CsVP2S7

inorganic papers

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Acta Crystallographica Section E

Structure Reports

Online ISSN 1600-5368

CsVP

S

Andreas Gutzmann, Christian NaÈther and Wolfgang Bensch*

Institut fuÈr Anorganische Chemie, Christian-Albrechts-UniversitaÈt Kiel, Olshausenstraûe 40, D-24089 Kiel, Germany

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 293 K

Mean(S±P) = 0.004 AÊ

Rfactor = 0.046

wRfactor = 0.100

Data-to-parameter ratio = 23.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain ± all rights reserved

The quaternary vanadium thiophosphate CsVP2S7 (caesium

vanadium diphosphorus heptasul®de) was synthesized by reacting a mixture of Cs2S3, V, P4S3and S. The crystal structure

is composed of VS6 octahedra, which are linked by

bitetrahedral [P2S7] groups to form two-dimensional anionic

[VP2S7]ÿlayers. The layers are stacked perpendicular to the

crystallographiccaxis and are separated by the Cs+_{ions. The}

VS6octahedra, the [P2S7] groups and the Cs+ions are located

in special positions. CsVP2S7 is isostructural to KVP2S7and

RbVP2S7.

Comment

In the past few years, new quaternary thiophosphates have been synthesized applying alkali metal halides or the low-melting alkali metal thiophosphate ¯uxes. In general,Ax[PySz]

(A= alkali metal) ¯uxes are formed byin situfusion ofA2Sx,

P2S5and S. In our investigations of quaternary group IVand V

thiophosphates, we have tried to develop alternative routes for the preparation of new compounds by a systematic variation of the reaction parameters, e.g. the use of binary transition metal sul®des or phosphides or P4S3instead of P2S5as educts.

Applying this technique, several new quaternary thio-phosphates with interesting structural features, such as

A3M2P5S18(A= Rb and Cs, andM= Zr and Hf; Gutzmannet

al., 2004a,b), K4VP2S9(Gutzmannet al., 2004c), Rb2Nb2P2S11

(Gutzmann & Bensch, 2002), Rb4Ta4P4S24 (Gutzmann &

Bensch, 2003), K0.38TaPS6and Rb0.46TaPS6(Gutzmannet al.,

2004d), have been obtained, demonstrating the high synthetic potential of the chemistry in alkali metal polythiophosphate ¯uxes. Analyzing the structures of the known ternary and

quaternary vanadium thiophosphates, 1D-PV2S10 (Brec,

Ouvrard, Evain et al., 1983), 2D-P0.2VS2 (Brec, Ouvrard,

Freour et al., 1983), 2D-V0.78PS3(Ouvrard et al., 1985),

2D-V2P4S13 (Evain et al., 1985), 0D-K4VP2S9 (Gutzmann et al.,

2004a), 1D-K2VP2S7 (Tremel et al., 1995), 1D-NaV0.84P2S6

(Costeet al., 2003) and 2D-AVP2S7(A= K and Rb; Kopninet

al., 2000; Durandet al., 1993), most of the compounds contain VS6octahedra as the general structural motif. Exceptions are

PV2S10and K4VP2S9for which VS8and VS5polyhedra were

observed. Applying the very successful method presented for quaternary alkali metal thiophosphates, we synthesized CsVP2S7, which is isostructural toAVP2S7(A= K and Rb). We

report here on the synthesis and structural characterization of this compound.

The crystal structure of CsVP2S7 is built up of [VP2S7]ÿ

layers and Cs+ _{ions (Fig. 1). The [VP}

2S7]ÿ anionic layers

extending in the (010) plane are separated by about 4 AÊ and are stacked perpendicular to [001] (Fig. 2). The charge

compensating Cs+ _{ions are situated between the layers. The}

electronic situation of the title compound may be represented as [Cs+_][V3+_][P

2S74ÿ]. The main feature of this structure type is

the presence of VS6 octahedra, which are joined by [P2S7]

groups to form the layered [VP2S7]ÿ anion. The VÐS

distances of the strongly distorted octahedra range between 2.439 (3) and 2.457 (2) AÊ and are in good agreement with the data observed forAVP2S7(A= K and Rb; Kopninet al., 2000;

