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The title complex, (C24H20P)2[WZnS4(S6)]·C3H6O or (Ph4P)2[WS2(μ-S)2{Zn(S6)}]·Me2CO, was unexpectedly obtained on attempted recrystallization of a mixed tungten–zinc complex of a tris­(pyrazolato)borate ligand. The two metal centres of the anion have distorted tetra­hedral coordination and the two tetra­hedra share one S...S edge; tungsten is additionally coordinated by two terminal sulfide ligands and zinc by a chelating S62− ligand, which has one central S—S bond significantly longer than the other four, a pattern found to be consistent for this ligand. This is the first reported example of a tetra­hedral zinc centre bridging an edge of a single tetra­thio­tungstate(VI) or tetra­thio­molybdate(VI) anion, although there are many previous examples with other metals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109029072/fg3117sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109029072/fg3117Isup2.hkl
Contains datablock I

CCDC reference: 749685

Comment top

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).

Related literature top

For related literature, see: Allen (2002); Beheshti et al. (2009); Crossland et al. (2008); McDonald et al. (1983); Wang et al. (2001).

Experimental top

(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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of the asymmetric unit with atom labels and 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
Bis(tetraphenylphosphonium) (hexasulfido-2κ2S1,S6)di- µ-sulfido-disulfido-1κ2S-tungsten(VI)zinc(II) acetone solvate top
Crystal data top
(C24H20P)2[WZnS4(S6)]·C3H6OF(000) = 2616
Mr = 1306.64Dx = 1.625 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 9044 reflections
a = 31.212 (3) Åθ = 2.2–28.3°
b = 11.3211 (9) ŵ = 3.09 mm1
c = 15.1140 (13) ÅT = 150 K
V = 5340.6 (8) Å3Plate, yellow
Z = 40.28 × 0.24 × 0.08 mm
Data collection top
Bruker SMART 1K CCD
diffractometer
10420 independent reflections
Radiation source: sealed tube9214 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 8.192 pixels mm-1θmax = 26.0°, θmin = 1.9°
thin–slice ω scansh = 3837
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
k = 1313
Tmin = 0.478, Tmax = 0.790l = 1818
40633 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-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 reflectionsΔρmax = 1.29 e Å3
597 parametersΔρmin = 3.27 e Å3
16 restraintsAbsolute structure: Flack (1983), 4973 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.058 (7)
Crystal data top
(C24H20P)2[WZnS4(S6)]·C3H6OV = 5340.6 (8) Å3
Mr = 1306.64Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 31.212 (3) ŵ = 3.09 mm1
