERCONDUCTORS OF THE TYPE Bi2SnCaCwOs
K Kitahama, T. Horiuchi and T. Kawai, The Institute of Scientific andIndustrial Research, Osaka University, 8-1 Mihogaoka Ibaraki 567
Japan.
To survey high Tc superconductors and to study the transport mechanism,
substitution of metal ions for Cu position in BhSrzCaCU20a+6 (Bi2212) has
extensively attempted. Significant elevation of Tc (flTc < 4 K) was noted in
Li addition to the starting material, which f~ct stimulated us to determine
the location of Li in the crystal. Since the substance include quite heavy
atoms like Bi, we cannot locate the Li atom without ambiguity. Therefore,
this study was intended to detect small change in atom positions andthermal parameters associated with the Li incorporation. Single crystals of
Bh.zSr~.aCaCwO. and Bh.2SruCaCu1.74Lio.zsO. were prepared by thetraveling solvent FZ method. Their chemical compositions were found froman ICP method. Three dimensional X-ray analysis has been performed on
both crystals. Both crystals easily cleave along the ab-plane. These crystals
were cut into square plates in dimensions 0.2x0.2x0.02 mma. Each crystal
was installed with the c axis along the t axis of the goniostat of a four-circle
diffractometer. Both crystal lattices are expressed by an approximate
space group Pbmb with a=5.416(2) b=5.411(3) c=30.858(11) for the undoped
crystal and a=5.411(4), b=5.408(3), c=30.914(13) A for the doped crystal,respectively. In addition, precession photographs of both crystals exhibit
incommensurate super spots along the b* axis with the separation 4.8 b*.
To avoid heavy absorption effects, hkL reflections with L<10 werewithdrawn from the succeeding least-squares refinement. Refinements
were initiated with the atom positions reported by Imai, et al. [1] , whichconverged to R - 10% for both crystals. However, only inter atomic
distances concerning metal atoms are meaningful and precision of oxygen
position is not enough due to presence of quite heavy atoms. Significant
change is noted in Sr.. ·Ca distance which extends from 3.360(5) to 3.374(5)A by Li incorporation. Location of Li will be conjectured based on the present Xray analysis and non-diffraction data like 7Li-nmr and Raman spectra.
[1] K Imai, I. Nakai, T. Kawashima, S. Sueno and Ono, A (1988) Jpn. J .
Appl. Phys. 27, L1661-L1664.

1P39
SYNTHESES AND CRYSTAL STRUCTURES OF ZIRCONOLITEPOLYTYPES
Y. Ono, The University of Tokyo, Hongo 7-3-1, Tokyo 113 , Japan*
Zirconolite(CaZrTi 2 0 7) has a layer structure which consists of Ti0 6
layers related to that of hexagonal tungsten bronze-type(HTB)
compounds and inter layer cations . Different stacking sequences of the
HTB layers yield some kinds of polytypes as seen in mica . According to
the description generally used in mica, these polytypes are described as
zirconolite(2M), zirkelite(3 T 1), polymignite(20) and pyrochl ore(3 T 2 ) .
In this work , the syntheses of these polytypes with two systems ofchemical composition were investigated to know what factor affect thedifferent polytype structures formation . Crystal structures were analyzed
by X-ray diffraction methods .
I . Substitution of Ca for REE and part of Ti for Mg or AI in CaZrTi0 7(REE=Nd,Sm,Dy,Y ,REE AI : REEZrTiAI0 7,
REE Mg : REEZrTiuMgo ;07)
As the substituted REE3- ion radius become larger from Y to Nd , a seriesof polytypes formation was obteined that theree polytypes appered in theorder of zirconolite(2M) :::::} zikelite(3T 1 ) :::::} polymignite(20), in both
Mg and AI system .
2 . Substitution of Ca for Nd and O. STi for Mg in CaZrTi0 7 withdifferent NdMg % .
In this solid solution system, the compositions are described bypercentage of NdMg(NdZrTiuMg 0 . 5 0 7 ) for NdMg + CaTi(CaZrTi0 7 ) .
There seems to be same series of polytypes formation, zirconolite :::::}
zikerite :::::} polymignite, as the NdMg percentage increased . Zirkelite
was obtained in the range of NdMg=40~80% .
This order of polytypes formation series is consistent with the order of a
localization degree of their five-coordinated cation sites occupied by Ti ,Mg or AI. The .localization degree was estimated by frequency of theirapperance along one cations column , which extends to the direction of
stacking . These five-coordinated cation sites are situated in every twelve
HTB layers along one cations column for zirconolite, but in every six
layers for zirkelite . Polymignite contains them in every layer.
One factor of different polytypes formation is suggested that it is thedifferent circumstances of these five-coodinated cation sites, including
correlations with neighbor eight-coordinated cation sites which occupied
by Ca or REE .
*present adress 'Sibaura Engineering Works co .,ltd . Sagamigaoka
6-25-22 , Kanagawa 228 , Japan .

1P40

H.Ohsato, H.Kato, M.Mizuta & T.Okuda, Nagoya Institute of Technology
Gokiso-cho, Showa-ku, Nagoya 466, Japan.
Ba6- 3xSm8+2xTi 180 54 solid solutions have high dielectric constant (Er=7080), high quality factor (Q·f>=9000) and low temperature coefficient(Ohsato et al. 1993, 1995). Recently, this dielectric ceramics have beenused for microwave resonator. Ohsato et al. ( 1992) investigated the crystal
structure of Ba 3 _ 87 S~.42Ti 18 0 54 (x=0.71) and found a superlattice withdoubled c-axis lattice parameter.
Crystal data of true cell: Orthrombic system, Pbn2 1 (No.33) or Pbnm
(No.62), Z=2, a=l2.131(3), b=22.271(5), c=7.639(5)A.
In this work, the superstructure of the Ba 3 _ 87 S~.42Ti 18 0 54 solid solution
was analyzed based on the fundamental structure reported by Ohsato et al.
(1993). Refinement of the structure was performed on Pbnm (No.62).
The solid solution has tungsten bronze type structure with 2x2 perovskite
blocks and pentagonal sites. The Ti0 6-octahedra tilts alternately along thec-axis. The tilting causes a doubling of the fundamental cell along the caxis. And the two-fold rotation axis of fundamental cell (Pbam (No.55))
changes to the two-fold screw axis of true cell (Pbnm (No.62)). Split of 0atom found in fourier map of the fundamental cell can be explained by thetilting of Ti0 6-octahedra.
Superstructure of this solid solution consists of repeat of two fundamental
cell along the c-axis, and is caused by the tilting of Ti0 6-octahedra.
Ohsato H., Ohhashi T. and Okuda T. : Ext. Abstr. AsCA'93 Conf.,
Singapore, November, 14U-50.
Ohsato H., Nishigaki S. & Okuda T. (1992). Jpn. J. Appl. Phys. 31, 31363138
Ohsato H., Ohhashi T., Nishigaki S. & Okuda T. (1993). Jpn. J. Appl.
Phys.32,4323-4326
Ohsato H., Ohhashi T., Kato H.; Nishigaki S. & Okuda T. (1995). Jpn. J.

1P41

INTRAMOLECULAR INTERACTIONS OBSERVEDIN FOUR BIS{PHTHALOCYANINATE)LANTHANOID{III) COMPLEXES
N. Koike, H. Uekusa, andY. Ohashi, Faculty of Science, Tokyo Institute of Technology, 0-okayama, Meguro-ku, Tokyo 152, Japan, and
C. Harnoode, F . Kitamura, T. Ohsaka, and K. Tokuda, Interdisciplinary Graduate School of Science and Engineering, Tokyo Instituteof Technology, Nagatsuta, Midori-ku, Yokohama 227,Japan.
The bis{phthalocyaninato )lantbanide(III) complexes have stimulated
a great deal of interest because of-their electrical conductivity andelectrochromic properties. In order to investigate the above properties, a series of structures of bis{phthalocyaninato )lanthanoid{III),[LnPc2]-, have been determined by X-ray diffraction analysis [Ln =Nd{III), Gd(III), Ho(III), Lu(III)) .
Each lanthanoid ion is eight-coordinated by two phthalocyanine ligands ,which rotate to each other from the eclipsed conformation
by 6.2, 26.2, 43.2, and 45.0° for (NdPc 2J-, (GdPc 2J-, [HoPc2J- and[LuPc2]-, respectively. Each crystal contains tetrabutylammonium,[NBu4]+. The [LnPc2]- anion and the [NBu 4j+ cation stacks alternatively as a column along a four-fold axis. Figure 1 shows the crystal
structure of [NBu4)[HoPc2) .
The difference in rotation angle among the four compounds
seems to be attributed to theionic radii of the central lanthanoid ions, i.e. the smaller
ionic radius is, the larger rotation angle is. This indicates afairly strong intramolecular 1r-1r
interaction of [LnPc2]-. Further
detail will be discussed on thebasis of the analyzed structures.

Figure 1. Structure of [NBu 4 lfHoPc2 )1P42

STRUCTURE ANALYSIS OF (NH4)3H(S04)z AT lSOK

Y. Noda, S.Fukuchi and l.Tamura, Faculty of Science, Chiba University,
Yayoi, Chiba 263, Japan
Triammonium hydrogen disulfate (NH4)3H(S04)z abbreviated as A3HS
shows successive phase transitions from phase I to VII. Not only that,
deuteration of sample gives a large isotope effect upon the phase transition
temperature, and an extra phase appears in d-A3HS. Concerning thestructures at low temperature phases, alm:ost no information was reported
except the structure of phase III given by M.Tanaka and Y.Shiozaki(1986).
Proposed space group was P2. However, our recent work with low
temperature Weissenberg photograph by using an Image-plate revealed thatthe space group was P2/n, and the transition was characterized by theappearance of superlattice reflections at Z-point in the A2/a space group.
We performed the structure analysis of the phase III(150K) by the offcenter-type four-circle diffractometer with a closed-type refrigerator
cryostat. The structure analysis at room temperature (phase II) was
consistent with the reported data, with A2/a and RF=0.0345.
Crystal data: 150K, (NH4)3H(S04)z monoclinic, space group P2/n (No.13)
a 15.582(7), b 5.821(3), c 10.064(7)A, {3 101.57(9).
Here, the lattice is chosen so that the compatible room temperature phase isexpressed by C2/c. Intensity of superlattice reflection and lattice
parameters are measured as a function of temperature. At the transition
temperature 263.5K, the lattice parameter a starts to deviate as a continuos
transition. Characteristics of the phase transition from the phase II to thephase III was analyzed based on the obtained structural parameters. The
remarkable change of positional parameters deviated from the room
temperature phase was seen for oxygen atoms, whose displacement pattern
was expressed by an anti-phase rotation of the S04 molecules. On the other
hand, N and S atoms are staying at the original position.

Tanaka ,M. and Shiozaki,Y. (1986). Acta Cryst. C42, 776-780.

1P43
INCOMMENS_U RATE-COMMENSURATE PHASE TRANSITIONOF INTRAMOLECULAR HYDROGEN-BONDED MATERIAL d· .
BrHPLN
I. Tamura, Y. Noda andY. Kuroiwa, Faculty of Science, Chiba University,
Yayoi, Chiba 263, Japan, and T. Mochida, Institute for Molecular Science,
Okazaki, Aichi 444, Japan ad T. Sugawara, Department of Pure andApplied Sciences, College of Arts and Science, The University of Tokyo,
Komaba, Tokyo 153, Japan.

The hydrogen-bonded materials are well-known to show a large isotope
effect. In order to investigate the origin of isotope effect, the simplesthydrogen bonded system was studied recent years. Since intramolecularhydrogen-bonded materials have no hydrogen network and a hydrogenbond is fixed by a molecular frame, such materials prevent us the· simplest
system which is not bothered by the 'geometrical model'. In order toinvestigate the structure change associated with the phase transition, X-ray
scattering experiment was performed on the deuterated 5-bromo-9hydroxyphenalenone (abbreviated d-BrHPLN). The d-BrHPLN undergoes
the phase transition at 34K and at 22K studied by dielectric measurements
by Mochida et al. (1994) and Moritomo et al. (1995). The temperaturedependence of lattice constants showed anomalous behavior at the points ofTc(=22.8K) and of TJ(=34.5K). Th·e superlattice reflections are found at (hk+O.S 0) below 14.4K by an X-ray Weissenberg photograph using theimage plate by Noda et al (1994). The phase transition at Tc ischaracterized by a commensurate-incommensurate transition, and the phasetransition at TJ is characterized by an incommensurate-normal transition.
The peak shift {J shows a thermal hysteresis and is pinned on the position
deviate(! from the exact commensurate position after the thermal cycles. It
was found that the pinning effect was caused by X-ray radiation damage.
The detailed structure analyses of H - and D - compounds at room
temperature were performed, and the results will be given.
Mochida, T. et al. (1994). J. Chern. Phys. 101, 7971-7974.
Moritomo, Y. et al. (1995). J. Phys. Soc. Jpn. 64, 1892-1895.
Noda, Y. et al. (1994). J. Phys. Soc. Jpn. 63,4286-4289.

1P44
OBSERVATION OF ANOMALOUS DIFFUSE ROD BELOW
200K IN BazNaNbs01s
T. Shobu, Y. Noda, Faculty of Science, Chiba University, Yayoi, Chiba
263, Japan, and K. Fujishiro andY. Uesu, School of Science andEngineering, Waseda University, Ohkubo, Tokyo 169, Japan.
Barium sodium niobate Ba2NaNbs0 1s (abbreviated BSN) has been reported
that the crystal undergoes transitions to an incommensurate phase at 573K
and that to a commensurate phase at 533K studied by J. M. Kiat et al(1994). It has been also reported that the crystal has reentrant phasetransition to the point-group symmetry of the high temperature phase below
llOK studied by W. F. Oliver et al (1990). In addition, anomalous changesof birefringence ~nab and strain X.l2 were observed at about 200K. We have
performed X-ray studies to clarify the nature of BSN at low temperature
region. At first we took a Weissenberg photograph using Imaging Plate at
low temperature. Diffuse rod connecting to superlattice reflections were
found below 200K. We also measured temperature dependence of this
diffuse scattering using a scintillation counter. Shown in Fig.1 is theintensity of •· diffuse scattering at
7000r----.---.-----,(6.25 -8.5 0.5) as a function oftemperature. The diffuse scattering
starts to increase at about 200K.
~ 4000We could not find any otherVicharacteristic scattering relevant toz 3000••the anomalous behavior of ~nab and2000••
X.l2. Therefore, only short range
1000~
order establishes below 200K. This
0
100
200
result indicates that the nature below
300
Temperature(K)200K is glass state. In this sample,
the so-called reentrant transition was Fig. I Temperature dependence of
not observed. The authors would like the intensity of diffuse scattering
at (6.25 -8.5 0.5).
to thank Dr. J.M .Kiat to provide asingle crystal of BSN.

..

~

..

""

Kiat.J.M. etal, (1994). Phys. Rev . B 49,776-785.
Oliver W. F. et al, (1990). Ferroelectrics , 112,3-25

....

1P45
Structure change investigation of perovskite-type(Nd,Sm)AI03 by X-ray powder diffraction.
Akjra Yoshjkawal), Hiroyuki Horiuchi!), Masahiko Tanaka2),
Toetsu Shishido3) and Tsuguo Fukuda3)
1) ~Institute, Faculty of&:ml:, UnM2sily of Tdcyo, ~ 7-3-I,Btri<ycH<u, Tdcyo 113, Japan
2) Photon Factory, National Laboratory for High Energy Physics, Oho,Tsukuba, lbaragi 305, Japan
3) Institute for Materials Research, Tohoku University, Katahira,Aoba-ku,Sendai 980, Japan.

Structure change of solid solution phases of (Sm 1.x,Ndx)Al03 wasinvestigated by the analyses of powder X-ray diffraction profiles using
samples obtained by a solid state reaction. They are based on a perovskitetype structure with slightly deformed lattices from an ideal cubic structure.
By substituting Sm3+ for Nd3+, the atomic position of (Sm,Nd) becomesclose to an ideal position, and the structure of solid solution phase finallychanges from orthorhombic to trigonal system at around x=0 .7 [Fig.l], while
the lattice distortion is the smallest in the phase with around x=O.O [Fig.2].
The partial substitute of Sm3+ for Nd3+ play a role to control the size of ionsin the structure, as a result, an apparent first order phase transition takes
place in the structure, and the structure change does not pass through an ideal
cubic structure.It is interesting that the phase transition of SmA10 3 fromorthorhombic to trigonal structure at high temperatures (O'Bryan et al.,I990)
showed the similar structure change
as observed by substituting Sm3+
92
for Nd3+ in this investigation.

5.1
1.J1

Pr Nd

SmEu Gdlb 0y Ho Er TmYb Lu

Change of lallice ronslanls depending on
the rare earth elemen!S. TI.e strudllre changes fromorthorhombic 10 trigonal at around x=Q. 7[Fig. I)

I.JI

Pr Nd

SmEuGdlb OyHoEr TmYblu(Fig.2) Change of lattice parnme1ers rorresponding
ro basic lallices. Tile Janice dislonion is the smallesr
in the phase with around x=Q.O

HMO'B1)'31l. PK~. GW.Belkslresser and CD. Brandle, (1990). J.Ma!er.Res,5, 183-189

1P46
STRUCTURAL PHASE TRANSITIONS AMONG COMPLEX METALOXIDES WITH PEROVSKITE- TYPE STRUCTURE : STUDIES BY
PRECISE X-RAY POWDER DIFFRACTOMETRY.
Sergey Ivanov, Vladimir Zhurov, X-ray laboratory, Karpov' Institute ofPhysical, Chemistry, Ul.Vorontsovo pole,IO 103064, Moscow K-64,
Russia.
The

applicationoftemperature

resolved

preciseX-ray

powderdiffractometry for the detailed investigation of atomic structure andphase transitions of ferroelectric and superconductive

materials

withperovskite-type structure is described. X-ray diffraction patterns werecollected in the temperature range 20 - I lOOK on the following complex
metal oxides: SrTi03 , Li doped KTa0 3 and BaPb03. Full-profile
analysis was carried out in order to obtain the high-precision estimatesof slight lattice distortions. Accurate values of profile parameters forsensitive reflections were calculated after separating and fitting ofoverlapping peaks which were carried out using our special software
package for IBM PC computer. From the temperature evalution of splittingofdiffraction

reflections

thetemperaturesofstructuralphasetransformations were determined. The components of thermal expansion
tensor of different phases and the volume changes during the phasetransitions were obtained. The crystal structures for different phases wererefined with the Rietveld method and the results were presented. Aninterpretation of physical properties df tested oxide materials as well as
possible mechanisms of structural phase transformations were discussed
also in detail using the obtained experimental results.

1P47
A SINGLE CRYSTAL X-RAY DIFFRACTION STUDY OF THE LOW
TEMPERATURE PHASE OF RbCN
Y.Yoshimura, S.Shinohara, N. Tsuda and H. Iwasaki, Department of
Physics, Ritsumeikan University, Noji, Kusatsu, Shiga 525 Japan.

At room temperature RbCN has the NaCl type cubic structure, with adisorder of linear CN ion orientations. As the temperature is decreased, thecrystal undergoes an order-disorder phase transition associated mainly withthe change in the orientation of the CN ions. Recent neutron powder
diffraction study confirmed that the structure of the low temperature phaseis monoclinic with the space group Cc. The space group Cc lacks a centerof symmetry and can accommodate either ferroelectric or antiferroelectricordering or anything in between. However, no ordering of the dipoles isobserved in dielectric and optical measurements. In order to clarify some of
the uncertainties in the crystal structure of the low temperature phase, thepresent authors took several precession photos at low temperatures. A
structural change was observed from the cubic phase to a low temperaturephase at about 125K. A variety of diffraction photos were obtained whichindicate a coexistence of various forms. Paying attention to the presence of
new reflections and splitting reflections, a monoclinic and a triclinic form
were found in the low temperature phase. The lattice constants of themonoclinic form are a~4 . 81(1), b~4 . 87(1), c~7 .92(l)A, P=122.7(1) 0 at
85K, and the structure is A-base-centered with the space group A2/m. The
lattice constants of the triclinic form are aT=9.84(1 ), b,-=4.665(1 ),cr=4.90(1)A, a=121.3(1) 0 , P=119.l(l) 0 , y =90.0(1) 0 at 85K.

1P48
SINGLE-CRYSTAL X-RAY DIFFRACTION -STUDY OF
AgGaS2 UNDER IDGH PRESSURES
H. Kitahara, N. Ishizawa, Research Laboratory of Engineering Materials,
Tokyo Institute of Technology, 4259 nagatsuta, Midori-ku, Yokohama
226, F. Marumo, Department of Earth Sciences, Nibon University, 3-2540 Sakurajosui, Setagaya-ku, Tokyo 156 and Y. Noda, Department ofMaterials Science, Faculty of Engineering, Tohoku University, Aramaki,
Aoba-ku, Sendai 980-77, JapanThe crystal of AgGaS2 has been reported by Carlone et al.(1980) toundergo the first phase transition at about 4.2 GPa and the second at 11.6
GPa. The present study was undertaken to obtain crystallographic
information of the intermediate high-pressure phase between 4.2 and11.6 GPa employing a single crystal X-ray diffraction technique with adiamond-anvil cell. Single-crystals of AgGaS2 were grown with the
Bridgman method. A mixture of Ag2S and Ga2SJ in the 1:1 molar ratio
was sealed in an evacuated silica ampoule, kept at IOso·c for 12h, andthen cooled at a lowering rate of 10 mm/day. The crystal is tetragonal,
I42d, a=5.7626(5) and c=10.3128(9) A at ambient pressure. The
precession photographs taken under pressures between 4.7 and 5.4 GPa
indicated that the systematic condition of 2h+l=4n for hhl reflections was
broken, suggesting that the diamond glide planes parallel to {110} havebeen disappeared in the high-pressure phase. In addition, several
diffraction spots became split in the high-pressure phase and again
became unified when the pressure was released. These results indicatethat (1) the unit cell of the high-pressure phase is close to the bodycentred tetragonal one at ambient pressure, but (2) the diamond glide
planes are lost and a twinning seems to take place above 4.2 GPa, and (3)the transition is essentially reversible. The high-pressure phase is thought
to possess a symmetry of I212121, one of the maximal non-isomorphic
subgroup for I42d.
C.Carlone, D.Oiego, A.Jayaraman, and M.Cardona (1980). Phys. Rev . B
22, 3877-3885

1P49
STRUCTURE OF PYRIDINIUM TETRAFLUOROBORATE AND ITS PHASE TRANSITIONS OBSERVEDBY A NEW DIFFRACTOMETER
T. Nemoto, Y. Ohashi, M. Hanaya and M. Oguni, Department ofChemistry, Tokyo Institute of Technology, 0-okayama, Meguroku, Tokyo 152, Japan.
The crystal of title compound belongs to the trigonal system R3
at room temperature (Phase I) . On cooling this crystal, first orderphase transition occurred at 239K, and the permitivity was significantly changed{Phase II). But the cell dimensions are almost
the same as those at room temperature. Below 205K, another low
temperature phase (Phase III) is observed. The crystal system
becomes to monoclinic system by this phase transition.
To examine the difference of crystal structure, the X-ray diffraction data sets are collected at 297K(Phase 1}, 223K(Phase II) and173K{Phase III) using IP-weissenberg camera.
Crystal structures at room temperature is shown in Fig. 1. Bothof the PyH+ and BF.j ions are disordered around 3 symmetry.
Because of increase of the mosaicity, the diffraction spots are enlarged and precise cell dimensions of low temperature phases are
not yet determined. Data reductions at two low temperaturephases are now in progress.

Fig 1. Crystal Structure at 297K.
(a) viewed along c axis.
(b) viewed along b axis.

1P50

BUNYIP: A NEW APPROACH TO DETECTING ERRANT SYMMETRYJames Hester, NIRIM, Namiki 1-1, Tsukuba, lbaraki 305, Japan [jrh@nirim.go.jp)
and Syd Hall, Crystallography Centre, University of Western Australia,
Nedlands [syd@crystal.uwa.edu.au)
The incorrect assignment of space group symmetry to crystal structuresappears to be on the increasel . The reasons are several fold. Automaticalignment and space group assigrunent software is more widely used on
diffractometers and these tend to assign lower symmetry space groups becauseof spurious systematic absence data. That is, the presence of intensities due tomultiple Bragg scattering complicates automatic symmetry identification.
Expert intervention is then needed. Additionally, structure analysts often lackadequate crystallographic training in symmetry identification. After all, "its not
the symmetry that counts; its the molewlar conformatioll " [if you agree with thisstatement, please come and argue this point with us at the poster!] .
BUNYIP is a new approach to identifying extra symmetry in a solved structure.
It complements the program MISSYM2 which can fail if the symmetry
relationships are badly distorted by refinement in the wrong space group .
The BUNYIP algorithm scans a structure for mid-points between any two sites
which coincide within a common centre (indicating the presence of an
inversion}, axis (indicating a 2-fold rotation or screw) or plane (indicating amirror or a glide) . If a large proportion of midpoints coincide within a specified
tolerance, the centre, the rotation/ screw, or the mirror I glide, are identified .
The mid-point search is performed in Cartesian coordinates (orthogonal
angstroms) and makes no assumptions about existing symmetry or cell, apart,that is, in aligning different molecules in the asymmetric unit into the
optimally packed cluster.
BUNYIP is a new addition to the Xtal System3 and has a direct link to theinteractive molecular display routine PIG4 . This enables the symmetry element
detected by BUNYIP to be displayed and manipulated as part of the structure.
This visualisation link is important to understanding the nature of theadditional symmetry detected.
1 Submission statistics to Acta Cn;stallographica (personal communicntioll).
2 Page, Y Le (1987) f. Appl. Cryst. , 20. 264-269.
3 Hall, S R, Flack & H D Stewart, J M(1992) Editors. Xtal System ofCn;stallographic Programs.
4 Bartsch, U and Hall, S R (1992) PIG: Display and Manipulate Ato111 Sites.
Xtal System of Crystallographic Programs.

1P51

A FLEXIBLE FOUR-CIRCLE DIFFRACTOMETERCONTROL SYSTEM FOR BEAM LINE 14A AT
THE PHOTON FACTORY
T. P. Vaalsta Crystallography Centre, University of Western
Australia, Nedlands, 'vVA 6709, Australia, N. Ishizawa, Research Laboratory of Engineering Materials, Tokyo Institute ofTechnology, 4259 Nagatsuta, Midori-Ku, Yokohama 227, Japan.
Abstract
An operating system independent user friendly single-crystal four-circle diffractometer control system that is user friendly is under development. The objective is toprovide greater flexibility of use for a number of applications of the powerful imaging capabilities of the vertical wiggler beam line. The system can operate acrossa diverse range of computers from UNIX workstations to 80x86 PCs. The control
system allows the same software to be used on other diffractometers, helping to prepare specimens for the beam line diffractometer. The orientation matrix and othercrystallographic related information thus obtained could be transfered electronicallywhen the specimen is mounted for study at the beam line. Ease of use is enhancedby the on-line help available and the program 's ability to run operating system commands from within it . The Crystallographer is not required to understand intricacies
in operating the computer, and is free to concentrate on the task at hand . The initial version has been tested on DEC and Silicon SGI-Iris workstations, as well as
80486-based PCs running high-quality freely available UNIX and X systems such as
Linux. The tests were conducted with four-circle diffractometers at the Crystallography Centre as well as on Beam-Line 14A at the Photon Factory at Tsukuba.
The new control system software conforms to the POSIX standard . That maximises
the portability of the code between different computing systems. In todays environment of rapidly changing computer hardware and operating systems such portabilityof software is essential. The program's modular nature enhances its portability
by separating hardware specific and generic elements of four-circle diffractometer
control. The generic elements includes the user interface, crystallographic related
computing, and storing-receiving data. Diffractometer specific elements include software that is unique to the control of a diffractometer-such as device driver modules
and its related code.
The trend towards networking computing and network transparent windowing systems is recognised in the software design . The program also offers the possibilityof monitoring the diffractometer from a remote location during data collection andintervention if necessary.

IP52
ANALYSIS OF METALLIC AND RELATED COMPOUNDS USING ICDDMETALS AND ALLOYS INDEXES. J. N. Dann, T. C. Huang, W. F. McClune, M. H.
Mueller, A. C. Roberts, and P. L. Wallace, Metals and Alloys Subcommittee of theTechnical Committee, International Centre for Diffraction Data, 12 Campus Boulevard,
Newtown Square, PA 19073, USA.
The interest in metals and alloys, as well as related nonmetallic and corrosive phases
have continuously increased in recent years. The properties of these materials strongly
depend on their crystalline structures, and a detailed study of the structures is important
for the research and development in materials science and technology. The powder
diffraction method is one of the techniques commonly used for the structuralcharacterization of these compounds. Information on crystalline phases and their unit celldata such as lattice parameters, space groups, etc. can be obtained from the Powder
Diffraction File (PDF) of the International Centre for Diffraction Data (lCD D). Anotheruseful tool for the analysis of metallic and related phases is the Metal and Alloys (M&A)
Indexes recently published by the ICDD. The M&A Indexes make the identification ofthese materials easier and more accurate by providing a chemical formula index; namely,
the Alphabetical Formula Index (AFI). The AFI allows systematic searches of chemical
analogs and a greater use of partial chemical knowledge. Other M&A indexes are thePearson Symbol Code Index which gives all the materials in a given structure and allows
for the comparison of atomic contents and lattice parameters; the Common Names Index
which cross-references common metallurgical names; and the Strukturbericht Symbol
Index which cross-references the Strukturbericht Symbols and the equivalent Pearson
Symbols and structure prototypes. The organization, selection of materials, and the useof alphabetical formulas in the M&A Indexes are similar to those of standard
metallurgical references such as Pearson, Villars and Calvert. The Indexes contain directreferences to the PDF, and thus, distinguishes them from other metallurgical references.
Additionally, it permits material characterization by comparison of the diffraction data
for an unknown with PDF data. Applications of the M&A indexes for the determinationof Pearson Symbols, prototype structures and so forth from indexed powder diffraction
patterns and for the indexing of new diffraction patterns will be presented.

