Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109029072/fg3117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109029072/fg3117Isup2.hkl |
CCDC reference: 749685
(NH4)2[WS4] (0.032 g, 0.05 mmol; McDonald et al., 1983) and (PPh4Cl) (0.032 g, 0.05 mmol) were dissolved in acetone (30 ml); solid Zn[HB(3,5-Me2Pz)3(OAc)] (0.011 g, 0.05 mmol; Beheshti et al., 2009) was added. The mixture was stirred for ca 4 h. The white solid that precipitated was filtered off, the filtrate was evaporated to dryness in vacuo, and the residue was washed with diethyl ether (2 × 5 ml) and dried in vacuo to give a yellow powder. The IR spectrum [ν(B—H) = 2541 cm-1 and ν(W—S) = 454 & 463 cm-1] confirms the presence of [HB(3,5-Me2Pz)3]- and WS42- ligands in the complex. This product decomposed during an attempted recrystallization by slow diffusion of diethyl ether into a saturated solution in acetone; on leaving the solution to stand in a refrigerator for two months, air-stable pale-yellow crystals of [PPh4]2[WS4ZnS6].Me2CO were obtained.
H atoms were positioned geometrically and refined with a riding model (including free rotation about C—C bonds), with the Uiso(H) values constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom. Similarity and rigid-bond restraints were applied to the displacement parameters of three C atoms in one phenyl ring, which otherwise had extreme anisotropic behaviour with large standard uncertainties.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.
Fig. 1. The structure of the asymmetric unit with atom labels and 50% probability displacement ellipsoids. H atoms have been omitted for clarity. |
(C24H20P)2[WZnS4(S6)]·C3H6O | F(000) = 2616 |
Mr = 1306.64 | Dx = 1.625 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 9044 reflections |
a = 31.212 (3) Å | θ = 2.2–28.3° |
b = 11.3211 (9) Å | µ = 3.09 mm−1 |
c = 15.1140 (13) Å | T = 150 K |
V = 5340.6 (8) Å3 | Plate, yellow |
Z = 4 | 0.28 × 0.24 × 0.08 mm |
Bruker SMART 1K CCD diffractometer | 10420 independent reflections |
Radiation source: sealed tube | 9214 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.0°, θmin = 1.9° |
thin–slice ω scans | h = −38→37 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | k = −13→13 |
Tmin = 0.478, Tmax = 0.790 | l = −18→18 |
40633 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0221P)2 + 12.3406P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max = 0.002 |
10420 reflections | Δρmax = 1.29 e Å−3 |
597 parameters | Δρmin = −3.27 e Å−3 |
16 restraints | Absolute structure: Flack (1983), 4973 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.058 (7) |
(C24H20P)2[WZnS4(S6)]·C3H6O | V = 5340.6 (8) Å3 |
Mr = 1306.64 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 31.212 (3) Å | µ = 3.09 mm−1 |
b = 11.3211 (9) Å | T = 150 K |
c = 15.1140 (13) Å | 0.28 × 0.24 × 0.08 mm |
Bruker SMART 1K CCD diffractometer | 10420 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 9214 reflections with I > 2σ(I) |
Tmin = 0.478, Tmax = 0.790 | Rint = 0.059 |
40633 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0221P)2 + 12.3406P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | Δρmax = 1.29 e Å−3 |
10420 reflections | Δρmin = −3.27 e Å−3 |
597 parameters | Absolute structure: Flack (1983), 4973 Friedel pairs |
16 restraints | Absolute structure parameter: 0.058 (7) |
Refinement. Restraints were applied to displacement parameters of 3 atoms (C1, C5, C6) [DELU and SIMU] to moderate the refinement of extremes of anisotropy; the refined parameters of C atoms have relatively high uncertainties in the presence of heavy atoms. |
x | y | z | Uiso*/Ueq | ||
W1 | 0.900249 (9) | 0.29421 (3) | 0.49736 (2) | 0.01971 (8) | |
Zn1 | 0.84936 (3) | 0.30655 (8) | 0.66050 (6) | 0.0232 (2) | |
S1 | 0.94844 (8) | 0.1673 (2) | 0.46084 (17) | 0.0354 (6) | |