b = 11.3211 (9) ÅT = 150 K
c = 15.1140 (13) Å0.28 × 0.24 × 0.08 mm
Data collection top
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 = 0.790Rint = 0.059
40633 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0221P)2 + 12.3406P]
where P = (Fo2 + 2Fc2)/3
S = 1.25Δρmax = 1.29 e Å3
10420 reflectionsΔρmin = 3.27 e Å3
597 parametersAbsolute structure: Flack (1983), 4973 Friedel pairs
16 restraintsAbsolute structure parameter: 0.058 (7)
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
W10.900249 (9)0.29421 (3)0.49736 (2)0.01971 (8)
Zn10.84936 (3)0.30655 (8)0.66050 (6)0.0232 (2)
S10.94844 (8)0.1673 (2)0.46084 (17)0.0354 (6)
S20.89255 (9)0.4212 (2)0.39249 (18)0.0427 (7)
S30.91845 (8)0.3855 (2)0.62276 (15)0.0290 (5)
S40.83913 (7)0.1991 (2)0.52251 (14)0.0295 (5)
S50.79291 (7)0.43168 (19)0.64834 (15)0.0240 (5)
S60.79505 (7)0.53901 (19)0.75706 (16)0.0259 (5)
S70.76104 (7)0.4562 (2)0.85468 (15)0.0288 (5)
S80.80170 (8)0.3431 (2)0.92229 (14)0.0296 (5)
S90.80600 (8)0.1879 (2)0.85362 (16)0.0289 (5)
S100.86192 (9)0.1931 (2)0.78296 (16)0.0362 (6)
P10.64231 (7)0.32845 (18)0.76775 (14)0.0183 (5)
C10.5846 (3)0.3152 (9)0.7611 (7)0.030 (2)
C20.5630 (3)0.3778 (10)0.6962 (7)0.043 (3)
H20.57810.43170.65940.052*
C30.5197 (3)0.3612 (11)0.6854 (9)0.057 (4)
H30.50480.40150.63970.069*
C40.4980 (4)0.2856 (11)0.7414 (11)0.065 (4)
H40.46790.27620.73480.079*
C50.5192 (3)0.2232 (10)0.8068 (9)0.049 (3)
H50.50410.17140.84520.058*
C60.5637 (3)0.2387 (8)0.8149 (7)0.034 (2)
H60.57920.19540.85820.040*
C70.6573 (2)0.4720 (7)0.7274 (6)0.0197 (18)
C80.6853 (3)0.4813 (7)0.6568 (6)0.0218 (18)
H80.69670.41260.62940.026*
C90.6966 (3)0.5955 (9)0.6261 (6)0.031 (2)
H90.71530.60480.57690.037*
C100.6801 (3)0.6924 (8)0.6689 (7)0.036 (3)
H100.68780.76930.64930.043*
C110.6529 (3)0.6804 (8)0.7386 (7)0.031 (2)
H110.64270.74910.76790.037*
C120.6399 (3)0.5711 (7)0.7676 (6)0.027 (2)
H120.61950.56370.81400.033*
C130.6607 (3)0.3046 (7)0.8800 (5)0.0240 (19)
C140.6662 (3)0.3966 (7)0.9402 (5)0.0189 (19)
H140.65980.47570.92390.023*
C150.6810 (3)0.3708 (8)1.0238 (6)0.029 (2)
H150.68510.43331.06490.035*
C160.6899 (3)0.2575 (8)1.0491 (6)0.032 (2)
H160.70010.24181.10710.039*
C170.6840 (3)0.1670 (8)0.9905 (8)0.042 (2)
H170.68950.08811.00850.050*
C180.6699 (3)0.1895 (8)0.9044 (6)0.034 (2)
H180.66680.12680.86310.041*
C190.6661 (3)0.2144 (7)0.7035 (5)0.0220 (18)
C200.6415 (3)0.1292 (7)0.6590 (6)0.026 (2)
H200.61110.13430.66030.031*
C210.6608 (3)0.0387 (7)0.6136 (6)0.0244 (19)
H210.64390.01990.58530.029*
C220.7055 (3)0.0333 (7)0.6091 (6)0.026 (2)
H220.71890.02690.57520.032*
C230.7301 (2)0.1151 (7)0.6537 (6)0.0209 (18)
H230.76050.10980.65200.025*
C240.7107 (3)0.2043 (8)0.7007 (6)0.0232 (18)
