inorganic papers
i42
Andreas Gutzmannet al. Cs3Hf2(P2S7)2(PS4) DOI: 10.1107/S1600536804002880 Acta Cryst.(2004). E60, i42±i44Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
Cs3Hf2(P2S7)2(PS4)
Andreas Gutzmann, Christian NaÈther and Wolfgang Bensch*
Institut fuÈr Anorganische Chemie, Christian-Albrechts-UniversitaÈt Kiel, Olshausenstraûe 40, D-24098 Kiel, Germany
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 180 K
Mean(S±P) = 0.007 AÊ Rfactor = 0.041 wRfactor = 0.104
Data-to-parameter ratio = 16.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The ®rst quaternary hafnium thiophosphate, tricaesium dihafnium pentaphosphorus octadecasul®de, Cs3Hf2P5S18 was synthesized by reacting HfS2with anin situformed melt of Cs2S3, P2S5 and S. The crystal structure is composed of a two-dimensional anionic [Hf2P5S18]3ÿ layer and intervening Cs+ cations. Each of the two independent Hf4+ ions is surrounded by seven S atoms forming a distorted pentagonal bipyramid. The HfS7polyhedra are connected by an unusual edge- and corner-sharing arrangement of [P2S7] groups and edge-sharing [PS4] tetrahedra into the ®nal double-layered anion.
Comment
Until now, only a few quaternary alkali metal thiophosphates of group 4 metals have been structurally characterized (Cieren et al., 1994; Do et al., 1996; Derstroff et al., 2002). All quaternary compounds contain titanium as the transition metal. In our investigations of theA±M±P±S family (A= alkali metal andM= group 4 metal), we prepared very recently the ®rst quaternary zirconium thiophosphates,viz.A3Zr2P5S18(A = Rb, Cs) (Gutzmann et al., 2004), enhancing the range of structures of the A±M±P±S family. One interesting observa-tion made in the past was that the ternary thiophosphates MP2S6withM= Ti, Zr and Hf are not isostructural (Jandaliet al., 1980; Simon et al., 1982, 1985; Lott et al., 1999). This observation was also made in the quaternary thiophosphates with the general formulaA3M2P5S18, where the Ti compound is structurally quite different from the Zr compound. In our effort to investigate and determine the relationships between the cation size, the M:S ratio and the dimensionality of the structures in group 4 metal thiophosphates, we have obtained the new compound Cs3Hf2P5S18, which is isostructural with the Zr compound.
The crystal structure of Cs3Hf2P5S18 is built up of [Hf2P5S18]3ÿlayers extending in the (001) plane and
charge-Received 13 January 2004 Accepted 5 February 2004 Online 14 February 2004
Figure 1
The crystal structure of Cs3Hf2P5S18, viewed in the direction of the
compensating Cs+cations. The main feature of this structure type is the presence of HfS7 polyhedra which are inter-connected via pentadentate [P2S7] groups and tetradentate [PS4] tetrahedra into a double-layered structure. Each of the two distinct Hf4+ions is surrounded by seven S atoms forming a distorted pentagonal bipyramid. The mean HfÐS bond lengths of 2.617 (5) AÊ in the Hf1S7 polyhedron and 2.621 (5) AÊ for Hf2S7are in good agreement with the sum of the ionic radii [1.84 AÊ for S2ÿ and 0.76 AÊ for Hf4+(CN7); Shannon, 1976]. The Hf1S7and Hf2S7polyhedra are linkedvia one [P2S7] group that acts in an unusual pentadentate fashion. Each of the HfS7groups shares two common edges and one corner with two symmetry-related [P2S7] units. Furthermore, the Hf1S7and Hf2S7polyhedra are interconnectedvia tetra-dentate [PS4] tetrahedra into the ®nal double-layered struc-ture. The average PÐS distances in the two unique pyrothiophosphate ligands and the [PS4] tetrahedra are 2.050, 2.052 and 2.038 AÊ. The longest PÐS bonds in the [P2S7] groups are observed for S atoms having bonds to two P atoms. The SÐPÐS angles in the thiophosphate ligands exhibit a signi®cant distortion. The three crystallographically indepen-dent Cs+ cations are surrounded either by nine S atoms (average Cs1ÐS distance 3.739 AÊ and average Cs3ÐS distance 3.735 AÊ) or by ten S atoms (average Cs2ÐS distance 3.780 AÊ); these distances agree well with the sum of the ionic radii. The charge balance of the compound may be formulated as [Cs+]
3[Hf4+]2[PS43ÿ][P2S74ÿ]2.