S2 | 0.89255 (9) | 0.4212 (2) | 0.39249 (18) | 0.0427 (7) | |
S3 | 0.91845 (8) | 0.3855 (2) | 0.62276 (15) | 0.0290 (5) | |
S4 | 0.83913 (7) | 0.1991 (2) | 0.52251 (14) | 0.0295 (5) | |
S5 | 0.79291 (7) | 0.43168 (19) | 0.64834 (15) | 0.0240 (5) | |
S6 | 0.79505 (7) | 0.53901 (19) | 0.75706 (16) | 0.0259 (5) | |
S7 | 0.76104 (7) | 0.4562 (2) | 0.85468 (15) | 0.0288 (5) | |
S8 | 0.80170 (8) | 0.3431 (2) | 0.92229 (14) | 0.0296 (5) | |
S9 | 0.80600 (8) | 0.1879 (2) | 0.85362 (16) | 0.0289 (5) | |
S10 | 0.86192 (9) | 0.1931 (2) | 0.78296 (16) | 0.0362 (6) | |
P1 | 0.64231 (7) | 0.32845 (18) | 0.76775 (14) | 0.0183 (5) | |
C1 | 0.5846 (3) | 0.3152 (9) | 0.7611 (7) | 0.030 (2) | |
C2 | 0.5630 (3) | 0.3778 (10) | 0.6962 (7) | 0.043 (3) | |
H2 | 0.5781 | 0.4317 | 0.6594 | 0.052* | |
C3 | 0.5197 (3) | 0.3612 (11) | 0.6854 (9) | 0.057 (4) | |
H3 | 0.5048 | 0.4015 | 0.6397 | 0.069* | |
C4 | 0.4980 (4) | 0.2856 (11) | 0.7414 (11) | 0.065 (4) | |
H4 | 0.4679 | 0.2762 | 0.7348 | 0.079* | |
C5 | 0.5192 (3) | 0.2232 (10) | 0.8068 (9) | 0.049 (3) | |
H5 | 0.5041 | 0.1714 | 0.8452 | 0.058* | |
C6 | 0.5637 (3) | 0.2387 (8) | 0.8149 (7) | 0.034 (2) | |
H6 | 0.5792 | 0.1954 | 0.8582 | 0.040* | |
C7 | 0.6573 (2) | 0.4720 (7) | 0.7274 (6) | 0.0197 (18) | |
C8 | 0.6853 (3) | 0.4813 (7) | 0.6568 (6) | 0.0218 (18) | |
H8 | 0.6967 | 0.4126 | 0.6294 | 0.026* | |
C9 | 0.6966 (3) | 0.5955 (9) | 0.6261 (6) | 0.031 (2) | |
H9 | 0.7153 | 0.6048 | 0.5769 | 0.037* | |
C10 | 0.6801 (3) | 0.6924 (8) | 0.6689 (7) | 0.036 (3) | |
H10 | 0.6878 | 0.7693 | 0.6493 | 0.043* | |
C11 | 0.6529 (3) | 0.6804 (8) | 0.7386 (7) | 0.031 (2) | |
H11 | 0.6427 | 0.7491 | 0.7679 | 0.037* | |
C12 | 0.6399 (3) | 0.5711 (7) | 0.7676 (6) | 0.027 (2) | |
H12 | 0.6195 | 0.5637 | 0.8140 | 0.033* | |
C13 | 0.6607 (3) | 0.3046 (7) | 0.8800 (5) | 0.0240 (19) | |
C14 | 0.6662 (3) | 0.3966 (7) | 0.9402 (5) | 0.0189 (19) | |
H14 | 0.6598 | 0.4757 | 0.9239 | 0.023* | |
C15 | 0.6810 (3) | 0.3708 (8) | 1.0238 (6) | 0.029 (2) | |
H15 | 0.6851 | 0.4333 | 1.0649 | 0.035* | |
C16 | 0.6899 (3) | 0.2575 (8) | 1.0491 (6) | 0.032 (2) | |
H16 | 0.7001 | 0.2418 | 1.1071 | 0.039* | |
C17 | 0.6840 (3) | 0.1670 (8) | 0.9905 (8) | 0.042 (2) | |
H17 | 0.6895 | 0.0881 | 1.0085 | 0.050* | |
C18 | 0.6699 (3) | 0.1895 (8) | 0.9044 (6) | 0.034 (2) | |
H18 | 0.6668 | 0.1268 | 0.8631 | 0.041* | |
C19 | 0.6661 (3) | 0.2144 (7) | 0.7035 (5) | 0.0220 (18) | |
C20 | 0.6415 (3) | 0.1292 (7) | 0.6590 (6) | 0.026 (2) | |
H20 | 0.6111 | 0.1343 | 0.6603 | 0.031* | |
C21 | 0.6608 (3) | 0.0387 (7) | 0.6136 (6) | 0.0244 (19) | |
H21 | 0.6439 | −0.0199 | 0.5853 | 0.029* | |
C22 | 0.7055 (3) | 0.0333 (7) | 0.6091 (6) | 0.026 (2) | |
H22 | 0.7189 | −0.0269 | 0.5752 | 0.032* | |
C23 | 0.7301 (2) | 0.1151 (7) | 0.6537 (6) | 0.0209 (18) | |
H23 | 0.7605 | 0.1098 | 0.6520 | 0.025* | |
C24 | 0.7107 (3) | 0.2043 (8) | 0.7007 (6) | 0.0232 (18) | |
H24 | 0.7278 | 0.2599 | 0.7318 | 0.028* | |
P2 | 0.89021 (6) | 0.80606 (18) | 0.85240 (14) | 0.0162 (4) | |
C25 | 0.8329 (2) | 0.8112 (7) | 0.8618 (5) | 0.0188 (17) | |
C26 | 0.8089 (3) | 0.8688 (8) | 0.7991 (5) | 0.0222 (19) | |
H26 | 0.8226 | 0.8999 | 0.7480 | 0.027* | |
C27 | 0.7650 (3) | 0.8822 (8) | 0.8095 (6) | 0.037 (2) | |
H27 | 0.7486 | 0.9253 | 0.7675 | 0.044* | |
C28 | 0.7452 (3) | 0.8307 (8) | 0.8834 (6) | 0.028 (2) | |
H28 | 0.7151 | 0.8363 | 0.8904 | 0.033* | |
C29 | 0.7690 (3) | 0.7729 (8) | 0.9448 (6) | 0.030 (2) | |
H29 | 0.7553 | 0.7400 | 0.9953 | 0.035* | |
C30 | 0.8129 (3) | 0.7610 (7) | 0.9352 (5) | 0.023 (2) | |
H30 | 0.8292 | 0.7192 | 0.9781 | 0.028* | |
C31 | 0.9117 (3) | 0.9343 (7) | 0.9050 (5) | 0.0190 (19) | |
C32 | 0.9548 (3) | 0.9629 (7) | 0.8897 (6) | 0.0223 (18) | |
H32 | 0.9714 | 0.9188 | 0.8485 | 0.027* | |
C33 | 0.9729 (3) | 1.0565 (7) | 0.9353 (6) | 0.028 (2) | |
