Tris­[di­phenyl(2-pyridyl)­phosphine]-[mu]₃-iodo-tri-[mu]₃-sulfido-sulfidotrisilvertungsten di­chloro­methane hemisolvate

The title compound, [Ag₃WIS₄(C₁₇H₁₄NP)₃]·0.5CH₂Cl₂, is a cubane-type heterometallic cluster containing di­phenyl(2-pyridyl)­phosphine (Ph₂PPy). The pyridyl group of Ph₂PPy remains uncoordinated, so the Ph₂PPy ligand is monodentate and coordinates to one Ag atom. The W atom and three Ag atoms form a distorted tetrahedral geometry, capped by one I atom and three S atoms.

S1. Comment

During the past two decades, many surprising results have been generated in the course of investigations of cluster complexes. Transition metal clusters, in particular, are appealing in coordination chemistry because of their intriguing structural diversity (Gade, 2000; Johnson et al., 2001) and their relevancy as industrial catalysts (Chandler et al., 2001), nonlinear optical materials (Zhang et al., 2000) and models for cluster sites in proteins (Davies et al., 2001). There are many kinds of sulfur-bridged heterometallic cluster compounds containing simple ligands, such as halogen, CO and PPh₃, with intact or altered [MS₄]²⁻ (M = Mo or W) units as essential structures. However, the cubane-type heterometallic cluster containing diphenyl-(2-pyridyl)phosphine (Ph₂PPy) has never been reported. We have synthesized the title compound, WS₄IAg₃(Ph₂PPy)₃·0.5(CH₂Cl₂), (I), and its structure is presented here.

In the cubane-type cluster moiety of (I), one W atom and three Ag atoms form a slightly distorted tetrahedral geometry, with W—Ag bond lengths of 2.9718 (7)–3.0324 (9) Å and Ag—W—Ag angles of 68.08 (2)–74.00 (2)° (Fig. 1 and Table 1). Three faces of this tetrahedron are capped by three µ₃-S ligands and the fourth face is capped by one µ₃-I ligand. Disregarding the metal–metal interactions, the W atom has an essentially tetrahedral geometry, with three µ₃-S ligands and one terminal S ligand, the S—W—S bond angles being 107.26 (7)–111.19 (6)°. The bond distances between the µ₃-S atoms and the W atom are 2.2314 (14)–2.2419 (15) Å. The S1═W1 bond distance is similar to reported values, e.g. 2.102 (2) Å in WS₄BrCu₃(PPh₃)₃ (Lang et al., 1993) and 2.15 (1) Å in WS₄IAg₃(AsPh₃)₃ (Sakane et al., 1996). Each Ag atom also has a tetrahedral geometry, with a small distortion surrounded by two µ₃-S liands, one µ₃-I ligand and one P atom. The Ph₂PPy ligand is monodentate and the pyridyl moiety of Ph₂PPy remains uncoordinated. The bond angles around the Ag atoms are as follows: P—Ag—S = 122.29 (6)–128.42 (5)°, P—Ag—I = 103.24 (5)–108.87 (5)°, S—Ag—I = 98.45 (4)–105.05 (4)°. The Ag—I bond lengths [3.0160 (10)–3.0870 (11) Å] are longer than the Ag—S bond lengths [2.5272 (17)–2.6450 (17) Å], whereas the Ag—I—Ag angles [67.845 (18)–72.55 (2) °] are much smaller than the Ag—S—Ag angles [81.61 (5)–87.91 (5) °]. These geometrical properties around the Ag atoms correspond well to those in WS₄IAg₃(PPh₃)₃ (Jin et al., 1999).

The CH₂Cl₂ solvent molecule shows orientational disorder. The C atom has two possible positions, viz. C55 and C55ⁱ (symmetry code: (i) 1 − x, −y, 2 − z), each having an occupancy of 50%, and atoms Cl1 and Cl1ⁱ are shared by the two orientations. There are evidently weak interactions between the S atoms and the phenyl rings (Table 2).

S2. Experimental

The synthesis was performed in dried glassware under a purified nitrogen atmosphere using standard Schlenk techniques. (NH₄)₂WS₄ was prepared in our laboratory, and the other reagents were commercially available and used without further purification. (NH₄)₂WS₄ (0.035 g, 0.1 mmol) and AgI (0.070 g, 0.3 mmol) were mixed and ground for 30 min. The mixture was then placed in a tinfoil-wrapped reaction tube with Ph₂PPy (0.079 g, 0.3 mmol), and CH₂Cl₂ (20 ml) was added. The final mixture was stired for 24 h at room temperature under a purified nitrogen atmosphere. After filtration, the resulting clear yellow solution was layered with i-PrOH (50 ml), and yellow crystals of (I) were obtained at room temperature after several days. Analysis calculated for C_51.5H₄₃Ag₃ClIN₃P₃S₄W: C 38.85, H 2.72, N 2.64%; found: C 38.79, H 2.68, N 2.66%.

