[Bis(2-diphenylphosphinoethyl) sulfide-κ³P,S,P′](triphenylphosphine-κP)platinum(II) diperchlorate acetone solvate

In the title compound, [Pt(C₁₈H₁₅P)(C₂₈H₂₈P₂S)]­(ClO₄)₂·­C₃H₆O or [Pt(PPh₃)(PSP)](ClO₄)₂·CH₃COCH₃, where PSP is the potentially tridentate chelate ligand bis(2-di­phenyl­phosphinoethyl) sulfide, all three donor groups of the PSP ligand are coordinated to the central Pt atom, with Pt—P = 2.310 (1) Å and Pt—S = 2.343 (1) Å. The fourth coordination site is occupied by the P donor of the tri­phenyl­phosphine ligand [Pt—P = 2.289 (1) Å]. The complex cation has exact mirror symmetry, with the S atom, the Pt atom and the P atom of the PPh₃ ligand in the mirror plane. The Pt atom has a distorted square-planar coordination geometry. A π–π interaction is present between the phenyl rings of the PPh₃ ligand and the terminal –PPh₂ group of the PSP chelate.

S1. Comment

A range of platinum complexes of phosphinothioether chelate ligands have been found to serve as efficient catalysts in homogeneous hydrogenation, carbonylation and asymmetric allylic alkylation reactions (Bayón et al., 1999; Dilworth et al., 1995; Sugama et al., 2001). In addition, the synthesis and characterization of Pt^II complexes of mixed P,S polydentate chelate ligands, these being acyclic or macrocyclic ligands, have attracted significant attention (Andreasen et al., 1999; Connolly et al., 1997; Kyba et al., 1987; Siah et al., 1994). The systematic geometric variation of the respective P and S donors within these ligands has provided insight into the trans influence of chelated phosphines on chelated thioethers and vice versa.

In the current investigation by us of the relationship between structure and reactivity of tridentately chelated Pt^II complexes, several complexes of the tridentate phosphinothioether chelate ligand PSP have been prepared and characterized (Andreasen et al., 1999; Andreasen; 2000). Two of these Pt^II—PSP complexes, [Pt(PSP)Cl]ClO₄ and [Pt(PSP)I]I, have been characterized by X-ray diffraction (Andreasen et al., 1999). We present here the X-ray structure of a third such complex, the title compound, (I). \sch

Complex (I) contains PPh₃ trans to the central thioether chelate donor; the molecular structure of the cation of (I) is shown in Fig. 1. The three donors of the PSP chelate ligand, the S and the two tertiary phosphine groups, are all coordinated to the Pt atom, forming two five-membered chelate rings, with the PPh₃ donor occupying the fourth coordination site. The [Pt(PSP)(PPh₃)]²⁺ cation has exact mirror symmetry with atoms S, Pt and P1 of the PPh₃ ligand in the mirror plane.

The coordination sphere of the [Pt(PSP)(PPh₃)]²⁺ cation is tetrahedrally distorted from planar geometry, with the two PSP P atoms (P2 and P2') deviating by 0.075 Å to the one side of the least-squares plane through the S and P donor atoms, while the remaining two donors, i.e. the PSP S and the PPh₃ P1, are located on the opposite side of this plane at 0.085 and 0.064 Å, respectively. The Pt atom is 0.04 Å from the plane on the same side as the S and PPh₃ P atoms. This tetrahedral distortion is, however, less pronounced than that in the [Pt(PSP)Cl]⁺ and [Pt(PSP)I]⁺ complexes.

In addition to the two ClO₄^- counter-anions, which are centred 4.950 (2) and 6.422 (2) Å from the closest Pt atom, a molecule of acetone has co-crystallized in (I). This acetone solvate is located close to the PPh₃ group, with a shortest distance to a phenyl ring C atom for O7···C26 of 3.293 (5) Å.

