Acta Cryst. (2007). E63, i167 [ doi:10.1107/S1600536807031029 ]
The title compound, dicaesium tetrathiotungstate(VI), was obtained from a dilute aqueous solution containing equimolar quantities of Cs2CO3 and (NH4)2[WS4]. The compound crystallizes in the orthorhombic space group Pnma and is isotypic with Cs2[MoS4], Rb2[WS4], (NH4)2[WS4] and K2[MoS4]. The structure contains discrete slightly distorted tetrahedral [WS4]2- anions (m symmetry), separated by Cs+ cations. One of the two unique Cs+ cations (both located on mirror planes) is surrounded by nine S atoms and the other by ten S atoms.
The title compound was crystallized from a very dilute aqueous solution (90 ml) containing equimolar quantities of (NH4)2[WS4] (174 mg, 0.5 mmol) and Cs2CO3 (163 mg, 0.5 mmol). It is to be noted that the use of more concentrated solutions leads to the formation of microcrystalline products. The crystals were filtered, washed with ice-cold water (2 ml), followed by 2-propanol (10 ml) and diethyl ether (10 ml), and air dried. The yield of the air stable yellow crystals was approximately 50%. The mid IR spectrum of (I) exhibits no signals above 500 cm−1. The intense signal at 460 cm−1 can be assigned to the triply degenerate asymmetric stretching vibration of the [WS4]2− tetrahedron. The Raman spectrum shows intense signals at 481 and 179 cm−1 and a weak signal at 460 cm−1, as expected for the tetrathiotungstate anion.
The largest peak in the residual electron density map is located at a distance of 0.68 Å from Cs2 and the deepest hole 0.78 Å from W1.
Data collection: DIF4 (Stoe & Cie, 1998); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).
![[Figure 1]](./wm2130fig1thm.gif)
| Fig. 1. Part of the crystal structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, −y + 1/2, z] |
![[Figure 2]](./wm2130fig2thm.gif)
| Fig. 2. A perspective view of the crystal packing of (I) along the b axis. Cs atoms are represented as blue spheres, W atoms as black spheres and S atoms as yellow spheres. |
![[Figure 3]](./wm2130fig3thm.gif)
| Fig. 3. A view of the surroundings of the Cs1 cation showing Cs1 linked to six different [WS4]2− units via nine S atoms (Cs···S distances are shown as dashed lines). [Symmetry codes: (ii) x − 1/2, y, −z + 1/2; (iii) −x + 3/2, y + 1/2, z − 1/2; (iv) −x + 3/2, −y, z − 1/2; (v) −x + 1, y + 1/2, −z + 1; (vi)-x + 1, −y, −z + 1; (vii) −x + 3/2, −y + 1, z − 1/2.] |
