A new polymorph of (O-ethyl dithio­carbonato-κ²S,S′)­bis­(tri­phenylphosphine-κP)silver(I)

A new triclinic polymorphic modification of the title compound, [Ag(C₃H₅OS₂)(C₁₈H₁₅P)₂], has been found and compared with the previously known orthorhombic modification [Tiekink (1988). Coord. Chem. 17, 239–243]. The two polymorphs have the same molecular shape, viz. a distorted tetrahedral geometry, with a chelating di­thio­carbonate (xanthate) and two PPh₃ ligands bonded to the Ag atom. However, in this new polymorph, the xanthate ligand is bonded asymmetrically to the Ag atom, with Ag—S distances of 2.5489 (6) and 2.8055 (7) Å, while for the orthorhombic polymorph these distances are 2.686 (4) and 2.601 (4) Å. The Ag—P distances are similar in both structures.

S1. Comment

In chemistry, the term polymorphism refers to the existence of more than one crystal structure for a chemical substance. In recent years, there has been a growing interest in the preparation and study of polymorphs, not only because they are an intrinsically interesting phenomenon that involve diverse scientific branches (mineralogy, material science, supramolecular chemistry, thermodynamics), but also because polymorphism has become a major issue in the pharmaceutical, optoelectronic, and dyes and pigments industries.

The addition of various ligands to suspensions of polymeric metal xanthates (dithiocarbonates) often results in the formation of monomeric adducts of different stoichiometries and structures. For instance, [Cu(S₂COEt)(PPh₃)₂] is tetracoordinated, with a chelating xanthate ligand (Bianchini et al., 1985); [Hg(S₂COEt)₂(PPh₃)] is five-coordinated (Watanabe, 1981); and the linear system [Au(S₂COMe)(PPh₃)] features a monodentate mode of coordination for the xanthate ligand (Tiekink, 1985). Complex [Ag(S₂COEt)(PPh₃)₂] was first prepared by the addition of PPh₃ to a suspension of Ag(S₂COEt) (Kowala & Swan, 1966), although the crystal structure was determined later (Tiekink, 1988). The complex crystallizes in the orthorhombic system, with the Ag atom in a distorted tetrahedral environment formed by two S atoms derived from the chelating S₂COEt ligand and by two PPh₃ groups, as in [Cu(S₂COEt)(PPh₃)₂] (Bianchini et al., 1985). The Ag—P distances [2.4193 (6) and 2.4614 (6) Å] are very similar and lie in the range expected for Ag-PPh₃ bonds (2.363–2.529 Å). The two Ag—S distances are also similar [2.686 (4) and 2.601 (4) Å], although they are a little longer than the distances found in other comparable Ag coordination compounds (Müller et al., 1979). Planes S1—Ag1—S2 and P1—Ag1—P2 are almost perpendicular (89.81 °).

We report here a new polymorph of [Ag(S₂COEt)(PPh₃)₂], (I), that crystallizes in the triclinic system. Compound (I) has the same general molecular shape as the orthorhombic polymorph, i.e. the Ag atom has a distorted tetrahedral environment, the distortion being due in part to the restricted bite angle of the chelating xanthate ligand [67.345 (19) °]. The Ag—P distances (Table 1) are comparable in both cases. The main difference between the two polymorphs is that (I) features an asymmetrically chelating xanthate ligand, with Ag—S distances of 2.5489 (6) and 2.8055 (7) Å. The latter is a very long Ag—S bond, although similar values have been found in other complexes (Drew et al., 1987). This difference cannot be attibuted to packing forces. The bite distance of the xanthate is 2.9764 (9) Å. The angle between planes S1—Ag1—S2 and P1—Ag1—P2 is 75.55 (2) °. Thus, the coordination sphere of the Ag atom in (I) is highly irregular, with a wide variation in bond lengths and angles. There are also some differences in the orientation of the phenyl groups between the two forms. The dihedral angles between the planes of the phenyl rings bonded to P1 and P2 and the plane P1—Ag1—P2 are 86.96 (6), 54.51 (6), 20.76 (8), 53.84 (5), 79.96 (6) and 47.38 (6)°, respectively, in (I). These angles are 69.39, 79.38, 38.47, 31.08, 59.22 and 74.79° for the orthorhombic polymorph.

