metal-organic compounds
Bis[μ2-bis(diphenylphosphino)methane]bis(μ2-ethane-1,2-dithiolato)-μ4-sulfido-μ2-sulfido-disulfidodimolybdenum(V)disilver(I) dimethylformamide trisolvate
aJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, People's Republic of China
*Correspondence e-mail: jxstnu2008@yahoo.cn
Treatment of [Et4N]2[(edt)2Mo2S2(μ-S)2] (edt = ethanedithiolate) with two equivalents of Ag(CH3CN)4ClO4 in the presence of bis(diphenylphosphino)methane (dppm) ligand gives rise to the title tetranuclear cluster, [Ag2Mo2(C2H4S2)2S4(C25H22P2)2]·3C3H7NO. The complex molecule and one of the dimethylformamide (DMF) solvent molecules occupy special positions on a mirror plane. The molecular structure of the complex may be visualized as being built of [Mo2S2(μ-S)2(edt)2]2− dianions and [Ag2(dppm)2]2+ dications connected by two Ag—μ-Sedt and two Ag—μ4-S bonds.
Related literature
For general background to the chemistry of sulfido-bridged dinuclear clusters consisting of a [M2S4] core (M = Mo, W) and various transition metals, see: Kuwata & Hidai (2001); Curtis et al. (1997); Halbert et al. (1985); Kawaguchi et al. (1997); Brunner et al. (1985). For the synthesis and structure of the starting material, see: Pan et al. (1984). For related structures, see: Zhu et al. (1990); Lin et al. (1997); Wei et al. (2008).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku/MSC, 2001); cell CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809048648/ya2110sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809048648/ya2110Isup2.hkl
To a solution of 1 (76 mg, 0.1 mmol) in 10 ml of CH2Cl2 was added dropwise a solution of Ag(CH3CN)4ClO4 (29 mg, 0.2 mmol) in 20 ml of MeCN. A bulk of deep red precipitate was formed within s. The red slurry was stirred for 10 minutes, and a solution of dppm (79 mg, 0.2 mmol) in CH2Cl2 (10 ml) was added. The resulting mixture was stirred for 30 min, forming a homogenous red solution. Addition of MeOH to this solution yielded a red microcrystalline solid, which was collected by filtration, washed with MeCN and Et2O, and dried in vacuo. Recrystallization of the solid in DMF/i-PrOH afforded red crystals of 2.3DMF two days later. Yield: 63 mg (50% based on Mo).
Even though packing analysis shows solvent accessible voids, our attempts to locate additional solvent proved unsuccessful, and none of the geometrically placed atoms, centered around the void, could be reasonably refined. Because of the quick loss of crystallinity upon removal from the mother liquor, the structure has a limited accuracy with high R-factors and goodness of fit; optimization of weighting scheme results in high value of the second coefficient. Some of the phenyl atoms show intense thermal motion, however attempts to introduce disorder of the phenyl ring did not produce noticeable improvement of the accuracy of the model.