| Cs2[WS4] | F000 = 992 |
| Mr = 577.91 | Dx = 4.129 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 8000 reflections |
| a = 10.0579 (9) Å | θ = 3.0–30.0º |
| b = 7.2362 (5) Å | µ = 20.95 mm−1 |
| c = 12.7740 (9) Å | T = 170 (2) K |
| V = 929.70 (12) Å3 | Block, yellow |
| Z = 4 | 0.08 × 0.07 × 0.04 mm |
| STOE IPDS 1 diffractometer | 1492 independent reflections |
| Radiation source: fine-focus sealed tube | 1322 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.060 |
| T = 170(2) K | θmax = 30.4º |
| φ–scans | θmin = 2.6º |
| Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | h = −14→14 |
| Tmin = 0.211, Tmax = 0.442 | k = −10→10 |
| 11509 measured reflections | l = −17→17 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0492P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.027 | (Δ/σ)max = 0.001 |
| wR(F2) = 0.069 | Δρmax = 2.31 e Å−3 |
| S = 1.03 | Δρmin = −2.62 e Å−3 |
| 1492 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 41 parameters | Extinction coefficient: 0.00164 (18) |
| Primary atom site location: structure-invariant direct methods |
| Cs2[WS4] | V = 929.70 (12) Å3 |
| Mr = 577.91 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 10.0579 (9) Å | µ = 20.95 mm−1 |
| b = 7.2362 (5) Å | T = 170 (2) K |
| c = 12.7740 (9) Å | 0.08 × 0.07 × 0.04 mm |
| STOE IPDS 1 diffractometer | 1492 independent reflections |
| Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | 1322 reflections with I > 2σ(I) |
| Tmin = 0.211, Tmax = 0.442 | Rint = 0.060 |
| 11509 measured reflections |
| R[F2 > 2σ(F2)] = 0.027 | 41 parameters |
| wR(F2) = 0.069 | Δρmax = 2.31 e Å−3 |
| S = 1.03 | Δρmin = −2.62 e Å−3 |
| 1492 reflections |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| W1 | 0.75191 (3) | 0.2500 | 0.57843 (2) | 0.00972 (10) | |
| Cs1 | 0.53579 (4) | 0.2500 | 0.16913 (3) | 0.01439 (12) | |
| Cs2 | 0.84172 (5) | 0.2500 | 0.89664 (4) | 0.01797 (12) | |
| S1 | 0.7079 (2) | 0.2500 | 0.41025 (14) | 0.0169 (3) | |
| S2 | 0.96862 (18) | 0.2500 | 0.60598 (15) | 0.0169 (3) | |
| S3 | 0.66310 (14) | 0.00367 (16) | 0.64964 (12) | 0.0186 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| W1 | 0.00771 (15) | 0.00837 (14) | 0.01308 (15) | 0.000 | 0.00028 (8) | 0.000 |
| Cs1 | 0.0121 (2) | 0.01475 (19) | 0.0163 (2) | 0.000 | −0.00075 (15) | 0.000 |
| Cs2 | 0.0160 (2) | 0.0149 (2) | 0.0230 (2) | 0.000 | 0.00236 (17) | 0.000 |