Experimental
The compound Cs3Hf2P5S18was obtained by the reaction of Cs2S3
(0.3 mmol), HfS2(0.15 mmol), P2S5(0.45 mmol) and S (1.5 mmol).
Cs2S3was prepared from stoichiometric amounts of Cs and S in liquid
ammonia under an argon atmosphere. The starting materials were loaded into a quartz tube which was evacuated (10ÿ3mbar) and
¯ame-sealed. The ampoule was heated to 873 K within 24 h. After 4 d, the sample was cooled down to 523 K at 2 K hÿ1and then to
room temperature within 10 h. To remove unreacted CsxPySz, the resultant melt was washed with dry N,N-dimethylformamide and diethyl ether. The product was dried in a vacuum and consisted of light-yellow plate-like crystals which are air- and moisture-sensitive.
Crystal data
Cs3Hf2(P2S7)2(PS4)
Mr= 1487.64 Monoclinic,Cc a= 9.3168 (4) AÊ
b= 9.8985 (6) AÊ
c= 34.0830 (17) AÊ = 94.236 (6) V= 3134.6 (3) AÊ3
Z= 4
Dx= 3.152 Mg mÿ3 MoKradiation Cell parameters from 8000
re¯ections = 1.3±23.3 = 11.51 mmÿ1
T= 180 (2) K Plate, yellow 0.20.20.1 mm
Data collection
Stoe IPDS diffractometer 'scans
Absorption correction: numerical (X-SHAPEandX-RED32; Stoe & Cie, 1998)
Tmin= 0.120,Tmax= 0.312
9627 measured re¯ections
4211 independent re¯ections 4119 re¯ections withI> 2(I)
Rint= 0.041
max= 23.1
h=ÿ10!10
k=ÿ10!10
l=ÿ37!37
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.041
wR(F2) = 0.104
S= 1.15 4211 re¯ections 254 parameters
w= 1/[2(F
o2) + (0.0238P)2 + 298.6042P] whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 1.82 e AÊÿ3
min=ÿ1.87 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.00031 (3) Absolute structure: Flack (1983) Flack parameter = 0.010 (13); 2064
Friedel pairs
Table 1
Selected geometric parameters (AÊ,).
Hf1ÐS7 2.554 (5)
Hf1ÐS6i 2.586 (5)
Hf1ÐS9 2.604 (5)
Hf1ÐS8 2.615 (5)
Hf1ÐS3 2.618 (5)
Hf1ÐS2 2.632 (5)
Hf1ÐS5i 2.713 (5)
Hf2ÐS14ii 2.570 (5)
Hf2ÐS13 2.574 (5)
Hf2ÐS11 2.597 (5)
Hf2ÐS16ii 2.611 (5)
Hf2ÐS17ii 2.640 (5)
Hf2ÐS10 2.644 (5)
Hf2ÐS12 2.712 (5)
P1ÐS1 1.969 (8)
P1ÐS2 2.010 (7)
P1ÐS3 2.032 (8)
P1ÐS4 2.172 (8)
P2ÐS7 2.023 (7)
P2ÐS5 2.039 (7)
P2ÐS6 2.046 (7)
P2ÐS4 2.115 (7)
P3ÐS9 2.017 (7)
P3ÐS10 2.037 (7)
P3ÐS8 2.047 (7)
P3ÐS11 2.051 (7)
P4ÐS14 2.028 (8)
P4ÐS12 2.031 (7)
P4ÐS13 2.045 (7)
P4ÐS15 2.132 (7)
P5ÐS18 1.982 (8)
P5ÐS17 2.014 (8)
P5ÐS16 2.024 (7)
P5ÐS15 2.160 (8)
S1ÐP1ÐS2 119.8 (3)
S1ÐP1ÐS3 116.4 (4)
S2ÐP1ÐS3 101.9 (3)
S1ÐP1ÐS4 103.4 (3)
S2ÐP1ÐS4 105.1 (3)
S3ÐP1ÐS4 109.6 (3)
S7ÐP2ÐS5 105.7 (3)
S7ÐP2ÐS6 115.8 (3)
S5ÐP2ÐS6 108.2 (3)
S7ÐP2ÐS4 113.3 (3)
S5ÐP2ÐS4 106.2 (3)
S6ÐP2ÐS4 107.1 (3)
S9ÐP3ÐS10 114.0 (3)
S9ÐP3ÐS8 103.6 (3)
S10ÐP3ÐS8 111.9 (3)
S9ÐP3ÐS11 113.0 (3)
S10ÐP3ÐS11 103.0 (3)
S8ÐP3ÐS11 111.6 (3)
S14ÐP4ÐS12 107.1 (3)
S14ÐP4ÐS13 115.0 (3)
S12ÐP4ÐS13 107.2 (3)
S14ÐP4ÐS15 112.9 (3)
S12ÐP4ÐS15 107.1 (3)
S13ÐP4ÐS15 107.1 (3)
S18ÐP5ÐS17 119.1 (3)
S18ÐP5ÐS16 115.1 (3)
S17ÐP5ÐS16 101.8 (3)
S18ÐP5ÐS15 103.6 (3)
S17ÐP5ÐS15 106.6 (3)
S16ÐP5ÐS15 110.4 (3)
Symmetry codes: (i)xÿ1
2;12y;z; (ii)xÿ12;yÿ12;z.