S3. Refinement

All H atoms were positioned geometrically (C–H = 0.93–0.97 Å) and refined as riding, with isotropic displacement parameters of 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids. The H atoms and the solvent molecule have been omitted for clarity.

Tris[diphenyl(2-pyridyl)phosphine]-µ₃-iodo-tri-µ₃-sulfido- sulfidotrisilvertungsten dichloromethane hemisolvate

Crystal data

[Ag3WIS4(C17H14NP)3]·0.5CH2Cl2	Z = 2
Mr = 1594.85	F(000) = 1534
Triclinic, P1	Dx = 1.911 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.045 (3) Å	Cell parameters from 6969 reflections
b = 13.367 (4) Å	θ = 2.3–27.2°
c = 19.886 (5) Å	µ = 3.99 mm^−1
α = 74.86 (1)°	T = 293 K
β = 87.99 (1)°	Brick, yellow
γ = 64.23 (1)°	0.3 × 0.2 × 0.2 mm
V = 2771.9 (13) Å^3

Data collection

Bruker Smart Apex CCD area detector diffractometer	9582 independent reflections
Radiation source: sealed tube	8034 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→11
Tmin = 0.411, Tmax = 0.452	k = −15→15
13773 measured reflections	l = −23→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.045P)^2 + 1.55P] where P = (Fo^2 + 2Fc^2)/3
9582 reflections	(Δ/σ)max < 0.001
613 parameters	Δρmax = 1.67 e Å^−3
0 restraints	Δρmin = −1.63 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0.75142 (5)	0.57985 (5)	0.24250 (3)	0.05763 (14)
Ag2	0.87176 (5)	0.34972 (5)	0.15779 (3)	0.06035 (14)
Ag3	0.68292 (5)	0.34359 (5)	0.28620 (3)	0.06304 (14)
C1	0.8126 (5)	0.6615 (5)	0.3893 (3)	0.0461 (13)
C2	0.8497 (6)	0.5483 (6)	0.4296 (3)	0.0602 (16)
H2	0.8750	0.4892	0.4078	0.072*
C3	0.8494 (7)	0.5226 (6)	0.5003 (3)	0.0651 (18)
H3	0.8738	0.4466	0.5265	0.078*
C4	0.8132 (7)	0.6090 (7)	0.5332 (4)	0.0670 (18)
H4	0.8135	0.5916	0.5817	0.080*
C5	0.7766 (7)	0.7210 (7)	0.4942 (3)	0.0690 (19)
H5	0.7511	0.7794	0.5166	0.083*
C6	0.7769 (6)	0.7486 (6)	0.4223 (3)	0.0627 (17)
H6	0.7534	0.8246	0.3965	0.075*
C7	0.7376 (6)	0.8401 (5)	0.2604 (3)	0.0490 (14)
C8	0.6119 (6)	0.8872 (6)	0.2501 (4)	0.0636 (17)
H8	0.5725	0.8394	0.2607	0.076*
C9	0.5426 (7)	1.0041 (6)	0.2244 (4)	0.0695 (18)
H9	0.4569	1.0347	0.2174	0.083*
C10	0.5969 (7)	1.0732 (7)	0.2094 (4)	0.0718 (19)
H10	0.5498	1.1525	0.1915	0.086*
C11	0.7208 (8)	1.0283 (7)	0.2202 (4)	0.073 (2)
H11	0.7585	1.0777	0.2100	0.088*
C13	0.9826 (6)	0.6512 (5)	0.2851 (3)	0.0519 (14)
C14	1.0419 (6)	0.6908 (6)	0.3217 (3)	0.0567 (16)
H14	1.0001	0.7323	0.3530	0.068*
C15	1.1630 (6)	0.6689 (6)	0.3120 (3)	0.0628 (17)
H15	1.2030	0.6962	0.3365	0.075*
C16	1.2250 (6)	0.6063 (6)	0.2660 (4)	0.0668 (18)
H16	1.3065	0.5928	0.2590	0.080*
C17	1.1691 (6)	0.5648 (6)	0.2312 (4)	0.0686 (19)
H17	1.2125	0.5216	0.2009	0.082*
C18	1.0458 (6)	0.5863 (6)	0.2401 (4)	0.0645 (17)
H18	1.0068	0.5574	0.2162	0.077*