1P54
ORGANO-TEMPLATE CONTROL OF INORGANICSTRUCTURES: A SHEET ALUMINOPHOSPHATE OF LOWSYMMETRY 3[NHJCHMeCH2NHJ][Al6PsOJ2][H20]
Ian D. Williams and Zhenyang Lin, Department of Chemistry, Hong Kong
University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong
and Qiuming Gao, Jiesheng Chen and Ruren Xu, Key Laboratory of
Inorganic Hydrothermal Synthesis, Jilin University, Changchun, China.
The 2-D ALPO family with (Al3P4016]3- anionic sheets are known with two
network types, (4.6.8 or 4.6.12) dependant on counter cation size, Gao eta!
(1995). Use of (+/-)1,2-diaminopropane as template results in the formationof crystals of the title compound with a new low symmetry (pg) network.

c) ...6 Network tcmplaicd by [l'o'H ~CHMeCH 1 NH 3 ) 2 •d) AI 3P" Building Blocks

Crystal Data: [C9H36N6][Al6P8032J.[H20], monoclinic, space group Ia (No 9),
a= 18.119(2), b = 16.236(2), c = 14.736(2)A, p = 91.35(1) 0 , V = 4333.8(1.0)A3. For
4451 data R = 0.040. Ave. lengths: Al-0 1.73, P-0 1.52, P=O 1.49A esd .0005A
The templating action of the organic base and alternate 2-D networks are
discussed. The results are encouraging for the idea of creating surfaces withhighly specific recognition properties via an organic-inorganic interface.
Gao, Q ., Li, S., Chen,J., Xu, R., Williams, J.D. ,Zheng, J. & Barber, D. J. (1995)
f. Solid State Chern., submitted

1P55
STRUCTURAL CHANGES IN MODIFIED SMECTITES:
Li-DIFFUSED MONTMORILLONITE CASE
A.Mulaba-Bafubiandi 1 , J.Helsen 2 , A.Maes3 , G.Langouche4 and R.Prost5
1: Faculty of Metallurgy and Materials Engineering, Ghulam Ishaq Khan Institute ofEnginee ring Sciences and Technology, Topi, district Swabi, NWFP, PAKISTAN 2: Departement Metaalkunde en Toegepaste Materiaalkunde, K. U.Leuve n, De Croylaan 2, B3001 Heverlee, Belgium 3: Laboratorium voor Colloidchemie, Kardinaal Mercierlaan
200D, B-3001 Heverlee, Belgium 4: Institute voor Kern-en Stralingsfystoa , K. U.Leuven,
Celestijmenlaan 200D, B-3001 Heverlee , Belgium . 5: Institut National de Ia Recherche
Agronomique, route de St-Cyr F-78026 Versailles, France.

Abstract
Montmorillonite is defined as 2:1 dioctahedral smectite with a cationic exchange
capacity due to isomorphic substitutions. Li migration in this clay mineral perturbs
the physico-chemistry within the lattice. The irreversible diffusion of this small
cation ( r < 0. 70 A) due to a heat treatment {between 200-300 •c) first observedby Hofmann and Klemen {1950) has been confirmed . The possible location of the
migrating Li is assessed. The changes in the "microstructure" of this fine divided
material and the influence of the migration of this small ion into the montmorillonite
lattice have been studied. The kinetics of the migration could be followed . Theseobservations are backed by XRD, FTIR, SEM and Miissbauer measurements. By
Mossbauer spectroscopy the perturbation of the iron ions, located in Montmorillonite of Camp-Berteaux mainly in the octahedral layer, is studied. As the Fe(III)substitution is not at the origin of the cation exchange capacity, only a second ordereffect can be expected. As it will be shown, the effect is indeed small but visible.When modifications are int introduced in a crystal lattice, the whole vibrationalsituation of the crystal will be affected . Consequently, the vibrational spectra will
be subject of change. The OR-stretching domain has been thoroughly explored by
Prost et al.{1969) . In this context a spectral study in the region below 2000cm- 1
will be presented. At first , it was tried to perform this by advanced decompositionof spectra. The spectra are, however, far too complex in order to obtain reliable results. Finally a technique was developed that enabled us to record difference spectraof self-supporting films . It allowed us to record spectra of Li/Na-montmorillonites
at given temperatures as a function of time and to study the kinetics of the Li
migration process. XRD and SEM observations have confirmed the above results.

Referencesl. U.HOFMANN and R.KLEMEN , Zeitschrift fur anorganische chemie band 262( 1950) 95-99
2. R.PROST and R.CALVET, note dans C.R. Acad.Sc.Paris t.269 {1969) 539-541

2P01
THE EFFECT OF ENDING ANGLE ON THE STRUCTURALPARAMETERSAND

PROFILEAGREEMENT

INDICESINRIETVELD REFINEMENT

Changlin KUO and Hongchao LIU, Shanghai institute of Ceramics, Chinese Academyof Sciences , Shanghai 200050, P . R. China

The diffraction pattern of Ca3 (P0 4)JF was taken as sample data.
The parameters determined by Rietveld refinement showed different sensitive to theending angle in the calculation. The coordinates of light atoms were influenced morethan the heavy ones. When the ending angle was great than 70 · , the results of theseparameters almost kept constant. The values of this region were plausible. The
determinations of these values were insensitive to the discrete position of ending angle,
even if the stop two theta angle was in the region of a reflection . The test of weighted
mean values and its two values of estimated standard deviation showed that no visible
systematic errors appeared in the varying ending angle determination, except for cellparameters . Although the spread of 0-atom coordinates was large due to its lower
scattering cross section , the weighted mean value determined was more agreement thanother methods . The determination of cell parameters appeared including systematic
errors. This may be attributed to the incompleteness of Rietveld method .
Most of the agreement indices was not sensitive to the fitting quality in the Rietveld
refinement. When the parameters were refined , the R agreement indices increased
slowly with the increase of ending angle. The high angle data should not be included as
many as possible according to the calculation results.
In fact, there is an inherent danger in .relying too heavily on the numerical values ofcriteria of the fit when these values are affected by factors unrelated to the fit of thecrystal structure and peak profile models, as shown above . It is urgent to introduce a
new set of agreement indices to access the fitting quality of Rietveld analysis of powder
diffraction data.

2P02
CRYSTAL STRUCTURE AND DATA ON Bi 4 (Si0 4 h BY X-RAY
RIETVELD ANALYSIS
Changlin KUO and Hongchao LIU , Shanghai Institute of Ceramics, Chinese Academyof Sciences , Shanghai 200050, P. R. China

The sample for diffraction analysis was prepared by grinding the powder manually andpassing the resultant powder through a 400 mesh sieve. Diffracion data were recorded
on a conventional diffractometer. Various copnting time strategy was applied to reduce
the statistical error in the high angular due to low counts.
F 30 was calculated based on the results of Rietveld analysis and observed data set. F30 is158.90 with 30 observed reflections out of 32 possible lines and 0.0059 • average
difference of 2e .
Initial values of parameters taken from the Model II proposed by Menzer gave
acceptable values. The final results showed that the cubic unit cell(a= 10.2867A)
contains four molecules in the following positions of space group I-43d (No. 220) : Bi
in 16c uuu with u=0.0849; Si in 12a 3/8 0 1/4 ; and 0 in 48e xyz with x =0.0581 ,y=0. 1319, z=0.2899 ; Rwp= 11.8; R8 ,..11 =4 .65.
In this crystal structure, the distance of Si-0 in one Si04 tetrahedra is 1.6 13A; such alength corresponds to the equilibrium distance of Si-0 bond . The Si atom is surroundedby four 0 atoms, four Bi atoms at distance of 3.543A, four other 0 atoms at 3.554A
and four other Bi atoms at 3.5781\. Eac h 0 atom is coordinated with one Si , two Bi
atoms at distances of 2.181 A and 2.590A, respectively, two 0 atoms with a distance of
2.595A and one 0 of 2.709A in the same tetrahedra, other six atoms with distances
ranging from 2.835A to 3.186A. The varied distances of 0-0 leads to the change of
Si-0 -Si angle from 107. 13 • to 114 .26 · ; the large angle corresponds to long distance of0 -0 bond .

2P03
CRYSTAL STRUCTURE ANALYSI~ OF ALKALINE PROTEASE (MPROTEASE) FORMl CRYSTAL.
T. Shirai, A. Suzuki, T. Yamane and T. Ashida, Nagoya university, Chikusa-ku,
Nagoya 464-01, Japan. T. Kobayashi and S. Ito, Research Laboratories of Kao
Corporation, 2606 Akabane, lchikai, Haga, Tochigi 231-34, Japan.

M-protease is an subtilisin-family serine protease produced by alkalophilic
bacteria Bacillus sp .. strain KMS-K16. A character of the enzyme is its
high alkali resistance. The optimum pH o(the M-protease is 12.3. The Xray crystal structure analysis of the M-protease was carried out to study
the mechanisms of high alkali resistance. Two morphologically different
crystal forms 1 and 2 of the enzyme were obtained under a crystallization
condition. The forml crystals belong to ortholombic crystal system, spacegroup P2 12 12p a=62.3, b=75.5 and c=47.2 A.
The form 1 crystal reflects beyond 1.A, which is much better thanpreviously analyzed form2 crystal (T. Yamane eta/. 1995). The reflection
data were collected using synchrotron radiation light source at the Photon
Factory, National Laboratory of High Energy Physics, Japan.
The crystal structure of form 1 was solved by the molecular replacement
method, using the structure of form2. The model has been refined to the
crystallographic R-factor of 0.175, using 9433 unique reflections between
8.0 and 1.7 A resolutions. The high-alkali adaptation mechanisms werestudied on the basis of the refined structure. From a comparison of primarystructures of high- alkali proteases (M-portease, PB92, Savinase, etc.) andother homologous proteins (Subtilisin bpn', Carlsberg, Protease K, etc.),
32 residue sites which side chains were replaced between two groups,
were selected. The spatial arrangements and interactions of these sites were
tested on the refined structure. These replaced sites are mainly localized
upon the C-terminal region of the protein. Some positively charged aminoacid residues on the C-terminal region are suggested to contribute instabilizing the conformation in high pH range. The salt bridges, Arg19 Glu271 - Arg275 is formed to connect theN- and C-terminals. Two basic
amino acid residues Arg170 and Lys251 which occured at the entrance of
the C-terminal calcium ion binding site, are possibly regulating thecalciwn ion binding.

2P04
CRYSTAL STRUCTURE OF AN ACYL-ENzyME INTERMEDIATEOF GUANIDINOHEXANOYL-TRYPSIN
Yasushi Nitanai, Shuji Noguchi, and Yoshinori Satow, Faculty of
Pharmaceutical Sciences, University ofTol-yo, Hongo, Bunk-yo, Tokyo 113,
and Chizuko Sasaki and Takao Matsuzaki, Research Center, Mitsubishi
Kagaku Corporation, Midori-ku, Yokohama, Kanagawa 227, Japan.
The crystal structure of an acyl-enzyme intermediate of bovine trypsin has
been determined at 2.2
resolution. Ethyl p -(6-guanidinohexanoyloxy)
benzoate is a substrate analog that is slowly hydrolyzed by serine proteases.
In order to clearly elucidate hydrolysis mechanisms of serine proteases by
the X-ray diffraction method, substrate-complexed crystals were preparedwith the soaking technique. First, the orthorhombic crystals of the lowpacking-density form inhibited by benzarnidine were obtained from anammonium sulfate solution. They belong to space group P212121 , withcell dimensions of a = 63.64 , b = 63.48 , and c = 68.89 . These
crystals were back-soaked in a benzarnidine-free solution, and finally were
soaked into a substrate-analog solution containing acetonitrile as co-solvent.
The diffraction data were collected from 8 crystals of the acylated enzyme,
by use of a specially designed Imaging Plate camera. From each crystal,reflections measured in the first 6 hours were merged into a complete data
set. The structure was refined to a crystallographic R-factor of 0.167.
A clear electron density corresponding to a guanidinohexanoyl moiety isextending from the Oy atom of Ser 195 to the side chain of Asp 189 oftrypsin. The guanidinohexanoyl group covalently bound to Ser 195 Oy.
forming an acyl intermediate, and is also involved in 7 van der Waals
interactions with trypsin. A water molecule hydrogen-bonded to His 57
Ne2 is located on the imidazole plane of His 57. The oxygen atom of thiswater is located right above the carbon atom in the plane of the acylated
carbonyl moiety, and is in a close contact with the carbon atom, at a
distance of2.95 . This geometrical arrangement ofthe water oxygen andthe catalytic residues indicates that this water would act as a catalytic
nucleophile in the subsequent deacylation step.

2P05
VISUALIZATION OF THE 3D-STRUCTURE OF CALOTROPIN DIIA PLANTTHIOL PROTEASE AT 3A RESOLUTION
Sreya Ghosh, Bishnu P. Mukhopadhyay, A. Pal, A. Seal, A. Bera, I. Dey,
N. K. Sinha and Asok Banerj~ Biophysics Deparnnent, Bose Institute,Calcutta-54, India.
The structure of a novel thiol protease, Calotropin DII, having two
independent molecules in the P2 1 space group (Banerjee et al. 16T-45,
AsCA92) each containing 215 amino acid residues has been solved at 3A
resolution by molecular replacement methods (X-PLOR) using the phasesof Papain(Pickersgill et al. Acta Cryst., B48, 59-67, 1992). The successiverefinement (X-PLOR) of the positional and isotropic thermal parameters
reduced the R index to 0.25. The molecules are related through anoncrystallographic pseudo diad. The electron density map is well defmed
for the two independent molecules.
The general Ca-backbone
conformations, geometries and the disposition of the characteristic a-helix
and the ~-sheets around the catalytic active site of Cys 25, within the cleftof two domains, seem nearly similar in both the molecules in theasymmetric unit. The presence of the catalytic triad and their involvementin the thiol-protease activity are visualized from this structuralinvestigation. Attempts for high resolutions studies are underway.

2P06
CRYSTAL STRUCTURE OF A COMPLEX OF WHEAT GERM
TRYPSIN INHIBITOR 11-5 WITH BOVINE TRYPSIN.
E. Kibushi , A . Suzuki, T. Shirai, T. Yamane, T. Ashida, Department of
Biotechnology, School of Engineering, Nagoya University, Nagoya 46401, Japan, and S. Odani, Department of Biology, Faculty of Science,
Niigata University, Niigata 951, Japan.
A trypsin inhibitor II-5 from wheat germ contains 61 amino acid residues
and five disulfide bridges , its molecular weight being 6,500 . We
determined the crystal structure of the complex between inhibitor ll-5
and bovine ()-trypsin. The crystals were obtained using polyethylene
glycol mono-ethylether (Mw 5,000) as a precipitant at pH 6.5 . The
crystals belong to space group P212121 with a=63.5, b=70.4 c=6l.OA. An
asymmetric unit contains one complex molecule. All diffraction data up
to 2.2A. were collected on a Weissenberg camera installed at BL-6A2
station of Photon Factory. The structure analysis was proceeded with themolecular replacement method using a trypsin as a search model.
Rotation search was performed using the modified Crowther fast rotation
function(Tanaka, N. (1977)Acta Crystallogr. A33, 191-193). In the
search, 6.0 to 3.5 A resolution data and a 20.4A integration radius wereused . Translation search was carried out using Crowther & Blow
method(Crowther R.A. & Blow, D.M. (1967)Acta Crystallogr. 23, 544548) at 3 .5 A resolution. Each of the search gave a significant uniquesolution. The structure of truly positioned trypsin in the unit cell was
refined to an R-factor of 0.230 at 3 .0A resolution by the program XPLOR. Then the structure of Il-5 was constructed on a 3A-resolutiondifference-Fourier map using the graphics program TURBO-FRODO .
Currently 46 residues of II-5 were built. The R-factor of the model is
0.220 for 11,631 reflections between 10.0 and 2.2A resolution . The
polypeptide folding of II-5 is similar to that of Bowman-Birk typeProtease inhibitors, especially near the reactive site. The interaction
manner of Il-5 with trypsin is essentially the same as that observed in theother trypsin inhibitor proteins.

2P07

Structure of a Kunitz-tYPe chymotrypsin inhibitor protein fromwinged bean seeds at 2.95 A resolution
J.K.Dattagupta, A.Podder, C.Chakrabarti and U.Sen, Crystallography andMolecular Biology Division, Saha Institute of Nuclear Physics,l!AF
Bidhan Nagar, Calcutta 700 064, India, and S.K.Dutta and M.Singh,
Indian Institute of Chemical Biology, Calcutta 700 032, India.

An a-chymotrypsin inhibitor protein(WCI) has been isolated from winged
bean (Psophocarpus tetragonolobus) seeds which is a single polypeptide
chain having a molecular weight of 20,244 Da with 183 amino acids. This
inhibitor belongs to the Kunitz(STI) family which is characterized by thepresence of two disulfide bridges and a molecular weight of around 20 K
Da. Structural information about the members of this family is limited only
to a few structures and none of them is a chymotrypsin inhibitor. This
protein also has the Wlique property of inhibiting bovine a-chymotrypsin in
the molar ratio 1:2 at higher concentrations of the enzyme. The crystal
structure of this inhibitor protein has been solved at 2.95A resolution using
x-ray diffraction methods. Crystals of the molecule belong to the hexagonal
space group P6122 with cell dimensions a=b=61.4A and c=210.9A. The
structure has been obtained by molecular replacement method using the
2.6A coordinates of Erythrina trypsin inhibitor as a starting model and it
has been refined to a R-factor of 19.1% with 58 water molecules
incorporated. The three-dimensional structure displayed by the protein
molecule consist of 12 antiparallel 13-strands with connecting loops
arranged in a characteristic folding common to other homologous serine
protease inhibitors in the Kunitz(STI) family . The crystallographic andstructural details and a comparison with related inhibitor structuresemphasizing the differences in the reactive site loop region will bepresented.

2P08
CRYSTAL STRUCTURE OF MACROCYCLIC INHIBITOR
FOR ELASTASE AND STRUCTURAL COMPARISONBETWEEN NON-BINDING AND BINDING STATES
T.Kinoshita, T.Tada, T.Yasuda, H.Fujita, and H.Hatanaka, Fujisawa
Phannaceutical Co., Ltd ., Osaka, JapanThe title compound(!) was isolated from Streptomyces resistomicificus.
(I) has a unique macrocyclic structure and exhibits potent inhibitory
activity for elastase. Elastase belongs to the serine protease family of
enzymes which are capable of cleaving connective tissue components.
Uncontrolled proteolysis by the elastase can cause some inflammatory
diseases. For the rational drug design, it is one of the most significant
infonnation to look into the difference between non-binding and binding
states. Three different crystal fonns of (I) were obtained from methanol
I water (a), ethanol I water (b), ethyleneglycol I water (c), respectively.
Each reflection data measured on the graphite-monochromateddiffractometer using a MoK a radiation. Only using data of (c), thepartial structure was obtained by direct method. Then the procedure of
the weighted fourier and the assignment some atoms were repeated . As aresult, the whole structure was obtained and eight water molecules were
found out. The final refinement converged to R=0.092. The final
structure of (I) is shown as figure 1. The binding structure in thecomplex with porcine pancreatic elastase was reported previously. The
difference of the both structures is slight(nnsd =0.58 A ) , especially, thebinding portion of the both is almost identical. The details of thecomparison will be reported .

figure I. slructure of the compound (I)2P09
Ligand-induced conformationa1 changes of 3isopropy1ma1ate
Thermusdehydrogenase
from
thermophi1us

H· Moriyama,

S. Kadono, M. Sakurai, T. Oshima, and
N. Tanaka, Faculty of Bioscience and Biotechnology,
Tokyo Institute of Technology,
Nagatsuta 4259,
Midori-ku,
Yokohama
226
Japan,andM.
Sato,
Institute for Protein Research, Osaka University,
3-2 Yamada-oka, Suita, Osaka 565, JapanThe structures of 3-isopropylmalate dehydrogenase(IPMDH; Imada et al, 1991; Moriyama et al, 1995)
from Thermus thermophilus ip complexes with its
substrate, cofactor, and a cofactor analog were
investigated by X-ray diffraction in a crystalline
state and by small-angle X-ray scattering (SAXS) in
solution (Sato et al, 1982). The structures at 2.8
A resolution of the complexes with the substrate,3-isopropylmalate (IPM), and with a cofactor analog
of NAD, ADP-ribose, were both very close to thestructure of the ligand-free enzyme with an open
conformation. However, the binding of a ligand
induced a small conformational change near thebinding site.
This result contrasts with that forNADP+-boundor
isocitrate-boundisocitrate
dehydrogenase (ICDH) from Escherichia coli, whichtakes a closed conformation. The SAXS analysis insolution clearly showed that the ligand-free IPMDH
adopts two distinct
intermediate
conformations
between the open and closed states upon binding of
NADH and IPM respectively, and does a fully closed
conformation in a ternary complex with NADH and
IPM.
Imada, K., Sato, M., Tanaka, N., Katsube, Y., &Oshima, T. (1991) ~. Mol. Biol. 222, 725-738.
Moriyama, H., Onodera, K., Sakurai, M., Tanaka,N., Kirino-Kagawa, H., Oshima, T., & Katsube, Y.
(1995) ~. Biochern. 117, 408-413.
Sato, M., Kasai, N., Hata, Y., Ii, Y., Miki, K.,
Tanaka, N., Kakudo, M., Tanaka, M., & Ozawa, T.
(1982). Biochemistry International 5, 595-602.

2P10
X-RAY
PRELIMINARYAND
CR YSTALLIZA TION
STREPTOMYCESOF
STUDY
CRYSTALLOGRAPHIC
OLIV ACEOVIRIDIS E-86 P-XYLANASE
Z. Fujimoto and H. Mizuno, National Institute of Agrobiological
Resources, Tsukuba, Japan., A. Kuno, S. Yoshida and I. Kusakabe,Institute of Applied Biochemistry, University of Tsukuba, Japan., and H.
Kobayashi, National Food Reserch Institute, Tsukuba, Japan.
P-Xylanase (EC 3.2.1.8) is a key enzyme for the degradation of xylan, amajor hemicellulose in plant cell wall, since it hydrolyzes P-1 ,4xylopyranosyl linkages of the backbone. P-Xylanases fall into two offamilies, denoted F and G, on the basis of-amino acid sequence. However,a few information of the structures of F family b\-xylanases has beenreported. The present study, therefore, is an attempt to determine thecrystal structure of Streptmyces olivaceoviridis E-86 P-xylanase, amember of the F family.
Crystallization was done by the hanging-drop method in tissue culture
plates. The droplets, consisted of 5 J.ll of protein solution (20 mg/ml) in
distilled water and 5 J.ll of reservoir solution, were equilibrated against 1
ml of reservoir solution at room temperature (25°C). Crystals appered in
the droplets within 1 week when the reservior solution of 25% saturated
ammonium sulfate in 50-fold dilution of Mcilvaine buffer (pH 5.7) was
used.
Diffraction experiments were carried out at the PF synchrotron facility,
Tsukuba. Cristals were orthorhombic with unit cell parameters, a = 79.6
A, b = 95.2A, c = 140.3 A . The value of Vm is 2.95 A3/Da, assuming two
molecules (MW = 45 K) in the asymmetric unit. Crystals diffract beyond
2.0 A.
Native data set was collected, and its processing is in progress. A searchfor heavy atom derivatives is also in progress.

2P11

ABILITY OF SOME SPECIFIC NATURAL STRUCTURESTO INTERACT CONCURENTLY CONTRARY TO DIOXIN. ESR STUDY.

Nguyen Van Tri, Pham The Vung, Dinh Pham Thai
Hanoi National University of Technology
Ha Van Mao, Dinh Ngoc Lam - Cancer Research Center.
Hanoi, Vietliam

On the basis of the ESR experimental results, some new active naturalcomplexes (symbolized XD*) present in speciai vegetable produces havebeen revealed. The nucleus structure of these complexes can show aelectron Spin combination almost similar to the one of Dioxin (2, 3, 7, 8 TCDD). However, it is especially remarkable that the Spin combination of
XD* occupies a quintuplet ground state with a deeply negative exchange
energy J < 0. This behaviour opposes entirely to the one .of Dioxin
possessing a combination of four 1t electron Spins with a singlet groundstate ( S =0) and a positive exchange energy J > 0.

Special binding complexes of Dioxin to XD* structures have been also
observed with a negative exchange energy J < 0. These [XD* - Dioxin]
3complexes appear with a very high probability, about 10 times of the oneof the [Hemoglobin - Dioxin] complex in human blood and of the [Mn Porphyrinoprotein - Dioxin] complex in humap liver. The properties ofthese interaction complexes corresponding with the results achieved insome respective experimental clinical studies over a long period of timesuggest that the specific natural XD* structures are able to conquer andarrest potently Dioxin molecules, i.e. to interact concurently contrary to thetoxicity of Dioxin, namely to its carcinogenous activity. This ability
depends on many factors such as the concentration and the lifetime of the
XD* state, the kinetic conditions of the surrounding and the interaction.

2P12
X-RAY CRYSTALLOGRAPHY OF METHIONYL-tRNA
SYNTHETASE FROM THERMUS THERMOPHILUS HBS
I Sugiura, Y. Ugaji, S. Maeda and M. Konno, Department of Chemistry,
Faculty of Science, Ochanomizu University, Bunkyo-ku, Tokyo, 112,
Japan, 0. Nurek.i and S. Yokoyama, Department of Biophysics andBiochemistry, School of Science, Tokyo University, Bunkyo-ku, Tokyo,
113, Japan
Arninoacyl-tRNA synthetases (aaRS) are.a class of enzymes that catalyze
the reaction of an ester linkage formed between the amino acid (aa) and ahydroxyl group of the 3'-terrninal adenosine of tRNA.
aa + ATP + tRNA -+ aa-tRNA +AMP+ PPi
Methionyl-tRNA synthetase (MetRS) was reported to recognize strictly
anticodon of tRNA. In order to know the mechanism of the anticodon
recognition and delineate the role of Mg2+ ion required for thisarninoacylation reaction, dimerization-domain-truncated MetRS from
Thermus thermophilus HB8 of molecular weight 58,000 have been
analyzed by X-ray crystallography . This truncated MetRS has been
expressed in E. coli. Crystals have been grown by the hanging drop
vapor diffusion method. A 10~-tl drop containing 15mg/ml protein, 5%
PEG6,000 and lOOmM HEPES was equilibrated against 25% PEG6,000
in the same buffer at pH7.5, 20°C. Small crystals was obtained after 24days. Small crystal was inserted as a seed into a protein drop with thesame condition except 10mg/ml protein. The crystal belongs to spacegroup P2J2121, Z=4, with unit cell dimensions of a=83 . l, b=l17.4,
c=56.7A . Intensity data for native and three CHJC02HgC6HtNH2,
K2PtC14 and Sm(OAc)J derivatives were collected using Weissenberg
camera at wavelength of 1.00A by synchrotron radiation source at KEK.
A data set for native crystals with 25611 independet reflections, R-mergeof 5.95% and the complete~ess of 88.7% to 2.2A resolution was obtained.
After refinement of metal parameters for derivative crystals, the overall
figure of merit was 0.65 by PROTEIN to 3.5A resolution. The electron
density maps calculated from this phase gave obvious molecular boundary
against solvent region. Moreover, the phase was improved by solvent
flattening method using the program DM.

2P13
CRYSTALLOGRAPHIC STUDIES OF HAMMERHEAD RIBOZYMES. II.
T. Chatake, 0 . Matsumoto*, Y. Chen, M. Tsunoda, N . Imaizumi and A. Takenaka, Facultyof Bioscience and Biotechnology, Tokyo Institute of Technology, Nagatsuta, Midori-ku,
Yokohama 226, Japan, A. Ohta, Y. Komatsu, M. Koizumi and E . Ohtsuka, Faculty of
Pharmaceutical Sciences, Hokkaido University, Sapporo, Hokkaido 060, Japan
It has been postulated that hanunerhead ribozymes have a common structure which isbasically composed of three RNA segments. In order to reveal the structure of
ribozymes and their reaction mechanism, we have been engaged in X-ray analysis.
Crystals obtained from a mixture of three RNA components were found to be composedof the two RNAs(l). In the present study we have investigated the structuralcomposition of the hanunerhead ribozymes, · and re-examined the crystallization
conditions.
Electrophoresis was carried out in poly-acrylamide gel with different combinations of theRNAs. Crystallization conditions were surveyed by the hanging- and the sitting-drop
vapor diffusion methods. Eleven kinds of hanunerhead ribozymes were examined. For
the enzymatic pan of the ribozyme, the binary complex of the two chains, CL-2 and CL4, was crystallized. For the full complex formation with its substrate, CL-3m, theternary mixture was crystallized.
5'-GCCUAGCUGAUGAAGGGUGAU-3'CL-25'-ACCCUGAAACCA-3'
CL-45'-GGUCmCUAGGA-3'
CL-3m
To ensure the complex formation, the ternary mixture was annealed after heating for 2minat 80 ·c. X-ray experiments were done using synchrotron radiation source (1..=1.0 A) at
the Photon Factory in Tsukuba. Diffraction patterns of crystals obtained from the binary
mixture were recorded on imaging plates by a Weissenberg camera.
Electrophoresis patterns indicated that the two chains except for the substrate one form abinary complex and that they form a ternary complex when mixed with the substratechain. Crystals of the binary complex between CL-2 and CL-4 were grown up to 0 .05 x
0.05 x 0.12mm, but those from the ternary mixture were too small for xcray
experiment. The newly obtained crystal had a good quality and gave reflections up to
4.5 A resolution. From diffraction patterns, it was determined that the unit cell had a
Laue symmetry of 32 with a space group of P321, P3o21 or P3>21, and that the lattice
constants were a =b =53.4 and c =59.4A. The number of the binary complexes in theasyrrunetric unit was estimated to be one from the volume per nucleotide. 3016
reflections with Fo > 3cr were collected, 519 of which were the independent reflections.
Rsym and Rmerge were 0.046 and 0.049 , respectively. Parallel to preparation of theheavy-atom derivatives, we are trying to solve the structure with the molecularreplacement method.
(1) 0. Matsumoto, Y. Chen. S . Hasegawa, A. Takenaka, A. Ohta, M. Koizumi and
E. Ohtsuka. 16th Congress and general assembly, International union of crystallography
MS-04.02.07, Beijing, China 1993.

* Present address : Faculty of Pharmaceutical Sciences, Kyoto University, Kyoto, Japan.

2P14

ON REFINEMENT OF PROTEIN STRUCTURES BY MEANS OFSHELXL-93
Geoffrey B. Jameson and Ross A. Edwards, Department of Chemistry andBiochemistry, Massey University, Palmerston North, New Zealand
The least-squares refinement program SHELXL93 (G.M. Sheldrick) is
increasingly being used for the refinement of protein structures whenreasonably high resolution data (better than 2.0 A) are available. We
report our experiences with SHELXL93 for the refinement of apo- andholo-azurin, both of which crystallize isomorphously with two moleculesin the asymmetric unit, features which facilitate analysis of refinements.
Both of these structures have been refined earlier to R - 0.16, by meansof PROLSQ. We have paid particular attention to the solvent watermolecules, which often have an artefactual existence. Comparison of therefinement of these proteins with SHELXL93 and other commonly used
programs for the refinement of macromolecules will be made.

