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Acta Cryst. (2007). E63, m3097    [ doi:10.1107/S1600536807058709 ]

cis-(Carbonato-[kappa]2O,O')bis(triphenylphosphine-[kappa]P)platinum(II)-benzene-dichloromethane mixed solvate (2/1/1)

A. Sivaramakrishna, H. Su and J. R. Moss

Abstract top

The title compound, [Pt(CO3)(C18H15P)2]·0.5C6H6·0.5CH2Cl2, is isotructural with the analogous tetrahydrofuran [Gregg, Powell & Sawyer (1988). Acta Cryst. C44, 43-46] and benzene monosolvates [Scholz, Lerner & Bolte (2006). Acta Cryst. E62, m312-m313]. The Pt atom shows a distorted square-planar coordination.

Comment top

The preparation of cis-(carbonato-O,O')-bis(triphenylphosphine)-platinum(II) [(Ph3P)2Pt(CO3)] was first reported by Cariati et al. (1967). Carbonato(phosphine)platinum(II) compounds are in general good precursors for the preparation of Pt(II) diolate and alditolate complexes, as well as other Pt(0) and Pt(IV) compounds (Andrews et al., 1994 and Clarke et al., 1984). Platinum carbonate complexes have been observed to form from the decomposition of platinum hydride complexes (Davies et al., 1987) or from the reactions of hydroxide or oxalate complexes (Porta et al., 1990).

Crystal structures of [(Ph3P)2Pt(CO3)] as solvates with different solvents have been reported in the Cambridge Structural Database [CSD (Allen, 2002), version 5.28], namely the tetrahydrofuran monosolvate (FUTVOF, Gregg et al., 1988), the chloroform disolvate (CISQOK, Abram et al., 1999) and the benzene monosolvate (CSD Refcode CAYWIJ, Scholz et al., 2006). These solvates were prepared mainly from the aerial hydrolysis of the Pt(PPh3)4 complex. Here, we present a semi-benzene semi-dichloromethane solvated complex, [(Ph3P)2Pt(CO3)].0.5C6H6.0.5CH2Cl2, Fig. 1, which was prepared by the hydrolysis of a dichloromethane solution of (PPh3)2bis(1-butenyl)platinum(II). The phenyl rings on the two P atoms are oriented such that some of the ortho H atoms form short Pt···H contacts (H26···Pt1 2.855 (5) Å; H42···Pt1 2.905 (5) Å; H56···Pt1 2.959 (6) Å). Similar contacts have been described as agostic (Crabtree et al. 1985) or non-primary valence interactions (Bennett et al. 1975). In addition to this, two phenyl rings from the opposite triphenylphosphine groups, the C31—C36 and C61—C66 rings, are almost overlapping, forming intramolecular π-π interaction with centroid distance of 3.474 Å. The coordination geometry around Pt atom can be described as a distorted square planar. The carbonato ligand is completely planar and makes an angle of ca 7.2 (2)° with the PPtP plane. In CHCl3 solution, the IR spectrum of the [(Ph3P)2Pt(CO3)] compound showed two peaks at 1676 (v) and 1632 (m) cm−1. Though only one fundamental carbonate vibrational mode is expected in this region, namely the C=O stretch, the extra band is attributed to an overtone of the out-of-plane carbonate bending mode as explained by Andrews et al. (1996).

Related literature top

For general background, see: Andrews et al. (1994, 1996); Cariati et al. (1967); Clarke et al. (1984); Davies et al. (1987); Dralle et al. (2005); Porta et al. (1990). For related structures, see: Abram et al. (1999); Gregg et al. (1988); Scholz et al. (2006). For related literature, see: Allen (2002); Bennett et al. (1975); Crabtree et al. (1985).

Experimental top

The [Ph3P)2Pt(CO3)] compound was prepared by the hydrolysis of a dichloromethane solution of (PPh3)2bis(1-butenyl)platinum(II) (Dralle et al., 2005) on exposure to air. This is probably due to either oxidation of organic chain under these conditions by forming the C—O bonds or absorption of CO2 from the air. The colour of the reaction mixture changed to yellow brown from colourless. It was also observed that the nature of ligand showed a marked effect on this oxidation reaction: the presence of diphosphine ligands like dppp, dppe did not show any signs of oxidation under these conditions. 1H-NMR showed only phenyl proton signals and 31P-NMR indicated a singlet at 27.2 p.p.m. with platinum satellites (JPt—P = 3998 Hz). A solution (326 mg, 1.072 mmol) of cis-(PPh3)2Pt(CH2CH2CH=CH2)2 in 20 ml of CH2Cl2 was exposed to air for 45 days. Removal of solvent in high vacuum and recrystallize from a mixture of CH2Cl2 and n-hexane (1:1) led to the isolation of compound [(Ph3P)2Pt(CO3)] as colourless crystals (166 mg, 54%). Anal. Calc. for [(Ph3P)2Pt(CO3)] (C37H30O3P2Pt): C, 57.00, H, 3.88, found: C, 56.92, H, 3.91. MS: M+ = 779.6, Pt(PPh3)2+ = 719.6. Recrystallization from a mixture of dichloromethane and benzene (1:1) yielded colourless crystals of the title compound I which was subjected to X-ray analysis.

