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Acta Cryst. (2008). E64, m1421    [ doi:10.1107/S1600536808030390 ]

Tris(diphenylpropylphosphine-[kappa]P)-[mu]2-iodido-tri-[mu]3-sulfido-sulfidotricopper(I)tungsten(VI)

G. Tang

Abstract top

A neutral W/S/Cu cluster, [Cu3WIS4(C15H17P)3], was formed by the reaction of tetrathiotungstate(VI), CuI and diphenylpropylphosphine (dpp) in dimethylformamide. The title compound exhibits a neutral half-open cubane-like skeleton, with Cu-I bonds of 2.8056 (8) and 2.9008 (8) Å, and one Cu...I short contact of 3.1722 (6) Å. The W atom exhibits a tetrahedral coordination geometry through bonding to three [mu]3-S and one terminal S atom. The three CuI atoms are in two different coordination environments: one Cu atom exhibits a triangular coordination geometry being coordinated by one P atom from dpp and two [mu]3-S atoms, whereas the remaining two Cu centers are tetrahedrally coordinated, forming the CuPIS2 core.

Comment top

Mo(W)/S/Cu(Ag) clusters have attracted much attention for their diverse architectures (How, Xin et al., 1996; Niu et al., 2004) and potential applications (Müller et al., 1981; Zhang et al., 2007) but the crystal structures of these clusters containing diphenylpropylphosphine ligands have not been reported until now. In order to explore the chemistry of Mo(W)/S/Cu(Ag) clusters extensively,we have synthesized the cluster by reaction in solution at normal temperatures.

As illustrated in Fig. 1, the title compound has a half-open cubane-like skeleton, in which W atom adopts a distorted tetrahedral coordination geometry through bonding to three µ3-S and a terminal S atoms. Three Cu atoms have two kinds of coordination environments: one is coordinated by one P atom from dpp and two µ3-S forming a triangular coordination geometry, and another two have a tetrahedral coordination geometry formed by one P atom from dpp, one µ2-I and two µ3-S. Interestingly, the Cu—I bonds [2.8056 (8) Å and 2.9008 (8) Å] in the title compound are obviously shorter than those [(2.942 (4) Å] in theanionic W/S/Cu cluster with the same skeleton (Hou, Liang et al., 1996).

Related literature top

For an anionic W/S/Cu cluster with a half-open cubane-like skeleton, see: Hou, Liang et al. (1996). Mo(W)/S/Cu(Ag) clusters have been reviewed by Hou, Xin et al., (1996) and Niu et al. (2004). The potential applications of Mo(W)/S/Cu(Ag) clusters have been reviewed by Müller et al. (1981) and Zhang et al. (2007).

Experimental top

3 mmol CuI, 1 mmol [NH4]2WS4 and 3 mmol dpp were added to 5 mL dmf with thorough stirring for 5 minutes. After filtration, the orange-red filtrate was carefully laid on the surface with 30 ml i-PrOH. Yellow block crystals were obtained after ten days. Yield: 0.0341 g in pure form, 70.1% (based on W). Analysis calculated for C45H51Cu3IP3S4W: C 41.12, H 3.91%; found: C 41.10, H 3.90%. IR: ν, cm-1,480.68, 444.74 s (W-µ3-S).

