cis-(Carbonato-κ²O,O′)bis­(triphenyl­phosphine-κP)platinum(II)–benzene–dichloro­methane mixed solvate (2/1/1)

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in solvent or counterion
• R factor = 0.036
• wR factor = 0.060
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.22 Ratio
PLAT231_ALERT_4_C Hirshfeld Test (Solvent)   Cl2A   -   C5B     ..       5.79 su
PLAT231_ALERT_4_C Hirshfeld Test (Solvent)   C2B    -   C3B     ..       5.04 su
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C2B
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C5B
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C1A
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C1B
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C3B
PLAT245_ALERT_2_C U(iso) H1A1    Smaller than U(eq) C6B     by ...       0.01 AngSq
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            O1  -PT1 -C1  -O3     87.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         36
            O2  -PT1 -C1  -O3    -97.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         37
            P1  -PT1 -C1  -O3     81.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         38
            P2  -PT1 -C1  -O3    -92.00  7.00   1.555   1.555   1.555   1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C7 H8 Cl2

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C40.5 H34 Cl1 O3 P2 Pt1
            Atom count from _chemical_formula_moiety:C41 H34 Cl1 O3 P2 Pt1
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  21 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
  14 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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 (J_Pt—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.

S3. Refinement

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

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

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)

Crystal data

[Pt(CO3)(C18H15P)2]·0.5C6H6·0.5CH2Cl2	Z = 2
Mr = 861.16	F(000) = 852
Triclinic, P1	Dx = 1.638 Mg m^−3
Hall symbol: -P 1	Melting point: 188-190°C K
a = 10.4676 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2005 (3) Å	Cell parameters from 37316 reflections
c = 15.2380 (4) Å	θ = 3.1–21.6°
α = 85.576 (1)°	µ = 4.22 mm^−1
β = 71.757 (1)°	T = 173 K
γ = 70.956 (1)°	Prism, colourless
V = 1746.40 (7) Å^3	0.10 × 0.07 × 0.04 mm