H33 | 1.0024 | 1.0745 | 0.9271 | 0.034* | |
C34 | 0.9486 (3) | 1.1240 (7) | 0.9926 (8) | 0.032 (2) | |
H34 | 0.9614 | 1.1889 | 1.0222 | 0.038* | |
C35 | 0.9055 (3) | 1.0986 (7) | 1.0077 (7) | 0.027 (2) | |
H35 | 0.8890 | 1.1446 | 1.0477 | 0.033* | |
C36 | 0.8872 (3) | 1.0032 (7) | 0.9621 (5) | 0.0237 (19) | |
H36 | 0.8577 | 0.9854 | 0.9703 | 0.028* | |
C37 | 0.9124 (2) | 0.6770 (7) | 0.9056 (6) | 0.0204 (19) | |
C38 | 0.8960 (3) | 0.5636 (7) | 0.8858 (6) | 0.0251 (19) | |
H38 | 0.8711 | 0.5561 | 0.8502 | 0.030* | |
C39 | 0.9160 (3) | 0.4639 (9) | 0.9177 (6) | 0.032 (2) | |
H39 | 0.9053 | 0.3875 | 0.9040 | 0.038* | |
C40 | 0.9517 (3) | 0.4773 (8) | 0.9697 (6) | 0.029 (2) | |
H40 | 0.9657 | 0.4087 | 0.9916 | 0.035* | |
C41 | 0.9678 (3) | 0.5865 (8) | 0.9913 (9) | 0.045 (3) | |
H41 | 0.9924 | 0.5936 | 1.0279 | 0.054* | |
C42 | 0.9477 (3) | 0.6849 (7) | 0.9590 (6) | 0.028 (2) | |
H42 | 0.9585 | 0.7607 | 0.9740 | 0.034* | |
C43 | 0.9054 (3) | 0.8085 (8) | 0.7379 (6) | 0.019 (2) | |
C44 | 0.9119 (3) | 0.9163 (8) | 0.6959 (6) | 0.030 (2) | |
H44 | 0.9083 | 0.9879 | 0.7279 | 0.036* | |
C45 | 0.9236 (3) | 0.9193 (8) | 0.6074 (6) | 0.030 (2) | |
H45 | 0.9290 | 0.9930 | 0.5794 | 0.037* | |
C46 | 0.9273 (3) | 0.8168 (9) | 0.5602 (6) | 0.035 (2) | |
H46 | 0.9350 | 0.8198 | 0.4994 | 0.042* | |
C47 | 0.9199 (3) | 0.7079 (8) | 0.6006 (6) | 0.030 (2) | |
H47 | 0.9222 | 0.6369 | 0.5675 | 0.037* | |
C48 | 0.9092 (3) | 0.7042 (9) | 0.6897 (6) | 0.031 (2) | |
H48 | 0.9044 | 0.6303 | 0.7178 | 0.037* | |
O1 | 0.9245 (3) | 0.3443 (7) | 0.1413 (5) | 0.0510 (19) | |
C49 | 0.9542 (3) | 0.3344 (9) | 0.1924 (7) | 0.034 (2) | |
C50 | 0.9780 (4) | 0.4377 (10) | 0.2233 (9) | 0.060 (4) | |
H50A | 1.0072 | 0.4354 | 0.1995 | 0.089* | |
H50B | 0.9791 | 0.4373 | 0.2881 | 0.089* | |
H50C | 0.9636 | 0.5098 | 0.2030 | 0.089* | |
C51 | 0.9685 (4) | 0.2176 (10) | 0.2238 (7) | 0.052 (3) | |
H51A | 0.9491 | 0.1566 | 0.2013 | 0.078* | |
H51B | 0.9682 | 0.2163 | 0.2887 | 0.078* | |
H51C | 0.9976 | 0.2022 | 0.2025 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.01802 (13) | 0.01971 (14) | 0.02140 (14) | 0.00279 (14) | 0.00424 (19) | 0.0041 (2) |
Zn1 | 0.0246 (5) | 0.0217 (5) | 0.0232 (5) | 0.0051 (4) | 0.0022 (4) | 0.0033 (5) |
S1 | 0.0293 (12) | 0.0319 (13) | 0.0451 (14) | 0.0107 (10) | 0.0161 (11) | 0.0073 (11) |
S2 | 0.0563 (18) | 0.0337 (14) | 0.0380 (15) | 0.0088 (13) | 0.0058 (13) | 0.0147 (12) |
S3 | 0.0230 (12) | 0.0315 (13) | 0.0324 (13) | −0.0063 (10) | −0.0036 (10) | −0.0047 (11) |
S4 | 0.0257 (11) | 0.0339 (12) | 0.0290 (14) | −0.0043 (10) | 0.0022 (8) | −0.0104 (10) |
S5 | 0.0233 (11) | 0.0258 (12) | 0.0230 (11) | 0.0047 (9) | 0.0013 (9) | 0.0022 (9) |
S6 | 0.0222 (11) | 0.0191 (11) | 0.0363 (13) | 0.0005 (9) | −0.0044 (10) | −0.0005 (10) |
S7 | 0.0231 (11) | 0.0341 (13) | 0.0291 (13) | 0.0019 (10) | 0.0056 (10) | −0.0083 (10) |
S8 | 0.0359 (13) | 0.0352 (13) | 0.0178 (11) | −0.0009 (11) | 0.0011 (10) | −0.0057 (10) |
S9 | 0.0419 (15) | 0.0205 (12) | 0.0241 (12) | −0.0015 (10) | 0.0043 (11) | 0.0030 (10) |
S10 | 0.0441 (15) | 0.0347 (15) | 0.0299 (13) | 0.0213 (13) | 0.0066 (11) | 0.0097 (11) |
P1 | 0.0184 (11) | 0.0179 (11) | 0.0187 (11) | −0.0008 (8) | −0.0004 (9) | 0.0005 (9) |
C1 | 0.021 (4) | 0.032 (5) | 0.035 (5) | 0.001 (4) | 0.007 (4) | −0.015 (4) |
C2 | 0.032 (6) | 0.065 (8) | 0.033 (6) | 0.003 (5) | −0.007 (5) | −0.009 (5) |
C3 | 0.025 (6) | 0.072 (9) | 0.075 (9) | 0.023 (6) | −0.023 (6) | −0.039 (7) |
C4 | 0.026 (6) | 0.060 (8) | 0.111 (12) | −0.014 (6) | 0.005 (7) | −0.052 (8) |
C5 | 0.031 (4) | 0.042 (6) | 0.074 (7) | −0.013 (4) | 0.023 (5) | −0.031 (5) |
C6 | 0.025 (4) | 0.032 (4) | 0.044 (5) | −0.001 (3) | 0.020 (4) | −0.025 (4) |
C7 | 0.013 (4) | 0.018 (4) | 0.027 (5) | −0.006 (3) | −0.007 (4) | 0.001 (4) |
C8 | 0.018 (4) | 0.023 (5) | 0.025 (5) | 0.006 (3) | −0.005 (4) | 0.011 (4) |