Refinement top

The non-H atoms of the molecule [(Ph3P)2Pt(CO3)] were refined anisotropically. The solvent molecules, benzene and dichloromethane are located with well defined unambiguous atomic positions in the differnce electron density maps in the same solvent area and then each was assigned site occupancy factor of 0.50. The non-H atoms of both solvent molecules were refined anisotropically with the C—Cl bond being constrained lengthly and the carbon atoms of the benzene being fitted to a regular pentagon. The hydrogen atoms were placed geometrically in idealized positions riding with their respective parent atoms. The highest peak (1.33 e Å−3) is located at 1.29Å from H5B and the deepest hole (−1.45 e Å−3)is at 0.02Å from Pt1.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. ORTEP drawing of structure I, showing atomic labelling scheme. Displacement ellipsoids are drawn at 30% probability level and all H atoms are omitted for clarity. The solvent molecules, benzene and dichloromethane, occupy the same area with site occupancy factors to be 0.50 each.
cis-(Carbonato-κ2O,O')bis(triphenylphosphine-κP)platinum(II)–benzene– dichloromethane (2/1/1) top
Crystal data top
[Pt(CO3)(C18H15P)2]·0.5C6H6·0.5CH2Cl2Z = 2
Mr = 861.16F000 = 852
Triclinic, P1Dx = 1.638 Mg m−3
Hall symbol: -P 1Melting point: 188-190°C K
a = 10.4676 (2) ÅMo Kα radiation
λ = 0.71073 Å
b = 12.2005 (3) ÅCell parameters from 37316 reflections
c = 15.2380 (4) Åθ = 3.1–21.6º
α = 85.576 (1)ºµ = 4.22 mm−1
β = 71.757 (1)ºT = 173 (2) K
γ = 70.956 (1)ºPrism, colourless
V = 1746.40 (7) Å30.10 × 0.07 × 0.04 mm
Data collection top
Nonius Kappa CCD
diffractometer		6847 independent reflections
Radiation source: fine-focus sealed tube5512 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.092
T = 173(2) Kθmax = 26.0º
1.2° φ scans and ω scansθmin = 3.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −12→12
Tmin = 0.677, Tmax = 0.849k = −15→15
37316 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.060  w = 1/[σ2(Fo2) + (0.0097P)2 + 1.8518P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
6847 reflectionsΔρmax = 1.33 e Å−3
459 parametersΔρmin = −1.45 e Å−3
2 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00138 (16)
Crystal data top
[Pt(CO3)(C18H15P)2]·0.5C6H6·0.5CH2Cl2γ = 70.956 (1)º
Mr = 861.16V = 1746.40 (7) Å3
Triclinic, P1Z = 2
a = 10.4676 (2) ÅMo Kα
b = 12.2005 (3) ŵ = 4.22 mm−1
c = 15.2380 (4) ÅT = 173 (2) K
α = 85.576 (1)º0.10 × 0.07 × 0.04 mm
β = 71.757 (1)º
Data collection top
Nonius Kappa CCD
diffractometer		6847 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		5512 reflections with I > 2σ(I)
Tmin = 0.677, Tmax = 0.849Rint = 0.092
37316 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0362 restraints
wR(F2) = 0.060H-atom parameters constrained
S = 1.05Δρmax = 1.33 e Å−3
6847 reflectionsΔρmin = −1.45 e Å−3
459 parameters
Special details top