Acta Cryst.(2004). E60, i42±i44 Andreas Gutzmannet al. Cs3Hf2(P2S7)2(PS4)
i43
inorganic papers
Figure 2
Interconnection of the two distinct HfS7 polyhedra via pentadentate
inorganic papers
i44
Andreas Gutzmannet al. Cs3Hf2(P2S7)2(PS4) Acta Cryst.(2004). E60, i42±i44The absolute structure was determined and, according to the Flack
xtest, is in agreement with the selected setting. In addition, re®ne-ment of the inverse structure leads to signi®cantly poorer reliability factors (Rfor all 4119Fo> 4(Fo) = 0.071;wRfor all re¯ections = 0.169).
Data collection:IPDS Program Package(Stoe & Cie, 1998); cell re®nement:IPDS Program Package; data reduction:IPDS Program Package; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:DIAMOND (Brandenburg, 1999);
soft-ware used to prepare material for publication: CIFTAB in
SHELXTL(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.
Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Cieren, X., Angenault, J., Couturier, J.-C. & Quarton, M. (1994).Powder Diffr. 9, 105±107.
Derstroff, V., Tremel, W., Regelsky, G., Schmedt auf der GuÈnne, J. & Eckert, H. (2002).Solid State Sci.4, 731±745.
Do, J., Lee, K. & Yun, H. (1996).J. Solid State Chem.125, 30±36. Flack, H. D. (1983).Acta Cryst.A39, 876±881.
Gutzmann, A., NaÈther, C. & Bensch, W. (2004).Solid State Sci.In the press. Jandali, M. Z., Eulenberger, G. & Hahn, H. (1980).Z. Anorg. Allg. Chem.470,
39±44.
Lott, D. R., Fincher, T., LeBret, G. C., Cleary, D. A. & Breneman, G. L. (1999).
J. Solid State Chem.143, 239±245.
Shannon, R. D. (1976).Acta Cryst.A32, 751±767.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Simon, A., Hahn, H. & Peters, K. (1985).Z. Naturforsch. Teil B,40, 730±732. Simon, A., Peters, K., Peters, E.-M. & Hahn, H. (1982).Z. Anorg. Allg. Chem.
491, 295±300.
Stoe & Cie (1998). IPDS Program Package (Version 2.89), X-SHAPE
(Version 1.03) and X-RED32 (Version 1.03). Stoe & Cie, Darmstadt, Germany.