C9 | 0.020 (5) | 0.045 (6) | 0.028 (5) | −0.004 (4) | −0.004 (4) | 0.017 (4) |
C10 | 0.046 (6) | 0.018 (5) | 0.044 (7) | −0.009 (5) | 0.001 (5) | 0.012 (5) |
C11 | 0.035 (6) | 0.019 (5) | 0.040 (6) | 0.010 (4) | −0.024 (5) | −0.001 (4) |
C12 | 0.032 (5) | 0.025 (5) | 0.025 (5) | 0.001 (4) | −0.006 (4) | −0.001 (4) |
C13 | 0.023 (4) | 0.029 (5) | 0.020 (4) | −0.002 (4) | −0.001 (4) | 0.001 (4) |
C14 | 0.020 (5) | 0.017 (4) | 0.020 (5) | 0.007 (3) | 0.004 (4) | 0.003 (4) |
C15 | 0.033 (5) | 0.024 (5) | 0.029 (6) | −0.005 (4) | −0.002 (4) | −0.005 (4) |
C16 | 0.035 (5) | 0.039 (6) | 0.024 (5) | −0.001 (4) | −0.001 (4) | 0.012 (4) |
C17 | 0.072 (7) | 0.024 (4) | 0.030 (5) | 0.010 (4) | 0.002 (6) | 0.009 (6) |
C18 | 0.058 (7) | 0.021 (5) | 0.024 (5) | −0.003 (4) | 0.010 (5) | 0.011 (4) |
C19 | 0.025 (4) | 0.017 (4) | 0.024 (4) | −0.012 (4) | −0.010 (4) | 0.007 (4) |
C20 | 0.030 (5) | 0.028 (5) | 0.019 (4) | −0.004 (4) | −0.003 (4) | −0.005 (4) |
C21 | 0.030 (5) | 0.021 (4) | 0.023 (5) | −0.006 (4) | −0.001 (4) | 0.003 (4) |
C22 | 0.039 (5) | 0.015 (4) | 0.025 (5) | 0.004 (4) | 0.004 (4) | 0.008 (4) |
C23 | 0.011 (4) | 0.027 (5) | 0.025 (4) | −0.005 (3) | −0.003 (4) | 0.008 (4) |
C24 | 0.027 (5) | 0.020 (4) | 0.023 (4) | −0.007 (4) | −0.001 (4) | 0.007 (4) |
P2 | 0.0118 (10) | 0.0149 (10) | 0.0220 (11) | −0.0007 (8) | −0.0023 (8) | 0.0018 (9) |
C25 | 0.017 (4) | 0.017 (4) | 0.023 (4) | −0.010 (3) | −0.002 (3) | −0.004 (4) |
C26 | 0.017 (4) | 0.032 (5) | 0.017 (4) | −0.002 (4) | −0.012 (3) | 0.007 (4) |
C27 | 0.040 (6) | 0.030 (5) | 0.041 (6) | −0.001 (5) | −0.020 (5) | 0.014 (5) |
C28 | 0.019 (4) | 0.027 (5) | 0.039 (5) | 0.004 (4) | 0.003 (4) | 0.001 (4) |
C29 | 0.011 (4) | 0.044 (6) | 0.034 (5) | −0.005 (4) | 0.002 (4) | 0.008 (4) |
C30 | 0.020 (4) | 0.028 (5) | 0.022 (5) | 0.001 (4) | −0.002 (4) | 0.010 (4) |
C31 | 0.022 (4) | 0.018 (4) | 0.017 (4) | −0.002 (3) | −0.014 (3) | 0.006 (3) |
C32 | 0.019 (4) | 0.023 (4) | 0.025 (5) | −0.002 (4) | 0.002 (4) | 0.000 (4) |
C33 | 0.038 (5) | 0.013 (4) | 0.033 (5) | −0.005 (4) | −0.003 (4) | −0.001 (4) |
C34 | 0.047 (5) | 0.017 (4) | 0.032 (5) | −0.008 (4) | −0.021 (6) | −0.005 (5) |
C35 | 0.045 (5) | 0.022 (4) | 0.014 (5) | 0.000 (4) | −0.003 (4) | 0.002 (4) |
C36 | 0.026 (5) | 0.022 (4) | 0.023 (4) | 0.005 (4) | 0.003 (3) | 0.010 (4) |
C37 | 0.011 (4) | 0.018 (4) | 0.032 (5) | 0.000 (3) | 0.000 (3) | 0.010 (4) |
C38 | 0.020 (4) | 0.026 (5) | 0.029 (5) | 0.000 (4) | −0.007 (4) | 0.008 (4) |
C39 | 0.025 (5) | 0.030 (5) | 0.041 (6) | 0.003 (4) | 0.007 (4) | 0.011 (4) |
C40 | 0.027 (5) | 0.026 (5) | 0.035 (6) | 0.005 (4) | −0.001 (4) | 0.016 (4) |
C41 | 0.037 (5) | 0.039 (5) | 0.059 (7) | −0.002 (4) | −0.019 (7) | 0.020 (7) |
C42 | 0.028 (5) | 0.022 (5) | 0.034 (5) | −0.004 (4) | −0.016 (4) | 0.010 (4) |
C43 | 0.014 (4) | 0.020 (5) | 0.024 (5) | −0.001 (4) | −0.006 (4) | −0.008 (4) |
C44 | 0.036 (6) | 0.023 (5) | 0.031 (5) | −0.001 (4) | 0.000 (4) | 0.008 (4) |
C45 | 0.038 (6) | 0.031 (5) | 0.022 (5) | −0.011 (4) | 0.002 (4) | 0.007 (4) |
C46 | 0.024 (5) | 0.055 (7) | 0.025 (5) | −0.005 (4) | 0.003 (4) | 0.000 (5) |
C47 | 0.031 (5) | 0.028 (5) | 0.032 (5) | 0.005 (4) | 0.002 (4) | −0.011 (5) |
C48 | 0.032 (5) | 0.031 (5) | 0.029 (5) | −0.005 (4) | −0.002 (4) | 0.000 (4) |
O1 | 0.050 (5) | 0.062 (5) | 0.041 (5) | −0.006 (4) | 0.000 (4) | 0.006 (4) |
C49 | 0.034 (6) | 0.039 (6) | 0.028 (5) | −0.005 (4) | 0.015 (5) | −0.010 (4) |
C50 | 0.063 (8) | 0.046 (7) | 0.069 (9) | −0.018 (6) | 0.019 (7) | −0.030 (6) |
C51 | 0.047 (7) | 0.069 (9) | 0.041 (6) | 0.008 (6) | 0.010 (5) | 0.019 (6) |
W1—Zn1 | 2.9363 (10) | C23—C24 | 1.376 (12) |
W1—S1 | 2.152 (2) | C24—H24 | 0.950 |
W1—S2 | 2.153 (3) | P2—C25 | 1.796 (8) |
W1—S3 | 2.232 (2) | P2—C31 | 1.786 (8) |
W1—S4 | 2.223 (2) | P2—C37 | 1.805 (8) |