Durand et al., 1993). Each VS6octahedron is surrounded by

three symmetry-related pyrothiophosphate ligands sharing common edges with two [P2S7] units and sharing two common

corners with the two [PS4] tetrahedra of another bitetrahedral

[P2S7]4ÿ anion (Fig. 3). The PÐS bond lengths range from

2.008 (4) to 2.138 (4) AÊ. The longest PÐS bond is observed for the bridging S atom having bonds to two P atoms. The [PS4]

tetrahedra of the pyrothiophosphate ligands are strongly distorted, as is evidenced by the SÐPÐS angles. The connection scheme leads to the formation of cavities within the layers running along [001]. The Cs+_{cation is in a 12-fold}

coordination of each six S atoms from two adjacent [VP2S7]ÿ

layers. The mean CsÐS distance is 3.768 AÊ and is in good agreement with the sum of the ionic radii [1.84 AÊ for S2ÿ_and

1.88 AÊ for Cs+ _{(CN12); Shannon, 1976]. Interestingly, the}

anharmonic behavior of the alkali metal cation, as in the isostructural compoundsAMP2S7(A= K and Rb, andM= Cr,

V and In; Kopnin et al., 2000; Durand et al., 1993), is not observed. In the electron density map of the title compound a regular distribution around the Cs+_{position is observed. In the}

isostructural K and Rb compounds, the alkali cations are

coordinated by eight S atoms, whereas the Cs+_{ions in the title}

compound are surrounded by 12 S atoms. It is likely that this larger coordination number stabilizes the Cs+_{cation, leading}

to the harmonic behavior.

Experimental

CsVP2S7 was obtained by the reaction of Cs2S3 (0.24 mmol), V (0.72 mmol), P4S3(0.24 mmol) and S (2.4 mmol). Cs2S3was prepared from a stoichiometric ratio of the elements in liquid ammonia under an argon atmosphere. In an N2-®lled glove-box, the starting materials were thoroughly mixed and loaded into a glass ampoule. After evacuation (10ÿ3 _{mbar) the ampoule was ¯ame-sealed and placed in} a computer-controlled furnace. The sample was heated to 823 K within 24 h. After four days the sample was cooled to room temperature at a rate of 3 K hÿ1_{. To remove the excess Cs}

xPySz¯ux, the resultant melt was washed with dryN,N-dimethylformamide and diethyl ether. The product was driedin vacuoand consisted of dark green needles which are stable in air and water. The yield based on vanadium was about 90%. The MIR spectra of CsVP2S7 displays strong absorptions at 598, 579, 526, 459 and 407 cmÿ1_{. These} absorptions are in good agreement with the vibrational frequencies reported for Na2FeP2S7(Menzelet al., 1990) and may be assigned to PÐS stretching modes.

Crystal data CsVP2S7 Mr= 470.21

Monoclinic,C2 a= 8.6010 (17) AÊ b= 9.5176 (19) AÊ c= 6.7287 (13) AÊ

= 98.17 (3)

V= 545.23 (19) AÊ3 Z= 2

Dx= 2.864 Mg mÿ3

MoKradiation

Cell parameters from 68 re¯ections

= 10±15

= 5.77 mmÿ1 T= 293 (2) K Needle, green 0.150.050.05 mm

Data collection Philips PW1100 four-circle

diffractometer

!/scans

Absorption correction: numerical (X-SHAPEandX-RED; Stoe & Cie, 1998) Tmin= 0.701,Tmax= 0.738 1280 measured re¯ections 1205 independent re¯ections

979 re¯ections withI> 2(I) Rint= 0.044

max= 27.0 h= 0!10 k=ÿ12!12 l=ÿ8!8 3 standard re¯ections every 120 min intensity decay: none

inorganic papers

Acta Cryst.(2005). E61, i6±i8 Gutzmannet al. CsVP₂S₇

i7

Figure 1

Crystal structure of CsVP2S7, viewed in the direction of the

crystal-lographicbaxis.

Figure 2

Crystal structure of CsVP2S7, viewed in the direction of the

Refinement Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.046} wR(F2_{) = 0.100} S= 1.01 1205 re¯ections 52 parameters

w= 1/[2_(Fo2_{) + (0.0566P)}2_P] whereP= (Fo2_{+ 2Fc}2_)/3

(/)max< 0.001 max= 1.49 e AÊÿ3 min=ÿ0.63 e AÊÿ3 Extinction correction: none Absolute structure: Flack (1983),

567 Friedel pairs Flack parameter:ÿ0.03 (4)

Table 1

Selected geometric parameters (AÊ,_).