| S1 | 0.0167 (9) | 0.0187 (8) | 0.0153 (8) | 0.000 | −0.0041 (6) | 0.000 |
| S2 | 0.0094 (7) | 0.0197 (8) | 0.0215 (8) | 0.000 | −0.0022 (6) | 0.000 |
| S3 | 0.0164 (6) | 0.0125 (5) | 0.0268 (7) | −0.0011 (4) | 0.0048 (5) | 0.0056 (4) |
| W1—S3 | 2.1915 (12) | Cs2—S1v | 3.6564 (4) |
| W1—S3i | 2.1915 (12) | Cs2—S1iv | 3.6564 (4) |
| W1—S1 | 2.1935 (18) | Cs2—S3xii | 3.7170 (15) |
| W1—S2 | 2.2079 (18) | Cs2—S3v | 3.7170 (15) |
| W1—Cs2ii | 4.1380 (7) | Cs2—S3xiii | 3.7384 (14) |
| W1—Cs2 | 4.1640 (6) | Cs2—S3xiv | 3.7384 (14) |
| W1—Cs1iii | 4.2606 (6) | Cs2—S2ii | 3.7527 (19) |
| W1—Cs1iv | 4.3580 (4) | Cs2—S2 | 3.926 (2) |
| W1—Cs1v | 4.3580 (4) | Cs2—S3 | 4.0448 (16) |
| W1—Cs2vi | 4.4011 (4) | Cs2—S3i | 4.0448 (16) |
| W1—Cs2vii | 4.4011 (4) | Cs2—W1xiv | 4.1380 (7) |
| Cs1—S1viii | 3.451 (2) | S1—Cs1iii | 3.451 (2) |
| Cs1—S1 | 3.5331 (19) | S1—Cs2vi | 3.6564 (4) |
| Cs1—S3ix | 3.5502 (14) | S1—Cs2vii | 3.6564 (4) |
| Cs1—S3vi | 3.5502 (14) | S2—Cs1iii | 3.579 (2) |
| Cs1—S3x | 3.5680 (14) | S2—Cs1iv | 3.7072 (5) |
| Cs1—S3xi | 3.5680 (14) | S2—Cs1v | 3.7072 (5) |
| Cs1—S2viii | 3.579 (2) | S2—Cs2xiv | 3.7527 (19) |
| Cs1—S2vi | 3.7072 (5) | S3—Cs1v | 3.5502 (14) |
| Cs1—S2vii | 3.7072 (5) | S3—Cs1xi | 3.5680 (14) |
| Cs1—W1viii | 4.2606 (6) | S3—Cs2vi | 3.7170 (15) |
| Cs1—W1vii | 4.3580 (4) | S3—Cs2ii | 3.7384 (14) |
| Cs1—W1vi | 4.3580 (4) | ||
| S3—W1—S3i | 108.86 (7) | S3x—Cs1—W1vi | 150.96 (2) |
| S3—W1—S1 | 108.92 (5) | S3xi—Cs1—W1vi | 91.15 (2) |
| S3i—W1—S1 | 108.92 (5) | S2viii—Cs1—W1vi | 80.295 (18) |
| S3—W1—S2 | 109.65 (4) | S2vi—Cs1—W1vi | 30.43 (3) |
| S3i—W1—S2 | 109.65 (4) | S2vii—Cs1—W1vi | 139.31 (3) |
| S1—W1—S2 | 110.82 (8) | W1viii—Cs1—W1vi | 97.530 (9) |
| S3—W1—Cs2ii | 64.00 (4) | W1vii—Cs1—W1vi | 112.242 (12) |
| S3i—W1—Cs2ii | 64.00 (4) | S1v—Cs2—S1iv | 163.39 (6) |
| S1—W1—Cs2ii | 82.76 (5) | S1v—Cs2—S3xii | 116.46 (4) |
| S2—W1—Cs2ii | 166.41 (5) | S1iv—Cs2—S3xii | 57.87 (3) |
| S3—W1—Cs2 | 71.53 (4) | S1v—Cs2—S3v | 57.87 (3) |
| S3i—W1—Cs2 | 71.53 (4) | S1iv—Cs2—S3v | 116.46 (4) |
| S1—W1—Cs2 | 179.12 (6) | S3xii—Cs2—S3v | 59.19 (4) |
| S2—W1—Cs2 | 68.30 (5) | S1v—Cs2—S3xiii | 126.67 (4) |
| Cs2ii—W1—Cs2 | 98.115 (10) | S1iv—Cs2—S3xiii | 69.74 (4) |
| S3—W1—Cs1iii | 125.54 (4) | S3xii—Cs2—S3xiii | 85.03 (4) |
| S3i—W1—Cs1iii | 125.54 (4) | S3v—Cs2—S3xiii | 112.60 (2) |
| S1—W1—Cs1iii | 53.73 (5) | S1v—Cs2—S3xiv | 69.74 (4) |