All H atoms were placed geometrically (C—H 0.93 Å for aromatic and formate, 0.96 Å and 0.97 Å for methyl and methylene groups respectively) and included in the
in the riding motion approximation with Uiso(H) = 1.2Ueq of the parent atom [1.5Ueq for methyl groups].Data collection: CrystalClear (Rigaku/MSC, 2001); cell
CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ag2Mo2(C2H4S2)2S4(C25H22P2)2]·3C3H7NO | F(000) = 3448 |
Mr = 1708.3 | Dx = 1.604 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 7734 reflections |
a = 26.022 (5) Å | θ = 2.0–25.0° |
b = 21.375 (4) Å | µ = 1.26 mm−1 |
c = 12.721 (3) Å | T = 223 K |
V = 7076 (3) Å3 | Platelet, red |
Z = 4 | 0.35 × 0.20 × 0.07 mm |
Rigaku Mercury diffractometer | 6401 independent reflections |
Radiation source: fine-focus sealed tube | 5931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
ω scans | θmax = 25.0°, θmin = 3.4° |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | h = −30→30 |
Tmin = 0.746, Tmax = 0.915 | k = −25→25 |
57121 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.085 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.35 | w = 1/[σ2(Fo2) + (0.0747P)2 + 33.869P] where P = (Fo2 + 2Fc2)/3 |
6401 reflections | (Δ/σ)max < 0.001 |
401 parameters | Δρmax = 0.95 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Ag2Mo2(C2H4S2)2S4(C25H22P2)2]·3C3H7NO | V = 7076 (3) Å3 |
Mr = 1708.3 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 26.022 (5) Å | µ = 1.26 mm−1 |
b = 21.375 (4) Å | T = 223 K |
c = 12.721 (3) Å | 0.35 × 0.20 × 0.07 mm |
Rigaku Mercury diffractometer | 6401 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 5931 reflections with I > 2σ(I) |
Tmin = 0.746, Tmax = 0.915 | Rint = 0.090 |
57121 measured reflections |
R[F2 > 2σ(F2)] = 0.085 | 0 restraints |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.35 | w = 1/[σ2(Fo2) + (0.0747P)2 + 33.869P] where P = (Fo2 + 2Fc2)/3 |
6401 reflections | Δρmax = 0.95 e Å−3 |
401 parameters | Δρmin = −0.58 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.00904 (2) | 0.17618 (3) | 0.71271 (5) | 0.0236 (2) | |
Mo1 | 0.12522 (3) | 0.18270 (3) | 0.92175 (5) | 0.0211 (2) | |
P1 | −0.07622 (8) | 0.17918 (10) | 0.79382 (16) | 0.0218 (5) | |
S1 | 0.20195 (11) | 0.16455 (14) | 0.8910 (3) | 0.0520 (7) | |
O1 | 0.3659 (4) | 0.2500 | −0.0188 (7) | 0.038 (2) | |
N1 | 0.3070 (4) | 0.2500 | 0.1140 (8) | 0.025 (2) | |
C1 | 0.0888 (5) | 0.0364 (4) | 0.9861 (8) | 0.046 (3) | |
H9A | 0.1210 | 0.0199 | 0.9597 | 0.055* | |
H9B | 0.0743 | 0.0058 | 1.0341 | 0.055* | |
C2 | 0.0528 (4) | 0.0471 (4) | 0.8971 (7) | 0.038 (2) | |
H16A | 0.0192 | 0.0582 | 0.9243 | 0.045* | |
H16B | 0.0493 | 0.0089 | 0.8565 | 0.045* | |
C3 | −0.0801 (4) | 0.1653 (4) | 0.9351 (7) | 0.028 (2) | |
C4 | −0.0361 (5) | 0.1676 (6) | 0.9945 (8) | 0.056 (3) | |
H8A | −0.0049 | 0.1781 | 0.9634 | 0.067* | |
C5 | −0.0384 (7) | 0.1543 (8) | 1.1014 (9) | 0.086 (5) | |
H1A | −0.0086 | 0.1561 | 1.1416 | 0.103* | |