There is no clear evidence of intermolecular hydrogen bonding; the shortest potential hydrogen-bond interaction involves atoms C8 and S2 at a separation of 3.568 (3) Å, with the corresponding H···S distance being 2.76 Å. This contact could be considered as a weak electrostatic interaction, since the separation is some 0.3 Å shorter than the sum of the Van der Waals radii for H (1.2 Å) and S (1.85 Å) (Whuler et al., 1980). In addition there is a weak intramolecular interaction S1···H2A of 2.76 Å that may be associated with the long distance Ag1—S1.

S2. Experimental

Compound (I) was obtained from the reaction of [Zn(S₂COEt)₂] (0.200 g, 0.651 mmol) with AgClPPh₃ (0.528 g, 1.302 mmol) in dichloromethane (20 ml) at room temperature. After 30 min, the solid product [a mixture of Ag(S₂COEt) and ZnCl₂] was filtered off and the filtrate evaporated to dryness. The addition of isopropyl alcohol to the residue gave (I) as a white solid (yield = 66%). Analysis; calculated for C₃₉H₃₅AgOP₂S₂: C 62.17, N 4.64, S 8.49; found: C 61.90, N 4.54, S 8.59. Single crystals were obtained by slow diffusion of n-hexane into a dichloromethane solution of (I) at room temperature.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP, SHELXTL (Bruker, 2000); software used to prepare material for publication: XCIF, SHELXTL (Bruker, 2000).

Figures

Fig. 1. The structure of (I), showing displacement ellipsoids at the 50% probability level and the atom-numbering scheme. H atoms have been omitted for clarity

(O-ethyldithiocarbonato-κ²S,S')bis(triphenylphosphine-κP)silver(I)