C19	1.1595 (5)	0.3054 (5)	0.0928 (3)	0.0494 (14)
C20	1.1111 (7)	0.4222 (6)	0.0817 (4)	0.0666 (18)
H20	1.0267	0.4657	0.0833	0.080*
C21	1.1911 (7)	0.4765 (7)	0.0677 (3)	0.0651 (18)
H21	1.1598	0.5559	0.0604	0.078*
C22	1.3128 (7)	0.4118 (7)	0.0650 (3)	0.0652 (18)
H22	1.3662	0.4464	0.0563	0.078*
C23	1.3565 (6)	0.2983 (6)	0.0749 (3)	0.0635 (17)
H23	1.4409	0.2554	0.0731	0.076*
C25	1.0257 (6)	0.2144 (5)	0.0268 (3)	0.0565 (16)
C26	1.1018 (7)	0.2130 (6)	−0.0264 (3)	0.0650 (18)
H26	1.1696	0.2279	−0.0229	0.078*
C27	1.0738 (6)	0.1884 (5)	−0.0855 (3)	0.0565 (16)
H27	1.1232	0.1894	−0.1225	0.068*
C28	0.9772 (6)	0.1631 (5)	−0.0919 (3)	0.0565 (16)
H28	0.9647	0.1421	−0.1310	0.068*
C29	0.8997 (6)	0.1690 (5)	−0.0404 (3)	0.0565 (15)
H29	0.8306	0.1564	−0.0448	0.068*
C30	0.9254 (7)	0.1949 (6)	0.0208 (4)	0.0680 (18)
H30	0.8734	0.1984	0.0566	0.082*
C31	1.1540 (5)	0.0883 (5)	0.1628 (3)	0.0475 (13)
C32	1.2212 (6)	0.0019 (6)	0.1324 (4)	0.0639 (17)
H32	1.2166	0.0169	0.0840	0.077*
C33	1.2964 (7)	−0.1085 (6)	0.1740 (4)	0.0711 (19)
H33	1.3429	−0.1670	0.1533	0.085*
C34	1.3020 (7)	−0.1314 (6)	0.2455 (4)	0.0681 (18)
H34	1.3512	−0.2055	0.2733	0.082*
C35	1.2346 (7)	−0.0443 (7)	0.2760 (4)	0.0686 (19)
H35	1.2397	−0.0590	0.3244	0.082*
C36	1.1589 (6)	0.0655 (6)	0.2343 (3)	0.0621 (17)
H36	1.1113	0.1238	0.2549	0.074*
C37	0.7879 (6)	0.0783 (5)	0.4177 (4)	0.0570 (16)
C38	0.8732 (6)	0.0386 (6)	0.3730 (4)	0.0640 (17)
H38	0.8601	0.0797	0.3261	0.077*
C39	0.9819 (7)	−0.0653 (6)	0.3979 (4)	0.0703 (19)
H39	1.0449	−0.0906	0.3691	0.084*
C40	0.9913 (6)	−0.1275 (5)	0.4663 (3)	0.0565 (15)
H40	1.0585	−0.1995	0.4829	0.068*
C41	0.9032 (6)	−0.0855 (5)	0.5105 (3)	0.0565 (15)
H41	0.9129	−0.1283	0.5569	0.068*
C42	0.8024 (7)	0.0176 (6)	0.4874 (3)	0.0631 (17)
H42	0.7442	0.0470	0.5177	0.076*
C43	0.5281 (5)	0.1791 (5)	0.3729 (3)	0.0513 (14)
C45	0.4253 (7)	0.0600 (7)	0.3938 (4)	0.0680 (18)
H45	0.4243	−0.0097	0.4170	0.082*
C46	0.3266 (7)	0.1404 (7)	0.3506 (4)	0.0676 (19)
H46	0.2598	0.1263	0.3426	0.081*
C47	0.3268 (7)	0.2414 (7)	0.3192 (4)	0.0716 (19)
H47	0.2581	0.2982	0.2894	0.086*
C48	0.4244 (6)	0.2653 (6)	0.3290 (3)	0.0598 (16)
H48	0.4214	0.3370	0.3068	0.072*
C49	0.6172 (5)	0.2713 (5)	0.4623 (3)	0.0455 (13)
C50	0.5434 (6)	0.2443 (6)	0.5104 (3)	0.0603 (17)
H50	0.5109	0.1953	0.5044	0.072*
C51	0.5164 (7)	0.2885 (7)	0.5676 (3)	0.0677 (19)
H51	0.4632	0.2721	0.5988	0.081*
C52	0.5689 (6)	0.3569 (6)	0.5780 (3)	0.0599 (16)
H52	0.5557	0.3830	0.6180	0.072*
C53	0.6418 (6)	0.3869 (6)	0.5288 (3)	0.0651 (18)
H53	0.6748	0.4358	0.5344	0.078*
C54	0.6643 (6)	0.3434 (6)	0.4715 (3)	0.0627 (17)
H54	0.7127	0.3637	0.4384	0.075*
I1	0.93800 (4)	0.32598 (3)	0.30808 (2)	0.05348 (11)
N1	0.7940 (5)	0.9106 (5)	0.2460 (3)	0.0701 (16)