P1ÐS3 2.008 (4)

P1ÐS1 2.013 (3)

P1ÐS2 2.027 (4)

P1ÐS4 2.138 (3)

V1ÐS2ii _{2.439 (3)}

V1ÐS3iii _{2.453 (3)}

V1ÐS3v _{2.453 (3)}

V1ÐS1ii _{2.457 (2)}

Cs1ÐS4vi _{3.5277 (13)}

Cs1ÐS3vii _{3.548 (3)} Cs1ÐS3viii _{3.548 (3)} Cs1ÐS1ix _{3.705 (2)}

Cs1ÐS2x _{3.711 (3)}

Cs1ÐS2v _{3.711 (3)}

Cs1ÐS1vii _{4.004 (3)} Cs1ÐS1viii _{4.004 (3)}

Cs1ÐS2x _{4.108 (3)}

Cs1ÐS2vi _{4.108 (3)}

S3ÐP1ÐS1 110.13 (15)

S3ÐP1ÐS2 120.02 (16)

S1ÐP1ÐS2 105.32 (14)

S3ÐP1ÐS4 109.79 (15)

S1ÐP1ÐS4 102.84 (15)

S2ÐP1ÐS4 107.33 (14)

S2ÐV1ÐS2ii _{99.35 (16)} S2ÐV1ÐS3iii _{163.10 (9)} S2ii_ÐV1ÐS3iii _{87.99 (9)} S2ÐV1ÐS3v _{87.99 (9)} S2ii_ÐV1ÐS3v _{163.10 (9)}

S3iii_ÐV1ÐS3v _{89.17 (14)}

S2ÐV1ÐS1 82.00 (9)

S2ii_{ÐV1ÐS1 90.23 (9)} S3iii_{ÐV1ÐS1 82.78 (9)} S3v_{ÐV1ÐS1 105.93 (10)} S2ÐV1ÐS1ii _{90.23 (9)} S2ii_ÐV1ÐS1ii _{82.00 (9)} S3iii_ÐV1ÐS1ii _{105.93 (10)} S3v_ÐV1ÐS1ii _{82.78 (9)} S1ÐV1ÐS1ii _{168.01 (17)}

Symmetry codes: (i) ÿx‡1;y;ÿz‡1; (ii) ÿx;y;ÿz‡1; (iii) xÿ1

2;yÿ12;z; (v) ÿx‡1

2;yÿ12;ÿz‡1; (vi)x;y;zÿ1; (vii)ÿx‡21;yÿ12;ÿz; (viii)x‡12;yÿ12;z; (ix) ÿx‡1;y;ÿz; (x)x‡1

2;yÿ12;zÿ1.

The absolute structure was determined and is, according to the Flack (1983) x test, in agreement with the selected setting. The highest peak in the difference electron density map is located 0.97 AÊ from Cs1, and the deepest hole 1.27 AÊ from S4.

Data collection:DIF4 (Stoe & Cie, 1992); cell re®nement:DIF4; data reduction:REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND(Brandenburg, 1999); software used to prepare material for publication:XCIFinSHELXTL(Bruker, 1998).

Financial support by the state of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged.

References

Brandenburg, K. (1999). DIAMOND. Version 2.1c. Crystal Impact GbR, Bonn, Germany.

Brec, R., Ouvrard, G., Evain, M., Grenouilleau, P. & Rouxel, J. (1983).J. Solid State Chem.47, 174±184.

Brec, R., Ouvrard, G., Freour, R., Rouxel, J. & Soubeyroux, J. L. (1983).Mater. Res. Bull.18, 689±696.

Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Coste, S., Gautier, E., Evain, M., Bujoli-Doeuff, M., Brec, R., Jobic, S. & Kanatzidis, M. G. (2003).Chem. Mater.15, 2323±2327.

Durand, E., Evain, M. & Brec, R. (1993).J. Solid State Chem.102, 146±155. Evain, M., Brec, R., Ouvrard, G. & Rouxel, J. (1985).J. Solid State Chem.56,

12±20.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Gutzmann, A. & Bensch, W. (2002).Solid State Sci.4, 835±840. Gutzmann, A. & Bensch, W. (2003).Solid State Sci.5, 1271±1276.