2P15

MEASUREMENTS OF THE FARADAY EFFECTS AND X-RAY
BIREFRINGENCE AT COBALT K-EDGE WITH THE X-RAY
POLARIMETER
Y . Amemiya, T. Oguchi, K. Okitsu, PF, KEK, Oho, Tsukuba, lbaraki
305, Japan, and H. Maruyama, Okayama Univ.
We have developed a tunable x-ray polarimeter in order to measure xray optical activities such as circular birefringence (Faraday effect),circular dichroism, linear birefringence, and linear dichroism. The xray polarimeter consists of an x-ray pola_rizer and an x-ray analyzer
which are placed orthogonal with each other around an x-ray beam
direction (Hart et al., 1991 ). It also includes two sets of ionizationchambers to measure an absorption spectroscopy of a specimen. Both
x-ray polarizer and x-ray analyzer are made of a channel-cut silicon
422 crystal of four-bound reflections with its offset angle adjustable.
The two reflection planes of the channel-cut silicon crystal is set to beslightly offset from parallel so that only the cr polarization is reflected
while the 1t polarization is diminished near 8B=45°. The state of thepolarization of an x-ray beam which transmits a specimen is obtained bymeasuring x-ray intensities from the analyzer with a SSD while theanalyzer is rotated around the x-ray beam direction . The accuracy ofmeasured rotation angles of the x-ray polarization is 30 jlrad and theminimum measurable ellipticity of the polarization (I(7t)/I(cr)) is- 10·7.
The Faraday rotation spectra of Co and CoFe were measured near Kabsorption edge by applying magnetic field to the specimen with its
direction parallel and anti-parallel to the x-ray beam direction. The
results were compared with those of magnetic circular dichroism whichwere obtained by using a circular polarized x-ray beam from an x-ray
undulator. It has been found that the results of Faraday effect and thoseof magnetic circular dichroism relates quantitatively with each other by
Kramers-Kronig equation. Linear birefringence and linear dichroismof a single crystal Cobalt (hcp) has also been observed near Kabsorption edge without applying magnetic field to the specimen. It isfound that linear birefringence and linear dichroism also relates
quantitatively with each other by Kramers-Kronig equation.
Hart, M. , Siddons, D . P., Amemiya, Y., Stojanoff, V. (1991). Rev.
Sci. lnstrum . 62, 2540-2544.

2P16

CRYSTAL AND MOLECULAR STRUCTURE OF A 1:1 COMPLEX OF
PHATHYLYL SULPHATHIAZOLE AND SALICYLIC ACID

Ashok. K. Verma and R. K. Tiwari, School of Studies inPhysics, Jiwaji University, Gwalior 474011, India.

The crystal and molecular structure of a 1:1 complex of phathylyl
sulphathiazole and salicylic acid [C 25 H 180 8N2S2] has been solved using"SHELX-76" from CAD-4 diffractometer data. The complex crystallizes
in the orthorhombic space group with two molecules in the unit cell ofdimensions a=5.555(3)A, b=7.506(1)A, c=24.539A and dffi=l.48 gm/cc in
all 1217 observed unique reflections were used for the refinement and final
R value is 0.035. The geometry obtained is compatible as observed insimilar structures. The structure is stabilized by The network of Hydrogenbonds. The structural geometry around sulphonamide group deviates asusual from the tetrahedral. The structural features compared with othersulpha drugs will be discussed and the geometry and packing details will
be highlighted in the presentation.

2P17
STRUCTURE CHARACTERIZATION OF CONSTITUENTS FROMBRJDELIA OVATA DECNE AND FROM DAVALLIA SOLIDA SW .
Kenneth J. Haller, Metallurgy and Materials Science Research Institute,
Chulalongkom University, Bangkok 10330 Thailand; Amorn Petsom, Sophon
Roengsumran, Preecha Lertpratchya, Suparb Boonyaratavej, Nisakorn
Thongkon, Jatupom Phaopongthai, Chemistry Department, Chulalongkorn
University, Bangkok 10330 Thailand.
Single crystal x-ray structural studies were undertaken on two crystalline
constituents isolated from the title plants in quantities too minute tocharacterize by conventional chemical and spectroscopic techniques.
From the rhizome of Davallia salida Sw, (1) 19-Hydroxyneohopane.
Crystal data: C 30H480, colorless, monoclinic P2 1 (No. 4), a = 12.587(3) ,b = 7.558(2), C = 13.620(3), (:J = 102.68(3) 0 , Z = 2, deale= 1. 112 Mg/m3.
From the leaves of Bridelia avaJa Decne, (2) the 2,4-diethyl-1,3,5,8Tetrarnethylporphine-6-formic acid ethyl ester-7-propionic acid ethyl ester.
Crystal data: c36H42N404, purple, triclinic PI (No. 2), a=9 .409(2),b= 12.589(2), c= 14.683(2), a= 103.19(2), (:J= 107.49(2), 'Y= 103 .40(2) 0 ,Z=2, dc.o 1c= 1.292 Mg/m3.
The x-ray structure of the previously identified Filicene (3), a constituent
available in larger quantity from Davallia salida Sw, was also determined.
Crystal data: C 30 H50 , colorless, monoclinic P2 1 (No. 4), a = 11.037(2),b = 7.669(1), C = 30. 106(2), {:J = 99.08(00 , Z = 4, deale= 1.084 Mg/m3.
R'

~R

(2)

R

R =MethylR' = EthylR • = Formic acid ethyl esterR • = Propionic acid ethyl ester

2P18

SYNTHESES AND CRYSTAL STRUCTURES OF GROUP 6 METAL CARBONYLS
CONTAINING POLYPHOSPHINE LIGANDS
Chuen-Her ~. Den-Nan Horng, Tzuoo-Tsair Luo and May-Hwai
Shieh, Department of Chemistry, National Taiwan Normal
University, Taipei 11718, TAIWAN
Eight types of group 6 metal carbonyl complexes werefrom[:i(C0) 6 J

polyphosphinePPhz)3Cr,:i=

1 igands(:ieC-Pf 3 ),(Pf-Pf-PF-Pf)):

1)

Moor

W)

and

PhP( ( CHz) zPPhz) 2P((CHz)zPPhz)3(P-Pf3)

Mononuclear

biligatePf3) I have a dangling phosphine group;thes ynthesized

corresponding( Pf-Pf-Pf),or

CH3C( CHz -{PhzP(CHz)zPPhCHz}zcomplex-[Mo(C0) 4 (HeC-

2) Mononuclear triligate

complex- The geometry of the coordination sphere of [W(C0) 3 (PfPf-Pf))

is a facial octahedron;3)

Homo-binuclear triligate

complex- Two isomers for [Cr(C0) 4 {Pf-Pf-Pf)Cr(C0) 5 ], one having a
5-membered chelating ring and the other having a 8-membered ring,are successfully isolated and characterizedj 4)

Hetero-binuclear

triligate complex- Each complex of [H(C0) 4 (Pf-Pf-Pf)M'(C0) 5 ) and[Ho(C0) 4 (MeC-Pf 3 )Mo(C0) 5 ] contains two different group 6 metals;5) Homo-binuclear tetraligate complex- [W(C0) 4 (P-Pf 3 )W(C0) 4 J havea

5-membered and abinuclear

8-membered

tetraligate

complex-chelating
Each

ring;

complex

6)ofHetero[M(C0} 3 (P-Pf3)M' (C0) 5 ] contains two different metals with the metal H are
trisubstituted ;7)

Trinuclear

triligate

complex-Eachphosphorus atom of the ligands of [(H(CO)s}3(L 3 ll is coordinatedto the M(C0) 5 moiety;8)tetranuclear

tetraligate complex -Thegeometry of the four metals for the complex containing tripodal
ligand is a distorted tetrahedron,but thefour metals

for

the

linear ligand are mutually opposite and are almost located in thesame plane.

2P19
APERIODIC CRYSTAL STRUCTURE IN VEGETABLE FIBRES
Nguyen Van Tri, Nguyen Van Thang, Pham The Vung Institute of Technical Physics, Tran Nhat Chuong and Hoang Thi
Linh - bepartment of Textiles . llat1oi University of Technology,

Hanoi Vtetnam

The particular molecular - electronic microstructure and related
properties of many different genera of vegetable fibers (such as cotton,
jute, pineapple, sisal) have been studied with ESR in combination withand especially a newother methods. The partner radicals C' and(2Fe-2S) exchange complex in the fibred structure were revealed. This
physical local structure coupled by fivefold (2Fe-2S) rhombic
combinations diagonally bonding a macromolecule chain with fiveneighbouring ones is based on a pentagon created by five sulfur atoms
whose plane is perpendicular to the axis of the fibre . The importantroles of this structure in the formation of the elementary fibres and inspecific features of the material (such .as the strength, the tensility, thetorsional module) have been pat1ly discovered. Some technologicaltreatments to improving fibre properties have been also efficiently
examined.

o·,This publication is completed with financial support from the
National Basic Research Program in Natural Sciences and the Textile
Research Institute2P20
Outer-sphere coordination of phenanthroline inaq uachlorotri(p-chlorophenyl)tin -1,1 0-phenan th roline dimer
Ng Seik Weng' and V.G. Kumar Das'1
lnstitute ofAdvanced Studies and 'Department ofChemistry, University ofMalaya, 59100 Kuala
Lumpur, Malaysia

Abstract
aquachlorotri(p-chlorophenyl)tin· 1, 1 0-phenanthroline
Dim eric[(p-ClCJ1 4) 3SnCIHp1, 1O·phen] 2 crystallizes in the triclinic P1- space group, with
a= 11.878(5); b = 12.747(4), c = 20.515(6) A, a= 84.37(1), fi = 80.74(3), y =69.39(2t, V = 2867(2) N; Z = 2. In the crystal structure, the two heterocyclicbases interact with the trans-C 3SnCIO trigonal-bipyramidal tin atoms through thecoordinated water molecules, each of which forms a hydrogen bond to its
phenanthro1ine and another to the phenanthroline belonging to the other moeity.
The location of the hydrogen atoms in this structure from the diffraction
measurements at -I 05°C has enabled the role of water in the Wlsubstituted
chlorotriphenyltin complex (Gabe, Lee & Smith, lnorg. Chim. Acta, 90, Lll,
1984) to be clarified.

Fig. 1. Hydrogen bonds involving the water and 1,10-phenanthroline molecules. O(la) ·N(lb}2.873(7), O(lb)N(la) = 2.864(8), O(la)···N(2a) = 3.083(8), O(Jb) ·N(2b) = 3.000(8) A;
N(lb)O(la}N(2a) = 130.9(2), N(la) O(Jb)N(ib) = 124.2(2)

=

0

•

2P21
NOVEL POLYCHALCOGEN-PNICOGEN COMPLEXES OF CHROMIUM

w.

Chen,

L.

Y.

Goh

and

R.

c.

s.

Wong,

DepartmentofChemistry, University of Malaya, Lembah Pantai, 59100 Kuala
Lumpur, Malaysia.

Structuralfeatures

of

novel

tetrachromium

complexes

obtained from reactions of [CpCr(Co) 3 ] 2 with P 4 s 3 (E = S,
Se) where P 4 E 3 undergoes multiple ·bond cleavage without
fragmentation(

not observed as yet in other transition

metals) (Goh, Chen & Wong (1993); Goh et al. (1995)) will be
described.

Goh, L.Y., Chen, W. & Wong, R.c.s. (1993). Angew. Chem. 105,
Nr.12, 1838-1840; Int. Ed. Engl. 32, No.12, 1728-1729.
Goh, L.Y., Chen, W., Wong, R.C.S., Zhou, Z.Y . & Fun, H.K .
(1995). Mendeleev Commun., 60-61

2P22

STRUCTURE ANALYSIS OF UNSTABLE CRYSTALS USING
RAPID X-RAY MEASUREMENT SYSTEM
T. Watanabe, N. Manabe, H. Nishiy ama , M. Yasui, F. Iwasaki,
Department. of Applied Physics and Chemistry, The University ofElectro-Communications, Chofu-shi, Tokyo 182, Japan
Recently a rapid X-ray measurement system with the imaging plates has
been developed by Kamiya & Iwasaki (1995). A performance test of thisequipment indicated that the accuracy of the intensity data are reliable
and the system can work as a tool of the structure analysis for typicalorganic crystals.(Iwasaki, et al., 1995) This equipment, however, hadsome retrictions of 28 range and an alignment of a specimen. We havedeveloped a new machine which will overcome the above problems. In
this system; 1) 28 range is widened from 45 • to 60·, 2) a three-circle
goniometer with K axis is equipped to align specimens in the wide range
and 3) the equi-inclination I! axis is equipped to rotate the Weissenbergtype IP camera in the horizontal plane. Using this system with MoKa
radiation (50kV, 200mA), we have determined the structures of unstable
crystals, 1, 2 and 3, for which intensity measurements by a four-circle
diffractometer were failed. The total time of intensity measurement was
7 - 14 hours for each crystal. Stable crystals of 4 were so tiny tomeasure intensities by a four-circle diffractometer. The crystal size
using intensity measurement was 0.08x0.03x0.15 mm . In this paper a
performance test of this system including the inclination axis (I! axis) willbe also reported .
1

2

3

4

FW
SP,. gr .

1166.56

1327.07988.20439.41

P2t/n

P2t/n

Pn

PT

all}

14.17926.44728.245
90.0
118.0
90.0
9351

28.12716.79714.103
90.0
101.2
90 .0
6536

15.9849.949
14.854
90.0
100.9
90.0
2319

8.753
11.17311.194
110.1
103.8
106.0
918.4

8

4

2

2

7
46719
15298
ll013
0.076

7
37227
12100
8552
0.106

7
14890
4688
4294
0.067

14
8213
3394
2084
0.102

b/A

ciA

ar
pr
v

y(

z

Meas. time/h
No .mcas.
No.uniqueNo.obsR

1 (CtoHt6N4SzPd)3·C6H6
2 Cs4H44CI3N4PzSzRh ·2CHCI3
3 C46H46CIN40PzSRh·CHzCiz 4 Ct7H12N4S3CI2
Iwasaki, F., Sakuratani, M., Kaneko, H. , Yasui, M. , Kamiya, N . & Iwasaki, H.

(1995). Acw Cryst., B51 , in press.
· Kamiy a, N . & Iwasaki , H. q995). J. App/. Cryst. , in press.

2P23

STRUCTVRE OF {((Ph2NCH2PPh2)Au]3S}CI · H20
Ju-Chun Wang & Lin-Shu Liou
Department of Chemistry, Soochow University,
Taipei, Taiwan 11102, REP OF CHINA
The title compound has been isolated as a minor product whenAu(Ph2NCH2PPh2)Cl was reacted with DMSO in the presence ofbase. The pale yellow crystals suitable for X-ray analysis weregrown by slow diffusion of Et20 into the DMSO solution of thecompound. The crystal structure has been determined at room
temperature using Cu Ka radiation. The S atom locates on a
crystallographic C3 axis and is bonded to threeAu(Ph2NCH2PPh2) unit. Thus each asymmetric unit contains
only 1/3 of the molecules. Three Au-atoms and one S-atom form
a perfect pyramidal geometry with S atom on the apex. The
coordination environmental of Au is as expected linear. The Au-S
and Au-P bond distances are 2.320(3) and 2.234(6) A,
respectively. Short Au-Au .contacts have been observed. This
contact distance 3.174(2) A is comparable to those foWld in other
Au dimers and trimers suggested that the so-called "relativistic
bonding interaction" may exit in this system. Small Au-S-Au
angle, 86 .3(2)0 , also supports existing this type of interaction.

Crystal Data: {[(Ph2NCH2PPh2)Aul3S}Cl · H20 is cubic,
a=23.967(2), V=13767(2)A3, Z=8, space group Pa-3 (NO 205).
Final R values are R=0.0460, Rw=0.0501 and S=l.49 for 1067
observed reflections [I > 3cr(I)] and 95 parameters.

2P24
CRYSTAL STRUCTURE OF BINUCLEAR 1:1 SILVER(!) 2HYDROXY -3,5-DINITROBENZOATE:TRIPHENYLPHOSPHINECOMPLEXA. Hamid Othman, Jabatan Kimia, Universiti Kebangsaan Malaysia,
43600 Bangi, Malaysia, and Effendi and Allan H. White, Department ofChemistry, The University of Western Australia, Nedlands W.A. 6907.
A binuclear complex [(Ph 3P)(Ag(jl-0-0Ac) 2-Ag(PPh 3)] was obtained byaddition of molar excess of triphenylphosphine to silver acetate in boiling
toulene. Reaction of this complex in methanol with 2-hydroxy-3,5dinitrobenzoic acid gave yellow crystals that retain the binuclear structureof the parent complex. The single crystal X-ray structure determination
of
the
1:1
adductofsilver(!)
2-hydroxy-3,5dinitrobenzoate:triphenylphosphine (AgL:PPh 3) shows it to be acentrosymmetric system with the silver atoms bridged by one of the
carboxylate oxygen atoms of each ligand, [(Ph3P)Ag(j.J.-0-LhAg(PPh3)]
as in the acetate (Othman & Ng, 1995).
Crystal data : [(Ph 3P)Ag(j.J.-0-LhAg(PPh 3)] triclinic, spacegroup Pl. a
15.846(5), b 9.444(3), c 9.084(3) A, a 62.73(2), p 77 .25(2), y 73.62 °, Z
1 (dimer), R was 0.051 for 3176 'observed' (1>3a(l)) reflections.
The Ag ... Ag' distances are identical, as are 0 .. .0' to those of the parent
acetate complex. The central Ag(j.J.-OhAg ring is exactly planar, and very
precisely so in the acetate despite the lack of inversion centre. The
phenolic oxygen is disordered over two possible sites.

Othman, A.H. & Ng Seik Weng (1995). Z. Krist. (submitted for
publication)

2P25
CRYSTAL

STRUCfURE

OF .

[4-[ro-(cholesteryloxycarbonyl)-

hexyloxycarbonyl] phenyl] ferrocene
N.Nakamura and T.Takayama, Department of Chemistry, Faculty of
Science and Engineering, Ritsumeikan University, 1916, Noji, Kusatsu,
Shiga 525, Japan
A selected orange needle crystal of C5 1H71 0 4 Fe having approximate
dimensions of 0.2 x 0.4 x 0.05 mm was mounted on a glass fiber. All
measurements were made on a Rigaku AFC5R diffractometer withgraphite monochromated Cu-Ka radiation and a 18kW rotating anodegenerator. Unit cell dimensions obtained from a least-squares refinement
using the setting angles of 25 carefully centered reflections in the range
46.4°<29<57.0°.
The data were collected at a room temperature of 296K using the ro-2e scan
technique to a maximum 2e value of 120.4°. Scans of (1.1+0.3tan9) 0 weremade at a speed of 4°min·l (in ro). Of the 7524 reflections which werecollected, 7021 were unique. The intensities of three representativereflection were measured after every 150 reflections. An empiricalabsorption correction based on azimuthal scans of several reflections wasapplied. The data were corrected for Lorentz and polarization effects. The
structure was solved by direct methods with SHELX86 (Sheldrick, G.M.,
1985) and expanded using Fourier with DIRDIF92 (Beurskens, P.T. et al,1992). The non-hydrogen atoms were refined anisotropically. Hydrogenatoms were included but not refmed. The final cycle of full-matrix leastsquares refinement was based on 3198 observed reflections (I> 3a(l)) and
1009 variable parameters, l:w(IFoi-IFcl)2 minimized, R=0.060, wR=0.082.

2P26

SOLVANT INFLUENCE ON CRYSTALLIZATION OF PHENYLCARBAMIDONITRILE

Qing-chuan Yang. Dan-mei Huang, Hui-ying Chen and You-qi Tang,
Deparnnent of Chemistry, Peking University, Beijing 100871, China.

The polymer of phenyl carbamidonitrile(l) has noticeable electricbistability properties. During the study on the crystal structure of themonomer I, it was found that the selection of solvant was important. The
crystals of compound I were obtained from the tetrahydrofuran solution,but other crystals of adduct of phenyl-carbamidonitrile: w,w'-diphenylbiuret (1 : 1) were obtained from the ethanol or ethyl acetate solution ofcompound I. The formation mechanism for the adduct product wasestimated.

The project was supported by the National Natural Science Foundation ofChina.

2P27
CRYSTAL STRUCTIJRE OF cis [-5-(2-Dimethylaminoethyl)-3-hydroxy2- (4-methoxypheny1)-2,3-dihydro-1,5-benzothiazepine ](±)
P.Kumaradhas and K.A .Nirmala, Department of Physics, Bangalore
University, Bangalore-560 056, India, and M.A.Sridhar, Department ofstudies in Physics, Mysore University, Mysore-570 006, India.
The title compound is a drug intermediate of Diltiazem. Diltiazem is anenantiomerically pure drug with calcium antagonist activity (Kojic Prodic et al., 1984). This compound was obtained by (2R,2S)-3-(4methoxyphenyl)methyl glycidate was treated with 2-amino thiophenol
in presence of triethyl amine the resulting product was hydrolysed
and treated with acetic anhydride and pyridine. Recrystallization wasfrom ethonal.
Crystal data: Cwfi22N20 3S, Orthorhombic, space group Pbcn,
a=11.447(1), b=12.978(1), c=24.881(l)A. R=0.048, wR=0.108.
The seven membered ring is distorted showing twist boat
conformation. Methoxyphenyl and hyroxy groups are cis oriented.
The methoxyphenyl group adopts axial and carbonyl oxygen atom andaminoethyl groups are psuedo-axial. The molecule is stabilized bycovalent bonding and weak hyrogen bonding, but the crystal packing isstabilized by van der Waals interactions.
Programs used to solve and refine the structure: SHELXS-86 and
SHELXL-93.
Kojic-Prodic, B., Ruzic-Toros, Z. & Sunjic, V. (1984).
Helv.Chim. Acta. 67, 916-926.

2P28
CRYSTAL STRUCTURE OF cis[l,5-Benzothiazepine-4(5H)-one- 1oxide-3-(acetoxy) - 2,3-dihydro-2-(4-methoxyphenyl))(±)

K.A.Nirmala and P.Kumaradhas, Department of Physics, Bangalore
University, Bangalore-560 056, India.

The title compound is a drug intermedi.ate of Diltiazem (Kojic-Prodic
et al., 1984). Diltiazem belongs to the family of drugs commonly named
calcium channel blockers or calcium

antagonists and is useful for thetreatment of cordiac and coronary

diseases . The crystals were grownfrom ethona1- acetone mixture at room temperature.
Crystal data: C 18H 17N0 5S, Orthorhombic, space group Pbca, a=8.200(8),b=l3.326(9), c=32.093(6)A, R=0.045, wR=O.l3.
The molecular packing is stabilized by weak hyrogen bonding between
the polar atoms and van der Waals interactions between the non-polar
atoms. The seven membered ringis distorted

showing

twist boat

conformation. Methoxyphenyl and acetoxy groups are cis oriented. The
methoxyphenyl group adopts axial position in the molecule but sulphoxide
oxygen in equitorial.

Programs used to solve and refine the structure: SHELXS-86 and
SHELXL-93.

Kojic-Prodic, B., Ruzic-Toros, Z. & Sunjic, V. (1984 ).
Helv. Chim. Acta. 67 , 916-926.

2P29

CRYSTAL STRUCTURE OF TIN XANTHATES.
M. I. Mohamed-Ibrahim•, Omar bin Shawkataly", Hoong-Kun Funb andK.Sivakumar', •chemical Sciences Programme, Centre for Distance Education. and bX-Ray Crystallography Unit, School of Physics, Universiti Sains Malaysia,
11800 USM, Penang, Malaysia.

The crystal structures of Me 2Sn(S2CO-c-C 6H 11 )2 and Ph 3Sn(S2CO-CH 2C6H5)
have been determined by X-ray diffraction methods. The former crystallises inorthorhombic Pnma, with cell dimensions a= 10.224(1), b = 21 .514(2), c == 4 and Ox = 1.474 Mgm· while the latter crystallises inmonoclinic P21/n with a = 12.636(1), b = 14.367(2), c = 13.415(1) A, p =10.230(1) A, Z

3

93 .09(1) 0 , Z = 4 and Ox= 1.456 Mgm·3 . Both structures were solved by direct
methods and refined by a full matrix least-squares technique to final R = 0.067
and 0.030 respectively. The environment about each tin atom in bothcompounds is a distorted tetrahedron with the xanthate ligands being
essentially unidentate. However in the first compound, the xanthate is in a 'S,S'
mode of orientation whereas in the second compound, an 'O ,S' mode wasfound. Details of the structure analysis will be presented in the conference.

2P30

CARBON NANOTUBES ON THE TOP SURFACE OF CATHODEDEPOSIT AT DC ARC-DISCHARGE
Y. Ando, X. Zhao and M. Ohkohchi , Department of Physics, Meijo University,
Tenpaku-ku , Nagoya 468, J apan , and M. Wang, Department of Physics, Nagoya
University, Chikusa-ku, Nagoya 464 , Japan
Carbon nanotubes were first found by lijima (1991) in the carbon deposit on thecathode, although the original specimens were prepared by one of the present authors (Y. A.) as byproduct for fullerene formation by de arc-discharge evaporationof graphite rods. The nanotubes can be prepar_ed in the atmospheric gas of He andCH 4 (Ando and Iijima, 1993) . Such carbon nanotubes could be observed by highresolution scanning electron microscopy (SEM) in the top surface of cathode deposit
also (Ando, 1993) , which is the part just finished arc-discharge.
The apparatus used for the preparation of carbon nanotubes was the same with thatused for the preparation of ultrafine particles of SiC by gas evaporation method . In
the case of fullerene formation , the Si-block of anode was replaced by graphite rod
installed vertically. After the evaporation of graphite rod of anode, a part of evaporated carbon deposits on the cathode. The section and the top surface of the cathodedeposits were observed by a high resolution SEM.
On the top surface of cathode deposit prepared in He gas, the co-existence of carbon
nanotubes and carbon nanopar ticles were usu ally found . When the evaporation
has been carried out in CH 4 gas, the top surface of cathode deposit shows various
morphology depending on the pressure of CH 4 gas and on current density of dearc-discharge. In the case ofhigh pressure CII 4 gas and highcurrent density, first preparedcarbon nanotubes are embelished by carbon nanoparticles as
seen in F ig. I . It means theactivity of the surface of carbon nanotubes prepared in CH,1gas.
Ando, Y. (1993) , Jpn. J. Appl.
Phys. 32 , Ll342-L1 345.
Ando, Y. & lijima (1993), Jpn.
Fig. 1 SEM image of carbon nanotubes
J. Appl. Phys. 32, Ll07-Ll09.
embellished by carbon nanoparticles.
Iijima, S. ( 1991 ), Nature, 354, 56-58.

2P31

CRYSTAL STRUCTURES OF GROUP 15 MIXED LIGAND DERIVATIVES OF
Ru3(C0), 2•
Omar bin Shawkataly", Sok-Tin Lee• , M.Parameswari ", Hoong-Kun Fun band
K.Sivakumaf, "Chemical Sciences Programme, Centre for Distance Education
and bX-Ray Crystallography Unit, School of Physics. Universiti Sains Malaysia,
11800, Minden, Penang, Malaysia.
The X-ray structural studies of group 15 ligand derivatives of Ru 3 (C0) 12 havebeen widely studied 1 • The M.I.Bruce-A.H.White research group has undertaken
the study of X-ray structures of numerous complexes of this type. However,crystal structure studies of group 15 mixed ligand derivatives of Ru 3 (C0) 12 havenot been reported so far. As a part of our study of mixed ligand substitutions on
Ru 3 (C0) 12 with group 15 ligands, we have undertaken the synthesis andstructural characterisation of a series of such compounds. Several mixed ligand
derivatives were prepared using the radical anion Ph 2CO method 2 .
Ru 3(C0) 8(dpam)(dppm) and Ru 3 (C0) 9 (dpam)(PCy2 Ph) were prepared by ligand
substitution on Ru 3 (CQ} 10 (dpam) and were purified by preparative TLC andcharacterised by spectroscopic methods (IR, 1H, 13 C and 3 1 P NMR) and X-ray
Ru 3 (C0) 8 (dpam)(dppm)
andofcrystallography. Single crystals
Ru 3 (CO}g(dpam)(PCy 2 Ph) were grown from dichloromethane/methanol bysolvent/solvent diffusion method. The former crystallises in orthorhombic spacegroup Pca2 1 with a= 21 .586(2) , b = 15.839(1 ). c = 18.383(1) A. Z = 4 and Ox =1.459 Mgm·3 while the latter crystallises in the triclinic system , space group P-1 ,a= 12.575(1) , b = 12.902(1) , c = 16.959(2) A. a = 92.07(1) , ~ = 110.50(1), y =98 .14( 1)0 , Z = 2, Ox = 1.704 Mgm·3 . This paper will describe and discuss theresults derived from the crystal structure analyses of these two compounds .
References :1.
M.I.Bruce, M.J.Liddell, O.b.Shawkataly, I. Bytheway, B.W.Skelton &A.H.White. (1989). J. Organomet. Chem ., 369, 217.
2.
M.I.Bruce, J.G.Matisons & B.K.Nicholson. (1983) . J. Organomet. Chem.,
247, 321 .

2P32

STRUCTURE
OF
1-(4,5-DIHYDRO-IH-IMIDAZOL-2-YL)IMIDAZOLIDIN -2-THIONE HYDROBROMIDE
Y. Wattanakanjana and C. Pakawatchai, Department of Chemistry, Princeof Songkla University, Hat Yai 90112, Thailand, and B. W. Skelton and
A. H . White, Department of Chemistry, University of Western Australia,
Nedlands, W.A. 6907, Australia.
The reaction of copper(l) or copper(II) halides with substituted
thioureas(L) yields a variety of complexes or compounds such as CuLX,
CuL2X, Cu2L3S04, L2 or LL' (where L' is a deprotonated ordesulfurated ligand) depending on the nature of L, solvent and the moleratio of halides and ligands. The title compound was obtained from thereaction between copper(l) bromide and ethylenethiourea(L) in the moleratio 1:2.5 using water as reaction medium. Qualitative elementary
analysis was performed using X-ray fluorescence spectrometry. The
crystal structure of this compound determined by single X-ray diffraction
methods revealed the compound to consist of discrete desulfurated
diethylnethiourea cations, [C6H 11 N4S) and bromide anions. All nonhydrogen atoms including the bromide ion, and t?e N-hydrogen atoms, lie
in the same plane. The C- S distance 1.647(4) A.' is short compared withthe parent ethylenethiourea molecule{ 1.688(2) A} due to the resonanceeffect.

C

NH\

+

-N

~

NH/ \

e- NH

ll

s

Fig. I Desulfurated diethylenethiourea cation .

Clystal data : C6H 11 BrN4S, orthorhombic, spac~ group Pnam(No . 62)
a 15 .295(3), b 9.063(2), c 6.895(7) A .

2P33
STRUCTURAL AND

CONFORMATIONALSTUDIESOF

TRITERPENOIDS: 19-EPIMERS OF LUPENES
Tamiko Kiyotani, Kazuo Masuda and Hiroyuki Ageta
Showa College of Phannaceutical Sciences, Machida, Tokyo 194, Japan
Ferns are known to produce various skeletal triterpenoids. We have isolated
many triterpenoids from ferns and elucidated their structures. Triterpenoids arebiosynthesized from squalene which consists of six isoprene (C 5H8 ) units. The titledcompounds, lup-20(29)-ene (I) and isolup-20(29)-ene (II) were isolated from the same
fern: Lemmaphyllum microphyllum (Polypodiaceae). Their structures were elucidatedby spectroscopic methods. In order to determine their conformations, especially anisopropenyl moiety, we investigated X-ray crystallographic analysis. As a result, I
seems to have two conformations (Ia and I b) at the side chain (isopropenyl group) as astable conformation, but II showed only one stable conformation (II) as shown in
Figure. The above result was also explained in CDClJ solution by the NMR NOE
experiments. Further, molecular mechanics calculations by Chem3D plus for several
kinds of the conformations considered at the side chains of C-19 ofl and ll respectively.
The conformations ofl and II at the side chain will be discussed.
Crystal data: Ia, C:J{ 50 , Mr-410.73, orthorhombic, space group P2 12 12 1, a=10.664(1),b=l4.054(1), c=l7.157(1) A, V=2571.4(2) AJ, Z=4, Dx=l.06 g cm·J, R=0.052,
wR=0.061 for 1890 reflections. II, CJ 0 H 50 , Mr-410.73, monoclinic, space group P2 1,
a=7.654(1), b=I6.521(2), c=l0.109(1) A. ~=97.85(1) 0 , V=I266.3(2) AJ, Z=2,
Dx=l.08 g cm·3 , R=0.042, wR=0.048 for 1598 reflections. Data collections were
performed on an Enraf-Nonius CAD4 express diffractometer with monochromatedgraphite Mo Ka radiation (A-=0.71073 A). Both were solved by direct method using
SIR88 and refined by full -matrix least-squares. Non-hydrogen atoms were refined
anisotropically and all hydrogen atoms were refined isotropically using riding model.

