Eur. J. Mineral.
1992,4, 1275-1283

Weinebeneite, СаВез(РО4)2(ОН)2 · 4Н20,
а new mineral species:
mineral data and crystal structure.

FRANZ W AL TER

Institut fiir Mineralogie-Кristal1ographie und Petrologie der Karl-Franzens-Universitiit Graz,
Universitiitsplatz 2, А-8010 Graz, Austria

Abstract: Weinebeneite is а new rnineral species from а spodumene pegmatite at Weinebene that occurs in the
blgh-grade metamorpblc rocks of Koralpe, CarintЫa, Austria. It occurs in small fractures as а secondary minera1
associated with fairfieldite, roscherite and uralolite. It forms clear, colorless, vitreous, platy crystals ир to 0.1 х
0.3 х 0.5 mm surrounding rosettes of xenomorpblc weinebeneite ир to 20 mm in diaтeter. It is brittle with а
splintery fracture. Mohs' hardness is 3 - 4; dтeas.= 2.15(4) g/стЗ and dca/c.=2.17 g/стЗ. Optically, weinebeneite
is biaxial positive but nearly uniaxial with 2Vymeas. < 10° ; Па = 1.520, n~ = 1.520, ТIY= 1.530 (589 mn); Z : е= 42° in acute angle ~. Weinebeneite is monoclinic, а = 11.897(2), Ь = 9.707(1), е = 9.633(1) А, Ь = 95.76(1)°,V = Ш~.8(3) АЗ and Z = 4. ТЪе three strongest lines of the X-ray powder diffraction pattern are [d (А), (hkl), 1] :2.513, (223), 100 ; 3.421, (221), 70 ; 5.92, (200), 60. ТЪе combined results of electron-microprobe, atomic
absorption, electron energy-Ioss-spectroscopy analyses and structure refmement yield the formula СаО.99ВеЗ.02Р1.97
07.88(ОН)2.11.4Н20( based оп О = 14) or, ideally, СаВез(РО4)2(ОН)2.4lliО. ТЪе пате refers to the type locality.
ТЪе crystal structure of weinebeneite has been solved Ьу direct methods and refmed in space group Се to R =0.043 and Rw = 0.044 using 1341 independent reflections. Weinebeneite is а framework beryllophosphate with
ca1cium and water molecules in the cavities of the structure. ТЪе beryl1ium- and phosphorus- tetrahedra sharecorners forrning а layer consisting of 4- and 8-rings. Two superirnposed 4.82 2О nets oriented parallel to (100)and related Ьу translation in Ь/2 are connected Ьу additional beryllium tetrahedra, giving rise to а fraтework withan unusual arrangement: five tetrahedra in two three-membered rings share а tetrahedron. Weinebeneite is the firstreported exaтple of а fraтework beryllophosphate containing three-membered rings. Ca1cium is located in channels parallel to [001], coordinated Ьу three О atoms of the fraтework and four water molecules. One of the watermolecules displays apparent positional disorder over two sites.

Key-words: weinebeneite, beryllophosphate, crystallography, crystal structure, fraтework.

Introduction
Weinebeneite was flfSt found in а pegmatite
vein from the spodumene deposit located in the
Carinthian area of the Koralpe, Austria. The
Koralpe is part of the Austroalpine crysta11ine
basement and is predominantly composed of теdium- to high-grade metamorphic rocks. GOd(1989) summarized the exploration results for а
lithium deposit that is the largest in Europe andshowed that there are two different pegmatite
types. Both types bear spodumene and occur as
unzoned, dike-like bodies strictly concordant
with the foliation of their host rocks. А coarsegrained type is hosted Ьу amphibolites andeclogitic amphibolites, while the second type of@0935-1221/92/0004-1275
1992 Е. Schweizerbart'sche

Verlagsbuchhand1ung.