Gutzmann, A., NaÈther, C. & Bensch, W. (2004a).Solid State Sci.6, 205±211. Gutzmann, A., NaÈther, C. & Bensch, W. (2004b).Acta Cryst.E60, i42±i44. Gutzmann, A., NaÈther, C. & Bensch, W. (2004c).Acta Cryst.C60, i11±i13. Gutzmann, A., NaÈther, C. & Bensch, W. (2004d).Solid State Sci.6, 1155±1162. Kopnin, E., Coste, S., Jobic, S., Evain, M. & Brec, R. (2000).Mater. Res. Bull.

35, 1401±1410.

Menzel, F., Ohse, L. & Brockner, W. (1990).Heteroat. Chem.1, 357±362. Ouvrard, G., Freour, R., Brec, R. & Rouxel, J. (1985).Mater. Res. Bull.20,

1053±1062.

Shannon, R. D. (1976).Acta Cryst.A32, 751±767.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Stoe & Cie (1992).DIF4 (Version 7.09X/DOS) andREDU4 (Version 7.03). Stoe & Cie GmbH, Darmstadt, Germany.

Stoe & Cie (1998).X-SHAPEandX-RED. Version 1.03. Stoe & Cie GmbH, Darmstadt, Germany.

Tremel, W., Kleinke, H., Derstroff, V. & Reisner, C. (1995).J. Alloys Compd.

219, 73±82.

inorganic papers

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Figure 3

Crystal structure of CsVP2S7, with labeling and displacement parameters

drawn at the 50% probability level, showing the interconnection of the VS6octahedra through [P2S7] groups sharing common edges and corners.

[Symmetry codes: (i) 1ÿx,y, 1ÿz; (ii)ÿx,y,ÿz + 1; (iii)ÿ1 2+x, ÿ1

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Acta Cryst. (2005). E61, i6–i8

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Acta Cryst. (2005). E61, i6–i8 [https://doi.org/10.1107/S1600536804031150]

CsVP

S

Andreas Gutzmann, Christian N

ä

ther and Wolfgang Bensch

Caesium vanadium diphosphorus heptasulfide

Crystal data CsVP2S7 Mr = 470.21 Monoclinic, C2 Hall symbol: C 2y a = 8.6010 (17) Å b = 9.5176 (19) Å c = 6.7287 (13) Å β = 98.17 (3)° V = 545.23 (19) Å3 Z = 2

F(000) = 440 Dx = 2.864 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 68 reflections θ = 10–15°

µ = 5.77 mm−1 T = 293 K Plate, green

0.15 × 0.05 × 0.05 mm

Data collection

Philips PW1100 4-circle-diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/θ scans

Absorption correction: numerical

X-SHAPE and X-RED (Stoe & Cie, 1998) Tmin = 0.701, Tmax = 0.738

1280 measured reflections

1205 independent reflections 979 reflections with I > 2σ(I) Rint = 0.044

θmax = 27.0°, θmin = 3.1° h = 0→10

k = −12→12 l = −8→8

3 standard reflections every 120 min intensity decay: none

Refinement Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.046} wR(F2_{) = 0.100} S = 1.01 1205 reflections 52 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

w = 1/[σ2_(F

o2) + (0.0566P)2P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 1.49 e Å−3 Δρmin = −0.63 e Å−3

Absolute structure: Flack (1983) Absolute structure parameter: −0.03 (4)

Special details

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Acta Cryst. (2005). E61, i6–i8

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used} only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

P1 0.3030 (3) 0.6425 (3) 0.4194 (4) 0.0169 (5)

S1 0.1582 (2) 0.5244 (3) 0.2257 (3) 0.0214 (6)

S2 0.1928 (3) 0.6633 (3) 0.6648 (4) 0.0235 (6)

S3 0.3703 (3) 0.8139 (3) 0.2801 (4) 0.0252 (6)

S4 0.5000 0.5068 (4) 0.5000 0.0175 (7)

V1 0.0000 0.4975 (2) 0.5000 0.0167 (5)

Cs1 0.5000 0.39532 (12) 0.0000 0.0370 (4)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