Crystal data

[Ag(C3H5OS2)(C18H15P)2]	Z = 2
Mr = 753.60	F(000) = 772
Triclinic, P1	Dx = 1.454 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3302 (6) Å	Cell parameters from 4690 reflections
b = 12.8582 (7) Å	θ = 2.3–26.4°
c = 13.8270 (8) Å	µ = 0.83 mm^−1
α = 87.432 (1)°	T = 100 K
β = 74.956 (1)°	Prism, pale yellow
γ = 76.067 (1)°	0.25 × 0.18 × 0.16 mm
V = 1721.17 (17) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	6873 independent reflections
Radiation source: fine-focus sealed tube	5720 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 8.26 pixels mm^-1	θmax = 26.4°, θmin = 1.5°
ω–scan	h = −12→12
Absorption correction: multi-scan SADABS (Bruker, 1999)	k = −16→10
Tmin = 0.819, Tmax = 0.879	l = −17→17
10445 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0289P)^2] where P = (Fo^2 + 2Fc^2)/3
6873 reflections	(Δ/σ)max = 0.001
406 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.49 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
Ag1	0.078862 (18)	0.338615 (16)	0.258549 (14)	0.01725 (6)
S1	0.03573 (6)	0.19811 (6)	0.41849 (5)	0.02165 (16)
S2	−0.16351 (6)	0.30637 (6)	0.30286 (5)	0.02031 (15)
P1	0.10533 (6)	0.51915 (5)	0.27054 (5)	0.01546 (15)
P2	0.24930 (6)	0.20063 (5)	0.14396 (5)	0.01576 (15)
O1	−0.21572 (16)	0.16904 (14)	0.43733 (13)	0.0212 (4)
C1	−0.1170 (2)	0.2192 (2)	0.39022 (18)	0.0178 (6)
C2	−0.1904 (3)	0.0939 (2)	0.5157 (2)	0.0273 (7)
H2A	−0.1591	0.1273	0.5658	0.033*
H2B	−0.1185	0.0293	0.4869	0.033*
C3	−0.3247 (3)	0.0645 (3)	0.5636 (2)	0.0341 (8)
H3A	−0.3120	0.0132	0.6170	0.051*
H3B	−0.3548	0.0320	0.5131	0.051*
H3C	−0.3947	0.1291	0.5921	0.051*
C4	0.2519 (2)	0.5257 (2)	0.31782 (17)	0.0146 (5)
C5	0.2519 (3)	0.6031 (2)	0.38452 (19)	0.0199 (6)
H5	0.1702	0.6570	0.4103	0.024*
C6	0.3714 (3)	0.6020 (2)	0.41364 (19)	0.0239 (6)
H6	0.3712	0.6547	0.4597	0.029*
C7	0.4905 (3)	0.5240 (2)	0.37542 (19)	0.0218 (6)
H7	0.5725	0.5242	0.3944	0.026*
C8	0.4908 (3)	0.4458 (2)	0.30978 (19)	0.0216 (6)
H8	0.5726	0.3921	0.2839	0.026*
C9	0.3717 (2)	0.4464 (2)	0.28219 (18)	0.0195 (6)
H9	0.3714	0.3918	0.2382	0.023*
C10	0.1461 (2)	0.5772 (2)	0.14646 (18)	0.0158 (5)
C11	0.0471 (3)	0.5942 (2)	0.09196 (19)	0.0209 (6)
H11	−0.0410	0.5807	0.1217	0.025*
C12	0.0761 (3)	0.6307 (2)	−0.0056 (2)	0.0241 (6)
H12	0.0076	0.6426	−0.0420	0.029*
C13	0.2042 (3)	0.6498 (2)	−0.05001 (19)	0.0240 (6)
H13	0.2240	0.6748	−0.1167	0.029*
C14	0.3034 (3)	0.6322 (2)	0.00349 (19)	0.0224 (6)
H14	0.3918	0.6448	−0.0269	0.027*
C15	0.2750 (2)	0.5966 (2)	0.10063 (18)	0.0181 (6)
H15	0.3439	0.5852	0.1366	0.022*
C16	−0.0424 (2)	0.6188 (2)	0.34006 (18)	0.0157 (5)
C17	−0.1461 (2)	0.5843 (2)	0.40994 (18)	0.0208 (6)