N2	1.2820 (5)	0.2403 (5)	0.0879 (3)	0.0592 (13)
N3	0.5296 (5)	0.0749 (5)	0.4061 (3)	0.0663 (15)
P1	0.82238 (13)	0.68472 (13)	0.29564 (7)	0.0411 (3)
P2	1.05522 (14)	0.23664 (13)	0.10951 (8)	0.0486 (4)
P3	0.65313 (14)	0.21576 (13)	0.38610 (7)	0.0469 (4)
S1	0.44866 (16)	0.62860 (15)	0.07774 (9)	0.0618 (4)
S2	0.75638 (13)	0.57776 (12)	0.11401 (7)	0.0460 (3)
S3	0.66150 (15)	0.34228 (13)	0.15796 (8)	0.0529 (4)
S4	0.54930 (13)	0.56460 (13)	0.25376 (8)	0.0487 (3)
W1	0.605554 (19)	0.528066 (18)	0.150811 (11)	0.03899 (8)
Cl1	0.59303 (19)	0.03187 (18)	1.02647 (10)	0.0787 (5)
C55	0.4682 (13)	0.0728 (13)	0.9588 (7)	0.070 (4)	0.50
H55A	0.4020	0.1476	0.9587	0.084*	0.50
H55B	0.5002	0.0797	0.9132	0.084*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0544 (3)	0.0748 (3)	0.0676 (3)	−0.0420 (3)	0.0084 (2)	−0.0337 (3)
Ag2	0.0497 (3)	0.0647 (3)	0.0770 (3)	−0.0283 (3)	0.0127 (2)	−0.0313 (3)
Ag3	0.0733 (4)	0.0683 (3)	0.0620 (3)	−0.0424 (3)	0.0123 (2)	−0.0217 (3)
C1	0.037 (3)	0.052 (4)	0.056 (3)	−0.024 (3)	0.010 (3)	−0.018 (3)
C2	0.067 (4)	0.066 (4)	0.060 (4)	−0.037 (4)	0.007 (3)	−0.025 (3)
C3	0.068 (5)	0.072 (5)	0.070 (4)	−0.041 (4)	0.012 (3)	−0.026 (4)
C4	0.068 (5)	0.088 (5)	0.063 (4)	−0.048 (4)	0.012 (3)	−0.026 (4)
C5	0.079 (5)	0.087 (6)	0.067 (4)	−0.049 (4)	0.015 (4)	−0.042 (4)
C6	0.065 (4)	0.075 (5)	0.065 (4)	−0.038 (4)	0.012 (3)	−0.036 (4)
C7	0.056 (4)	0.044 (3)	0.049 (3)	−0.023 (3)	0.000 (3)	−0.014 (3)
C8	0.055 (4)	0.052 (4)	0.082 (5)	−0.024 (3)	0.003 (3)	−0.013 (3)
C9	0.060 (4)	0.060 (4)	0.077 (5)	−0.016 (4)	−0.004 (3)	−0.017 (4)
C10	0.074 (5)	0.068 (5)	0.079 (5)	−0.034 (4)	−0.005 (4)	−0.024 (4)
C11	0.083 (6)	0.066 (5)	0.087 (5)	−0.045 (4)	0.002 (4)	−0.025 (4)
C13	0.046 (3)	0.062 (4)	0.056 (3)	−0.030 (3)	0.000 (3)	−0.019 (3)
C14	0.044 (4)	0.077 (4)	0.058 (4)	−0.032 (3)	0.000 (3)	−0.024 (3)
C15	0.053 (4)	0.077 (5)	0.064 (4)	−0.035 (4)	−0.002 (3)	−0.017 (4)
C16	0.047 (4)	0.077 (5)	0.085 (5)	−0.033 (4)	0.005 (3)	−0.025 (4)
C17	0.055 (4)	0.087 (5)	0.083 (5)	−0.042 (4)	0.015 (3)	−0.037 (4)
C18	0.040 (4)	0.069 (4)	0.086 (5)	−0.023 (3)	0.007 (3)	−0.025 (4)
C19	0.044 (3)	0.053 (4)	0.046 (3)	−0.015 (3)	0.001 (3)	−0.016 (3)
C20	0.050 (4)	0.052 (4)	0.091 (5)	−0.016 (3)	0.008 (3)	−0.021 (4)
C21	0.067 (5)	0.075 (5)	0.074 (4)	−0.044 (4)	0.004 (3)	−0.030 (4)
C22	0.067 (5)	0.083 (5)	0.072 (4)	−0.050 (4)	0.015 (3)	−0.034 (4)
C23	0.053 (4)	0.076 (5)	0.071 (4)	−0.036 (4)	0.008 (3)	−0.024 (4)
C25	0.056 (4)	0.046 (3)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C26	0.066 (5)	0.081 (5)	0.060 (4)	−0.040 (4)	0.008 (3)	−0.026 (4)
C27	0.056 (4)	0.046 (4)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C28	0.056 (4)	0.046 (4)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C29	0.056 (4)	0.046 (3)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C30	0.058 (4)	0.081 (5)	0.081 (5)	−0.035 (4)	0.002 (3)	−0.038 (4)