D-7000$ 2.25
Stuttgart1Р. Walter

1276

pegmatite is hosted Ьу kyanite-bearing micaschists and has а fine-grained gneissic texture,caused Ьу an extensive metamorphic overprint(G6d, 1989). The amphibolite-hosted pegmatites
have а contact zone ир to 0.5 т wide characterized Ьу biotitization of amphibolites and Ьу
the occurrence of holmquistite. The crystallographic data and the description of the refined
crystal structure of this holmquistite were reported Ьу Walter & Walitzi (1985) and Walter etal. (1989). Petrographic and crystal chemical investigations of spodumene of the Weinebenepegmatites and other much sтаПеr spodumenebearing pegmatites in the Austroalpine basementof Styria and Carinthia were described Ьу КоПеr
et al. (1983), Heritsch (1984), Moser et al.
(1987), G6d (1989) and Wenger & Armbruster(1990).
In addition to the common pegmatite mineralsof the Weinebene deposit, numerous primary andsecondary accessory minerals have been described (Niedermayr et al., 1986, 1987, 1988,
1989,1990; Сету' et al., 1989; G6d, 1989). The
fme-grained pegmatites, еsресiаПу, show тапуnarrow fractures filled with the rare secondary
phosphates fairfieldite, roscherite and uralolite, but
a1soprovided samples of а mineral which could notЬе identified, and that subsequently was shownto Ье the new mineral weinebeneite.
The new mineral weinebeneite is named forthe type locality. Both the new mineral and theпате have been approved Ьу the Commission оп
New Minerals and Mineral Names, IMA. Туреspecimens of weinebeneite are deposited in theLandesmuseum J oanneum, Graz/Styria; theK1imtner Landesmuseum, Кlagenfurt/Carinthia;
and the Naturhistorisches Museum, Vienna.

Physical and chemical properties
Crystals of weinebeneite are transparent totranslucent, colorless, with vitreous luster, white
streak and Mohs' hardness 3 - 4 .The mineral isbrittle and shows an irregular, splintery fracture;по cleavage was observed. It does not fluorescein ultraviolet radiation. Density is 2.15(4) g/cm3,
measured Ьу pycnometer, compared to the calculated value of 2.17 g/cm3. Most observed crystalsof weinebeneite have the same simple morphology: platy оп {001} and elongated раrаПеlto [100] with crystal sizes ир to 0.1 х 0.3 х 0.5
mm ; dominant forms (point group т) are {ОО1},{ооГ}, {1l0}, {Гl0} and {010}; rare forms are{100}, {100}, {11l}, {Гll}, {1l3} and {Г13};(Fig. 1). The stereographic projection is shown in
Walter et al. (1990). No twinning was found. The
а:Ь:с ratio calculated from measurements with an
optical two-circle reflection goniometer is 1227 :1 : 0.994 compared with the ratio calculated fromunit сеП parameters of 1.2256 : 1 : 0.9924.
Optically, weinebeneite is biaxial positive,
non-pleochroic, with а very small 2 Vymeas.
< 100, and indices of refraction (л = 589 nm) па= 1.520, пr>= 1.520, ny = 1.530 (аП +/- 0.001).
The orientation is Z : с = 420 in acute angle ~.
Ропr crystals were measured оп а spindle-stage
using the л - t - variation method.

Occurrence and paragenesis
Weinebeneite is found about 2 km west of theWeinebene

Pass, Koralpe,

Carinthia/ Austria,

atthe dump of the exploration adit ( 1:50.000 тар,Osterreichische Karte 188 Wolfsberg, 140 59'
29" Е, 460 50' 11" N) , 1575 т аЬоуе sea level.
Weinebeneite occurs in narrow fractures of thefine-grained pegmatites and is associated with
uralolite, roscherite and fairfieldite. Weinebeneite occurs as platy colorless crystals ир to
0.5 mm in length, surrounding rosettes of xenomorphic weinebeneite ир to 20 mm in diameter.
Paragenesis and morphological data of weinebeneite are described in Walter et al. (1990).

Fig. 1. SEM photograph of weinebeneite from Weinebene. Crystal platy оп {001}, elongated paral1el to[lOO], showing the dominant forms {OOlk {110},{НО} and {010}; the rare forms {100} and {Нl} arerepresented Ьу very small faces; scale bar : 40 11т.