H17	−0.1375	0.5099	0.4220	0.025*
C18	−0.2625 (3)	0.6585 (2)	0.4621 (2)	0.0258 (6)
H18	−0.3326	0.6348	0.5107	0.031*
C19	−0.2764 (3)	0.7658 (2)	0.4437 (2)	0.0259 (7)
H19	−0.3570	0.8160	0.4784	0.031*
C20	−0.1730 (3)	0.8017 (2)	0.37432 (19)	0.0239 (6)
H20	−0.1823	0.8760	0.3618	0.029*
C21	−0.0571 (3)	0.7279 (2)	0.32404 (19)	0.0206 (6)
H21	0.0143	0.7521	0.2774	0.025*
C22	0.2954 (2)	0.2296 (2)	0.01008 (18)	0.0166 (6)
C23	0.3112 (3)	0.1549 (2)	−0.06383 (19)	0.0217 (6)
H23	0.2988	0.0852	−0.0457	0.026*
C24	0.3451 (3)	0.1814 (2)	−0.1643 (2)	0.0260 (6)
H24	0.3550	0.1299	−0.2145	0.031*
C25	0.3645 (3)	0.2819 (2)	−0.1914 (2)	0.0264 (7)
H25	0.3876	0.2998	−0.2602	0.032*
C26	0.3501 (3)	0.3565 (2)	−0.1183 (2)	0.0252 (6)
H26	0.3653	0.4255	−0.1369	0.030*
C27	0.3137 (3)	0.3313 (2)	−0.0179 (2)	0.0221 (6)
H27	0.3013	0.3838	0.0320	0.026*
C28	0.4152 (2)	0.1666 (2)	0.17535 (18)	0.0161 (5)
C29	0.4172 (3)	0.1675 (2)	0.27561 (19)	0.0224 (6)
H29	0.3328	0.1847	0.3261	0.027*
C30	0.5408 (3)	0.1436 (2)	0.3024 (2)	0.0244 (6)
H30	0.5405	0.1438	0.3712	0.029*
C31	0.6646 (2)	0.1194 (2)	0.23020 (19)	0.0209 (6)
H31	0.7493	0.1029	0.2489	0.025*
C32	0.6641 (2)	0.1195 (2)	0.13038 (19)	0.0201 (6)
H32	0.7490	0.1035	0.0803	0.024*
C33	0.5405 (2)	0.1427 (2)	0.10282 (19)	0.0194 (6)
H33	0.5414	0.1423	0.0340	0.023*
C34	0.2035 (2)	0.0723 (2)	0.14536 (18)	0.0163 (5)
C35	0.2907 (3)	−0.0244 (2)	0.15798 (18)	0.0193 (6)
H35	0.3768	−0.0252	0.1709	0.023*
C36	0.2538 (3)	−0.1205 (2)	0.15195 (19)	0.0226 (6)
H36	0.3144	−0.1865	0.1609	0.027*
C37	0.1284 (3)	−0.1197 (2)	0.13286 (18)	0.0216 (6)
H37	0.1041	−0.1852	0.1261	0.026*
C38	0.0391 (3)	−0.0233 (2)	0.1237 (2)	0.0235 (6)
H38	−0.0480	−0.0227	0.1124	0.028*
C39	0.0745 (2)	0.0724 (2)	0.13063 (19)	0.0213 (6)
H39	0.0114	0.1383	0.1254	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.01452 (10)	0.01736 (11)	0.01931 (11)	−0.00492 (8)	−0.00235 (8)	0.00053 (8)
S1	0.0155 (3)	0.0302 (4)	0.0212 (4)	−0.0070 (3)	−0.0077 (3)	0.0065 (3)
S2	0.0148 (3)	0.0243 (4)	0.0233 (4)	−0.0060 (3)	−0.0073 (3)	0.0072 (3)
P1	0.0133 (3)	0.0165 (4)	0.0162 (3)	−0.0041 (3)	−0.0028 (3)	0.0012 (3)
P2	0.0143 (3)	0.0163 (4)	0.0165 (3)	−0.0042 (3)	−0.0031 (3)	0.0009 (3)
O1	0.0178 (9)	0.0246 (11)	0.0231 (10)	−0.0104 (8)	−0.0049 (8)	0.0076 (8)
C1	0.0159 (12)	0.0187 (14)	0.0174 (13)	−0.0042 (11)	−0.0013 (11)	−0.0036 (11)
C2	0.0265 (14)	0.0290 (17)	0.0284 (16)	−0.0100 (13)	−0.0096 (13)	0.0134 (14)
C3	0.0285 (15)	0.0366 (19)	0.0364 (18)	−0.0118 (14)	−0.0056 (14)	0.0163 (15)
C4	0.0137 (11)	0.0166 (14)	0.0146 (13)	−0.0063 (11)	−0.0037 (10)	0.0061 (11)
C5	0.0191 (13)	0.0194 (15)	0.0196 (14)	−0.0027 (11)	−0.0040 (11)	0.0021 (12)