Figure 3
supporting information
sup-1 Acta Cryst. (2004). E60, i42–i44
supporting information
Acta Cryst. (2004). E60, i42–i44 [https://doi.org/10.1107/S1600536804002880]
Cs
3Hf
2(P
2S
7)
2(PS
4)
Andreas Gutzmann, Christian N
ä
ther and Wolfgang Bensch
tricaesium dihafnium pentaphosphorus octadecasulfide
Crystal data
Cs3Hf2(P2S7)2(PS4)
Mr = 1487.64
Monoclinic, Cc
Hall symbol: C -2yc
a = 9.3168 (4) Å
b = 9.8985 (6) Å
c = 34.0830 (17) Å
β = 94.236 (6)°
V = 3134.6 (3) Å3
Z = 4
F(000) = 2688
Dx = 3.152 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8000 reflections
θ = 1.3–23.3°
µ = 11.51 mm−1
T = 180 K Plate, yellow 0.2 × 0.2 × 0.1 mm
Data collection
Stoe Image Plate Diffraction System diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ scans
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 1998)
Tmin = 0.120, Tmax = 0.312
9627 measured reflections 4211 independent reflections 4119 reflections with I > 2σ(I)
Rint = 0.041
θmax = 23.1°, θmin = 2.4°
h = −10→10
k = −10→10
l = −37→37
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.104
S = 1.15 4211 reflections 254 parameters 2 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
w = 1/[σ2(F
o2) + (0.0238P)2 + 298.6042P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 1.82 e Å−3
Δρmin = −1.87 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
supporting information
sup-2 Acta Cryst. (2004). E60, i42–i44
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) 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
Hf1 0.56305 (8) 0.41115 (8) 0.34548 (3) 0.0134 (2) Hf2 0.66761 (7) 0.29213 (8) 0.53642 (3) 0.0122 (2) P1 0.5973 (6) 0.2515 (6) 0.26157 (16) 0.0158 (12) P2 0.8836 (6) 0.1871 (5) 0.32596 (15) 0.0129 (11) P3 0.5879 (5) 0.3522 (5) 0.44087 (15) 0.0114 (11) P4 0.9599 (6) 0.4668 (5) 0.55559 (15) 0.0136 (11) P5 1.0287 (6) 0.7216 (5) 0.62040 (15) 0.0135 (11) S1 0.5236 (7) 0.1750 (6) 0.21068 (16) 0.0280 (14) S2 0.5910 (6) 0.4522 (5) 0.27014 (16) 0.0183 (12) S3 0.5074 (6) 0.1804 (5) 0.31004 (14) 0.0157 (11) S4 0.8247 (6) 0.2005 (5) 0.26494 (15) 0.0181 (11) S5 1.1028 (5) 0.1779 (5) 0.33151 (16) 0.0170 (11) S6 0.8050 (5) 0.0076 (5) 0.34505 (15) 0.0148 (11) S7 0.8302 (6) 0.3532 (5) 0.35626 (15) 0.0164 (11) S8 0.4787 (6) 0.2409 (5) 0.39774 (14) 0.0162 (11) S9 0.6390 (6) 0.5234 (5) 0.41293 (15) 0.0177 (11) S10 0.7611 (5) 0.2505 (5) 0.46605 (15) 0.0143 (11) S11 0.4653 (6) 0.3863 (5) 0.48743 (15) 0.0174 (11) S12 0.9568 (5) 0.2629 (5) 0.54899 (16) 0.0165 (11) S13 0.7608 (5) 0.5369 (5) 0.53606 (15) 0.0135 (11) S14 1.1250 (6) 0.5378 (5) 0.52590 (16) 0.0174 (12) S15 0.9865 (6) 0.5071 (5) 0.61715 (14) 0.0159 (11) S16 0.9323 (5) 0.8168 (5) 0.57293 (15) 0.0145 (11) S17 1.2386 (6) 0.7460 (6) 0.61166 (15) 0.0180 (12) S18 0.9582 (6) 0.7748 (6) 0.67164 (15) 0.0228 (12) Cs1 0.20183 (16) 0.35539 (15) 0.24510 (5) 0.0290 (4) Cs2 0.11285 (15) 0.39023 (14) 0.43180 (4) 0.0252 (4) Cs3 0.61868 (14) 0.59948 (14) 0.63653 (4) 0.0261 (4)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2004). E60, i42–i44
P3 0.013 (3) 0.012 (2) 0.010 (2) 0.003 (2) 0.000 (2) −0.002 (2) P4 0.013 (3) 0.015 (3) 0.013 (3) −0.005 (2) −0.003 (2) 0.001 (2) P5 0.016 (3) 0.019 (3) 0.005 (2) −0.004 (2) 0.000 (2) 0.000 (2) S1 0.035 (4) 0.036 (3) 0.012 (3) 0.006 (3) −0.005 (3) 0.000 (2) S2 0.021 (3) 0.015 (3) 0.019 (3) 0.009 (2) 0.002 (2) 0.006 (2) S3 0.023 (3) 0.016 (3) 0.009 (2) −0.001 (2) 0.001 (2) −0.002 (2) S4 0.017 (3) 0.026 (3) 0.012 (3) 0.006 (2) 0.004 (2) 0.001 (2) S5 0.011 (3) 0.016 (3) 0.024 (3) −0.002 (2) 0.004 (2) 0.006 (2) S6 0.010 (3) 0.011 (3) 0.024 (3) 0.000 (2) 0.005 (2) 0.002 (2) S7 0.011 (3) 0.018 (3) 0.020 (3) 0.006 (2) −0.003 (2) −0.005 (2) S8 0.025 (3) 0.013 (3) 0.010 (2) −0.004 (2) −0.002 (2) 0.004 (2) S9 0.027 (3) 0.014 (3) 0.013 (3) 0.001 (2) 0.003 (2) 0.001 (2) S10 0.013 (3) 0.018 (3) 0.012 (2) 0.004 (2) 0.004 (2) 0.002 (2) S11 0.013 (3) 0.025 (3) 0.014 (3) 0.004 (2) −0.002 (2) −0.001 (2) S12 0.009 (2) 0.013 (3) 0.027 (3) 0.0040 (19) −0.004 (2) 0.000 (2) S13 0.009 (3) 0.012 (2) 0.019 (3) −0.006 (2) 0.000 (2) 0.001 (2) S14 0.018 (3) 0.014 (3) 0.021 (3) −0.002 (2) 0.008 (2) 0.000 (2) S15 0.016 (3) 0.021 (3) 0.010 (3) −0.007 (2) −0.003 (2) 0.005 (2) S16 0.014 (3) 0.017 (3) 0.013 (3) 0.004 (2) 0.002 (2) 0.003 (2) S17 0.013 (3) 0.028 (3) 0.013 (3) −0.011 (2) 0.000 (2) 0.000 (2) S18 0.031 (3) 0.032 (3) 0.005 (2) −0.003 (3) 0.002 (2) −0.005 (2) Cs1 0.0263 (8) 0.0294 (8) 0.0302 (8) −0.0045 (6) −0.0049 (7) 0.0040 (6) Cs2 0.0236 (8) 0.0270 (8) 0.0243 (8) −0.0021 (6) −0.0023 (6) −0.0080 (6) Cs3 0.0238 (8) 0.0247 (8) 0.0297 (8) 0.0031 (6) 0.0006 (7) −0.0046 (6)
Geometric parameters (Å, º)
Hf1—S7 2.554 (5) S5—Cs1vi 3.607 (5)