| S2—W1—Cs1iii | 57.09 (5) | S1iv—Cs2—S3xiv | 126.67 (4) |
| Cs2ii—W1—Cs1iii | 136.492 (11) | S3xii—Cs2—S3xiv | 112.60 (2) |
| Cs2—W1—Cs1iii | 125.393 (12) | S3v—Cs2—S3xiv | 85.03 (4) |
| S3—W1—Cs1iv | 139.88 (4) | S3xiii—Cs2—S3xiv | 56.95 (4) |
| S3i—W1—Cs1iv | 54.13 (4) | S1v—Cs2—S2ii | 82.19 (3) |
| S1—W1—Cs1iv | 111.06 (3) | S1iv—Cs2—S2ii | 82.19 (3) |
| S2—W1—Cs1iv | 58.259 (13) | S3xii—Cs2—S2ii | 89.70 (4) |
| Cs2ii—W1—Cs1iv | 117.909 (7) | S3v—Cs2—S2ii | 89.70 (4) |
| Cs2—W1—Cs1iv | 68.543 (7) | S3xiii—Cs2—S2ii | 149.68 (2) |
| Cs1iii—W1—Cs1iv | 82.470 (9) | S3xiv—Cs2—S2ii | 149.68 (2) |
| S3—W1—Cs1v | 54.13 (4) | S1v—Cs2—S2 | 95.12 (3) |
| S3i—W1—Cs1v | 139.88 (4) | S1iv—Cs2—S2 | 95.12 (3) |
| S1—W1—Cs1v | 111.06 (3) | S3xii—Cs2—S2 | 145.74 (3) |
| S2—W1—Cs1v | 58.259 (13) | S3v—Cs2—S2 | 145.74 (3) |
| Cs2ii—W1—Cs1v | 117.909 (7) | S3xiii—Cs2—S2 | 64.49 (3) |
| Cs2—W1—Cs1v | 68.543 (7) | S3xiv—Cs2—S2 | 64.49 (3) |
| Cs1iii—W1—Cs1v | 82.470 (8) | S2ii—Cs2—S2 | 108.46 (3) |
| Cs1iv—W1—Cs1v | 112.242 (12) | S1v—Cs2—S3 | 62.64 (3) |
| S3—W1—Cs2vi | 57.53 (4) | S1iv—Cs2—S3 | 114.37 (4) |
| S3i—W1—Cs2vi | 143.17 (4) | S3xii—Cs2—S3 | 152.884 (17) |
| S1—W1—Cs2vi | 55.946 (9) | S3v—Cs2—S3 | 117.054 (10) |
| S2—W1—Cs2vi | 107.18 (3) | S3xiii—Cs2—S3 | 118.09 (2) |
| Cs2ii—W1—Cs2vi | 80.054 (9) | S3xiv—Cs2—S3 | 92.90 (2) |
| Cs2—W1—Cs2vi | 124.159 (7) | S2ii—Cs2—S3 | 63.19 (3) |
| Cs1iii—W1—Cs2vi | 75.627 (8) | S2—Cs2—S3 | 53.61 (3) |
| Cs1iv—W1—Cs2vi | 158.065 (11) | S1v—Cs2—S3i | 114.37 (4) |
| Cs1v—W1—Cs2vi | 64.062 (9) | S1iv—Cs2—S3i | 62.64 (3) |
| S3—W1—Cs2vii | 143.17 (4) | S3xii—Cs2—S3i | 117.054 (10) |
| S3i—W1—Cs2vii | 57.53 (4) | S3v—Cs2—S3i | 152.884 (17) |
| S1—W1—Cs2vii | 55.946 (9) | S3xiii—Cs2—S3i | 92.90 (2) |
| S2—W1—Cs2vii | 107.18 (3) | S3xiv—Cs2—S3i | 118.09 (2) |
| Cs2ii—W1—Cs2vii | 80.054 (9) | S2ii—Cs2—S3i | 63.19 (3) |
| Cs2—W1—Cs2vii | 124.159 (7) | S2—Cs2—S3i | 53.61 (3) |
| Cs1iii—W1—Cs2vii | 75.627 (8) | S3—Cs2—S3i | 52.30 (3) |
| Cs1iv—W1—Cs2vii | 64.062 (9) | S1v—Cs2—W1xiv | 97.60 (3) |
| Cs1v—W1—Cs2vii | 158.065 (11) | S1iv—Cs2—W1xiv | 97.60 (3) |
| Cs2vi—W1—Cs2vii | 110.588 (13) | S3xii—Cs2—W1xiv | 86.91 (2) |
| S1viii—Cs1—S1 | 136.42 (4) | S3v—Cs2—W1xiv | 86.91 (2) |
| S1viii—Cs1—S3ix | 142.64 (3) | S3xiii—Cs2—W1xiv | 31.796 (19) |
| S1—Cs1—S3ix | 69.10 (4) | S3xiv—Cs2—W1xiv | 31.796 (19) |
| S1viii—Cs1—S3vi | 142.64 (3) | S2ii—Cs2—W1xiv | 176.10 (3) |