P1 0.0134 (11) 0.0173 (14) 0.0202 (11) −0.0010 (9) 0.0027 (9) 0.0009 (10)

S1 0.0153 (11) 0.0275 (15) 0.0214 (12) −0.0070 (11) 0.0023 (9) −0.0025 (11)

S2 0.0214 (12) 0.0228 (15) 0.0284 (12) −0.0062 (10) 0.0109 (10) −0.0090 (11)

S3 0.0254 (13) 0.0223 (14) 0.0255 (13) −0.0077 (11) −0.0044 (10) 0.0067 (11)

S4 0.0171 (15) 0.0133 (18) 0.0219 (16) 0.000 0.0015 (11) 0.000

V1 0.0134 (10) 0.0162 (13) 0.0211 (11) 0.000 0.0048 (8) 0.000

Cs1 0.0264 (5) 0.0629 (8) 0.0216 (5) 0.000 0.0029 (4) 0.000

Geometric parameters (Å, º)

P1—S3 2.008 (4) S4—Cs1iii _{3.5277 (13)}

P1—S1 2.013 (3) V1—S2vi _{2.439 (3)}

P1—S2 2.027 (4) V1—S3vii _{2.453 (3)}

P1—S4 2.138 (3) V1—S3viii _{2.453 (3)}

P1—Cs1 4.211 (3) V1—S1vi _{2.457 (2)}

S1—V1 2.457 (2) Cs1—S4ix _{3.5277 (13)}

S1—Cs1 3.705 (2) Cs1—S3x _{3.548 (3)}

S1—Cs1i _{4.004 (3) Cs1—S3}xi _{3.548 (3)}

S2—V1 2.439 (3) Cs1—S1xii _{3.705 (2)}

S2—Cs1ii _{3.711 (3) Cs1—S2}xiii _{3.711 (3)}

S2—Cs1iii _{4.108 (3) Cs1—S2}viii _{3.711 (3)}

S3—V1iv _{2.453 (3) Cs1—S1}x _{4.004 (3)}

S3—Cs1i _{3.548 (3) Cs1—S1}xi _{4.004 (3)}

S4—P1v _{2.138 (3) Cs1—S2}v _{4.108 (3)}

S4—Cs1 3.5277 (13) Cs1—S2ix _{4.108 (3)}

S3—P1—S1 110.13 (15) S4—Cs1—S1 53.26 (4)

S3—P1—S2 120.02 (16) S4ix_{—Cs1—S1 113.50 (5)}

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Acta Cryst. (2005). E61, i6–i8