C6 | −0.0835 (8) | 0.1388 (6) | 1.1481 (10) | 0.083 (5) | |
H2A | −0.0845 | 0.1296 | 1.2195 | 0.099* | |
C7 | −0.1276 (7) | 0.1368 (6) | 1.0894 (10) | 0.071 (5) | |
H6A | −0.1588 | 0.1270 | 1.1210 | 0.085* | |
C8 | −0.1255 (5) | 0.1492 (5) | 0.9838 (8) | 0.044 (3) | |
H5A | −0.1554 | 0.1468 | 0.9441 | 0.053* | |
C9 | −0.1156 (3) | 0.1152 (4) | 0.7415 (6) | 0.0232 (18) | |
C10 | −0.0974 (4) | 0.0548 (4) | 0.7605 (7) | 0.0274 (19) | |
H22A | −0.0673 | 0.0489 | 0.7988 | 0.033* | |
C11 | −0.1241 (4) | 0.0037 (4) | 0.7223 (7) | 0.034 (2) | |
H29A | −0.1122 | −0.0364 | 0.7365 | 0.041* | |
C12 | −0.1677 (4) | 0.0114 (4) | 0.6640 (8) | 0.038 (2) | |
H17A | −0.1854 | −0.0231 | 0.6376 | 0.046* | |
C13 | −0.1850 (4) | 0.0714 (5) | 0.6449 (8) | 0.040 (2) | |
H13A | −0.2148 | 0.0771 | 0.6054 | 0.049* | |
C14 | −0.1595 (3) | 0.1233 (4) | 0.6829 (7) | 0.031 (2) | |
H20A | −0.1718 | 0.1633 | 0.6690 | 0.037* | |
C15 | 0.0903 (3) | 0.1697 (3) | 0.4725 (6) | 0.0202 (17) | |
C16 | 0.1304 (3) | 0.1645 (4) | 0.5441 (7) | 0.0269 (19) | |
H26A | 0.1235 | 0.1638 | 0.6158 | 0.032* | |
C17 | 0.1805 (4) | 0.1605 (5) | 0.5084 (8) | 0.040 (2) | |
H7A | 0.2071 | 0.1577 | 0.5569 | 0.048* | |
C18 | 0.1916 (4) | 0.1606 (4) | 0.4042 (8) | 0.035 (2) | |
H14A | 0.2255 | 0.1576 | 0.3817 | 0.042* | |
C19 | 0.1521 (3) | 0.1651 (4) | 0.3318 (7) | 0.031 (2) | |
H30A | 0.1596 | 0.1646 | 0.2603 | 0.037* | |
C20 | 0.1019 (4) | 0.1704 (4) | 0.3646 (7) | 0.0277 (19) | |
H31A | 0.0756 | 0.1745 | 0.3154 | 0.033* | |
C21 | −0.0123 (3) | 0.1164 (4) | 0.4566 (6) | 0.0224 (17) | |
C22 | 0.0119 (3) | 0.0654 (4) | 0.4086 (7) | 0.029 (2) | |
H25A | 0.0475 | 0.0638 | 0.4033 | 0.035* | |
C23 | −0.0184 (4) | 0.0170 (4) | 0.3688 (7) | 0.034 (2) | |
H19A | −0.0027 | −0.0173 | 0.3373 | 0.041* | |
C24 | −0.0713 (4) | 0.0194 (4) | 0.3758 (7) | 0.036 (2) | |
H18A | −0.0912 | −0.0130 | 0.3488 | 0.043* | |
C25 | −0.0947 (4) | 0.0702 (4) | 0.4231 (7) | 0.034 (2) | |
H15A | −0.1304 | 0.0721 | 0.4270 | 0.041* | |
C26 | −0.0657 (3) | 0.1177 (4) | 0.4643 (7) | 0.0282 (19) | |
H27A | −0.0818 | 0.1511 | 0.4977 | 0.034* | |
C27 | −0.1134 (5) | 0.2500 | 0.7688 (9) | 0.024 (3) | |
H33A | −0.1248 | 0.2500 | 0.6963 | 0.028* | |
H33B | −0.1436 | 0.2500 | 0.8134 | 0.028* | |
C28 | 0.0006 (4) | 0.2500 | 0.4579 (8) | 0.018 (2) | |
H34A | 0.0108 | 0.2500 | 0.3845 | 0.021* | |
H34B | −0.0366 | 0.2500 | 0.4605 | 0.021* | |
C29 | 0.3438 (7) | 0.2500 | 0.1950 (14) | 0.081 (7) | |
H3A | 0.3744 | 0.2296 | 0.1711 | 0.121* | 0.50 |
H3B | 0.3303 | 0.2281 | 0.2549 | 0.121* | 0.50 |
H3C | 0.3516 | 0.2923 | 0.2144 | 0.121* | 0.50 |
C30 | 0.2532 (5) | 0.2500 | 0.1436 (13) | 0.042 (3) | |
H30B | 0.2436 | 0.2909 | 0.1677 | 0.063* | 0.50 |
H30C | 0.2477 | 0.2202 | 0.1989 | 0.063* | 0.50 |
H30D | 0.2326 | 0.2389 | 0.0839 | 0.063* | 0.50 |
C31 | 0.3212 (5) | 0.2500 | 0.0161 (11) | 0.033 (3) | |
H12 | 0.2950 | 0.2500 | −0.0337 | 0.040* | |