C6	0.0287 (14)	0.0263 (16)	0.0214 (14)	−0.0129 (13)	−0.0086 (12)	0.0004 (12)
C7	0.0184 (13)	0.0294 (16)	0.0223 (14)	−0.0114 (12)	−0.0095 (12)	0.0083 (13)
C8	0.0161 (12)	0.0256 (16)	0.0212 (14)	−0.0030 (12)	−0.0036 (11)	0.0035 (12)
C9	0.0194 (13)	0.0207 (15)	0.0182 (14)	−0.0041 (11)	−0.0048 (11)	−0.0003 (12)
C10	0.0164 (12)	0.0121 (13)	0.0177 (13)	−0.0027 (10)	−0.0028 (11)	−0.0007 (11)
C11	0.0162 (12)	0.0233 (15)	0.0228 (14)	−0.0047 (11)	−0.0043 (11)	−0.0010 (12)
C12	0.0277 (14)	0.0253 (16)	0.0225 (15)	−0.0040 (13)	−0.0143 (12)	0.0002 (12)
C13	0.0327 (15)	0.0210 (15)	0.0159 (14)	−0.0049 (13)	−0.0036 (12)	0.0010 (12)
C14	0.0215 (13)	0.0214 (15)	0.0230 (15)	−0.0085 (12)	−0.0004 (12)	0.0008 (12)
C15	0.0173 (12)	0.0177 (14)	0.0193 (14)	−0.0034 (11)	−0.0054 (11)	0.0006 (11)
C16	0.0139 (12)	0.0203 (14)	0.0134 (13)	−0.0044 (11)	−0.0042 (10)	0.0004 (11)
C17	0.0217 (13)	0.0227 (15)	0.0175 (14)	−0.0075 (12)	−0.0018 (11)	−0.0011 (12)
C18	0.0196 (13)	0.0380 (18)	0.0194 (14)	−0.0110 (13)	0.0000 (12)	−0.0012 (13)
C19	0.0174 (13)	0.0347 (18)	0.0225 (15)	0.0022 (13)	−0.0060 (12)	−0.0077 (13)
C20	0.0284 (14)	0.0200 (15)	0.0209 (14)	0.0009 (12)	−0.0084 (12)	0.0002 (12)
C21	0.0198 (13)	0.0233 (15)	0.0176 (14)	−0.0060 (12)	−0.0023 (11)	0.0015 (12)
C22	0.0117 (11)	0.0201 (14)	0.0175 (13)	−0.0026 (11)	−0.0044 (10)	0.0023 (11)
C23	0.0237 (13)	0.0204 (15)	0.0226 (14)	−0.0072 (12)	−0.0069 (12)	0.0018 (12)
C24	0.0317 (15)	0.0278 (17)	0.0177 (14)	−0.0057 (13)	−0.0059 (12)	−0.0028 (13)
C25	0.0266 (14)	0.0324 (18)	0.0190 (14)	−0.0055 (13)	−0.0058 (12)	0.0060 (13)
C26	0.0272 (14)	0.0210 (15)	0.0258 (15)	−0.0076 (13)	−0.0035 (13)	0.0073 (13)
C27	0.0224 (13)	0.0212 (15)	0.0219 (14)	−0.0057 (12)	−0.0038 (12)	−0.0007 (12)
C28	0.0171 (12)	0.0134 (13)	0.0186 (13)	−0.0052 (11)	−0.0048 (11)	0.0022 (11)
C29	0.0173 (12)	0.0274 (16)	0.0195 (14)	−0.0044 (12)	−0.0009 (11)	0.0026 (12)
C30	0.0240 (14)	0.0305 (17)	0.0204 (14)	−0.0083 (13)	−0.0071 (12)	0.0012 (13)
C31	0.0162 (12)	0.0213 (15)	0.0262 (15)	−0.0049 (11)	−0.0070 (12)	0.0003 (12)
C32	0.0149 (12)	0.0208 (15)	0.0234 (14)	−0.0063 (11)	−0.0012 (11)	0.0001 (12)
C33	0.0198 (13)	0.0211 (15)	0.0177 (14)	−0.0065 (12)	−0.0041 (11)	0.0000 (12)
C34	0.0162 (12)	0.0189 (14)	0.0127 (13)	−0.0068 (11)	0.0007 (10)	−0.0002 (11)
C35	0.0196 (13)	0.0212 (15)	0.0181 (14)	−0.0072 (12)	−0.0047 (11)	0.0022 (12)
C36	0.0268 (14)	0.0161 (14)	0.0220 (15)	−0.0038 (12)	−0.0032 (12)	0.0039 (12)
C37	0.0274 (14)	0.0202 (15)	0.0176 (14)	−0.0129 (12)	0.0004 (12)	0.0003 (12)
C38	0.0163 (13)	0.0276 (16)	0.0264 (15)	−0.0087 (12)	−0.0022 (12)	0.0012 (13)
C39	0.0179 (13)	0.0196 (15)	0.0254 (15)	−0.0040 (12)	−0.0040 (12)	0.0000 (12)