Milleral data and structure of weinebeneiteТаЫе 1. Chemica! data for weinebeneite from WeineЬеnе.
1

2

3

4

3.02

20.66

ВеО

21.1

СаО

15.5

15.1 -15.9

0.99

15.44

P20s

39.2

38.1 - 40.3

1.97

39.09

Н2О

25.5

10.11

24.81

L

101.3

СаоЭ9Вез.Q2Р

100.003. cations based оп О 14==
4. theoretical wt.% far the ideal forтulaСа Вез (РО4)2 (ОН)2 . 4Н2О

Тhe chemical analysis was сапiеd out with an
ARL-SEMQ
electron microprobe using а
wavelength dispersive system and the data reduction method of Вепсе & А1Ьее (1968). Operating
conditions were 15 kV accelerating voltage and20 пА sample current, measured оп brass.
Apatite was used as а standard. Except for Саand Р, по detectable amounts of elements withan atomic number greater than 8 were found. One
analysis Ьу electron energy-loss-spectroscopyТаЫе 2. Powder diffraction pattem of weinebeneite(diffractometer, СиКа - radiation, intema! standard
quartz).
h k I

dobs

dca1c

Iobs Ica1c

h k I

dobs

dca1c

1 1 О

7.49

7.51

13

17

2.39472.3961

14

6

111

6.10

12

20

2.38392.3840

2 ОО
111

5.92

6.10
5.92

ОО4
33 1

60 100223

2.35952.3597

5
16

3
11

5.74

5.73

42

62

114

2.32612.3260

7

5

О2 О

4.85
4.79

4.85

44

32

3 1 3

11

32
49

31

5 1 1

2.30152.28672.30174.79
4.33

2.2876

5

4
2

50

24О}

4.16

35 34

114

2.2417

15 {;

25 {

~.24 124 1

2.20422.204813

52.16662.16788

4

4.33

1"1 2 4.16~12} 3.92

2 О2

{393)
3.92

2.2433 {Iobs Icalc

2.2453}

3 1 О

3.66

3.66

8

7

422

2.1615

2.159913

3.2 2 1

3.57

3.57

15

11

2.14822.1486

6

2

2 О2

3.554

3554

10

11

024
:j 1 42.09622.095342:3 1 1

3.526
3.421

7

2.0699

70

7
56

423

1

3.524
3.421

242

2.06422.07002.0636

8
14

5
8

3 1 1

3.313

3.314

9

6 ОО

1.97311.972813

8

13 О:j 1 2

3.123

3.121

10

8
4

4 о4

1.96081.9609

12

5

3.046

3.046

31

27

043

1.9323

1.9325

4

3

11 3

3.00В

3.009

18

3 1 4

1.9243

1.92365

6

1" 3 1
4 ОО

2.991

29
60

333

1.91151.9116

15

6

2.959

2.991
2.959

13
17
33

13 1

2.945

2.945

45

30

53

1 1 3

2.874

2.874

34

24

:14 3

1.87131.8708

15

10

3 12

2.78402.7841

36

29

620

1.82781.827663

4 о 2:j 1 32.63882.63906

32.52452.5246

4

3

442}
5 1 3

:12 3

2.51302.5129

100

58

025

.7863)
1.7860{' 1.7858
1.7831 1.7829

330
j
3 1
040

2.50142.50202.4594108622.45982.4265

24
18

19
13

350

22

2.4267~23} 1.9039 с.9О4О}

044

1

1

(EELS) detected а significant amount of berylНит, subsequently quantified Ьу AAS analysis
with ВеО as standard. Н20 was dеtепninеd Ьу
10ss оп ignition. Тhe results of the chemical anаlyses are listed in ТаЫе 1 and yield the empiricalfопnulа, based оп О = 14 :1.90351.9707.88(ОН)2.11.4Н20

which тау Ье written in simplified fопn asСаВеЗ(РО4)2(ОН)2.4Н20,Z = 4.
Ca1culations using the Gladstone - Dale relationship with the constants of Mandarino (1981) indicate superior compatibility (Mandarino, 1979):
1-(Кр!Кс) = -0.012.

1. теап апаlуtiсаl results
weinebeneite wt.°j,'аг
2. electron microprobe ranges

ОО2
02 1

1277

33 {

13
14

4

Single-crystal rotation and Weissenberg photographs showed weinebeneite to Ье monoclinic
and the systematic absences indicate С2/е and Сеas possible space groups. Unit-cel1 dimensions(ТаЫе 3) were obtained Ьу least-squares fittingof data for 33 ref1ections (internal standard:quartz) obtained using а Siemens D-5000 X-ray
powder diffractometer with СиКа radiation. Тhe
X-ray powder pattern of weinebeneite is reportedin ТаЫе 2. Further work was done with а STOE
four-circle diffractometer and graphite-monochromatized МоКа radiation (л = 0.71069 А).
Intensity data were obtained at room temperaturefrom one single crystal; experimental detai1s arepresented in ТаЫе 3. Data reduction includingсопесtiопs for background and Lorentz-polarization was done. An absorption сопесtiоп was notapplied because of the smal1 crystal dimensions
and the 10w linear absorption coefficient. Scattering functions with anomalous dispersion tепnsТаЫе З. Experimenta!