Refinement top

H atoms were positioned geometrically with C-H = 0.95-0.99 Å and refined in riding model approximation, with Uiso = 1.5Ueq for methyl H atoms and 1.2Ueq for H atoms from methylene and phenyl groups.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalStructure (Rigaku, 2000); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted.
Tris(diphenylpropylphosphine-κP)-µ2-iodido-tri-µ3-sulfido- sulfidotricopper(I)tungsten(VI) top
Crystal data top
[Cu3WIS4(C15H17P)3]Z = 2
Mr = 1314.38F(000) = 1288
Triclinic, P1Dx = 1.760 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 11.7161 (10) ÅCell parameters from 9051 reflections
b = 13.1040 (13) Åθ = 3.2–25.3°
c = 17.1958 (15) ŵ = 4.50 mm−1
α = 86.491 (6)°T = 193 K
β = 77.568 (5)°Block, orange
γ = 74.103 (5)°0.38 × 0.37 × 0.13 mm
V = 2479.5 (4) Å3
Data collection top
Rigaku Mercury
diffractometer		9073 independent reflections
Radiation source: fine-focus sealed tube7765 reflections with I > 2σ(I)
graphiteRint = 0.039
Detector resolution: 7.31 pixels mm-1θmax = 25.4°, θmin = 3.2°
ω scansh = −14→13
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −15→15
Tmin = 0.196, Tmax = 0.557l = −20→18
24291 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0305P)2 + 3.084P]
where P = (Fo2 + 2Fc2)/3
9073 reflections(Δ/σ)max = 0.001
506 parametersΔρmax = 1.36 e Å−3
0 restraintsΔρmin = −1.20 e Å−3
Crystal data top
[Cu3WIS4(C15H17P)3]γ = 74.103 (5)°
Mr = 1314.38V = 2479.5 (4) Å3
Triclinic, P1Z = 2
a = 11.7161 (10) ÅMo Kα radiation
b = 13.1040 (13) ŵ = 4.50 mm−1
c = 17.1958 (15) ÅT = 193 K
α = 86.491 (6)°0.38 × 0.37 × 0.13 mm
β = 77.568 (5)°
Data collection top
Rigaku Mercury
diffractometer		9073 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		7765 reflections with I > 2σ(I)
Tmin = 0.196, Tmax = 0.557Rint = 0.039
24291 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.083Δρmax = 1.36 e Å−3
S = 1.09Δρmin = −1.20 e Å−3
9073 reflectionsAbsolute structure: ?
506 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
W10.231242 (18)0.395552 (17)0.228219 (12)0.02162 (7)
I10.04088 (3)0.15726 (3)0.25752 (2)0.03494 (11)
Cu10.27335 (6)0.18233 (5)0.24969 (4)0.03150 (17)
Cu20.03224 (6)0.35612 (6)0.32704 (4)0.02940 (17)
Cu30.11527 (6)0.32641 (6)0.13088 (4)0.03415 (18)
S10.22840 (12)0.31168 (11)0.34612 (7)0.0243 (3)
S20.03705 (12)0.46591 (11)0.21720 (8)0.0270 (3)
S30.31753 (12)0.27256 (11)0.13230 (8)0.0280 (3)
S40.32984 (14)0.51184 (13)0.21978 (9)0.0412 (4)
P10.39067 (13)0.02190 (11)0.26649 (9)0.0293 (3)
P2−0.12091 (12)0.39157 (11)0.43205 (8)0.0235 (3)
P30.04133 (13)0.30253 (11)0.02686 (8)0.0266 (3)
C10.4102 (5)−0.0724 (4)0.1889 (3)0.0290 (13)
C20.3512 (6)−0.1520 (5)0.1976 (4)0.0519 (19)
H20.2976−0.15940.24630.062*
C30.3705 (8)−0.2213 (6)0.1347 (4)0.065 (2)
H30.3294−0.27550.14090.078*
C40.4476 (7)−0.2122 (5)0.0642 (4)0.0519 (18)
H40.4610−0.26050.02210.062*
C50.5052 (6)−0.1336 (5)0.0547 (4)0.0462 (17)
H50.5581−0.12670.00550.055*
C60.4871 (5)−0.0641 (5)0.1159 (3)0.0378 (15)
H60.5277−0.00950.10820.045*
C70.5437 (5)0.0212 (5)0.2712 (3)0.0326 (13)
C80.6366 (5)−0.0748 (5)0.2656 (4)0.0400 (15)
H80.6197−0.13960.25700.048*
C90.7516 (6)−0.0749 (6)0.2725 (4)0.0492 (17)
H90.8142−0.13940.26800.059*