Hf1—S6i 2.586 (5) S5—Cs2vi 4.008 (6)
Hf1—S9 2.604 (5) S6—Hf1iii 2.586 (5)
Hf1—S8 2.615 (5) S6—Cs2iii 3.752 (5)
Hf1—S3 2.618 (5) S6—Cs1iii 3.783 (5)
Hf1—S2 2.632 (5) S7—Cs2vi 3.563 (5)
Hf1—S5i 2.713 (5) S8—Cs2iii 3.840 (5)
Hf1—Cs1 4.6512 (17) S8—Cs2 3.967 (6)
Hf2—S14ii 2.570 (5) S9—Cs2iv 3.699 (5)
Hf2—S13 2.574 (5) S10—Cs2vi 3.818 (5)
Hf2—S11 2.597 (5) S10—Cs2iii 3.969 (5)
Hf2—S16ii 2.611 (5) S11—Cs2 3.669 (5)
Hf2—S17ii 2.640 (5) S12—Cs3iii 3.623 (5)
Hf2—S10 2.644 (5) S13—Cs3 3.812 (5)
Hf2—S12 2.712 (5) S14—Hf2iv 2.570 (5)
Hf2—Cs3 4.6190 (16) S14—Cs2vi 3.518 (6)
P1—S1 1.969 (8) S15—Cs3 3.654 (6)
P1—S2 2.010 (7) S16—Hf2iv 2.611 (5)
P1—S3 2.032 (8) S16—Cs3iv 3.872 (5)
P1—S4 2.172 (8) S17—Hf2iv 2.640 (5)
supporting information
sup-4 Acta Cryst. (2004). E60, i42–i44
P1—Cs1iii 4.088 (6) S17—Cs3vi 3.863 (6)
P2—S7 2.023 (7) S18—Cs1vii 3.499 (6)
P2—S5 2.039 (7) S18—Cs3 3.727 (6)
P2—S6 2.046 (7) S18—Cs3iv 3.776 (6)
P2—S4 2.115 (7) Cs1—S18viii 3.499 (6)
P3—S9 2.017 (7) Cs1—S5ix 3.607 (5)
P3—S10 2.037 (7) Cs1—S4i 3.650 (6)
P3—S8 2.047 (7) Cs1—S1i 3.722 (6)
P3—S11 2.051 (7) Cs1—S6i 3.783 (5)
P4—S14 2.028 (8) Cs1—S4ix 3.938 (6)
P4—S12 2.031 (7) Cs1—P1i 4.088 (6)
P4—S13 2.045 (7) Cs2—S14ix 3.518 (6)
P4—S15 2.132 (7) Cs2—S7ix 3.563 (5)
P5—S18 1.982 (8) Cs2—S9ii 3.699 (5)
P5—S17 2.014 (8) Cs2—S6i 3.752 (5)
P5—S16 2.024 (7) Cs2—S10ix 3.818 (6)
P5—S15 2.160 (8) Cs2—S8i 3.840 (5)
P5—Cs3iv 3.864 (6) Cs2—S10i 3.969 (5)
P5—Cs3 4.083 (6) Cs2—S5ix 4.008 (6)
S1—Cs3v 3.534 (6) Cs3—S1x 3.534 (6)
S1—Cs1iii 3.722 (6) Cs3—S12i 3.623 (5)
S1—Cs1 3.751 (6) Cs3—S18ii 3.776 (6)
S2—Cs1 3.787 (6) Cs3—S17ii 3.788 (6)
S3—Cs1 3.882 (5) Cs3—S17ix 3.863 (6)
S4—Cs1iii 3.650 (6) Cs3—P5ii 3.864 (6)
S4—Cs1vi 3.938 (6) Cs3—S16ii 3.872 (5)
S5—Hf1iii 2.713 (5)
S7—Hf1—S6i 168.37 (16) S18viii—Cs1—S6i 154.05 (13)
S7—Hf1—S9 76.73 (17) S5ix—Cs1—S6i 61.45 (12)
S6i—Hf1—S9 92.26 (17) S4i—Cs1—S6i 53.50 (11)
S7—Hf1—S8 95.50 (18) S1i—Cs1—S6i 91.32 (12)
S6i—Hf1—S8 85.17 (17) S1—Cs1—S6i 108.39 (12)
S9—Hf1—S8 75.48 (16) S18viii—Cs1—S2 144.52 (13)
S7—Hf1—S3 91.62 (17) S5ix—Cs1—S2 103.75 (12)
S6i—Hf1—S3 99.61 (16) S4i—Cs1—S2 55.90 (11)
S9—Hf1—S3 144.23 (16) S1i—Cs1—S2 104.68 (13)
S8—Hf1—S3 72.10 (16) S1—Cs1—S2 54.33 (12)
S7—Hf1—S2 90.53 (17) S6i—Cs1—S2 61.38 (11)
S6i—Hf1—S2 95.54 (16) S18viii—Cs1—S3 130.79 (12)
S9—Hf1—S2 139.08 (17) S5ix—Cs1—S3 62.50 (12)