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of φ and ω scans of 1.2°, 30 s per °, 2 iterations.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pt10.68157 (2)0.619084 (16)0.722116 (14)0.01730 (7)
Cl1A−0.2308 (4)1.2485 (3)1.0422 (3)0.0629 (12)0.50
Cl2A0.0109 (4)1.2327 (3)0.8803 (3)0.0590 (10)0.50
P10.61853 (12)0.77338 (9)0.63764 (8)0.0169 (3)
P20.79888 (13)0.68445 (10)0.79647 (9)0.0208 (3)
O10.6013 (3)0.5118 (3)0.6748 (2)0.0230 (7)
O20.7197 (3)0.4556 (2)0.7765 (2)0.0231 (7)
O30.6483 (3)0.3258 (3)0.7215 (2)0.0320 (8)
C10.6555 (5)0.4223 (4)0.7241 (3)0.0214 (11)
C110.4805 (5)0.7670 (4)0.5907 (3)0.0183 (10)
C120.3494 (5)0.8540 (4)0.6099 (3)0.0242 (11)
H120.32840.91690.65070.029*
C130.2493 (5)0.8491 (4)0.5694 (4)0.0325 (13)
H130.16030.90900.58240.039*
C140.2782 (5)0.7585 (4)0.5108 (4)0.0321 (13)
H140.21000.75650.48240.039*
C150.4063 (5)0.6700 (4)0.4929 (3)0.0264 (11)
H150.42510.60610.45360.032*
C160.5070 (5)0.6744 (4)0.5321 (3)0.0217 (11)
H160.59520.61370.51900.026*
C210.7630 (5)0.7745 (4)0.5340 (3)0.0183 (10)
C220.7417 (5)0.8449 (4)0.4596 (3)0.0232 (11)
H220.65000.89760.46400.028*
C230.8533 (5)0.8383 (4)0.3797 (3)0.0278 (12)
H230.83810.88780.33010.033*
C240.9874 (5)0.7599 (4)0.3715 (3)0.0251 (11)
H241.06390.75630.31680.030*
C251.0086 (5)0.6873 (4)0.4431 (3)0.0227 (11)
H251.09940.63200.43700.027*
C260.8986 (5)0.6947 (4)0.5237 (3)0.0202 (10)
H260.91500.64490.57290.024*
C310.5409 (5)0.9146 (4)0.6962 (3)0.0215 (11)
C320.5610 (5)1.0156 (4)0.6548 (4)0.0280 (12)
H320.62501.01270.59440.034*
C330.4857 (5)1.1221 (4)0.7033 (4)0.0370 (14)
H330.50121.19140.67640.044*
C340.3900 (6)1.1266 (5)0.7892 (4)0.0459 (16)
H340.33671.19950.82040.055*
C350.3699 (6)1.0267 (5)0.8309 (4)0.0428 (15)
H350.30471.03040.89100.051*
C360.4458 (5)0.9206 (4)0.7845 (4)0.0328 (13)
H360.43250.85150.81320.039*
C410.7442 (5)0.6453 (4)0.9163 (3)0.0222 (11)
C420.6065 (5)0.6427 (4)0.9562 (4)0.0343 (13)
H420.54390.65860.91990.041*
C430.5593 (6)0.6170 (5)1.0493 (4)0.0397 (14)
H430.46480.61561.07620.048*
C440.6494 (6)0.5940 (4)1.1017 (4)0.0372 (13)
H440.61750.57621.16500.045*
C450.7866 (6)0.5965 (4)1.0630 (4)0.0351 (13)
H450.84850.58071.09980.042*
C460.8341 (5)0.6221 (4)0.9709 (3)0.0280 (12)
H460.92860.62380.94470.034*
C510.9892 (5)0.6088 (4)0.7531 (3)0.0201 (10)
C521.0905 (5)0.6579 (4)0.7568 (4)0.0317 (13)
H521.06130.73450.78130.038*
C531.2324 (5)0.5957 (4)0.7250 (4)0.0346 (13)
H531.30050.63060.72680.042*
C541.2770 (5)0.4851 (5)0.6911 (3)0.0347 (13)