C100.7756 (6)0.0192 (6)0.2860 (4)0.0501 (18)
H100.85470.01870.29160.060*
C110.6864 (6)0.1135 (6)0.2916 (4)0.0490 (17)
H110.70370.17820.30030.059*
C120.5709 (6)0.1129 (5)0.2844 (4)0.0390 (15)
H120.50900.17790.28890.047*
C130.3401 (8)−0.0445 (6)0.3588 (4)0.0693 (14)
H13A0.2615−0.05820.35770.083*
H13B0.3997−0.11380.36220.083*
C140.3255 (8)0.0205 (6)0.4322 (4)0.0693 (14)
H14A0.39790.04760.42690.083*
H14B0.25430.08270.43400.083*
C150.3100 (8)−0.0366 (6)0.5076 (4)0.0693 (14)
H15A0.3786−0.09980.50600.104*
H15B0.2344−0.05810.51610.104*
H15C0.30660.00960.55120.104*
C16−0.0945 (5)0.3076 (4)0.5184 (3)0.0270 (12)
C17−0.0496 (6)0.1991 (5)0.5066 (4)0.0390 (15)
H17−0.03190.17120.45440.047*
C18−0.0303 (6)0.1313 (5)0.5699 (4)0.0449 (16)
H18−0.00060.05700.56090.054*
C19−0.0537 (5)0.1701 (5)0.6459 (4)0.0407 (15)
H19−0.03980.12310.68930.049*
C20−0.0970 (6)0.2770 (5)0.6583 (3)0.0440 (16)
H20−0.11330.30420.71070.053*
C21−0.1173 (6)0.3462 (5)0.5954 (3)0.0397 (15)
H21−0.14700.42030.60500.048*
C22−0.2653 (5)0.3793 (4)0.4156 (3)0.0279 (13)
C23−0.3520 (6)0.3547 (6)0.4772 (4)0.0503 (18)
H23−0.33350.33530.52820.060*
C24−0.4655 (6)0.3587 (7)0.4637 (5)0.066 (2)
H24−0.52410.34000.50540.080*
C25−0.4946 (6)0.3891 (6)0.3913 (5)0.058 (2)
H25−0.57360.39390.38320.070*
C26−0.4092 (6)0.4123 (6)0.3311 (4)0.0530 (19)
H26−0.42880.43230.28060.064*
C27−0.2940 (5)0.4073 (5)0.3421 (4)0.0383 (15)
H27−0.23520.42300.29930.046*
C28−0.1643 (5)0.5282 (4)0.4691 (3)0.0262 (12)
H28A−0.23420.53650.51450.031*
H28B−0.09600.54040.48900.031*
C29−0.1980 (5)0.6121 (4)0.4067 (3)0.0345 (14)
H29A−0.12820.60450.36120.041*
H29B−0.26660.60050.38670.041*
C30−0.2334 (6)0.7239 (4)0.4396 (3)0.0384 (15)
H30A−0.30110.73140.48560.058*
H30B−0.25800.77510.39830.058*
H30C−0.16390.73750.45610.058*
C31−0.1234 (5)0.3445 (4)0.0415 (3)0.0257 (12)
C32−0.1901 (5)0.3094 (4)0.1096 (3)0.0322 (13)
H32−0.14950.26790.14780.039*
C33−0.3154 (5)0.3345 (5)0.1222 (3)0.0364 (14)
H33−0.35980.30740.16780.044*
C34−0.3758 (5)0.3977 (5)0.0697 (4)0.0432 (16)
H34−0.46180.41590.07930.052*
C35−0.3106 (6)0.4350 (6)0.0024 (4)0.0500 (18)
H35−0.35200.4795−0.03420.060*
C36−0.1849 (5)0.4074 (5)−0.0117 (3)0.0389 (15)
H36−0.14070.4322−0.05850.047*
C370.0811 (5)0.1674 (5)−0.0073 (3)0.0334 (14)
C380.0241 (6)0.1409 (5)−0.0636 (4)0.0476 (17)
H38−0.04210.1916−0.07930.057*
C390.0649 (8)0.0396 (6)−0.0965 (4)0.069 (3)
H390.02720.0207−0.13500.082*
C400.1613 (8)−0.0331 (6)−0.0723 (6)0.073 (3)
H400.1900−0.1020−0.09520.087*
C410.2148 (7)−0.0084 (6)−0.0176 (6)0.072 (2)
H410.2803−0.0598−0.00170.086*
C420.1754 (6)0.0913 (5)0.0161 (4)0.0480 (17)
H420.21320.10780.05560.058*
C430.0976 (5)0.3685 (5)−0.0647 (3)0.0347 (14)
H43A0.06030.3537−0.10770.042*
H43B0.07250.4461−0.05600.042*
C440.2350 (5)0.3321 (5)−0.0910 (4)0.0432 (16)
H44A0.27230.3505−0.04920.052*
H44B0.26050.2540−0.09680.052*
C450.2813 (6)0.3820 (5)−0.1691 (4)0.0529 (19)
H45A0.24590.3630−0.21100.079*
H45B0.36990.3560−0.18340.079*
H45C0.25810.4594−0.16340.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
W10.01802 (12)0.02671 (13)0.01979 (12)−0.00629 (9)−0.00151 (9)−0.00471 (9)
I10.0288 (2)0.0363 (2)0.0431 (2)−0.01358 (18)−0.00673 (17)−0.00604 (18)
Cu10.0310 (4)0.0281 (4)0.0307 (4)0.0010 (3)−0.0059 (3)−0.0068 (3)