S8—Hf1—S2 145.15 (16) S4i—Cs1—S3 96.04 (11)
S3—Hf1—S2 73.44 (16) S1i—Cs1—S3 148.23 (12)
S7—Hf1—S5i 95.72 (17) S1—Cs1—S3 52.89 (11)
S6i—Hf1—S5i 77.21 (16) S6i—Cs1—S3 62.45 (10)
S9—Hf1—S5i 73.02 (16) S2—Cs1—S3 48.30 (11)
S8—Hf1—S5i 142.99 (17) S18viii—Cs1—S4ix 55.91 (12)
supporting information
sup-5 Acta Cryst. (2004). E60, i42–i44
S2—Hf1—S5i 69.75 (16) S4i—Cs1—S4ix 127.17 (15)
S7—Hf1—Cs1 136.35 (12) S1i—Cs1—S4ix 90.12 (13)
S6i—Hf1—Cs1 54.39 (12) S1—Cs1—S4ix 127.75 (13)
S9—Hf1—Cs1 146.59 (12) S6i—Cs1—S4ix 99.85 (11)
S8—Hf1—Cs1 100.78 (11) S2—Cs1—S4ix 155.74 (12)
S3—Hf1—Cs1 56.57 (11) P1—Cs1—S4ix 137.04 (12)
S2—Hf1—Cs1 54.49 (12) S3—Cs1—S4ix 110.76 (11)
S5i—Hf1—Cs1 95.00 (11) S14ix—Cs2—S7ix 132.34 (13)
S14ii—Hf2—S13 165.98 (17) S14ix—Cs2—S11 64.28 (12)
S14ii—Hf2—S11 99.47 (17) S7ix—Cs2—S11 163.31 (13)
S13—Hf2—S11 83.57 (16) S14ix—Cs2—S9ii 124.61 (12)
S14ii—Hf2—S16ii 91.79 (17) S7ix—Cs2—S9ii 80.09 (12)
S13—Hf2—S16ii 102.11 (16) S11—Cs2—S9ii 90.66 (12)
S11—Hf2—S16ii 71.20 (16) S14ix—Cs2—S6i 127.21 (12)
S14ii—Hf2—S17ii 89.49 (17) S7ix—Cs2—S6i 80.37 (12)
S13—Hf2—S17ii 96.15 (16) S11—Cs2—S6i 87.11 (12)
S11—Hf2—S17ii 143.54 (18) S9ii—Cs2—S6i 97.21 (12)
S16ii—Hf2—S17ii 73.27 (16) S14ix—Cs2—S10ix 80.92 (12)
S14ii—Hf2—S10 77.21 (17) S7ix—Cs2—S10ix 65.06 (12)
S13—Hf2—S10 90.48 (16) S11—Cs2—S10ix 126.43 (12)
S11—Hf2—S10 75.21 (16) S9ii—Cs2—S10ix 76.50 (12)
S16ii—Hf2—S10 142.32 (16) S6i—Cs2—S10ix 145.41 (11)
S17ii—Hf2—S10 141.12 (17) S14ix—Cs2—S8i 83.58 (12)
S14ii—Hf2—S12 93.38 (16) S7ix—Cs2—S8i 70.60 (11)
S13—Hf2—S12 76.69 (15) S11—Cs2—S8i 115.13 (12)
S11—Hf2—S12 143.64 (17) S9ii—Cs2—S8i 149.21 (11)
S16ii—Hf2—S12 142.56 (16) S6i—Cs2—S8i 69.23 (11)
S17ii—Hf2—S12 69.72 (16) S10ix—Cs2—S8i 98.76 (12)
S10—Hf2—S12 74.74 (16) S14ix—Cs2—S8 116.81 (12)
S14ii—Hf2—Cs3 136.52 (13) S7ix—Cs2—S8 110.82 (12)
S13—Hf2—Cs3 55.62 (12) S11—Cs2—S8 52.53 (11) S11—Hf2—Cs3 97.58 (12) S9ii—Cs2—S8 60.94 (12)
S16ii—Hf2—Cs3 56.93 (11) S6i—Cs2—S8 54.16 (10)
S17ii—Hf2—Cs3 55.10 (13) S10ix—Cs2—S8 136.88 (11)
S10—Hf2—Cs3 146.09 (12) S8i—Cs2—S8 121.06 (14)
S12—Hf2—Cs3 96.01 (11) S14ix—Cs2—S10i 51.09 (11)
S1—P1—S2 119.8 (3) S7ix—Cs2—S10i 121.84 (12)
S1—P1—S3 116.4 (4) S11—Cs2—S10i 65.08 (11)
S2—P1—S3 101.9 (3) S9ii—Cs2—S10i 155.14 (12)
S1—P1—S4 103.4 (3) S6i—Cs2—S10i 77.15 (11)
S2—P1—S4 105.1 (3) S10ix—Cs2—S10i 121.56 (14)