details and unit сеВ parameters.

unit сеJl parameters{~71.76534

31.74191.70541.74191.70504

2
1011.897(2) А
9.707(1) АЬ
9.633(1) Ае=Р ~ 95.76(1)'V ~ 1106.8(3) АЗСе
4
2.17 gсm-З
0.08 х 0.13 х 0.24 тт
9.08 ст-1
30<28<700-19-.s;hs19,
0.s;ks15,
O.s; Is 15
ro-scan, дro 1.250
=
а

~

~

space groupZ
calculated
density
crystal size).1МоКо:data collection

limjts23

1.766113

Structure determination

scan modeпumЬег/fгеquепсу ofstапdагd refJectionsuпiquе reflections
reflections > 5a(F о)
refined parametersRRw
1/[a(Fo)]2
w=

3/100
2504
1341
158
0.043
0.044

1278
Table 4. Atomic

Р. Walter
coordinates,

equiva!ent

Atom

х

Р1
Р2
Веl
Ве2
Ве3
Са
01

0.2785(1)-0.2780(1)-0.3006(8)-0.1925(8)0.0014(9)0.1124(2)-0.0939(4)0.2150(4)0.2388(4)0.2431 (4)

02
03
04
0.2853(5)05
0.2573(4)06
0.0943(4)07
0.2597(4)08
09(ОН)
0.0638(4)010(ОН} -0.0622(4)WI
W2
W3
W4(1)'
W4(2)2-0.5254(5)0.4918(5)0.4905(5)0_2250(9)0.1950(11)у
0.0985(2)0.0992(2)0.8817(9)0.3821 (9)0.5184(7)0.0853(2)0.6163(5)0.7795(5)0.9725(5)0.9230(6)0.7213(6)0.5836(6)0.6210(6}0.4676(5}0.4212(6)0.4263(6)0.6453(6)0.3807(6)0.3629(7)0.7474(15)0.7323(16)isotropic

z0.1409(2)0.3606(2}0.1613(10}0.3460(1 О}
0.2517(12)0.3718(2)0.1650(5}0.6971 (6)0.2213(5}0.4847(5)0.3029(6}0.5177(5)0.3323(6)0.2905(6)0_1442(6)0.3603(6)0.1881(6)0.3780(7)0.0437(7)0.0035(15)0.0061(17)(Веч) and anisotropicВео0.54(3)0.71(3}0.65(17)0.78(17)0.66(10)1.32(2)0.87(10)0.97(10)0.71(9)0.89(9)1.02(10)0.91(9)1.25(11)0.99(11 )1.08(9)1.04(9)1.85(11)
2.20(13)
2.09(13)
2.19(32)
1.74(30)

U11
71(6)
81(6)
83(31)
136(35)59(21)
144(5)
103(21)135(22)107(21)123(19)163(24)144(19)49(20}
84(19}
116(19)84(20)
234(25}278(33}265(32}277(76}221 (72)

U22

therma! parameters

UЗЗ

57(8)
76(7)
94(9)
95(7)
91(45) 73(35)36(42} 125(41)120(28) 72(25)191(7) 160(6)109(27) 117(23)68(23} 166(26)79(23} 83(21)114(23) 100(20)96(24) 128(24)167(24) 35(18)178(31) 249(29)123(27) 169(27)143(26) 150(24)182(26) 129(22)

U,2

U,з

17(7)
9(7)

15(6)
14(5)

-8(27)-7(27)-19(40)41(6)-24(29)89(32)
2(19)

12(17)-21 (20)-24(18}43(20)
11(18)
25(17)
71(20)
5(16)
11(19)-29(17)55(20)-29(21}-6(23)
19(17)-4(18)
10(23)-5(21)

49(4)-35(19)29(18)
38(19)(Uij) of weinebeneite.