C31	0.038 (3)	0.039 (3)	0.055 (3)	−0.008 (3)	−0.001 (2)	−0.011 (3)
C32	0.064 (4)	0.061 (4)	0.062 (4)	−0.018 (4)	0.005 (3)	−0.024 (3)
C33	0.069 (5)	0.067 (5)	0.085 (5)	−0.029 (4)	0.008 (4)	−0.034 (4)
C34	0.067 (5)	0.038 (4)	0.080 (5)	−0.010 (3)	−0.001 (4)	−0.009 (3)
C35	0.073 (5)	0.078 (5)	0.058 (4)	−0.034 (4)	0.002 (3)	−0.022 (4)
C36	0.060 (4)	0.063 (4)	0.065 (4)	−0.024 (4)	0.004 (3)	−0.025 (3)
C37	0.043 (4)	0.047 (4)	0.083 (5)	−0.021 (3)	−0.004 (3)	−0.018 (3)
C38	0.057 (4)	0.071 (5)	0.080 (4)	−0.036 (4)	0.010 (3)	−0.034 (4)
C39	0.067 (5)	0.063 (5)	0.088 (5)	−0.029 (4)	0.012 (4)	−0.030 (4)
C40	0.056 (4)	0.046 (3)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C41	0.056 (4)	0.046 (4)	0.053 (4)	−0.011 (3)	−0.007 (3)	−0.008 (3)
C42	0.068 (5)	0.052 (4)	0.063 (4)	−0.024 (4)	−0.006 (3)	−0.009 (3)
C43	0.046 (3)	0.057 (4)	0.049 (3)	−0.024 (3)	−0.004 (3)	−0.009 (3)
C45	0.067 (5)	0.081 (5)	0.075 (4)	−0.047 (4)	0.003 (4)	−0.026 (4)
C46	0.061 (5)	0.085 (5)	0.082 (5)	−0.047 (4)	0.007 (4)	−0.036 (4)
C47	0.052 (4)	0.083 (5)	0.089 (5)	−0.035 (4)	−0.005 (4)	−0.027 (4)
C48	0.055 (4)	0.050 (4)	0.068 (4)	−0.020 (3)	−0.007 (3)	−0.010 (3)
C49	0.040 (3)	0.048 (3)	0.043 (3)	−0.018 (3)	0.001 (2)	−0.005 (3)
C50	0.064 (4)	0.074 (5)	0.063 (4)	−0.045 (4)	0.010 (3)	−0.025 (3)
C51	0.065 (5)	0.092 (5)	0.064 (4)	−0.048 (4)	0.010 (3)	−0.028 (4)
C52	0.063 (4)	0.064 (4)	0.051 (4)	−0.024 (4)	0.000 (3)	−0.020 (3)
C53	0.065 (4)	0.079 (5)	0.069 (4)	−0.040 (4)	0.009 (3)	−0.035 (4)
C54	0.060 (4)	0.072 (5)	0.059 (4)	−0.036 (4)	−0.001 (3)	−0.009 (3)
I1	0.0455 (2)	0.0486 (2)	0.0580 (2)	−0.01312 (19)	−0.00365 (17)	−0.01381 (18)
N1	0.065 (4)	0.072 (4)	0.087 (4)	−0.041 (3)	−0.002 (3)	−0.024 (3)
N2	0.053 (3)	0.059 (3)	0.064 (3)	−0.024 (3)	−0.001 (3)	−0.014 (3)
N3	0.068 (4)	0.075 (4)	0.071 (3)	−0.044 (3)	0.001 (3)	−0.021 (3)
P1	0.0349 (8)	0.0455 (8)	0.0500 (8)	−0.0218 (7)	0.0021 (6)	−0.0169 (6)
P2	0.0396 (8)	0.0420 (8)	0.0556 (9)	−0.0088 (7)	0.0037 (7)	−0.0159 (7)
P3	0.0474 (9)	0.0473 (9)	0.0460 (8)	−0.0245 (7)	0.0028 (6)	−0.0062 (7)
S1	0.0552 (10)	0.0607 (10)	0.0670 (10)	−0.0231 (8)	−0.0070 (8)	−0.0162 (8)
S2	0.0426 (8)	0.0434 (8)	0.0514 (8)	−0.0212 (7)	0.0077 (6)	−0.0084 (6)
S3	0.0563 (10)	0.0489 (9)	0.0642 (9)	−0.0293 (8)	0.0045 (7)	−0.0214 (7)
S4	0.0341 (8)	0.0550 (9)	0.0628 (9)	−0.0201 (7)	0.0150 (6)	−0.0262 (7)
W1	0.03000 (12)	0.03933 (13)	0.04724 (14)	−0.01474 (10)	−0.00220 (9)	−0.01144 (10)
Cl1	0.0788 (13)	0.0924 (14)	0.0825 (12)	−0.0496 (12)	0.0043 (10)	−0.0303 (10)
C55	0.057 (9)	0.079 (10)	0.066 (8)	−0.023 (8)	0.004 (6)	−0.023 (7)

