A tetra­silver(I)ditungsten(VI) cluster with sulfide and bis­(diphenyl­phosphino)methane ligands

Wang, R.; Song, L.-L.; Hu, K.-Y.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536810034197

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages m1185-m1186

doi:10.1107/S1600536810034197

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A tetrasilver(I)ditungsten(VI) cluster with sulfide and bis(diphenylphosphino)methane ligands

Rong Wang,^a Li-Li Song,^a Ke-Yi Hu,^a ^* Qiong-Hua Jin ^a and Cun-Lin Zhang ^b

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and ^bBeijing Key Laboratory for Terahertz Spectroscopy and Imaging, Key Laboratory of Terahertz Optoelectronics, Ministry of Education, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: jinqh204@163.com

(Received 9 July 2010; accepted 25 August 2010; online 4 September 2010)

The asymmetric unit of the title complex, [Ag₄W₂S₈(C₂₅H₂₂P₂)₃]·2C₃H₇NO, tris[μ₂-bis(diphenylphosphino)methane]-3:6κ²P:P′;4:5κ²P:P′;5:6κ²P:P′-μ₅-sulfido-2:3:4:5:6κ⁵S-μ₃-sulfido-1:3:4κ³S-tetra-μ₂-sulfido-1:3κ²S;1:4κ²S;2:5κ²S;2:6κ²S-disulfido-1κS,2κS-tetrasilver(I)ditungsten(VI) N,N-dimethylformamide disolvate, contains two [WS₄]²⁻ anions, four silver cations, three bidentate–bridging bis(diphenylphosphino)methane (dppm) ligands and two N,N-dimethylformamide (DMF) solvent molecules. The coordination geometry of each Ag atom is distorted tetrahedral. Two Ag ions are coordinated by μ₂-S and μ₅-S atoms, and by two P atoms from two dppm ligands, while the other two Ag atoms are coordinated by μ₂-S, μ₃-S and μ₅-S atoms, and by one P atom from a dppm ligand.

Related literature

For related structures, see: Yu et al. (2001 ). For general background to Mo(W)—Cu(Ag)—S clusters derived from tetrathiotungstate and tetrathiomolybdate [MS₄]²⁻(M = Mo, W) synthons, see: George et al.(2000 , 2003 ); Hong et al. (1997 ); Lang et al. (2006 ); Niu et al. (2005 ); Ren et al. (2006 ); Shi et al. (1995 ); Yu et al. (2001); Zhang et al. (2000 , 2004 ).

Experimental

Crystal data

[Ag₄W₂S₈(C₂₅H₂₂P₂)₃]·2C₃H₇NO
M_r = 2354.95
Monoclinic, P 2₁ /c
a = 22.931 (2) Å
b = 14.0395 (12) Å
c = 27.855 (3) Å
β = 107.224 (1)°
V = 8565.6 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.93 mm⁻¹
T = 93 K
0.47 × 0.43 × 0.43 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.262, T_max = 0.281
69256 measured reflections
19520 independent reflections
18777 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.089
S = 1.14
19520 reflections
950 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.36 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034197/dn2590sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034197/dn2590Isup2.hkl

checkCIF report

Comment top

In the recent years, Mo(W)—Cu(Ag)—S clusters derived from the well known synthons tetrathiotungstate and tetrathiomolybdate([MS₄]^2-(M=Mo, W)) have been extensively investigated due to their rich structural chemistry (Zhang et al., 2000; Zhang et al., 2004; Lang et al., 2006; Ren et al., 2006) and potential applications in biological systems (George et al., 2000; George et al. 2003), and optical materials (Shi et al., 1995; Hong et al., 1997; Niu et al., 2005). Herein a new complex [(WS₄)₂Ag₄(dppm)₃].2DMF (1) [dppm=bis(diphenylphosphino)methane,DMF=N,N-dimethylformamide] is reported.

The asymmetric unit contains two [WS₄]^2- anions, four silver cations, three bridging dppm ligands and two DMF solvent molecules(Fig. 1). One [WS₄]^2- anion bridges two Ag atoms whereas the other [WS₄]^2- anion bridges four Ag atoms. In both anions three sulfur atoms are coordinating to silver atoms whereas the W=S unit remaining intact. There are three kinds of bridging S atom: µ₂-S (atoms S1, S3, S6 and S7, each is bonded to one W and one Ag atom), µ₃-S (S2, bonded to W1, Ag1 and Ag2) and µ₅-S (S5, bonded to W2 and four Ag atoms).

In complex 1, Ag1 and Ag2 are coordinated by one P atom from one dppm ligand, one µ₂-S atom, one µ₃-S atom and one µ₅-S, while Ag3 and Ag4 are coordinated by two P atoms from two dppm ligands, one µ₂-S atom and one µ₅-S atom. It is noticeable that the coordination mode of µ₅-S bonding to mixed metal ions is unique.

In two [WS₄]^2- units, the average length of W-µ₂-S (2.2085 Å) is longer than that of W=S (2.1496 Å), but is shorter than those of W-µ₃-S of (2.273 Å) and W-µ₅-S (2.7102 Å). The Ag—S bond distances are in the range of 2.5140 (12)–2.8409 (12) Å. The average distance of Ag1(Ag2)—P (2.3919 Å) is shorter than that of Ag3(Ag4)—P.

Interestingly, the fragment [(WS₄)₂Ag₄(dppm)₃] in the title complex I is an isomer of [(WS₄)₂Ag₄(dppm)₃](II)(Yu et al., 2001) (Figure 2). The main difference being the occurence of the µ₅-S in complex I. Consequently, in complex I each Ag atom is four-coordinated, while in complex II two Ag atoms are three-coordinated, the other two Ag atoms are four-coordinated. The mean distance of W—S(2.086 Å) in I is shorter than that observed in complex II (2.136 Å). The average W—Ag length in complex I (3.0356 Å) is similar to that in complex II (3.0406 Å).

The formation of this two isomers may be related to the choice of the solvent. Complex I was synthesized in the mixed solvents DMF and MeCN, while complex II is obtained in CH₂Cl₂. In this paper, complex I was prepared by using different Ag salts as starting materials: AgBF₄ or AgNO₃. From this we know, the fragment [(WS₄)₂Ag₄(dppm)₃] may be easily obtained because of its stable structure with high symmetry.

Related literature top

For related structures, see: Yu et al. (2001). For general background to Mo(W)—Cu(Ag)—S clusters derived from tetrathiotungstate and tetrathiomolybdate [MS₄]^2-(M = Mo, W) synthons, see: George et al.(2000, 2003); Hong et al. (1997); Lang et al. (2006); Niu et al. (2005); Ren et al. (2006); Shi et al. (1995); Yu et al. (2001); Zhang et al. (2000, 2004).

Experimental top

The title complex was prepared by the reaction of AgNO₃, bis(diphenylphosphino)methane(dppm), (NH₄)₂WS₄ and Phen (phenathroline) in molar ratio of 2:4:1:0.5 in the mixed solvents MeCN and DMF(10 ml,V/V=1/1). The mixture was stirred at room temperature for 8 h, then filtered. Subsequent slow evaporation of the filtrate resulted in the formation of yellow crystals of the title complex. Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared. Analysis found(percentage): C 41.33, H 3.40, N 1.18; calculated: C 41.31, H 3.42, N 1.19.