H541.37550.44320.67000.042*
C551.1791 (5)0.4336 (4)0.6873 (4)0.0337 (13)
H551.20980.35640.66370.040*
C561.0350 (5)0.4960 (4)0.7183 (3)0.0276 (12)
H560.96730.46110.71560.033*
C610.7872 (5)0.8355 (4)0.8016 (4)0.0263 (12)
C620.8509 (5)0.8877 (4)0.7226 (4)0.0335 (13)
H620.90210.84310.66670.040*
C630.8402 (7)1.0033 (5)0.7248 (5)0.0501 (18)
H630.88541.03750.67110.060*
C640.7638 (7)1.0693 (5)0.8053 (6)0.058 (2)
H640.75481.14920.80660.070*
C650.7008 (6)1.0193 (5)0.8836 (5)0.0528 (17)
H650.64901.06440.93910.063*
C660.7127 (6)0.9029 (4)0.8816 (4)0.0390 (14)
H660.66900.86890.93600.047*
C1A−0.1603 (13)1.3141 (13)0.9414 (10)0.046 (5)0.50
H1A1−0.22201.32640.90140.056*0.50
H1A2−0.16011.39110.95760.056*0.50
C1B−0.1889 (14)1.3178 (7)0.9804 (9)0.055 (6)0.50
H1B−0.24421.39470.97250.065*0.50
C2B−0.2077 (12)1.2719 (10)1.0681 (7)0.117 (12)0.50
H2B−0.27591.31741.12020.141*0.50
C3B−0.1268 (12)1.1593 (10)1.0797 (6)0.055 (4)0.50
H3B−0.13961.12791.13970.067*0.50
C4B−0.0270 (11)1.0926 (7)1.0035 (9)0.082 (5)0.50
H4B0.02831.01571.01140.098*0.50
C5B−0.0082 (10)1.1386 (11)0.9158 (7)0.086 (6)0.50
H5B0.06001.09300.86370.103*0.50
C6B−0.0891 (13)1.2511 (11)0.9042 (7)0.070 (5)0.50
H6B−0.07631.28250.84420.084*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01714 (10)0.01846 (10)0.01863 (11)−0.00798 (7)−0.00715 (8)0.00441 (7)
Cl1A0.045 (2)0.061 (2)0.057 (3)−0.0059 (19)0.004 (2)0.016 (2)
Cl2A0.043 (2)0.074 (2)0.053 (2)−0.015 (2)−0.009 (2)0.0072 (18)
P10.0156 (6)0.0182 (6)0.0172 (7)−0.0055 (5)−0.0051 (5)0.0007 (5)
P20.0229 (7)0.0188 (6)0.0248 (8)−0.0089 (5)−0.0120 (6)0.0058 (5)
O10.0217 (18)0.0280 (18)0.024 (2)−0.0127 (14)−0.0095 (16)0.0048 (15)
O20.0232 (18)0.0262 (17)0.0223 (19)−0.0117 (15)−0.0078 (16)0.0071 (14)
O30.034 (2)0.0233 (18)0.042 (2)−0.0129 (16)−0.0135 (18)0.0061 (16)
C10.020 (3)0.019 (3)0.023 (3)−0.008 (2)−0.003 (2)0.003 (2)
C110.019 (2)0.018 (2)0.020 (3)−0.008 (2)−0.009 (2)0.006 (2)
C120.024 (3)0.021 (2)0.029 (3)−0.011 (2)−0.006 (2)0.001 (2)
C130.020 (3)0.025 (3)0.053 (4)−0.005 (2)−0.016 (3)0.009 (3)
C140.031 (3)0.036 (3)0.042 (4)−0.017 (3)−0.022 (3)0.008 (3)
C150.028 (3)0.032 (3)0.022 (3)−0.015 (2)−0.006 (2)0.001 (2)
C160.019 (2)0.024 (2)0.022 (3)−0.009 (2)−0.004 (2)0.003 (2)
C210.022 (3)0.017 (2)0.017 (3)−0.008 (2)−0.006 (2)−0.0039 (19)
C220.023 (3)0.020 (2)0.022 (3)−0.002 (2)−0.007 (2)0.003 (2)
C230.033 (3)0.025 (3)0.019 (3)−0.007 (2)−0.001 (2)0.005 (2)
C240.022 (3)0.027 (3)0.023 (3)−0.011 (2)0.001 (2)−0.004 (2)