| S1—Cs1—S3vi | 69.10 (4) | S2—Cs2—W1xiv | 75.44 (3) |
| S3ix—Cs1—S3vi | 62.27 (4) | S3—Cs2—W1xiv | 120.19 (2) |
| S1viii—Cs1—S3x | 69.81 (4) | S3i—Cs2—W1xiv | 120.19 (2) |
| S1—Cs1—S3x | 73.08 (4) | S1v—Cs2—W1 | 90.97 (3) |
| S3ix—Cs1—S3x | 104.94 (3) | S1iv—Cs2—W1 | 90.97 (3) |
| S3vi—Cs1—S3x | 142.16 (2) | S3xii—Cs2—W1 | 147.771 (19) |
| S1viii—Cs1—S3xi | 69.81 (4) | S3v—Cs2—W1 | 147.77 (2) |
| S1—Cs1—S3xi | 73.08 (4) | S3xiii—Cs2—W1 | 91.90 (3) |
| S3ix—Cs1—S3xi | 142.16 (2) | S3xiv—Cs2—W1 | 91.90 (3) |
| S3vi—Cs1—S3xi | 104.94 (3) | S2ii—Cs2—W1 | 76.96 (3) |
| S3x—Cs1—S3xi | 61.92 (4) | S2—Cs2—W1 | 31.50 (3) |
| S1viii—Cs1—S2viii | 62.03 (4) | S3—Cs2—W1 | 30.924 (18) |
| S1—Cs1—S2viii | 161.55 (5) | S3i—Cs2—W1 | 30.924 (18) |
| S3ix—Cs1—S2viii | 95.29 (4) | W1xiv—Cs2—W1 | 106.942 (12) |
| S3vi—Cs1—S2viii | 95.29 (4) | W1—S1—Cs1iii | 95.44 (7) |
| S3x—Cs1—S2viii | 122.10 (4) | W1—S1—Cs1 | 162.32 (9) |
| S3xi—Cs1—S2viii | 122.10 (4) | Cs1iii—S1—Cs1 | 102.24 (5) |
| S1viii—Cs1—S2vi | 85.68 (3) | W1—S1—Cs2vi | 94.25 (3) |
| S1—Cs1—S2vi | 101.28 (3) | Cs1iii—S1—Cs2vi | 96.68 (3) |
| S3ix—Cs1—S2vi | 119.97 (4) | Cs1—S1—Cs2vi | 83.78 (3) |
| S3vi—Cs1—S2vi | 59.36 (3) | W1—S1—Cs2vii | 94.25 (3) |
| S3x—Cs1—S2vi | 129.54 (4) | Cs1iii—S1—Cs2vii | 96.68 (3) |
| S3xi—Cs1—S2vi | 68.43 (4) | Cs1—S1—Cs2vii | 83.78 (3) |
| S2viii—Cs1—S2vi | 77.53 (3) | Cs2vi—S1—Cs2vii | 163.39 (6) |
| S1viii—Cs1—S2vii | 85.68 (3) | W1—S2—Cs1iii | 91.71 (6) |
| S1—Cs1—S2vii | 101.28 (3) | W1—S2—Cs1iv | 91.31 (3) |
| S3ix—Cs1—S2vii | 59.36 (3) | Cs1iii—S2—Cs1iv | 102.47 (3) |
| S3vi—Cs1—S2vii | 119.97 (4) | W1—S2—Cs1v | 91.31 (3) |
| S3x—Cs1—S2vii | 68.43 (4) | Cs1iii—S2—Cs1v | 102.47 (3) |
| S3xi—Cs1—S2vii | 129.54 (4) | Cs1iv—S2—Cs1v | 154.83 (6) |
| S2viii—Cs1—S2vii | 77.53 (3) | W1—S2—Cs2xiv | 170.32 (8) |
| S2vi—Cs1—S2vii | 154.83 (6) | Cs1iii—S2—Cs2xiv | 78.61 (4) |
| S1viii—Cs1—W1viii | 30.83 (3) | Cs1iv—S2—Cs2xiv | 90.80 (3) |
| S1—Cs1—W1viii | 167.25 (4) | Cs1v—S2—Cs2xiv | 90.80 (3) |
| S3ix—Cs1—W1viii | 121.31 (3) | W1—S2—Cs2 | 80.20 (5) |
| S3vi—Cs1—W1viii | 121.31 (3) | Cs1iii—S2—Cs2 | 171.91 (6) |
| S3x—Cs1—W1viii | 96.08 (3) | Cs1iv—S2—Cs2 | 77.90 (3) |
| S3xi—Cs1—W1viii | 96.08 (3) | Cs1v—S2—Cs2 | 77.90 (3) |
| S2viii—Cs1—W1viii | 31.20 (3) | Cs2xiv—S2—Cs2 | 109.48 (5) |
| S2vi—Cs1—W1viii | 80.24 (3) | W1—S3—Cs1v | 95.85 (4) |
| S2vii—Cs1—W1viii | 80.24 (3) | W1—S3—Cs1xi | 156.39 (6) |