Alternative method to synthesize complex 1 is using AgBF₄ in place of AgNO₃ in the starting materials.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of compound I with the atom labeling scheme. Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. Comparison of the two isomers [(WS₄)₂Ag₄(dppm)₃] I and II.

tris[µ₂-bis(diphenylphosphino)methane]- 3:6κ²P:P';4:5κ²P:P'; 5:6κ²P:P'-µ₅-sulfido-2:3:4:5:6κ⁵S- µ₃-sulfido-1:3:4κ³S- tetra-µ₂-sulfido-1:3κ²S;1:4κ²S; 2:5κ²S;2:6κ²S-disulfido-1κS,2κS- tetrasilver(I)ditungsten(VI) N,N-dimethylformamide disolvate top

Crystal data top

[Ag₄W₂S₈(C₂₅H₂₂P₂)₃]·2C₃H₇NO	F(000) = 4600
M_r = 2354.95	D_x = 1.826 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27248 reflections
a = 22.931 (2) Å	θ = 3.0–27.5°
b = 14.0395 (12) Å	µ = 3.93 mm⁻¹
c = 27.855 (3) Å	T = 93 K
β = 107.224 (1)°	Block, yellow
V = 8565.6 (14) Å³	0.47 × 0.43 × 0.43 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	19520 independent reflections
Radiation source: Rotating Anode	18777 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −29→20
T_min = 0.262, T_max = 0.281	k = −18→18
69256 measured reflections	l = −35→36

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0341P)² + 13.8363P] where P = (F_o² + 2F_c²)/3
19520 reflections	(Δ/σ)_max = 0.009
950 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −1.36 e Å⁻³