C250.017 (2)0.024 (2)0.026 (3)−0.007 (2)−0.005 (2)−0.003 (2)
C260.022 (3)0.022 (2)0.020 (3)−0.009 (2)−0.010 (2)0.002 (2)
C310.018 (2)0.020 (2)0.026 (3)−0.004 (2)−0.008 (2)0.000 (2)
C320.021 (3)0.024 (3)0.039 (3)−0.005 (2)−0.011 (2)0.001 (2)
C330.032 (3)0.021 (3)0.055 (4)−0.002 (2)−0.013 (3)−0.005 (3)
C340.041 (4)0.030 (3)0.057 (4)0.008 (3)−0.015 (3)−0.024 (3)
C350.032 (3)0.052 (4)0.027 (3)0.007 (3)−0.005 (3)−0.013 (3)
C360.033 (3)0.028 (3)0.032 (3)−0.001 (2)−0.011 (3)−0.003 (2)
C410.027 (3)0.018 (2)0.024 (3)−0.004 (2)−0.015 (2)−0.002 (2)
C420.035 (3)0.041 (3)0.033 (3)−0.014 (3)−0.018 (3)0.005 (3)
C430.036 (3)0.056 (4)0.025 (3)−0.020 (3)−0.002 (3)0.008 (3)
C440.039 (3)0.044 (3)0.019 (3)−0.004 (3)−0.007 (3)0.003 (2)
C450.040 (3)0.038 (3)0.021 (3)0.003 (3)−0.015 (3)−0.003 (2)
C460.025 (3)0.027 (3)0.029 (3)−0.001 (2)−0.011 (2)−0.006 (2)
C510.018 (2)0.024 (2)0.020 (3)−0.010 (2)−0.007 (2)0.008 (2)
C520.033 (3)0.026 (3)0.048 (4)−0.017 (2)−0.024 (3)0.014 (2)
C530.032 (3)0.042 (3)0.041 (4)−0.022 (3)−0.021 (3)0.020 (3)
C540.021 (3)0.058 (4)0.023 (3)−0.013 (3)−0.004 (2)0.004 (3)
C550.023 (3)0.042 (3)0.033 (3)−0.001 (2)−0.011 (3)−0.012 (3)
C560.027 (3)0.037 (3)0.025 (3)−0.016 (2)−0.011 (2)−0.001 (2)
C610.026 (3)0.024 (3)0.040 (3)−0.011 (2)−0.024 (3)0.008 (2)
C620.043 (3)0.027 (3)0.045 (4)−0.020 (3)−0.027 (3)0.011 (3)
C630.072 (5)0.035 (3)0.074 (5)−0.036 (3)−0.052 (4)0.031 (3)
C640.066 (5)0.024 (3)0.107 (7)−0.022 (3)−0.056 (5)0.019 (4)
C650.051 (4)0.024 (3)0.083 (5)−0.008 (3)−0.023 (4)−0.004 (3)
C660.038 (3)0.024 (3)0.058 (4)−0.011 (2)−0.019 (3)0.005 (3)
C1A0.061 (12)0.039 (10)0.025 (11)−0.001 (8)−0.010 (8)0.001 (6)
C1B0.072 (12)0.051 (10)0.060 (15)−0.032 (9)−0.035 (11)0.001 (10)
C2B0.14 (2)0.16 (3)0.084 (19)−0.082 (19)−0.029 (15)−0.035 (16)
C3B0.075 (10)0.066 (9)0.057 (10)−0.048 (8)−0.044 (9)0.032 (8)
C4B0.061 (10)0.052 (8)0.132 (16)0.018 (8)−0.069 (11)0.007 (10)
C5B0.048 (9)0.126 (15)0.055 (11)0.014 (10)−0.023 (8)0.014 (10)
C6B0.060 (13)0.125 (18)0.037 (11)−0.041 (12)−0.024 (11)0.018 (10)
Geometric parameters (Å, °) top
Pt1—O12.045 (3)C36—H360.9500
Pt1—O22.063 (3)C41—C421.388 (7)
Pt1—P12.2324 (11)C41—C461.392 (6)
Pt1—P22.2533 (12)C42—C431.396 (7)
Pt1—C12.501 (5)C42—H420.9500
Cl1A—C1A1.741 (9)C43—C441.367 (7)
Cl2A—C1A1.733 (9)C43—H430.9500
P1—C311.815 (4)C44—C451.381 (7)
P1—C211.815 (5)C44—H440.9500
P1—C111.826 (4)C45—C461.382 (7)
P2—C411.811 (5)C45—H450.9500