Geometric parameters (Å, º)

Ag1—P1	2.4196 (7)	C16—C17	1.390 (3)
Ag1—P2	2.4612 (7)	C17—C18	1.391 (4)
Ag1—S2	2.5489 (6)	C17—H17	0.9500
Ag1—S1	2.8055 (7)	C18—C19	1.372 (4)
S1—C1	1.680 (2)	C18—H18	0.9500
S2—C1	1.693 (3)	C19—C20	1.392 (4)
P1—C16	1.817 (3)	C19—H19	0.9500
P1—C4	1.818 (2)	C20—C21	1.378 (3)
P1—C10	1.827 (2)	C20—H20	0.9500
P2—C34	1.820 (3)	C21—H21	0.9500
P2—C28	1.823 (2)	C22—C23	1.385 (4)
P2—C22	1.833 (2)	C22—C27	1.390 (4)
O1—C1	1.347 (3)	C23—C24	1.390 (3)
O1—C2	1.452 (3)	C23—H23	0.9500
C2—C3	1.502 (3)	C24—C25	1.375 (4)
C2—H2A	0.9900	C24—H24	0.9500
C2—H2B	0.9900	C25—C26	1.381 (4)
C3—H3A	0.9800	C25—H25	0.9500
C3—H3B	0.9800	C26—C27	1.386 (3)
C3—H3C	0.9800	C26—H26	0.9500
C4—C5	1.387 (3)	C27—H27	0.9500
C4—C9	1.391 (3)	C28—C33	1.392 (3)
C5—C6	1.391 (3)	C28—C29	1.393 (3)
C5—H5	0.9500	C29—C30	1.381 (3)
C6—C7	1.383 (4)	C29—H29	0.9500
C6—H6	0.9500	C30—C31	1.379 (3)
C7—C8	1.383 (4)	C30—H30	0.9500
C7—H7	0.9500	C31—C32	1.382 (3)
C8—C9	1.378 (3)	C31—H31	0.9500
C8—H8	0.9500	C32—C33	1.387 (3)
C9—H9	0.9500	C32—H32	0.9500
C10—C11	1.392 (3)	C33—H33	0.9500
C10—C15	1.396 (3)	C34—C35	1.382 (3)
C11—C12	1.390 (3)	C34—C39	1.399 (3)
C11—H11	0.9500	C35—C36	1.389 (4)
C12—C13	1.382 (4)	C35—H35	0.9500
C12—H12	0.9500	C36—C37	1.385 (3)
C13—C14	1.384 (3)	C36—H36	0.9500
C13—H13	0.9500	C37—C38	1.379 (4)
C14—C15	1.380 (3)	C37—H37	0.9500
C14—H14	0.9500	C38—C39	1.379 (4)
C15—H15	0.9500	C38—H38	0.9500
C16—C21	1.387 (4)	C39—H39	0.9500
P1—Ag1—P2	123.04 (2)	C21—C16—C17	118.9 (2)
P1—Ag1—S2	118.85 (2)	C21—C16—P1	122.41 (19)
P2—Ag1—S2	113.08 (2)	C17—C16—P1	118.7 (2)
P1—Ag1—S1	125.71 (2)	C16—C17—C18	120.1 (3)
P2—Ag1—S1	94.25 (2)	C16—C17—H17	120.0
S2—Ag1—S1	67.345 (19)	C18—C17—H17	120.0
C1—S1—Ag1	80.29 (9)	C19—C18—C17	120.1 (2)
C1—S2—Ag1	88.26 (9)	C19—C18—H18	119.9
C16—P1—C4	107.20 (11)	C17—C18—H18	119.9
C16—P1—C10	103.25 (11)	C18—C19—C20	120.4 (3)
C4—P1—C10	102.67 (11)	C18—C19—H19	119.8
C16—P1—Ag1	117.95 (8)	C20—C19—H19	119.8
C4—P1—Ag1	113.43 (8)	C21—C20—C19	119.1 (3)
C10—P1—Ag1	110.80 (8)	C21—C20—H20	120.5
C34—P2—C28	103.73 (11)	C19—C20—H20	120.5
C34—P2—C22	102.82 (12)	C20—C21—C16	121.4 (2)
C28—P2—C22	103.39 (11)	C20—C21—H21	119.3
C34—P2—Ag1	114.89 (8)	C16—C21—H21	119.3
C28—P2—Ag1	111.97 (8)	C23—C22—C27	118.9 (2)
C22—P2—Ag1	118.37 (8)	C23—C22—P2	122.8 (2)
C1—O1—C2	119.32 (19)	C27—C22—P2	118.3 (2)
O1—C1—S1	122.45 (18)	C22—C23—C24	120.4 (3)
O1—C1—S2	113.66 (17)	C22—C23—H23	119.8
S1—C1—S2	123.87 (15)	C24—C23—H23	119.8
O1—C2—C3	106.7 (2)	C25—C24—C23	120.3 (3)