The P1—Pt—S bond angle of 178.29 (4)° is close to the ideal value of 180°, while the P2—Pt—P2' angle of 161.57 (5)° is significantly bent. The large steric demand of the PPh₃ group is indicated by the large cis P—Pt—P angles between the –PPh₂ and the PPh₃ groups; P1—Pt—P2 is 98.79 (2)°, exceeding the reported cis P—Pt—I angles in the [Pt(PSP)I]⁺ cation, in spite of the fact that I is likewise a sterically demanding ligand. The cis P—Pt—P angles for (I) are, however, not unusual in complexes having two non-chelated mutually cis phosphine ligands (Battan et al., 1999). This steric crowding is illustrated further by the smallest P—Pt—S angles [P2—Pt—S 81.30 (2)°] yet observed in the five-membered chelate ring of Pt^II—PSP complexes.

The mirror plane of the cation in (I) results in equal Pt—P bond lengths [Pt—P2 2.310 (1) Å] and this Pt—P distance is within the normal range observed for two mutually trans –PPh₂ donors (Andreasen et al., 1999; Siah et al., 1994). The Pt—S bond length in (I) [Pt—S 2.343 (1) Å] is approximately 0.09 Å longer than the Pt—S bonds in the Pt^II—PSP salts [Pt(PSP)Cl]ClO₄ and [Pt(PSP)I]I, which is in line with the larger trans influence of the PPh₃ donor compared with Cl or I. Only scant information is available on bond distances in Pt^II complexes having the trans S—Pt-PPh₃ motif, with S being both a monodentate thioether ligand and a part of a chelate system; one example is [Pt({ⁱPrS(CH₂)₃}₂S)(PPh₃)](BF₄)₂ [{ⁱPrS(CH₂)₃}₂S is 2,12-dimethyl-3,7,11-trithiatridecane, C₁₂H₂₆S₃; Loeb & Mansfield, 1996]. The Pt—S distance in (I) is similar to the values for chelated thioether donors in the trans position both to PPh₃ in [Pt({ⁱPrS(CH₂)₃}₂S)(PPh₃)]²⁺ (Loeb & Mansfield, 1996) and to intraligand –PPh₂ donors (Connolly et al., 1997).

The Pt—P bond length in (I) to the coordinated PPh₃ ligand [Pt—P1 2.289 (1) Å] is significantly shorter than the reported Pt-PPh₃ distance of 2.332 (2) Å in [Pt({ⁱPrS(CH₂)₃}₂S)(PPh₃)]²⁺, where the PPh₃ donor is also positioned trans to a chelated thioether group. The latter length, however, is longer than the Pt—P distance in trans-[PtI₂(PPh₃)₂] [2.318 (2) Å; Boag et al., 1991]. This is remarkable, since it is generally accepted that the trans influence of PPh₃ is greater than that of a thioether group (Connolly et al., 1997).

In (I), the PPh₃ phenyl ring C21—C26 and the phenyl ring C41—C46 of PSP are positioned so that they are approximately slipped-parallel and only tilted by 3°, with a C21···C41 separation of 3.370 (5) Å for the two C_ipso atoms. This magnitude is similar to the calculated optimum distance of 3.5 Å obtained for slipped-parallel benzene dimers, as reported in a recent computational calculation by Tsuzuki et al. (2002). This indicates that a π–π interaction may exist between the phenyl rings of PPh₃ and PSP, and the C21···C41 distance is in the range reported for overlap between arene moieties (Breu et al., 1997; Fanizzi et al., 1994).

S2. Experimental

Compound (I) was prepared as previously reported by Andreasen et al. (1999). Colourless crystals suitable for single-crystal X-ray diffraction were grown by slow diffusion of diethyl ether into an acetone/methanolic solution of (I).

S3. Refinement

The H atoms were kept fixed at calculated positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq for the atoms to which they were attached. Refinement of (I) in the centrosymmetric space group Pnma gave very elongated displacement ellipsoids for atom C1. This elongation could either result from disorder or from a wrong choice of space group. Solving and refining the structure in the polar space group Pna2₁ gave many non-positive definite displacement ellipsoids and refinement of the polarity gave a Rogers factor (Rogers, 1981) close to zero instead of ±1, indicating that the structure was non-polar. The structure was therefore refined in Pnma with C1 split over two sites, C1A and C1B, each with 50% site occupancy.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1996) and KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.