29

30

20 ~ 19

21

22
28

2
3

23

30

29

30

~

{:B

24

Ia

lb

II

29

2P34

SYNTHESES, CHARACTERISATION AND CRYSTAL STRUCTURE OFTRIOSMIUM ALKYLIDYNE CARBONYL CLUSTER CONTAININGCHIRAL AUXILIARIESW AI-YEUNG WONG and WING-T AK WONG 'Department of Chemistry, Th e University of Hong Kong , Pokfulam Road, Hong Kong.
Treatment of [Os3(1J.-H)3(C0)9(1J.3-CCl)) with a large excess of(-)-(R)-N,N-diroethyl-1[(S)-1 ',2-bis(diphenylphosphino)ferrocenyl]ethylamine [(R,S)-bppfa] in the presence of
DBU leads to the air-stable chiral complex (R,S)-[0s3(1J.-H)2(C0)9{1l3-CPPh2(T\5_Csl-4)Fe(115-CsH3(PPh2)CH(Me)NMe2)}) 1 in moderate yield. Yellow crystals of 1 wereobtained from slow evaporation of a dichloromethane solution at room temperature.
Complex 1 consists of a triosmium al.lcylidyne metal core with the chiralligand (R,S)-bppfa
co-ordinated directly through the PPh2 group on the Csl-4 ring to the apical carbon atom .
The other PPh2 moiety on the disubstituted cyclopentadienyl ring remains pendant, see
Figure 1.

Figure 1

07

OS

2P35

MOLECULAR STRUCTURES OF ORGANIC LANTHANIDECOMPLEXES HAVING ETIIYLENE POLYMERIZATION ACTIVITY
N. Kanehisa. H. Hashimoto, M. Yamagashira. andY. Kai, Department ofApplied Chemistry, Faculty of Engineering, Osaka University, Suita,
Osaka 565, Japan
M. Nodono, E. Ihara, and H. Yasuda
Department of Applied Chemistry, Faculty of Engineering, Hiroshima
University, Higashihiroshima, Hiroshima 724, Japan
We have proceeded the X-ray structure analyses of a series oforganic lanthanide complexes to elucidate the correlation between themolecular structure and the activity for ethylene polymerization.
Recently, we obtained the single crystals of an organic lanthanide
complex of this series without the activity for ethylene polymerization.
We have carried out the X-ray structure analysis for this complex andcompared the structure with the ones having the polymerization activities.
Crystal data: SiMe2[Tl5-C5H2SiMe3SiMe2(tBu)]2Sm(THF)2 (THF)(l),C42H8203SmSi5, F .W.=925 .94, monoclinic, P2}/c, a=l2.147(3),b=20.780(3), c=21.718(2)A, ,8=103.55(1) 0 , V=5329(l)A3 , Z=4,
X-ray intensity data were collected on a Rigaku AFC-5R
diffractometer with graphite monochromatized MoKa radiation. A total
number of observed reflections [IF ol >3cr(F o)] are 3540. Structure
analysis was carried out by using the TEXSAN program system. The
crystal structure was solved by the heavy atom method and refined by thefull-matrix least-squares . At the present stage of the refinement, thediscrepancy factors; R (Rw) is 0.070(0.089).
Fig.l shows the molecular structure of 1.
The complex I has a slightly distorted tetrahedral geometry around the Sm atom formedby two THF ligands and two Cp ligands.
This complex has a non-crystallographic
C2 symmetry with pseudo 2-fold rotation
OJ
axis passing through the Sm and thebridged Si atoms. For ethylene polymerization activity, it may be considerable that
one of the important factors is a nonsymmetrical geometry around the central
metal atom in the catalyst monomer.

"'''

Fig. I. Molecular structure of 1

2P36

CRYSTAL STRUCTURE OF 2,10-DICHLORO -6- (2,4
DIMETHYL PHENOXY )- DffiENZO [d,g] [l ,3,6,2]
DIOXATHIAPHOSPHOCIN -6- SULFIDE.
N.Jagadeesh Kumar!, M.Krishnaiah\ B.Sankara Reddy 1 & C .D.Reddy\
Department of Physics§/Chemistry\ Sri Venkateswara University,
Tirupati-517 502, INDIA.

Considerable interest has been shown to study the X-ray crystallographic
studies on dibenzo [d,g] [1 ,3,6,2] dioxathiaphosphocins because of theirpotential use as antioxidants and stabilizers in polymers and oils. We
present the crystal structure of the title compound, to understand the effectof the substituents on the molecular geometry and conformation of hetero
cyclic ring.
The colourless transparent crystals of the title compound (C 20Hn0 3CI 2PS 2)
obtained from 2-propanol are monoclinic, P2/n with cell parameters
a=l3 .272(2), b=9.225(1), c=l7 .25l(l)A, 6=90.39(1)", V=2112 .8(4)A3 ,Z=4, Dc=l.475Mg/m3 , F(OOO)= 960, A(MoKa)=0.7107A. The structure
has been solved by direct methods (SHELXS-86) using 3153 reflections,collected at room temperature by Enraf- Nonious CAD-4 diffractometer withmonochromated radiation using w-26 scan. The structure was refined by full matrix least-squares method using SHELXL-93 to the final value of

R=0.0359 for 3,011 significant reflections I> 2a(l). The eight membereddioxathiaphosphocin ring has boat-chair conformation. The sulfur substituent
is axial and the dimethyl phenoxy group is equatorial to the hetero ring .
There is no short contacts between the molecules and the structure wasstabilised by van der Waals interaction.

2P37

X-RAY

STRUCTURALSTUDIESON

SUBSTITUTEDTHIOUREADERIVATIVES
K. Sivakumar", R. Akilanb, K.Subramanianb and Fun Hoong-Kun•,•x-RayCrystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM,
Penang , Malaysia and bDepartment of Physics, Anna University, Madras - 600
025, India.

Crystal structure analyses of many metal complexes of thiourea and only a few
of those with substituted thioureas have been reported in the past. There is no
structural report exclusively on the substituted thiourea derivatives; this may be
due the difficulty in getting good crystals suitable for X-ray diffraction studies .
These thioureas find applications as rubber accelerator and intermediates fordye preparation ; they are also very useful agrochemical intermediates. We areinterested in the molecular conformations and N-H ... S hydrogen bond formation
details of these molecules in the solid state. We were able to crystallise morethan fifteen thiourea derivatives and determined their molecular structure by
X-ray diffraction methods. We have classified them as symmetrically
substituted

andunsymmetrically

substituted

thioureas . The

structural

information we observed are highly interesting with respect to various
substitutions. The packing of the molecules in the crystal lattice are governed
mainly by N-H ... S hydrogen bonds and leads to one dimensional chains ofmolecules, dimer formation and two dimensional nets as the case may be . A
detailed analysis of individual structures and a comparison of all of them will
be presented .

2P38'Sheet with Holes' Structure of Lead(II) lodide-Nmethylethylenediamine(3/2),(Pbl2)3( Me-en) 2
H. Miyamae, T. Ito, G. Hihara. Department of Chemistry, Josai
University, Keyakidai 1-1, Sakado-shi, Saitama 350-02, Japan
Ethylenediamine sometimes forms nonstoichiometric addition
compounds with lead(Il) halides .!) 0.1 ml of N-methylethylenediamine (Me -en) are added to 5 ml of saturated solution of Pbi2 in
DMF. After allowing the solution for absorbing MeOH in a sealedcontainer, we have obtained crystals of the title compound.
Structure determination of the compound at 298K by single-crytal
X-ray diffraction method showed that 2/3 of the Pb atom werecoordinated by a Me-en in a form of distorted octahedral Pbi4N 2
coordination [Pb(2)). while the other were surrounded by six I
atoms almost octahedrally [Pb(1)]. Thus the [(Me-en)Pbi3Pbi3Pb(Me-en)] moieties are connected through I atoms to form asheet in ac plane as shown in Fig. 1. All of the Pb-1 bond distances
around the Pb( 1) are ca . 3.21 A, but those around the Pb(2) arescattered between 3.14 to 3.58 A.
Crystal data : [Pb3I6(Me-enhl
orthorhombic, spacegroup Pbca (No. 61)
a 12.440(5) A
b 16 .879(6)c 12.106(6)v 2541.9(16) A3.

~aFig. l.

Perspective view of a sheet of the title compound .

I) G .Hihara, H.Miyam ae, and M.Nagata, Chem.Lett., 647-650 ( 1982).

2P39

STRUCTURES OF FURO AND THIENO DERIVATIVES
OF 5-AMIN0-8-METHYL-1,2-DIHYDR0[2,3-h] [1,6]NAPHTHYRIDINES
R. Kingsford-Adaboh and S. Kashino, Department of Chemistry,
Faculty of Science, Okayama University, Tsushima, Okayama 700,
Japan, and K. Sasaki, R.A.S. Shamsur and T. Hirota, Faculty of
Pharmaceutical Sciences, Okayama University, Tsushima,
Okayama 700, JapanThe crystal structures of pharmacological agents having trachealrelaxation activity, 5-amino-8-methyl-1,2-dihydrofuro[2,3-h] [ 1,6]
naphthyridine, C,,H 11 N 30 (I) and 5-amino-8-methyl-1,2dihydrothieno[2,3-h] [1 ,6] naphthridine, C 11 H 11 N 3S (II) have been
determined. The crystals of I and ll are isomorphous: monoclinic,
space group P2I/n (No.l4), Z=4; a=9.975(5), b=9.695(5),c=l0.145(9) A, P=97.92(6) 0 for I, and a=l0.04(1), b=9.572(4),c=l0.680(5) A, P=98.16(6) 0 for n. For both molecules, N(9)-C(8),C(6)-C(7), C(5)-N(4), and C(lO)- C(11) bonds show a double bondcharacter. Widening of the bond angles C(l)-C(10)-C(13) andN(4)-C(11)-C(10) are remarkable, and is more pronounced in I
[133.2(2) and 129.0(2) 0 for I, 127.4(2) and 126.9(2) for ll]. The
molecules related by a center of symmetry are linked through an NH .. .N hydrogen bond with N .. .N 3.060(3) Afor I (Fig. 1) and
3.135(4) A for ll. The crystal and molecular structures arecompared with those of related compounds.

Fig. I

2P40
X-RAY INVESTIGATION ON STRUCTURAL PHASE
TRANSITION IN HOOC{CH 2 ) 4 COOH
M. Machida and S. Nishimoto, Department of Physics, Kyushu
University, Hakozaki, Higashi-ku, Fukuoka 812, T . Kobayashi,
Department of Physics, Hokuriku University, Kanagawa-machi,
Kanazawa 920-11
Adipic acid ( HOOC(CH2) 4 COOH } is known to be monoclinic atroom temperature and its symmetry is described by P2J/c with two
formula units in the unit cell 1l. The adipic molecules are linked
by two hydrogen bonds one another and resultant hydrogen bondsystems run along the a-axis. An occurrence of the phase transition has been indicated by differential thermal analysis and Raman
scattering 2 l. New bands appear at Tc in the Raman spectra and behave like an order-parameter; the critical exponent {3 is determined
to be 0.33 which corresponds to that of the three-dimensionally interacted system. However no investigation on the structure and symmetry of the low temperature phase has been performed so far. We haveinvestigated the phase transition in this crystal by X-ray diffractionin order to elucidate the above interesting behavior.
It was found that additional reflections defined by the modulation
wave-vector q "' a• /3 appear at Tc associated with the phase transition; the intensities of these reflections increase with decreasing
temperature in the low temperature phase. The modulation of thestructure will be discussed in connection with the phase transition.
1} P .J .Housty and M.Hospital, Acta Cryst ., 18,639(1965}.
2} H.Ohki, N.Nakamura and H.Chihara, J . Phys. Soc. Jpn., 57,382(1988}.

2P41
VERY RAPID PHOTOISOMERIZATIO N OF 1-CYANOETHYL GROUP IN COBALOXIME CRYSTALS
6
P. lnthapanya, 0 Y. Ohgo, 6 D. Hashizume 6 and Y. Ohashi,
0Department of Biology and Chemistry, Pedagogy Institute, Dongdok, Vientiane, Laos
6Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan
It has been found that the chiral 1-cyanoethyl groups bonded tothe cobalt atom in some cobaloxime complexes are racemized on
exposure to visible light with retention of the single crystal form .
The reaction rate was well explained by the size of the reaction
cavity. Recently we prepared the 1-cyanoethyl complexes with 2mercaptobenzimidazole 1 and 4-chloropyridine 2 as axial base ligands. Crystal data is shown in Table 1 and crystal structure of
4-chloropyridine derivative is shown in Fig. 1. On exposure to axenon lamp the reaction rates of the two crystals were too fast thatthe crystals were easily decomposed, although the reaction cavity
calculated from the analyzed structures, however, are smaller thanthose showing the crystalline-state reaction.
Table 1. Crplal Data.

a/A
b/A
c/A

a;o

f3r
"(r

v;A 3

z
Space
Group

2
1
11 .334(2) 8.621(5)11.647(2) 28.645(3)8.565{1) 8.891{4)95.10(1)101.14(1) 115.60{4)78.08{2)1084.0(3) 1980.0(2)
2
4

PI

P21
Fig. I2P42

CRYSTALLINE-STATE RACEMIZATION OF
CHIRAL METHOXYCARBONYLETHYL GROUP IN
COBALOXIME COMPLEXES
Masaru Saito, Daisuke Hashizume, Hidehiro Uekusa, and Yuji Ohashi
Department of Chemistry, Tokyo Institute of Technology,
0-okayama, Meguro-ku, Tokyo 152, Japan.
It was reported that crystalline-state racemization of 1-methoxycarbonylethyl (mce) group bonded to the cobalt atom occurs only at hightemperatures in a few cobaloxime complexes. In order to investigate moredetails of this reaction we have synthesized three cobaloxirne complexes
with (a)cyclohexylamine, (b)cyclopentylamine and (c)benzylamine (Fig. 1)
and examined their reactivities.
0HII~c-c~~t~o1~:::
I

H3c-c

Co

:::::-t("
I '~ ~cH3
0 - -j-HO
Base

NH2

NH 2

CH
H C/
'CH
21
I 2

CH
H C/
'CH
21
I 2
H2c--CH2

cS'

(b)

(c)

I

H2C...._

,CH2
CH 2

(a)

I

~

I

Fig. 1

All the crystals were changed after the irradiation of a xenon lamp. X-ray
analysis of these crystals
showed mce groups have nocontact with each other but
have close contact withcrystal solvents ( Fig. 2). The ~~~~t:Q,o-osolvent molecules appear toplay an important role in thecrys talline-photoracem ization. Further discussion willcbe done comparing with theracemization reported so far.

2P43

A CHIRAL N-METHYLBENZAMIDE
K. Yamaguchi, Chemical Analysis Center, Chiba University, 1-33
Yayoi-cho, Inage-ku, Chiba, 263, Japan, and I. Azumaya, I. Okamoto,
H. Kagechika and K. Shuda, Faculty of Pharmaceutical Sciences,
University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113 Japan.
We found an interesting compound, 1,2-bis(.N-benzoyl-.N-methylamino)benzene (1), which exists in an optically active form insolution and in the crystal.

Recrystallization of 1 from distilled

ethyl acetate yielded beautiful crystals, each of which is optically
active. Sometimes all the crystals belong to the same chiral group,
or one large crystal spontaneously forms a solution in good yield.
The optically active crystals are orthorhombic and are classified
into the space group P21212 1. The absolute configuration of 1 wasdeterminedusing

cocrystallization with(R)-1,1 '-bi(2-naphtol).

The structure of the mixed crystal contains one molecule of 1 andone molecule of 1,1'-bi(2-naphtol) in an asymmetric unit. This may
be regarded as an example of the chirality induction from theracemic solution of 1.

Detailed crystallographic study will beshown.

Two enantiomeric anti-cis/cis conformations of 1

2P44
ASYMMETRIC PHOTOISOMERIZATION OF ( 2-CYANOETHYL )( 2-BUTYLAMINE) COBALOXIME COMPLEXES IN THE SOLID STATE

T.Koura . H.Kogo and Y.Ohashl . Department of Chemistry . Tokyo
Institute of Technology. 0-okayama. Meguro-ku. Tokyo 152 . Japan .
It is known that 2-cyanoethyl group bonded to cobaloxime complexes isisomerized to 1-cyanoethyl group with a chiral carbon atom on exposure
to visible light in the solid state . The configuration of the chiral carbon
atom in the produced complex Is seemed to depend on the chirality of
the crystalline field around cyanoethyl group . In order to examine
above result 2-cyanoethyl cobaloxime complexes with [R]- or [S]-2~butylamine were prepared and were exposed to visible light under thesame conditions .
The specific rotation of the Irradiated sample was measured by apolarimeter in a chloroform solution and the crystal structures of [R]and [S)-2-butylamine complexes were analyzed by X-ray diffraction
method .
The speciftc rotations Increased by +1.63" for [R]-2-butylarnlne complex
and decreased by 1.51" for [S] -2-butylamine complex . This result
indicates that [S] - 1-cyanoethyl group were produced from [R]-2butylarnine complex and [R]-1-cyanoethyl group were produced from [S)2-butylamine complex . Such asymmetric induction is well-explained by
the reaction cavity around cyanoethyl group . as shown in Figure 1 .

9 .82 A'

Figure 1

16.63 A'.

Reaction cavity around cyanoethyl group

2P45
Structure of A Briarein Diterpenoid : (lS*, 2S*, SZ, 7S*, 8R*, 9S*,
lOS*, liZ, 14S*, 17R*)-2,14-diacetoxy-8,17-epoxy-9-hydroxy-briarn5,11-dien-18-one ++Tsong-Jen Lee and Arlohun Wang, Department of Physics, National
Tsing Hua University, Hsinchu, Taiwan 300 and Jyh-Horng Sheu &Ping-Jyun Sung, Department of Marine Resources, National Sun fatSen University, Kaohsiung, Taiwan 804, ROC & Fun Hoong Kun,Schoolof Physics, Univer.;itti Sains Malaysia, 11800 Minden, Penang,Malaysia.
Diterpenoids of the briarein class, are commonly found in the Gorgonacean genus Briareum and the Alcyonacaean genus Minabea as wellas in sea pancy and sea pens. Several briareins have been found to showinteresting biological activities, such as antifouling activity, cytotoxicity
and antiinflammatory activity. As part of our studies directed in searching bioactive compounds from marine organisms of southern Taiwan, an
investigation of the secondary metabolites from Taiwan soft coral
Briareum sp. has been carried out. In this work, we report the isolation
and relative stereo-chemistry of a briarein diterpene, (IS*, 2S*, 5Z, 7S*,
8R*, 9S*,IOS*, 1 IZ, 14S*, 17R*)-2,14-diacetoxy-8,17-epoxy-9-hydroxybriara-5,11-dien-18-one (1) from Briareum sp. The ethyl acetate extractof the soft coral, collected at Kengting, Taiwan, in 1991 by SCUBA
diving, was chromatographed on a silica gel column (hexane/ ethyl
acetate, 1/3~ 112) yielding (1) as colorless prisms (from slow evaporationof ethyl acetate solution) : mp 238-240 oc; [a) 0 12.2° (C 0.23, (2HC1 3 ) .
1
H-NMR and 13C-NMR spectra of (I) are in full agreement with thosereported previously. Structure determination of the title compound at
300 K by single crystal X-ray diffraction methods reveals that five andsix membered rings are in plannar form and the ten membered ring are
in a chair form .
Absolute configuration of the molecule will be
determined by use of anomalous dispersion effects of 25 reflections,selected in that the absorption effect of I(hkl) is nearly equal to that of1(-h,-k,-1) (private communication with Dr.Mamoru Sato, Institute forProtein Research, Osaka University, March 24,1995).Crystal dnta :Orthorhombic P2 1212 1 a= 9.729(2), b=I3.794(3), c=20.014(4) A.
++Work supported by National Council of Taiwan under contract
number NSC82-0212-M007-I 18, NSC81-0418-B110-511-BR.

2P46

GRAZING-INCIDENCE DIFFRACTION OF X-RAYS ON SINGLECRYSTAL WITH NEAR-SURFACE LATTICE DISTORTION
V. S. Haroutvunyan, Dept. of Solid State Physics,
University, A. Manoukian 1, 375049 Yerevan, Armenia

Yerevan StateThe original and sensitive X-ray diffraction scheme under conditions ofradiation specular reflection with nonc6planar geometry of the scatteringhas been considered in [1 to 3]. This scheme enables to carry out
structural investigations of thin subsurface layers of crystals.In [3] theequations of diffraction are solved in the kinematical limit for crystal
with depth-dependent arbitrary variation of its lattice distortion.
In present paper the diffraction of plane monochromatic X-ray wave on
single crystal for above-mentioned geometry of scattering is considered
provided that there is a small distortion of crystal lattice in thin surface
layer. It is supposed that this distortion varies along the entrance
surface with weak constant gradient directed parallel to reciprocal lattice
vector of active reflection (in present scheme reflecting atomic planes areperpendicular to the entrance surface, i.e Laue reflection scheme isused). The solution of diffraction equations is found with use of
perturbation theory. The angular dependence as well as the integrated
intensity dependence of a specular reflected diffraction beam on theparameter of incidence and the value of gradient of lattice distortion
are obtained. These results are compared with data corresponding to caseof grazing-incidence diffraction on a perfect crystal.
Theoretical approach developed in the present paper can be useful forinvestigations of lattice distortions caused in a crystal by near-surface
impurities, vacancies and other defects with inhomogeneous distribution
along the entrance surface.
I. Marra, W .C., Eisenberger, P. & Cho,A .Y. (1979).J.Appl. Phys. 50,
6927-6931.
2. Afanasev, A.M. & Melkonyan, M.K.(l983).Acta Cryst.A39, 207-211.
3. Melikian, O.G .(199l). Kristallografia 36, 549-553 .

2P47
MODEL-INDEPENDENT DETERMINATION OF ELECTRON DENSITYPROFILES FOR AI-C MULTILA YERS USING ANOMALOUSDISPERSION X-RAY REFLECTOMETRY DATA
T. Ohkawa, Y. Yamaguchi, 0 . Sakata and H. Hashizume, Res. Lab. of Eng. Mater. ,Tokyo Inst. of Tech., Nagatsuta, Midori, Yokohama 226, Japan, and A. Datta and M. K.
Sanyal, Saha Inst. of Nuclear Physics, 1/AF Bidhan Nagar, Calcutta 700 064, India

A method of obtaining a model-independent electron density profile for a thinfilm deposited on a substrate using anomalous X-ray reflectivity measurements
has been applied to single and triple bilayers of 30 A aluminum and 70 A carbon
on germanium substrate, prepared with the magnetron sputtering technique.
Specular reflection data were collected at a synchrotron source in Photon Factoryusing X-ray wavelengths 1.3 A away from and 1.117 A close to the GeK
absorption edge. The measurements covered intensity ranges of 1 : 1o-s by theuse of attenuators. For each sample the obtained profiles are different at the two
X-ray wavelengths, demonstrating changed amplitudes and phases of thereflectance at the film-substrate interface. The profiles involve features similar to
those in specular-reflectance coefficients calculated assuming/= -8.0,/' = 0.496
for the anomalous scattering factors of Ge at 1.117 A_ The data are used to solve
Eq.(3) of Sanyal, Sinha et al. [l] to obtain the real and imaginary parts of theFourier transform of t.g(z), the deviation of film electron density from the meanvalue as a function of depth z. The equation uses a distorted-wave Born
approximation to calculate specular reflectivities over a wide scattering-angle
range and recovers the lost phase information. The results are inversely Fouriertransformed to reconstruct real-space electron . density profiles for the AI-C
multilayers. The density profile obtained for the single bilayer AI-C shows adensity step height which is smaller by 0.02 e/A 3 than the calculated value.
Deviations of the obtained profiles from the model structures are discussed interms of the finite q, range (q, < 0.6 A- 1) used for the Fourier transform. The
specular data are also least-squares fit to Parratt's formula to evaluate the layer
thickness, surface/interface roughness and density variation, which are comparedwith the information available from the reconstructed electron density profiles.
[I] Sanyal, M. K., Sinha, S. K. , Gibaud, A. , Huang, K. G., Carvalho, B. L. , Rafailovich,
M., Sokolov, J. , Zhao, X. & Zhao, W., (1993). Europhys. Leu. 21,691-696.

2P48
IN-PLANE STRUCTURE OF ARSENIC-DEPOSITED SILICON SURFACESSTUDIED USING GRAZING-ANGLE X-RAY STANDING WAVES.
0 Sakata, S. Kumano, A. M. Nikolaenko and H. Hashizume, Res . Lab. Eng. Mater.,
Tokyo Institute of Technology, Nagatsuta, Midori, Yokohama 226, Japan.
Grazing-angle diffraction of X-rays by crystal planes normal to a surface produces dynamical standing waves with intensity modulates along the surface. The X-ray fieldoutside the surface has two components, B(x) and A, with and without lattice-position
dependence in the direction of the reciprocal-lattice vector parallel to the surface. The
profile of A and B(x) as a function of 69 behave distinctly when the glancing incidence
angle cp, is varied near the critical angle for total external reflection (Sakata, Hashizume &Kurashina (1993)) . This property has been exploited to accurately determine the position

x and disorder of As atoms on an Si(lll) : As 1x1 surface. AsK emission profiles, observed from a sample in ultra-high vacuum environment at a synchrotron source, showed

As atoms located in the threefold coordinated sites of the bulklike Si(lll) surface withlittle disorder. The displacement is smaller than 2% of the d spacing of the (2ZO) planes
and the coherent fraction is higher than 80% (Sakata & Hashizume (1995)) . The same
technique was applied to an As-deposited Si(IOO) surface with mixed 1 x 2 and 2 x I
domains. The substrate surface was cut at 4 ° to the (100) plane towards the (011) axis, on
which As was deposited in an MBE facility . A LEED picture showed strong 2 x I spots
and weak 1 x 2 spots, indicating predominant As dimers parallel to the double-layerheight step edges along the [OT 1) direction. We collected As emission data in the vicinity of the 022 and 022 Bragg peaks, which were used to evaluate the h parameter definedby '1 =/;+ J;cos(2n/) (ij=1,2), where/; and .1; are the fractions of the As atoms formingI x 2 and 2 x 1 dimers and I is one half the dimer bond length normalized to the (022) d
spacing. The indeterminate equations can be solved using an assumed value for the fra ction of the ordered As atoms to evaluate/,./, and/.
Sakata, 0 . , Hashizume, H. & Kurashina , H. (1993) Phys. Re1•. 848, 11408-11411 .
Sakata, 0 . & Hashizume, H, (1995) Acta Cryst. AS I. 375-384.

2P49
MICROMORPHOLOGY OF POLISHED SILICON SURFACESSTUDIED BY X-RAy 'REFLECTOMETRY
Y. Yamaguchi, M. Nakanishi, 0. Sakata and H. Hashizume, Res. Lab. of Eng.
Mater., Tokyo Inst. of Tech., Nagatsuta, Yokohama 226, Japan, and M.
Nakano, Shin-Etsu Handoutai Co. Ltd., Shirakawa, Japan, and J.M Bennett,
Naval Air Warfare Center, China Lake CA, USA
Micromorphology of polished silicon surfaces has been studied using X-ray
reflectometry at a synchrotron source, in conjunction with classicalprofilometry techniques using optical (WYKO) and mechanical (Talystep)
probes. The samples studied are Si (1 00) wafers polished with a standard
mechanochemical technique to four distinct roughness levels A, B, C and D.
X-ray experiments at a Photon Factory source measured specular reflectivity
profiles of the samples using 1.38 A X-rays, which were fit to Parratt's formula.
The fits determined the r.m.s. values of the vertical roughness at 14.8, 7.4, 3.9,
4.1 A for surfaces A, B, C and D respectively, which compare with those fromWYKO (11.3, 3.7, 2.5, 2.5 A) and Talystep (19.5, 6.1, 2.9, 2.6 A>. The lateral
resolutions of these methods are quite different, 10 A for X-rays, 1 J.lm for
WYKO, and about 0.5 J.lm for Talystep. The similar roughness values
obtained with the three methods for each surface indicate that the statisticalfluctuation of the polished silicon surfaces includes structures of quite wide
spatial wavelength ranges in the lateral direction. To give information on
correlated structures, we measured diffuse X-ray intensity profiles at nonspecular scattering angles and analyzed the data using the theory developed by
Sinha et al. [1). The height-height correlation lengths thus determined are 1.8,
1.7, 0.02, 0.03 J.lm for surfaces A, B, C and D respectively. These values arequite different from 3.6-6.0, 1.5-6.7, 10.2-3Q.O, 14.7-45.4 J.lm determinedfrom the Talystep traces over surface lengths of 0.2 to 1 mm. The data showthat surfaces C and D include short-wavelength fluctuations superposed onlong-range waviness which is detected by Talystep, but not X-rays.
[1) Sinha, S. K., Sirota, E. B., Garoff, S. & Stanley, H. B., (1988). Phys. Rev.
B38, 2297-2311

2P50

DISLOCATION STRUCTURE OF SOME INDUSTRIAL ALUMINUM
ALLOYS AFTER ROLLING.
Tran Quoc Thang, Materials Science Center, Hanoi University ofTechnology, Dai Co Viet Road , Hanoi, Vietnam, F. Louchet, L. T. P. C.
M., E. N. S. E. E. G., I. N. P. Grenoble, France.
AI, Al-Mg, Al-Mn-Si alloys heavily strained by rolling are submitted to
examine in transmission electron microscopy.
The results of observation show that dislocation cells are formed during
rolling, which are elongated along the rolling direction.
Dislocation cell's formation is retarded in Al-Mg solid solution and in AlMn-Si with dense incoherent precipitation.
The cell's thickness, D, depends on rolling deformation, e, by 2 steps:
Fore 5

E:cr• D vs. e corresponding to modification of macro-size in rolling,

agrees with a dislocation walls multiplication. For e ?:E:cr• D decrease

towards constant, that could be explained by walls annihilation. Someenergetic model has been proposed to account for observations.