Cu20.0182 (3)0.0405 (4)0.0250 (4)−0.0046 (3)0.0008 (3)0.0003 (3)
Cu30.0281 (4)0.0449 (4)0.0304 (4)−0.0048 (3)−0.0112 (3)−0.0121 (3)
S10.0218 (7)0.0306 (8)0.0204 (7)−0.0050 (6)−0.0057 (5)−0.0032 (6)
S20.0207 (7)0.0312 (8)0.0257 (7)−0.0008 (6)−0.0054 (6)−0.0007 (6)
S30.0226 (7)0.0374 (8)0.0210 (7)−0.0046 (6)−0.0002 (6)−0.0096 (6)
S40.0408 (9)0.0425 (10)0.0435 (9)−0.0205 (8)−0.0023 (7)−0.0038 (7)
P10.0255 (8)0.0270 (8)0.0332 (8)−0.0029 (6)−0.0053 (6)−0.0056 (6)
P20.0173 (7)0.0291 (8)0.0242 (7)−0.0073 (6)−0.0020 (6)−0.0035 (6)
P30.0241 (8)0.0305 (8)0.0261 (8)−0.0056 (6)−0.0076 (6)−0.0065 (6)
C10.030 (3)0.022 (3)0.033 (3)−0.004 (2)−0.004 (3)−0.006 (2)
C20.067 (5)0.056 (4)0.037 (4)−0.034 (4)0.005 (3)−0.007 (3)
C30.100 (6)0.046 (4)0.061 (5)−0.046 (4)−0.006 (5)−0.004 (4)
C40.066 (5)0.037 (4)0.051 (4)−0.006 (4)−0.013 (4)−0.018 (3)
C50.041 (4)0.056 (4)0.035 (4)−0.003 (3)0.000 (3)−0.015 (3)
C60.036 (4)0.037 (4)0.037 (4)−0.008 (3)−0.003 (3)−0.004 (3)
C70.035 (3)0.035 (3)0.032 (3)−0.011 (3)−0.013 (3)0.002 (3)
C80.036 (4)0.039 (4)0.046 (4)−0.010 (3)−0.011 (3)0.003 (3)
C90.034 (4)0.052 (4)0.057 (4)−0.004 (3)−0.010 (3)0.015 (3)
C100.030 (4)0.065 (5)0.061 (5)−0.017 (4)−0.017 (3)0.009 (4)
C110.042 (4)0.053 (4)0.058 (4)−0.019 (4)−0.015 (3)0.003 (3)
C120.037 (4)0.029 (3)0.049 (4)−0.002 (3)−0.013 (3)0.002 (3)
C130.099 (4)0.059 (3)0.042 (2)−0.016 (3)−0.004 (2)−0.004 (2)
C140.099 (4)0.059 (3)0.042 (2)−0.016 (3)−0.004 (2)−0.004 (2)
C150.099 (4)0.059 (3)0.042 (2)−0.016 (3)−0.004 (2)−0.004 (2)
C160.017 (3)0.029 (3)0.032 (3)−0.007 (2)0.001 (2)−0.002 (2)
C170.044 (4)0.034 (4)0.039 (4)−0.010 (3)−0.009 (3)−0.002 (3)
C180.055 (4)0.026 (3)0.054 (4)−0.009 (3)−0.015 (3)0.003 (3)
C190.036 (4)0.038 (4)0.043 (4)−0.005 (3)−0.005 (3)0.010 (3)
C200.050 (4)0.050 (4)0.023 (3)−0.002 (3)−0.003 (3)0.002 (3)
C210.045 (4)0.033 (3)0.033 (3)−0.002 (3)−0.001 (3)−0.005 (3)
C220.018 (3)0.031 (3)0.033 (3)−0.003 (2)−0.003 (2)−0.010 (2)
C230.031 (4)0.071 (5)0.050 (4)−0.023 (4)0.002 (3)0.001 (4)
C240.027 (4)0.099 (6)0.077 (6)−0.031 (4)0.004 (4)−0.012 (5)
C250.029 (4)0.077 (5)0.073 (5)−0.013 (4)−0.013 (4)−0.037 (4)
C260.036 (4)0.072 (5)0.056 (4)−0.008 (4)−0.019 (3)−0.024 (4)
C270.036 (4)0.045 (4)0.036 (4)−0.010 (3)−0.008 (3)−0.015 (3)
C280.023 (3)0.031 (3)0.027 (3)−0.009 (2)−0.007 (2)−0.007 (2)
C290.040 (4)0.032 (3)0.033 (3)−0.008 (3)−0.014 (3)0.001 (3)
C300.048 (4)0.029 (3)0.039 (4)−0.011 (3)−0.010 (3)0.003 (3)
C310.025 (3)0.030 (3)0.024 (3)−0.007 (2)−0.009 (2)−0.005 (2)
C320.034 (3)0.029 (3)0.031 (3)−0.004 (3)−0.006 (3)−0.006 (2)
C330.030 (3)0.042 (4)0.036 (3)−0.010 (3)−0.001 (3)−0.010 (3)
C340.022 (3)0.059 (4)0.045 (4)−0.004 (3)−0.006 (3)−0.011 (3)
C350.038 (4)0.065 (5)0.044 (4)−0.002 (3)−0.021 (3)0.006 (3)
C360.029 (3)0.058 (4)0.031 (3)−0.013 (3)−0.008 (3)0.001 (3)
C370.032 (3)0.033 (3)0.034 (3)−0.015 (3)0.005 (3)−0.010 (3)
C380.058 (4)0.049 (4)0.039 (4)−0.026 (4)0.000 (3)−0.009 (3)
C390.103 (7)0.065 (5)0.043 (4)−0.047 (5)0.013 (4)−0.024 (4)
C400.068 (6)0.037 (5)0.091 (7)−0.013 (4)0.032 (5)−0.012 (4)
C410.047 (5)0.047 (5)0.109 (7)−0.008 (4)0.005 (5)−0.004 (5)
C420.040 (4)0.032 (4)0.068 (5)−0.006 (3)−0.008 (3)0.001 (3)
C430.035 (3)0.036 (3)0.035 (3)−0.009 (3)−0.010 (3)−0.003 (3)