H240.72780.25990.73180.028*
P20.89021 (6)0.80606 (18)0.85240 (14)0.0162 (4)
C250.8329 (2)0.8112 (7)0.8618 (5)0.0188 (17)
C260.8089 (3)0.8688 (8)0.7991 (5)0.0222 (19)
H260.82260.89990.74800.027*
C270.7650 (3)0.8822 (8)0.8095 (6)0.037 (2)
H270.74860.92530.76750.044*
C280.7452 (3)0.8307 (8)0.8834 (6)0.028 (2)
H280.71510.83630.89040.033*
C290.7690 (3)0.7729 (8)0.9448 (6)0.030 (2)
H290.75530.74000.99530.035*
C300.8129 (3)0.7610 (7)0.9352 (5)0.023 (2)
H300.82920.71920.97810.028*
C310.9117 (3)0.9343 (7)0.9050 (5)0.0190 (19)
C320.9548 (3)0.9629 (7)0.8897 (6)0.0223 (18)
H320.97140.91880.84850.027*
C330.9729 (3)1.0565 (7)0.9353 (6)0.028 (2)
H331.00241.07450.92710.034*
C340.9486 (3)1.1240 (7)0.9926 (8)0.032 (2)
H340.96141.18891.02220.038*
C350.9055 (3)1.0986 (7)1.0077 (7)0.027 (2)
H350.88901.14461.04770.033*
C360.8872 (3)1.0032 (7)0.9621 (5)0.0237 (19)
H360.85770.98540.97030.028*
C370.9124 (2)0.6770 (7)0.9056 (6)0.0204 (19)
C380.8960 (3)0.5636 (7)0.8858 (6)0.0251 (19)
H380.87110.55610.85020.030*
C390.9160 (3)0.4639 (9)0.9177 (6)0.032 (2)
H390.90530.38750.90400.038*
C400.9517 (3)0.4773 (8)0.9697 (6)0.029 (2)
H400.96570.40870.99160.035*
C410.9678 (3)0.5865 (8)0.9913 (9)0.045 (3)
H410.99240.59361.02790.054*
C420.9477 (3)0.6849 (7)0.9590 (6)0.028 (2)
H420.95850.76070.97400.034*
C430.9054 (3)0.8085 (8)0.7379 (6)0.019 (2)
C440.9119 (3)0.9163 (8)0.6959 (6)0.030 (2)
H440.90830.98790.72790.036*
C450.9236 (3)0.9193 (8)0.6074 (6)0.030 (2)
H450.92900.99300.57940.037*
C460.9273 (3)0.8168 (9)0.5602 (6)0.035 (2)
H460.93500.81980.49940.042*
C470.9199 (3)0.7079 (8)0.6006 (6)0.030 (2)
H470.92220.63690.56750.037*
C480.9092 (3)0.7042 (9)0.6897 (6)0.031 (2)
H480.90440.63030.71780.037*
O10.9245 (3)0.3443 (7)0.1413 (5)0.0510 (19)
C490.9542 (3)0.3344 (9)0.1924 (7)0.034 (2)
C500.9780 (4)0.4377 (10)0.2233 (9)0.060 (4)
H50A1.00720.43540.19950.089*
H50B0.97910.43730.28810.089*
H50C0.96360.50980.20300.089*
C510.9685 (4)0.2176 (10)0.2238 (7)0.052 (3)
H51A0.94910.15660.20130.078*
H51B0.96820.21630.28870.078*
H51C0.99760.20220.20250.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
W10.01802 (13)0.01971 (14)0.02140 (14)0.00279 (14)0.00424 (19)0.0041 (2)
Zn10.0246 (5)0.0217 (5)0.0232 (5)0.0051 (4)0.0022 (4)0.0033 (5)
S10.0293 (12)0.0319 (13)0.0451 (14)0.0107 (10)0.0161 (11)0.0073 (11)
S20.0563 (18)0.0337 (14)0.0380 (15)0.0088 (13)0.0058 (13)0.0147 (12)
S30.0230 (12)0.0315 (13)0.0324 (13)0.0063 (10)0.0036 (10)0.0047 (11)
S40.0257 (11)0.0339 (12)0.0290 (14)0.0043 (10)0.0022 (8)0.0104 (10)
S50.0233 (11)0.0258 (12)0.0230 (11)0.0047 (9)0.0013 (9)0.0022 (9)
S60.0222 (11)0.0191 (11)0.0363 (13)0.0005 (9)0.0044 (10)0.0005 (10)
S70.0231 (11)0.0341 (13)0.0291 (13)0.0019 (10)0.0056 (10)0.0083 (10)