S3—P1—S4 109.79 (15) S3xi_{—Cs1—S1 124.00 (6)}

S1—P1—S4 102.84 (15) S1xii_{—Cs1—S1 141.26 (9)}

S2—P1—S4 107.33 (14) S4—Cs1—S2xiii _{144.98 (6)}

S3—P1—Cs1 88.33 (12) S4ix_—Cs1—S2xiii _{62.54 (6)}

S1—P1—Cs1 61.64 (9) S3x_—Cs1—S2xiii _{89.55 (6)}

S2—P1—Cs1 151.62 (12) S3xi_—Cs1—S2xiii _{75.41 (6)}

S4—P1—Cs1 56.81 (6) S1xii_—Cs1—S2xiii _{59.95 (6)}

P1—S1—V1 85.96 (11) S1—Cs1—S2xiii _{153.56 (6)}

P1—S1—Cs1 89.81 (10) S4—Cs1—S2viii _{62.54 (6)}

V1—S1—Cs1 146.05 (10) S4ix_—Cs1—S2viii _{144.98 (6)}

P1—S1—Cs1i _{84.21 (11) S3}x_—Cs1—S2viii _{75.41 (6)}

V1—S1—Cs1i _{100.51 (9) S3}xi_—Cs1—S2viii _{89.55 (6)}

Cs1—S1—Cs1i _{112.55 (6) S1}xii_—Cs1—S2viii _{153.56 (6)}

P1—S2—V1 86.14 (12) S1—Cs1—S2viii _{59.95 (6)}

P1—S2—Cs1ii _{148.66 (13) S2}xiii_—Cs1—S2viii _{106.97 (9)}

V1—S2—Cs1ii _{109.13 (8) S4—Cs1—S1}x _{125.51 (7)}

P1—S2—Cs1iii _{92.75 (11) S4}ix_—Cs1—S1x _{87.10 (6)}

V1—S2—Cs1iii _{100.99 (9) S3}x_—Cs1—S1x _{51.32 (5)}

Cs1ii_—S2—Cs1iii _{110.11 (7) S3}xi_—Cs1—S1x _{103.88 (6)}

P1—S3—V1iv _{115.70 (13) S1}xii_—Cs1—S1x _{112.55 (6)}

P1—S3—Cs1i _{97.41 (11) S1—Cs1—S1}x _{101.61 (4)}

V1iv_—S3—Cs1i _{117.51 (10) S2}xiii_—Cs1—S1x _{53.27 (5)}

P1v_{—S4—P1 105.7 (2) S2}viii_—Cs1—S1x _{63.18 (6)}

P1v_{—S4—Cs1 108.42 (7) S4—Cs1—S1}xi _{87.10 (6)}

P1—S4—Cs1 92.71 (7) S4ix_—Cs1—S1xi _{125.51 (7)}

P1v_—S4—Cs1iii _{92.71 (7) S3}x_—Cs1—S1xi _{103.88 (6)}

P1—S4—Cs1iii _{108.42 (7) S3}xi_—Cs1—S1xi _{51.32 (5)}

Cs1—S4—Cs1iii _{144.99 (12) S1}xii_—Cs1—S1xi _{101.61 (4)}

S2—V1—S2vi _{99.35 (16) S1—Cs1—S1}xi _{112.55 (6)}

S2—V1—S3vii _{163.10 (9) S2}xiii_—Cs1—S1xi _{63.18 (6)}

S2vi_—V1—S3vii _{87.99 (9) S2}viii_—Cs1—S1xi _{53.27 (5)}

S2—V1—S3viii _{87.99 (9) S1}x_—Cs1—S1xi _{56.32 (7)}

S2vi_—V1—S3viii _{163.10 (9) S4—Cs1—S2}v _{51.46 (5)}

S3vii_—V1—S3viii _{89.17 (14) S4}ix_—Cs1—S2v _{104.46 (6)}

S2—V1—S1 82.00 (9) S3x_—Cs1—S2v _{152.36 (6)}

S2vi_{—V1—S1 90.23 (9) S3}xi_—Cs1—S2v _{52.07 (6)}

S3vii_{—V1—S1 82.78 (9) S1}xii_—Cs1—S2v _{62.18 (5)}

S3viii_{—V1—S1 105.93 (10) S1—Cs1—S2}v _{93.15 (5)}

S2—V1—S1vi _{90.23 (9) S2}xiii_—Cs1—S2v _{113.26 (3)}

S2vi_—V1—S1vi _{82.00 (9) S2}viii_—Cs1—S2v _{110.11 (7)}

S3vii_—V1—S1vi _{105.93 (10) S1}x_—Cs1—S2v _{155.91 (5)}

S3viii_—V1—S1vi _{82.78 (9) S1}xi_—Cs1—S2v _{100.47 (5)}

S1—V1—S1vi _{168.01 (17) S4—Cs1—S2}ix _{104.46 (6)}

S4—Cs1—S4ix _{144.99 (12) S4}ix_—Cs1—S2ix _{51.46 (5)}

S4—Cs1—S3x _{116.79 (5) S3}x_—Cs1—S2ix _{52.07 (6)}

S4ix_—Cs1—S3x _{71.38 (5) S3}xi_—Cs1—S2ix _{152.36 (6)}

S4—Cs1—S3xi _{71.38 (5) S1}xii_—Cs1—S2ix _{93.15 (5)}

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S3x_—Cs1—S3xi _{154.77 (9) S2}xiii_—Cs1—S2ix _{110.11 (7)}

S4—Cs1—S1xii _{113.50 (5) S2}viii_—Cs1—S2ix _{113.26 (3)}

S4ix_—Cs1—S1xii _{53.26 (4) S1}x_—Cs1—S2ix _{100.47 (5)}

S3x_—Cs1—S1xii _{124.00 (6) S1}xi_—Cs1—S2ix _{155.91 (5)}

S3xi_—Cs1—S1xii _{65.52 (6) S2}v_—Cs1—S2ix _{103.25 (8)}