Crystal data top

[Ag₄W₂S₈(C₂₅H₂₂P₂)₃]·2C₃H₇NO	V = 8565.6 (14) Å³
M_r = 2354.95	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.931 (2) Å	µ = 3.93 mm⁻¹
b = 14.0395 (12) Å	T = 93 K
c = 27.855 (3) Å	0.47 × 0.43 × 0.43 mm
β = 107.224 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	19520 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	18777 reflections with I > 2σ(I)
T_min = 0.262, T_max = 0.281	R_int = 0.045
69256 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0341P)² + 13.8363P] where P = (F_o² + 2F_c²)/3
19520 reflections	Δρ_max = 1.20 e Å⁻³
950 parameters	Δρ_min = −1.36 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
W1	0.685156 (8)	0.527538 (12)	0.590934 (6)	0.00959 (5)
W2	0.828154 (8)	0.329261 (13)	0.458854 (7)	0.01383 (5)
Ag1	0.701283 (16)	0.55717 (2)	0.490031 (13)	0.01578 (7)
Ag2	0.797387 (15)	0.41531 (2)	0.598751 (13)	0.01418 (7)
Ag3	0.776781 (15)	0.20725 (2)	0.532723 (12)	0.01373 (7)
Ag4	0.693052 (15)	0.34050 (2)	0.401396 (12)	0.01168 (7)
S1	0.60897 (5)	0.52790 (8)	0.52055 (4)	0.0157 (2)
S2	0.77015 (5)	0.59208 (8)	0.57931 (4)	0.0129 (2)
S3	0.70064 (5)	0.37936 (8)	0.62017 (4)	0.0136 (2)
S4	0.65859 (5)	0.61359 (8)	0.64489 (4)	0.0154 (2)
S5	0.75460 (5)	0.37745 (8)	0.49394 (4)	0.0136 (2)
S6	0.84065 (6)	0.17432 (9)	0.46535 (5)	0.0247 (3)
S7	0.79958 (5)	0.36970 (9)	0.37903 (4)	0.0156 (2)
S8	0.91157 (6)	0.40177 (12)	0.49661 (5)	0.0332 (3)
P1	0.70165 (5)	0.64377 (8)	0.41615 (4)	0.0122 (2)
P2	0.90214 (5)	0.37198 (8)	0.63471 (4)	0.0119 (2)
P3	0.86722 (5)	0.16721 (8)	0.60311 (4)	0.0123 (2)
P4	0.68282 (5)	0.11687 (8)	0.49608 (4)	0.0110 (2)
P5	0.65584 (5)	0.17597 (8)	0.38414 (4)	0.0100 (2)
P6	0.64487 (5)	0.47428 (8)	0.34787 (4)	0.0112 (2)
C1	0.7730 (2)	0.7088 (3)	0.42479 (17)	0.0187 (10)
C2	0.8271 (2)	0.6582 (4)	0.4461 (2)	0.0272 (12)
H2	0.8255	0.5942	0.4567	0.033*
C3	0.8832 (3)	0.7019 (5)	0.4518 (2)	0.0370 (15)
H3	0.9200	0.6673	0.4655	0.044*
C4	0.8853 (3)	0.7961 (5)	0.4374 (2)	0.0437 (18)
H4	0.9236	0.8258	0.4412	0.052*
C5	0.8326 (3)	0.8468 (5)	0.4178 (2)	0.0433 (17)
H5	0.8345	0.9118	0.4090	0.052*
C6	0.7761 (3)	0.8030 (4)	0.4107 (2)	0.0288 (12)
H6	0.7396	0.8377	0.3962	0.035*
C7	0.6402 (2)	0.7312 (3)	0.39761 (17)	0.0153 (9)
C8	0.6100 (2)	0.7549 (3)	0.43287 (19)	0.0203 (10)
H8	0.6220	0.7256	0.4651	0.024*
C9	0.5629 (3)	0.8202 (4)	0.4214 (2)	0.0282 (12)
H9	0.5431	0.8370	0.4457	0.034*
C10	0.5449 (2)	0.8609 (4)	0.3743 (2)	0.0281 (12)
H10	0.5121	0.9051	0.3661	0.034*
C11	0.5742 (3)	0.8380 (4)	0.3387 (2)	0.0257 (11)
H11	0.5612	0.8665	0.3064	0.031*
C12	0.6221 (2)	0.7741 (3)	0.35032 (18)	0.0191 (10)
H12	0.6426	0.7594	0.3262	0.023*
C13	0.6964 (2)	0.5780 (3)	0.35824 (16)	0.0130 (9)
H13A	0.7378	0.5560	0.3592	0.016*
H13B	0.6820	0.6220	0.3293	0.016*
C14	0.5696 (2)	0.5181 (3)	0.34616 (17)	0.0141 (9)
C15	0.5491 (2)	0.5052 (3)	0.38825 (17)	0.0155 (9)
H15	0.5748	0.4752	0.4174	0.019*
C16	0.4916 (2)	0.5358 (3)	0.38777 (19)	0.0201 (10)
H16	0.4786	0.5278	0.4168	0.024*
C17	0.4532 (2)	0.5778 (3)	0.3455 (2)	0.0224 (11)
H17	0.4136	0.5978	0.3453	0.027*
C18	0.4728 (2)	0.5907 (4)	0.30313 (19)	0.0236 (11)
H18	0.4464	0.6193	0.2738	0.028*
C19	0.5311 (2)	0.5619 (3)	0.30380 (19)	0.0196 (10)
H19	0.5446	0.5722	0.2751	0.024*
C20	0.6363 (2)	0.4418 (3)	0.28259 (18)	0.0152 (9)
C21	0.6730 (2)	0.4792 (3)	0.25509 (17)	0.0169 (9)
H21	0.7017	0.5278	0.2694	0.020*
C22	0.6680 (2)	0.4458 (4)	0.20679 (19)	0.0234 (11)
H22	0.6928	0.4719	0.1882	0.028*
C23	0.6265 (2)	0.3743 (4)	0.18612 (19)	0.0256 (11)
H23	0.6230	0.3515	0.1533	0.031*
C24	0.5905 (3)	0.3362 (4)	0.21297 (19)	0.0269 (12)
H24	0.5630	0.2860	0.1989	0.032*
C25	0.5941 (2)	0.3709 (3)	0.26080 (18)	0.0201 (10)
H25	0.5678	0.3462	0.2785	0.024*
C26	0.57227 (19)	0.1766 (3)	0.36167 (16)	0.0112 (8)
C27	0.5416 (2)	0.2602 (3)	0.36530 (18)	0.0173 (9)
H27	0.5644	0.3144	0.3807	0.021*
C28	0.4787 (2)	0.2666 (4)	0.3470 (2)	0.0244 (11)
H28	0.4587	0.3248	0.3496	0.029*
C29	0.4448 (2)	0.1873 (4)	0.32495 (19)	0.0215 (10)
H29	0.4016	0.1913	0.3118	0.026*
C30	0.4751 (2)	0.1017 (3)	0.32236 (18)	0.0189 (10)
H30	0.4522	0.0465	0.3087	0.023*
C31	0.5378 (2)	0.0973 (3)	0.33959 (17)	0.0173 (9)
H31	0.5580	0.0395	0.3364	0.021*
C32	0.6776 (2)	0.1222 (3)	0.33224 (16)	0.0114 (8)
C33	0.6938 (2)	0.1824 (3)	0.29875 (17)	0.0162 (9)
H33	0.6965	0.2491	0.3049	0.019*
C34	0.7063 (2)	0.1462 (4)	0.25613 (18)	0.0201 (10)
H34	0.7169	0.1880	0.2333	0.024*
C35	0.7029 (2)	0.0485 (4)	0.24736 (18)	0.0209 (10)
H35	0.7113	0.0236	0.2184	0.025*
C36	0.6874 (2)	−0.0127 (3)	0.28086 (18)	0.0200 (10)
H36	0.6848	−0.0793	0.2747	0.024*
C37	0.6757 (2)	0.0242 (3)	0.32364 (18)	0.0183 (10)
H37	0.6664	−0.0178	0.3471	0.022*
C38	0.6761 (2)	0.0792 (3)	0.43110 (16)	0.0134 (9)
H38A	0.7154	0.0511	0.4304	0.016*
H38B	0.6446	0.0288	0.4212	0.016*
C39	0.6064 (2)	0.1611 (3)	0.49084 (16)	0.0119 (8)
C40	0.5981 (2)	0.2566 (3)	0.50130 (18)	0.0187 (10)
H40	0.6324	0.2970	0.5143	0.022*
C41	0.5393 (2)	0.2920 (4)	0.4926 (2)	0.0233 (11)
H41	0.5335	0.3568	0.4998	0.028*
C42	0.4894 (2)	0.2340 (4)	0.4736 (2)	0.0248 (11)
H42	0.4494	0.2594	0.4672	0.030*
C43	0.4970 (2)	0.1386 (4)	0.46372 (18)	0.0193 (10)
H43	0.4624	0.0985	0.4513	0.023*
C44	0.5557 (2)	0.1020 (3)	0.47208 (17)	0.0159 (9)
H44	0.5612	0.0370	0.4650	0.019*
C45	0.6863 (2)	0.0014 (3)	0.52730 (17)	0.0144 (9)
C46	0.7188 (2)	−0.0738 (3)	0.51465 (18)	0.0198 (10)
H46	0.7371	−0.0662	0.4885	0.024*