Figures

Fig. 1. A view of the cation of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 50% probability level and H atoms have been omitted for clarity [symmetry code: (i) x, 1/2 - y, z].

[Bis(2-diphenylphosphinoethyl) sulfide-κ³P,S,P'](triphenylphosphine- κP)platinum(II) diperchlorate acetone solvate

Crystal data

[Pt(C28H28P2S)(C18H15P)](ClO4)2·C3H6O	F(000) = 2352
Mr = 1172.84	Dx = 1.621 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 8192 reflections
a = 15.698 (3) Å	θ = 2.0–30.4°
b = 15.337 (3) Å	µ = 3.23 mm^−1
c = 19.957 (4) Å	T = 120 K
V = 4804.9 (16) Å^3	Octahedron, colourless
Z = 4	0.26 × 0.24 × 0.24 mm

Data collection

Siemens SMART CCD area-detector diffractometer	7613 independent reflections
Radiation source: X-ray tube	5723 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.054
ω rotation scans with narrow frames	θmax = 30.5°, θmin = 2.0°
Absorption correction: integration XPREP (Siemens, 1995)	h = −16→21
Tmin = 0.448, Tmax = 0.594	k = −22→22
41330 measured reflections	l = −27→24

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.032	w = 1/{[σcs(F^2) + 1.03F^2]^1/2-|F|}^2
wR(F^2) = 0.036	(Δ/σ)max < 0.001
S = 0.99	Δρmax = 1.3 (2) e Å^−3
5723 reflections	Δρmin = −1.5 (2) e Å^−3
329 parameters	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 88 (9)

