Bis[μ2-bis­(diphenyl­phosphino)methane]bis­(μ2-ethane-1,2-dithiol­ato)-μ4-sulfido-μ2-sulfido-disulfidodimolybdenum(V)disilver(I) dimethyl­formamide tris­olvate

Wang, X.-C.; You, X.-L.

doi:10.1107/S1600536809048648

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1615

doi:10.1107/S1600536809048648

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Bis[μ₂-bis(diphenylphosphino)methane]bis(μ₂-ethane-1,2-dithiolato)-μ₄-sulfido-μ₂-sulfido-disulfidodimolybdenum(V)disilver(I) dimethylformamide trisolvate

Xing-Cong Wang ^a and Xiu-Li You ^a ^*

^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

(Received 6 October 2009; accepted 16 November 2009; online 21 November 2009)

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-S_edt 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

[Ag₂Mo₂(C₂H₄S₂)₂S₄(C₂₅H₂₂P₂)₂]·3C₃H₇NO
M_r = 1708.3
Orthorhombic, P n m a
a = 26.022 (5) Å
b = 21.375 (4) Å
c = 12.721 (3) Å
V = 7076 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 223 K
0.35 × 0.20 × 0.07 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.746, T_max = 0.915
57121 measured reflections
6401 independent reflections
5931 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.188
S = 1.35
6401 reflections
401 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048648/ya2110sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048648/ya2110Isup2.hkl

checkCIF report

Comment top

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 [Cp^x₂Mo₂S₂(µ-S)₂] (Cp^x = 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 S_t and the bridging µ-S_b 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 S_t, the doubly bridging µ-S_b, and chelating S_edt 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-S_edt and two Ag-µ₄-S_b 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 S_t, one S_edt, one µ-S_edt, and two µ-S atoms. Each Ag center has a distorted tetrahedral coordination made up of one µ-S_edt, 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 S_edt 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.

Related literature top

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 top

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).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: 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).

Figures top

Fig. 1. Molecular structure of 2.3DMF with thermal ellipsoids, drawn at 30% probability level; hydrogen atoms are omitted for clarity. The unlabeled atoms are derived from the reference atoms by means of the (x, 1/2 - y, z) symmetry transformation.

Bis[µ₂-bis(diphenylphosphino)methane]bis(µ₂-ethane-1,2-dithiolato)- µ₄-sulfido-µ₂-sulfido-disulfidodimolybdenum(V)disilver(I) dimethylformamide trisolvate top

Crystal data top

[Ag₂Mo₂(C₂H₄S₂)₂S₄(C₂₅H₂₂P₂)₂]·3C₃H₇NO	F(000) = 3448
M_r = 1708.3	D_x = 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

Data collection top

Rigaku Mercury diffractometer	6401 independent reflections
Radiation source: fine-focus sealed tube	5931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
ω scans	θ_max = 25.0°, θ_min = 3.4°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −30→30
T_min = 0.746, T_max = 0.915	k = −25→25
57121 measured reflections	l = −15→15

Refinement top

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(F_o²) + (0.0747P)² + 33.869P] where P = (F_o² + 2F_c²)/3
6401 reflections	(Δ/σ)_max < 0.001
401 parameters	Δρ_max = 0.95 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Ag₂Mo₂(C₂H₄S₂)₂S₄(C₂₅H₂₂P₂)₂]·3C₃H₇NO	V = 7076 (3) Å³
M_r = 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

Data collection top

Rigaku Mercury diffractometer	6401 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	5931 reflections with I > 2σ(I)
T_min = 0.746, T_max = 0.915	R_int = 0.090
57121 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	0 restraints
wR(F²) = 0.188	H-atom parameters constrained
S = 1.35	w = 1/[σ²(F_o²) + (0.0747P)² + 33.869P] where P = (F_o² + 2F_c²)/3
6401 reflections	Δρ_max = 0.95 e Å⁻³
401 parameters	Δρ_min = −0.58 e Å⁻³

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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.746, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	57121, 6401, 5931
R_int	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(F_o²) + (0.0747P)² + 33.869P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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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