C47	0.7243 (3)	−0.1603 (4)	0.54060 (19)	0.0254 (11)
H47	0.7460	−0.2117	0.5318	0.030*
C48	0.6979 (2)	−0.1708 (4)	0.57924 (19)	0.0245 (11)
H48	0.7016	−0.2295	0.5968	0.029*
C49	0.6666 (2)	−0.0966 (4)	0.59207 (19)	0.0246 (11)
H49	0.6486	−0.1044	0.6185	0.030*
C50	0.6608 (2)	−0.0102 (4)	0.56679 (18)	0.0204 (10)
H50	0.6395	0.0410	0.5763	0.024*
C51	0.9045 (2)	0.0612 (3)	0.58746 (16)	0.0156 (9)
C52	0.8728 (3)	−0.0241 (4)	0.5823 (2)	0.0297 (12)
H52	0.8345	−0.0265	0.5890	0.036*
C53	0.8965 (3)	−0.1062 (4)	0.5675 (2)	0.0377 (15)
H53	0.8744	−0.1643	0.5638	0.045*
C54	0.9519 (3)	−0.1034 (4)	0.5582 (2)	0.0327 (13)
H54	0.9682	−0.1597	0.5483	0.039*
C55	0.9841 (3)	−0.0190 (4)	0.5631 (2)	0.0297 (12)
H55	1.0223	−0.0171	0.5563	0.036*
C56	0.9603 (2)	0.0633 (4)	0.5781 (2)	0.0246 (11)
H56	0.9826	0.1212	0.5819	0.030*
C57	0.8633 (2)	0.1414 (3)	0.66613 (17)	0.0137 (9)
C58	0.9155 (2)	0.1100 (3)	0.70346 (17)	0.0182 (10)
H58	0.9518	0.0962	0.6950	0.022*
C59	0.9142 (2)	0.0992 (4)	0.75240 (18)	0.0200 (10)
H59	0.9496	0.0777	0.7775	0.024*
C60	0.8614 (2)	0.1197 (4)	0.76500 (18)	0.0209 (10)
H60	0.8610	0.1132	0.7989	0.025*
C61	0.8097 (2)	0.1492 (3)	0.72898 (19)	0.0188 (10)
H61	0.7737	0.1628	0.7379	0.023*
C62	0.8100 (2)	0.1593 (3)	0.67889 (18)	0.0170 (9)
H62	0.7739	0.1783	0.6538	0.020*
C63	0.92682 (19)	0.2589 (3)	0.61403 (16)	0.0116 (8)
H63A	0.9638	0.2360	0.6399	0.014*
H63B	0.9377	0.2695	0.5826	0.014*
C64	0.9232 (2)	0.3680 (3)	0.70338 (17)	0.0138 (9)
C65	0.9833 (2)	0.3707 (4)	0.73330 (18)	0.0212 (10)
H65	1.0153	0.3700	0.7181	0.025*
C66	0.9974 (2)	0.3745 (4)	0.78542 (19)	0.0251 (11)
H66	1.0388	0.3787	0.8055	0.030*
C67	0.9514 (3)	0.3723 (4)	0.80778 (19)	0.0286 (12)
H67	0.9612	0.3739	0.8434	0.034*
C68	0.8912 (3)	0.3677 (4)	0.77874 (19)	0.0277 (12)
H68	0.8595	0.3658	0.7943	0.033*
C69	0.8771 (2)	0.3658 (3)	0.72647 (18)	0.0191 (10)
H69	0.8357	0.3630	0.7065	0.023*
C70	0.9557 (2)	0.4595 (3)	0.62351 (17)	0.0142 (9)
C71	1.0132 (2)	0.4363 (3)	0.61976 (17)	0.0153 (9)
H71	1.0264	0.3718	0.6227	0.018*
C72	1.0514 (2)	0.5073 (3)	0.61178 (17)	0.0173 (9)
H72	1.0904	0.4913	0.6087	0.021*
C73	1.0329 (2)	0.6012 (4)	0.60827 (18)	0.0205 (10)
H73	1.0593	0.6496	0.6030	0.025*
C74	0.9756 (2)	0.6252 (4)	0.61239 (19)	0.0226 (11)
H74	0.9633	0.6900	0.6108	0.027*
C75	0.9368 (2)	0.5540 (3)	0.61882 (19)	0.0193 (10)
H75	0.8970	0.5699	0.6200	0.023*
O1	0.71217 (18)	0.7272 (3)	0.26992 (15)	0.0286 (9)
N1	0.78968 (19)	0.6532 (3)	0.24912 (16)	0.0215 (9)
C76	0.7377 (2)	0.7023 (3)	0.2391 (2)	0.0230 (11)
H76	0.7188	0.7196	0.2050	0.028*
C77	0.8220 (2)	0.6244 (4)	0.3001 (2)	0.0287 (12)
H77A	0.8074	0.6621	0.3239	0.043*
H77B	0.8659	0.6350	0.3065	0.043*
H77C	0.8145	0.5567	0.3044	0.043*
C78	0.8173 (3)	0.6276 (4)	0.2097 (2)	0.0303 (12)
H78A	0.7921	0.6525	0.1773	0.045*
H78B	0.8199	0.5581	0.2078	0.045*
H78C	0.8583	0.6550	0.2177	0.045*
O2	0.9365 (2)	0.6952 (4)	0.83007 (18)	0.0508 (13)
N2	0.8745 (2)	0.6405 (3)	0.75669 (18)	0.0266 (10)
C79	0.8866 (3)	0.6654 (4)	0.8036 (2)	0.0352 (14)
H79	0.8546	0.6604	0.8186	0.042*
C80	0.9225 (3)	0.6454 (5)	0.7310 (3)	0.0405 (15)
H80A	0.9587	0.6772	0.7530	0.061*
H80B	0.9072	0.6815	0.6997	0.061*
H80C	0.9334	0.5808	0.7235	0.061*
C81	0.8168 (3)	0.6078 (5)	0.7255 (3)	0.0424 (16)
H81A	0.7874	0.6068	0.7448	0.064*
H81B	0.8213	0.5434	0.7135	0.064*
H81C	0.8021	0.6507	0.6966	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.00959 (9)	0.01051 (8)	0.00897 (8)	0.00050 (6)	0.00322 (7)	0.00076 (6)
W2	0.01041 (9)	0.02124 (10)	0.00953 (9)	−0.00198 (7)	0.00248 (7)	0.00324 (7)
Ag1	0.01769 (18)	0.01876 (17)	0.01144 (16)	0.00004 (13)	0.00515 (13)	0.00419 (13)
Ag2	0.00979 (16)	0.01623 (16)	0.01571 (17)	0.00196 (12)	0.00253 (13)	0.00284 (13)
Ag3	0.01196 (17)	0.01387 (16)	0.01320 (16)	−0.00216 (12)	0.00038 (13)	0.00199 (12)
Ag4	0.01172 (16)	0.01111 (15)	0.01114 (15)	−0.00089 (12)	0.00175 (12)	0.00073 (12)
S1	0.0119 (5)	0.0230 (6)	0.0107 (5)	−0.0008 (4)	0.0009 (4)	0.0018 (4)
S2	0.0118 (5)	0.0124 (5)	0.0151 (5)	−0.0015 (4)	0.0049 (4)	0.0014 (4)
S3	0.0149 (5)	0.0121 (5)	0.0154 (5)	0.0014 (4)	0.0069 (4)	0.0030 (4)
S4	0.0166 (6)	0.0149 (5)	0.0165 (5)	0.0016 (4)	0.0077 (4)	−0.0022 (4)
S5	0.0178 (6)	0.0134 (5)	0.0100 (5)	−0.0002 (4)	0.0047 (4)	0.0002 (4)
S6	0.0313 (7)	0.0250 (6)	0.0236 (6)	0.0131 (5)	0.0168 (6)	0.0079 (5)
S7	0.0139 (6)	0.0241 (6)	0.0093 (5)	−0.0017 (4)	0.0043 (4)	0.0032 (4)
S8	0.0199 (7)	0.0608 (10)	0.0151 (6)	−0.0208 (6)	−0.0006 (5)	0.0056 (6)
P1	0.0146 (6)	0.0116 (5)	0.0102 (5)	−0.0019 (4)	0.0036 (4)	0.0007 (4)
P2	0.0103 (5)	0.0127 (5)	0.0118 (5)	−0.0002 (4)	0.0019 (4)	0.0012 (4)
P3	0.0126 (6)	0.0123 (5)	0.0105 (5)	−0.0008 (4)	0.0012 (4)	0.0014 (4)
P4	0.0119 (5)	0.0107 (5)	0.0099 (5)	−0.0015 (4)	0.0026 (4)	0.0009 (4)
P5	0.0110 (5)	0.0100 (5)	0.0089 (5)	−0.0003 (4)	0.0027 (4)	0.0002 (4)
P6	0.0111 (6)	0.0112 (5)	0.0111 (5)	0.0000 (4)	0.0032 (4)	0.0017 (4)
C1	0.024 (3)	0.021 (2)	0.014 (2)	−0.0047 (19)	0.0099 (19)	−0.0057 (19)
C2	0.020 (3)	0.031 (3)	0.030 (3)	−0.004 (2)	0.006 (2)	−0.009 (2)
C3	0.021 (3)	0.056 (4)	0.034 (3)	−0.010 (3)	0.007 (2)	−0.016 (3)
C4	0.039 (4)	0.067 (5)	0.032 (3)	−0.035 (3)	0.020 (3)	−0.021 (3)
C5	0.050 (4)	0.041 (4)	0.040 (4)	−0.030 (3)	0.016 (3)	−0.005 (3)
C6	0.034 (3)	0.027 (3)	0.025 (3)	−0.015 (2)	0.009 (2)	0.003 (2)
C7	0.018 (2)	0.011 (2)	0.017 (2)	−0.0027 (17)	0.0049 (19)	0.0010 (17)
C8	0.025 (3)	0.016 (2)	0.021 (2)	−0.0004 (19)	0.010 (2)	−0.0008 (19)