2P51

STRUCfURE .O F MICROCRYSTALLINE Ag-BASED AMALGAM
ALLOYSDo Minh Nghiep, Materials Science Center, Hanoi University ofTechnology, Vietnam, Cao The Ha, Department of Chemistry, National
University of Hanoi, Vietnam, Nguyen Van Dzan, Center for New
Materials, Technical University of Ho Chi Minh City, Vietnam, andLecong Dzuong, Materials Science Center, Hanoi University ofTechnology, Vietnam
The influence of Cu content (6-32 weight%) of Ag-based amalgam alloys
prepared from microcrystalline melt - spun ribbon powders on their phasestructure has been studied by XRD, EMPA and optical microscopy. For
these alloys the Cu atoms either existed in Cu - Sn phases or dissolved in "(and I p phases as "activated" atoms. The quantity of the last atoms plays
an important role in the phases formation depending on the Cu content andthe solidification rate. In comparison with conventional amalgam alloys ofthe same composition the rapidly solidificated alloys are characterized by:
1. a very fme and homogeneous microcrystalline structure,
2. a decrease of the Cu 3Sn phase and at higher Cu content the 8 phase(Cu 31 Sn 8) may be present,

3. a supersaturation of the "activated" Cu atoms in"( and I 13 phases,
which may lead to clustering of Cu atoms or to formation of the Cu 6Sn5
phase during a proper aging and
4. a decreased amount of y2 phase (Sn8Hg) in consequence of decreasing
Cu 3Sn phase and increasing "activated" Cu atoms with Cu content.

Such variations of the alloy structure improved markedly the amalgam
properties.

2P52
COMMON FEATURES OF P-TYPE AND N-TYPE POROUS
SILICON LAYERS WITH VISIBLE PHOTOL_l]MINESCENCE
Osamu NITTONO and KWJiko TAKEMOTO, Department of MetallurgicalEngineering,Tokyo Institute of Technology, Meguro- ku, Tokyo 152, japan

Porous silicon (PS) is a kind of silicon having a pore structure. Recently,
Canham demonstrated strong visible photoluminescence from p-type PS. andstated that the visible light emission is attributed to a quantum size effect.
Our previous studies have revealed that the microstructure of PS layer
formed on p-type silicon (Si) wafer including pore size and morphology is .
strongly dependent on doping quantity and wafer resistivity as well as
anodization conditions such as formming current density and electrolyte
concentration. In this study, PS layers, formed on heavily doped p-type
and n-type silicon wafers of low resistivity less than 0 .02 Q em , have been
investigated by mainly X-ray multi-crystal diffractometry, supplemented
with electron diffraction and electron microscopy including scanning electron
microscopy and transmission electron microscopy. Observed X-ray
diffraction profiles give directly the lattice mismatch between PS layer and Si
substrate. Broad diffuse scattering is always seen under a coherent peak for
PS layer in a large angular range as shown in Fig. 1, indicating somemodification of the nanostructure of PS layer. It is also- shown that PS
layers which exhibit intensive photoluminescence under He-Cd laser
illumination at room temperature are not amOJllhous, but crystalline, andtheir crystallinity is still preserved in the residue until they are heavily
distorted and finally divided into small crystallites when anodized with higher
forming current densities. The experimental results reveal that the visible
photoluminescence was strongly related to the microstructure of PS layer
ncar the surface that shows a spongclike structure consisting of a large
number of silicon cr~·stallinc parts of few nm's in size.
(a)

~
=

i

'1 (b)o J Om.Vcm'

- -\-

i

r.,

;

S i ;:

i'

~

!·

~

.j

, 6. 50 mAJc m ·•.
·'j•; ···-· e -IOOmAic:n:· fo r m m~ c u rrent d ens• ()' - - - ~-,-~~ '-,-~ 10.

. PS :::

- --

~

~0¥f;

.

!i I

- --·----r:-1~ O!~~'t;-----+-~
"\..i

-

50

l00

R cl3 livc c~· l t :l l rot:u ioo ~ n g\d ;l r t sec)

Fig. I1t. 200m.V<::tf

3 04 ~ - -----:--.-- -- - -· ~-

20

!I

l

)

"

~0

• ~?

1 HI

. : !
!0::0

-7

! tO

Rcl;:arivc crys1a l rot:Hi o n 1n glc (:u c sec)

X-ray rocking curves of Jl-type in (a) and n-tyJle PS in (b) layers

ICO

·3P01
On Cross-sectional Transmission Electron Microscopy Stud.y of
Carbon Nanotubules
G. Hu, X.F. Zhang and Z. Zhang
Beijing Laboratory of Electron Microscopy, Chinese Academy of Sciences,
P.O. Box 2724, Beijing 100080, China
Both coil-shaped and straight carbon nanotubules have been investigated bycross-sectional transmission electron microscopy (XTEM), especially bycross-sectional high resolution electron microscopy (XHREM). Thesetubules are hallow and consist of concentric graphene sheets but withdifferent shapes in the cross-sectional view. The XTEM images of the coiledshaped tubules exhibiting a polyhedral shape, while the XHREM images
show that the cross-section of strait tubules are normally with elllpticalshape.
A coil-shaped coaxial carbon nanotubules is imaged along the coil-axis
direction. It has been demonstrated that one pitch of the coiled tubule
contains twelve straight segments with a joint angle of 30o between eachother. Each straight segment is composed of coaxial graphite multilayer
tubules with turbostratic stacking between neighbouring layers as confirmed
by nanomicro electron diffraction (llJ.l·ED). These experimental results
strongly support the models for tubule joints relevant to pentagon-heptagon
pairs. A comparison of J.lJ.l·ED patterns obtained from adjacent straightsegments allows to determine the joint rules even for helical tubules.
Primary evidence for toroidal form of car bon cage is also presented.
Bundles of strait carbon nanotubules were collected from the cathodic
graphitic deposits, embedded in an epoxy mould, and then cut into slices ofthickness of 20-30 nm by aultramicrotomy with diamond knife. XHREM
images reveal that the strait tubules consist of concentric cylindricalgraphene sheets, but normally with elliptical shapes, rather then circulars,in cross-section. This may corresponding to the observation of nonsymmetrical lattice spacing of tubules view along the longitudinal projection
in a certain direction. Dislocation walls have also been observed in the crosssection view. The crystallographic structure of the carbon nanotubules are
discussed based on a comparison of the theoretical cons·ideration with thenumber of the dislocation walls observed in the complete circumference ofeach successive concentric graphene sheets of tubule.

3P02
LOCAL STRUCTURE AROUND MAGNESIUM IN CaMgSiz06
GLASS BY OXYGEN K-EDGE EXELFS ANALYSIS
Y. Tabira, Research and Development Center, RICOH, Co. Ltd., Shin'eicho, Tsuzuki, Yokohama 224, N. Ishizawa, Research Laboratory ofEngineering Materials, Tokyo Institute of Technology, Nagatsuta, Midori,
Yokohama 226, and F. Marumo, Department of Earth Sciences, Nihon
University, Setagaya, Tokyo 156, JapanAn electron energy-loss spectroscopic study was performed using atransmission electron microscope (TEM). Previous study on the glass andthe high-temperature melt with the title composition by the X-ray
diffraction technique showed that Mg atoms in both compounds have coordination numbers less than six as found in the diopside crystal with thesame chemical composition . In order to confirm the local structurearound Mg in the glass, the extended energy-loss fine structure(EXELFS) around the oxygen K-edge of the powdered glass was investigated. The Mg K-edge was unsuitable for quantitative analysis because of
its low peak-to-background ratio. The EXELFS spectra up to over 1400
eV (loss-energy) were collected by the parallel-type detector with the
TEM operated at 200 kV. Diameter of the selected area of a fragment was
200 nm and the maximum scattering angle collected in a spectrometer
aperture was 16 mrad. The interatomic distance obtained from the radial
distribution function around the oxygen atom was longer by 0.006 nm
than that in a synthetic MgAlz04 spinel crystal in which Mg atoms are
surrounded regularly by four nearest-neighbor oxygen atoms . The
difference of 0.006 nm is significantly small compared with thedifference of 0.017 nm observed between the 0-Mg distances of diopsideand spinel. This result is concordant with the implication from the X-ray
diffraction experiment.

3P03

Optimization of Prolyl endopeptidase Crystal Growth
Y. Kagawa, Y.Kawauchi and T.Sato, Faculty of engineering, University of Tokushima,
Tokushima 770, Japan, and E.Yamashita and T. Tsukihara, Institute for Protein
Research, Osaka University, Suita 565, Japan and G. Sazaki and H.Komastu, Institutefor Materials Research, Tohoku University, Sendai 980, Japan

Protein crystal growth often depends on the combination of many different factors. Some
affect protein solubility and aggregation state directly; others may act indirectly by causing
conformational changes. Systematiccharacterizationof these factors can be important foryielding good crystals. It can also give the useful indication into the biochemical behavior· ·of the protein being crystallized. Here we focus on biochemical technique and statisticalmethod to achieve two directions as followed. (1) Characterization of the protein
conformation under different levels of biochemical parameters, such as pH. Tests of the
reproducibility of crystal growth experiments indicate the quantitative scales of crystal
quality can be statistically significant. Analysis of variance for a replicated, incomplete
factorial design in which four factors which are [pH], [Protein concentration], [Precipitantconcentration] and [temperature] were tested, has been used to demonstrate highly
significant, biochemically relevant, two-factor interactions strongly implicating pH andconformational changes, corresponding to a result of the isoelectrictitrationcurve used the
Optimization of crystal growth for response-surface(2)
zymogram analysis.
experiments. 'Minimum predicted variance' designs provide for efficient responsesurface experiments aimed at constructing quadratic models in several parameters. We
have used such models to improve crystal size and quality significantlyofFlavobacterium
meningosepticumprolyl endopeptidase. Recently advances in this recombinant DNA andthe protein expression technologies permit such a systematic search of potential
crystallization conditions with large quantities of highly purified starting sample. The
two-dimensional level surfaces have a number of 'ridges', where the same result is
obteined for many combinations of the factors usually varied when trying to improve
crystals. An imponantinference is drawn from the surface that it may be better to sample
simultaneously for theinteractioneffects of protein concentration and molecule aggerate.
For a system involving only one crystallizing agent ( PEG1500 ), supersaturation can beapproximated as the product of [Protein concentaration] and [Precipitant concentration].
Use of this search method will significantly improve the performance of response-surface
experiments. Growing crystals at stationary points of their response surfaces generatebetter crystals and high reproducibility, since crystal growth at stationary points is not
influenced by any harmful effects of experimental errors. This arises because thederivatives of the model function are by definition zero with respect to the experimental
variables. Quantitative analysis of appropriate design for crystal growth experiments canthus be a powerful tool to characterizecomplex and interacting biochemical dependencies
in macromolecular systems and to optimize parameters imponant to the crystallization.
OptimaizedCrystallizationCondition:[Buffer] = 50mM NaPi + 0.2M NaCI, [Final pH] = pH6.9, [Temperature]= 25"C,[Protein concentration]=25mg/ml, [Precipitantconcentaration]= 18-20%w/v PEG1500

3P04

Use of Dynamic Light Scattering to Compare Crystallinities of
the Single Stranded DNA Binding Protein (SSB) and Ribosome
A. Nakagawa, Y.Kawauchi, T.Sato, Faculty of engineering, University of Tokushima,
Tokushima 770, Japan, and T. Tsukihara, Institute for Protein Research, Osaka
University, Suita 565, Japan and G. Sazaki and H.Komastu, Institute for Materials
Research, Tohoku University, Sendai 980, Japan

Crystallization frequently represents the main rate limiting step in X-ray crystallographic
studies of the structure of biological macromolecules and organelle. Recently introduced
incomplete factorial and/or sparse matrix strategies and advances in reconbinant DNA and ·protein expression technologies have had a dramatic effect on the area of protein
crystallization. Certein criteria may be set before crystallization trials are started, such assolubility, purity and aggregation tendencies. Crystallization trials depend on varying
many different parameters, searching for supersaturation conditions where homogeneous
preparations will first nucleate and then support crystal growth. Unfortunately, inpurity (commonly assayed by SDS-PAGE electrophoresis or ion-spray mass spectrometry) or
macroheterogeniety coupled with wide screening offers no insulant of success. The
protein sample is then examined using laser light-scattering techniques. This method
allows us to detect the presence of aggregates in the protein and organelle solution bywhich may be disturbed to crystal nucleation or growth. Empiricalobservations suggestthat mocromolecules and organelle that are monodisperse, which are all the same size,
under 'normal' solvent conditions crystallize readily, on the other hand randomly
aggregating or polydisperse systems rarely, if ever, produce crystals. Monodispersity
which lead to crystal was found by the single starandedDNA binding protein (SSB) andpolydispersity to form aggregates which lead to precipitates was detected with Ribosome,early in the evolution of a supersaturated solution of macromolecules and organelle. We
hereinafter refer to the former as pre-crystalline aggregates and the latter as preprecipitating aggregates. Dynamic light scattering (DLS) can be employed to detect
monodispersity as candidates for crystallization. A measure of the translational diffusion
coefficient, 'D', of SSB and Ribosome molecules in various precipitating agent solutions
as a founction of salt and protein concentration using DLS . Assuming a spherical modelfor the protein, its hydrodynamic diameter, 'd', can then be calculated. Variationof 'd' as
a function of certain biochemical solution properties such as [Protein concentration],[pH], [Precipitant concentration], or [Temperature] can be estimated. The protein
concentration dependence of 'd' has been suggested as a way to differentiate between preThe protein
crystalline aggregates and pre-precipitating aggregates in solution .
concentrationdependenceof 'd' has been the two types of aggregates
Crystallization efforts may be limited to monodisperse preparations, saving valuable
time-loss on trials with samples which are not enough to be transferred to the
crystallization procedure. Application of this technique to find unknown crystallization
conditions of other proteins or Ribosome is discussed on the basis of a quantitative
experimentalmeasurementof SSB .

3P05

SINGLE CRYSTAL GROWTH OF VACANCY DEFECT TYPE SULFIDESPINEL COMPOUNDS USING BRIDGMAN TECHNIQUE
T. Ohachi, Y. Ohmuro, K. Asahi and I. Taniguchi
Department of Electrical Engineering, DOSHISHA UNIVERSITY, Tanabe, h.'YOTO 610-03, Japan
Single crystals of vacancy type sulfide spinel (M=Cu,Ag),Mln 7S 11 , Mln 9 Si4' Mln 11 S 17 ,Mln 21 S 32 , Coln 8S 13 and Coln 18s 28 were grown by a horizontal Bridgeman method withsuccessive annealing at high temperature.
The crystal structures were analyzed by a X-ray
diffraction method. Lattice constants of crystals are calculated by the diffraction pallem using silicon
powder as a standard material. X-ray photoelectron spectroscopy (XPS) is used to analyze thevalence of metallic ions. The single crystallinily was checked by Laue photographs.
Spinel structure is known as one of structures of ferrite and is expected to show electronic andionic mixed conduction. Studying sulfide spinels is more advantage than that of oxide in order toinvent a large ionic conductor because lattice constants of sulfides are larger than those of oxide ones.
From phase diagrams of In 2S 3-Cu 2sl 11, In 2S 3-Ag2si2J and Jn 2S 3-CoSI3J each vacancy typesulfide spinel is a solid solution between normal sulfide spinel, Mln5 S 8 (M=Cu,Ag) or Coln 2S 4 anda defect spinel , In 2S 3. These ternary compounds dose not decompose before melting, large single
crystals arc possible In grow by a melt technique. The amount of vacancy defects arc able In becontrolled by the amount of indium contcnt14 1.

Because of spinel structure, in which chemical

diffusion coefficients of metallic atom arc large, and large amount of vaca~cy dcfccts,thc uniform
composition of the vacancy defect spinels arc obtained.
Stoichiometric amounts of high purity copper or silver and indium of about 2 g and a proper
quantity of sulfur are sealed into a transparent quartz tube . The tube was evacuated, scaled, andhealed in an electric furnace al the temperature 1150-1200"C which is over melting point( 1075,
1085, or 1110 "C for Cu, Ag, or Co system), and are melted 1-3 hours. To make single crystals
by horizontal Bridgeman method of single directional solidification, one end of this quartz tube was
kepi at lOO"C lower than the other part. It is cooled down to 900"C at the cooling rate of 10-IOO"C/h, and annealed 30-40 hours at 900-1 OOO"C to make an uniform crystal of vacancy distribution.
Specimen made by this method arc used for measurement of electrical characteristics. Ionic
conductivity has been studied by a vector network analyzer in the range of 26 .5GHz-60GHz for Cu
and Ag systems. IS)
References:(! JJ.J. M. ninsma, L. J. Giling and J. ntocm, J. Crystal Growth 50 (19RO) 429.
12] (i. l'ct:w w, G. Effcnhcrg, " Tcrnally Allnys: A Cumrrchcnsivc Cumpcmlium uf Evalualctl C'unslilulinnal Data andPhase Diagrams", VCH vo;.l.
(3) R. E. Johnson , J . Eleccrochem. Soc. 110 (1963) 593.
(4) T. Ohachi and B.R. Pamplin, J. Crystal Growth 42 (1977) 598.
(5 ) Y. Ohmuro, T. Ohachi and I. Taniguchi, Solid Stale tonics in press (1995).

3P06
CRYSTAL STRUCTURE OF THE C-TERMINAL DOMAIN OFRABBIT SERUM HAEMOPEXIN AT 1.8 A RESOLUTION
E.N. Baker, H.M Baker, H.R. Faber and C.R. Groom, Department ofChemistry and Biochemistry, Massey University, Palmerston North, New
Zealand and W.T. Morgan and A. Smith, School of Biological Sciences,
University of Missouri-Kansas City, MO 64IIO, USA.
Haemopexin is a serum protein that binds and transports haem as part ofthe body's mechanism for iron conservation and protection against free
radical damage. Haemopexin is a glycoprotein (60 kDa) that consists of
two homologous domains; the N-terminal domain binds haem throughtwo His residues, while the C-terminal domain modulates haem binding
and is involved in receptor interactions. Both domains are related tosimilar domains that occur in proteins of quite unrelated function , forexample collagenases and the serum adhesion protein vitronectin.
We have crystallized the C-terminal domain of rabbit haemopexin, after
first removing its attached carbohydrate. The three-dimensional
structure has been determined by multiple isomorphous replacement (3heavy atom derivatives) and has been refined at I.S A resolution; the final
R-factor is 0.176 for a model comprising I630 protein atoms (209residues), 2 Na+, I cr, I phosphate and IOO water molecules.
The structure of the haemopexin domain shows a remarkable pseudofourfold symmetry. The molecule is folded into four modules of 40-50
residues each, which are arranged successively round a central tunnel, tocreate a disc-shaped structure. Each module is based on a four-stranded
13-sheet, of W topology. A striking feature of the structure is a row ofbound ions that fills the central tunnel, comprising two cations (Na+ orMg2+) and two anions (Cr and phosphate). The end of the tunnel where
the phosphate is bound widens into a funnel shape and a shallow surface
cleft; we propose that it is a similar feature in the N-terminal domain thatenables haem to be bound. The relationship of this domain to the similar
domain in human collagenase will be discussed, as will the relationshipwith other 13-propellor proteins.

3P07
CRYSTAL STRUCTURE OF L-2-HALOACID DEHALOGENASE
FROM Pseudomonas sp. YL AT 2.5 A RESOLUTION
T. Hisano, Y. Hata, T. Fujii, T. Kurihara, N. Esaki and K. Soda, Institutefor Chemical Research, Kyoto University, Uji, Kyoto 611, Japan.
L-2-haloacid dehalogenase from Pseudomonas sp. YL is a thermostable
dimeric enzyme formed by two identical subunits consisting of 232 aminoacid residues. It catalyses the hydrolysis of carbon-halogen bond of L-2haloalkanoic acids with various carbon-chain lengths to produce D-2hydroxyalkanoic acids. The catalytic mechanism of the enzyme is still
unclear. In order to elucidate the catalytic mechanism from structural
viewpoints, we have analyzed the crystal structure of L-2-haloaciddehalogenase from Pseudomonas sp. YL by X-ray diffraction method.
Crystals were obtained at 4°C by vapor diffusion against 50 mM
potassium dihydrogenphosphate solution (pH 4.5) containing 15% (w/v)
PEG 8000 and 1% (v/v) n-propanol. They belong to the space group C2
with unit cell dimensions a:::: 92.21 A, b =62.78 A, c = 50.84 A and f3 =122.38°, and contain one subunit per asymmetric unit. The structure wassolved by a multiple isomorphous replacement method using Au- and Uderivatives, and refined at 2.5 A resolution with X-PLOR to the R-valueof 0.198 for 7,848 intensity data (12!2cr(l)) collected on a R-AXIS IIC.
The structure of the enzyme consists of two structural domains. The core
domain which occupies about 70% of the total residues has an a./~structure where a six-stranded parallel ~-sheet is flanked with five a.helices as often observed in nucleotide-binding domains. The subdomain
inserted between the first 13-strand and a.-helix of the core domain isconnected to the core domain by two antiparallel ~-strands. The twodomains compass the cleft having the active site in its inside. Mutagenesis
studies have suggested that AsplO, Lysl51, Tyrl57, Serl75, Asn 177 andAspl80 may be involved in the activity. These residues are found to beclusterd at the bottom of the cleft, implying that they are positioned in theactive site and may include catalytic residues. Two subunits of the
dimeric molecule are related to each other by the intramolecular two-foldaxis equivalent to the crystallographic symmetry axis. The contact
surface between the subunits is mainly formed by hydrophobic residues.

3P08
CRYSTAL STRUCTURE OF 3-ISOPROPYLMALATE DEHYDROGENASE FROM FACULTATIVE THERMOPHILE, BACILLUS
COAGULANS
D. Tsuchiya, 0. Matsumoto" and A. Takenaka, Department of Life Science,
Tokyo Institute of Technology, Yokohama, Japan , and T. Murakami, T.
Sekiguchi and Y. Nosoh, Department of Fundamental Science, Iwaki Meisei
University, Fukushima, Japan
3-Isopropylmalate dehydrogenase (IPMDH ; EC1.1.1.85) catalyzes theoxidative decarboxylation of 3-isopropylmalate using NAD as cofactor.
IPMDH from facultative thermophile Bacillus coagulans (BciPMDH) is
composed of two identical subunits (Mw=39,808 ; 366 amino acid residues). To
reveal the reaction mechanism and the thermostability, we have engaged in the
x-ray analysis.
Several crystalline forms were obtained by surveying various conditions using
hanging drop vapor diffusion method . One of them, which belongs to a spacegroup of P3,21 with cell dimensions of a=b=ll4.4 and c=l94.9 A, was foundto be suitable for x-ray analysis because the asymmetric unit contains one
dimeric molecule. The x-ray diffraction data were collected on imaging plates
using the weissemberg camera at the Photon Factory in Japan . 86,904
reflections were processed, of which 27,274 independent reflections wereobtained within 2.8 A resolution (R-merge = 0 .069, completeness= 73.62 %).
Their primary phases were estimated by the molecular replacement method
using IPMDH from exrreme thermophile Thermus thermophilus (TtiPMDH) asa probe molecule. The molecular model was constructed on electron density
maps, modified using solvent flattening, NCS averaging and histogram
matching technique. Almost all amino acid side chains except for 12 C-terrninal
residues were assigned and the atomic parameters were refined to be R-factorof0 .204 using the data within 10-3.0 Aresolution .
BciPMDH takes an open a/~ structure
similar to that of TtiPMDH. As seen in
the figure, remarkable differences areobserved around the inserted residues in
the loop region . The 12 C-terminal
residues could not be identified inelectron density maps, suggesting somedisorder by extruding into solvent-Ilc!PMDH·- - • TtlPMDH
region.
Present address : Faculty of Phannaceutical Sciences. Kyoto University. Kyoto, Japan

3P09

Structures of Substrate-Complexed G4-Amylase
Inactivated by Mutation of Catalytic Residues
K. Hasegawa, H. Yamaguchi, Y. Yoshioka, Y. Matsuura, Institute for Protein Research,
Osaka University, Suita, Osaka 565, Japan, and M . Kubota, Hayashibara Biochemical
Lab. Inc., Amase-minami, Okayama 700, Japan
Maltotetraose fanning ex-amylase (G4-amylase) consisting of 429 amino acid residues
from Pseudomonas stut=eri is an exo-type ex-amylase which degrades starch from its
nonreducingend. We previously determined the structure of wild-type enzyme and thatof E219Q mutant complexed with maltotetraose (G4). Although we cocrystallized
inactivated mutant enzyme (E219Q) with maltopentaose, structure analysis revealed
that maltopentaose was hydrolyzed to give maltotetraose and also showed that the
fourth glucose unit from the nonreducing end was defonned adopting half-chairconformal ion. For the purpose of revealing the structure of this enzyme comp lexed with
non-hydrolyzed substrate and of determining the residue that is crucial to deformationof the sugar ring, we analyzed the structure of E219G and D 193G mutants complexedwith the substrate by X-ray crystallography.
The complexed mutant crystals were obtained by cocrystallization with maltopentaose.
Intensity data to 2.0 A resolution were collected on the imaging plate diffractometer
RAXIS-IJC. In the case of E219G , the crystal form was same as that of E219Q/G4
complex and we used the coordinates of E219Q/G4 complex structure as a starting
model for the refmement. The cell dimensions of Dl93G complex crystal were slightly
different from those of E219Q/G4 complex, and the structure was solved by themolecular replacement method with the program AUTOMR by using E219Q/G4
complex as the search model.
In both structures, maltopentaose was hydrolyzed to maltotetraose and the fourth
glucose unit was still deformed. In E219G/G4 complex structure, two water moleculesthat were not . observed in E219Q/G4 complex were found ncar the catalytic site
structure. One of these water molecules was located at the position that was occupiedby the atom Gln219CD in E219Q/G4 complex. The position of the sugar ring; wasalmost same as that of E219Q/G4 complex. In DI93G/G4 structure the fourth glucose
unit moved toward the Cex atom of Gly 193 and the side chain of Glu219 took different
conformation from that of Gln219 in the E219Q/G4 complex. The position that was
occupied by the atom Asp 19300 in E219Q/G4 complex was rep laced by a watermolecule.

3P10
X-RAY STRUCTURAL ANALYSIS OF THE FIVE ISOLEUCINE TO VALINE
MUTANTS OF HUMAN LYSOZYME: CONTRIBUTION OF HYDROPHOBICRESIDUES TO THE STABILITY
YurikoYamagata,

Hidetomo

Kaneda,andSatoshiFujii ,

FacultyofPharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565,
Japan. and Kazufumi Takano, Kyoko Ogasahara and Katsuhide Yutani, Institutefor Protein Research, Osaka University, Yamadaoka, Suita 565, Japan.

In order to understand the contribution of hydrophobic residues to theconformational stability of human lysozyme, five lie mutants (lle->Val ; 123V,
156V, I59V, 189V and 1106V) in the interior parts were constructed. The
thermodynamic parameters characterizing the denaturation of theses mutant
proteins w~re obtained by scanning calorimetry. X-ray analyses (resolution=1 .8A;
R-factor=0 .154-0.160; completeness of data=86.3- 95.4%) showed that theoverall st(uctures of all the mutant proteins examined were identical to that of thewild-type protein, but small structural arrangements were observed locallyaround some of the mutation sites. The most striking change among the mutant
proteins was found in the 159V protein, which contains a new water molecule inthe cavity created by the methylene deleted mutation. This water is fixed by twohydrogen bonds with the carbonyl oxygen of Ala92 and one of the internal waters
found in the wild-type and mutant crystal structures. The· B-factor of the newly
2bound water is 24.0A 2 , which is smaller than the averaged value (36.5A ) of thesolvent molecules. In the case of 123V, the movements were observed in theloop region (residues 99 to ·105) facing position 23, rather than in the vicinity ofresidue 23 . The largest backbone shift, 1.0A, is in the oxygen atom of Pro1 03.
We observed the better correlation between changes in the thermodynamic
parameters of denaturation and the accumulation of subtle structural changes,
suc~.as. ·in ASA(solvent accessible surface area) values and cavity volumes. The

total structural rearrangements involved in the overall structure partiallycompensated for the destabilization due to the removal of the methylene groupby the mutation.

3P11
CRYSTAL STRUCTURE OF ACIDIC PHOSPHOLIPASE A2 FROM
THE VENOM OF AGKISTRODON HALYS PALLAS AT HIGHRESOLUTION
X. Q. Wang, J. Yang, L. L. Gui, Z. J. Lin, National Laboratory ·of
Biomacromolecules, Institute of Biophysics, Academia Sinica, Beijing,
China, and Y. C. Zhou, Shanghai Institute of Biochemistry, Academia
Silica, Shanghai, China.
The venom of Agkisttodon halys pallas contains three highly homologous
phospholipase A2 (PLA2), which are quite different from each other in enzymatic
activity, toxicity and pharmacological activity. The sttuctural analysis and comparisonof these three PLA2 will be beneficial to understanding of the relationship between the
structure and function of this enzyme. The acidic PLA2 showing weak toxicity has afunction of inhibiting platelet aggregation.
Single crystals were grown by vapour diffusion technique. The space group is P6 1,with a=b=83 .57A and c=32.72A,and one molecule per asymmetric unit. Diffraction
data to 2.0A (Rmerge=4.18%) were collected on a Siemens multiwire X200-B area
detector. The sttucture was solved by molecular replacement with Crowther's fast
rotation and translation function, and the search molecule constructed from one subunit(L) of C. attox PLA2. The sttucture was refined using programs PROLSQ and XPLOR and model building techniques. The current model containing 133 watermolecules gives a crystallographic R-factor of 0.157 and stereochemistry with rootmean-square deviation from ideality of O.OI3A or bond lengths and 2.7 degree for bondangles. The overall structure of the molecule is very similar to those of otherphospholipase A2 of known srructure. The catalytic site, hydrophobic channel as wellas the N-terminal region show greatest structural conservation. The calcium-binding
region has a conformation that resembles closely to that of bovine PLA2 , but not C.
attox PLA2. Compared with other PLA2, the conformation of C-terminal ridge shows
significant difference due to the insertion of two residues . The putative site for platelet
function was proposed.
Calcium ion is an essential cofactor for the catalysis. In order to study calcium ion
induced conformational changes, calcium- free and calcium-containing PLA2 were
crystallized and their diffraction data were collected to 2.0 and 1.6A resolution
respectively. The crystal sttucture analysis and comparison of the both PLA2 forms arein progress. The results will be presented.
Acknowledgments: This work was supponed by grants from Academia Sinica andnational natural science foundation .