Zn1—S3 | 2.403 (3) | P2—C43 | 1.794 (10) |
Zn1—S4 | 2.436 (2) | C25—C26 | 1.370 (11) |
Zn1—S5 | 2.268 (2) | C25—C30 | 1.394 (11) |
Zn1—S10 | 2.286 (3) | C26—H26 | 0.950 |
S5—S6 | 2.045 (3) | C26—C27 | 1.390 (13) |
S6—S7 | 2.045 (3) | C27—H27 | 0.950 |
S7—S8 | 2.072 (3) | C27—C28 | 1.401 (13) |
S8—S9 | 2.046 (3) | C28—H28 | 0.950 |
S9—S10 | 2.047 (4) | C28—C29 | 1.357 (12) |
P1—C1 | 1.810 (10) | C29—H29 | 0.950 |
P1—C7 | 1.797 (8) | C29—C30 | 1.386 (11) |
P1—C13 | 1.810 (8) | C30—H30 | 0.950 |
P1—C19 | 1.777 (9) | C31—C32 | 1.405 (11) |
C1—C2 | 1.385 (15) | C31—C36 | 1.392 (11) |
C1—C6 | 1.355 (14) | C32—H32 | 0.950 |
C2—H2 | 0.950 | C32—C33 | 1.384 (11) |
C2—C3 | 1.375 (14) | C33—H33 | 0.950 |
C3—H3 | 0.950 | C33—C34 | 1.383 (13) |
C3—C4 | 1.382 (18) | C34—H34 | 0.950 |
C4—H4 | 0.950 | C34—C35 | 1.392 (12) |
C4—C5 | 1.383 (18) | C35—H35 | 0.950 |
C5—H5 | 0.950 | C35—C36 | 1.403 (12) |
C5—C6 | 1.408 (13) | C36—H36 | 0.950 |
C6—H6 | 0.950 | C37—C38 | 1.413 (11) |
C7—C8 | 1.384 (11) | C37—C42 | 1.369 (11) |
C7—C12 | 1.386 (12) | C38—H38 | 0.950 |
C8—H8 | 0.950 | C38—C39 | 1.377 (12) |
C8—C9 | 1.418 (12) | C39—H39 | 0.950 |
C9—H9 | 0.950 | C39—C40 | 1.372 (12) |
C9—C10 | 1.374 (13) | C40—H40 | 0.950 |
C10—H10 | 0.950 | C40—C41 | 1.374 (13) |
C10—C11 | 1.359 (14) | C41—H41 | 0.950 |
C11—H11 | 0.950 | C41—C42 | 1.370 (11) |
C11—C12 | 1.374 (13) | C42—H42 | 0.950 |
C12—H12 | 0.950 | C43—C44 | 1.391 (13) |
C13—C14 | 1.394 (11) | C43—C48 | 1.393 (12) |
C13—C18 | 1.385 (11) | C44—H44 | 0.950 |
C14—H14 | 0.950 | C44—C45 | 1.387 (12) |
C14—C15 | 1.376 (11) | C45—H45 | 0.950 |
C15—H15 | 0.950 | C45—C46 | 1.367 (13) |
C15—C16 | 1.367 (13) | C46—H46 | 0.950 |
C16—H16 | 0.950 | C46—C47 | 1.395 (13) |
C16—C17 | 1.367 (14) | C47—H47 | 0.950 |
C17—H17 | 0.950 | C47—C48 | 1.388 (13) |
C17—C18 | 1.397 (15) | C48—H48 | 0.950 |
C18—H18 | 0.950 | O1—C49 | 1.212 (12) |
C19—C20 | 1.404 (11) | C49—C50 | 1.462 (14) |
C19—C24 | 1.398 (12) | C49—C51 | 1.473 (14) |
C20—H20 | 0.950 | C50—H50A | 0.980 |
C20—C21 | 1.373 (12) | C50—H50B | 0.980 |
C21—H21 | 0.950 | C50—H50C | 0.980 |
C21—C22 | 1.397 (12) | C51—H51A | 0.980 |
C22—H22 | 0.950 | C51—H51B | 0.980 |
C22—C23 | 1.380 (12) | C51—H51C | 0.980 |
C23—H23 | 0.950 | ||
S1—W1—S2 | 109.58 (10) | C19—C24—H24 | 119.5 |
S1—W1—S3 | 110.44 (10) | C23—C24—H24 | 119.5 |
S1—W1—S4 | 108.67 (9) | C25—P2—C31 | 108.2 (4) |
S2—W1—S3 | 110.13 (10) | C25—P2—C37 | 111.9 (4) |
S2—W1—S4 | 110.69 (10) | C25—P2—C43 | 109.8 (4) |
S3—W1—S4 | 107.31 (8) | C31—P2—C37 | 108.4 (4) |
S3—Zn1—S4 | 95.76 (8) | C31—P2—C43 | 108.5 (4) |
S3—Zn1—S5 | 116.45 (9) | C37—P2—C43 | 109.9 (4) |
S3—Zn1—S10 | 104.32 (10) | P2—C25—C26 | 120.3 (6) |
S4—Zn1—S5 | 98.08 (9) | P2—C25—C30 | 119.6 (6) |
S4—Zn1—S10 | 115.80 (9) | C26—C25—C30 | 120.0 (8) |
S5—Zn1—S10 | 123.33 (9) | C25—C26—H26 | 119.6 |
W1—S3—Zn1 | 78.52 (7) | C25—C26—C27 | 120.8 (8) |
W1—S4—Zn1 | 77.99 (7) | H26—C26—C27 | 119.6 |
Zn1—S5—S6 | 106.30 (11) | C26—C27—H27 | 120.7 |
S5—S6—S7 | 106.88 (13) | C26—C27—C28 | 118.6 (8) |
S6—S7—S8 | 108.73 (13) | H27—C27—C28 | 120.7 |
S7—S8—S9 | 108.71 (14) | C27—C28—H28 | 119.8 |
S8—S9—S10 | 107.19 (15) | C27—C28—C29 | 120.4 (8) |
Zn1—S10—S9 | 107.01 (13) | H28—C28—C29 | 119.8 |
C1—P1—C7 | 108.3 (4) | C28—C29—H29 | 119.5 |
C1—P1—C13 | 110.8 (5) | C28—C29—C30 | 121.1 (8) |
C1—P1—C19 | 109.0 (4) | H29—C29—C30 | 119.5 |
C7—P1—C13 | 111.7 (4) | C25—C30—C29 | 119.1 (8) |
C7—P1—C19 | 111.3 (4) | C25—C30—H30 | 120.5 |
C13—P1—C19 | 105.8 (4) | C29—C30—H30 | 120.5 |
P1—C1—C2 | 118.7 (8) | P2—C31—C32 | 118.3 (7) |
P1—C1—C6 | 119.9 (9) | P2—C31—C36 | 121.7 (6) |
C2—C1—C6 | 121.2 (10) | C32—C31—C36 | 120.0 (8) |
C1—C2—H2 | 120.2 | C31—C32—H32 | 120.5 |
C1—C2—C3 | 119.5 (12) | C31—C32—C33 | 119.1 (8) |
H2—C2—C3 | 120.2 | H32—C32—C33 | 120.5 |
C2—C3—H3 | 120.2 | C32—C33—H33 | 119.7 |