C9	0.032 (3)	0.022 (3)	0.036 (3)	0.004 (2)	0.019 (3)	0.004 (2)
C10	0.024 (3)	0.022 (3)	0.039 (3)	0.004 (2)	0.009 (2)	0.005 (2)
C11	0.029 (3)	0.019 (2)	0.029 (3)	0.002 (2)	0.008 (2)	0.006 (2)
C12	0.028 (3)	0.015 (2)	0.015 (2)	0.0009 (19)	0.008 (2)	0.0018 (18)
C13	0.014 (2)	0.014 (2)	0.010 (2)	−0.0012 (17)	0.0027 (17)	0.0031 (17)
C14	0.015 (2)	0.014 (2)	0.015 (2)	−0.0031 (17)	0.0063 (18)	−0.0027 (17)
C15	0.015 (2)	0.015 (2)	0.016 (2)	−0.0023 (17)	0.0044 (18)	−0.0044 (18)
C16	0.018 (3)	0.024 (3)	0.019 (2)	−0.0012 (19)	0.008 (2)	−0.003 (2)
C17	0.015 (2)	0.020 (2)	0.034 (3)	0.0037 (19)	0.009 (2)	−0.001 (2)
C18	0.020 (3)	0.026 (3)	0.021 (3)	0.004 (2)	0.000 (2)	0.004 (2)
C19	0.019 (3)	0.021 (2)	0.021 (2)	0.0055 (19)	0.008 (2)	0.006 (2)
C20	0.014 (2)	0.010 (2)	0.020 (2)	0.0033 (17)	0.0036 (18)	0.0031 (18)
C21	0.013 (2)	0.022 (2)	0.015 (2)	0.0022 (18)	0.0031 (18)	0.0002 (18)
C22	0.023 (3)	0.032 (3)	0.016 (2)	0.009 (2)	0.007 (2)	0.001 (2)
C23	0.031 (3)	0.028 (3)	0.014 (2)	0.003 (2)	0.001 (2)	−0.003 (2)
C24	0.042 (3)	0.015 (2)	0.017 (2)	−0.005 (2)	−0.002 (2)	−0.0003 (19)
C25	0.025 (3)	0.016 (2)	0.016 (2)	−0.0064 (19)	0.000 (2)	0.0033 (18)
C26	0.009 (2)	0.017 (2)	0.0078 (19)	0.0001 (16)	0.0029 (16)	0.0040 (16)
C27	0.018 (2)	0.016 (2)	0.019 (2)	−0.0002 (18)	0.0084 (19)	0.0023 (18)
C28	0.019 (3)	0.020 (2)	0.037 (3)	0.005 (2)	0.012 (2)	0.000 (2)
C29	0.011 (2)	0.033 (3)	0.022 (3)	−0.002 (2)	0.0048 (19)	0.002 (2)
C30	0.018 (2)	0.021 (2)	0.017 (2)	−0.0063 (19)	0.0049 (19)	−0.0068 (19)
C31	0.019 (2)	0.018 (2)	0.014 (2)	−0.0008 (18)	0.0030 (19)	−0.0003 (18)
C32	0.013 (2)	0.012 (2)	0.0088 (19)	0.0016 (16)	0.0031 (16)	−0.0014 (16)
C33	0.018 (2)	0.014 (2)	0.017 (2)	0.0010 (17)	0.0056 (19)	0.0008 (18)
C34	0.020 (3)	0.026 (3)	0.017 (2)	−0.003 (2)	0.010 (2)	0.002 (2)
C35	0.024 (3)	0.027 (3)	0.013 (2)	0.000 (2)	0.007 (2)	−0.004 (2)
C36	0.028 (3)	0.011 (2)	0.020 (2)	0.0032 (19)	0.006 (2)	−0.0052 (18)
C37	0.025 (3)	0.017 (2)	0.014 (2)	0.0002 (19)	0.007 (2)	0.0025 (18)
C38	0.016 (2)	0.012 (2)	0.012 (2)	−0.0024 (17)	0.0048 (18)	−0.0011 (17)
C39	0.011 (2)	0.017 (2)	0.0081 (19)	−0.0030 (16)	0.0038 (16)	0.0013 (16)
C40	0.018 (2)	0.017 (2)	0.019 (2)	−0.0022 (18)	0.0034 (19)	−0.0039 (19)
C41	0.023 (3)	0.017 (2)	0.033 (3)	0.003 (2)	0.013 (2)	−0.002 (2)
C42	0.018 (3)	0.033 (3)	0.025 (3)	0.003 (2)	0.009 (2)	−0.003 (2)
C43	0.015 (2)	0.023 (2)	0.019 (2)	−0.0064 (19)	0.0053 (19)	−0.005 (2)
C44	0.017 (2)	0.017 (2)	0.015 (2)	−0.0040 (18)	0.0071 (18)	−0.0027 (18)
C45	0.013 (2)	0.018 (2)	0.012 (2)	−0.0051 (17)	0.0032 (17)	0.0018 (17)
C46	0.028 (3)	0.017 (2)	0.015 (2)	−0.0001 (19)	0.006 (2)	0.0006 (18)
C47	0.037 (3)	0.017 (2)	0.018 (2)	0.000 (2)	0.001 (2)	−0.001 (2)
C48	0.030 (3)	0.018 (2)	0.019 (3)	−0.006 (2)	−0.003 (2)	0.002 (2)
C49	0.027 (3)	0.030 (3)	0.017 (2)	−0.006 (2)	0.007 (2)	0.009 (2)
C50	0.024 (3)	0.024 (2)	0.015 (2)	0.001 (2)	0.007 (2)	0.0054 (19)
C51	0.019 (2)	0.014 (2)	0.010 (2)	0.0035 (18)	−0.0017 (18)	0.0002 (17)
C52	0.028 (3)	0.023 (3)	0.037 (3)	0.000 (2)	0.008 (3)	−0.003 (2)
C53	0.044 (4)	0.015 (3)	0.051 (4)	−0.004 (2)	0.008 (3)	−0.012 (3)
C54	0.050 (4)	0.024 (3)	0.020 (3)	0.011 (3)	0.003 (3)	−0.008 (2)
C55	0.034 (3)	0.027 (3)	0.029 (3)	0.013 (2)	0.011 (2)	0.004 (2)
C56	0.027 (3)	0.020 (2)	0.029 (3)	0.004 (2)	0.011 (2)	0.003 (2)
C57	0.014 (2)	0.013 (2)	0.013 (2)	−0.0018 (17)	0.0026 (17)	0.0019 (17)
C58	0.015 (2)	0.026 (2)	0.014 (2)	−0.0007 (19)	0.0050 (18)	0.0014 (19)
C59	0.019 (3)	0.025 (3)	0.013 (2)	0.001 (2)	0.0019 (19)	0.0066 (19)
C60	0.026 (3)	0.024 (2)	0.014 (2)	−0.002 (2)	0.009 (2)	0.0015 (19)
C61	0.018 (2)	0.018 (2)	0.024 (3)	−0.0007 (18)	0.013 (2)	0.0030 (19)
C62	0.014 (2)	0.015 (2)	0.022 (2)	−0.0009 (17)	0.0066 (19)	0.0015 (18)
C63	0.008 (2)	0.016 (2)	0.012 (2)	−0.0002 (16)	0.0050 (16)	0.0009 (17)
C64	0.017 (2)	0.0093 (19)	0.013 (2)	−0.0019 (17)	0.0017 (18)	−0.0012 (16)
C65	0.018 (3)	0.027 (3)	0.016 (2)	0.002 (2)	0.0018 (19)	0.001 (2)
C66	0.020 (3)	0.030 (3)	0.019 (2)	−0.002 (2)	−0.005 (2)	−0.001 (2)
C67	0.035 (3)	0.036 (3)	0.011 (2)	−0.002 (2)	0.001 (2)	−0.005 (2)
C68	0.034 (3)	0.036 (3)	0.017 (3)	−0.005 (2)	0.013 (2)	−0.006 (2)
C69	0.018 (2)	0.021 (2)	0.018 (2)	−0.0015 (19)	0.0045 (19)	−0.0052 (19)
C70	0.012 (2)	0.017 (2)	0.012 (2)	−0.0031 (17)	0.0015 (17)	0.0004 (17)
C71	0.013 (2)	0.017 (2)	0.014 (2)	−0.0020 (17)	0.0021 (18)	0.0007 (18)
C72	0.016 (2)	0.024 (2)	0.015 (2)	−0.0050 (19)	0.0088 (19)	−0.0020 (19)
C73	0.021 (3)	0.023 (2)	0.016 (2)	−0.008 (2)	0.004 (2)	0.0018 (19)
C74	0.021 (3)	0.017 (2)	0.027 (3)	−0.0029 (19)	0.004 (2)	0.004 (2)
C75	0.010 (2)	0.018 (2)	0.028 (3)	−0.0020 (18)	0.0035 (19)	−0.001 (2)
O1	0.031 (2)	0.0237 (19)	0.035 (2)	0.0058 (16)	0.0170 (18)	0.0087 (17)
N1	0.020 (2)	0.022 (2)	0.023 (2)	−0.0003 (17)	0.0074 (18)	0.0044 (18)
C76	0.021 (3)	0.017 (2)	0.031 (3)	0.0007 (19)	0.009 (2)	0.012 (2)
C77	0.022 (3)	0.034 (3)	0.026 (3)	−0.001 (2)	0.001 (2)	0.008 (2)
C78	0.029 (3)	0.028 (3)	0.037 (3)	0.006 (2)	0.014 (3)	0.004 (2)
O2	0.026 (2)	0.071 (3)	0.043 (3)	−0.006 (2)	−0.008 (2)	−0.016 (3)
N2	0.017 (2)	0.028 (2)	0.032 (3)	0.0030 (18)	0.0038 (19)	−0.007 (2)
C79	0.029 (3)	0.043 (4)	0.032 (3)	0.004 (3)	0.005 (3)	−0.001 (3)
C80	0.039 (4)	0.045 (4)	0.043 (4)	0.001 (3)	0.020 (3)	−0.006 (3)
C81	0.027 (3)	0.034 (3)	0.056 (4)	−0.002 (3)	−0.003 (3)	−0.016 (3)