3P12
CRYSTALLIZATION AND PRELIMINARY X-RAY STUDIES OFPHOSPHOENOLPYRUVATE CARBOXYLASE FROM Escherichia coli
Y. Nagara, T. Inoue, Y. Suzuki, R. Ohtsuka, K. Fukuhara, S. Nishiura,
R. Kitagawa, H. Nakanishi, M. Hayashi, M. Inoue, S. Sugimoto and Y. Kai,
Department of Applied Chemistry, Faculty of Engineering, Osaka
University, Suita, Osaka 565, JapanK. Izui, Department of Applied Botany, Faculty of Agriculture, Kyoto
University, Sakyou-ku, Kyoto 606, Japan
Phosphoenolpyruvate carboxylase (PEPCaset; EC4. 1. 1. 31) from
Escherichia coli
catalyzes C02-fixation to form oxaloacetate andinorganic phosphate. It is composed of four identical subunits withmolecular weight of ca. 100,000 dalton. Although the primary structure
was determined in 1984,'> the molecular of PEPCase has not been
determined. In order to study its biological function based on the three
dimensional structure, we have crystallized PEPCase by using PEG4000
as precipitant,2> however, the quality of the diffraction patterns was rather
low. To get crystals suitable for X-ray crystallographic studies, hanging
drop vapor diffusion method were examined in many conditions withvariety of pH, molecular weight of PEG, and additives as control
parameters. The crystals under the best conditions appeared in tetragonal
bypyramidal shape with orthorhombic crystal lattice, space group 1222.
The unit cell parameters were determined to be a=117 .9, b=250.0, and
c=81.8A (1 A= 0. 1 nm). A set of intensity data for native PEPCase wasobtained up to 3.4A resolution using an imaging plate detector operated in
the Rigaku RAXIS-IIc system with graphite monochromated CuKa
radiation from a 12kW rotating anode generator . Among 93,327 accepted
observations up to 3.4A resolution, 29,756 independent reflections wereobtained, the completeness of which was 87.6% with an R-merge of 7.4%.
Another set of diffraction data was collected with synchrotron radiation in
the Photon Factory, the National Laboratory for High Energy Physics(KEK), Tsukuba, Japan. Now, many data sets of heavy-atom derivatives
are collecting to get the low resolution map of the enzyme.
I) Fujita, N., Miwa, T., Ishijima, S. , Izui , K. & Katsuki, H. (1984)

1. biochem, 95, 909-916
2) Inoue, M., Hayashi, M., Sugimoto, S. , Harada, S., Kai, Y. & Kasai, N.
(1989) J. Mol. Bioi., 208, 509-510

t Abbreviations used: PEPCase, phosphoenolpyruvate carboxylase

3P13
CRYSTAL STRUCTURE OF FERREDOXIN
THERMOACIDOPHILIC ARCHAEON

FROM

A

T. Fujii andY. Hata, Institute for Chemical Research, Kyoto University,
Uji, Kyoto 611, Japan, and M. Oozeki, H. Moriyama, T. Wakagi, N.
Tanaka and T. Oshima, Department of Life Science, Faculty of
Bioscience and Biotechnology, Tokyo Institute of Technology, Nagatsuta,
Yokohama, Kanagawa 226, Japan.
Archaea are classified into a third kingdom of biological world different
from Bacteria and Eukarya. Many studies on the evolution of archaeon
have been performed from the biochemical and biophysical aspects. In
order to elucidate the molecular evolution of thermoacidophilic archaeal
ferredoxin, we have determined the crystal structure of the ferredoxinfrom a thermoacidophilic archaeon, Sulfolobus sp. strain 7 .
Crystals belong to the space group P4J2t2 with unit cell dimensions a= b
= 50.12 A and c = 69.52 A. Intensity data of the native and two heavyatom derivative crystals were collected on an R-AXIS IIC using Cu-Ka
radiation. Phase angles were determined at 2.0 A resolution by a MIR
method supplemented with anomalous effects from iron atoms of theiron-sulfur clusters. An electron density map calculated with these phaseangles were improved by a solvent-flattening method. The density map
enabled us to build the model. In spite of the entire interpletation, one
high peak remained in the density map. The peak was identified to a zincatom by anomalous Fourier techniques using data collected with X-raysof wavelengths 1.275 A and 1.290 A produced by the synchrotron
radiation source of Photon Factory, KEK, Japan. The model was refinedwith X-PLOR to the present R-value of 19.1 %at 2.0 A resolution.
The molecule consists of two parts: a core and an N-terminal extended
parts. The folding of the core part is similar to the common folding
among bacterial dicluster type ferredoxins, and has the [3Fe-4S] and [4Fe4S] clusters. The N-terminal extended part is mainly constructed fromthree /3-strands. The zinc atom is tetrahedrally liganded by four aminoacid residues, and is placed at the interface between the core part and the
N-terminal extended part. The analysis of the present ferredoxin is thefirst example for the presence of structural zinc in ferredoxin.

3P14
THE REFINED CRYSTAL STRUCTIRE OF BENCE JONESPROTEIN PA V AT 2.4A AND ITS DOMAIN-DOMAINASSOCIATIONS
Chwan-Deng Hsiao1, John Rose2, S. Swaminathan3, W. Furey3, and BiCheng Wang2, 1crystallographic Laboratory, Institute of Molecular
Biology Academia Sinica, Taipei, Taiwan, 11529, 2oepartments ofCrystallography and Biological Sciences, University of Pittsburgh,
Pittsburgh, PA 15260, Biocrystallography Laboratory, VA Medical
center, Pittsburgh, PA 15240
The crystal structure of the protein Pav, a lambda type light-chain
dimers, has been determined at 2.4A resolution by Iterative Single
Isomorphous Replacement (ISIR) with phase extension andcrystallographic refinement. The final model consists of 3220 nonhydrogen atoms (no solvent atom) from 436 residues (two monomers)
with a crystallographic R-factor of 0.234 for 15,570 reflections between
8-2.4A. resolution. The structure has root-mean-square deviations of
0.015A from "ideal" bond length and 1.7060 from "ideal" bond angles.
The angle formed by the local two-fold axes of the "variable" (V) and"constant" (C) domains, the "elbow bend" is 132.50, similar to Meg lightchain dimer crystallized in deionized water. Whereas, the hapten-bindingsite formed by the two V domains of Pav light-chain dimer is similar to
Loc light-chain dimer crystallized in ammonium sulfate in which the twovariable domains formed a protrusion instead of the concave hapten
binding cavity in other light-chain dimer and Fabs. The large side chainsof residue Trp-92 from both V-domain in Pav are located in the middleof the entrance of the binding pocket when compare to concave hapten
binding cavity. Therefore, the three-dimensional structure of Pav in theantigen-binding site may be considered as two independent concave
binding pocket on opposite sides divided by two Trp-92 residues .

3P15

STRUCTUR:E OF BOVINE CYTOCHROME C OXIDASE AT
2.8A RESOLUTION.
Hiroshi Aoyama 1, Eiki Yamashita 1, Takashi Tomizaki 1, Hiroshi
Yamaguchi 1, Tomitake Tsukiharal, Kyoko Shinzawa-ltoh2, Ryosuke
Nakajima2, Rieko Yaono2 and Shinya Yoshikawa2!Institute for Protein Research, Osaka University, 3-2 Yamada-oka, Suita
565, Japan, Department of Life Science, 2Himeji Institute of Technology,
Kamigohri Akoh, Hyogo 678-12, Japan.
Bovine heart cytochrome c oxidase is a membrane protein complex
with molecular weight of 200 KDa containing 13 different polypeptide
subunits, 2 hemes A, two redox active copper sites, one zinc, one
magnesium and possibly some phospholipids as the intrinsic constituents.
This enzyme is one of the most intriguing biological macromolecules in thecell, since it reduces 02 to H20 at the active site with the four redox active
transition metals coupling with proton pumping across the mitochondrial
inner membrane. This enzyme have been explored most extensively among
the enzymes involved in biological oxidation, ever since this enzyme wasdiscovered. However, in spite of these extensive efforts, lack of the crystal
structure at atomic resolution limits seriously understanding of the reaction
mechanism of this enzyme.
Electron density distribution of oxidized bovine cytochrome c oxidase
at 2.8 A resolution indicated a dinuclear copper center with a novel
structure similar to [2Fe-2S] type iron-sulfur center and the 02 bindingsite containing heme a3 iron and copper atoms (CuB) with an inter-atomic
distance of 4.5 A without any detectable bridging ligand between iron andcopper atoms, in spite of a strong antiferromagnetic coupling between
them. A hydrogen bond between a hydroxyl group of the long alkyl side
chain of heme a3 and a phenol OH of a tyrosine located near an imidazole
group bonded to CuB and a phenyl alanine sandwiched between the heme
a3 and an imidazole liganded to the other heme (heme a) could either
provide intra-molecular electron transfer pathways or induce the redox
coupled conformational change.

3P16

Pll: The Structure of a Signal Transducing Protein
D.L.OIIis, E. Cheah, P. Carr, P. Suffolk
Research School of Chemistry,
ANU, Canberra, ACT 0200, Australia
The balance of nitrogen in organisms is a key growth determinant and studiesof the machinery that regulate this balance are of fundamental importance. Pll
is a signal transducing protein involved in the regulation of nitrogenmetabolism in bacteria. It participates in the regulation of glutaminesynthetase at the level of transcription and enzymatic activity and in so doing,
interacts with a number of other proteins.
The protein is a trimer and at low resolution , could be described as a barrel
with a loop projecting from the top surface. The protein fits into the alpha +beta category with three internal beta sheets packed against one anotheraround a three fold axis. Each sheet consists of 8 strands which emanatefrom the three subunits. Each subunit also has two alpha helices which form
the side of the barrel.
The loop of Pll contains an exposed tyrosine that is uridylylated as part of thesignalling process. Sequence comparison and other evidence suggest thatthe top of the barrel is important for interacting with other molecules. Pllinteracts with a number of effector molecules and these may bind in a cleft on
the side of the molecule.

3P17
THE UTILITY OF 4-AMINOBENZOIC ACID IN ·THE PROMOTION OF
HYDROGEN BONDING IN CRYSTALLIZATION PROCESSES

G. Smith, Centre for Instrumental and Developmental Chemistry, Queensland UniversityofTechnology, GPO Box 2434, Brisbane, 4001, Australia.

4-Aminobenzoic acid (4-ABA) is one of the most versatile of the carboxylic acids forcocrystal formation, promoting molecular self-assembly via hydrogen bonding throughboth the carboxylic acid group and the ring-substituted amino group. Since the first
crystallographic characterization of a I: I adduct with 4-nitropyridine-N-oxide (Lechat,1984 ), only two other complexes having potential as non-linear optical materials havebeen described [with 1,3-dimethyl-1-imidazolidinone (1:1) (Ueda eta/., 1986) and 3,5dinitrobenzoic acid ( 1:1) (Etter & Frankenbach, 1989)), until the work completed by ourgroup, summarized in this report. This includes five adducts with carboxylic acids, threewith Lewis bases and one with a neutral organic species, while an unusual (3 : I: I) 4aminobenzoic acid : 2,4,6-trinitrobenzoic acid : 1,3,5-trinitrobenzene triheteromolecularadduct has also been found, being one of the three components associated with the 4ABA : TNBA co crystal product (Lynch et a/., 1992). While most of the ad ducts
described are (1:1), both (1 :2) and (2: I) cocrystals have been found [with 3,5dinitrosalicylic acid (2: I) and 4-(4-nitrobenzyl)pyridine ( 1:2) (Smith et a/., 1995)].
Hydrogen bonding patterns are analyzed and the enhancement of the stability of thesesytems noted particularly in those examples where protonation of the amino group of 4ABA occurs {with 3,5-dinitrosalicylic acid[(4-ABAr<DNSA)"(DNSA)] and withpyrazine-2,6-dicarboxylic acid [(4-ABAr(PDCArJ} . In each case, the protonated groupis subsequently involved in up to five interactive hydrogen bonding associations.

Etter, M.C. & Frankenbach, G.M. (1990). Chem. Mater. 1 ,10-12 .
Lechat, J. (1984). Acta Cryst. A40, C-264.
Lynch, D.E., Smith, G., Byriel, K.A & Kennard, C.H.L. (1992). J. Chem. Soc. Chem.
Commzm., 300-301.

Smith, G., Lynch, D.E., Byriel, K.A. & Kennard, C.H.L. ( 1995). (unpublished work).
Ueda, M., Onishi, H. & Nagu, T. (1986). Acta Cryst. C42, 462-464 .

3P18

MAD Analysis of Rat Liver Macrophage Migration Inhibitory Factor
Mamoru Suzuki~* , Hiroshi Sugimotol , Atsushi Nakagawal, lsao Tanakal ,Mami Fujinaga2, and Jun Nishihira2l Division of Biological Sciences, Graduate School of Science, Hokkaido
University, Sapporo 060, Japan*Present address : Photon Factory, National Laboratory for High Energy
Physics, Tsukuba 305, Japan
2Central Research Institutes, School of Medicine, Hokkaido University,
Sapporo 060, Japan
Lymphocytes secrete a large number of soluble protein mediators, known
as lymphokines, in response to antigenic or mitogenic stimulation. The first
lymphokine discovered was macrophage migration inhibitory factor (MIF),
which was originally identified by its ability to prevent the migration ofguinea pig macrophage out of capillary tubes in vitro. It was speculated
that MIF concentrates macrophages at the infection site and make them
function in antigen processing and phagocytosis.
The recombinant macrophage migration inhibitory factor (MIF) of a rat
liver was crystallized using the hanging-drop vapor diffusion method. We
also crystallized a selenomethionyl rat MIF under similar conditions for Xray structure analysis using multiwavelength anomalous diffraction (MAD)method. Furthermore, two kinds of selenomethionyl rat MIF mutants, inwhich one or two of three methionine residues were replaced by alanine
were constructed and crystallized. These crystals belong to two different
forms of the hexagonal space group P63. The first form(large cell) has celldimensions of a= b = 95 .7A and c = 87 .9A and contains 2 dimers in an
asymmetric unit. The second form( small cell) has cell dimensions of a = b= 6l.8A and c = 53.4A with one monomer in an asymmetric unit. Intensity
data sets of small cell were collected with synchrotron radiation at the
BLl8B beam line of Photon Factory, National Laboratory for High Energy
Physics, Tsukuba, Japan.
We will report MAD analysis by selenomethionine anomalous scattering.

3P19
STRUCTURE
CRYSTAL
PHOSPHATASE.

OF

VHR,

A

DUAL-SPECIFIC

J. Yuvaniyama, M. A. Saper, Biophysics Research Division, The
University of Michigan, 930 North University, Arm Arbor, MI 481091055, USA, J. M. Denu, and J. E . Dixon, Department of Biological
Chemistry, The University of Michigan, Medical Science I Bldg., Ann
Arbor, MI 48109-0606, USA.
The human VHR (VHl -related) phosphatase is a member of the class ofphosphatases that possess an in vitro dual specificity towards both
phosphoseryl or phosphothreonyl (alkyl phosphates) and phosphotyrosyl(aryl phosphate) substrates (1 ). Examples of other members of this group of proteins include cdc25, and the mitogen-activated protein (MAP)kinase phosphatases 3CH134, CLlOO, and PACl. Thus, these dualspecificphosphatases are believed to be important regulators of cell cycle control
and mitogenic signal transduction. Despite a limited sequence similarity
between these dual-specific phosphatases and the protein tyrosine
phosphatases (PTPases), they share the PTPase signature motif,
HCxxGxxR. Biochemical studies have also shown similar trends inkinetic behavior between the two groups of enzymes.
We have recently determined the crystal structure of VHR to 2.4
resolution by the method of multiple isomorphous replacement (MIR)
using three heavy-atom derivatives. This first structure of the dualspecific phosphatase shows structural similarity to the known structures of
PTPases: human PTPlB and Yersinia YOP51, suggesting that the dualspecific phosphatases are indeed PTPases but with less specificity towards
aryl phosphates. The comparison of these phosphatase structures reveals
the substrate recognition loop present in PTPlB and YOP51, but absentin
VHR. This missing loop responsible for phosphotyrosine recognition
explains the basis of dual specificity in VHR. We show VHR can be used
as a "core" structure to model structures of other dualspecificphosphatases such as 3CH134, CL100, and PACl.
1) Denu, J. M., Zhou, G., Wu, L., Zhao, R., Yuvaniyama, J., Saper, M.
A. & Dixon, J. E . (1995) J. Biol. Chern. 270(8), 3796-3803.

3P20

CRYSTAL STRUCTURES OF THE ACTIVE-SITE MUTANTS OFESCHERICHIA COLI ASPARTATE AMINOTRANSFERASE
I. Miyahara, K. Okada, K.Hosomi and K.Hirotsu, Faculty of Science, Osaka
City University, Sumiyoshi-ku, Osaka 558, Japan, and H. Kagarniyama,
Department of Medical Chemistry, Osaka Medical College, Takatsuki,
Osaka 569, Japan.

Aspartate aminotransferase (AspAT), which has a coenzyme, pyrydoxal 5 '- ·phosphate (PLP) , catalyzes a reversible transamination reaction. On thebasis of the X-ray structures of wild-type AspAT, a detailed reaction
mechanism has been proposed. In order to understand the role of eachactive-site residue on the reaction, X-ray crystallographic study of single ormultiple replacement mutants by site-directed mutagenesis have been
undertaken.
The transamination reaction consists of many elementary steps in which theelectron distribution within coenzyme or coenzyme-substrate conjugate must
be changed. Some polar active-site residues, which have direct or indirectinteractions with PLP, delicately control the pKa of the PLP-Lys258 or PLPsubstrate aldimine for the reversible proton transfer reaction. These activesite residues were replaced by non-polar amino acids and crystal structuresof their mutants were detennined. (Nl94A, Nl94N Y225F, NI94NR386L,
etc.)
The replacement of polar side chains by non-polar ones has large effects on
the enzyme activity, nevertheless, the active-site structures of the mutants arevery similar to those of wild-type enzyme. The reason for this is that a watermolecule occupies the position of the polar side chain or main chain to keep
the hydrogen bonds previously formed . W140G belongs to an unusual case.
In wild-type AspAT, the role of Trp 140 is not only to make hydrogen bondwith a substrate but also to make a parallel stacking to the pyridine ring of
PLP. In the case of Wl40G, Trp is replaced by Gly and a water molecule
which are too small to take the place of Trp, therefore, the distal residue,
Prol41 stacks to the pyridine ring ofPLP instead ofTrpl40.

3P21

UNIQUEPOLYMORPHISMAND

INCLUSIONCOMPLEXFORMATION OF DIANILINEGOSSYPOL
B.T.Ibragimov, K.M.Beketov and S.A.Talipov., Institute of Bioorganic
Chemistry, H.Abdullaev, Str.,83, Tashkent, 700143, Uzbekistan
It is well known that gossypol, physiologically active compound of
cottonseeds, is a versatile host giving clath rates with practically all small
and mediwn size molecules.
In order to explain the universality of gossypol as host we have graduallychanged its chemical structure and investi gated including properties of theobtained derivatives. Di aniline derivative of gossypol, a product of thecondensa tion of gossypol with any line, is one of them.
Dianilinegossypol has a good including ability too, but it cannot form
clathrates with first members of the carbon acids and alcohols. The single
crystals of 34 host-guest complexes are obtained and their crystallograp hie
parameters are determined. The structure of 10 of them is solved. The
peculiarities of dianilinegossypol clathra teformation are discussed incomparision with gossypol ones.
By changing the crystallization conditions 7 dianili negossypol polymorphs
is obtained and identified by X-ray method. Another 3 polymorphic
modifications of dianiline gossypol are obtained by decomposition its
unstable host-guest complexes. The structure of 3 polymorphs is determined. It is shown that no solid state thermotropic transitions between
these polyrnorphs.

Other alotof interesting peculiaritiesof

dianilinegossypol polymorphism and clathrateformation will be discussed.

3P29

STRUCTURE ANALYSIS OF N-(2,4-DINITROPHENYL)-o-ANISIDINE
AT HIGH TEMPERATURE USING IP-DIFFRACTOMETER
K. Takada, T. Watanabe, K. Taguchi, M. Yasui and F. Iwasaki, Dept. ofApplied Physics and Chemistry, The Univ. of Electro-Communications,
Chofu, Tokyo 182, Japan.
The structure analyses at several temperatures of N-(2,4-dinitrophenyl)-oanisidine were performed. The diffraction data were measured by the
Imaging-Plate-diffractometer equipped with the N2-gas-stream hightemperature apparatus. This crystal has two modifications, orange andred forms, and exhibits a phase transition at the wide temperature range
from 110 to 158°C depending on the specimen. We expected to catch
some intermediate state of this phase transition from the diffraction data of
the single crystal. Each data set was measured within 2 hours using same
specimen. In order to study the time-dependent variation, 3 and 2 sets ofdata were measured every 3 hours at 120 and 130°C, respectively.
Crystal Data: Ct3HttN305, monoclinic, P2/a
24
50
75
tOO
120
21.554
21 .555
21.51421.59221.538
4.328
4.253
4.272
4.310
4.228
16.714
16.69416.74316.73616.655122.12
122.29122.28122.22
122.211517
1370
No. observed 1612
1652
1601
0.092
0.090
R
0.084
0.090
0.091

Temp .( 0 C)
alA
b!A
c/A
p ;o

130
21.5944.344
16.716122.081289
0.089

The crystal structures were successfully refined using each data set.
The structure was revealed to be an orange form at the 130°C. Thus thephase transition did not occur in this case. However the cell parameterschanged anisotropically during the heating. The b axis simply elongatedwhile the a and c axes did not show significant changes. This lengthening
corresponds to the widening of the distance between molecular planes
which arrange vertically to the b axis. These results may partially support
our plausible mechanism of the phase transition (Yasui, eta!., 1995). The
data collections at higher temperature will be carried out.
Yasui, M ., Taguchi, K. and Iwasaki, F. a paper in AsCA95 .

3P30
CRYSTAl.. STRUCTURES OF TEMPO RADICALS SHOWINGFERROMAGNETIC INTERACTION
H. "Yamamoto, H. Yoshikawa·, H. Mitsuda, K. Takada-, M. Yasui, T.
Ishida·, T. Nogami and F. Iwasaki, Department of Applied Physics andChemistry, The University of Electro-Cemmunicat'ions, Chofu, Tokyo
182,Japan

Recently, some 4-arylmethyleneamino-TEMPO
radicals (TEMPO = 2,2,6,6-tetramethyl-piperidin1-oxyl) were revealed to shew an intermolecularferromagnetic interaction, of whieh 1 - 4· exhibit
a ferromagnetic transiti0n (Tc) at an extremely low temperature (Ishida,
et al., 1994; Nogami, et al., 1994). 5 - 8 showed only a ferromagnetic
interaction (6 > 0), while 9 showed an anti-ferromagnetic interaction (6 <@). The X-ray structure analyses were performed on these crystals atroom temperature to in:vestigate whether any systematic intermolecularinteractions were demon·strated among these crystals.
Crystal Data
1

2
J
4
5
6
7

8
9

Ar
Ph
. p-CI-Ph
p-bi-Php-phenOli)'· Ph
p-Br-Ph
3,5-di-Cl-Ph
3' pyridyl
naphthylp-F-Ph

Tc/K
0.18
0.4
0.4
0.2

9/K Sp. gr.
0.7
P211c
0.7
P211c
0.6
P21/E
0.4
Pbc21
0.5
P211c
0.7
Plica
0.4
P2 r/c0.3
Pna2'1
-2.6
Pbca

a1A
b!A
etA
12.684 11 .740 11.024
5.909 24.475 11.421
5.955 28.486 11.795
5.993 30.565 22.032
7.541 20.847 10.590
14.035 22.964 10.71'0
12.426 11.598 11.038
20.084
5.69'7 15.107
20.010 15.249 10.417

Ill'
111.40103.84106.7290.0
91 .5690.0
1"09.52
90.0
90.0

V/A3
1528
1604
1916
4035
1664
3452
1499
1<7-28
3l78

z
4
4
4

8
4

8
4
4

8

The molecular structures of these comp·ounds are very similar. The
arylmethyleneamino moieties are planar and almost perpend'icular to thepiperidine rings of which· conformation is a chair form. For all crystals,
1 - 9, two-dimensional 0---0 networks are constructed', although 0f
which forms are various. The 0---0 distances are 5.47-8.75 A. Between
sheets the aryl groups of each sheet arrange alternately. The intersheet
Q ... Q distances are 8.96-13.40 A. The sheet-like arrangement of theNO radicals is considered to· be essentially imJ!lortant for the magnetic
interactions.
Ishida, T., Tsuboi, H., Nogami, T ., YoshiRawa, H., Y,asui, M., Iwasaki, F .., lwamura,H., Takeda, N. & Ishikawa, M. (1994). Chem. Letters, 919-922.
Nogami, T., Tomioka, K. , Ishida, T ., Yoshikawa, H., Yasui, M., Iwasaki, F. ,I:wamura, H., Takeda, N . & Isl\ikawa, M. (1994). Chem. letters, 29 - 3i2.

3P31
THE CENTRAL C-C BOND LENGTH IN THE
Bl(ANTHRACENE-9,10-DIM ETHYLENE) PHOTOISOMER:UNUSUAL ELONGATION AND CRYSTALLINE STATE
REACTION
Jun Harada, Keiichiro Ogawa, and Shuji Tomoda, Department ofChemistry, College of Arts and Sciences, The University of Tokyo,
Komaba, Meguro, Tokyo 153, JapanThe central bond length in the title compound (1) has been a subject ofconsiderable interest because of the anomalously long C-C bond ( 1. 77 A) ·obtained from X-ray analysis by Ehrenberg (1966). This has been widely
accepted as one of the longest C-C single bonds and several attempts torationalize it have been made. Allinger and his co-workers estimated thebond length to be 1.64 A from the molecular mechanics and the ab initio
calculations (1993). They state "it seems clear that the X-ray results areunreliable." Very recently Siegel and his co-workers redetermined the Xray structure of 1 and showed that the C-C bond length is 1.648(3) A(1995). This value closely agrees with the structures obtained from HF
and DFf calculations. This paper shows that the anomalous elongation of
C9-Cl0' bond of 1 in the previously reported X-ray structure is ascribedto an unresolved disorder caused by the partial cycloreversion of 1 to 2
in the crystalline state and that the true bond length of C9-Cl0' is 1.66 A.

in crystal

2

Battersby, T. R., Gantzel, P., Baldrigde, K. K. & Siegel, J. S. (1995)
Tetrahedron Lett., 36, 845-848.
Ehrenberg, M. (1966). Acta Cryst., 20, 183-186.
Zhou, X., Liu, R. & Allinger, N. L. (1993). J . Am. Chern . Soc ., 115,
7525-7526.

3P32
CRYSTAL STRUCTURES OF COPPER COMPLEXES SHOWINGFERROMAGNETIC INTERACTION
Y. Ishikawa, M. Yasui, F. Iwasaki, T. Ishida and T. Nogami, Dept. ofApplied Physics and Chemistry, The Univ. of Electro-Communications,
Chofu, Tokyo 182, Japan.
We have determined the crystal structures of complexes of copper(II)bis( 1,1, 1,5 ,5,5-hexafluoropentane-2,4-dionate ), Cu(hfac )2, with aquinazoline (I) and a pyrimidine (II). Both complexes were revealed to
exhibit a ferromagnetic interaction. The ferromagnetic transition of I wa:sobserved at about 0. 12K (Ishida et a/., 1994). However II does notshow a ferromagnetic transition at a low temperature.
Crystal Data: .
Sp. Gr.
P2tln
D
/4tcd

a/A
b!A
ciA
12.300(2) 12.123(2) 15.155(2)18.598(1) 18.598(1) 22.331(3)p/0102.46(1)90.0

Observed
2704
1559

R
0.044
0.060

In each crystal, Cu atoms have the distorted octahedral structures. For I,
two quinazoline moieties coordinate to a Cu atom on both axial positions
and bridge the complexes to form a one-dimensional chain. There are two
types of crystallographically independent Cu atoms which are located on
the center of symmetry. The cu .. ·Cu distance within a chain is 6.06A. In
II, one pyrimidine coordinates on the axial and another one on theequatorial position . II also has a structure of a one-dimensional chain.
The cu .. ·Cu distance within a chain is 6.0IA . The first and second
shortest cu .. ·Cu distances between chains are 8.68 and l0.59A for I, and9.30 and 9.82A for II . We presume that some critical differences may
exist in the inter-chain interaction between I and II.

I ~
(~

I
,.-N~N,Cu(hfac)2

)(

~

/N~N,

n

Cu(hfac) 2)nDIshida, T., Mitsubori, S., Nogami, T., Ishikawa, Y., Yasui, M., Iwasaki, F., Iwamura, ·H., Takeda, N., and Ishikawa, M. (1995). Synthetic Metals, 71, 1791-1792

3P33
CRYSTALLINE-STATE RACEMIZATION OF BULKY GROUPS ON
EXPOSURE TO VISIBLE LIGHT
Yuji Ohashi and Hiroyuki Sato, Department of Chemistry, Tokyo
Institute of Technology, Ookayama, Meguro-ku, Tokyo 152, Japan,
and Yoshifusa Arai and Yoshiaki Ohgo, Niigata College of Pharmacy,
Kamishineicho, Niigata 950-21, Japan
we found that the chiral cyanoethyl group bonded to the cobalt atom
in some cobaloxime complex crystals was racemized by X-ray orvisible light with retention of the single crystal form. The rate of
the racemization was so slow that we can see the structuralchange directly by X-ray analysis. Recently the chiral group was
replaced with bulkier groups, bis(ethoxycarbonyl)ethyl (bece) and
Several cobaloximebis(allyoxycarbonyl)ethyl (bace) groups .
ligands. Among
base
axial
differentwithcomplexes were prepared
the complex crystals, the bace complex with pyridine as an axial
base ligand (bece-py) and the bace complex with water as an axial
base ligand (bace-aqua) showed the gradual cell changes on
exposure to aXe lamp and the racemization occurred with retentionof the single crystal form .
The bece-py crystal has the space group P2 1 2 12 1 and has one
molecule in the asymmetric unit. When the crystal was exposed tothe chiral bece group was transformed to thethe Xe lamp,
disordered racemates. 01 the other hand, the bace-aqua crystal has
the space group P2 1 and has two crystallographically independent
molecules in the asymmetric unit. One of the two bace groups was
fully inverted to the opposite configuration on exposure to the Xelamp and the space group was changed to P2 1/n .
In order to explain why only these two crystals were converted toracemic crystals without degradation of the crystallinity, thereaction cavity was drawn for each crystals. From the size andshape of the reaction cavity, the inversion mechanism of the chiralgroup was made clear .

3P34
CYCLIC 0-H···N/C-H···O H-BOND COUPLING IN THE DESIGNOF SUPRAMOLECULAR ASSEMBLIES

v. R. Pedjreddi and W. Jones, Department of Chemistry, University ofCambridge, Lensfield Road, Cambridge CB2 lEW, U. K. and A P.
Chorlton and R. Docherty, Zeneca Specialities, PO Box 42, Hexagon House,
Blackley, Manchester, M9 3DA, U.K.
The exploitation of both strong (0-H···O, N-H···O etc.) and weak (C-H···O)
H-bonds in the design of supramolecular assemblies is currently of interest.
In many cases, individual H-bonds are arranged as rings - the well-known
case of carboxylic acid pairs is a good example, Scheme l(a). To date,however, no cyclic couplings which have been identified as being importantin building assemblies consist of both a strong and a weak H-bond.Schemel(b).
so-H-.?-o
(a)

--{

)--

(b)

--{

)--

0--H-C

0 · -·H-Owss=strongI

0-H·-- N..,

w=weakScheme 1

To illustrate the use of this particular coupling in building supramoleculararrays we have studied the co-crystal formation of phenazine with various
carboxylic acids. We have also investigated the extent to which thisparticular coupling exists within structures in the Cambridge Structural
Database (CSD). Whilst structures containing this motif have been
deposited, its role in influencing crystal packing does not seem to have been
appreciated.