Data collection

Nonius Kappa CCD diffractometer	6847 independent reflections
Radiation source: fine-focus sealed tube	5512 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
1.2° ϕ scans and ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→12
Tmin = 0.677, Tmax = 0.849	k = −15→15
37316 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0097P)^2 + 1.8518P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
6847 reflections	Δρmax = 1.33 e Å^−3
459 parameters	Δρmin = −1.45 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00138 (16)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.68157 (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
Cl2A	0.0109 (4)	1.2327 (3)	0.8803 (3)	0.0590 (10)	0.50
P1	0.61853 (12)	0.77338 (9)	0.63764 (8)	0.0169 (3)
P2	0.79888 (13)	0.68445 (10)	0.79647 (9)	0.0208 (3)
O1	0.6013 (3)	0.5118 (3)	0.6748 (2)	0.0230 (7)
O2	0.7197 (3)	0.4556 (2)	0.7765 (2)	0.0231 (7)
O3	0.6483 (3)	0.3258 (3)	0.7215 (2)	0.0320 (8)
C1	0.6555 (5)	0.4223 (4)	0.7241 (3)	0.0214 (11)
C11	0.4805 (5)	0.7670 (4)	0.5907 (3)	0.0183 (10)
C12	0.3494 (5)	0.8540 (4)	0.6099 (3)	0.0242 (11)
H12	0.3284	0.9169	0.6507	0.029*
C13	0.2493 (5)	0.8491 (4)	0.5694 (4)	0.0325 (13)
H13	0.1603	0.9090	0.5824	0.039*
C14	0.2782 (5)	0.7585 (4)	0.5108 (4)	0.0321 (13)
H14	0.2100	0.7565	0.4824	0.039*
C15	0.4063 (5)	0.6700 (4)	0.4929 (3)	0.0264 (11)
H15	0.4251	0.6061	0.4536	0.032*
C16	0.5070 (5)	0.6744 (4)	0.5321 (3)	0.0217 (11)
H16	0.5952	0.6137	0.5190	0.026*
C21	0.7630 (5)	0.7745 (4)	0.5340 (3)	0.0183 (10)
C22	0.7417 (5)	0.8449 (4)	0.4596 (3)	0.0232 (11)
H22	0.6500	0.8976	0.4640	0.028*
C23	0.8533 (5)	0.8383 (4)	0.3797 (3)	0.0278 (12)
H23	0.8381	0.8878	0.3301	0.033*
C24	0.9874 (5)	0.7599 (4)	0.3715 (3)	0.0251 (11)
H24	1.0639	0.7563	0.3168	0.030*
C25	1.0086 (5)	0.6873 (4)	0.4431 (3)	0.0227 (11)
H25	1.0994	0.6320	0.4370	0.027*
C26	0.8986 (5)	0.6947 (4)	0.5237 (3)	0.0202 (10)
H26	0.9150	0.6449	0.5729	0.024*
C31	0.5409 (5)	0.9146 (4)	0.6962 (3)	0.0215 (11)
C32	0.5610 (5)	1.0156 (4)	0.6548 (4)	0.0280 (12)
H32	0.6250	1.0127	0.5944	0.034*
C33	0.4857 (5)	1.1221 (4)	0.7033 (4)	0.0370 (14)
H33	0.5012	1.1914	0.6764	0.044*
C34	0.3900 (6)	1.1266 (5)	0.7892 (4)	0.0459 (16)
H34	0.3367	1.1995	0.8204	0.055*
C35	0.3699 (6)	1.0267 (5)	0.8309 (4)	0.0428 (15)
H35	0.3047	1.0304	0.8910	0.051*
C36	0.4458 (5)	0.9206 (4)	0.7845 (4)	0.0328 (13)
H36	0.4325	0.8515	0.8132	0.039*
C41	0.7442 (5)	0.6453 (4)	0.9163 (3)	0.0222 (11)
C42	0.6065 (5)	0.6427 (4)	0.9562 (4)	0.0343 (13)
H42	0.5439	0.6586	0.9199	0.041*
C43	0.5593 (6)	0.6170 (5)	1.0493 (4)	0.0397 (14)
H43	0.4648	0.6156	1.0762	0.048*
C44	0.6494 (6)	0.5940 (4)	1.1017 (4)	0.0372 (13)
H44	0.6175	0.5762	1.1650	0.045*
C45	0.7866 (6)	0.5965 (4)	1.0630 (4)	0.0351 (13)