Geometric parameters (Å, º) top

W1—S4	2.1523 (11)	C32—C33	1.390 (6)
W1—S1	2.2062 (11)	C32—C37	1.395 (6)
W1—S3	2.2240 (11)	C33—C34	1.396 (6)
W1—S2	2.2579 (11)	C33—H33	0.9500
W1—Ag2	2.9701 (4)	C34—C35	1.391 (7)
W1—Ag1	2.9707 (5)	C34—H34	0.9500
W2—S8	2.1470 (13)	C35—C36	1.390 (7)
W2—S6	2.1945 (13)	C35—H35	0.9500
W2—S7	2.1985 (11)	C36—C37	1.396 (6)
W2—S5	2.2878 (11)	C36—H36	0.9500
W2—Ag4	3.0410 (4)	C37—H37	0.9500
W2—Ag3	3.1609 (4)	C38—H38A	0.9900
Ag1—P1	2.3924 (12)	C38—H38B	0.9900
Ag1—S1	2.5374 (12)	C39—C40	1.396 (6)
Ag1—S2	2.5677 (12)	C39—C44	1.398 (6)
Ag1—S5	2.7919 (12)	C40—C41	1.390 (7)
Ag2—P2	2.3914 (12)	C40—H40	0.9500
Ag2—S3	2.5132 (11)	C41—C42	1.376 (7)
Ag2—S2	2.5772 (11)	C41—H41	0.9500
Ag2—S5	2.8412 (12)	C42—C43	1.389 (7)
Ag3—P4	2.4478 (12)	C42—H42	0.9500
Ag3—P3	2.4602 (12)	C43—C44	1.394 (7)
Ag3—S5	2.6096 (12)	C43—H43	0.9500
Ag3—S6	2.7403 (13)	C44—H44	0.9500
Ag4—P6	2.4485 (12)	C45—C46	1.396 (7)
Ag4—P5	2.4601 (11)	C45—C50	1.400 (6)
Ag4—S5	2.5984 (12)	C46—C47	1.400 (7)
Ag4—S7	2.7248 (12)	C46—H46	0.9500
P1—C1	1.826 (5)	C47—C48	1.390 (8)
P1—C7	1.824 (5)	C47—H47	0.9500
P1—C13	1.831 (4)	C48—C49	1.371 (8)
P2—C70	1.829 (5)	C48—H48	0.9500
P2—C64	1.830 (5)	C49—C50	1.389 (7)
P2—C63	1.835 (4)	C49—H49	0.9500
P3—C57	1.820 (5)	C50—H50	0.9500
P3—C51	1.831 (5)	C51—C56	1.380 (7)
P3—C63	1.836 (4)	C51—C52	1.387 (7)
P4—C39	1.823 (5)	C52—C53	1.390 (8)
P4—C45	1.830 (5)	C52—H52	0.9500
P4—C38	1.848 (4)	C53—C54	1.369 (9)
P5—C32	1.826 (4)	C53—H53	0.9500
P5—C26	1.832 (4)	C54—C55	1.381 (8)
P5—C38	1.847 (4)	C54—H54	0.9500
P6—C14	1.820 (5)	C55—C56	1.394 (7)
P6—C20	1.828 (5)	C55—H55	0.9500
P6—C13	1.844 (4)	C56—H56	0.9500
C1—C6	1.387 (7)	C57—C62	1.395 (6)
C1—C2	1.399 (7)	C57—C58	1.403 (6)
C2—C3	1.392 (8)	C58—C59	1.381 (6)
C2—H2	0.9500	C58—H58	0.9500
C3—C4	1.386 (10)	C59—C60	1.387 (7)
C3—H3	0.9500	C59—H59	0.9500
C4—C5	1.369 (10)	C60—C61	1.371 (7)
C4—H4	0.9500	C60—H60	0.9500
C5—C6	1.394 (8)	C61—C62	1.404 (7)
C5—H5	0.9500	C61—H61	0.9500
C6—H6	0.9500	C62—H62	0.9500
C7—C12	1.395 (6)	C63—H63A	0.9900
C7—C8	1.400 (6)	C63—H63B	0.9900
C8—C9	1.380 (7)	C64—C69	1.389 (6)
C8—H8	0.9500	C64—C65	1.385 (7)
C9—C10	1.376 (8)	C65—C66	1.392 (7)
C9—H9	0.9500	C65—H65	0.9500
C10—C11	1.388 (8)	C66—C67	1.375 (8)
C10—H10	0.9500	C66—H66	0.9500
C11—C12	1.381 (7)	C67—C68	1.380 (8)
C11—H11	0.9500	C67—H67	0.9500
C12—H12	0.9500	C68—C69	1.395 (7)
C13—H13A	0.9900	C68—H68	0.9500
C13—H13B	0.9900	C69—H69	0.9500
C14—C19	1.390 (7)	C70—C71	1.392 (6)
C14—C15	1.399 (6)	C70—C75	1.390 (6)
C15—C16	1.381 (7)	C71—C72	1.388 (6)
C15—H15	0.9500	C71—H71	0.9500
C16—C17	1.376 (7)	C72—C73	1.378 (7)
C16—H16	0.9500	C72—H72	0.9500
C17—C18	1.394 (7)	C73—C74	1.394 (7)
C17—H17	0.9500	C73—H73	0.9500
C18—C19	1.390 (7)	C74—C75	1.385 (6)
C18—H18	0.9500	C74—H74	0.9500
C19—H19	0.9500	C75—H75	0.9500
C20—C21	1.398 (6)	O1—C76	1.224 (6)
C20—C25	1.396 (6)	N1—C76	1.333 (6)
C21—C22	1.397 (6)	N1—C77	1.452 (6)
C21—H21	0.9500	N1—C78	1.465 (7)
C22—C23	1.384 (8)	C76—H76	0.9500
C22—H22	0.9500	C77—H77A	0.9800
C23—C24	1.376 (8)	C77—H77B	0.9800
C23—H23	0.9500	C77—H77C	0.9800
C24—C25	1.398 (7)	C78—H78A	0.9800
C24—H24	0.9500	C78—H78B	0.9800
C25—H25	0.9500	C78—H78C	0.9800
C26—C27	1.387 (6)	O2—C79	1.237 (7)
C26—C31	1.399 (6)	N2—C79	1.300 (7)
C27—C28	1.383 (7)	N2—C81	1.427 (7)
C27—H27	0.9500	N2—C80	1.481 (7)
C28—C29	1.392 (7)	C79—H79	0.9500
C28—H28	0.9500	C80—H80A	0.9800
C29—C30	1.401 (7)	C80—H80B	0.9800
C29—H29	0.9500	C80—H80C	0.9800
C30—C31	1.376 (7)	C81—H81A	0.9800
C30—H30	0.9500	C81—H81B	0.9800
C31—H31	0.9500	C81—H81C	0.9800