C2—C3—C4 | 119.6 (12) | C32—C33—C34 | 120.7 (8) |
H3—C3—C4 | 120.2 | H33—C33—C34 | 119.7 |
C3—C4—H4 | 119.4 | C33—C34—H34 | 119.4 |
C3—C4—C5 | 121.3 (10) | C33—C34—C35 | 121.3 (8) |
H4—C4—C5 | 119.4 | H34—C34—C35 | 119.4 |
C4—C5—H5 | 120.9 | C34—C35—H35 | 120.9 |
C4—C5—C6 | 118.1 (11) | C34—C35—C36 | 118.2 (9) |
H5—C5—C6 | 120.9 | H35—C35—C36 | 120.9 |
C1—C6—C5 | 120.2 (11) | C31—C36—C35 | 120.7 (8) |
C1—C6—H6 | 119.9 | C31—C36—H36 | 119.6 |
C5—C6—H6 | 119.9 | C35—C36—H36 | 119.6 |
P1—C7—C8 | 119.6 (6) | P2—C37—C38 | 120.2 (6) |
P1—C7—C12 | 118.8 (7) | P2—C37—C42 | 121.2 (6) |
C8—C7—C12 | 121.5 (8) | C38—C37—C42 | 118.3 (7) |
C7—C8—H8 | 120.7 | C37—C38—H38 | 119.7 |
C7—C8—C9 | 118.6 (8) | C37—C38—C39 | 120.5 (8) |
H8—C8—C9 | 120.7 | H38—C38—C39 | 119.7 |
C8—C9—H9 | 120.6 | C38—C39—H39 | 120.7 |
C8—C9—C10 | 118.7 (8) | C38—C39—C40 | 118.6 (9) |
H9—C9—C10 | 120.6 | H39—C39—C40 | 120.7 |
C9—C10—H10 | 119.4 | C39—C40—H40 | 118.9 |
C9—C10—C11 | 121.2 (9) | C39—C40—C41 | 122.2 (8) |
H10—C10—C11 | 119.4 | H40—C40—C41 | 118.9 |
C10—C11—H11 | 119.3 | C40—C41—H41 | 120.7 |
C10—C11—C12 | 121.5 (9) | C40—C41—C42 | 118.6 (9) |
H11—C11—C12 | 119.3 | H41—C41—C42 | 120.7 |
C7—C12—C11 | 118.3 (9) | C37—C42—C41 | 121.8 (8) |
C7—C12—H12 | 120.9 | C37—C42—H42 | 119.1 |
C11—C12—H12 | 120.9 | C41—C42—H42 | 119.1 |
P1—C13—C14 | 122.7 (6) | P2—C43—C44 | 119.5 (7) |
P1—C13—C18 | 117.1 (7) | P2—C43—C48 | 120.9 (7) |
C14—C13—C18 | 120.2 (8) | C44—C43—C48 | 119.5 (9) |
C13—C14—H14 | 120.6 | C43—C44—H44 | 120.0 |
C13—C14—C15 | 118.9 (8) | C43—C44—C45 | 120.0 (9) |
H14—C14—C15 | 120.6 | H44—C44—C45 | 120.0 |
C14—C15—H15 | 119.2 | C44—C45—H45 | 119.8 |
C14—C15—C16 | 121.6 (9) | C44—C45—C46 | 120.3 (9) |
H15—C15—C16 | 119.2 | H45—C45—C46 | 119.8 |
C15—C16—H16 | 120.2 | C45—C46—H46 | 119.8 |
C15—C16—C17 | 119.7 (9) | C45—C46—C47 | 120.5 (9) |
H16—C16—C17 | 120.2 | H46—C46—C47 | 119.8 |
C16—C17—H17 | 119.7 | C46—C47—H47 | 120.3 |
C16—C17—C18 | 120.6 (8) | C46—C47—C48 | 119.4 (9) |
H17—C17—C18 | 119.7 | H47—C47—C48 | 120.3 |
C13—C18—C17 | 119.1 (9) | C43—C48—C47 | 120.2 (9) |
C13—C18—H18 | 120.5 | C43—C48—H48 | 119.9 |
C17—C18—H18 | 120.5 | C47—C48—H48 | 119.9 |
P1—C19—C20 | 122.2 (7) | O1—C49—C50 | 121.1 (11) |
P1—C19—C24 | 119.5 (6) | O1—C49—C51 | 121.3 (10) |
C20—C19—C24 | 118.3 (8) | C50—C49—C51 | 117.5 (10) |
C19—C20—H20 | 119.6 | C49—C50—H50A | 109.5 |
C19—C20—C21 | 120.8 (8) | C49—C50—H50B | 109.5 |
H20—C20—C21 | 119.6 | C49—C50—H50C | 109.5 |
C20—C21—H21 | 120.2 | H50A—C50—H50B | 109.5 |
C20—C21—C22 | 119.7 (8) | H50A—C50—H50C | 109.5 |
H21—C21—C22 | 120.2 | H50B—C50—H50C | 109.5 |
C21—C22—H22 | 119.9 | C49—C51—H51A | 109.5 |
C21—C22—C23 | 120.2 (8) | C49—C51—H51B | 109.5 |
H22—C22—C23 | 119.9 | C49—C51—H51C | 109.5 |
C22—C23—H23 | 120.0 | H51A—C51—H51B | 109.5 |
C22—C23—C24 | 119.9 (8) | H51A—C51—H51C | 109.5 |
H23—C23—C24 | 120.0 | H51B—C51—H51C | 109.5 |
C19—C24—C23 | 121.0 (8) | ||
S1—W1—S3—Zn1 | −123.66 (8) | C7—P1—C19—C24 | 62.6 (7) |
S2—W1—S3—Zn1 | 115.18 (9) | C13—P1—C19—C20 | 117.4 (7) |
S4—W1—S3—Zn1 | −5.37 (10) | C13—P1—C19—C24 | −58.9 (7) |
S4—Zn1—S3—W1 | 4.71 (9) | P1—C19—C20—C21 | −176.7 (6) |
S5—Zn1—S3—W1 | −97.30 (10) | C24—C19—C20—C21 | −0.3 (12) |
S10—Zn1—S3—W1 | 123.20 (9) | C19—C20—C21—C22 | −2.1 (13) |
S1—W1—S4—Zn1 | 124.74 (9) | C20—C21—C22—C23 | 3.2 (12) |
S2—W1—S4—Zn1 | −114.89 (9) | C21—C22—C23—C24 | −1.9 (12) |
S3—W1—S4—Zn1 | 5.31 (10) | C22—C23—C24—C19 | −0.6 (12) |
S3—Zn1—S4—W1 | −4.73 (9) | P1—C19—C24—C23 | 178.2 (6) |
S5—Zn1—S4—W1 | 113.07 (8) | C20—C19—C24—C23 | 1.7 (12) |
S10—Zn1—S4—W1 | −113.69 (10) | C31—P2—C25—C26 | 87.8 (7) |
S3—Zn1—S5—S6 | −77.59 (13) | C31—P2—C25—C30 | −89.3 (7) |
S4—Zn1—S5—S6 | −178.18 (11) | C37—P2—C25—C26 | −152.8 (7) |
S10—Zn1—S5—S6 | 53.54 (16) | C37—P2—C25—C30 | 30.1 (8) |
Zn1—S5—S6—S7 | −88.56 (14) | C43—P2—C25—C26 | −30.5 (8) |