C440.028 (3)0.045 (4)0.052 (4)−0.006 (3)−0.003 (3)0.003 (3)
C450.037 (4)0.053 (4)0.058 (4)−0.008 (3)0.006 (3)0.004 (3)
Geometric parameters (Å, °) top
W1—S42.1314 (15)C17—C181.380 (8)
W1—S12.2445 (13)C17—H170.9500
W1—S32.2483 (13)C18—C191.376 (8)
W1—S22.2533 (13)C18—H180.9500
W1—Cu32.7033 (7)C19—C201.365 (8)
W1—Cu12.7173 (8)C19—H190.9500
W1—Cu22.7272 (7)C20—C211.386 (8)
I1—Cu12.8056 (8)C20—H200.9500
I1—Cu22.9008 (8)C21—H210.9500
Cu1—P12.2150 (16)C22—C271.378 (8)
Cu1—S32.3094 (15)C22—C231.391 (8)
Cu1—S12.3194 (14)C23—C241.385 (9)
Cu2—P22.2241 (14)C23—H230.9500
Cu2—S12.3015 (15)C24—C251.369 (10)
Cu2—S22.3036 (15)C24—H240.9500
Cu3—P32.2209 (15)C25—C261.358 (10)
Cu3—S22.2833 (15)C25—H250.9500
Cu3—S32.2849 (15)C26—C271.386 (8)
P1—C11.809 (5)C26—H260.9500
P1—C71.809 (6)C27—H270.9500
P1—C131.826 (7)C28—C291.522 (7)
P2—C161.823 (6)C28—H28A0.9900
P2—C221.825 (5)C28—H28B0.9900
P2—C281.835 (5)C29—C301.519 (7)
P3—C371.804 (6)C29—H29A0.9900
P3—C311.821 (5)C29—H29B0.9900
P3—C431.833 (6)C30—H30A0.9800
C1—C21.386 (8)C30—H30B0.9800
C1—C61.397 (7)C30—H30C0.9800
C2—C31.396 (9)C31—C361.378 (8)
C2—H20.9500C31—C321.390 (7)
C3—C41.367 (9)C32—C331.385 (8)
C3—H30.9500C32—H320.9500
C4—C51.362 (9)C33—C341.365 (8)
C4—H40.9500C33—H330.9500
C5—C61.378 (8)C34—C351.384 (9)
C5—H50.9500C34—H340.9500
C6—H60.9500C35—C361.387 (8)
C7—C121.369 (8)C35—H350.9500
C7—C81.413 (8)C36—H360.9500
C8—C91.378 (8)C37—C421.385 (9)
C8—H80.9500C37—C381.395 (8)
C9—C101.380 (9)C38—C391.392 (9)
C9—H90.9500C38—H380.9500
C10—C111.376 (9)C39—C401.386 (12)
C10—H100.9500C39—H390.9500
C11—C121.388 (8)C40—C411.337 (12)
C11—H110.9500C40—H400.9500
C12—H120.9500C41—C421.378 (10)
C13—C141.520 (10)C41—H410.9500
C13—H13A0.9900C42—H420.9500
C13—H13B0.9900C43—C441.521 (8)
C14—C151.458 (9)C43—H43A0.9900
C14—H14A0.9900C43—H43B0.9900
C14—H14B0.9900C44—C451.516 (8)
C15—H15A0.9800C44—H44A0.9900
C15—H15B0.9800C44—H44B0.9900
C15—H15C0.9800C45—H45A0.9800
C16—C171.384 (8)C45—H45B0.9800
C16—C211.392 (8)C45—H45C0.9800
S4—W1—S1110.37 (6)H15A—C15—H15B109.5
S4—W1—S3111.01 (6)C14—C15—H15C109.5
S1—W1—S3107.67 (5)H15A—C15—H15C109.5
S4—W1—S2112.73 (6)H15B—C15—H15C109.5
S1—W1—S2107.37 (5)C17—C16—C21118.2 (5)
S3—W1—S2107.48 (5)C17—C16—P2118.0 (4)
Cu3—W1—Cu173.06 (2)C21—C16—P2123.8 (4)
Cu3—W1—Cu275.35 (2)C18—C17—C16120.7 (6)
Cu1—W1—Cu271.69 (2)C18—C17—H17119.7
Cu1—I1—Cu267.91 (2)C16—C17—H17119.7
P1—Cu1—S3119.19 (6)C19—C18—C17120.6 (6)
P1—Cu1—S1120.30 (6)C19—C18—H18119.7
S3—Cu1—S1103.18 (5)C17—C18—H18119.7
P1—Cu1—W1153.07 (5)C20—C19—C18119.3 (6)
S3—Cu1—W152.37 (4)C20—C19—H19120.3
S1—Cu1—W152.20 (4)C18—C19—H19120.3
P1—Cu1—I1106.09 (5)C19—C20—C21120.7 (6)
S3—Cu1—I1105.67 (4)C19—C20—H20119.6
S1—Cu1—I199.94 (4)C21—C20—H20119.6
W1—Cu1—I1100.82 (2)C20—C21—C16120.4 (6)
P2—Cu2—S1119.38 (6)C20—C21—H21119.8
P2—Cu2—S2121.62 (6)C16—C21—H21119.8
S1—Cu2—S2103.81 (5)C27—C22—C23119.3 (5)
P2—Cu2—W1152.86 (5)C27—C22—P2118.5 (4)
S1—Cu2—W152.18 (3)C23—C22—P2121.7 (5)
S2—Cu2—W152.40 (4)C24—C23—C22119.4 (7)
P2—Cu2—I1108.79 (4)C24—C23—H23120.3
S1—Cu2—I197.69 (4)C22—C23—H23120.3
S2—Cu2—I1101.62 (4)C25—C24—C23121.0 (7)
W1—Cu2—I198.23 (2)C25—C24—H24119.5
P3—Cu3—S2125.45 (6)C23—C24—H24119.5
P3—Cu3—S3122.84 (6)C26—C25—C24119.3 (6)
S2—Cu3—S3105.23 (5)C26—C25—H25120.4