S4—W1—S1	107.81 (4)	C25—C24—H24	119.8
S4—W1—S3	108.47 (4)	C20—C25—C24	120.0 (5)
S1—W1—S3	109.03 (4)	C20—C25—H25	120.0
S4—W1—S2	108.04 (4)	C24—C25—H25	120.0
S1—W1—S2	111.20 (4)	C27—C26—C31	118.3 (4)
S3—W1—S2	112.14 (4)	C27—C26—P5	118.7 (3)
S4—W1—Ag2	131.67 (3)	C31—C26—P5	123.0 (3)
S1—W1—Ag2	120.49 (3)	C28—C27—C26	121.5 (5)
S3—W1—Ag2	55.67 (3)	C28—C27—H27	119.2
S2—W1—Ag2	57.14 (3)	C26—C27—H27	119.2
S4—W1—Ag1	136.25 (3)	C27—C28—C29	119.8 (5)
S1—W1—Ag1	56.40 (3)	C27—C28—H28	120.1
S3—W1—Ag1	115.24 (3)	C29—C28—H28	120.1
S2—W1—Ag1	56.88 (3)	C28—C29—C30	119.2 (5)
Ag2—W1—Ag1	78.214 (10)	C28—C29—H29	120.4
S8—W2—S6	110.73 (6)	C30—C29—H29	120.4
S8—W2—S7	109.18 (5)	C31—C30—C29	120.2 (4)
S6—W2—S7	109.38 (5)	C31—C30—H30	119.9
S8—W2—S5	108.25 (5)	C29—C30—H30	119.9
S6—W2—S5	110.66 (4)	C30—C31—C26	120.9 (4)
S7—W2—S5	108.61 (4)	C30—C31—H31	119.5
S8—W2—Ag4	148.67 (5)	C26—C31—H31	119.5
S6—W2—Ag4	100.53 (4)	C33—C32—C37	119.0 (4)
S7—W2—Ag4	60.14 (3)	C33—C32—P5	118.1 (3)
S5—W2—Ag4	56.25 (3)	C37—C32—P5	122.8 (3)
S8—W2—Ag3	112.82 (4)	C32—C33—C34	120.8 (4)
S6—W2—Ag3	58.26 (3)	C32—C33—H33	119.6
S7—W2—Ag3	137.85 (3)	C34—C33—H33	119.6
S5—W2—Ag3	54.42 (3)	C33—C34—C35	119.6 (4)
Ag4—W2—Ag3	81.533 (11)	C33—C34—H34	120.2
P1—Ag1—S1	125.90 (4)	C35—C34—H34	120.2
P1—Ag1—S2	125.34 (4)	C36—C35—C34	120.2 (4)
S1—Ag1—S2	92.36 (4)	C36—C35—H35	119.9
P1—Ag1—S5	112.32 (4)	C34—C35—H35	119.9
S1—Ag1—S5	103.87 (4)	C35—C36—C37	119.7 (4)
S2—Ag1—S5	89.89 (3)	C35—C36—H36	120.2
P1—Ag1—W1	156.66 (3)	C37—C36—H36	120.2
S1—Ag1—W1	46.40 (3)	C32—C37—C36	120.6 (4)
S2—Ag1—W1	47.43 (2)	C32—C37—H37	119.7
S5—Ag1—W1	90.70 (2)	C36—C37—H37	119.7
P2—Ag2—S3	134.21 (4)	P5—C38—P4	114.5 (2)
P2—Ag2—S2	118.94 (4)	P5—C38—H38A	108.6
S3—Ag2—S2	93.86 (4)	P4—C38—H38A	108.6
P2—Ag2—S5	112.41 (4)	P5—C38—H38B	108.6
S3—Ag2—S5	98.39 (4)	P4—C38—H38B	108.6
S2—Ag2—S5	88.61 (3)	H38A—C38—H38B	107.6
P2—Ag2—W1	155.06 (3)	C40—C39—C44	119.8 (4)
S3—Ag2—W1	46.95 (3)	C40—C39—P4	119.9 (3)
S2—Ag2—W1	47.38 (2)	C44—C39—P4	120.1 (3)
S5—Ag2—W1	89.76 (2)	C41—C40—C39	119.5 (4)
P4—Ag3—P3	130.09 (4)	C41—C40—H40	120.3
P4—Ag3—S5	105.22 (4)	C39—C40—H40	120.3
P3—Ag3—S5	123.65 (4)	C42—C41—C40	120.6 (5)
P4—Ag3—S6	102.12 (4)	C42—C41—H41	119.7
P3—Ag3—S6	90.68 (4)	C40—C41—H41	119.7
S5—Ag3—S6	87.08 (4)	C41—C42—C43	120.5 (5)
P4—Ag3—W2	117.46 (3)	C41—C42—H42	119.8
P3—Ag3—W2	104.71 (3)	C43—C42—H42	119.8
S5—Ag3—W2	45.48 (2)	C42—C43—C44	119.6 (4)
S6—Ag3—W2	42.93 (3)	C42—C43—H43	120.2
P6—Ag4—P5	122.24 (4)	C44—C43—H43	120.2
P6—Ag4—S5	117.74 (4)	C39—C44—C43	120.0 (4)
P5—Ag4—S5	115.87 (4)	C39—C44—H44	120.0
P6—Ag4—S7	91.08 (4)	C43—C44—H44	120.0
P5—Ag4—S7	112.28 (4)	C46—C45—C50	119.2 (4)
S5—Ag4—S7	86.36 (4)	C46—C45—P4	120.1 (3)
P6—Ag4—W2	124.47 (3)	C50—C45—P4	120.5 (4)
P5—Ag4—W2	107.12 (3)	C45—C46—C47	119.9 (5)
S5—Ag4—W2	47.06 (3)	C45—C46—H46	120.0
S7—Ag4—W2	44.41 (2)	C47—C46—H46	120.0
W1—S1—Ag1	77.20 (4)	C48—C47—C46	119.9 (5)
W1—S2—Ag1	75.69 (3)	C48—C47—H47	120.0
W1—S2—Ag2	75.48 (3)	C46—C47—H47	120.0
Ag1—S2—Ag2	93.50 (4)	C49—C48—C47	120.2 (5)
W1—S3—Ag2	77.39 (3)	C49—C48—H48	119.9
W2—S5—Ag4	76.69 (3)	C47—C48—H48	119.9
W2—S5—Ag3	80.10 (3)	C48—C49—C50	120.7 (5)
Ag4—S5—Ag3	102.12 (4)	C48—C49—H49	119.7
W2—S5—Ag1	128.34 (4)	C50—C49—H49	119.7
Ag4—S5—Ag1	92.22 (4)	C49—C50—C45	120.0 (5)
Ag3—S5—Ag1	150.82 (5)	C49—C50—H50	120.0
W2—S5—Ag2	114.86 (4)	C45—C50—H50	120.0
Ag4—S5—Ag2	167.86 (5)	C56—C51—C52	119.1 (5)
Ag3—S5—Ag2	77.31 (3)	C56—C51—P3	123.5 (4)
Ag1—S5—Ag2	83.40 (3)	C52—C51—P3	117.4 (4)
W2—S6—Ag3	78.81 (4)	C51—C52—C53	120.6 (6)
W2—S7—Ag4	75.45 (3)	C51—C52—H52	119.7
C1—P1—C7	106.7 (2)	C53—C52—H52	119.7
C1—P1—C13	101.0 (2)	C54—C53—C52	119.9 (5)
C7—P1—C13	104.3 (2)	C54—C53—H53	120.0
C1—P1—Ag1	111.83 (16)	C52—C53—H53	120.0
C7—P1—Ag1	112.73 (15)	C53—C54—C55	120.3 (5)
C13—P1—Ag1	119.05 (14)	C53—C54—H54	119.8
C70—P2—C64	102.5 (2)	C55—C54—H54	119.8
C70—P2—C63	104.0 (2)	C56—C55—C54	119.7 (6)
C64—P2—C63	106.9 (2)	C56—C55—H55	120.1
C70—P2—Ag2	113.57 (15)	C54—C55—H55	120.1
C64—P2—Ag2	111.52 (15)	C51—C56—C55	120.4 (5)
C63—P2—Ag2	116.97 (15)	C51—C56—H56	119.8
C57—P3—C51	103.1 (2)	C55—C56—H56	119.8
C57—P3—C63	103.1 (2)	C62—C57—C58	119.2 (4)
C51—P3—C63	103.4 (2)	C62—C57—P3	120.5 (3)
C57—P3—Ag3	122.93 (15)	C58—C57—P3	120.2 (3)
C51—P3—Ag3	109.79 (15)	C59—C58—C57	120.2 (4)
C63—P3—Ag3	112.48 (15)	C59—C58—H58	119.9
C39—P4—C45	104.2 (2)	C57—C58—H58	119.9
C39—P4—C38	102.7 (2)	C58—C59—C60	120.2 (5)
C45—P4—C38	101.0 (2)	C58—C59—H59	119.9
C39—P4—Ag3	124.25 (15)	C60—C59—H59	119.9
C45—P4—Ag3	110.63 (15)	C61—C60—C59	120.5 (4)