S80.0359 (13)0.0352 (13)0.0178 (11)0.0009 (11)0.0011 (10)0.0057 (10)
S90.0419 (15)0.0205 (12)0.0241 (12)0.0015 (10)0.0043 (11)0.0030 (10)
S100.0441 (15)0.0347 (15)0.0299 (13)0.0213 (13)0.0066 (11)0.0097 (11)
P10.0184 (11)0.0179 (11)0.0187 (11)0.0008 (8)0.0004 (9)0.0005 (9)
C10.021 (4)0.032 (5)0.035 (5)0.001 (4)0.007 (4)0.015 (4)
C20.032 (6)0.065 (8)0.033 (6)0.003 (5)0.007 (5)0.009 (5)
C30.025 (6)0.072 (9)0.075 (9)0.023 (6)0.023 (6)0.039 (7)
C40.026 (6)0.060 (8)0.111 (12)0.014 (6)0.005 (7)0.052 (8)
C50.031 (4)0.042 (6)0.074 (7)0.013 (4)0.023 (5)0.031 (5)
C60.025 (4)0.032 (4)0.044 (5)0.001 (3)0.020 (4)0.025 (4)
C70.013 (4)0.018 (4)0.027 (5)0.006 (3)0.007 (4)0.001 (4)
C80.018 (4)0.023 (5)0.025 (5)0.006 (3)0.005 (4)0.011 (4)
C90.020 (5)0.045 (6)0.028 (5)0.004 (4)0.004 (4)0.017 (4)
C100.046 (6)0.018 (5)0.044 (7)0.009 (5)0.001 (5)0.012 (5)
C110.035 (6)0.019 (5)0.040 (6)0.010 (4)0.024 (5)0.001 (4)
C120.032 (5)0.025 (5)0.025 (5)0.001 (4)0.006 (4)0.001 (4)
C130.023 (4)0.029 (5)0.020 (4)0.002 (4)0.001 (4)0.001 (4)
C140.020 (5)0.017 (4)0.020 (5)0.007 (3)0.004 (4)0.003 (4)
C150.033 (5)0.024 (5)0.029 (6)0.005 (4)0.002 (4)0.005 (4)
C160.035 (5)0.039 (6)0.024 (5)0.001 (4)0.001 (4)0.012 (4)
C170.072 (7)0.024 (4)0.030 (5)0.010 (4)0.002 (6)0.009 (6)
C180.058 (7)0.021 (5)0.024 (5)0.003 (4)0.010 (5)0.011 (4)
C190.025 (4)0.017 (4)0.024 (4)0.012 (4)0.010 (4)0.007 (4)
C200.030 (5)0.028 (5)0.019 (4)0.004 (4)0.003 (4)0.005 (4)
C210.030 (5)0.021 (4)0.023 (5)0.006 (4)0.001 (4)0.003 (4)
C220.039 (5)0.015 (4)0.025 (5)0.004 (4)0.004 (4)0.008 (4)
C230.011 (4)0.027 (5)0.025 (4)0.005 (3)0.003 (4)0.008 (4)
C240.027 (5)0.020 (4)0.023 (4)0.007 (4)0.001 (4)0.007 (4)
P20.0118 (10)0.0149 (10)0.0220 (11)0.0007 (8)0.0023 (8)0.0018 (9)
C250.017 (4)0.017 (4)0.023 (4)0.010 (3)0.002 (3)0.004 (4)
C260.017 (4)0.032 (5)0.017 (4)0.002 (4)0.012 (3)0.007 (4)
C270.040 (6)0.030 (5)0.041 (6)0.001 (5)0.020 (5)0.014 (5)
C280.019 (4)0.027 (5)0.039 (5)0.004 (4)0.003 (4)0.001 (4)
C290.011 (4)0.044 (6)0.034 (5)0.005 (4)0.002 (4)0.008 (4)
C300.020 (4)0.028 (5)0.022 (5)0.001 (4)0.002 (4)0.010 (4)
C310.022 (4)0.018 (4)0.017 (4)0.002 (3)0.014 (3)0.006 (3)
C320.019 (4)0.023 (4)0.025 (5)0.002 (4)0.002 (4)0.000 (4)
C330.038 (5)0.013 (4)0.033 (5)0.005 (4)0.003 (4)0.001 (4)
C340.047 (5)0.017 (4)0.032 (5)0.008 (4)0.021 (6)0.005 (5)
C350.045 (5)0.022 (4)0.014 (5)0.000 (4)0.003 (4)0.002 (4)
C360.026 (5)0.022 (4)0.023 (4)0.005 (4)0.003 (3)0.010 (4)
C370.011 (4)0.018 (4)0.032 (5)0.000 (3)0.000 (3)0.010 (4)
C380.020 (4)0.026 (5)0.029 (5)0.000 (4)0.007 (4)0.008 (4)
C390.025 (5)0.030 (5)0.041 (6)0.003 (4)0.007 (4)0.011 (4)
C400.027 (5)0.026 (5)0.035 (6)0.005 (4)0.001 (4)0.016 (4)