P3—Cu3—W1163.37 (5)C24—C25—H25120.4
S2—Cu3—W152.91 (4)C25—C26—C27121.2 (7)
S3—Cu3—W152.77 (4)C25—C26—H26119.4
W1—S1—Cu273.71 (4)C27—C26—H26119.4
W1—S1—Cu173.06 (4)C22—C27—C26119.7 (6)
Cu2—S1—Cu187.25 (5)C22—C27—H27120.1
W1—S2—Cu373.15 (4)C26—C27—H27120.1
W1—S2—Cu273.51 (4)C29—C28—P2113.9 (4)
Cu3—S2—Cu292.70 (6)C29—C28—H28A108.8
W1—S3—Cu373.21 (4)P2—C28—H28A108.8
W1—S3—Cu173.18 (4)C29—C28—H28B108.8
Cu3—S3—Cu189.22 (5)P2—C28—H28B108.8
C1—P1—C7104.3 (3)H28A—C28—H28B107.7
C1—P1—C13104.6 (3)C30—C29—C28112.3 (5)
C7—P1—C13103.2 (3)C30—C29—H29A109.2
C1—P1—Cu1115.09 (19)C28—C29—H29A109.2
C7—P1—Cu1113.47 (19)C30—C29—H29B109.2
C13—P1—Cu1114.9 (3)C28—C29—H29B109.2
C16—P2—C22104.4 (2)H29A—C29—H29B107.9
C16—P2—C28105.2 (2)C29—C30—H30A109.5
C22—P2—C28101.2 (2)C29—C30—H30B109.5
C16—P2—Cu2114.21 (17)H30A—C30—H30B109.5
C22—P2—Cu2115.37 (18)C29—C30—H30C109.5
C28—P2—Cu2114.94 (17)H30A—C30—H30C109.5
C37—P3—C31103.9 (3)H30B—C30—H30C109.5
C37—P3—C43100.6 (3)C36—C31—C32118.6 (5)
C31—P3—C43105.7 (3)C36—C31—P3123.7 (4)
C37—P3—Cu3115.4 (2)C32—C31—P3117.8 (4)
C31—P3—Cu3115.10 (17)C33—C32—C31120.4 (5)
C43—P3—Cu3114.50 (19)C33—C32—H32119.8
C2—C1—C6117.9 (5)C31—C32—H32119.8
C2—C1—P1123.4 (4)C34—C33—C32120.7 (6)
C6—C1—P1118.7 (4)C34—C33—H33119.7
C1—C2—C3119.9 (6)C32—C33—H33119.7
C1—C2—H2120.0C33—C34—C35119.5 (6)
C3—C2—H2120.0C33—C34—H34120.3
C4—C3—C2120.9 (6)C35—C34—H34120.3
C4—C3—H3119.5C34—C35—C36120.1 (6)
C2—C3—H3119.5C34—C35—H35120.0
C5—C4—C3119.7 (6)C36—C35—H35120.0
C5—C4—H4120.2C31—C36—C35120.8 (6)
C3—C4—H4120.2C31—C36—H36119.6
C4—C5—C6120.4 (6)C35—C36—H36119.6
C4—C5—H5119.8C42—C37—C38119.1 (6)
C6—C5—H5119.8C42—C37—P3120.6 (5)
C5—C6—C1121.2 (6)C38—C37—P3120.0 (5)
C5—C6—H6119.4C39—C38—C37119.6 (7)
C1—C6—H6119.4C39—C38—H38120.2
C12—C7—C8118.3 (5)C37—C38—H38120.2
C12—C7—P1120.8 (5)C40—C39—C38119.1 (8)
C8—C7—P1120.8 (4)C40—C39—H39120.4
C9—C8—C7120.3 (6)C38—C39—H39120.4
C9—C8—H8119.8C41—C40—C39121.3 (8)
C7—C8—H8119.8C41—C40—H40119.3
C8—C9—C10119.8 (6)C39—C40—H40119.3
C8—C9—H9120.1C40—C41—C42120.5 (8)
C10—C9—H9120.1C40—C41—H41119.7
C11—C10—C9120.8 (6)C42—C41—H41119.7
C11—C10—H10119.6C41—C42—C37120.3 (7)
C9—C10—H10119.6C41—C42—H42119.9
C10—C11—C12119.0 (6)C37—C42—H42119.9
C10—C11—H11120.5C44—C43—P3112.6 (4)
C12—C11—H11120.5C44—C43—H43A109.1
C7—C12—C11121.8 (6)P3—C43—H43A109.1
C7—C12—H12119.1C44—C43—H43B109.1
C11—C12—H12119.1P3—C43—H43B109.1
C14—C13—P1112.5 (5)H43A—C43—H43B107.8
C14—C13—H13A109.1C45—C44—C43112.7 (5)
P1—C13—H13A109.1C45—C44—H44A109.1
C14—C13—H13B109.1C43—C44—H44A109.1
P1—C13—H13B109.1C45—C44—H44B109.1
H13A—C13—H13B107.8C43—C44—H44B109.1
C15—C14—C13114.9 (6)H44A—C44—H44B107.8
C15—C14—H14A108.5C44—C45—H45A109.5
C13—C14—H14A108.5C44—C45—H45B109.5
C15—C14—H14B108.5H45A—C45—H45B109.5
C13—C14—H14B108.5C44—C45—H45C109.5
H14A—C14—H14B107.5H45A—C45—H45C109.5
C14—C15—H15A109.5H45B—C45—H45C109.5
C14—C15—H15B109.5
S4—W1—Cu1—P1−1.55 (13)S1—Cu1—S3—Cu3−85.43 (6)
S1—W1—Cu1—P1−83.29 (11)W1—Cu1—S3—Cu3−72.68 (4)
S3—W1—Cu1—P180.94 (11)I1—Cu1—S3—Cu319.04 (5)
S2—W1—Cu1—P1178.85 (11)S3—Cu1—P1—C1−54.4 (2)
Cu3—W1—Cu1—P1138.44 (11)S1—Cu1—P1—C1176.6 (2)
Cu2—W1—Cu1—P1−141.79 (11)W1—Cu1—P1—C1−118.1 (2)
S4—W1—Cu1—S3−82.49 (8)I1—Cu1—P1—C164.4 (2)
S1—W1—Cu1—S3−164.23 (6)S3—Cu1—P1—C765.6 (2)