P2—C611.813 (5)C46—H460.9500
P2—C511.824 (4)C51—C561.389 (6)
O1—C11.348 (5)C51—C521.393 (6)
O2—C11.349 (5)C52—C531.374 (7)
O3—C11.208 (5)C52—H520.9500
C11—C121.394 (6)C53—C541.361 (7)
C11—C161.395 (6)C53—H530.9500
C12—C131.391 (6)C54—C551.382 (7)
C12—H120.9500C54—H540.9500
C13—C141.369 (7)C55—C561.392 (6)
C13—H130.9500C55—H550.9500
C14—C151.382 (6)C56—H560.9500
C14—H140.9500C61—C661.382 (7)
C15—C161.381 (6)C61—C621.398 (7)
C15—H150.9500C62—C631.380 (7)
C16—H160.9500C62—H620.9500
C21—C221.398 (6)C63—C641.382 (9)
C21—C261.404 (6)C63—H630.9500
C22—C231.384 (6)C64—C651.374 (9)
C22—H220.9500C64—H640.9500
C23—C241.391 (6)C65—C661.385 (7)
C23—H230.9500C65—H650.9500
C24—C251.377 (6)C66—H660.9500
C24—H240.9500C1A—H1A10.9900
C25—C261.381 (6)C1A—H1A20.9900
C25—H250.9500C1B—C2B1.3900
C26—H260.9500C1B—C6B1.3900
C31—C321.389 (6)C1B—H1B0.9500
C31—C361.391 (7)C2B—C3B1.3900
C32—C331.404 (6)C2B—H2B0.9500
C32—H320.9500C3B—C4B1.3900
C33—C341.369 (8)C3B—H3B0.9500
C33—H330.9500C4B—C5B1.3900
C34—C351.378 (8)C4B—H4B0.9500
C34—H340.9500C5B—C6B1.3900
C35—C361.388 (7)C5B—H5B0.9500
C35—H350.9500C6B—H6B0.9500
O1—Pt1—O265.16 (11)C35—C36—C31120.5 (5)
O1—Pt1—P198.84 (9)C35—C36—H36119.7
O2—Pt1—P1163.83 (9)C31—C36—H36119.7
O1—Pt1—P2161.52 (8)C42—C41—C46118.7 (5)
O2—Pt1—P296.43 (9)C42—C41—P2119.1 (3)
P1—Pt1—P299.48 (4)C46—C41—P2122.1 (4)
O1—Pt1—C132.57 (12)C41—C42—C43120.6 (5)
O2—Pt1—C132.62 (12)C41—C42—H42119.7
P1—Pt1—C1131.28 (11)C43—C42—H42119.7
P2—Pt1—C1128.96 (11)C44—C43—C42119.8 (5)
C31—P1—C21110.5 (2)C44—C43—H43120.1
C31—P1—C11102.4 (2)C42—C43—H43120.1
C21—P1—C11102.5 (2)C43—C44—C45120.3 (5)
C31—P1—Pt1117.35 (15)C43—C44—H44119.9
C21—P1—Pt1111.32 (14)C45—C44—H44119.9
C11—P1—Pt1111.45 (14)C44—C45—C46120.3 (5)
C41—P2—C61104.5 (2)C44—C45—H45119.9
C41—P2—C51105.7 (2)C46—C45—H45119.9
C61—P2—C51103.8 (2)C45—C46—C41120.3 (5)
C41—P2—Pt1107.31 (15)C45—C46—H46119.8
C61—P2—Pt1123.70 (14)C41—C46—H46119.8
C51—P2—Pt1110.53 (15)C56—C51—C52118.6 (4)
C1—O1—Pt192.7 (2)C56—C51—P2118.6 (3)
C1—O2—Pt191.8 (2)C52—C51—P2122.7 (4)
O3—C1—O1125.0 (4)C53—C52—C51120.2 (5)
O3—C1—O2124.8 (4)C53—C52—H52119.9
O1—C1—O2110.2 (4)C51—C52—H52119.9
O3—C1—Pt1177.0 (4)C54—C53—C52121.1 (5)
O1—C1—Pt154.7 (2)C54—C53—H53119.4
O2—C1—Pt155.5 (2)C52—C53—H53119.4
C12—C11—C16118.5 (4)C53—C54—C55120.1 (5)
C12—C11—P1121.8 (3)C53—C54—H54120.0
C16—C11—P1119.7 (3)C55—C54—H54120.0
C13—C12—C11120.2 (4)C54—C55—C56119.4 (5)
C13—C12—H12119.9C54—C55—H55120.3
C11—C12—H12119.9C56—C55—H55120.3