C32 | 0.2952 (5) | −0.0235 (6) | 0.1897 (11) | 0.067 (4) | |
H4A | 0.3174 | −0.0415 | 0.1376 | 0.100* | |
H4B | 0.2776 | −0.0563 | 0.2268 | 0.100* | |
H4C | 0.3152 | 0.0006 | 0.2384 | 0.100* | |
C33 | 0.2240 (5) | −0.0106 (7) | 0.0615 (11) | 0.070 (4) | |
H10A | 0.2012 | −0.0397 | 0.0950 | 0.105* | |
H10B | 0.2438 | −0.0320 | 0.0090 | 0.105* | |
H10C | 0.2043 | 0.0220 | 0.0288 | 0.105* | |
C34 | 0.2541 (4) | 0.0767 (5) | 0.1667 (10) | 0.051 (3) | |
H11 | 0.2296 | 0.1006 | 0.1316 | 0.061* | |
P2 | 0.02494 (8) | 0.17823 (9) | 0.52142 (16) | 0.0187 (4) | |
S2 | 0.10053 (10) | 0.11032 (11) | 1.05640 (18) | 0.0370 (6) | |
N2 | 0.2582 (3) | 0.0164 (4) | 0.1394 (7) | 0.042 (2) | |
O2 | 0.2797 (3) | 0.1029 (4) | 0.2337 (7) | 0.069 (3) | |
S3 | 0.11821 (12) | 0.2500 | 1.0644 (2) | 0.0269 (7) | |
S4 | 0.07638 (8) | 0.10971 (9) | 0.81247 (16) | 0.0246 (5) | |
S5 | 0.09599 (12) | 0.2500 | 0.7891 (2) | 0.0243 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0258 (3) | 0.0255 (3) | 0.0194 (3) | 0.0015 (3) | 0.0011 (3) | 0.0018 (3) |
Mo1 | 0.0231 (4) | 0.0186 (4) | 0.0217 (4) | 0.0017 (3) | −0.0047 (3) | 0.0009 (3) |
P1 | 0.0248 (11) | 0.0197 (10) | 0.0210 (11) | 0.0013 (8) | 0.0007 (9) | 0.0021 (9) |
S1 | 0.0415 (15) | 0.0467 (16) | 0.0678 (19) | 0.0071 (12) | −0.0064 (14) | −0.0074 (14) |
O1 | 0.038 (6) | 0.040 (5) | 0.035 (5) | 0.000 | 0.010 (4) | 0.000 |
N1 | 0.022 (5) | 0.027 (5) | 0.026 (6) | 0.000 | 0.004 (4) | 0.000 |
C1 | 0.074 (8) | 0.027 (5) | 0.036 (6) | −0.007 (5) | −0.017 (5) | 0.010 (4) |
C2 | 0.053 (6) | 0.023 (5) | 0.037 (5) | −0.002 (4) | −0.015 (5) | 0.008 (4) |
C3 | 0.040 (5) | 0.020 (4) | 0.024 (5) | 0.008 (4) | 0.003 (4) | 0.002 (4) |
C4 | 0.057 (7) | 0.084 (9) | 0.026 (5) | 0.029 (6) | −0.001 (5) | −0.006 (6) |
C5 | 0.111 (12) | 0.130 (13) | 0.018 (6) | 0.066 (11) | −0.010 (7) | −0.005 (7) |
C6 | 0.159 (16) | 0.064 (9) | 0.025 (6) | 0.053 (10) | 0.024 (9) | 0.017 (6) |
C7 | 0.131 (14) | 0.043 (7) | 0.039 (7) | −0.022 (8) | 0.047 (8) | −0.006 (6) |
C8 | 0.068 (7) | 0.037 (6) | 0.028 (5) | −0.015 (5) | 0.018 (5) | −0.005 (4) |
C9 | 0.025 (5) | 0.029 (4) | 0.015 (4) | 0.000 (4) | 0.002 (3) | 0.000 (3) |
C10 | 0.037 (5) | 0.020 (4) | 0.025 (5) | −0.002 (4) | 0.002 (4) | 0.000 (4) |
C11 | 0.046 (6) | 0.023 (4) | 0.032 (5) | 0.001 (4) | 0.009 (5) | 0.004 (4) |
C12 | 0.055 (6) | 0.018 (5) | 0.042 (6) | −0.009 (4) | −0.002 (5) | −0.002 (4) |
C13 | 0.035 (5) | 0.035 (5) | 0.052 (6) | −0.006 (4) | −0.008 (5) | −0.003 (5) |
C14 | 0.034 (5) | 0.021 (4) | 0.037 (5) | 0.002 (4) | −0.006 (4) | 0.006 (4) |
C15 | 0.022 (4) | 0.014 (4) | 0.025 (4) | 0.000 (3) | −0.004 (3) | −0.002 (3) |
C16 | 0.036 (5) | 0.024 (4) | 0.021 (4) | 0.002 (4) | −0.006 (4) | −0.004 (3) |
C17 | 0.033 (5) | 0.044 (6) | 0.044 (6) | 0.003 (4) | −0.009 (5) | 0.001 (5) |
C18 | 0.025 (5) | 0.029 (5) | 0.050 (6) | 0.000 (4) | 0.009 (4) | 0.000 (4) |