Geometric parameters (Å, º)

Ag1—P1	2.3856 (15)	C26—C27	1.389 (9)
Ag1—S4	2.5274 (15)	C26—H26	0.9300
Ag1—S2	2.5609 (16)	C27—C28	1.364 (9)
Ag1—W1	2.9718 (7)	C27—H27	0.9300
Ag1—I1	3.0870 (11)	C28—C29	1.357 (9)
Ag2—P2	2.4072 (17)	C28—H28	0.9300
Ag2—S3	2.5772 (17)	C29—C30	1.426 (9)
Ag2—S2	2.6450 (17)	C29—H29	0.9300
Ag2—I1	3.0201 (10)	C30—H30	0.9300
Ag2—W1	3.0324 (9)	C31—C32	1.367 (8)
Ag2—Ag3	3.3685 (10)	C31—C36	1.372 (8)
Ag3—P3	2.3885 (15)	C31—P2	1.846 (6)
Ag3—S3	2.5777 (17)	C32—C33	1.391 (10)
Ag3—S4	2.5839 (18)	C32—H32	0.9300
Ag3—W1	2.9846 (9)	C33—C34	1.370 (10)
Ag3—I1	3.0160 (10)	C33—H33	0.9300
C1—C6	1.385 (8)	C34—C35	1.376 (10)
C1—C2	1.391 (9)	C34—H34	0.9300
C1—P1	1.815 (6)	C35—C36	1.388 (9)
C2—C3	1.358 (9)	C35—H35	0.9300
C2—H2	0.9300	C36—H36	0.9300
C3—C4	1.374 (9)	C37—C38	1.355 (9)
C3—H3	0.9300	C37—C42	1.384 (9)
C4—C5	1.372 (10)	C37—P3	1.811 (6)
C4—H4	0.9300	C38—C39	1.412 (10)
C5—C6	1.379 (9)	C38—H38	0.9300
C5—H5	0.9300	C39—C40	1.376 (9)
C6—H6	0.9300	C39—H39	0.9300
C7—N1	1.354 (7)	C40—C41	1.375 (9)
C7—C8	1.363 (8)	C40—H40	0.9300
C7—P1	1.815 (6)	C41—C42	1.356 (9)
C8—C9	1.370 (9)	C41—H41	0.9300
C8—H8	0.9300	C42—H42	0.9300
C9—C10	1.319 (9)	C43—N3	1.369 (8)
C9—H9	0.9300	C43—C48	1.397 (8)
C10—C11	1.346 (10)	C43—P3	1.820 (6)
C10—H10	0.9300	C45—C46	1.336 (10)
C11—N1	1.386 (9)	C45—N3	1.394 (8)
C11—H11	0.9300	C45—H45	0.9300
C13—C14	1.372 (8)	C46—C47	1.332 (10)
C13—C18	1.384 (9)	C46—H46	0.9300
C13—P1	1.800 (6)	C47—C48	1.377 (9)
C14—C15	1.374 (8)	C47—H47	0.9300
C14—H14	0.9300	C48—H48	0.9300
C15—C16	1.380 (10)	C49—C54	1.363 (8)
C15—H15	0.9300	C49—C50	1.369 (8)
C16—C17	1.341 (9)	C49—P3	1.816 (6)
C16—H16	0.9300	C50—C51	1.382 (9)
C17—C18	1.399 (9)	C50—H50	0.9300
C17—H17	0.9300	C51—C52	1.375 (9)
C18—H18	0.9300	C51—H51	0.9300
C19—N2	1.365 (8)	C52—C53	1.390 (9)
C19—C20	1.366 (9)	C52—H52	0.9300
C19—P2	1.829 (6)	C53—C54	1.377 (9)
C20—C21	1.420 (9)	C53—H53	0.9300
C20—H20	0.9300	C54—H54	0.9300
C21—C22	1.348 (10)	S1—W1	2.1102 (17)
C21—H21	0.9300	S2—W1	2.2314 (14)
C22—C23	1.332 (10)	S3—W1	2.2380 (17)
C22—H22	0.9300	S4—W1	2.2419 (15)
C23—N2	1.399 (8)	Cl1—C55^i	1.805 (14)
C23—H23	0.9300	Cl1—C55	1.848 (13)
C25—C30	1.357 (9)	C55—Cl1^i	1.805 (14)
C25—C26	1.374 (9)	C55—H55A	0.9700
C25—P2	1.819 (6)	C55—H55B	0.9700
P1—Ag1—S4	128.42 (5)	C31—C32—C33	120.0 (6)
P1—Ag1—S2	127.03 (5)	C31—C32—H32	120.0
S4—Ag1—S2	92.96 (5)	C33—C32—H32	120.0
P1—Ag1—W1	161.04 (4)	C34—C33—C32	120.1 (7)
S4—Ag1—W1	47.27 (4)	C34—C33—H33	119.9
S2—Ag1—W1	46.85 (3)	C32—C33—H33	119.9
P1—Ag1—I1	103.24 (5)	C33—C34—C35	119.8 (6)