C38—P4—Ag3	111.39 (15)	C61—C60—H60	119.7
C32—P5—C26	103.6 (2)	C59—C60—H60	119.7
C32—P5—C38	100.7 (2)	C60—C61—C62	120.1 (4)
C26—P5—C38	105.3 (2)	C60—C61—H61	120.0
C32—P5—Ag4	112.51 (15)	C62—C61—H61	120.0
C26—P5—Ag4	109.23 (15)	C57—C62—C61	119.8 (4)
C38—P5—Ag4	123.52 (15)	C57—C62—H62	120.1
C14—P6—C20	103.7 (2)	C61—C62—H62	120.1
C14—P6—C13	107.2 (2)	P2—C63—P3	112.0 (2)
C20—P6—C13	103.2 (2)	P2—C63—H63A	109.2
C14—P6—Ag4	121.93 (15)	P3—C63—H63A	109.2
C20—P6—Ag4	108.08 (14)	P2—C63—H63B	109.2
C13—P6—Ag4	110.97 (15)	P3—C63—H63B	109.2
C6—C1—C2	119.4 (5)	H63A—C63—H63B	107.9
C6—C1—P1	123.9 (4)	C69—C64—C65	118.7 (4)
C2—C1—P1	116.7 (4)	C69—C64—P2	118.9 (4)
C3—C2—C1	119.9 (6)	C65—C64—P2	122.4 (4)
C3—C2—H2	120.1	C64—C65—C66	120.7 (5)
C1—C2—H2	120.1	C64—C65—H65	119.6
C2—C3—C4	119.8 (6)	C66—C65—H65	119.6
C2—C3—H3	120.1	C67—C66—C65	120.0 (5)
C4—C3—H3	120.1	C67—C66—H66	120.0
C5—C4—C3	120.6 (6)	C65—C66—H66	120.0
C5—C4—H4	119.7	C66—C67—C68	120.3 (5)
C3—C4—H4	119.7	C66—C67—H67	119.9
C4—C5—C6	120.1 (6)	C68—C67—H67	119.9
C4—C5—H5	120.0	C67—C68—C69	119.6 (5)
C6—C5—H5	120.0	C67—C68—H68	120.2
C1—C6—C5	120.2 (6)	C69—C68—H68	120.2
C1—C6—H6	119.9	C64—C69—C68	120.7 (5)
C5—C6—H6	119.9	C64—C69—H69	119.7
C12—C7—C8	119.3 (4)	C68—C69—H69	119.7
C12—C7—P1	123.2 (4)	C71—C70—C75	119.5 (4)
C8—C7—P1	117.6 (4)	C71—C70—P2	123.7 (4)
C9—C8—C7	120.7 (5)	C75—C70—P2	116.8 (3)
C9—C8—H8	119.6	C70—C71—C72	120.0 (4)
C7—C8—H8	119.6	C70—C71—H71	120.0
C8—C9—C10	119.4 (5)	C72—C71—H71	120.0
C8—C9—H9	120.3	C73—C72—C71	120.2 (4)
C10—C9—H9	120.3	C73—C72—H72	119.9
C9—C10—C11	120.8 (5)	C71—C72—H72	119.9
C9—C10—H10	119.6	C72—C73—C74	120.2 (4)
C11—C10—H10	119.6	C72—C73—H73	119.9
C12—C11—C10	120.2 (5)	C74—C73—H73	119.9
C12—C11—H11	119.9	C75—C74—C73	119.6 (5)
C10—C11—H11	119.9	C75—C74—H74	120.2
C11—C12—C7	119.7 (5)	C73—C74—H74	120.2
C11—C12—H12	120.2	C74—C75—C70	120.4 (5)
C7—C12—H12	120.2	C74—C75—H75	119.8
P1—C13—P6	114.1 (2)	C70—C75—H75	119.8
P1—C13—H13A	108.7	C76—N1—C77	121.0 (5)
P6—C13—H13A	108.7	C76—N1—C78	121.9 (4)
P1—C13—H13B	108.7	C77—N1—C78	117.1 (4)
P6—C13—H13B	108.7	O1—C76—N1	125.7 (5)
H13A—C13—H13B	107.6	O1—C76—H76	117.1
C19—C14—C15	118.8 (4)	N1—C76—H76	117.1
C19—C14—P6	122.1 (3)	N1—C77—H77A	109.5
C15—C14—P6	119.1 (4)	N1—C77—H77B	109.5
C16—C15—C14	120.5 (4)	H77A—C77—H77B	109.5
C16—C15—H15	119.7	N1—C77—H77C	109.5
C14—C15—H15	119.7	H77A—C77—H77C	109.5
C17—C16—C15	120.6 (5)	H77B—C77—H77C	109.5
C17—C16—H16	119.7	N1—C78—H78A	109.5
C15—C16—H16	119.7	N1—C78—H78B	109.5
C16—C17—C18	119.7 (5)	H78A—C78—H78B	109.5
C16—C17—H17	120.2	N1—C78—H78C	109.5
C18—C17—H17	120.2	H78A—C78—H78C	109.5
C19—C18—C17	120.0 (5)	H78B—C78—H78C	109.5
C19—C18—H18	120.0	C79—N2—C81	125.7 (5)
C17—C18—H18	120.0	C79—N2—C80	120.2 (5)
C14—C19—C18	120.4 (4)	C81—N2—C80	114.1 (5)
C14—C19—H19	119.8	O2—C79—N2	125.1 (6)
C18—C19—H19	119.8	O2—C79—H79	117.4
C21—C20—C25	118.8 (4)	N2—C79—H79	117.4
C21—C20—P6	123.1 (4)	N2—C80—H80A	109.5
C25—C20—P6	117.8 (4)	N2—C80—H80B	109.5
C22—C21—C20	120.7 (5)	H80A—C80—H80B	109.5
C22—C21—H21	119.7	N2—C80—H80C	109.5
C20—C21—H21	119.7	H80A—C80—H80C	109.5
C23—C22—C21	119.7 (5)	H80B—C80—H80C	109.5
C23—C22—H22	120.2	N2—C81—H81A	109.5
C21—C22—H22	120.2	N2—C81—H81B	109.5
C24—C23—C22	120.3 (5)	H81A—C81—H81B	109.5
C24—C23—H23	119.9	N2—C81—H81C	109.5
C22—C23—H23	119.9	H81A—C81—H81C	109.5
C23—C24—C25	120.5 (5)	H81B—C81—H81C	109.5
C23—C24—H24	119.8

Experimental details

Crystal data
Chemical formula	[Ag₄W₂S₈(C₂₅H₂₂P₂)₃]·2C₃H₇NO
M_r	2354.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	22.931 (2), 14.0395 (12), 27.855 (3)
β (°)	107.224 (1)
V (Å³)	8565.6 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.93
Crystal size (mm)	0.47 × 0.43 × 0.43

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.262, 0.281
No. of measured, independent and observed [I > 2σ(I)] reflections	69256, 19520, 18777
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.089, 1.14
No. of reflections	19520
No. of parameters	950
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0341P)² + 13.8363P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.36

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Acknowledgements

This work was supported by the National Keystone Basic Research Program (973 Program) under grant No. 2007CB310408, No. 2006CB302901 and the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of Beijing Municipality. It was also supported by the State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences.

References

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