C410.037 (5)0.039 (5)0.059 (7)0.002 (4)0.019 (7)0.020 (7)
C420.028 (5)0.022 (5)0.034 (5)0.004 (4)0.016 (4)0.010 (4)
C430.014 (4)0.020 (5)0.024 (5)0.001 (4)0.006 (4)0.008 (4)
C440.036 (6)0.023 (5)0.031 (5)0.001 (4)0.000 (4)0.008 (4)
C450.038 (6)0.031 (5)0.022 (5)0.011 (4)0.002 (4)0.007 (4)
C460.024 (5)0.055 (7)0.025 (5)0.005 (4)0.003 (4)0.000 (5)
C470.031 (5)0.028 (5)0.032 (5)0.005 (4)0.002 (4)0.011 (5)
C480.032 (5)0.031 (5)0.029 (5)0.005 (4)0.002 (4)0.000 (4)
O10.050 (5)0.062 (5)0.041 (5)0.006 (4)0.000 (4)0.006 (4)
C490.034 (6)0.039 (6)0.028 (5)0.005 (4)0.015 (5)0.010 (4)
C500.063 (8)0.046 (7)0.069 (9)0.018 (6)0.019 (7)0.030 (6)
C510.047 (7)0.069 (9)0.041 (6)0.008 (6)0.010 (5)0.019 (6)
Geometric parameters (Å, º) top
W1—Zn12.9363 (10)C23—C241.376 (12)
W1—S12.152 (2)C24—H240.950
W1—S22.153 (3)P2—C251.796 (8)
W1—S32.232 (2)P2—C311.786 (8)
W1—S42.223 (2)P2—C371.805 (8)
Zn1—S32.403 (3)P2—C431.794 (10)
Zn1—S42.436 (2)C25—C261.370 (11)
Zn1—S52.268 (2)C25—C301.394 (11)
Zn1—S102.286 (3)C26—H260.950
S5—S62.045 (3)C26—C271.390 (13)
S6—S72.045 (3)C27—H270.950
S7—S82.072 (3)C27—C281.401 (13)
S8—S92.046 (3)C28—H280.950
S9—S102.047 (4)C28—C291.357 (12)
P1—C11.810 (10)C29—H290.950
P1—C71.797 (8)C29—C301.386 (11)
P1—C131.810 (8)C30—H300.950
P1—C191.777 (9)C31—C321.405 (11)
C1—C21.385 (15)C31—C361.392 (11)
C1—C61.355 (14)C32—H320.950
C2—H20.950C32—C331.384 (11)
C2—C31.375 (14)C33—H330.950
C3—H30.950C33—C341.383 (13)
C3—C41.382 (18)C34—H340.950
C4—H40.950C34—C351.392 (12)
C4—C51.383 (18)C35—H350.950
C5—H50.950C35—C361.403 (12)
C5—C61.408 (13)C36—H360.950
C6—H60.950C37—C381.413 (11)
C7—C81.384 (11)C37—C421.369 (11)
C7—C121.386 (12)C38—H380.950
C8—H80.950C38—C391.377 (12)
C8—C91.418 (12)C39—H390.950
C9—H90.950C39—C401.372 (12)
C9—C101.374 (13)C40—H400.950
C10—H100.950C40—C411.374 (13)
C10—C111.359 (14)C41—H410.950
C11—H110.950C41—C421.370 (11)
C11—C121.374 (13)C42—H420.950
C12—H120.950C43—C441.391 (13)
C13—C141.394 (11)C43—C481.393 (12)
C13—C181.385 (11)C44—H440.950
C14—H140.950C44—C451.387 (12)
C14—C151.376 (11)C45—H450.950
C15—H150.950C45—C461.367 (13)
C15—C161.367 (13)C46—H460.950
C16—H160.950C46—C471.395 (13)
C16—C171.367 (14)C47—H470.950
C17—H170.950C47—C481.388 (13)
C17—C181.397 (15)C48—H480.950
C18—H180.950O1—C491.212 (12)
C19—C201.404 (11)C49—C501.462 (14)
C19—C241.398 (12)C49—C511.473 (14)
C20—H200.950C50—H50A0.980
C20—C211.373 (12)C50—H50B0.980
C21—H210.950C50—H50C0.980
C21—C221.397 (12)C51—H51A0.980
C22—H220.950C51—H51B0.980
C22—C231.380 (12)C51—H51C0.980
C23—H230.950
S1—W1—S2109.58 (10)C19—C24—H24119.5
S1—W1—S3110.44 (10)C23—C24—H24119.5
S1—W1—S4108.67 (9)C25—P2—C31108.2 (4)
S2—W1—S3110.13 (10)C25—P2—C37111.9 (4)
S2—W1—S4110.69 (10)C25—P2—C43109.8 (4)