S4—Ag1—I1	100.76 (4)	C33—C34—H34	120.1
S2—Ag1—I1	98.45 (4)	C35—C34—H34	120.1
W1—Ag1—I1	95.67 (3)	C34—C35—C36	119.8 (6)
P2—Ag2—S3	127.44 (6)	C34—C35—H35	120.1
P2—Ag2—S2	122.73 (5)	C36—C35—H35	120.1
S3—Ag2—S2	89.83 (5)	C31—C36—C35	120.2 (6)
P2—Ag2—I1	108.87 (5)	C31—C36—H36	119.9
S3—Ag2—I1	104.95 (4)	C35—C36—H36	119.9
S2—Ag2—I1	98.26 (4)	C38—C37—C42	121.7 (6)
P2—Ag2—W1	154.79 (4)	C38—C37—P3	119.3 (5)
S3—Ag2—W1	46.15 (4)	C42—C37—P3	119.0 (5)
S2—Ag2—W1	45.66 (3)	C37—C38—C39	119.8 (7)
I1—Ag2—W1	95.82 (2)	C37—C38—H38	120.1
P2—Ag2—Ag3	145.11 (4)	C39—C38—H38	120.1
S3—Ag2—Ag3	49.20 (4)	C40—C39—C38	117.5 (7)
S2—Ag2—Ag3	91.80 (4)	C40—C39—H39	121.2
I1—Ag2—Ag3	56.02 (2)	C38—C39—H39	121.2
W1—Ag2—Ag3	55.28 (2)	C41—C40—C39	121.3 (6)
P3—Ag3—S3	125.86 (5)	C41—C40—H40	119.4
P3—Ag3—S4	122.33 (6)	C39—C40—H40	119.4
S3—Ag3—S4	91.08 (5)	C42—C41—C40	120.7 (6)
P3—Ag3—W1	155.18 (4)	C42—C41—H41	119.6
S3—Ag3—W1	46.75 (4)	C40—C41—H41	119.6
S4—Ag3—W1	46.80 (4)	C41—C42—C37	118.7 (7)
P3—Ag3—I1	107.69 (4)	C41—C42—H42	120.7
S3—Ag3—I1	105.05 (4)	C37—C42—H42	120.7
S4—Ag3—I1	101.31 (4)	N3—C43—C48	119.8 (6)
W1—Ag3—I1	96.92 (2)	N3—C43—P3	123.2 (4)
P3—Ag3—Ag2	142.22 (5)	C48—C43—P3	116.8 (5)
S3—Ag3—Ag2	49.19 (4)	C46—C45—N3	123.5 (7)
S4—Ag3—Ag2	95.26 (4)	C46—C45—H45	118.2
W1—Ag3—Ag2	56.63 (2)	N3—C45—H45	118.2
I1—Ag3—Ag2	56.14 (2)	C47—C46—C45	118.0 (6)
C6—C1—C2	119.1 (6)	C47—C46—H46	121.0
C6—C1—P1	123.7 (5)	C45—C46—H46	121.0
C2—C1—P1	117.1 (5)	C46—C47—C48	122.8 (7)
C3—C2—C1	121.0 (6)	C46—C47—H47	118.6
C3—C2—H2	119.5	C48—C47—H47	118.6
C1—C2—H2	119.5	C47—C48—C43	118.4 (6)
C2—C3—C4	120.0 (7)	C47—C48—H48	120.8
C2—C3—H3	120.0	C43—C48—H48	120.8
C4—C3—H3	120.0	C54—C49—C50	118.9 (6)
C5—C4—C3	119.6 (6)	C54—C49—P3	118.9 (4)
C5—C4—H4	120.2	C50—C49—P3	122.2 (5)
C3—C4—H4	120.2	C49—C50—C51	121.2 (6)
C4—C5—C6	121.2 (7)	C49—C50—H50	119.4
C4—C5—H5	119.4	C51—C50—H50	119.4
C6—C5—H5	119.4	C52—C51—C50	119.3 (6)
C5—C6—C1	119.1 (7)	C52—C51—H51	120.3
C5—C6—H6	120.5	C50—C51—H51	120.3
C1—C6—H6	120.5	C51—C52—C53	119.8 (6)
N1—C7—C8	119.1 (6)	C51—C52—H52	120.1
N1—C7—P1	122.6 (5)	C53—C52—H52	120.1
C8—C7—P1	118.2 (5)	C54—C53—C52	119.1 (6)
C7—C8—C9	121.0 (6)	C54—C53—H53	120.5
C7—C8—H8	119.5	C52—C53—H53	120.5
C9—C8—H8	119.5	C49—C54—C53	121.5 (6)
C10—C9—C8	120.3 (7)	C49—C54—H54	119.2
C10—C9—H9	119.9	C53—C54—H54	119.2
C8—C9—H9	119.9	Ag3—I1—Ag2	67.845 (18)
C9—C10—C11	119.5 (8)	Ag3—I1—Ag1	69.78 (2)
C9—C10—H10	120.2	Ag2—I1—Ag1	72.55 (2)
C11—C10—H10	120.2	C7—N1—C11	118.3 (6)
C10—C11—N1	121.8 (7)	C19—N2—C23	116.6 (6)
C10—C11—H11	119.1	C43—N3—C45	117.4 (6)