U23
1(7)
-6(8)
-73(31)-22(31}9(46)19(6)
44(18)-6(21)
43(18)
27(22)
10(21)-9(23)-82(22)-41(21)-35(25)51(25)

Siie occupanciesare 1.0, only 1W4(1}occupancy 0.55 and 2W4(2) occupancy0.45.Theslarredalomsare refinedisotropically.
==anisotropictemperalurelactorsare inthe 'ОrлleXP[-2n2(h2а.2U11+...+2kIЬ'С.U2з)J;
Uijare multipJied
Ьу 104
Beq 8/Зл;2(U11+U22+UЗЗ):=for neutral atoms were taken from the International Tables for X-ray Crystallography, vol.
IV (1974).
The crystal structure was solved Ьу direct
methods in space group Се, using the SHELXS86 system (Sheldrick, 1986). А flfst Е-тар gave
reliable Р-О and Т-0- Т distances, which correspond to the features of the tetrahedral framework. Fourier syntheses were used to locate otheratoms in the tetrahedral framework and showed
additional peaks for the extraframework positions.The values of IE2-11 are intermediate tothose of centrosymmetric and non-centrosymmetric structures. Тhe subsequent structure refmement, using the program SHELX-76 (Sheldrick, 1976), was carried out twice, flfSt using
space group С2/е and then space group Се.
In space group С2/е, the extraframework cation (calcium) and the water molecules оссиру
general positions. These sites, when fully осcupied, give 8 Са and 32 Н20 per unit-cell.
Least-squares refinement of isotropic displacement factors of calcium and water resulted in ехtremely high values. Тhis indicates that the assumed site occupation factors were wrong. As
implied Ьу the chemical analyses, оnlу 4 Са and16 Н20 are required. Тhe site occupancies forspace group С2/е were thus set to 0.5 for Са andwater and refmement continued with isotropic displacement factors, giving R = 0.18 (2cr(Fo)cut-ofi).
Тhe refmement converged to R = 0.09 in spacegroup Се with ful1y occupied Са and Н20 posi-tions. Pairs of atoms of the framework are nearlycentrosymmetrically related in space group Се,
but the extraframework atoms do not form suchpairs. Тherefore the structure was subsequently
refined in non-centrosymmetric space group Се.
Final anisotropic refmement (the displacement
factors of water were refmed isotropically, the Нatoms were not located) converged with R =0.043 and Rw = 0.044. Тhe last difference-Fourierтар showed residual electron density of -0.6 to
1.0 е А-з.
Тhe fmal positional and thermal parameters are
given in ТаЫе 4. Lists of structure factors areavailable from the author ироп request.

Description of the structureТhe details of the crystal structure of weinebeneite are best seen in projections along [100](Fig.3) and [001] (Fig.4). Weinebeneite is аframework beryllophosphate with calcium andwater molecules in cavities. Selected interatomic
distances and angles are given in Tables 5 and 6.
ТЬе tetrahedral

frameworkАН Р- and Be-tetrahedra share vertices forming
а framework, which consists of 3-, 4- and 8membered rings. Two phosphorous and two berуШum tetrahedra are connected in 4-rings withthe sequence of ир (U) and down (D) linkage:

1279

Mineral data and structure of weinebeneiteТаЫе 5. Interatomic

РI-01
-02
-03
-04
Р1-0

1.522(6)1.532(6)1.547(5)01 -02
01 -0301 -04
02-03
02-04
03-04
о-о

2.535(7)2.534(7)2.500(7)2.432(7)2.525(7)РI
01 -02
01 -0301 -04
02-03
02-04
03-04
О-Р1-0

1.534

2.504

109.5

1.539(6)1.537(5)1.531(6)L5З.З(6)1.535

Ве1 -02-06-08-09
Веl -о

tiЩ1Q.l
1.627

05-06
05-07
05-08
06-07
06-08
~07-08о-о

2.513(8)2.514(8)2.483(8)2.527(8)2.464(8)
2.505

02-06
02-08
02-09
06-08
06-09
~08-09о-о

2.651(8)2.598(7)2.666(7)2.672(8)2.711(7).2.2:Ш(!!1
2.656

109.7(3)110.0(3)107.9(3)111.0(3)106.8(3)JJ.Lill)
109.5

Ве1
02-06
02-08
02-09
06-08
06-09
08-09
0-8е1-0

109.4(6)107.7(6)109.7(6)110.8(6)111.0(6)J..QR.1(Q)
109.5

ring P1-ВеЗ-Ве2
129.5(5)Р1-0З-Ве2
129.7(5)P1-01-ВеЗ
127.1(6)Be2-010-ВеЗТаЫе 6. Interatomic
bond system.