S3—W1—S4107.31 (8)C31—P2—C37108.4 (4)
S3—Zn1—S495.76 (8)C31—P2—C43108.5 (4)
S3—Zn1—S5116.45 (9)C37—P2—C43109.9 (4)
S3—Zn1—S10104.32 (10)P2—C25—C26120.3 (6)
S4—Zn1—S598.08 (9)P2—C25—C30119.6 (6)
S4—Zn1—S10115.80 (9)C26—C25—C30120.0 (8)
S5—Zn1—S10123.33 (9)C25—C26—H26119.6
W1—S3—Zn178.52 (7)C25—C26—C27120.8 (8)
W1—S4—Zn177.99 (7)H26—C26—C27119.6
Zn1—S5—S6106.30 (11)C26—C27—H27120.7
S5—S6—S7106.88 (13)C26—C27—C28118.6 (8)
S6—S7—S8108.73 (13)H27—C27—C28120.7
S7—S8—S9108.71 (14)C27—C28—H28119.8
S8—S9—S10107.19 (15)C27—C28—C29120.4 (8)
Zn1—S10—S9107.01 (13)H28—C28—C29119.8
C1—P1—C7108.3 (4)C28—C29—H29119.5
C1—P1—C13110.8 (5)C28—C29—C30121.1 (8)
C1—P1—C19109.0 (4)H29—C29—C30119.5
C7—P1—C13111.7 (4)C25—C30—C29119.1 (8)
C7—P1—C19111.3 (4)C25—C30—H30120.5
C13—P1—C19105.8 (4)C29—C30—H30120.5
P1—C1—C2118.7 (8)P2—C31—C32118.3 (7)
P1—C1—C6119.9 (9)P2—C31—C36121.7 (6)
C2—C1—C6121.2 (10)C32—C31—C36120.0 (8)
C1—C2—H2120.2C31—C32—H32120.5
C1—C2—C3119.5 (12)C31—C32—C33119.1 (8)
H2—C2—C3120.2H32—C32—C33120.5
C2—C3—H3120.2C32—C33—H33119.7
C2—C3—C4119.6 (12)C32—C33—C34120.7 (8)
H3—C3—C4120.2H33—C33—C34119.7
C3—C4—H4119.4C33—C34—H34119.4
C3—C4—C5121.3 (10)C33—C34—C35121.3 (8)
H4—C4—C5119.4H34—C34—C35119.4
C4—C5—H5120.9C34—C35—H35120.9
C4—C5—C6118.1 (11)C34—C35—C36118.2 (9)
H5—C5—C6120.9H35—C35—C36120.9
C1—C6—C5120.2 (11)C31—C36—C35120.7 (8)
C1—C6—H6119.9C31—C36—H36119.6
C5—C6—H6119.9C35—C36—H36119.6
P1—C7—C8119.6 (6)P2—C37—C38120.2 (6)
P1—C7—C12118.8 (7)P2—C37—C42121.2 (6)
C8—C7—C12121.5 (8)C38—C37—C42118.3 (7)
C7—C8—H8120.7C37—C38—H38119.7
C7—C8—C9118.6 (8)C37—C38—C39120.5 (8)
H8—C8—C9120.7H38—C38—C39119.7
C8—C9—H9120.6C38—C39—H39120.7
C8—C9—C10118.7 (8)C38—C39—C40118.6 (9)
H9—C9—C10120.6H39—C39—C40120.7
C9—C10—H10119.4C39—C40—H40118.9
C9—C10—C11121.2 (9)C39—C40—C41122.2 (8)
H10—C10—C11119.4H40—C40—C41118.9
C10—C11—H11119.3C40—C41—H41120.7
C10—C11—C12121.5 (9)C40—C41—C42118.6 (9)
H11—C11—C12119.3H41—C41—C42120.7
C7—C12—C11118.3 (9)C37—C42—C41121.8 (8)
C7—C12—H12120.9C37—C42—H42119.1
C11—C12—H12120.9C41—C42—H42119.1
P1—C13—C14122.7 (6)P2—C43—C44119.5 (7)
P1—C13—C18117.1 (7)P2—C43—C48120.9 (7)
C14—C13—C18120.2 (8)C44—C43—C48119.5 (9)
C13—C14—H14120.6C43—C44—H44120.0
C13—C14—C15118.9 (8)C43—C44—C45120.0 (9)
H14—C14—C15120.6H44—C44—C45120.0
C14—C15—H15119.2C44—C45—H45119.8
C14—C15—C16121.6 (9)C44—C45—C46120.3 (9)
H15—C15—C16119.2H45—C45—C46119.8
C15—C16—H16120.2C45—C46—H46119.8
C15—C16—C17119.7 (9)C45—C46—C47120.5 (9)
H16—C16—C17120.2H46—C46—C47119.8
C16—C17—H17119.7C46—C47—H47120.3
C16—C17—C18120.6 (8)C46—C47—C48119.4 (9)
H17—C17—C18119.7H47—C47—C48120.3
C13—C18—C17119.1 (9)C43—C48—C47120.2 (9)
C13—C18—H18120.5C43—C48—H48119.9
C17—C18—H18120.5C47—C48—H48119.9