C19 | 0.033 (5) | 0.030 (5) | 0.030 (5) | −0.005 (4) | 0.007 (4) | 0.002 (4) |
C20 | 0.035 (5) | 0.028 (5) | 0.020 (4) | 0.000 (4) | 0.000 (4) | 0.000 (4) |
C21 | 0.029 (4) | 0.019 (4) | 0.019 (4) | 0.001 (3) | −0.005 (4) | 0.001 (3) |
C22 | 0.028 (5) | 0.027 (4) | 0.032 (5) | −0.001 (4) | 0.004 (4) | 0.000 (4) |
C23 | 0.046 (6) | 0.023 (5) | 0.032 (5) | 0.000 (4) | 0.000 (4) | −0.009 (4) |
C24 | 0.040 (5) | 0.034 (5) | 0.034 (5) | −0.011 (4) | −0.006 (4) | −0.010 (4) |
C25 | 0.028 (5) | 0.042 (5) | 0.033 (5) | −0.010 (4) | 0.007 (4) | −0.003 (4) |
C26 | 0.025 (5) | 0.033 (5) | 0.026 (5) | 0.002 (4) | 0.002 (4) | −0.007 (4) |
C27 | 0.032 (7) | 0.015 (5) | 0.023 (6) | 0.000 | −0.004 (5) | 0.000 |
C28 | 0.020 (6) | 0.020 (5) | 0.013 (5) | 0.000 | −0.001 (5) | 0.000 |
C29 | 0.058 (12) | 0.14 (2) | 0.044 (10) | 0.000 | −0.026 (9) | 0.000 |
C30 | 0.022 (7) | 0.041 (8) | 0.062 (10) | 0.000 | 0.008 (7) | 0.000 |
C31 | 0.029 (7) | 0.032 (7) | 0.039 (8) | 0.000 | −0.003 (6) | 0.000 |
C32 | 0.048 (7) | 0.057 (8) | 0.095 (10) | −0.003 (6) | 0.008 (7) | 0.018 (7) |
C33 | 0.048 (7) | 0.080 (9) | 0.082 (9) | −0.010 (7) | 0.003 (7) | −0.023 (8) |
C34 | 0.042 (6) | 0.052 (7) | 0.060 (7) | 0.007 (5) | 0.005 (6) | 0.003 (6) |
P2 | 0.0201 (10) | 0.0189 (10) | 0.0171 (10) | 0.0009 (8) | 0.0003 (8) | −0.0010 (8) |
S2 | 0.0540 (15) | 0.0328 (12) | 0.0243 (12) | −0.0104 (11) | −0.0123 (11) | 0.0080 (10) |
N2 | 0.030 (4) | 0.041 (5) | 0.056 (6) | −0.007 (4) | 0.008 (4) | −0.005 (4) |
O2 | 0.061 (6) | 0.064 (6) | 0.080 (6) | 0.000 (4) | −0.012 (5) | −0.032 (5) |
S3 | 0.0349 (17) | 0.0261 (15) | 0.0197 (15) | 0.000 | −0.0050 (13) | 0.000 |
S4 | 0.0325 (11) | 0.0182 (10) | 0.0229 (11) | 0.0005 (8) | −0.0081 (9) | 0.0003 (8) |
S5 | 0.0351 (17) | 0.0176 (14) | 0.0203 (15) | 0.000 | −0.0031 (13) | 0.000 |
Ag1—P1 | 2.448 (2) | C16—C17 | 1.384 (13) |
Ag1—P2 | 2.469 (2) | C16—H26A | 0.9300 |
Ag1—S4 | 2.588 (2) | C17—C18 | 1.356 (14) |
Ag1—S5 | 2.924 (3) | C17—H7A | 0.9300 |
Ag1—Ag1i | 3.1558 (14) | C18—C19 | 1.383 (13) |
Mo1—S1 | 2.071 (3) | C18—H14A | 0.9300 |
Mo1—S3 | 2.322 (2) | C19—C20 | 1.377 (13) |
Mo1—S5 | 2.344 (2) | C19—H30A | 0.9300 |
Mo1—S2 | 2.396 (2) | C20—H31A | 0.9300 |
Mo1—S4 | 2.446 (2) | C21—C26 | 1.392 (12) |
Mo1—Mo1i | 2.8772 (14) | C21—C22 | 1.400 (12) |
P1—C27 | 1.824 (7) | C21—P2 | 1.834 (8) |
P1—C3 | 1.824 (9) | C22—C23 | 1.396 (12) |
P1—C9 | 1.835 (8) | C22—H25A | 0.9300 |
O1—C31 | 1.245 (15) | C23—C24 | 1.382 (13) |
N1—C31 | 1.300 (16) | C23—H19A | 0.9300 |
N1—C29 | 1.406 (18) | C24—C25 | 1.382 (13) |
N1—C30 | 1.450 (16) | C24—H18A | 0.9300 |
C1—C2 | 1.487 (13) | C25—C26 | 1.370 (12) |
C1—S2 | 1.842 (10) | C25—H15A | 0.9300 |
C1—H9A | 0.9700 | C26—H27A | 0.9300 |
C1—H9B | 0.9700 | C27—P1i | 1.824 (7) |
C2—S4 | 1.824 (9) | C27—H33A | 0.9700 |
C2—H16A | 0.9700 | C27—H33B | 0.9700 |
C2—H16B | 0.9700 | C28—P2i | 1.846 (6) |
C3—C4 | 1.372 (15) | C28—P2 | 1.846 (6) |