3P35
LAYERED STRUCTURES OF
ANTIFERROELECTRIC MESOGENS
K. Okuyama, N. Kawano, S. Uehori and K. Noguchi, Faculty of Technology,
Tokyo University of Agriculrure and Technology, Koganei, Tokyo 184, Japan,
and N. Okabe, Y. Suzuki and I. Kawamura, Central Research and Development
Laboratory, Showa Shell Sek.iyu Co. Ltd., 123-1 Shimokawairi , Atsugi 24302, Japan
Recently, anti ferroelectric meso gens attract much attention not only from theirapplication to flat-panel displays but also from relationships between physicalproperties and their unique bilayered superstructures . Based on thephysicochemical observations, the structure of antiferroelectric liquid crystal
phase was proposed to be one of the smectic C phases and termed theantiferroelectric chiral smectic liquid crystal (SCA *) phase. According to the
proposed structure for this phase, all the mesogen molecules in one smectic
layer tilt in one direction and those in the neighboring layers tilt in the opposite
direction (herringbone structure). Because of this alternate tilting from layer
to layer, the total spontaneous polarization in one layer is canceled by that in
the adjacent layer. By applying external electric field, the spontaneouspolarization were aligned in the same direction, which induced a ferroelectricstate. In this study, the crystal structures of several anti ferroelectric mesogens
were investigated by an X-ray diffraction method.
In spite of the chemical similarities of mesogen compounds, they showed
different characteristics. Three of them ((1), (2) and (4) in Fig.l) have their
SCA * phases just above their crystal phases. Structure analyses showed thatthe layer structures of (1) and (4)were a herringbone structure similar~ n....£\.....r~F,
to the proposed structure of SCA * c,n,~o~o~oc,n.,phase mentioned above. The(I) TFMHPBC
packing structure of (2), however,
was rather similar to that of (3) which
11
had the intermediate phase between c,H.,co---Q--0-co~~~.""SCA * and crystal phases. No close*
relation was found between these(2) MHPCBC
structures and the proposed strucrurefor SCA * phase. The direction ofc;ndipole moments calculated from the c,H.,~oo-Q-co~~'""
obtained conformations of (1) and(4) in one layer coincided with one(3) MHPOBCof the axes parallel to the layer plane.
However, since the dipole moment_fH,
in the next layer had the same . c,H,--Q-0-coo-Q-co~nc,H.,magnitude and the opposite
direction, the over-all dipole moment(4) MHPBC-JO
became zero as proposed for the
Fig . I Chemical structures of
SCA * phase.
antiferroelectric mesogens

3P36

COMPLEX FORMATION OF SURFACTANT
MOLECULES WITH AROMATICCOMPOUNDS IN A MORTAR
Keiju Sawada and Yuji Ohashi, Department of Chemistry, Tokyo
Institute of Technology, 2-12-1 , 0-okayama, Meguro-ku, Tokyo 152,
Japan, and Nahoko Iimura and Hirotaka Hirata, Niigata College of
Pharmacy, 2-13-5 Kamishin'eicho, Niigata, 950-21, Japan
Various complexes were recrystallized from an aqueous solution withcationic surfactants and aromatic compounds; i.e. Cetyltrimethylammoniumbromide (C16H33N(CH3)3, CTAB)
and o-iodophenol(I-C6H 4-0H). Their structures were analyzed using X-ray diffraction analysis. The mixture of the two compounds in a mortar werealso analyzed using powder X-ray diffraction analysis, which revealed
that the complexes were formed only by mixing surfactant moleculeswith aromatic compounds in a mortar. There are hydrogen bonds
between these molecules. It was expected that the hydrogen bond isa driving force to form these complexes.
In this study, we succeeded to obtain complex of CTAB and biphenyl(CIOHs) in aqueous-methanol solution (Fig.l ). But these molecules
have no interaction as hydrogen bonds. CTAB and biphenyl weremixed in a mortar, then the mixture were also analyzed by X-ray
powder diffract meter. The
same pattern as that of theacomplex crystals was obtained. This means that
there should be an interaction between the alkyl
group and the aromaticcrings and that the driving force of these formation
Fig. I Crystal Shllcture of crAS/Biphenyl
must be the interaction.

3P37
GENERATION OF ASYMMETRY IN THE CRYSTALLINE STATEPHOTOISOMERIZATION OF COBALOXIME COMPLEX
T. Yoshimiya, A. Sekine and Y. Ohashi, Department of Chemistry,
Tokyo Institute of Technology. 0 -okayama. Meguro-ku. Tokyo 152.
It has been found that the 2-cyanoethyl group bonded to the cobalt
atom in some cobaloxime complex crystals is isomerized to the 1cyanoethyl group on exposure to visible light in the solid state.
Recently the 2-cyanoethyl group of the complexes with 3methylpyridine , 4-methylpyridine as axial base ligands was found to beisomerized with retention of the single crystal form . The generation of
the asymmetry of the produced 1-cyanoethyl group was clearly observedby the crystal structure analysis after the isomerization. In order to .
obtain the quantitative relation between the chirality of the producedgroup and the asymmetry around the reactive group. the isomerizationof the complex with 4-ethylpyridine as an axial base ligand has been
analyzed .
The title complex was synthesized in the same way . as reported
previously and the crystal structure before the irradiation was analyzed
by X-rays. The crystal is triclinic, the space group being Pi and Z=2.;
a=ll.218(3) , b=11.265(3) , c=9.390(2)A. and , a=93 .30(2). 13=114.05(2),y=98.68(2) 0 and V=1061.8(5) A3 . The crystal was exposed to a 500W Xe
lamp for 168 hours . The crystal was not decomposed, but the celldimensions were significantly changed: a=11.162(3) . b=ll.309(2).
c=9.347(2)A. and, a=93 .38(2) . P=ll3 .78(2). y=97.66(2) o and V=l061.8(5)AJ. The produced 1-cyanoethyl group does not take a disordered
racemate but an ordered chiral one. This clearly indicates that theasymmetry is generated in the chiral crystal environment.

Molecular Structure
before the irradiation

Crystal Structure
after the irradiation

3P38
CHEMICAL BOND AND ATOMIC DISPLACEMENTS IN
Bao. 87 Ko.13Bi03 CRYSTAL

Yu. A. Abramov*,I.M. Reznik* and V.G. Tsirelsons* National Institute For Research in Inorganic Materials, Tsukuba, Japan# Physical Technical Institute, Donetsk, Ukraine$ Mendeleev University of Chemical Technology, Moscow, Russia

The electron density distribution and Bi atom displacements in
Bao. 87 Ko.1JBi03 perovskite single crystal are studied using both X-ray diffraction data (Wignacourt J.P. et al. (1980). Appl.Phys.Lett. 53. 1753-1756)
and modified statistical method calculations. A noticeable covalent component in the Bi bond with neighbouring oxygens is revealed. The nature of the
Bi atom anharmonic displacements reflect either dynamic or static instability
in its ideal crystallographic position. The results obtained indirectly support
the interpretation of the nature of incommensurate modulation in
BaJ.x K.Bi03 crystals under electron-irradiation (Verweft M. et al. (1991).
Phys. Rev. B44. 9547-9555)
Support of this research by the International Scientific Foundation (Grant
Ul GOOO) is gratefully acknowledged.

3P39
HATEM CHARACTERIZATION OF HOMOLOGOUS SERIES OF
SUPERCONDUCTORS GaSr2Can-1Cun02n+3 (n=3 AND 4)

J. Ramirez-Castellanos· , Y Matsui and E. Takayama-Muromachi, National
Institute for Research in Inorganic Materials, Tsukuba, lbaraki 305, Japan, andM. lsobe, Sony Co . Research Center, Yokohama 240, Japan . ("Also at,
Department of Applied Physics, Tsukuba University, Tsukuba 305, Japan)
Recently. lsobe et al. (1] reported that a new homologous series ofsuperconductors , GaSr2Can-1 Cun02n+3; or Ga-12(n-1 )n. are obtained
under high-pressure (6GPa, 1250°C), and that superconductivity apper at
Tc=70 K (for n=2 and 3) and at Tc=1 07 K (for n=4).
Powder X-ray andneutron diffraction data suggested that they have pseudo-tetragonal
orthorhombic structures (/c2m), with lattice parameters a=b=..f2ap &c=(2n+2)ap. where ap is the parameter for the cubic perovskite. The electron
diffraction patterns. however, shows weak extra-reflections in some diffraction
networks and this indicates that a double periodicity along b-axis (b=2--12ap)
are formed, due to "intra-layer" ordering of two types of Ga04 chains (Rand
L) . It is also found that these extra reflection spots have strong streaking
along the c·-direction, as seen in Fig.1 (2] . This indicates that "inter-layer"
disordering of the R and L-types of Ga04 chains is formed, as previously
suggested for Ga-1212 structures (3]. The corresponding HATEM image, inFig.2, shows such disordering clearly (2].
References(1] M. lsobe et al. (1994) Physica
C222, 310.
(2] J. Ramirez-Castellanos et al.
(1995) Physica
in the press.
(3] T . Krekels et al. (1993) J. Solid
State. Chem. 105, 313.

c.

Fig. 1. Electron diffraction patteQl of
Ga-1223 projected on (11 0].
showing streaking along the c·direction .

Fig. 2. HATEM ima~ of Ga-1223
projected along (11 0], showing"inter-layer" disordering of Ga04
chains.

3P40
ANALYSIS OF QUASICRYSTAL STRUCTURES BY USE OF POWDER NEUTRON AND SINGLE CRYSTAL X-RAY DATA
Akiji Yamamoto, National Inst. Res. Inorg. Mat. Namiki 1,
Tsukuba, 305 Japan, Tsuyoshi Kajitani, Dept. Appl. Phys. Toholm University, Aramaki, Sendai, 980, Japan, Yukio Morii, Japan
Atomic Energy Research Institute, Tohkai-Mura, Ibaraki, 319-11,
Japan
There exist many difficulties in the structure analysis of quasicrystals, which are usually ternary alloys. One of them is the determination of partial occupancies of a site. It is known that one site
is occupied by AI and Cu statistically in icosahedral Al-Cu-Li quasicrystals. In order to determine the partial occupancy of a site, itis efficient to refine it in binary alloys. On the other hand, there
are two partial occupancies for a site in t~rnary alloys and there exists the correlation between them when ·only one data set is used.
The combined use of X-ray and neutron diffraction data will reducethe correlation because these two have independent information forthe partial occupancies. For this purpose, we developed a programin which the Rietveld method and the single crystal method areused . In the program, the sum of the weighted R factors of two
data sets are minimized by the least-squares method. It was applied
to the analysis of face-centered icosahedral Al-Pd-Mn with the 6dimensional superspace group Fm35, where single crystal X-ray andpowder neutron data were used. The X-ray data include 1137 independent reflections (Yamamoto, et al. 1993) while 249. reflections areused in the Rietveld method . The correlation between two partial
occupancies seems to be large but the divergence of the least-squares
method could be restrained by using a large Marquardt parameterin the normal matrix and the partial occupancies were refined . The
final Rw factors were 0.103 for X-ray and 0.107 for neutron data.
Yamamoto A ., Sato A., Kato K. Tsai A. P. and Masumoto T . (1993)
Mat . Sci. FoTum 150-151, 211-221.

3P41
A NEW BARIUM COPPER OXYCHI..DRIDE, Ba2Cu304Cl2; ITSSYNTHESIS AND CRYSTALLOGRAPlllC CHARACTERIZATION
Zhigang . Zou, 0 . Tachikawaand

H . Horiuchi

Mineralogical Institute, Graduate School of Science,
University ofTokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113, Japan.
A new crystalline phase of oxychloride, Ba2Cu304Cl2, wassynthesized by a reaction of the mixture of CuO, BaCl2, Ba(OH)2and KCl, and by a heat treatment of the hold for 6 hours at 800°C
and gradual decrease of the temperature to 650°C by 48 hours.
Ba(OH)2 and KCl apparently play a role of flux . The atomic ratio of
the product was analyzed by EPMA, and the result of
Ba:Cu:Cl=2:3:2 was obtained. In order to examine the oxygen
content of the product, it was heated up to 850°C by the rate of
5°C/min in air, and the weight loss by this heat treatment was 9 .17%.
The final phase obtained by this process was identified as
Ba2Cu30s[1] by X-ray powder diffraction. As a result, the chemicalcomposition of the initial phase was confirmed as Ba2Cu304Cl2.
By these experiments, the valency of Cu was concluded to be +2 inthis crystal structure. The product was cystallographically examinedby precession camera, X-ray powder and single crystal diffraction
methods . As a result, the crystal structure was found to belong to atetragonal system with lattice constants of a=5 .519(l)A andc=l3.834(2)A. Diffraction symmetry is 4/mmm with a bodycentered lattice.

Detailed crystal structure of the product is now

under investigation.
[I] Kubel , F. and Janner, A.-M.(1993). Acta Cryst. C49, 657.

3P42

SYNCHROTRON RADIATION IMAGING OF THE
DEFORMATION ELECTRON DENSITY IN LiNb03 and LiTa03
R Hsu, E N Maslen and V A Streltsov, Crystallography Centre, Universityof Western Australia, Nedlands, WA 6907, Australia and N Ishizawa,Research Laboratory of Engineering Materials , Tokyo Institute ofTechnology, 4259 Nagatsuta, Midori -Ku, Yokohama 227, Japan
Diffraction imaging of the deformation density (Lip) in LiNb03 and LiTa03,
using the four-circle diffractometer on BL14A at the Photon Factory in
Tsukuba, Japan, has clarified the relationship of ferroelectricity to structure,
atomic vibrations and deformation density . Both analyses indicate
substantial exchange transfer of electron density from the Nb(Ta) atom to amore open region of the structure within the large 03 triangle near the Li
atom . Hirshfeld partitioning of Lip indicates that approximately twoelectrons are transferred to the Li atom, whereas the 0 atoms carry a chargeof only -0.3 electrons . The Nb(Ta) atoms carry a positive charge ofapproximately 3 e. Spontaneous polarisations PUNb03 = 43 and PUTa03 =33 (x1o-2cm-2) calculated from these charges agree qualitatively with theexperimental values of 71 and 50 (x1o-2cm-2) respectively. The calculated
and experimental ratios PUNb03/PLiTa03 are similar. The Li atom' rolein the polarisation process is pivotal. In the high temperature paraelectricphase the Li atom forms three short Li-0 bonds to coplanar 0 atoms,
whereas the Nb(Ta) atom is the central metal atom in a regular M06
octahedron. In the low temperature ferroelectric phase both the Li and theNb(Ta) atoms move from the ideal paraelectric positions to off-centre
positions in irregular M06 octahedra. The 0 atoms have limited influenceon the deformation density in both compounds, which has strong but
approximate symmetry determined by the cation lattices. The two strongest
Li- Nb(Ta) vectors in the structures are both markedly shorter than all Li-Li,
Nb-Nb or Ta-Ta vectors, as would be expected if the A and B cations in the
distorted perovskite structure carry charges of opposite sign.
Structure factors for small flux grown LiNb03 crystals measured using
focused A. = 0.7 A synchrotron X-radiation (Tsukuba, Japan). Space group
R3c, rhombohedral, Mr = 147.8, a= 5.493 (2) A,a =55.89. (3), V = 318.2(3) A3,
Z =2, Dx = 4.629 Mg m-3, tJ0.7 =5.01 mm-1, F(OOO) = 136, T = 293 K, R = 0.015,
wR =0.015, S = 3.276 (84), Ymin = 0.27 for 773 unique reflections.

3P43
TOPOLOGICAL STIJDY ON THE ELECTRON DENSITY
DISTRIBUTION OF BIS(DIIMINOSUCCINONITRILO)NICKEL,
NI(C4N4H2)2
Tsong-Song Hwang and Yu Wang* , Department of Chemistry, National
Taiwan University, Taipei, Taiwan
Planar molecule Ni(C 4N 4 H2) 2 is roughly in D2 h symmetry and its electronic
structure can be written as a combination of several resonance forms . Its
bonding character is very interesting and suitable to be analyzed via lowtemperature x-ray diffraction experimentally and molecular orbital calculation
theoretically. Deformation density distribution using these two methods give
solid confmnation on 7t-delocalization phenomena on the ligand. The
asphericity on electron density around Ni atom conforms to the crystal field
theory. Topological study based on the total electron density of the molecule
gives also valuable information about chemical bond. Atom domains, bondpaths and bond critical points can be deduced both experimentally andtheoretically. There are two ring critical points(RCP) located at the center of
each ligand. Bond critical points(BCP) are formed along Ni-N, N-H, N-C, C-C,
C=C, C=N bonds. From the charge density (p), the laplacian (V2p) and thethree hessian eigenvalues(A.l,A2,A3) at the bond critical points, the bonding
characters are quantitatively described. According to these values, the bondstrength as well as <J, 7t-characters can be compared. It is apparent that C=N
bond is the strongest bond and the electron density along the bond iscylindrically distributed, characterized as triple bond. Each atom in molecule isenclosed by a zero-flux surface called atom domain . It contains constant charge,
dipole, quadrupole and higher moment within this atom domain. The bond pathis the maximum density line between two bonded atoms. The collection of allthese bond paths in molecule should give the shape of the molecule. The
gradient vector of charge density p helps to locate the critical point and atom
domain. The agreement on the topological properties derived from experimentand theory is very good. This means that the experimental multipole model andthe molecular orbital calculation are complementary with each other.

3P44

Electron Density Studies of Cobalt(II) Octaaza
Bis - a - diimine Macrocyclic Complex[Co(CIOH20N8)(H20)2]2+[Cl04h2Jey-Jau Lee, Yuan-Shyane You, Gene-Hsiang Lee, Yu Wang.,
Department of Chemistry, National Taiwan University, Taipei, Taiwan
Abstract:
The Crystal and molecular structure of [Co(C1oH2oNg)(H20)2]2+ ·[CI04h2- has been determinated by single - crystal X-ray diffraction
method at 295 and 125 K. It crystallizes in the space group of P bca at 125
K with cell parameter a=ll.655(2), b=16.930(4), c=l0.508(2)A,
Mw=556.27, V=2073.4(6)(A3), Z=4. The fmal agreement index R is 0.033
and Rw is 0.037 based on 5547 observed reflections ; the site symmetry ofcobalt is at -1 .
The Cobalt is in the same plane of the macrocyclic ring , the two axial
directions are coordinated by two water molecules. The Co-N distances ofthe macrocyclic ring plane is 1.9026(7)A and 1.9153(7)A, the axial Co-O
distance is 2.2854(9)A. The CoN402 can be associated as a tetragonal
distorted octahedron due to Jahn - Teller distortion . The ligand is a partially
7t-delocalized a- diirnine, the C-N bond distance is 1.30l(l),indicating adouble bond character .
Electron density distribution based on multipole refmement confirms thepredication on the asphericity in electron density around Cobalt. The
bonding between a - diirnine nitrogen and Co can be described as a weakcovalent bond with N at the ligand served as a cr - donor. The d-orbital
populations are derived from the multipole model, the populations in dn
orbitals are more than those on dcr orbitals. This gives a low spin d7
configuration. the C-C,C-N bond of the ligand are showing strong covalentbond character as indicated in the electron density distribution. Further
analyses on the bond characterization will be made by comparative study onmolecular orbital calculation.

3P45
EFFECT OF A MAGNETIC FIELD ON HICKEL-PLATINUM ALLOYS
D.

K.

1000,

Saha, Atomic Energy Centre, P . 0.
Bangladesh

and

K.

Ohshima,Box -Institute

164,
of

Dhaka

Applied

Physics, University of Tsukuba, Tsukuba 305, Japan.
Magnetic properties of Ni 1• 1 Pt 1 alloys were studied in both
the disordered and ordered states for x•0.25, 0 . 35 , 0.44 and
0 . 50. Different magnetic fields were applied in the range
from 0 to 800 Oe for the disordered state and from 0 to 10 kOe

for

the

ordered

state

under

the

zero-fieldcooling

condition with the temperature range from 5 to 400 K.

Forx•0 . 25 and 0 ~ 35 alloys, a ferromagnetic moment was observedin boththedisordered andmagnetic-field
behaviorofindependent

theofrange.

In

magnetic
magneticordered states

theorderedmoment was
field.

For

for the wholestate,

anobserved,
thex•O. 44

unusalwhich

isalloy,

aferromagnetic moment was observed in the disordered state,
but peculiar results were observed in the ordered state. A
weak ferromagnetic moment appeared at 0 to 10 Oe
field

but

from

50

up

antiferromagnetic-type

to

1000

featuremagnetic

field,

an

is

seen,

where

the

antiferromagnetic-paramagnetictransition

decreases

increasing

momotonicallywith

Further , from 1200 Oe up to 10 kOe

magne~icOetemperaturemagnetic

T1
field.

, the paramagnetism isevident . Hysteresis-loop data and the curve of the inverseof the magnetic susceptibility confirmed antiferromagnetismin the alloy. This is the first observation to our knowledge
for such a change under an applied magnetic field in thebinary alloys . For the x • O.SO alloy , a ferromagnetic mementin the disordered state and a clear paramagnetic moment intheorderedrange.

state observed

for

the

whole

magnetic-field3P46
ATOMIC RADII FROM ELECTRON DENSITIES
E. N. Maslen and BE. Etschmann
Crystallography Centre, University ofWestem Australia, Ned lands, 6907, Australia
In principle the radius of an atom is a physical property that can be defmed uniquely, but

the values obtained by partitioning bonds between identical atoms [I) are not necessarily
appropriate to bonds between different atoms [2]. In practice different scales proposed forradii reflect alternative methods for partitioning interatomic distances. We have tested theexistence of a well defined relationship between the ground state electron configuration
for free atoms, the corresponding one-electron density and the atomic radii invoked when
predicting structural geometry.
The invariant component of the radius associated with the atomic cores can be equatedquite accurately to the value at which the integral of the density equals the number of coreelectrons. The most significant additional contributions is from the valence electrons
which, unlike the cores, must be treated as penetrable when determining their contribution
to the radius. The main requirement when evaluating atomic radii from atomic electron
densities is to evaluate the penetrability of the valence subshells. Sub-shell penetrability
increases with bond order, and decreases with the angular momentum quantum number.
The investigation so far indicates that the effect of the principle quantum number on thepenetrability of the valence sub-shells is small. Interatomic distances can be represented
only approximately as sums of invariant atomic radii . The distances are affected to second
order by exchange interactions with electrons that do not participate directly in bonding,including those in other neighbouring atoms. Predicting accurate bond lengths requires
the development of formul ae which specify those second order corrections. The
approaches have been tried out so far on diatomic molecules, where the results arepromising. It is likely that they will extend successfully to poly-atomic molecules andcrystalline materials.
[I) Shannon, R.D. & Prewitt , C.T. (1 969) . Acta Cryst B25, 925-946[2) Slater J.C. (1965) Qllallltlm Theory of Molectlles and Solids. Vol II, McGraw-Hill:
New York

3P47
Crystal Structure Refinement of Silk Fibroin:Bombyx mori
Yasuhiro Takahashi, Department of Macromolecular Science, Faculty of
Science, Osaka University, Toyonaka, Osaka 560, JapanIn 1955, the crystal structure of silk fibroin was proposed by Marsh etal.l Their model was based on quantitative intensity estimation of six
equatorial reflections and qualitative intensity comparison of the layer linereflections. In the previous papers,2, 3 the crystal structure analysis ofsilk was reexamined based on 35 reflections newly collected by using thedrum scan densitometer. And it was clarified that the crystal region iscomposed of rather irregular stacking of the sheet structures formed byhydrogen bonds, in which the pleated-sheet molecules are arranged in the
different antiparallel manner (antipolar-) from the one proposed by
Marsh et a!. (polar-). Silk assumes the crystal structure in which two
antipolar-antiparallel sheets related by a two-fold rotation axis parallel tothe b-axis statistically occupy a crystal site with different probabilities.
The refinement was made by using theconstrained least-squares method,4where the bond lengths and bond·...:angles were fixed on the acceptedvalues, the same conformation was
assumed for the symmetricallyindependent molecules, and theanisotropic temperature factor exp{ -[(ha */2)2Bx + (kb */2)2By + (lc* /2)2Bz)} was adopted. The R-factor
reduced to 7.5 %. The crystal
structure is shown in Figure.
1. Marsh, R. E. et al. (1955).
Biochim. Biophys. Acta 16, 1.
2. Takahashi, Y. et al. (1991) . 1.
Polym. Sci. Polym. Phys. Ed. 29, 889.
3. Takahashi, Y. ACS Symposium
Series 544 "Silk Polymers", Chapter
15, 1993.
4 . Takahashi, Y. et al. (1973) . 1.
a =9 . 38A
Polym. Sci. Polym. Phys. Ed. II, 233.

3P48
Physicochemical investigations on natural spinel (MgA120 4 )C. P. Udawatte, Institute of Fundamental Studies, Kandy, Sri Lanka
R. P. Gunawardena, University of Peradeniya, Peradeniya, Sri Lanka
H. Annersten, University of Uppsala, Uppsala, Sweden
The spinel structure is described as a double oxide, AB 20 •. where A and B occupy
tetrahedral and octahedral sites respectively. Such an arrangement is known as the"ordered" cation distribution denoted by (A)[B 2]0.. The opposite extreme is the"disordered" arrangement (B)[AB)04 which is frequently found in natural spinels . Other
distributions between these two extremes are also possible.
The chemical analyses of natural spinels has been performed by using a Cameca
SX 50 automated electron microprobe. The lattice constants and the distribution of AI
among the octahedral and tetrahedral sites in the spinels were determined using a Phillips
PW 1710 X-ray powder diffractometer and a 27 Al-MAS-NMR spectrometer respectively .
Mossbauer spectroscopic technique was used to obtain further information on the natureof the site of iron in the natural spinels. The variation of the lattice constants withtemperature was studied by x-ray powder diffraction.
Spinels contain high amounts of FeO (0.6-3 .5 wt%) and ZnO (0.07-4.50 wt%)
besides the major consistents of Al 20 3 and MgO. Among the other transition metals ions,
iron is the predominant element and its concentration was found to be in the range 0.51.8% by weight. In most samples iron is found predominantly as Fe2+ in the tetrahedral
sites .
The spinels belonging to the cubic space group have cell parameters (a=b=c) in
the range 8.087-8.091

A. The observed decrease in the cell edge with increasing

temperature is in general agreement with the expected behavior of cell parameters withincreasing disorder in the spinel structure. The results also indicate that, complete orderingof natural spinels occurs at 280± 175•C. Disorder in the cation distribution as measured
by the fraction of AI in the tetrahedral site described by the inversion parameter, x,
increased with temperature from 0 to 0 . 13 at 10000C.
This study indicate that, the natural spinels have ordered cation distribution as
regard to All+ , Fe3+ , Fe 2 + and Cr• . Cation distribution also depends on the heat treatmentof the crystals.

3P49
STRUCTURAL STUDIES ON a- AND(TETRAMETHYLENE SUCCINATE)~FORMSOF POLY

K. Noguchi, Y. Igarashi, and K. Okuyama, Faculty of Technology, Tokyo
University of Agriculture and Technology, Koganei Tokyo 184, JapanY. Ichikawa, M. Imaizumi, andY. Moteki, Showa Denko K. K., Kawasaki
Plastics Laboratory, Chidori-cho, Kawasaki-ku Kawasaki 210, JapanT. Fujimaki, Showa High Polymer Co. Ltd., Kanda-Nishiki-cho, Chiyodaku Tokyo 101, Japan

Recently, much attention is being denoted to biodegradable polymers,
especially from the ecological viewpoint. It is well known that some ofsynthetic aliphatic polyesters, such as poly(tetramethylene succinate)(PTMS), poly(ethylene succinate) and their copolymers, show excellent
biodegradability. These are crystalline polymers. Physical properties ofcrystalline polymers, in general, depend strongly on their crystal structure.
The molecular conformation and crystal structure of PTMS (a-form) werefirst investigated by Chatani and coworkers (1971). Recently, we foundthat the new crystal modification of PTMS (13-form) was induced by strain(Y. Ichikawa et al. 1994). The solid-state crystal transition from the aform to the 13-form and vice versa was found to be reversible with respect
to the repeated application and removal of strain. In order to clarify the
crystal transition mechanisms of PTMS, their crystal structures have been
investigated by an X-ray diffraction method.
Diffraction patterns wererecorded using an Imaging Plate system (DIP-100S, Mac Science) withAll the 36 observed
graphite monochromatized CuKa radiation.
reflections of a-form could be indexed in terms of a monoclinic cell withcell dimensions of a::: 5.23(2), b = 9.12(3), c(fiber axis)= 10.90(5) A, and
13 = 123.9(2)". Two plausible structural models were obtained for a-form(model A, R = 0.14; model B, R = 0.20). Model A was essentially thesame as that proposed by Chatani and coworkers. Its chain conformation
is T 7 GTG. On the other hands, the observed fiber period of 13-form (11.90
A) indicates that the chain conformation is planar zigzag (all trans, T10).
The detailed structure analysis of 13-form is now in progress.
Chatani, Y., Hasegawa, R., & Tadokoro, H., (1971). A. Meet., Soc. Polym.
Sci. (Japan), page 420.
Ichikawa, Y., Suzuki, J., Washiyama, J., Moteki, Y., Noguchi, K. &Okuyama, K., (1994). Polymer 35, 3338-3339.

3P50
ON THE INTERPRETATION OF SMALL ANGLE SCATTERING DATAT M Sabine, W K Bertram and L P Aldridge
Advanced Materials Program, ANSTO, Menai, NSW 2234, Australia

The results of a small angle scattering experiment are usually presented as agraph ofl(q) versus q. This graph is then compared with calculations of thescattering profile to be expected from inhomogeneities of different shapes
and sizes to obtain infonnation about the micro-structure of the specimen.
The shape of the profile is determined by the square of the fonn factor of thescattering object which is designated F(q) and nonnalised so that F(O) equals
unity.

It is proposed that [F(q)] 2 is expanded in powers of the variable Xj which isdefined by the equation

Rj is a parameter with the dimensions of length specifying an average size or

correlation length in the scattering object. In the Guinier region, ( q ~ o ),J3 .
x 1 ~exp<-.!.(qR1Y)whileinthePorodregion, (q~oo),x ~ qR
61

1

It will be demonstrated that the first, second and fourth powers of Xj give
excellent approximations to the classical solutions for the rod, the disc andthe sphere respectively while non-integral powers provide the modem fractal
type solutions.
The use of this method for the interpretation of small angle neutron
scattering data from hydrating cement will be described.