| S1viii—Cs1—W1vii | 112.968 (15) | Cs1v—S3—Cs1xi | 99.60 (3) |
| S1—Cs1—W1vii | 89.53 (2) | W1—S3—Cs2vi | 92.64 (5) |
| S3ix—Cs1—W1vii | 30.016 (19) | Cs1v—S3—Cs2vi | 79.44 (3) |
| S3vi—Cs1—W1vii | 89.58 (2) | Cs1xi—S3—Cs2vi | 107.62 (3) |
| S3x—Cs1—W1vii | 91.15 (2) | W1—S3—Cs2ii | 84.20 (4) |
| S3xi—Cs1—W1vii | 150.96 (2) | Cs1v—S3—Cs2ii | 174.41 (5) |
| S2viii—Cs1—W1vii | 80.296 (18) | Cs1xi—S3—Cs2ii | 82.13 (3) |
| S2vi—Cs1—W1vii | 139.31 (3) | Cs2vi—S3—Cs2ii | 94.97 (3) |
| S2vii—Cs1—W1vii | 30.43 (3) | W1—S3—Cs2 | 77.54 (4) |
| W1viii—Cs1—W1vii | 97.530 (8) | Cs1v—S3—Cs2 | 78.13 (3) |
| S1viii—Cs1—W1vi | 112.968 (15) | Cs1xi—S3—Cs2 | 88.26 (3) |
| S1—Cs1—W1vi | 89.53 (2) | Cs2vi—S3—Cs2 | 154.38 (4) |
| S3ix—Cs1—W1vi | 89.58 (2) | Cs2ii—S3—Cs2 | 107.29 (3) |
| S3vi—Cs1—W1vi | 30.016 (19) |
| Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, y, −z+3/2; (iii) x+1/2, y, −z+1/2; (iv) −x+3/2, −y+1, z+1/2; (v) −x+3/2, −y, z+1/2; (vi) −x+3/2, −y, z−1/2; (vii) −x+3/2, −y+1, z−1/2; (viii) x−1/2, y, −z+1/2; (ix) −x+3/2, y+1/2, z−1/2; (x) −x+1, y+1/2, −z+1; (xi) −x+1, −y, −z+1; (xii) −x+3/2, y+1/2, z+1/2; (xiii) x+1/2, −y+1/2, −z+3/2; (xiv) x+1/2, y, −z+3/2. |
| W1—S3 | 2.1915 (12) | Cs1—S2vii | 3.7072 (5) |
| W1—S3i | 2.1915 (12) | Cs2—S1viii | 3.6564 (4) |
| W1—S1 | 2.1935 (18) | Cs2—S1ix | 3.6564 (4) |
| W1—S2 | 2.2079 (18) | Cs2—S3x | 3.7170 (15) |
| Cs1—S1ii | 3.451 (2) | Cs2—S3viii | 3.7170 (15) |
| Cs1—S1 | 3.5331 (19) | Cs2—S3xi | 3.7384 (14) |
| Cs1—S3iii | 3.5502 (14) | Cs2—S3xii | 3.7384 (14) |
| Cs1—S3iv | 3.5502 (14) | Cs2—S2xiii | 3.7527 (19) |
| Cs1—S3v | 3.5680 (14) | Cs2—S2 | 3.926 (2) |
| Cs1—S3vi | 3.5680 (14) | Cs2—S3 | 4.0448 (16) |
| Cs1—S2ii | 3.579 (2) | Cs2—S3i | 4.0448 (16) |
| Cs1—S2iv | 3.7072 (5) | ||
| S3—W1—S3i | 108.86 (7) | S3—W1—S2 | 109.65 (4) |
| S3—W1—S1 | 108.92 (5) | S1—W1—S2 | 110.82 (8) |
| Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, y, −z+1/2; (iii) −x+3/2, y+1/2, z−1/2; (iv) −x+3/2, −y, z−1/2; (v) −x+1, y+1/2, −z+1; (vi) −x+1, −y, −z+1; (vii) −x+3/2, −y+1, z−1/2; (viii) −x+3/2, −y, z+1/2; (ix) −x+3/2, −y+1, z+1/2; (x) −x+3/2, y+1/2, z+1/2; (xi) x+1/2, −y+1/2, −z+3/2; (xii) x+1/2, y, −z+3/2; (xiii) x−1/2, y, −z+3/2. |
This work was supported by the Department of Science and Technology (DST), New Delhi, under grant No. SR/S1/IC-41/2003. BRS and WB thank the DST and the Deutscher Akademischer Austauschdienst (DAAD), Bonn, for the sanction of a DST-DAAD (PPP) project.