C14—C13—C12120.4 (4)C51—C56—C55120.6 (4)
C14—C13—H13119.8C51—C56—H56119.7
C12—C13—H13119.8C55—C56—H56119.7
C13—C14—C15120.1 (4)C66—C61—C62118.3 (5)
C13—C14—H14119.9C66—C61—P2121.7 (4)
C15—C14—H14119.9C62—C61—P2120.0 (4)
C16—C15—C14120.0 (5)C63—C62—C61120.7 (6)
C16—C15—H15120.0C63—C62—H62119.6
C14—C15—H15120.0C61—C62—H62119.6
C15—C16—C11120.7 (4)C62—C63—C64120.0 (6)
C15—C16—H16119.6C62—C63—H63120.0
C11—C16—H16119.6C64—C63—H63120.0
C22—C21—C26118.1 (4)C65—C64—C63120.0 (5)
C22—C21—P1122.3 (3)C65—C64—H64120.0
C26—C21—P1119.4 (3)C63—C64—H64120.0
C23—C22—C21120.4 (4)C64—C65—C66120.0 (6)
C23—C22—H22119.8C64—C65—H65120.0
C21—C22—H22119.8C66—C65—H65120.0
C22—C23—C24120.5 (4)C61—C66—C65121.0 (6)
C22—C23—H23119.7C61—C66—H66119.5
C24—C23—H23119.7C65—C66—H66119.5
C25—C24—C23119.6 (5)Cl2A—C1A—Cl1A112.8 (6)
C25—C24—H24120.2Cl2A—C1A—H1A1109.0
C23—C24—H24120.2Cl1A—C1A—H1A1109.0
C24—C25—C26120.3 (4)Cl2A—C1A—H1A2109.0
C24—C25—H25119.8Cl1A—C1A—H1A2109.0
C26—C25—H25119.8H1A1—C1A—H1A2107.8
C25—C26—C21121.0 (4)C2B—C1B—C6B120.0
C25—C26—H26119.5C2B—C1B—H1B120.0
C21—C26—H26119.5C6B—C1B—H1B120.0
C32—C31—C36119.6 (4)C3B—C2B—C1B120.0
C32—C31—P1123.8 (4)C3B—C2B—H2B120.0
C36—C31—P1116.3 (3)C1B—C2B—H2B120.0
C31—C32—C33119.3 (5)C2B—C3B—C4B120.0
C31—C32—H32120.3C2B—C3B—H3B120.0
C33—C32—H32120.3C4B—C3B—H3B120.0
C34—C33—C32120.3 (5)C5B—C4B—C3B120.0
C34—C33—H33119.9C5B—C4B—H4B120.0
C32—C33—H33119.9C3B—C4B—H4B120.0
C33—C34—C35120.7 (5)C4B—C5B—C6B120.0
C33—C34—H34119.6C4B—C5B—H5B120.0
C35—C34—H34119.6C6B—C5B—H5B120.0
C34—C35—C36119.6 (5)C5B—C6B—C1B120.0
C34—C35—H35120.2C5B—C6B—H6B120.0
C36—C35—H35120.2C1B—C6B—H6B120.0
O1—Pt1—P1—C31135.33 (19)C22—C23—C24—C250.8 (7)
O2—Pt1—P1—C31143.2 (4)C23—C24—C25—C26−1.9 (7)
P2—Pt1—P1—C31−47.15 (17)C24—C25—C26—C210.9 (7)
C1—Pt1—P1—C31138.7 (2)C22—C21—C26—C251.2 (6)
O1—Pt1—P1—C21−96.03 (17)P1—C21—C26—C25175.3 (3)
O2—Pt1—P1—C21−88.2 (4)C21—P1—C31—C3217.0 (4)
P2—Pt1—P1—C2181.48 (15)C11—P1—C31—C32−91.6 (4)
C1—Pt1—P1—C21−92.7 (2)Pt1—P1—C31—C32146.0 (3)
O1—Pt1—P1—C1117.72 (19)C21—P1—C31—C36−169.4 (3)
O2—Pt1—P1—C1125.6 (4)C11—P1—C31—C3682.1 (4)
P2—Pt1—P1—C11−164.77 (16)Pt1—P1—C31—C36−40.3 (4)
C1—Pt1—P1—C1121.0 (2)C36—C31—C32—C330.6 (7)
O1—Pt1—P2—C41−51.4 (3)P1—C31—C32—C33174.1 (4)
O2—Pt1—P2—C41−46.50 (17)C31—C32—C33—C34−2.2 (7)
P1—Pt1—P2—C41136.39 (15)C32—C33—C34—C352.5 (8)
C1—Pt1—P2—C41−49.2 (2)C33—C34—C35—C36−1.2 (8)
O1—Pt1—P2—C61−172.9 (3)C34—C35—C36—C31−0.3 (8)
O2—Pt1—P2—C61−168.0 (2)C32—C31—C36—C350.6 (7)