N1—C11—H11	119.1	C13—P1—C7	105.7 (3)
C14—C13—C18	120.1 (6)	C13—P1—C1	104.0 (3)
C14—C13—P1	119.7 (5)	C7—P1—C1	104.0 (3)
C18—C13—P1	120.2 (4)	C13—P1—Ag1	113.0 (2)
C13—C14—C15	119.9 (6)	C7—P1—Ag1	113.20 (19)
C13—C14—H14	120.0	C1—P1—Ag1	115.92 (18)
C15—C14—H14	120.0	C25—P2—C19	106.0 (3)
C14—C15—C16	119.9 (6)	C25—P2—C31	102.6 (3)
C14—C15—H15	120.1	C19—P2—C31	104.2 (3)
C16—C15—H15	120.1	C25—P2—Ag2	114.3 (2)
C17—C16—C15	120.8 (6)	C19—P2—Ag2	111.2 (2)
C17—C16—H16	119.6	C31—P2—Ag2	117.38 (19)
C15—C16—H16	119.6	C37—P3—C49	103.6 (3)
C16—C17—C18	120.2 (7)	C37—P3—C43	105.0 (3)
C16—C17—H17	119.9	C49—P3—C43	104.5 (3)
C18—C17—H17	119.9	C37—P3—Ag3	114.0 (2)
C13—C18—C17	119.0 (6)	C49—P3—Ag3	113.96 (18)
C13—C18—H18	120.5	C43—P3—Ag3	114.64 (19)
C17—C18—H18	120.5	W1—S2—Ag1	76.31 (4)
N2—C19—C20	121.5 (6)	W1—S2—Ag2	76.38 (4)
N2—C19—P2	119.6 (5)	Ag1—S2—Ag2	87.91 (5)
C20—C19—P2	118.8 (5)	W1—S3—Ag2	77.71 (5)
C19—C20—C21	119.2 (6)	W1—S3—Ag3	76.24 (5)
C19—C20—H20	120.4	Ag2—S3—Ag3	81.61 (5)
C21—C20—H20	120.4	W1—S4—Ag1	76.83 (4)
C22—C21—C20	119.3 (7)	W1—S4—Ag3	76.04 (5)
C22—C21—H21	120.3	Ag1—S4—Ag3	86.16 (5)
C20—C21—H21	120.3	S1—W1—S2	108.76 (6)
C23—C22—C21	119.8 (6)	S1—W1—S3	107.68 (6)
C23—C22—H22	120.1	S2—W1—S3	111.19 (6)
C21—C22—H22	120.1	S1—W1—S4	107.26 (7)
C22—C23—N2	123.4 (7)	S2—W1—S4	111.15 (5)
C22—C23—H23	118.3	S3—W1—S4	110.64 (6)
N2—C23—H23	118.3	S1—W1—Ag1	134.75 (5)
C30—C25—C26	120.8 (6)	S2—W1—Ag1	56.85 (4)
C30—C25—P2	116.3 (5)	S3—W1—Ag1	117.54 (4)
C26—C25—P2	122.8 (5)	S4—W1—Ag1	55.90 (4)
C25—C26—C27	117.7 (6)	S1—W1—Ag3	139.12 (5)
C25—C26—H26	121.2	S2—W1—Ag3	112.12 (4)
C27—C26—H26	121.2	S3—W1—Ag3	57.02 (4)
C28—C27—C26	123.0 (6)	S4—W1—Ag3	57.16 (4)
C28—C27—H27	118.5	Ag1—W1—Ag3	71.77 (2)
C26—C27—H27	118.5	S1—W1—Ag2	139.31 (5)
C29—C28—C27	118.9 (6)	S2—W1—Ag2	57.96 (4)
C29—C28—H28	120.5	S3—W1—Ag2	56.14 (4)
C27—C28—H28	120.5	S4—W1—Ag2	113.40 (4)
C28—C29—C30	119.2 (6)	Ag1—W1—Ag2	74.00 (2)
C28—C29—H29	120.4	Ag3—W1—Ag2	68.08 (2)
C30—C29—H29	120.4	C55^i—Cl1—C55	68.2 (7)
C25—C30—C29	120.2 (7)	Cl1^i—C55—Cl1	111.8 (7)
C25—C30—H30	119.9	Cl1^i—C55—H55A	109.2
C29—C30—H30	119.9	Cl1—C55—H55A	109.2
C32—C31—C36	119.9 (6)	Cl1^i—C55—H55B	109.2
C32—C31—P2	121.5 (5)	Cl1—C55—H55B	109.2
C36—C31—P2	118.6 (5)	H55A—C55—H55B	107.9

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···S4^ii	0.93	2.78	3.706 (7)	172
C52—H52···S4^iii	0.93	2.92	3.810 (7)	160
C41—H41···I1^iv	0.93	3.15	4.010 (6)	155
C36—H36···I1	0.93	3.04	3.962 (7)	174

Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y, −z+1.