S5—S6—S7—S8 | 87.21 (15) | C43—P2—C25—C30 | 152.4 (7) |
S6—S7—S8—S9 | −83.01 (17) | P2—C25—C26—C27 | −174.4 (7) |
S7—S8—S9—S10 | 99.67 (16) | C30—C25—C26—C27 | 2.7 (13) |
S8—S9—S10—Zn1 | −79.30 (16) | C25—C26—C27—C28 | −3.0 (14) |
S3—Zn1—S10—S9 | 153.25 (13) | C26—C27—C28—C29 | 2.4 (14) |
S4—Zn1—S10—S9 | −102.96 (14) | C27—C28—C29—C30 | −1.5 (14) |
S5—Zn1—S10—S9 | 17.36 (19) | C28—C29—C30—C25 | 1.1 (14) |
C7—P1—C1—C2 | 29.1 (9) | P2—C25—C30—C29 | 175.5 (7) |
C7—P1—C1—C6 | −155.6 (8) | C26—C25—C30—C29 | −1.6 (12) |
C13—P1—C1—C2 | 151.9 (8) | C25—P2—C31—C32 | −166.3 (6) |
C13—P1—C1—C6 | −32.8 (9) | C25—P2—C31—C36 | 15.6 (8) |
C19—P1—C1—C2 | −92.2 (9) | C37—P2—C31—C32 | 72.2 (7) |
C19—P1—C1—C6 | 83.1 (8) | C37—P2—C31—C36 | −106.0 (7) |
P1—C1—C2—C3 | 174.6 (8) | C43—P2—C31—C32 | −47.2 (7) |
C6—C1—C2—C3 | −0.7 (16) | C43—P2—C31—C36 | 134.7 (7) |
C1—C2—C3—C4 | 2.3 (16) | P2—C31—C32—C33 | −175.0 (6) |
C2—C3—C4—C5 | −1.9 (17) | C36—C31—C32—C33 | 3.2 (12) |
C3—C4—C5—C6 | −0.1 (16) | C31—C32—C33—C34 | −2.6 (13) |
P1—C1—C6—C5 | −176.5 (7) | C32—C33—C34—C35 | 1.5 (14) |
C2—C1—C6—C5 | −1.4 (14) | C33—C34—C35—C36 | −0.9 (14) |
C4—C5—C6—C1 | 1.7 (14) | P2—C31—C36—C35 | 175.4 (6) |
C1—P1—C7—C8 | −122.0 (7) | C32—C31—C36—C35 | −2.7 (12) |
C1—P1—C7—C12 | 57.3 (8) | C34—C35—C36—C31 | 1.5 (13) |
C13—P1—C7—C8 | 115.8 (7) | C25—P2—C37—C38 | 51.4 (8) |
C13—P1—C7—C12 | −65.0 (8) | C25—P2—C37—C42 | −134.9 (7) |
C19—P1—C7—C8 | −2.2 (8) | C31—P2—C37—C38 | 170.6 (7) |
C19—P1—C7—C12 | 177.1 (6) | C31—P2—C37—C42 | −15.7 (9) |
P1—C7—C8—C9 | 180.0 (6) | C43—P2—C37—C38 | −70.9 (8) |
C12—C7—C8—C9 | 0.7 (12) | C43—P2—C37—C42 | 102.8 (8) |
C7—C8—C9—C10 | 1.4 (12) | P2—C37—C38—C39 | 172.2 (7) |
C8—C9—C10—C11 | −0.8 (14) | C42—C37—C38—C39 | −1.7 (13) |
C9—C10—C11—C12 | −1.9 (15) | C37—C38—C39—C40 | 0.7 (14) |
C10—C11—C12—C7 | 4.0 (13) | C38—C39—C40—C41 | 0.5 (15) |
P1—C7—C12—C11 | 177.4 (6) | C39—C40—C41—C42 | −0.6 (17) |
C8—C7—C12—C11 | −3.4 (13) | P2—C37—C42—C41 | −172.2 (9) |
C1—P1—C13—C14 | −92.1 (8) | C38—C37—C42—C41 | 1.6 (15) |
C1—P1—C13—C18 | 88.9 (8) | C40—C41—C42—C37 | −0.5 (17) |
C7—P1—C13—C14 | 28.7 (8) | C25—P2—C43—C44 | 89.0 (8) |
C7—P1—C13—C18 | −150.3 (7) | C25—P2—C43—C48 | −88.5 (8) |
C19—P1—C13—C14 | 150.0 (7) | C31—P2—C43—C44 | −29.0 (8) |
C19—P1—C13—C18 | −29.0 (8) | C31—P2—C43—C48 | 153.4 (7) |
P1—C13—C14—C15 | −178.9 (7) | C37—P2—C43—C44 | −147.5 (7) |
C18—C13—C14—C15 | 0.1 (13) | C37—P2—C43—C48 | 35.0 (8) |
C13—C14—C15—C16 | −0.7 (13) | P2—C43—C44—C45 | −179.9 (7) |
C14—C15—C16—C17 | −0.1 (15) | C48—C43—C44—C45 | −2.3 (13) |
C15—C16—C17—C18 | 1.5 (16) | C43—C44—C45—C46 | 2.3 (14) |
P1—C13—C18—C17 | −179.7 (7) | C44—C45—C46—C47 | −0.7 (14) |
C14—C13—C18—C17 | 1.3 (14) | C45—C46—C47—C48 | −0.7 (14) |
C16—C17—C18—C13 | −2.1 (15) | C46—C47—C48—C43 | 0.7 (14) |
C1—P1—C19—C20 | −1.7 (9) | P2—C43—C48—C47 | 178.4 (7) |
C1—P1—C19—C24 | −178.0 (7) | C44—C43—C48—C47 | 0.9 (13) |
C7—P1—C19—C20 | −121.1 (7) |
Experimental details
Crystal data | |
Chemical formula | (C24H20P)2[WZnS4(S6)]·C3H6O |
Mr | 1306.64 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 150 |
a, b, c (Å) | 31.212 (3), 11.3211 (9), 15.1140 (13) |
V (Å3) | 5340.6 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.09 |
Crystal size (mm) | 0.28 × 0.24 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.478, 0.790 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40633, 10420, 9214 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.100, 1.25 |
No. of reflections | 10420 |
No. of parameters | 597 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0221P)2 + 12.3406P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.29, −3.27 |
Absolute structure | Flack (1983), 4973 Friedel pairs |
Absolute structure parameter | 0.058 (7) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.