P1—Pt1—P2—C6114.9 (2)P1—C31—C36—C35−173.3 (4)
C1—Pt1—P2—C61−170.7 (2)C61—P2—C41—C4299.9 (4)
O1—Pt1—P2—C5163.4 (3)C51—P2—C41—C42−151.0 (4)
O2—Pt1—P2—C5168.29 (17)Pt1—P2—C41—C42−33.0 (4)
P1—Pt1—P2—C51−108.82 (15)C61—P2—C41—C46−77.5 (4)
C1—Pt1—P2—C5165.6 (2)C51—P2—C41—C4631.6 (4)
O2—Pt1—O1—C1−2.2 (2)Pt1—P2—C41—C46149.6 (3)
P1—Pt1—O1—C1175.4 (2)C46—C41—C42—C43−0.1 (7)
P2—Pt1—O1—C13.1 (5)P2—C41—C42—C43−177.7 (4)
O1—Pt1—O2—C12.2 (2)C41—C42—C43—C44−0.1 (8)
P1—Pt1—O2—C1−6.4 (5)C42—C43—C44—C450.3 (8)
P2—Pt1—O2—C1−176.1 (2)C43—C44—C45—C46−0.2 (8)
Pt1—O1—C1—O3−176.3 (4)C44—C45—C46—C41−0.1 (7)
Pt1—O1—C1—O23.3 (4)C42—C41—C46—C450.2 (7)
Pt1—O2—C1—O3176.3 (4)P2—C41—C46—C45177.7 (4)
Pt1—O2—C1—O1−3.3 (3)C41—P2—C51—C5686.8 (4)
O1—Pt1—C1—O387 (7)C61—P2—C51—C56−163.5 (4)
O2—Pt1—C1—O3−97 (7)Pt1—P2—C51—C56−29.0 (4)
P1—Pt1—C1—O381 (7)C41—P2—C51—C52−90.6 (4)
P2—Pt1—C1—O3−92 (7)C61—P2—C51—C5219.1 (5)
O2—Pt1—C1—O1176.3 (4)Pt1—P2—C51—C52153.6 (4)
P1—Pt1—C1—O1−6.1 (3)C56—C51—C52—C531.0 (7)
P2—Pt1—C1—O1−178.72 (19)P2—C51—C52—C53178.4 (4)
O1—Pt1—C1—O2−176.3 (4)C51—C52—C53—C54−1.2 (8)
P1—Pt1—C1—O2177.65 (18)C52—C53—C54—C550.6 (8)
P2—Pt1—C1—O25.0 (3)C53—C54—C55—C560.1 (8)
C31—P1—C11—C12−4.8 (4)C52—C51—C56—C55−0.4 (7)
C21—P1—C11—C12−119.3 (4)P2—C51—C56—C55−177.9 (4)
Pt1—P1—C11—C12121.5 (3)C54—C55—C56—C51−0.2 (7)
C31—P1—C11—C16173.6 (4)C41—P2—C61—C66−16.0 (4)
C21—P1—C11—C1659.0 (4)C51—P2—C61—C66−126.5 (4)
Pt1—P1—C11—C16−60.1 (4)Pt1—P2—C61—C66106.8 (4)
C16—C11—C12—C13−1.5 (7)C41—P2—C61—C62165.9 (4)
P1—C11—C12—C13176.9 (4)C51—P2—C61—C6255.4 (4)
C11—C12—C13—C140.4 (7)Pt1—P2—C61—C62−71.3 (4)
C12—C13—C14—C151.3 (8)C66—C61—C62—C630.4 (7)
C13—C14—C15—C16−1.8 (7)P2—C61—C62—C63178.5 (4)
C14—C15—C16—C110.7 (7)C61—C62—C63—C64−1.2 (8)
C12—C11—C16—C151.0 (7)C62—C63—C64—C651.3 (9)
P1—C11—C16—C15−177.5 (3)C63—C64—C65—C66−0.6 (9)
C31—P1—C21—C22−63.3 (4)C62—C61—C66—C650.3 (7)
C11—P1—C21—C2245.3 (4)P2—C61—C66—C65−177.8 (4)
Pt1—P1—C21—C22164.5 (3)C64—C65—C66—C61−0.2 (8)
C31—P1—C21—C26122.9 (3)C6B—C1B—C2B—C3B0.0
C11—P1—C21—C26−128.6 (3)C1B—C2B—C3B—C4B0.0
Pt1—P1—C21—C26−9.3 (4)C2B—C3B—C4B—C5B0.0
C26—C21—C22—C23−2.4 (6)C3B—C4B—C5B—C6B0.0
P1—C21—C22—C23−176.3 (4)C4B—C5B—C6B—C1B0.0
C21—C22—C23—C241.4 (7)C2B—C1B—C6B—C5B0.0
Acknowledgements top

The authors thank Johnson Matthey (London), the Anglo Platinum Corporation and the University of Cape Town for financial support.

references
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