O1—C2—H2A	110.4	C25—C24—H24	119.9
C3—C2—H2A	110.4	C23—C24—H24	119.9
O1—C2—H2B	110.4	C24—C25—C26	119.7 (2)
C3—C2—H2B	110.4	C24—C25—H25	120.2
H2A—C2—H2B	108.6	C26—C25—H25	120.2
C2—C3—H3A	109.5	C25—C26—C27	120.3 (3)
C2—C3—H3B	109.5	C25—C26—H26	119.8
H3A—C3—H3B	109.5	C27—C26—H26	119.8
C2—C3—H3C	109.5	C26—C27—C22	120.3 (3)
H3A—C3—H3C	109.5	C26—C27—H27	119.8
H3B—C3—H3C	109.5	C22—C27—H27	119.8
C5—C4—C9	119.2 (2)	C33—C28—C29	118.4 (2)
C5—C4—P1	124.95 (19)	C33—C28—P2	122.61 (19)
C9—C4—P1	115.87 (19)	C29—C28—P2	118.93 (19)
C4—C5—C6	120.0 (2)	C30—C29—C28	120.7 (2)
C4—C5—H5	120.0	C30—C29—H29	119.6
C6—C5—H5	120.0	C28—C29—H29	119.6
C7—C6—C5	119.9 (3)	C31—C30—C29	120.5 (2)
C7—C6—H6	120.0	C31—C30—H30	119.7
C5—C6—H6	120.0	C29—C30—H30	119.7
C8—C7—C6	120.4 (2)	C30—C31—C32	119.4 (2)
C8—C7—H7	119.8	C30—C31—H31	120.3
C6—C7—H7	119.8	C32—C31—H31	120.3
C9—C8—C7	119.5 (2)	C31—C32—C33	120.5 (2)
C9—C8—H8	120.2	C31—C32—H32	119.8
C7—C8—H8	120.2	C33—C32—H32	119.8
C8—C9—C4	121.0 (2)	C32—C33—C28	120.5 (2)
C8—C9—H9	119.5	C32—C33—H33	119.8
C4—C9—H9	119.5	C28—C33—H33	119.8
C11—C10—C15	118.5 (2)	C35—C34—C39	118.8 (2)
C11—C10—P1	118.03 (18)	C35—C34—P2	123.35 (19)
C15—C10—P1	123.19 (18)	C39—C34—P2	117.80 (19)
C12—C11—C10	120.6 (2)	C34—C35—C36	120.8 (2)
C12—C11—H11	119.7	C34—C35—H35	119.6
C10—C11—H11	119.7	C36—C35—H35	119.6
C13—C12—C11	120.3 (2)	C37—C36—C35	119.8 (2)
C13—C12—H12	119.9	C37—C36—H36	120.1
C11—C12—H12	119.9	C35—C36—H36	120.1
C12—C13—C14	119.5 (2)	C38—C37—C36	119.6 (3)
C12—C13—H13	120.3	C38—C37—H37	120.2
C14—C13—H13	120.3	C36—C37—H37	120.2
C15—C14—C13	120.6 (2)	C39—C38—C37	120.8 (2)
C15—C14—H14	119.7	C39—C38—H38	119.6
C13—C14—H14	119.7	C37—C38—H38	119.6
C14—C15—C10	120.6 (2)	C38—C39—C34	120.0 (2)
C14—C15—H15	119.7	C38—C39—H39	120.0
C10—C15—H15	119.7	C34—C39—H39	120.0
P1—Ag1—S1—C1	112.92 (9)	P1—C10—C15—C14	174.6 (2)
P2—Ag1—S1—C1	−110.46 (9)	C4—P1—C16—C21	73.5 (2)
S2—Ag1—S1—C1	2.80 (9)	C10—P1—C16—C21	−34.5 (2)
P1—Ag1—S2—C1	−122.23 (9)	Ag1—P1—C16—C21	−157.06 (18)
P2—Ag1—S2—C1	82.07 (9)	C4—P1—C16—C17	−108.3 (2)
S1—Ag1—S2—C1	−2.74 (9)	C10—P1—C16—C17	143.7 (2)
P2—Ag1—P1—C16	168.55 (9)	Ag1—P1—C16—C17	21.2 (2)
S2—Ag1—P1—C16	15.40 (9)	C21—C16—C17—C18	0.3 (4)
S1—Ag1—P1—C16	−66.23 (9)	P1—C16—C17—C18	−178.02 (19)
P2—Ag1—P1—C4	−64.95 (9)	C16—C17—C18—C19	1.1 (4)
S2—Ag1—P1—C4	141.90 (8)	C17—C18—C19—C20	−1.5 (4)
S1—Ag1—P1—C4	60.27 (9)	C18—C19—C20—C21	0.4 (4)
P2—Ag1—P1—C10	49.92 (9)	C19—C20—C21—C16	1.0 (4)
S2—Ag1—P1—C10	−103.24 (8)	C17—C16—C21—C20	−1.3 (4)