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As part of an ongoing research programme, we are investigating the synthesis and structural characterization of organic ammonium tetrathiometalates of the group VI metals Mo and W (Srinivasan et al., 2007). While several tetrathiotungstates containing organic ammonium cations are known (Srinivasan et al., 2007, and literature therein), the structures of only two tetrathiotungstates with inorganic counter cations, viz. Rb2[WS4] (Yao & Ibers, 2004) and (NH4)2[WS4] (Srinivasan et al., 2004) are reported so far. Here we describe the structure of dicesium tetrathiotungstate(VI) (I) which is isotypic with the corresponding Mo compounds Cs2[MoS4] (Raymond et al., 1995), K2[MoS4] (Emirdag-Eanes & Ibers, 2001), Rb2[MoS4] (Ellermeier et al., 1999), and with the aforementioned Rb2[WS4] and (NH4)2[WS4]. The lattice parameters of (I) are consistent with a previous determination from X-ray powder data (a = 10.05 Å, b = 7.24 Å, c = 12.85 Å and V = 935.4 Å3; Müller & Sievert, 1974).
The structure of (I) consists of discrete tetrahedral [WS4]2− ions (m symmetry), separated by Cs+ cations (Fig. 1). The [WS4] tetrahedron is slightly distorted with S—W—S angles between 108.86 (7) and 110.82 (8) ° (Table 1). The W—S bond lengths range from 2.1915 (12) to 2.2079 (18) Å with an average value of 2.196 Å which is comparable with the bond lengths ranging from 2.1710 (17) to 2.2053 (14) Å in the lighter homologue Rb2[WS4] (Yao & Ibers, 2004). Interestingly, the difference Δ between the longest and the shortest W—S bond of 0.0164 Å in (I) is comparable to the Δ value of 0.0134 Å in (NH4)2[WS4] (Srinivasan et al., 2004), but much less than the Δ value of 0.0343 Å for the isotypic Rb2[WS4]. Two crystallographically independent Cs+ cations are present in the asymmetric unit and both are coordinated by S atoms leading to irregular polyhedra. The packing of the structure is illustrated in Fig. 2. The Cs1—S distances range from 3.451 (2) to 3.7072 (5) Å (average 3.579 Å) while the Cs2—S distances vary between 3.6564 (4) and 4.0448 (16) Å. The mean Cs2—S distance (3.799 Å) is significantly longer than the average Cs1—S distance. Cs1 is surrounded by six symmetry related [WS4]2− tetrahedra via nine S atoms (Fig. 3), while Cs2 is surrounded by five symmetry related [WS4]2− tetrahedra via ten S atoms.