Special details

Refinement. Sfls: F calc weight full matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt	0.31948 (1)	0.25000	0.02781 (1)	0.0127 (1)
S	0.36778 (8)	0.25000	−0.08328 (6)	0.0178 (6)
P1	0.26818 (7)	0.25000	0.13518 (6)	0.0114 (6)
P2	0.33400 (6)	0.39869 (7)	0.01321 (5)	0.0202 (5)
C1A	0.4141 (5)	0.3558 (6)	−0.1004 (4)	0.026 (4)	0.50
C1B	0.4633 (5)	0.3169 (6)	−0.0710 (4)	0.030 (4)	0.50
C2	0.4331 (3)	0.4059 (3)	−0.0353 (2)	0.035 (2)
C11	0.3505 (3)	0.2500	0.1982 (2)	0.015 (2)
C12	0.4356 (3)	0.2500	0.1782 (3)	0.021 (3)
C13	0.5008 (4)	0.2500	0.2257 (3)	0.032 (3)
C14	0.4797 (4)	0.2500	0.2935 (3)	0.031 (3)
C15	0.3959 (4)	0.2500	0.3135 (3)	0.027 (3)
C16	0.3312 (3)	0.2500	0.2663 (2)	0.019 (2)
C21	0.2009 (2)	0.3447 (2)	0.1518 (2)	0.015 (2)
C22	0.2140 (2)	0.4011 (3)	0.2053 (2)	0.022 (2)
C23	0.1617 (3)	0.4729 (3)	0.2147 (2)	0.028 (2)
C24	0.0961 (3)	0.4900 (3)	0.1698 (2)	0.027 (2)
C25	0.0834 (2)	0.4348 (3)	0.1161 (2)	0.025 (2)
C26	0.1352 (2)	0.3626 (3)	0.1066 (2)	0.020 (2)
C31	0.2549 (3)	0.4423 (3)	−0.0432 (2)	0.027 (2)
C32	0.1854 (3)	0.3925 (3)	−0.0631 (2)	0.028 (2)
C33	0.1287 (3)	0.4239 (4)	−0.1112 (2)	0.041 (3)
C34	0.1423 (3)	0.5049 (4)	−0.1391 (2)	0.043 (3)
C35	0.2105 (4)	0.5556 (3)	−0.1189 (2)	0.041 (3)
C36	0.2668 (3)	0.5242 (3)	−0.0715 (2)	0.035 (3)
C41	0.3489 (2)	0.4748 (3)	0.0814 (2)	0.023 (2)
C42	0.4181 (3)	0.4610 (3)	0.1250 (2)	0.025 (2)
C43	0.4319 (3)	0.5175 (3)	0.1775 (2)	0.031 (2)
C44	0.3787 (3)	0.5882 (3)	0.1874 (2)	0.032 (2)
C45	0.3103 (3)	0.6029 (3)	0.1444 (2)	0.034 (2)
C46	0.2957 (3)	0.5456 (3)	0.0915 (2)	0.028 (2)
Cl1	0.63190 (9)	0.25000	0.06144 (8)	0.0301 (8)
Cl2	0.93226 (9)	0.25000	−0.21850 (7)	0.0274 (7)
O1	0.5796 (2)	0.1738 (2)	0.0657 (2)	0.050 (2)
O2	0.6888 (4)	0.2500	0.1167 (4)	0.102 (6)
O3	0.6820 (5)	0.2500	0.0029 (4)	0.080 (5)
O4	0.8527 (3)	0.2500	−0.1856 (3)	0.053 (3)
O5	0.9969 (4)	0.2500	−0.1713 (3)	0.132 (9)
O6	0.9389 (4)	0.1760 (3)	−0.2598 (3)	0.087 (4)
O7	1.0280 (3)	0.2500	−0.0058 (2)	0.044 (3)
C3	0.9535 (4)	0.2500	−0.0183 (3)	0.030 (3)
C4	0.9046 (4)	0.1675 (4)	−0.0265 (3)	0.048 (3)
H1Aa	0.3753	0.3888	−0.1268	0.031*	0.50
H1Ab	0.4657	0.3480	−0.1245	0.031*	0.50
H1Ba	0.4890	0.3295	−0.1130	0.037*	0.50
H1Bb	0.5030	0.2871	−0.0433	0.037*	0.50
H2a	0.4468	0.4650	−0.0447	0.042*	0.50
H2b	0.4789	0.3796	−0.0116	0.042*	0.50
H2a'	0.4253	0.4487	−0.0691	0.042*	0.50
H2b'	0.4771	0.4240	−0.0057	0.042*	0.50
H12	0.4492	0.2500	0.1318	0.026*
H13	0.5588	0.2500	0.2120	0.038*
H14	0.5236	0.2500	0.3262	0.037*
H15	0.3823	0.2500	0.3599	0.033*
H16	0.2734	0.2500	0.2804	0.023*
H22	0.2593	0.3903	0.2357	0.026*
H23	0.1707	0.5105	0.2519	0.034*
H24	0.0602	0.5393	0.1761	0.032*
H25	0.0387	0.4464	0.0853	0.030*
H26	0.1261	0.3252	0.0693	0.024*
H32	0.1764	0.3367	−0.0437	0.034*
H33	0.0812	0.3898	−0.1247	0.049*
H34	0.1045	0.5261	−0.1724	0.052*
H35	0.2186	0.6120	−0.1376	0.049*
H36	0.3140	0.5589	−0.0582	0.042*
H42	0.4551	0.4128	0.1182	0.030*