distances(А) and angles

Р2- 05
-06
-07
~-08
Р2-0

Р2
05-06
05-07
05-08
06-07
06-08
07-08
О-Р2-0112.2(3)111.3(3)109.7(3)104.4(3)110.8(3)1QМ(З)

distancesring P2-ВеЗ-Ве1
130.3(5)Р2-08-Ве1
128.0(5)Р2-07 -Ве3
125.0(6)8е1-09-8е3

1.609(10)1.642(10)1.606(11)о-о

2.578(7)2.604(8)2.640(7)2.707(8)2.715(7)U1.:1Щ\
2.659

Ве2
03-04
03-05
03-01004-05
04-01005-010О-Ве2-0103.1(6)105.7(6)109.1(6)111.0(6)112.9(6)J..1.4.J.Шl
109.3

03-04
03-05
03-01004-05
04-01005 010ring Р1-Ве1-Р2-Ве2
136.5(5)Р1-02-Ве1
130.9(5)P1-Q4-Be2
135.9(5)Р2-05-Ве2
135.5(5)Р2-06-Ве1

-03
-04
-т
-W2
-W3
-W4(1)"
Са-О

2.541(6)2.449(5)2.396(6)2.362(6)2.453(6)2.362(7)2.ЗШ14)2.422

02 -0302 -WI
02 -W4(1)"03 -0403 -W204 -W204 -W4(1)"
W1-W2
W1-W3
W2-W3
W3-W4(1)"~о-о

2.432(7)2.945(8)2.960(20)
2.578(7)3.549(8)3.089(8)3.220(20)
3.148(8)3.413(9)2.958(9)Са

2.349(16)02 - W4(2)"04 W4(2)"W3 W4(2)'-3.040(20)
3.410(20)2.800(1 О)

3.090(9)3.025(8)2.927(8)2.709(8)2.854(8)2.929(8)

W3-01
W3-06
W4(1)"-05
W4(1)"-08
W4(2)' 05
W4(2)" 08-2.888(8)2.809(8)2.910(20)2.980(20)2.950(20)3.000(20)-W4(2)"

09 -07010-01
W1-09
W1-05
W2-07
W2-08

W4(1)" W4(2)"Note:

1.638(10)- 03
1.654(10)-041.630(10)-0501О
1.ШЩ1Q)
1.631
8е2-0
Ве2

(А) and angles (О)of the extraframework

Са-02

.

indicatesthe(") of the framework.

3.033

ВеЗ -01
-07
-09
-010
Ве3-0

1.642(11)1.625(11)1.634(11)J..fiZJ..Шl
1.631

01 -07
01 -0901 -01007-09
07-01009-0102.625(8)2.687(7)2.635(8)2.654(9)2.685(8)о-оВе3
01 -07
01-09
01 -01007-09
07-01009-010О-В03-0

2.ШИUU
2.662

106.9(5)110.1(6)107.8(7)109.0(7)111.8(6)J.1.1.2ill
109.5

Nole : 09 and 01 О аге (OH)-groups

sites and 0..0Са
02 -0302 -WI
02 -W4(1)"03 -0403 -W204 -W204 -W4(1)"
WI-W2
WI-W3
W2-W3
~W3-W4(1)'О-Са-О
02 - W4(2)"04 W4(2)"W3 - W4(2)"distances(А) of the hydrogen58.3(2)73.7(2)73.8(5)64.3(2)92.4(2)79.1(2)84.4(4)81.6(2)92.5(2)75.7(2)77.8
76.9(5)91.7(4)72.9(4)0.389(18)disorderedwatermolecule.

UUDD - (РI-Ве2-Р2-Веl),
This kind of ring
contributes to а two-dimensional net consisting
only of 8-rings that connect 4-rings, The layer
contains crankshaft chains with an orientation oftetrahedra corresponding to the 4.82 2D net по.
2З in the classification of Smith (1978), In silicates, this type of net is represented Ьу the structиres of gismondine, garronite and zeolite Рl(Liebau, 1985; Smith, 1978), In the structure ofweinebeneite, two such layers are oriented parallel (100), They are shifted one relative to theother through the translation Ь/2 and connectedЬу beryllium tetrahedra ВеЗ, which are locatedbetween the layers. The ВеЗ-tеtrahеdrа are foundat positions where а pair of upwards pointing tetrahedra of the lower net cross а pair ofdownwards pointing tetrahedra of the upper net(Fig, 2), The layer-connecting ВеЗ-tеtrahеdrоп is1280