C3—C8 | 1.378 (13) | C28—H34A | 0.9700 |
C4—C5 | 1.392 (16) | C28—H34B | 0.9700 |
C4—H8A | 0.9300 | C29—H3A | 0.9600 |
C5—C6 | 1.36 (2) | C29—H3B | 0.9600 |
C5—H1A | 0.9300 | C29—H3C | 0.9600 |
C6—C7 | 1.37 (2) | C30—H30B | 0.9600 |
C6—H2A | 0.9300 | C30—H30C | 0.9600 |
C7—C8 | 1.370 (16) | C30—H30D | 0.9600 |
C7—H6A | 0.9300 | C31—H12 | 0.9300 |
C8—H5A | 0.9300 | C32—N2 | 1.437 (15) |
C9—C14 | 1.373 (12) | C32—H4A | 0.9600 |
C9—C10 | 1.396 (11) | C32—H4B | 0.9600 |
C10—C11 | 1.382 (12) | C32—H4C | 0.9600 |
C10—H22A | 0.9300 | C33—N2 | 1.452 (14) |
C11—C12 | 1.365 (14) | C33—H10A | 0.9600 |
C11—H29A | 0.9300 | C33—H10B | 0.9600 |
C12—C13 | 1.382 (13) | C33—H10C | 0.9600 |
C12—H17A | 0.9300 | C34—O2 | 1.218 (13) |
C13—C14 | 1.381 (13) | C34—N2 | 1.339 (14) |
C13—H13A | 0.9300 | C34—H11 | 0.9300 |
C14—H20A | 0.9300 | S3—Mo1i | 2.322 (2) |
C15—C16 | 1.389 (11) | S5—Mo1i | 2.344 (2) |
C15—C20 | 1.405 (12) | S5—Ag1i | 2.924 (3) |
C15—P2 | 1.820 (8) | ||
P1—Ag1—P2 | 124.54 (7) | C16—C17—H7A | 119.3 |
P1—Ag1—S4 | 114.92 (7) | C17—C18—C19 | 119.5 (9) |
P2—Ag1—S4 | 112.31 (7) | C17—C18—H14A | 120.2 |
P1—Ag1—S5 | 123.16 (8) | C19—C18—H14A | 120.2 |
P2—Ag1—S5 | 100.85 (8) | C20—C19—C18 | 120.6 (9) |
S4—Ag1—S5 | 67.02 (6) | C20—C19—H30A | 119.7 |
P1—Ag1—Ag1i | 88.50 (5) | C18—C19—H30A | 119.7 |
P2—Ag1—Ag1i | 88.98 (5) | C19—C20—C15 | 119.9 (8) |
S4—Ag1—Ag1i | 123.29 (5) | C19—C20—H31A | 120.1 |
S5—Ag1—Ag1i | 57.35 (4) | C15—C20—H31A | 120.1 |
S1—Mo1—S3 | 109.83 (12) | C26—C21—C22 | 119.7 (8) |
S1—Mo1—S5 | 106.97 (12) | C26—C21—P2 | 118.8 (6) |
S3—Mo1—S5 | 99.01 (8) | C22—C21—P2 | 121.2 (7) |
S1—Mo1—S2 | 105.81 (11) | C23—C22—C21 | 118.8 (8) |
S3—Mo1—S2 | 79.66 (8) | C23—C22—H25A | 120.6 |
S5—Mo1—S2 | 145.47 (11) | C21—C22—H25A | 120.6 |
S1—Mo1—S4 | 105.92 (10) | C24—C23—C22 | 120.8 (8) |
S3—Mo1—S4 | 142.96 (10) | C24—C23—H19A | 119.6 |
S5—Mo1—S4 | 79.26 (7) | C22—C23—H19A | 119.6 |
S2—Mo1—S4 | 81.67 (8) | C23—C24—C25 | 119.7 (8) |
S1—Mo1—Mo1i | 100.80 (8) | C23—C24—H18A | 120.1 |
S3—Mo1—Mo1i | 51.72 (5) | C25—C24—H18A | 120.1 |
S5—Mo1—Mo1i | 52.15 (5) | C26—C25—C24 | 120.4 (9) |
S2—Mo1—Mo1i | 130.22 (6) | C26—C25—H15A | 119.8 |
S4—Mo1—Mo1i | 129.64 (5) | C24—C25—H15A | 119.8 |
C27—P1—C3 | 106.1 (5) | C25—C26—C21 | 120.5 (8) |
C27—P1—C9 | 105.0 (4) | C25—C26—H27A | 119.7 |
C3—P1—C9 | 101.8 (4) | C21—C26—H27A | 119.7 |
C27—P1—Ag1 | 115.4 (4) | P1i—C27—P1 | 112.2 (6) |
C3—P1—Ag1 | 117.4 (3) | P1i—C27—H33A | 109.2 |
C9—P1—Ag1 | 109.5 (3) | P1—C27—H33A | 109.2 |
C31—N1—C29 | 120.6 (13) | P1i—C27—H33B | 109.2 |
C31—N1—C30 | 121.6 (11) | P1—C27—H33B | 109.2 |
C29—N1—C30 | 117.8 (13) | H33A—C27—H33B | 107.9 |
C2—C1—S2 | 110.0 (7) | P2i—C28—P2 | 112.4 (6) |
C2—C1—H9A | 109.7 | P2i—C28—H34A | 109.1 |
S2—C1—H9A | 109.7 | P2—C28—H34A | 109.1 |
C2—C1—H9B | 109.7 | P2i—C28—H34B | 109.1 |
S2—C1—H9B | 109.7 | P2—C28—H34B | 109.1 |
H9A—C1—H9B | 108.2 | H34A—C28—H34B | 107.9 |