H43	0.4783	0.5079	0.2071	0.037*
H44	0.3888	0.6268	0.2237	0.038*
H45	0.2740	0.6516	0.1511	0.040*
H46	0.2490	0.5552	0.0621	0.034*
H4a	0.8469	0.1769	−0.0141	0.057*
H4b	0.9286	0.1236	0.0012	0.057*
H4c	0.9070	0.1494	−0.0720	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.0111 (1)	0.0160 (1)	0.0109 (1)	0.0000	0.0006 (1)	0.0000
S	0.0156 (6)	0.0252 (7)	0.0125 (5)	0.0000	0.0012 (4)	0.0000
P1	0.0100 (5)	0.0122 (6)	0.0119 (5)	0.0000	0.0005 (4)	0.0000
P2	0.0262 (5)	0.0191 (5)	0.0153 (4)	−0.0059 (4)	0.0010 (3)	0.0033 (3)
C1A	0.029 (4)	0.031 (5)	0.018 (4)	−0.003 (4)	0.011 (3)	0.003 (3)
C1B	0.020 (4)	0.048 (6)	0.023 (4)	−0.009 (4)	0.006 (3)	−0.005 (4)
C2	0.042 (2)	0.036 (2)	0.026 (2)	−0.018 (2)	0.013 (2)	−0.002 (2)
C11	0.013 (2)	0.014 (2)	0.018 (2)	0.000	−0.002 (2)	0.000
C12	0.019 (2)	0.019 (3)	0.026 (3)	0.000	−0.002 (2)	0.000
C13	0.016 (3)	0.040 (4)	0.040 (4)	0.000	−0.008 (2)	0.000
C14	0.032 (3)	0.030 (3)	0.031 (3)	0.000	−0.019 (3)	0.000
C15	0.038 (3)	0.023 (3)	0.021 (3)	0.000	−0.013 (2)	0.000
C16	0.023 (3)	0.018 (3)	0.017 (2)	0.000	−0.003 (2)	0.000
C21	0.013 (1)	0.014 (2)	0.019 (2)	0.002 (1)	0.003 (1)	0.001 (1)
C22	0.023 (2)	0.024 (2)	0.019 (2)	0.005 (2)	−0.001 (1)	−0.001 (2)
C23	0.037 (2)	0.020 (2)	0.028 (2)	0.006 (2)	0.003 (2)	−0.005 (2)
C24	0.024 (2)	0.024 (2)	0.032 (2)	0.008 (2)	0.007 (2)	0.000 (2)
C25	0.020 (2)	0.023 (2)	0.031 (2)	0.003 (2)	−0.001 (2)	0.005 (2)
C26	0.016 (2)	0.022 (2)	0.022 (2)	0.000 (1)	−0.001 (1)	0.002 (2)
C31	0.041 (2)	0.025 (2)	0.014 (2)	0.001 (2)	−0.002 (1)	0.002 (2)
C32	0.029 (2)	0.032 (2)	0.024 (2)	0.009 (2)	0.000 (2)	0.007 (2)
C33	0.030 (2)	0.058 (3)	0.033 (2)	0.014 (2)	−0.002 (2)	0.009 (2)
C34	0.048 (3)	0.058 (4)	0.023 (2)	0.027 (3)	0.001 (2)	0.012 (2)
C35	0.070 (3)	0.030 (3)	0.022 (2)	0.013 (2)	0.003 (2)	0.010 (2)
C36	0.059 (3)	0.026 (2)	0.021 (2)	0.001 (2)	−0.003 (2)	0.005 (2)
C41	0.029 (2)	0.021 (2)	0.020 (2)	−0.008 (2)	0.001 (1)	0.002 (2)
C42	0.028 (2)	0.026 (2)	0.022 (2)	−0.008 (2)	0.002 (2)	0.002 (2)
C43	0.029 (2)	0.044 (3)	0.020 (2)	−0.014 (2)	0.001 (2)	−0.001 (2)
C44	0.038 (2)	0.033 (3)	0.024 (2)	−0.014 (2)	0.006 (2)	−0.006 (2)
C45	0.042 (3)	0.029 (2)	0.030 (2)	−0.002 (2)	0.002 (2)	−0.004 (2)
C46	0.034 (2)	0.024 (2)	0.026 (2)	−0.002 (2)	−0.003 (2)	0.002 (2)
Cl1	0.0175 (6)	0.0410 (9)	0.0318 (8)	0.0000	−0.0017 (5)	0.0000
Cl2	0.0253 (7)	0.0395 (9)	0.0173 (6)	0.0000	0.0034 (5)	0.0000
O1	0.026 (2)	0.040 (2)	0.083 (3)	−0.003 (2)	0.001 (2)	0.011 (2)
O2	0.059 (4)	0.145 (8)	0.101 (6)	0.000	−0.061 (4)	0.000
O3	0.084 (5)	0.071 (5)	0.087 (5)	0.000	0.052 (4)	0.000
O4	0.031 (2)	0.088 (5)	0.040 (3)	0.000	0.014 (2)	0.000
O5	0.029 (3)	0.327 (14)	0.040 (4)	0.000	−0.013 (3)	0.000
O6	0.117 (5)	0.047 (3)	0.096 (4)	0.018 (3)	0.044 (3)	−0.022 (3)
O7	0.034 (2)	0.066 (4)	0.033 (2)	0.000	−0.020 (2)	0.000
C3	0.032 (3)	0.040 (4)	0.016 (3)	0.000	−0.005 (2)	0.000
C4	0.057 (3)	0.051 (3)	0.035 (2)	−0.017 (3)	−0.008 (2)	0.005 (3)