S1—Ag1—P1—C10	175.13 (8)	P1—C16—C21—C20	176.93 (19)
P1—Ag1—P2—C34	−177.95 (9)	C34—P2—C22—C23	−10.1 (2)
S2—Ag1—P2—C34	−23.41 (9)	C28—P2—C22—C23	97.6 (2)
S1—Ag1—P2—C34	43.75 (9)	Ag1—P2—C22—C23	−137.93 (18)
P1—Ag1—P2—C28	64.07 (9)	C34—P2—C22—C27	169.28 (19)
S2—Ag1—P2—C28	−141.40 (8)	C28—P2—C22—C27	−83.0 (2)
S1—Ag1—P2—C28	−74.24 (9)	Ag1—P2—C22—C27	41.4 (2)
P1—Ag1—P2—C22	−56.04 (10)	C27—C22—C23—C24	0.1 (4)
S2—Ag1—P2—C22	98.50 (9)	P2—C22—C23—C24	179.46 (19)
S1—Ag1—P2—C22	165.66 (9)	C22—C23—C24—C25	0.6 (4)
C2—O1—C1—S1	0.1 (3)	C23—C24—C25—C26	0.0 (4)
C2—O1—C1—S2	−178.61 (19)	C24—C25—C26—C27	−1.3 (4)
Ag1—S1—C1—O1	176.8 (2)	C25—C26—C27—C22	1.9 (4)
Ag1—S1—C1—S2	−4.69 (15)	C23—C22—C27—C26	−1.3 (4)
Ag1—S2—C1—O1	−176.26 (18)	P2—C22—C27—C26	179.27 (19)
Ag1—S2—C1—S1	5.09 (16)	C34—P2—C28—C33	92.1 (2)
C1—O1—C2—C3	171.7 (2)	C22—P2—C28—C33	−14.9 (2)
C16—P1—C4—C5	−8.0 (2)	Ag1—P2—C28—C33	−143.4 (2)
C10—P1—C4—C5	100.4 (2)	C34—P2—C28—C29	−89.8 (2)
Ag1—P1—C4—C5	−140.01 (19)	C22—P2—C28—C29	163.1 (2)
C16—P1—C4—C9	172.58 (18)	Ag1—P2—C28—C29	34.6 (2)
C10—P1—C4—C9	−79.0 (2)	C33—C28—C29—C30	−1.0 (4)
Ag1—P1—C4—C9	40.6 (2)	P2—C28—C29—C30	−179.1 (2)
C9—C4—C5—C6	1.1 (4)	C28—C29—C30—C31	0.6 (4)
P1—C4—C5—C6	−178.27 (19)	C29—C30—C31—C32	0.1 (4)
C4—C5—C6—C7	0.5 (4)	C30—C31—C32—C33	−0.5 (4)
C5—C6—C7—C8	−1.2 (4)	C31—C32—C33—C28	0.2 (4)
C6—C7—C8—C9	0.3 (4)	C29—C28—C33—C32	0.6 (4)
C7—C8—C9—C4	1.3 (4)	P2—C28—C33—C32	178.6 (2)
C5—C4—C9—C8	−2.0 (4)	C28—P2—C34—C35	−5.8 (2)
P1—C4—C9—C8	177.41 (19)	C22—P2—C34—C35	101.6 (2)
C16—P1—C10—C11	−62.6 (2)	Ag1—P2—C34—C35	−128.4 (2)
C4—P1—C10—C11	−173.9 (2)	C28—P2—C34—C39	175.62 (19)
Ag1—P1—C10—C11	64.7 (2)	C22—P2—C34—C39	−76.9 (2)
C16—P1—C10—C15	123.0 (2)	Ag1—P2—C34—C39	53.1 (2)
C4—P1—C10—C15	11.7 (2)	C39—C34—C35—C36	2.7 (4)
Ag1—P1—C10—C15	−109.8 (2)	P2—C34—C35—C36	−175.81 (19)
C15—C10—C11—C12	−0.6 (4)	C34—C35—C36—C37	0.1 (4)
P1—C10—C11—C12	−175.3 (2)	C35—C36—C37—C38	−2.4 (4)
C10—C11—C12—C13	0.5 (4)	C36—C37—C38—C39	1.7 (4)
C11—C12—C13—C14	0.0 (4)	C37—C38—C39—C34	1.2 (4)
C12—C13—C14—C15	−0.4 (4)	C35—C34—C39—C38	−3.4 (4)
C13—C14—C15—C10	0.3 (4)	P2—C34—C39—C38	175.2 (2)
C11—C10—C15—C14	0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···S2^i	0.95	2.76	3.568 (3)	144
C13—H13···S2^ii	0.95	2.79	3.632 (3)	148
C31—H31···S2^i	0.95	3.14	3.625 (3)	113
C5—H5···S1^iii	0.95	3.08	3.943 (3)	152
C2—H2A···S1	0.99	2.76	2.963 (3)	92
C29—H29···S1	0.95	2.97	3.856 (3)	156

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