C1—C2—S4 | 110.5 (7) | N1—C29—H3A | 109.5 |
C1—C2—H16A | 109.5 | N1—C29—H3B | 109.5 |
S4—C2—H16A | 109.5 | H3A—C29—H3B | 109.5 |
C1—C2—H16B | 109.5 | N1—C29—H3C | 109.5 |
S4—C2—H16B | 109.5 | H3A—C29—H3C | 109.5 |
H16A—C2—H16B | 108.1 | H3B—C29—H3C | 109.5 |
C4—C3—C8 | 118.5 (9) | N1—C30—H30B | 109.5 |
C4—C3—P1 | 119.4 (8) | N1—C30—H30C | 109.5 |
C8—C3—P1 | 122.1 (8) | H30B—C30—H30C | 109.5 |
C3—C4—C5 | 119.6 (13) | N1—C30—H30D | 109.5 |
C3—C4—H8A | 120.2 | H30B—C30—H30D | 109.5 |
C5—C4—H8A | 120.2 | H30C—C30—H30D | 109.5 |
C6—C5—C4 | 121.0 (14) | O1—C31—N1 | 127.4 (13) |
C6—C5—H1A | 119.5 | O1—C31—H12 | 116.3 |
C4—C5—H1A | 119.5 | N1—C31—H12 | 116.3 |
C5—C6—C7 | 119.6 (11) | N2—C32—H4A | 109.5 |
C5—C6—H2A | 120.2 | N2—C32—H4B | 109.5 |
C7—C6—H2A | 120.2 | H4A—C32—H4B | 109.5 |
C8—C7—C6 | 119.7 (13) | N2—C32—H4C | 109.5 |
C8—C7—H6A | 120.2 | H4A—C32—H4C | 109.5 |
C6—C7—H6A | 120.2 | H4B—C32—H4C | 109.5 |
C7—C8—C3 | 121.5 (12) | N2—C33—H10A | 109.5 |
C7—C8—H5A | 119.2 | N2—C33—H10B | 109.5 |
C3—C8—H5A | 119.2 | H10A—C33—H10B | 109.5 |
C14—C9—C10 | 119.6 (8) | N2—C33—H10C | 109.5 |
C14—C9—P1 | 124.5 (7) | H10A—C33—H10C | 109.5 |
C10—C9—P1 | 115.9 (6) | H10B—C33—H10C | 109.5 |
C11—C10—C9 | 119.9 (8) | O2—C34—N2 | 125.5 (11) |
C11—C10—H22A | 120.1 | O2—C34—H11 | 117.3 |
C9—C10—H22A | 120.1 | N2—C34—H11 | 117.3 |
C12—C11—C10 | 121.0 (8) | C15—P2—C21 | 105.5 (4) |
C12—C11—H29A | 119.5 | C15—P2—C28 | 104.7 (4) |
C10—C11—H29A | 119.5 | C21—P2—C28 | 102.7 (4) |
C11—C12—C13 | 118.5 (9) | C15—P2—Ag1 | 119.5 (3) |
C11—C12—H17A | 120.7 | C21—P2—Ag1 | 110.0 (3) |
C13—C12—H17A | 120.7 | C28—P2—Ag1 | 112.9 (3) |
C14—C13—C12 | 121.8 (9) | C1—S2—Mo1 | 104.6 (3) |
C14—C13—H13A | 119.1 | C34—N2—C32 | 120.7 (10) |
C12—C13—H13A | 119.1 | C34—N2—C33 | 120.7 (10) |
C9—C14—C13 | 119.3 (8) | C32—N2—C33 | 118.6 (10) |
C9—C14—H20A | 120.4 | Mo1—S3—Mo1i | 76.55 (10) |
C13—C14—H20A | 120.4 | C2—S4—Mo1 | 107.9 (3) |
C16—C15—C20 | 118.7 (8) | C2—S4—Ag1 | 117.7 (3) |
C16—C15—P2 | 119.0 (6) | Mo1—S4—Ag1 | 106.28 (8) |
C20—C15—P2 | 122.2 (6) | Mo1i—S5—Mo1 | 75.71 (9) |
C17—C16—C15 | 119.8 (8) | Mo1i—S5—Ag1 | 145.22 (13) |
C17—C16—H26A | 120.1 | Mo1—S5—Ag1 | 99.16 (6) |
C15—C16—H26A | 120.1 | Mo1i—S5—Ag1i | 99.16 (6) |
C18—C17—C16 | 121.4 (9) | Mo1—S5—Ag1i | 145.22 (13) |
C18—C17—H7A | 119.3 | Ag1—S5—Ag1i | 65.31 (7) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ag2Mo2(C2H4S2)2S4(C25H22P2)2]·3C3H7NO |
Mr | 1708.3 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 223 |
a, b, c (Å) | 26.022 (5), 21.375 (4), 12.721 (3) |
V (Å3) | 7076 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.35 × 0.20 × 0.07 |
Data collection | |
Diffractometer | Rigaku Mercury diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.746, 0.915 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 57121, 6401, 5931 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.085, 0.188, 1.35 |