Geometric parameters (Å, º)

Pt—P1	2.289 (1)	Cl1—O1	1.431 (4)
Pt—P2	2.310 (1)	Cl1—O3	1.408 (6)
Pt—P2^i	2.310 (1)	Cl1—O2	1.418 (6)
Pt—S	2.343 (1)	Cl2—O4	1.411 (5)
P1—C11	1.804 (5)	Cl2—O5	1.385 (6)
P1—C21	1.826 (4)	Cl2—O6	1.407 (4)
P2—C31	1.805 (4)	O7—C3	1.196 (7)
P2—C41	1.809 (4)	C3—C4	1.489 (6)
P2—C2	1.835 (4)	C3—C4^i	1.489 (6)
S—C1A	1.810 (9)	C1A—H1Aa	0.950
S—C1A^i	1.810 (9)	C1A—H1Ab	0.950
S—C1B	1.834 (8)	C1B—H1Ba	0.950
S—C1B^i	1.834 (8)	C1B—H1Bb	0.950
C1A—C1B	1.139 (12)	C2—H2a	0.950
C1A—C2	1.540 (9)	C2—H2b	0.950
C1B—C2	1.612 (10)	C2—H2a'	0.950
C11—C12	1.394 (7)	C2—H2b'	0.950
C11—C16	1.391 (7)	C12—H12	0.950
C12—C13	1.396 (8)	C13—H13	0.950
C13—C14	1.393 (9)	C14—H14	0.950
C14—C15	1.375 (9)	C15—H15	0.950
C15—C16	1.386 (7)	C16—H16	0.950
C21—C22	1.390 (5)	C22—H22	0.950
C21—C26	1.397 (5)	C23—H23	0.950
C22—C23	1.387 (6)	C24—H24	0.950
C23—C24	1.390 (6)	C25—H25	0.950
C24—C25	1.381 (6)	C26—H26	0.950
C25—C26	1.388 (5)	C32—H32	0.950
C31—C32	1.389 (6)	C33—H33	0.950
C31—C36	1.390 (6)	C34—H34	0.950
C32—C33	1.396 (6)	C35—H35	0.950
C33—C34	1.377 (8)	C36—H36	0.950
C34—C35	1.383 (8)	C42—H42	0.950
C35—C36	1.381 (7)	C43—H43	0.950
C41—C42	1.407 (5)	C44—H44	0.950
C41—C46	1.385 (6)	C45—H45	0.950
C42—C43	1.378 (6)	C46—H46	0.950
C43—C44	1.382 (7)	C4—H4a	0.950
C44—C45	1.392 (6)	C4—H4b	0.950
C45—C46	1.393 (6)	C4—H4c	0.950
P1—Pt—P2	98.79 (2)	O6—Cl2—O6^i	107.6 (4)
P1—Pt—P2^i	98.79 (2)	O7—C3—C4	121.8 (3)
P2—Pt—P2^i	161.57 (5)	C4—C3—C4^i	116.4 (6)
S—Pt—P1	178.29 (5)	S—C1A—H1Aa	109.0
S—Pt—P2	81.30 (2)	S—C1A—H1Ab	109.0
S—Pt—P2^i	81.30 (2)	S—C1B—H1Ba	110.1
Pt—P1—C11	113.6 (2)	S—C1B—H1Bb	110.1
Pt—P1—C21	111.9 (1)	H1Aa—C1A—H1Ab	109.5
Pt—P1—C21^i	111.9 (1)	C2—C1A—H1Aa	109.0
Pt—P2—C31	112.1 (1)	C2—C1A—H1Ab	109.0
Pt—P2—C41	123.7 (1)	H1Ba—C1B—H1Bb	109.5
Pt—P2—C2	102.1 (2)	C2—C1B—H1Ba	110.1
Pt—S—C1A	108.0 (2)	C2—C1B—H1Bb	110.1
Pt—S—C1A^i	108.0 (2)	H2a—C2—H2b	109.5
Pt—S—C1B	98.0 (3)	C1A—C2—H2a	110.7
Pt—S—C1B^i	98.0 (3)	C1A—C2—H2b	110.7