S2—W1—Cu1—S397.92 (6)S1—Cu1—P1—C7−63.4 (2)
Cu3—W1—Cu1—S357.51 (5)W1—Cu1—P1—C72.0 (2)
Cu2—W1—Cu1—S3137.27 (5)I1—Cu1—P1—C7−175.5 (2)
S4—W1—Cu1—S181.74 (8)S3—Cu1—P1—C13−176.0 (3)
S3—W1—Cu1—S1164.23 (6)S1—Cu1—P1—C1355.0 (3)
S2—W1—Cu1—S1−97.86 (6)W1—Cu1—P1—C13120.4 (3)
Cu3—W1—Cu1—S1−138.27 (5)I1—Cu1—P1—C13−57.1 (3)
Cu2—W1—Cu1—S1−58.50 (4)S1—Cu2—P2—C16−38.1 (2)
S4—W1—Cu1—I1175.99 (6)S2—Cu2—P2—C16−170.09 (19)
S1—W1—Cu1—I194.25 (5)W1—Cu2—P2—C16−101.8 (2)
S3—W1—Cu1—I1−101.52 (5)I1—Cu2—P2—C1672.6 (2)
S2—W1—Cu1—I1−3.61 (4)S1—Cu2—P2—C22−159.1 (2)
Cu3—W1—Cu1—I1−44.02 (2)S2—Cu2—P2—C2268.9 (2)
Cu2—W1—Cu1—I135.75 (2)W1—Cu2—P2—C22137.2 (2)
Cu2—I1—Cu1—P1144.60 (5)I1—Cu2—P2—C22−48.4 (2)
Cu2—I1—Cu1—S3−87.95 (4)S1—Cu2—P2—C2883.6 (2)
Cu2—I1—Cu1—S118.89 (4)S2—Cu2—P2—C28−48.3 (2)
Cu2—I1—Cu1—W1−34.24 (2)W1—Cu2—P2—C2820.0 (2)
S4—W1—Cu2—P2−0.94 (13)I1—Cu2—P2—C28−165.68 (19)
S1—W1—Cu2—P281.23 (11)S2—Cu3—P3—C37−157.25 (19)
S3—W1—Cu2—P2177.22 (11)S3—Cu3—P3—C3755.3 (2)
S2—W1—Cu2—P2−87.04 (11)W1—Cu3—P3—C37124.5 (2)
Cu3—W1—Cu2—P2−142.85 (11)S2—Cu3—P3—C31−36.1 (2)
Cu1—W1—Cu2—P2140.49 (11)S3—Cu3—P3—C31176.4 (2)
S4—W1—Cu2—S1−82.17 (8)W1—Cu3—P3—C31−114.4 (2)
S3—W1—Cu2—S195.99 (6)S2—Cu3—P3—C4386.6 (2)
S2—W1—Cu2—S1−168.27 (6)S3—Cu3—P3—C43−60.8 (2)
Cu3—W1—Cu2—S1135.92 (5)W1—Cu3—P3—C438.4 (3)
Cu1—W1—Cu2—S159.26 (4)C7—P1—C1—C2131.6 (6)
S4—W1—Cu2—S286.10 (8)C13—P1—C1—C223.6 (7)
S1—W1—Cu2—S2168.27 (6)Cu1—P1—C1—C2−103.4 (5)
S3—W1—Cu2—S2−95.74 (6)C7—P1—C1—C6−49.4 (5)
Cu3—W1—Cu2—S2−55.81 (5)C13—P1—C1—C6−157.5 (5)
Cu1—W1—Cu2—S2−132.47 (5)Cu1—P1—C1—C675.5 (5)
S4—W1—Cu2—I1−175.54 (7)C6—C1—C2—C30.6 (10)
S1—W1—Cu2—I1−93.37 (5)P1—C1—C2—C3179.6 (6)
S3—W1—Cu2—I12.62 (5)C1—C2—C3—C40.3 (12)
S2—W1—Cu2—I198.36 (5)C2—C3—C4—C5−1.0 (12)
Cu3—W1—Cu2—I142.55 (2)C3—C4—C5—C60.7 (11)
Cu1—W1—Cu2—I1−34.11 (2)C4—C5—C6—C10.2 (10)
Cu1—I1—Cu2—P2−143.59 (5)C2—C1—C6—C5−0.9 (9)
Cu1—I1—Cu2—S1−18.92 (4)P1—C1—C6—C5−179.9 (5)
Cu1—I1—Cu2—S286.96 (4)C1—P1—C7—C12142.3 (5)
Cu1—I1—Cu2—W133.81 (2)C13—P1—C7—C12−108.6 (5)
S4—W1—Cu3—P33.64 (19)Cu1—P1—C7—C1216.3 (5)
S1—W1—Cu3—P3−175.22 (17)C1—P1—C7—C8−41.2 (5)
S3—W1—Cu3—P3−80.55 (17)C13—P1—C7—C867.9 (5)
S2—W1—Cu3—P390.54 (17)Cu1—P1—C7—C8−167.2 (4)
Cu1—W1—Cu3—P3−138.54 (17)C12—C7—C8—C9−0.7 (9)
Cu2—W1—Cu3—P3146.52 (17)P1—C7—C8—C9−177.3 (5)
S4—W1—Cu3—S2−86.90 (8)C7—C8—C9—C100.9 (9)
S1—W1—Cu3—S294.24 (6)C8—C9—C10—C11−0.9 (10)
S3—W1—Cu3—S2−171.09 (7)C9—C10—C11—C120.8 (10)
Cu1—W1—Cu3—S2130.92 (5)C8—C7—C12—C110.6 (9)
Cu2—W1—Cu3—S255.97 (5)P1—C7—C12—C11177.2 (5)
S4—W1—Cu3—S384.19 (8)C10—C11—C12—C7−0.6 (10)
S1—W1—Cu3—S3−94.67 (6)C1—P1—C13—C14176.6 (6)
S2—W1—Cu3—S3171.09 (7)C7—P1—C13—C1467.8 (7)
Cu1—W1—Cu3—S3−57.99 (5)Cu1—P1—C13—C14−56.3 (7)
Cu2—W1—Cu3—S3−132.93 (5)P1—C13—C14—C15−167.9 (6)
S4—W1—S1—Cu2133.16 (5)C22—P2—C16—C1779.5 (5)
S3—W1—S1—Cu2−105.53 (5)C28—P2—C16—C17−174.4 (4)
S2—W1—S1—Cu29.93 (5)Cu2—P2—C16—C17−47.4 (5)
Cu3—W1—S1—Cu2−47.70 (4)C22—P2—C16—C21−100.2 (5)
Cu1—W1—S1—Cu2−92.11 (4)C28—P2—C16—C215.9 (5)
S4—W1—S1—Cu1−134.73 (5)Cu2—P2—C16—C21132.9 (4)
S3—W1—S1—Cu1−13.42 (5)C21—C16—C17—C181.2 (9)
S2—W1—S1—Cu1102.04 (5)P2—C16—C17—C18−178.6 (5)
Cu3—W1—S1—Cu144.41 (4)C16—C17—C18—C19−0.9 (10)
Cu2—W1—S1—Cu192.11 (4)C17—C18—C19—C200.3 (10)
P2—Cu2—S1—W1−148.84 (6)C18—C19—C20—C21−0.1 (10)