S3—P1—S4 109.6 (3) S8i—Cs2—S10i 51.32 (10)
S7—P2—S5 105.7 (3) S8—Cs2—S10i 97.64 (11)
S7—P2—S6 115.8 (3) S14ix—Cs2—S5ix 172.89 (12)
S5—P2—S6 108.2 (3) S7ix—Cs2—S5ix 50.23 (11)
S7—P2—S4 113.3 (3) S11—Cs2—S5ix 113.51 (12)
S5—P2—S4 106.2 (3) S9ii—Cs2—S5ix 48.29 (11)
supporting information
sup-6 Acta Cryst. (2004). E60, i42–i44
S9—P3—S10 114.0 (3) S10ix—Cs2—S5ix 95.99 (11)
S9—P3—S8 103.6 (3) S8i—Cs2—S5ix 103.27 (11)
S10—P3—S8 111.9 (3) S8—Cs2—S5ix 61.41 (10)
S9—P3—S11 113.0 (3) S10i—Cs2—S5ix 135.05 (11)
S10—P3—S11 103.0 (3) S1x—Cs3—S12i 101.29 (13)
S8—P3—S11 111.6 (3) S1x—Cs3—S15 125.13 (13)
S14—P4—S12 107.1 (3) S12i—Cs3—S15 107.57 (12)
S14—P4—S13 115.0 (3) S1x—Cs3—S18 74.21 (14)
S12—P4—S13 107.2 (3) S12i—Cs3—S18 110.39 (13)
S14—P4—S15 112.9 (3) S15—Cs3—S18 52.37 (12) S12—P4—S15 107.1 (3) S1x—Cs3—S18ii 100.67 (14)
S13—P4—S15 107.1 (3) S12i—Cs3—S18ii 119.36 (12)
S18—P5—S17 119.1 (3) S15—Cs3—S18ii 104.06 (12)
S18—P5—S16 115.1 (3) S18—Cs3—S18ii 129.87 (16)
S17—P5—S16 101.8 (3) S1x—Cs3—S17ii 146.86 (13)
S18—P5—S15 103.6 (3) S12i—Cs3—S17ii 109.86 (12)
S17—P5—S15 106.6 (3) S15—Cs3—S17ii 55.42 (11)
S16—P5—S15 110.4 (3) S18—Cs3—S17ii 104.16 (13)
Cs3v—S1—Cs1iii 129.26 (19) S18ii—Cs3—S17ii 54.20 (12)
Cs3v—S1—Cs1 99.86 (15) S1x—Cs3—S13 150.12 (13)
Cs1iii—S1—Cs1 130.87 (18) S12i—Cs3—S13 58.93 (12)
P2—S4—P1 104.4 (3) S15—Cs3—S13 53.44 (11)
Cs1iii—S4—Cs1vi 127.17 (15) S18—Cs3—S13 91.21 (12)
Cs1vi—S5—Cs2vi 116.72 (13) S18ii—Cs3—S13 108.56 (11)
Cs2iii—S8—Cs2 121.06 (14) S17ii—Cs3—S13 61.39 (11)
Cs2vi—S10—Cs2iii 121.56 (14) S1x—Cs3—S17ix 69.24 (13)
P4—S15—P5 104.0 (3) S12i—Cs3—S17ix 48.12 (11)
Cs3iv—S17—Cs3vi 125.34 (14) S15—Cs3—S17ix 155.67 (12)
Cs1vii—S18—Cs3 123.27 (16) S18—Cs3—S17ix 129.66 (13)
Cs1vii—S18—Cs3iv 106.81 (15) S18ii—Cs3—S17ix 90.63 (12)
Cs3—S18—Cs3iv 129.87 (16) S17ii—Cs3—S17ix 125.34 (14)
S18viii—Cs1—S5ix 102.32 (13) S13—Cs3—S17ix 103.74 (11)
S18viii—Cs1—S4i 130.94 (13) S1x—Cs3—S16ii 136.99 (14)
S5ix—Cs1—S4i 113.59 (12) S12i—Cs3—S16ii 73.70 (11)
S18viii—Cs1—S1i 80.60 (13) S15—Cs3—S16ii 96.07 (11)
S5ix—Cs1—S1i 122.42 (14) S18—Cs3—S16ii 148.36 (12)
S4i—Cs1—S1i 52.37 (13) S18ii—Cs3—S16ii 52.45 (11)
S18viii—Cs1—S1 95.28 (13) S17ii—Cs3—S16ii 48.28 (11)
S5ix—Cs1—S1 106.38 (13) S13—Cs3—S16ii 63.31 (11)
S4i—Cs1—S1 104.87 (13) S17ix—Cs3—S16ii 77.43 (11)
S1i—Cs1—S1 130.87 (18)