Р. Wa!ter

*u
*u
1

1

Fig. 2. А pair of sиperimposed 2D nets p!otted with therefined atomic parameters of the Р- and Be-sites of theweinebeneite
structure.
The two !ayers are shifted
throиgh the trans!ation Ь{2. Filled circ!es indicate ирward- and ореn circ!es downward-pointing
tetrahedra.
The !ayers are connected throиgh additiona! tetrahedra
а! positions indicated Ьу !arge ореn circ!es. The иnit сеllof weinebeneite
is given Ьу solid !ines.

ап important structura! e!ement, wblch is shared
between two three-membered rings (РI-Ве3-Ве2and Р2-Ве3-Веl, Fig.3). Such ап unиsua! arrangement of five tetrahedra composed of two
three-membered rings, and sharing а tetrahedron,is a!so found in the !ovdarite structure, which isthe first recorded ехаmр!е of а framework bery!!osi!icate containing three-membered rings(Merlino, 1981,1990). However, in the !ovdarite
structure the 2D-net-tetrahedra are orienteddifferent!y than in the weinebeneite structure.
The two unique P-tetrahedra in the weinebeneite structure have а typica! range of bond!engths and ang!es. Р is coordinated оп!у Ьу О
atoms and has the shortest (РI-0l = 1.522 А)
and the !ongest (РI-03 = 1.547 А) Р-О bond!engths. Тhe mеan Р-О distances in both tetrahedra are near!y equa! and the variation in bond!engths is in good agreement with !оса! bondуа!епсе requirements (ТаЫе 7), ca!cu!ated асcording to data of Brown & A!termatt (1985).
Тhe three unique Ве tetrahedra are a!so tetrahedrally coordinated Ьу four О atoms, with а rangeof bond distances and ang!es typica! of Ве tetrahedra a!so found in the structures of the framework beryllophosphates tiptopite (Peacor et al.,1987) and pahasapaite (Rouse et al., 1989). The

ь*
Fig. 3. Projection a!ong [100] of the crysta! structure ofweinebeneite showing а s!ice between х=0.05 andх=0.95. The tetrahedra are nиmbered : 1 = Рl, 2 = Р2,
3 = Веl, 4 = Ве2, 5 = ВеЗ. Bonds (sticks) are shown
between Calciиm (large ореn circ!es) and water
mo!ecи!es (filled circ!es) and between Calciиm andframework oxygens (tetrahedra comers).

Ве2 tetrahedron has the shortest (Ве2-010 =
1.601 А) and the !ongest (Ве2-04 = 1.654 А)
Ве-О distances in the structure. Тhe variation inВе-О bond !engths сап Ье rationa!ized in termsof the !осаl anion bond-va!ence requirements ofthis structure (ТаЫе 7). 09 and 010 be!ong to(ОН)-grouрs, bonded опlу to Ве tetrahedra andН atoms (not !ocated in the structure refinement),
and are invo!ved in а hydrogen bond system, asconfirmed Ьу the bond-va!ence requirements(ТаЫе 7). Channe!s a!ong [001] with approximate free dirnensions of 4.4 х 6.3 А are an important feature of the weinebeneite framework(Fig. 4).
Extraframeworksites

Са atoms and water mo!ecu!es are !ocated inchanne!s of the structure. Calcium is coordinatedЬу three О atoms of the framework and fourwater mo!ecu!es

with bond !engths of 2.349

А to

2.541 А. Тhe water mo!ecu!es Wl, W2 and W3
are !ocated in channe!s (Fig. 4), whereas W4 is
positioned in the !ayers of the framework near
the centers of 8-membered rings. On1y the water

1281

Mineral data and structure of weinebeneiteТаЫе 7. Empirica! bond-valences (У.и.) in weinebeneite calcu!ated folIowing Brown & A!termatt (1985) andFerraris & Ivaldi (! 988).
w
Р1

Р2

Ве1

Ве2

Ве3

Са

Н9 Н10

0.49

l'

w
l'

2'

w

w
2'

3'

4'

4'

r

01

1.29

02

1.26

03

1.21

0.50

0.27

1.98

04

1.25

0.48

0.31

2.04

1.24

06

1.24

07

1.26

ОВ
09(ОН)

1.26

0.51

0.22
0.52

012

0.51

0.88

2.07
0.15

0.55

0.52

0.13* 2.08

0.15

2.03

0.78 0.85

1.97

0.87
0.34

W2

027

W3

0.34

1.94
0.83 0.85

1.95
0.84 0.82

0.34.