3P52
Crystal Structures of the copper complexes toward thefunctional model compound of Dopamine ~-Hydroxylase
C. Li ; N. Kanehisa; Y. Kai; S. Itoh ; T. Kondo; M. Komatsu; Y. Ohshiro; S.
Fukuzumi, Department of Applied Chemistry, Faculty of Engineering ,Osaka University, Suita 565, JAPANDopamine P-hydroxylase catalyzes the ascorbate dependent
benzylic hydro_x lation of phenyethylamines such as dopamine to thecorresponding norepinephrine . However its functional models are veryrare up to now . In order to mimic the enzyme active center, we
synthesized [Cu(II)(py2phe)(Cl04)2) (py2phe =N, N-bis[2-(2-pyridyl)ethyl
2-phenylethylamine) in which a phenethylamine (substrate) moiety is incorporated into the ligand. After [Cu(Il)(py2phe)(Cl04)2) was treated withan equimolar amount of benzoin and triethylamine in CH2Ci2(Sml) at room
temperature, its product was found to be a dimer. The ligandhydroxylation occurred selectively at the benzylic position of the substratemoiety, which was confirmed by its x-ray crystal structure analysis.
Crystal structure analysis also found its crystal belongs to monoclinic
system, space group P2Jic, a=l6.176(2), b=l5.082(2), c=4l.608(2)A,
13=96.54(1) 0 , V=10084(l)A3, Z=8, Dc=l.Slgcm-3. Two molecules were
found in the asymmetric unit. Final R and Rw values were 0.070 and
0.069 , respectively. The dimer(ORTEP) has an approximate C2 symmetry,and both copper ions also have nearly square pyramidal structures . Detailsof its structure infom1ation and comparison with other enzyme structures
will be discussed in our report.

ORTEPI )Stewart, L. C. ; Klinman, J. P. Annu. Rev. Bioclzem. 1988, 57. 551
2)Thompson, J. S. 1. Am . Chem . Soc . 1984 , 106,8308
3)Amadei, E. eta/. J Clzem . Soc., Chem. Comnum. 1992, 1782
4)Itoh, Set a!. J. Am. Chem . Soc . 1995, 117, 4714

Author IndexAbe, H.
Abovian, E.S.
Abramov , Y. A.
Abramov , Y. A.
Abramov, Y. A.
Achiwa, N.
Ageta, H.
Aizawa, K.
Akilan , R.
Akimitsu, J .
Aldridge, L.P.
Amemiya, Y
Amemiya, Y
Anderson, B.F .
Ando, M.
Ando, Y.
Annersten, H.
Aoyama, H.
Aoyama, H.
Arai , Y.
Armstrong, N.
Asahi , K.
Asjoda, T .
Aswal , V.K.
Avilov , A.S .
Azumaya , l.
Baker, E.N.
Baker, E.N.
Baker, E.N .
Baker, H.
Baker, H.M.
Baker, H.M.
Banerjee, A.
Banerjee, S.
Bekenova, G.K.
Beketov, K.M.
Belokoneva, E .L.
Bennett, J .M.
Bera, A.
Berman, H. M.
Bertram, W .K.
Bewley, M.C.
Bezirganyan, A.P.
Bezirganyan, S.E.
Boonyaratavej, S.
Boukay, D. D.
Bourne, P. E.
Cambridge, A.P.
Campbell, S.J.
Carr , P.
Carvalho, C .M.
Chakomakos, B.
Chakrabarti, C .
Chan , J.-R.
Chang, S.-L.

1C26
1Al5
1A23
3All
3P38
I POl
2P33
1P04
2P37
3A12
3P50
2Cll
2Pl5
2Al2
lPLl
2P30
3P48
2AI1
3Pl5
3P33
1B14
3P05
2P03
1P23
1A23
2P43
2A12
2Al4
3P06
2AI4
2A12
3P06
2P05
2B23
1P25
3P21
1A23
2P49
2P05
1B22
3P50
2Al4
1P07
1P07
2P17
1B13
1B21
3P34
2C21
3P16
2B24
1P20
2P07
2C15
1Cl4

Chang, S.- L.
Chatake, T .
Cheah , E.
Chen, H.-Y.
Chen, H.C.
Chen , J .
Chen, W
Chen , X.
Chen, Y.- L.
Chen, Y.
Chiari , G .
Christy, A. G .
Cline, J .P.
Clowney, L.
Coppens, P.
Creagh, D.C.
Dann , J.N .
Dann, T .-E.
Dasannacharya, B.A .
Datta, A.
Datta, A.
Dattagupta, J .K.
Demartin, F.
Denu , J .M.
Desiraju, G. R.
Dey, I.
Dixon, J.E .
Do,M . N.
Docherty, R.
Dooley, D.M.
Dutta, S.K.
Dzan, N. V.
Dzuong, L.
Edwards , R. A.
Egikian , D.L.
Elcombe, M.M.
Esaki, N.
Etschmann , D.
Faber , H.R.
Faber , II . R.
Fan, 11 .-F.
Feil , D.
Feil , D.
Freeman , H.C .
Fujii, s.
Fujii, T .
Fujii , T .
Fujii, Y .
Fujimoto , z.
Fujinaga, M.
Fujita , H.
Fukuchi , S.
Fukuda , M.
Fukuda , M.
Fukuda , T .

2C 15
2Pl3
3P16
2P26
3Bll
1P54
2P21
3A21
3A22
2P13
IB 24
1C25
1B14
1B22
3PL3
1P09
1P52
2Cl5
2C26
2B23
2P47
2P07
1P02
3P19
2PL2
2P05
3Pl9
2P51
3P34
3A24
2P07
2P51
2P51
2P14
lPll
2C21
3P07
3P46
2A12
3P06
1PL2
1A23
3All
3A24
3Pl0
3P07
3Pl3
2B21
2PIO
3P18
2P08
1P42
3A23
3P51
1P29

Fukuhara , K.
Fukuzumi , S.
Fun, H.-K .
Fun, H.-K.
Fun , IL-K.
Fun , 11.-K.
Fun , H.-K .
Furuen , W .

Futterer, K.
Ganguly, R.
Gao, Q.
Gelbin , A.
Ghosh , S.
Gilbert , E.P.
Goh , L. Y.
Goyal , P.S.
Gramaccioli, C . M.
Green, A. J .
Grigorian , A.H.
Grigoryan, A. H.
Groom , C.R.
Grossie , D.
Gui , L.L.
Gunawardena, R.P.
Gureyev , T .E .
Guss , J .M.
Ha , C . T .
Haga , N.
Hagiya , K.
llagiya, K.
Hall , S.
Hall , S.
Haller, K. J .
llanaya, M.
Harada , J.
llaroutunyan , L.
Haroutyunyan , V.S.
Hasegawa , K.
Hashimoto, H.
llashizume , D.
Hashizume , D.
Hashizume, D.
Hashizume, D.
Hashizume, H.
Hashizume , II .
llashi zume, H.
ll ashizume , II .
Hashizume , H.
Hata, Y.
Hata , Y.
Hatan aka, II .
Hayashi , M.
Hayashi , M.
Helsen , J .
Hester, J .

3P12
3P52
2P29
2P31
2P37
3D26
3P27
3Pl4
1A21
IP21
1P54
IB22
2P05
1P24
2P21
1P23
1P02
2A23
IA15
2C13
3P06
1B13
3Pll
3P48
1Cll
3A24
2P51
1P35
IA12
1P35
1Bl3
1P50
2Pl7
1P49
3P31
2Cl2
2P46
3P09
2P35
2P41
2P42
3B21
3P22
1Cl1
2D24
2P47
2P48
2P49
3P07
3P13
2P08
IP17
3P12
1P55
1B13

Hester , J .
Hester, J . R .
Hibino, H.
Hihara, G.
Hirano, T.
Hirata, H.
Hirotsu, K.
Hisano, T .
Horiuchi, H.
Horiuchi, H.
Horiuchi, H.
Horiuchi, H.
Horiuchi, T .
Horng, 0 .-N .
Hoskins, B. F.
Hoskins, B. F.
Hosomi, K.
Howard, C.J.
Hsiao, C .D.
Hsieh, S. H.
Hsu, C.-H.
Hsu, R.
Hu , G.
Huang, 0 .-M .
Huang, T.C.
Hung, H.- H.
Hunter , K. A.
Hunter, K. A.
Hwang, T .-S.
Ibragimov, B.T .
Ichikawa, Y.
Igarashi, Y.
lhara, E.
lishi, K.
lkemoto, I.
lmaizumi , M.
lmaizumi, N.
lmura, N.
Inoue, A.
Inoue, A.
Inoue, M .
Inoue, T.
lnthapanya, P.
Ishida, K.
Ishida, K.
Ishida, K.
Ishida, K.
Ishida , T .
Ishida, T .
Ishii , Y.
Ishikawa, Y.
Ishizawa, N.
lshizawa , N.
lshizawa, N.
lshizawa, N.

IPSO
3Al2
IAI3
2P38
3BI2
3P36
3P20
3P07
1C23
IP29
1P45
3P41
IP38
2PI8
3B24
3P25
3P20
2C21
3Pl4
IB22
2CI5
3P42
3POI
2P26
1P52
2CI5
IB23
IP53
3P43
3P21
3P49
3P49
2P35
IP35
3P28
3P49
2Pl3
3P36
IP03
IP01
3PI2
3PI2
2P41
1Cl2
IP03
IP04
2C22
3P30
3P32
2C22
3P32
lAll
1A21
1Pl4
!PI S

lshizawa, N.
Ishizawa, N.
lshizawa, N.
Jshizawa, N.
Ishizawa, N.
Jshizawa, N.
Ishizawa, N.
Isobe , 1\1 .
Ito, S.
Ito, T .
ltoh , M.
ltoh, S.
Itoh K.,
Iwasaki, F.
Iwasaki, F.
Iwasaki, F.
Iwasaki, F.
Iwasaki, F.
Iwasaki, F.
Iwasaki, H.
Iwasaki , H.
Iwasaki, H.
Iwata , Y.
lwsaki , F.
lzui, K.
Izumi, F.
lzunome, K.
Jameson , G .B.
Jang , L.-Y .
Jang, S.
Jean , Y.-C.
Jiang , Q.Z.
Jones , W.
Kabir-Ud-Oin,
Kadono, S.
Kadowaki, K.
Kagamiyama, H.
Kagawa , Y.
Kagechika, H.
Kai, Y.
Kai, Y.
Kai , Y.
Kai, Y.
Kai , Y.
Kajitani , T .
Kalceff, W.
Kamiya , N.
Kanamaru , T .
Kanamaru , T .
Kaneda , H.
Kanehisa, N.
Kanehisa, N.
Kanehisa, N.
Kanehisa, N.
Kashino, S.

1PI6
IP17
IP18
IP48 •
IPS I
3P02
3P42
3P39
2P03
2P38
IPI8
3P52
IP05
2A25
2P22
3B25
3P26
3P29
3P30
1Pl2
IP13
IP47
2C25
3P32
3PI2
IP20
3BI3
2P14
2Cl5
IP26
2Cl5
3Bll
3P34
1P23
2P09
3Bl2
3P20
3P03
2P43
2P35
3D23
3Pl2
3P24
3P52
3P40
1Bl4
1Pl3
IP03
1P04
3PIO
2P35
3B23
3P24
3P52
2P39

Kataoka, M.
Kato, H.
Katoh , H.
Katoh, H.
Kawai , T .
Kawamura, I.

Kawanishi, S.
Kawano, N.

Kawauchi, Y.
Kawauchi, Y.
Kazumata, Y .
Kharisum ,Khasanova, N.R.
Kibushi , E.
Kikuchi, M.
Kim, U.
Kim , Y.
Kimbara, K.
Kimbara , K.
Kimia, J.
Kimura, S.
Kingsford-Adaboh, R .
Kingston, R.
Kino, N.
Kinoshita, T.
Kishimoto, S.
Kitagawa , R.
Kitahama , K.
Kitahara, H.
Kitazawa, K .

Kiyotani, T.
Klooster , W.T .
Kobayashi, H.
Kobayashi , T.
Kodama , N.
Koetzle, T .F.
Kogo, II .
Koike , N.
Koizumi, M.

Kojima, R.
Komatsu, H.
Komatsu , II.
Komatsu, M.
Komatsu, Y.
Kondo, T .
Konno, M.
Koura , T .
Krishnaiah , 1\1 .
Kubota, 1\1 .
Kumano , S.
Kumar, N.J .
Kumar , S.
Kumar, V.
Kumar Das, V.K.
Kumaradhas, P.

IP15
IP40
1P03
IP04
IP38
3P35
3Bl3
3P35
3P03
3P04
IP04
IP37
1P20
2P06
IP20
1P26
1P26
3A23
3P51
2P24
3Bl3
2P39
2AI4
IC23
2P08
ICI2
3Pl2
1P38
1P48
IC23
2P33
2C24
IP06
2P03
IP16
2C24
2P44
1P41
2Pl3
2B22
3P03
3P04
3P52
2PI3
3P52
2Pl2
2P44
2P36
3P09
2P48
2P36
1P23
3A24
2P20
2P27

Kumaradhas, P.
Kumazawa, S.
Kumazawa, S.
Kun, F.-H.
Kuno, A.
Kuo, C.-L.
Kuo, C.-L.
Kuo, C.-L.
Kurasawa, T .
Kuribayashi, M.
Kuribayashi, M.
Kurihara , T .
Kuroiwa, l.
Kusaka, K.
Kusakabe, l.
Kwon, J .
Lai , L.U.
Langouche, G .
Lee, C.-H .
Lee , G.-H.
Lee, G.-H.
Lee, 11.-Y.
Lee, J .-F.
Lee , J .-J .
Lee, J .S.
Lee , S.-T.
Lee , T.-J .
Lertpratchya, P.
Li , C.
Li, J .
Liaw, Y.-C.
Lii , K.-H .
Lii , K.- H.
Lin , C.-C.
Lin,J .-Y.
Lin , K.-J .
Lin , Z.
Lin , Z.J .
Lion , L.-S .
Liu, 11 .-C.
Liu, H.-C .
Liu , 11.-C.
Liu , L.-K.
Lobo, C.J.
Lu , T .-H.
Lu , X.L.
Luh , L.-S.
Luo, T .-T .
Machida , M.
Machida, M.
Maeda, S.
Maes, A.
Malabusarakam , W .
Manabe , N.
Manabe , N.

2P28
IC12
2C22
2P4 5
2PIO
2812
2P01
2P02
!Cl2
1P03
1P04
3P07
1P43
1P35
2Pl0
1P26
2Al3
IP55
2Cl5
IA24
3P44
2C!5
2Cl5
3P44
IP33
2P31
2P45
2Pl7
3P52
1C23
3A22
IP28
1P30
1A24
3A22
1P28
1P54
3Pll
2P23
2812
2POI
2P02
2A24
1P31
3A22
3Bll
2A24
2PI8
I PO!
2P40
2P!2
IP55
2A22
2A25
2P22

Marumo, F.
Marumo, F.
Maslen , E.N.
Maslen , E.N.
Maslen, E.N.
Masuda , K.
Matsui , Y.
Matsumoto, 0 .
Matsumoto, 0 .
Matsumoto , T .
Matsumura , N.
Matsushima , Y.
Matsuura , Y.
Matsuzaki , T .
Matsuzaki , T .
Matumo, F.

Mayo , S.C.
Mazumder , S.
McClune , W .F.
McGuirt , M.A.
McMahon , B.
1\-liki , K.
Misaki , H.
Mitsuda, H.
Mitsui , Y.
Mitsui , Y.
Mitsuki, T .
Miyahara , Illliyamae , H.
Miyamoto, M.
Mizuno , H.
Mizuta , M.
Mochida , T .
Mohamed-Ibrahim, M.J.
Morgan , W .T .
Mori, T .
Morii, Y.
Morii , Y.
Morimoto, S
Morita , K.
Moriyama, H.
Moriyama , II .
Moteki , Y.
lllueller , M.H.
Mukhopadhyay, B. P.
Mulaba-Bafubiandi , A.
Murakami , T .
Nagano, T .
Nagara , Y.
Nakagawa , A.
Nakagawa , A.
Nakajima , R.
Nakajima . Y.
Nakamura, N.
Nakanishi , H.

IP14
!PIS
IA14
3P42
3P46
2P33
3P39
2Pl3
3P08
1P08
2A25
1P17
3P09
2P04
2PL1
3P02
1C21
1P22
IP52
3A24
lBll
IP13
2822
3P30
3A23
3P51
IC23
3P20
2P38
IA12
2P10
IP40
IP43
2P29
3P06
IC12
2C22
3P40
1P36
1Pl6
2P09
3Pt3
3P49
IP52
2P05
1P55
3P08
1CI2
3Pl2
3P04
3Pl8
3PI5
2All
2P25
3PI2

Nakanish i, 11·1.
Nakano, M.
Nakatsuka , A.
Narita , H.
Narita , H.
Nashiyama , II .
Nemoto, T ..
Nguyen, V. T .
Nguyen, V. T .
Nickogosian, S.K.
Nikolaenko, A.M.
Nikulin , A.Y.
Nirmala , K.A.
Nirmala , K.A
Nishihira , J .
Nishimoto, S.
Nishiura, S.
Nitanai, Y.
Nittono, 0 .
Noda, Y.
Noda , Y.
Noda , Y.
Noda, Y.
Nodono , M.
Nogami , T .
Nogami , T .
Noguchi, K.
Noguchi , K.
Noguchi, K.
Noguchi, K.
Noguchi, S.
Nosoh , Y.
Nureki, 0 .
O'Connor, B.H .
Ogawa , K
Oguni , 111 .
Ohachi, T .
Ohahima, E.
Ohashi , Y.
Ohashi , Y.
Ohashi , Y.
Ohashi, Y.
Ohashi, Y.
Ohashi , Y.
Ohashi , Y.
Ohashi , Y.
Ohashi , Y.
Ohashi, Y.
Ohashi , Y.
Ohashi , Y.
Ohgo, Y.
Ohgo, Y.
Ohgo, Y.
Ohkawa , M.
Ohkawa , T .

2P49
2P49
1P32
3A23
3P51
2P22
1P49
2Pll
2P19
lPlO
2P48
lCll
2P27
2P28
3Pl8
2P40
3PI2
2P04
2P52
1P42
IP43
IP44
IP48
2P35
3P30
3P32
3822
3P23
3P35
3P49
2P04
3P08
2Pl2
3PL1
3P31
IP49
3P05
IP20
IP41
IP49
2A21
2C t4
2C24
2P42
2P44
3821
3P22
3P33
3P36
3P37
2C24
2P41
3P33
1P27
2P47

Ohkohchi, M.
Ohmasa, M.
Ohmasa, M.
Ohmasa, M.
Ohmuro, Y .
Ohnuki, Y.
Ohsato, H.
Ohshima, K.
Ohshima, K.
Ohshiro, Y .
Ohsumi, K.
Ohsumi, K.
Ohsumi , K.
Ohsumi, K.
Ohta, A.
Ohtaka, 0 .
Ohtsuka, E.
Ohtsuka, R.
Okabe, N.
Okada, K.
Okamoto, I.
Okamura, F .P.
Okamura, F .P.
Okuda, T .
Okuyama, K.
Okuyama, K.
Okuyama, K.
Okuyama, K.
Ollis, D
Ono, Y.
Oozeki, M.
Orii , D.
Oshima, T .
Oshima, T .
Othman, A. H.
Oyanagi , H.
Pakawatchai, C .
Pakawatchai, C.
Pal, A.
Parameswari , M.

Pedireddi , V.R.
Peng, S.-M.
Petson, A.
Phaopongthai, J .
Pilati,T.
Podder, A.
Prost, R.
Rae, A.D .
Rajagopal, H.
Rajagopal, H.
Rajagopal, H.
Ramakrishnan , B.
Ramasamy, P.
Ramirez-Castellanos, J .
Reddy, B.S.

2P30
IA12
IP35
2811
3P05
IA22
1P40
1C22
IC26
3P52
1Al2
IA13
IP15
2Bll
2PI3
1C24
2Pl3
3Pl2
3P35
3P20
2P43
1A23
3Al2
1P40
3B22
3P23
3P35
3P49
3Pl6
1P39
3Pl3
1P06
2P09
3Pl3
2P24
1Pl7
2A22
2P32
2P05
2P31
3P34
1A24
2Pl7
2Pl7
1P02
2P07
1P55
1P37
1P21
2C23
2C26
3A21
2C26
3P39
2P36

Reddy, C .D.
Reynolds, P.A .
Reznik , I.M .
Robert , A.C .
Robinson, I.K .
Robson , R.
Robson, R.
Roengsumran , S.
Rose, J .
Rushdi, K.
Sabine, T.l\1 .
Saha, D.K.
Saha, D.K.
Sahakian, A.A.
Saito, K.
Saitoh , 1\f .
Sakata, M.
Sakata, 0 .
Sakata, 0 .
Sakata, 0 .
Sakurai, M.
Sanyal, M.K.
Sanyal , M.K.
Saper, M.A.
Sasaki, C.
Sasaki, H.
Sasaki, K.
Sasaki, S.
Sasaki, S.
Sastry, P.U .M.
Sato, II .
Sato, T .
Sato, T .
Satow , Y .
Sawada, A.
Sawada, K.
Sazaki , G .
Sazaki , G .
Schmid , S.
Schmid , S.
Seal. A.
Self, I< .
Sekiguchi, T .
Sekine, A.
Sen , U.
SenGupta, S.
SenGupta, S.P.
Senda, T .
Senda , T .
Sequeira , A.
Sequeira, A.
Sequeira, A
Sequeira, A
Sergey, I.
Sharma, R.

2P36
IP24
3P38
1P5l!
2B24
3B24
3P25
2Pl7
3PI4
1A23
3P50
IC22
3P45
IPIO
3P28
2P42
2C22
2P47
2P48
2P49
2P09
2023
2P47
3Pl9
2P04
3Bl3
2P39
1CI2
1Pl9
2C26
3P33
3P03
3P04
2P04
2C25
3P36
3P03
3P04
1A21
1P31
2P05
1P26
3P08
3P37
2P07
3Bl4
3814
3A23
3P51
IP21
IP22
2C23
2C26
1P46
2C23

Shawkaraly, 0 . B.
Shawkataly, 0 . B.
Sheu , H.-S .
Sheu, H.-S.
Sheu, J .-H.
Shida, 1\1.
Shieh, M.-H.
Shimamoto, S.
Shimomura, 0 .
Shimura, T.
Shingh, M.
Shinohara, S.
Shinzawa-Itoh, K.
Shinzawa-ltoh, K.
Shiono, M.
Shirai , T .
Shirai, T .
Shishido, T .
Shivakumar, K.
Shivakumar, K.
Shobu, T .
Shudo, K.
Simpson, J .
Simpson, J .
Sinha, N.K .
Sivakumar, K.
Sivakumar, K.
Sivakumar, K.
Skelton, B.W .
Skelton, B.W.
Slizys, D. A.
Slizys, D. A.
Slusarev, A.P.
Smith, A.
Smith, G.
Soda, K.
Sohn , J .-11 .
Sridhar, M.A.
Stevenson , A.W.
Stevenson, A.W .
Stranger, R.
Streltsov , V. A.
Streltsov, V .A.
Subramanian, K.
Suda, I' .
Suda, K.
Suda, I< .
Suda, K.
Suffolk . P.,
Sugawara, T .
Sugimoto, H.
Sugimoto, K.
Sugimoto, K.
Sugimoto, S.
Sugiura, I.

2P29
2P31
1P34
2Cl5
2P45
1P20
2Pl8
2A25
IC24
2822
2P07
1P47
2All
3Pl5
1Cl3
2P03
2P06
1P29
3B26
3P27
1P44
2P43
1823
1P53
2P05
2P29
2P31
2P37
2A22
2P32
3824
3P25
2813
3P06
3Pl7
3P07
I PIS
-2P27
lCll
2B24
IP31
1A14
3P42
2P37
1Pl5
IP16
IP17
I PIS
3P16
1P43
3Pl8
3A23
3P51
3Pl2
2Pl2

Sundaralingam , M.
Sung, P.-J.
Sussman, J . L.
Suzuki, A.
Suzuki, A.
Suzuki, H.
Suzuki, H.
Suzuki, M.
Suzuki, Y.
Suzuki, Y.
Swaminathan, S.
Syono, Y.
Tabira, Y.
Tachikawa, 0 .
Tada, T.
Taguchi, K.
Taguchi, K.
Taguchi, K.
Tahirov, T . H.
Takada, K.
Takada, K.
Takahashi, Y.
Takama, T .
Takano, K.
Takata, M.
Takayama, T.
Takayama-M. , E.
Takemoto, K.
Takenaka, A.
Takenaka, A.
Takeno, S.
Takeya , H.
Talipov, S.A.
Tamura, I.
Tamura, I.
Tanabe, K.
Tanaka , I.
Tanaka, K
Tanaka, K.
Tanaka, K.
Tanaka, M.
Tanaka, M.
Tanaka, M.
Tanaka, M.
Tanaka, N.
Tanaka , N.
Tanaka, N.
Tanemura, M.
Tang, 1\1 .-T .
Tang, Y.-Q.
Taniguchi, I.
Taraya, H.
Taylor , M. R.
Taylor, W .C .
Terashima, K.

3A21
2P45
1Bl2
2?03
2P06
3B23
3P24
3Pl8
3?12
3P35
3?14
IP20
3P02
3P41
2?08
3B25
3P26
3P29
3A22
3P29
3P30
3P47
lPOS
3PIO
2C22
2P25
3P39
2P52
2Pl3
3P08
IP27
3Bl2
3P21
1P42
1P43
1Pl8
3Pl8
1A22
3B23
3P24
1Pl9
1P29
1P36
1P45
IPI3
2P09
3P13
IPOS
2C15
2P26
3P05
2Bl1
1P37
2A22
3Bl3

Thai , D. P.
Thang, N. V.
Thang, T . Q.
Thompson, J . G.
Thompson, J .G.
Thongkon, N.
Tiwari, R.K.
Toda, F.
Toda, F.
Togano , K.
Togawa , A.
Tomimitu, II .
Tomimoto, K.
Tomizaki, T.
Tomizaki, T.
Tomoda, S.
Toraya, H.
Toyoda, T .
Trouni , K.G .
Trouni , K.G .
Trouni , K.G .
Tsang, K.- L.
Tsirelson , V.G .
Tsirelson, V.G.
Tsirelson, V.G.
Tsuchiya, D.
Tsuda , N.
Tsuji, E.
Tsukihara, T.
Tsukihara, T .
Tsukihara, T .
Tsukihara, T .
Tsunoda, M
Udawatte, C.P.
Uehori , S.
Ueki, M.
Ueki, T .
Uekusa, H.
Uekusa , H.
Uekusa, II .
Uekusa , II.
Ueng, C .-H .
Uesu , Y.
Ugaji, Y.
Ugliengo, P.
Umeno , M.
Uragami , T .
Yaalsta , T .P.
Verma , A . K.
Viterbo, D.
Vongbupnimit, K.
Yongbupnimit, K.
Vung , P. T .
Vung , P. T.
Wada , M.

2? 11
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2P50
IA21
1P31
2?17
2?16
3B23
3P24
3B I 2
3B I3
1?04
3A12
2All
3Pl5
3P31
1Al3
1Pl9
IAI5
2CI2
2Cl3
2Cl5
IA23
3AII
3P38
3P08
IP47
1C12
2All
3P03
3P04
3P15
2P13
3P48
3P35
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1P13
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2A21
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2P12
2Pl8
1P41
2PI2
IB24
2B22
lPOG
1P51
2P16
1D24
3D22
3P23
2P ll
2Pl9
2C25

Wakagi, T.
Wallace, P.L.
Wang , A.
Wang , B.-C .
Wang, C.- M.
Wang , C.P.
Wang , J .cC.
Wang, J .P.
Wang , M.
Wang , X.Q .
Wang , Y.
Wang , Y.
Wang, Y.
Wang, Y.
Wang, Y .
Watanabe , T .
Watanabe, T .
Wattanakanjana, Y.
Welberry, T.R .
Weng, N. S.
Westbrook, J.
White , A. H.
White, A.ll .
White, E.
White, J . M.
White , J .W.
Wilkins, S.W .
Williams, I. D.
Wiriyachitra, P.
Withers, R. L.
Withers, R.L.
Wong, R.C.S.
Wong, W .. T .
Wong, W .-Y .
Xu, R.
Yagi, T .
Yakhmi , J .V.
Yamada, T .
Yamaga, M.
Yamagashira , M.
Yamagata, Y.
Yamaguchi, II .
Yamaguchi , H.
Yamaguchi, H.
Yamaguchi, K.
Yamaguchi, Y.
Yamaguchi, Y .
Yamamoto, A .

Yamamoto, H.
Yamanaka, T .

Yamanaka , T.
Yamanaka, T .
Yamanaka , T .
Yamane , T .
Yamane , T .

3?13
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1?33
2P23
2Cl5
2?30
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3?43
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2P22
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2P32
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2P24
2P32
2P24
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3P09
3?15
2P43
2P47
2P49
3P40
3P30
IC24
IP32
1P36
2Dl4
2P03
2P06

Yamashita, E.
Yamashita, E.
Yamashita, E.
Yamauchi, Y.
Yang, E.-C.
Yang, J .
Yang, Q .-C.
Yaono, R.
Yasuda, H
Yasuda, T .
Yasui , M.
Yasui , M.
Yasui, M.
Yasui , M.
Yasui, M.
Yasui, M.
Yasui, M.
Yazawa, I.
Yeritsian, G.N .
Yip , B.-C.
Yip , B.-C.
Yokota, 0 .
Yokoyama, S.
Yoshiasa , A.
Yoshiasa, A.
Yoshida, K.
Yoshida, K.
Yoshida, S.
Yoshika, Y.
Yoshikawa, A.
Yoshikawa, H.
Yoshikawa, S.
Yoshikawa, S.
Yoshimiya, T .
Yoshimura, Y.
You , Y.-S.
Yu , S.C.
Yutani, K.
Yuvaniyama , J .
Zavodnik , V .E.
Zhang, X.F.
Zhang, Z.
Zhao, X.
Zhou , Y.C.
Zhurov, V.
Zou , Z ..
Zubak , V.M.

2All
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3Pl5
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2P26
3Pl5
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1P47
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86 Kcal/h

THROUGH

100, 000 Kcal/h

Our Highly Efficient compact System
Cooling Crystal Monocrometor

Model TCW-2000CP
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Power Requ iremen ts

II3¢ 200 v 50/ 60Hz 6KVA
Pumps.

40L/ min at 0.4Mpa(10.56gpm at 56.89 psi)

Dimensions

60W X 850 X l60H em

Cooling X-Ray Spectrometers
T ypesCooling
Capacity

Air-Coo led

Water-Cooled Kca i/ Hr

TCA-2000C-AW

TCW-2000C

2.000

TCA·4000C-AW

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San- Ei Giken Co., Ltd.
4-7-6 Iizuka Kawaguti City,
Saitama 332 Japan

Water Flow
Temp.

Press

("C)

(kg/em' I

X - Ray
Equip.
l\1ax Power

2kw
l G-25
± l'C

4k w

1.5-3
12k w
18 kw

Phone 048-258-0010
FAX 048-258-0911

The JEM-2010, a 200 KV ultrahigh resolution analytical electron
microscope applies existing technologies to combine our best
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instruments. The result is a microscope, the JEM-2010, whichsurpasses the capabilities of any previous system .

JEM-201 0
Ultrahigh Resolution Analytical

Electron Microscope• UltraDuo condenser objective lens (UD 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
coefficientUHR

0 .194nm

0 .5mm1.1mm

HT

0 .25nm

1.4mm

I

1.8mm

Optional functions includeddEDL
tpjil?lllf·M@i,'301mmntiti,l;IJ

1-2 Musashino 3-chome Akishima Tokyo 196 Japan
Telephone: (0425) 43-1111 Telex: 0-2842-135 Facsimile: (0425) 46-3353

rill ~NIUS~INSTRUMENT'S

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