P1—C19—C20122.2 (7)O1—C49—C50121.1 (11)
P1—C19—C24119.5 (6)O1—C49—C51121.3 (10)
C20—C19—C24118.3 (8)C50—C49—C51117.5 (10)
C19—C20—H20119.6C49—C50—H50A109.5
C19—C20—C21120.8 (8)C49—C50—H50B109.5
H20—C20—C21119.6C49—C50—H50C109.5
C20—C21—H21120.2H50A—C50—H50B109.5
C20—C21—C22119.7 (8)H50A—C50—H50C109.5
H21—C21—C22120.2H50B—C50—H50C109.5
C21—C22—H22119.9C49—C51—H51A109.5
C21—C22—C23120.2 (8)C49—C51—H51B109.5
H22—C22—C23119.9C49—C51—H51C109.5
C22—C23—H23120.0H51A—C51—H51B109.5
C22—C23—C24119.9 (8)H51A—C51—H51C109.5
H23—C23—C24120.0H51B—C51—H51C109.5
C19—C24—C23121.0 (8)
S1—W1—S3—Zn1123.66 (8)C7—P1—C19—C2462.6 (7)
S2—W1—S3—Zn1115.18 (9)C13—P1—C19—C20117.4 (7)
S4—W1—S3—Zn15.37 (10)C13—P1—C19—C2458.9 (7)
S4—Zn1—S3—W14.71 (9)P1—C19—C20—C21176.7 (6)
S5—Zn1—S3—W197.30 (10)C24—C19—C20—C210.3 (12)
S10—Zn1—S3—W1123.20 (9)C19—C20—C21—C222.1 (13)
S1—W1—S4—Zn1124.74 (9)C20—C21—C22—C233.2 (12)
S2—W1—S4—Zn1114.89 (9)C21—C22—C23—C241.9 (12)
S3—W1—S4—Zn15.31 (10)C22—C23—C24—C190.6 (12)
S3—Zn1—S4—W14.73 (9)P1—C19—C24—C23178.2 (6)
S5—Zn1—S4—W1113.07 (8)C20—C19—C24—C231.7 (12)
S10—Zn1—S4—W1113.69 (10)C31—P2—C25—C2687.8 (7)
S3—Zn1—S5—S677.59 (13)C31—P2—C25—C3089.3 (7)
S4—Zn1—S5—S6178.18 (11)C37—P2—C25—C26152.8 (7)
S10—Zn1—S5—S653.54 (16)C37—P2—C25—C3030.1 (8)
Zn1—S5—S6—S788.56 (14)C43—P2—C25—C2630.5 (8)
S5—S6—S7—S887.21 (15)C43—P2—C25—C30152.4 (7)
S6—S7—S8—S983.01 (17)P2—C25—C26—C27174.4 (7)
S7—S8—S9—S1099.67 (16)C30—C25—C26—C272.7 (13)
S8—S9—S10—Zn179.30 (16)C25—C26—C27—C283.0 (14)
S3—Zn1—S10—S9153.25 (13)C26—C27—C28—C292.4 (14)
S4—Zn1—S10—S9102.96 (14)C27—C28—C29—C301.5 (14)
S5—Zn1—S10—S917.36 (19)C28—C29—C30—C251.1 (14)
C7—P1—C1—C229.1 (9)P2—C25—C30—C29175.5 (7)
C7—P1—C1—C6155.6 (8)C26—C25—C30—C291.6 (12)
C13—P1—C1—C2151.9 (8)C25—P2—C31—C32166.3 (6)
C13—P1—C1—C632.8 (9)C25—P2—C31—C3615.6 (8)
C19—P1—C1—C292.2 (9)C37—P2—C31—C3272.2 (7)
C19—P1—C1—C683.1 (8)C37—P2—C31—C36106.0 (7)
P1—C1—C2—C3174.6 (8)C43—P2—C31—C3247.2 (7)
C6—C1—C2—C30.7 (16)C43—P2—C31—C36134.7 (7)
C1—C2—C3—C42.3 (16)P2—C31—C32—C33175.0 (6)
C2—C3—C4—C51.9 (17)C36—C31—C32—C333.2 (12)
C3—C4—C5—C60.1 (16)C31—C32—C33—C342.6 (13)
P1—C1—C6—C5176.5 (7)C32—C33—C34—C351.5 (14)
C2—C1—C6—C51.4 (14)C33—C34—C35—C360.9 (14)
C4—C5—C6—C11.7 (14)P2—C31—C36—C35175.4 (6)
C1—P1—C7—C8122.0 (7)C32—C31—C36—C352.7 (12)
C1—P1—C7—C1257.3 (8)C34—C35—C36—C311.5 (13)
C13—P1—C7—C8115.8 (7)C25—P2—C37—C3851.4 (8)
C13—P1—C7—C1265.0 (8)C25—P2—C37—C42134.9 (7)
C19—P1—C7—C82.2 (8)C31—P2—C37—C38170.6 (7)
C19—P1—C7—C12177.1 (6)C31—P2—C37—C4215.7 (9)
P1—C7—C8—C9180.0 (6)C43—P2—C37—C3870.9 (8)
C12—C7—C8—C90.7 (12)C43—P2—C37—C42102.8 (8)
C7—C8—C9—C101.4 (12)P2—C37—C38—C39172.2 (7)
C8—C9—C10—C110.8 (14)C42—C37—C38—C391.7 (13)