W4
5.00

Note:'indicaies calculated

2.06

1.91

017

0.54
0.49

5.01

2.11

0.14'
0.18

W1

I

2.01

0.49

01О(0Н)

2.07

0.16

0.21

0.54

05

0.13

3'

2.04

sum torW4(1} and

2.04

2.08

2.00
0.86'0.81'

1.001.00

1.001.00

1.001.00

1.001.00

2.07

1.001.00

W4(2)molecule W4 displays disorder over two distinct
positions. During refinement, а single position
for W4 gave very high isotropic displacement
factors for this site. А subsequent differenceFourier тар resulted in two distinct positions
W4(1) and W4(2). Variation in Са-О and Саwater bond lengths are in good agreement withthe local anion bond-valence requirements of theweinebeneite structure. ТаЫе 7 presents bondvalence balance ca1culated according to Brown &Altermatt (1985) for cation-oxygen bonds andhydrogen bond strengths using the 0...0 distances (ТаЫе б) ca1culated according to Ferraris& Ivaldi (1988). Bond-valence requirements сопfirm that Wl to W4 correspond to watermolecules, аН involved in а hydrogen bond sys-1*саFig. 4. Projection along [001] of the crystal structure of weinebeneite showing а slice between z = О and z = 1.05.
Тhe tetrahedra are numbered as in Fig.3. Calcium (!arge ореп circles), Wl, W2, and W3 (filled circles) are locatedin channe!s of the framework. ТЬе disordered water molecu!e W4 (filled circles) is !ocated within the layers of
the framework near the centers of 8-membered rings.

1282

Р. Waltertem. The bond-va1ence sums around the donor
anions were set to the ideal values 2.0 for watermolecules and 1.0 for ОН groups.

Conclusions
The results of the structure refinement ofweinebeneite confirm the formula calculated
from the chemical analyses. Isotypes of weinebeneite were not found. However, some specificfeatures of the framework of the lovdarite structure are similar to those of the weinebeneite
structure. According to lovdarite, which is named
а zeolite-like mineral (Merlino, 1981, 1990) andreported as а new structure type in the zeolite
at1as of Meier & Olson (1987), weinebeneite
could Ье named а beryl1ophosphate with а zeolite-like structure.
The weinebeneite formula is identical to theoriginal formula for uralolite, СаВеЗ(РО4)2(ОН)2.4Н20, proposed Ьу Grigor'ev (1964). However,Dunn & Gaines (1978) found that uralolite fromthe Dunton gem mine, Newry, Maine, has theformula Са2Ве4(РО4)з(ОН)з.5Н20 and that the
X-ray powder pattern is identical to that ofuralolite from the Ural Mountains. Chemical andsingle crystal work with uralolite from theWeinebene pegmatites verify the chemical
formula given Ьу Dunn & Gaines (1978;
Mereiter, personal communication ). The X-ray
powder data and chemical formulae of weinebeneite and uralolite are distinctly different.
Therefore uralolite and weinebeneite are twodifferent mineral species.
Weinebeneite is also different from glucine,
CaBe4(p04)2(OHkO.5H20, reported Ьу Grigor'ev(1963) and different
from fransoletite,Н2СазВе2(РО4)4.4Н20, reported Ьу Peacor et al.
(1983).

Acknowledgements: Sincere thanks are ехpressed to Prof. Dr. Е. М. Walitzi for many helpful discussions and for reviewing the manuscript,
and to Dr. С. Kratky for making the STOE fourcircle diffractometer available. 1 ат also gratefulto Dr. Р. ОоlоЬ and Dr. Р. Hofer for EELS-analyses, to Dr. К. Ettinger for electron microprobe
work and to Р. Bahr for making SEM photographs. J. Taucher and Dr. W. Postl are acknowledged for kindly supplying the type specimens
used in this study. Dr. Mereiter kindly provided
results of the refinement of the uralolite structure.

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-

Received
Accepted

29 Septeтber
1991
30 March 1992