C1A—S—C1B^i	101.5 (4)	C1B—C2—H2a'	107.9
C11—P1—C21	106.7 (1)	C1B—C2—H2b'	107.9
C21—P1—C21^i	105.3 (2)	C11—C12—H12	119.7
C31—P2—C41	108.6 (2)	C13—C12—H12	119.7
C2—P2—C31	103.4 (2)	C12—C13—H13	120.5
C2—P2—C41	104.3 (2)	C14—C13—H13	120.5
S—C1A—C2	111.5 (5)	C13—C14—H14	119.6
S—C1B—C2	107.0 (5)	C15—C14—H14	119.6
P2—C2—C1A	104.5 (4)	C14—C15—H15	119.9
P2—C2—C1B	115.6 (4)	C16—C15—H15	119.9
C12—C11—C16	119.3 (5)	C15—C16—H16	119.9
P1—C11—C16	121.6 (4)	C11—C16—H16	119.9
P1—C11—C12	119.1 (4)	C21—C22—H22	119.6
C11—C12—C13	120.5 (5)	C23—C22—H22	119.6
C12—C13—C14	119.0 (5)	C22—C23—H23	120.0
C13—C14—C15	120.7 (5)	C24—C23—H23	120.0
C14—C15—C16	120.2 (6)	C23—C24—H24	120.3
C11—C16—C15	120.3 (5)	C25—C24—H24	120.3
C22—C21—C26	118.9 (3)	C24—C25—H25	119.6
P1—C21—C22	123.3 (3)	C26—C25—H25	119.6
P1—C21—C26	117.8 (3)	C25—C26—H26	120.0
C21—C22—C23	120.7 (3)	C21—C26—H26	120.0
C22—C23—C24	120.1 (4)	C31—C32—H32	119.8
C23—C24—C25	119.4 (4)	C33—C32—H32	119.8
C24—C25—C26	120.8 (4)	C32—C33—H33	120.3
C21—C26—C25	120.1 (4)	C34—C33—H33	120.3
C32—C31—C36	119.1 (4)	C33—C34—H34	119.7
P2—C31—C32	120.9 (3)	C35—C34—H34	119.7
P2—C31—C36	119.8 (3)	C36—C35—H35	120.1
C31—C32—C33	120.5 (4)	C34—C35—H35	120.1
C32—C33—C34	119.4 (5)	C35—C36—H36	119.7
C33—C34—C35	120.7 (4)	C31—C36—H36	119.7
C34—C35—C36	119.9 (4)	C41—C42—H42	120.1
C31—C36—C35	120.5 (5)	C43—C42—H42	120.1
C42—C41—C46	119.6 (4)	C42—C43—H43	119.8
P2—C41—C46	122.5 (3)	C44—C43—H43	119.8
P2—C41—C42	117.9 (3)	C43—C44—H44	119.8
C41—C42—C43	119.8 (4)	C45—C44—H44	119.8
C42—C43—C44	120.5 (4)	C44—C45—H45	120.3
C43—C44—C45	120.3 (4)	C46—C45—H45	120.3
C44—C45—C46	119.5 (4)	C41—C46—H46	119.8
C41—C46—C45	120.3 (4)	C45—C46—H46	119.8
O1—Cl1—O1^i	109.6 (3)	H4a—C4—H4b	109.5
O1—Cl1—O2	108.3 (3)	H4a—C4—H4c	109.5
O1—Cl1—O3	111.7 (2)	C3—C4—H4a	109.5
O2—Cl1—O3	107.0 (5)	H4b—C4—H4c	109.5
O4—Cl2—O5	109.4 (4)	C3—C4—H4b	109.5
O4—Cl2—O6	109.8 (3)	C3—C4—H4c	109.4
O5—Cl2—O6	110.1 (3)

Symmetry code: (i) x, −y+1/2, z.