C9—C10—C11—C121.9 (15)C37—C38—C39—C400.7 (14)
C10—C11—C12—C74.0 (13)C38—C39—C40—C410.5 (15)
P1—C7—C12—C11177.4 (6)C39—C40—C41—C420.6 (17)
C8—C7—C12—C113.4 (13)P2—C37—C42—C41172.2 (9)
C1—P1—C13—C1492.1 (8)C38—C37—C42—C411.6 (15)
C1—P1—C13—C1888.9 (8)C40—C41—C42—C370.5 (17)
C7—P1—C13—C1428.7 (8)C25—P2—C43—C4489.0 (8)
C7—P1—C13—C18150.3 (7)C25—P2—C43—C4888.5 (8)
C19—P1—C13—C14150.0 (7)C31—P2—C43—C4429.0 (8)
C19—P1—C13—C1829.0 (8)C31—P2—C43—C48153.4 (7)
P1—C13—C14—C15178.9 (7)C37—P2—C43—C44147.5 (7)
C18—C13—C14—C150.1 (13)C37—P2—C43—C4835.0 (8)
C13—C14—C15—C160.7 (13)P2—C43—C44—C45179.9 (7)
C14—C15—C16—C170.1 (15)C48—C43—C44—C452.3 (13)
C15—C16—C17—C181.5 (16)C43—C44—C45—C462.3 (14)
P1—C13—C18—C17179.7 (7)C44—C45—C46—C470.7 (14)
C14—C13—C18—C171.3 (14)C45—C46—C47—C480.7 (14)
C16—C17—C18—C132.1 (15)C46—C47—C48—C430.7 (14)
C1—P1—C19—C201.7 (9)P2—C43—C48—C47178.4 (7)
C1—P1—C19—C24178.0 (7)C44—C43—C48—C470.9 (13)
C7—P1—C19—C20121.1 (7)

Experimental details

Crystal data
Chemical formula(C24H20P)2[WZnS4(S6)]·C3H6O
Mr1306.64
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)150
a, b, c (Å)31.212 (3), 11.3211 (9), 15.1140 (13)
V3)5340.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)3.09
Crystal size (mm)0.28 × 0.24 × 0.08
Data collection
DiffractometerBruker SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.478, 0.790
No. of measured, independent and
observed [I > 2σ(I)] reflections
40633, 10420, 9214
Rint0.059
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.100, 1.25
No. of reflections10420
No. of parameters597
No. of restraints16
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0221P)2 + 12.3406P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.29, 3.27
Absolute structureFlack (1983), 4973 Friedel pairs
Absolute structure parameter0.058 (7)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Selected geometric parameters (Å, º) top
W1—S12.152 (2)Zn1—S102.286 (3)
W1—S22.153 (3)S5—S62.045 (3)
W1—S32.232 (2)S6—S72.045 (3)
W1—S42.223 (2)S7—S82.072 (3)
Zn1—S32.403 (3)S8—S92.046 (3)
Zn1—S42.436 (2)S9—S102.047 (4)
Zn1—S52.268 (2)
S1—W1—S2109.58 (10)S4—Zn1—S10115.80 (9)
S1—W1—S3110.44 (10)S5—Zn1—S10123.33 (9)
S1—W1—S4108.67 (9)W1—S3—Zn178.52 (7)
S2—W1—S3110.13 (10)W1—S4—Zn177.99 (7)
S2—W1—S4110.69 (10)Zn1—S5—S6106.30 (11)
S3—W1—S4107.31 (8)S5—S6—S7106.88 (13)
S3—Zn1—S495.76 (8)S6—S7—S8108.73 (13)
S3—Zn1—S5116.45 (9)S7—S8—S9108.71 (14)
S3—Zn1—S10104.32 (10)S8—S9—S10107.19 (15)
S4—Zn1—S598.08 (9)Zn1—S10—S9107.01 (13)
S10—Zn1—S5—S653.54 (16)S7—S8—S9—S1099.67 (16)
Zn1—S5—S6—S788.56 (14)S8—S9—S10—Zn179.30 (16)
S5—S6—S7—S887.21 (15)S5—Zn1—S10—S917.36 (19)
S6—S7—S8—S983.01 (17)
 

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