S2—Cu2—S1—W1−9.55 (5)C19—C20—C21—C160.4 (10)
I1—Cu2—S1—W194.48 (3)C17—C16—C21—C20−0.9 (9)
P2—Cu2—S1—Cu1138.01 (6)P2—C16—C21—C20178.8 (5)
S2—Cu2—S1—Cu1−82.69 (6)C16—P2—C22—C27−161.2 (4)
W1—Cu2—S1—Cu1−73.15 (4)C28—P2—C22—C2789.7 (5)
I1—Cu2—S1—Cu121.33 (4)Cu2—P2—C22—C27−35.0 (5)
P1—Cu1—S1—W1148.60 (6)C16—P2—C22—C2326.4 (6)
S3—Cu1—S1—W112.78 (5)C28—P2—C22—C23−82.7 (5)
I1—Cu1—S1—W1−96.05 (3)Cu2—P2—C22—C23152.5 (5)
P1—Cu1—S1—Cu2−137.59 (6)C27—C22—C23—C240.0 (10)
S3—Cu1—S1—Cu286.58 (5)P2—C22—C23—C24172.4 (5)
W1—Cu1—S1—Cu273.81 (4)C22—C23—C24—C25−1.7 (11)
I1—Cu1—S1—Cu2−22.24 (4)C23—C24—C25—C262.2 (12)
S4—W1—S2—Cu3130.20 (5)C24—C25—C26—C27−1.0 (11)
S1—W1—S2—Cu3−108.04 (5)C23—C22—C27—C261.1 (9)
S3—W1—S2—Cu37.55 (6)P2—C22—C27—C26−171.5 (5)
Cu1—W1—S2—Cu3−50.10 (4)C25—C26—C27—C22−0.6 (10)
Cu2—W1—S2—Cu3−98.11 (5)C16—P2—C28—C29−176.6 (4)
S4—W1—S2—Cu2−131.70 (5)C22—P2—C28—C29−68.1 (4)
S1—W1—S2—Cu2−9.93 (5)Cu2—P2—C28—C2956.9 (4)
S3—W1—S2—Cu2105.66 (5)P2—C28—C29—C30180.0 (4)
Cu3—W1—S2—Cu298.11 (5)C37—P3—C31—C36−101.5 (5)
Cu1—W1—S2—Cu248.01 (4)C43—P3—C31—C363.9 (6)
P3—Cu3—S2—W1−159.43 (6)Cu3—P3—C31—C36131.3 (4)
S3—Cu3—S2—W1−7.34 (5)C37—P3—C31—C3277.4 (5)
P3—Cu3—S2—Cu2128.70 (7)C43—P3—C31—C32−177.1 (4)
S3—Cu3—S2—Cu2−79.21 (6)Cu3—P3—C31—C32−49.7 (5)
W1—Cu3—S2—Cu2−71.87 (4)C36—C31—C32—C332.1 (8)
P2—Cu2—S2—W1147.65 (6)P3—C31—C32—C33−176.9 (4)
S1—Cu2—S2—W19.52 (5)C31—C32—C33—C34−2.8 (9)
I1—Cu2—S2—W1−91.50 (3)C32—C33—C34—C351.4 (9)
P2—Cu2—S2—Cu3−140.81 (6)C33—C34—C35—C360.5 (10)
S1—Cu2—S2—Cu381.06 (6)C32—C31—C36—C35−0.1 (9)
W1—Cu2—S2—Cu371.54 (4)P3—C31—C36—C35178.8 (5)
I1—Cu2—S2—Cu3−19.96 (5)C34—C35—C36—C31−1.2 (10)
S4—W1—S3—Cu3−131.24 (6)C31—P3—C37—C42−143.2 (5)
S1—W1—S3—Cu3107.85 (5)C43—P3—C37—C42107.6 (5)
S2—W1—S3—Cu3−7.54 (6)Cu3—P3—C37—C42−16.2 (5)
Cu1—W1—S3—Cu394.37 (5)C31—P3—C37—C3842.7 (5)
Cu2—W1—S3—Cu350.12 (5)C43—P3—C37—C38−66.5 (5)
S4—W1—S3—Cu1134.38 (6)Cu3—P3—C37—C38169.7 (4)
S1—W1—S3—Cu113.47 (5)C42—C37—C38—C39−1.6 (9)
S2—W1—S3—Cu1−101.92 (5)P3—C37—C38—C39172.6 (5)
Cu3—W1—S3—Cu1−94.37 (5)C37—C38—C39—C400.3 (10)
Cu2—W1—S3—Cu1−44.26 (4)C38—C39—C40—C410.7 (11)
P3—Cu3—S3—W1160.37 (6)C39—C40—C41—C42−0.4 (12)
S2—Cu3—S3—W17.36 (5)C40—C41—C42—C37−1.0 (11)
P3—Cu3—S3—Cu1−126.98 (6)C38—C37—C42—C412.0 (9)
S2—Cu3—S3—Cu180.01 (6)P3—C37—C42—C41−172.2 (5)
W1—Cu3—S3—Cu172.65 (4)C37—P3—C43—C44−65.6 (5)
P1—Cu1—S3—W1−149.18 (6)C31—P3—C43—C44−173.5 (4)
S1—Cu1—S3—W1−12.75 (5)Cu3—P3—C43—C4458.8 (5)
I1—Cu1—S3—W191.72 (3)P3—C43—C44—C45176.9 (4)
P1—Cu1—S3—Cu3138.14 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···I1i0.953.143.936 (7)142
Symmetry codes: (i) x+1, y, z.
Table 1
Selected geometric parameters (Å) top
W1—S42.1314 (15)Cu1—P12.2150 (16)
W1—S12.2445 (13)Cu1—S32.3094 (15)
W1—S32.2483 (13)Cu1—S12.3194 (14)
W1—S22.2533 (13)Cu2—P22.2241 (14)
W1—Cu32.7033 (7)Cu2—S12.3015 (15)
W1—Cu12.7173 (8)Cu2—S22.3036 (15)
W1—Cu22.7272 (7)Cu3—P32.2209 (15)
I1—Cu12.8056 (8)Cu3—S22.2833 (15)
I1—Cu22.9008 (8)Cu3—S32.2849 (15)
Acknowledgements top

Financial support from the Science and Technology Development Fund of Huai'an city (No. HAG07014) for Zhang Chi, Zhang Jinfang and Zhang Yu is acknowledged.

references
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