W1—S1 | 2.152 (2) | Zn1—S10 | 2.286 (3) |
W1—S2 | 2.153 (3) | S5—S6 | 2.045 (3) |
W1—S3 | 2.232 (2) | S6—S7 | 2.045 (3) |
W1—S4 | 2.223 (2) | S7—S8 | 2.072 (3) |
Zn1—S3 | 2.403 (3) | S8—S9 | 2.046 (3) |
Zn1—S4 | 2.436 (2) | S9—S10 | 2.047 (4) |
Zn1—S5 | 2.268 (2) | ||
S1—W1—S2 | 109.58 (10) | S4—Zn1—S10 | 115.80 (9) |
S1—W1—S3 | 110.44 (10) | S5—Zn1—S10 | 123.33 (9) |
S1—W1—S4 | 108.67 (9) | W1—S3—Zn1 | 78.52 (7) |
S2—W1—S3 | 110.13 (10) | W1—S4—Zn1 | 77.99 (7) |
S2—W1—S4 | 110.69 (10) | Zn1—S5—S6 | 106.30 (11) |
S3—W1—S4 | 107.31 (8) | S5—S6—S7 | 106.88 (13) |
S3—Zn1—S4 | 95.76 (8) | S6—S7—S8 | 108.73 (13) |
S3—Zn1—S5 | 116.45 (9) | S7—S8—S9 | 108.71 (14) |
S3—Zn1—S10 | 104.32 (10) | S8—S9—S10 | 107.19 (15) |
S4—Zn1—S5 | 98.08 (9) | Zn1—S10—S9 | 107.01 (13) |
S10—Zn1—S5—S6 | 53.54 (16) | S7—S8—S9—S10 | 99.67 (16) |
Zn1—S5—S6—S7 | −88.56 (14) | S8—S9—S10—Zn1 | −79.30 (16) |
S5—S6—S7—S8 | 87.21 (15) | S5—Zn1—S10—S9 | 17.36 (19) |
S6—S7—S8—S9 | −83.01 (17) |
We have recently reported the structure of [hydrotris(3,5-dimethylpyrazolyl)borato](acetato-κO)zinc(II), Zn[HB(3,5-Me2Pz)3(OAc)] (Beheshti et al., 2009). In an attempt to prepare a complex in which the acetate ligand is replaced by the sulfur-donating metalloligand [WS4]2-, we treated the zinc complex with ammonium tetrathiotungstate(VI). Infrared spectroscopy indicates a successful reaction, but attempted recrystallization from acetone by vapour diffusion of diethyl ether as precipitant leads to decomposition and the unexpected isolation of the title mixed-metal complex (I), in which all the ligands are composed exclusively of S atoms, [(S)2W(µ-S)2Zn(S6)]2-, as an acetone solvate of the tetraphenylphosphonium salt. The product was identified through crystal structure determination. The structure of the anion is shown in Fig. 1, with selected bond lengths, angles and torsion angles given in Table 1. The well known cations and solvent molecule have unremarkable structures.
Mixed-metal complexes in which one or more MLn units (M is any metal and Ln are terminal or chelating ligands bonded only to M) are attached to tetrathiometalate(VI) centres [M'S4]2- (M' = Mo or W) or their mixed oxo–thio analogues [M'S3O]2- and [M'S2O2]2- are very common. The MLn units bridge one or more of the S···S edges of the M' coordination tetrahedron. Only one of these complexes (Wang et al., 2001) has M = Zn and M' = W, apart from polymorphs of (Ph4)2[Zn(WS4)2], in which two tetrathiotungstate anions are coordinated to a central Zn2+ ion in a linear trinuclear array (Paulat-Böschen et al., 1978; Crossland et al., 2008).
In the title complex, both metal centres have distorted tetrahedral coordination, the two tetrahedra sharing an S···S edge. In the case of atom W1, the minor distortion consists mainly of an elongation of the bonds to the bridging S atoms relative to the terminal S atoms, which is expected; angular distortions from the regular tetrahedral geometry are very small. By contrast, both distance and angle distortions are found for atom Zn1. The bonds to the bridging sulfide ligands are significantly longer than those to the chelating hexasulfide ligand, and the angle between the bridging ligands is markedly reduced from the ideal tetrahedral value, while the opposite bite angle of the chelate ligand is enlarged; furthermore, the dihedral angle between the S3/Zn1/S4 and S5/Zn1/S10 planes, which would be 90° for an ideal tetrahedron, is only 78.97 (7)°. The bridging ligands display very acute W—S—Zn angles. The four-membered WS2Zn ring is approximately planar [the `hinge' dihedral angle between the WS2 and ZnS2 planes is 7.81 (15)°; this angle adopts a wide range of values in other complexes with two sulfide bridges].
The S62- ligand, together with the Zn centre, has a crown-like conformation, with torsion angles around the S—S bonds slightly exceeding the range 80–100 Å with alternating positive and negative signs (Table 1). A search of the Cambridge Structural Database (CSD; Version 5.30 with updates to February 2009; Allen, 2002) gives 30 entries with this ligand as a chelating ligand to a single metal centre, as well as five entries in which it is a bridging ligand bonded to two metal ions, and 11 cases of an uncoordinated dianion. For each of these situations, the central S—S bond of the S6 chain (taken as the mean value within each of the three distinct groups) is significantly longer than the four other S—S bonds. This pattern is found for the title complex also, with a central bond length of 2.072 (3) Å and other S—S bond lengths essentially identical at 2.046 Å. The Zn—S bonds to this ligand have lengths of 2.268 (2) and 2.286 (3) Å in the title complex, similar to those of other zinc complexes of this ligand (mean 2.296, range 2.261–2.341 Å for eight entries in the CSD).