No. of reflections | 6401 |
No. of parameters | 401 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0747P)2 + 33.869P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.95, −0.58 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge Jiangxi Science and Technology Normal University for funding.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In the past decades, the chemistry of the sulfido-bridged dinuclear clusters consisting of [M2S4] core (M = Mo, W) and various transition metals has attracted much attention. For example, precursors [(dtc)2Mo2S2(µ-S)2] (dtc = S2CNEt2) (Kuwata & Hidai, 2001) and [Cpx2Mo2S2(µ-S)2] (Cpx = pentamethyl-, pentaethyl- or pentabutyl-cyclopentadienyl) (Curtis et al.,1997; Halbert et al., 1985; Kawaguchi et al., 1997; Brunner et al., 1985) were shown to react with transition metals to form both incomplete cubane-like [Mo2M'S4] and complete cubane-like [Mo2M'2S4] clusters. The type of cluster formed is dependent upon the ability of the terminal St and the bridging µ-Sb groups in [Mo2S4] core to bind further metal centers. Recently, another precursor [Et4N]2[(edt)2Mo2S2(µ-S)2] (1), which has a chelating edt at each Mo site of the [Mo2S4] core, has been introduced; its terminal St, the doubly bridging µ-Sb, and chelating Sedt are capable of binding Cu(I) centers (Zhu et al.,1990; Lin et al., 1997; Wei et al., 2008). However, until now, only quite limited data have been reported involving precursor 1 bound to Ag(I) complexes. In this paper we describe the result of our efforts to generate a Mo/Ag/S cluster [Mo2S2(µ-S)2(edt)2Ag2(dppm)2].3DMF (2.3DMF) by reaction of 1 with two equivalents of Ag(CH3CN)4ClO4 in the presence of dppm ligand.
The asymmetric unit of 2.3DMF contains half of the [Mo2S2(µ-S)2(edt)2Ag2(dppm)2] molecule, and one and a half DMF molecules (Fig. 1). The complex may be considered as having a [Mo2S2(µ-S)2(edt)2]2- anionic unit bound to a [Ag2(dppm)2]2+ cation via two Ag-µ-Sedt and two Ag-µ4-Sb bonds. A crystallographic mirror plane runs through S3, S5, C27 and C28 atoms. Each Mo center has a distorted square pyramidal environment, consisting of one terminal St, one Sedt, one µ-Sedt, and two µ-S atoms. Each Ag center has a distorted tetrahedral coordination made up of one µ-Sedt, one µ4-S and two P atoms from two dppm ligands. The Ag1—S5 bond [2.924 (3) Å], involving the µ4-S atom, is much longer than Ag1—S4 with the Sedt atom [2.588 (2) Å]. The eight-membered [Ag—P—C—P—Ag—P—C—P] ring in the [Ag2(dppm)2]2+ dication adopts a boat conformation. The Mo···Mo distance [2.8772 (14) Å] is longer than that in the precursor 1 [2.863 (3) Å] (Pan et al.,1984). The Mo1-µ-S4 bond length is elongated by 0.05 Å relative to that of Mo1—S2 as the S4 atom is involved in coordination to the Ag1 atom. The Mo1—S5 bond [2.344 (2) Å] is slightly longer than Mo1—S3 [2.322 (2) Å] due to the µ4-character of the S5 atom.