H45	0.8485	0.5807	1.0998	0.042*
C46	0.8341 (5)	0.6221 (4)	0.9709 (3)	0.0280 (12)
H46	0.9286	0.6238	0.9447	0.034*
C51	0.9892 (5)	0.6088 (4)	0.7531 (3)	0.0201 (10)
C52	1.0905 (5)	0.6579 (4)	0.7568 (4)	0.0317 (13)
H52	1.0613	0.7345	0.7813	0.038*
C53	1.2324 (5)	0.5957 (4)	0.7250 (4)	0.0346 (13)
H53	1.3005	0.6306	0.7268	0.042*
C54	1.2770 (5)	0.4851 (5)	0.6911 (3)	0.0347 (13)
H54	1.3755	0.4432	0.6700	0.042*
C55	1.1791 (5)	0.4336 (4)	0.6873 (4)	0.0337 (13)
H55	1.2098	0.3564	0.6637	0.040*
C56	1.0350 (5)	0.4960 (4)	0.7183 (3)	0.0276 (12)
H56	0.9673	0.4611	0.7156	0.033*
C61	0.7872 (5)	0.8355 (4)	0.8016 (4)	0.0263 (12)
C62	0.8509 (5)	0.8877 (4)	0.7226 (4)	0.0335 (13)
H62	0.9021	0.8431	0.6667	0.040*
C63	0.8402 (7)	1.0033 (5)	0.7248 (5)	0.0501 (18)
H63	0.8854	1.0375	0.6711	0.060*
C64	0.7638 (7)	1.0693 (5)	0.8053 (6)	0.058 (2)
H64	0.7548	1.1492	0.8066	0.070*
C65	0.7008 (6)	1.0193 (5)	0.8836 (5)	0.0528 (17)
H65	0.6490	1.0644	0.9391	0.063*
C66	0.7127 (6)	0.9029 (4)	0.8816 (4)	0.0390 (14)
H66	0.6690	0.8689	0.9360	0.047*
C1A	−0.1603 (13)	1.3141 (13)	0.9414 (10)	0.046 (5)	0.50
H1A1	−0.2220	1.3264	0.9014	0.056*	0.50
H1A2	−0.1601	1.3911	0.9576	0.056*	0.50
C1B	−0.1889 (14)	1.3178 (7)	0.9804 (9)	0.055 (6)	0.50
H1B	−0.2442	1.3947	0.9725	0.065*	0.50
C2B	−0.2077 (12)	1.2719 (10)	1.0681 (7)	0.117 (12)	0.50
H2B	−0.2759	1.3174	1.1202	0.141*	0.50
C3B	−0.1268 (12)	1.1593 (10)	1.0797 (6)	0.055 (4)	0.50
H3B	−0.1396	1.1279	1.1397	0.067*	0.50
C4B	−0.0270 (11)	1.0926 (7)	1.0035 (9)	0.082 (5)	0.50
H4B	0.0283	1.0157	1.0114	0.098*	0.50
C5B	−0.0082 (10)	1.1386 (11)	0.9158 (7)	0.086 (6)	0.50
H5B	0.0600	1.0930	0.8637	0.103*	0.50
C6B	−0.0891 (13)	1.2511 (11)	0.9042 (7)	0.070 (5)	0.50
H6B	−0.0763	1.2825	0.8442	0.084*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01714 (10)	0.01846 (10)	0.01863 (11)	−0.00798 (7)	−0.00715 (8)	0.00441 (7)
Cl1A	0.045 (2)	0.061 (2)	0.057 (3)	−0.0059 (19)	0.004 (2)	0.016 (2)
Cl2A	0.043 (2)	0.074 (2)	0.053 (2)	−0.015 (2)	−0.009 (2)	0.0072 (18)
P1	0.0156 (6)	0.0182 (6)	0.0172 (7)	−0.0055 (5)	−0.0051 (5)	0.0007 (5)
P2	0.0229 (7)	0.0188 (6)	0.0248 (8)	−0.0089 (5)	−0.0120 (6)	0.0058 (5)
O1	0.0217 (18)	0.0280 (18)	0.024 (2)	−0.0127 (14)	−0.0095 (16)	0.0048 (15)
O2	0.0232 (18)	0.0262 (17)	0.0223 (19)	−0.0117 (15)	−0.0078 (16)	0.0071 (14)
O3	0.034 (2)	0.0233 (18)	0.042 (2)	−0.0129 (16)	−0.0135 (18)	0.0061 (16)
C1	0.020 (3)	0.019 (3)	0.023 (3)	−0.008 (2)	−0.003 (2)	0.003 (2)
C11	0.019 (2)	0.018 (2)	0.020 (3)	−0.008 (2)	−0.009 (2)	0.006 (2)
C12	0.024 (3)	0.021 (2)	0.029 (3)	−0.011 (2)	−0.006 (2)	0.001 (2)
C13	0.020 (3)	0.025 (3)	0.053 (4)	−0.005 (2)	−0.016 (3)	0.009 (3)
C14	0.031 (3)	0.036 (3)	0.042 (4)	−0.017 (3)	−0.022 (3)	0.008 (3)
C15	0.028 (3)	0.032 (3)	0.022 (3)	−0.015 (2)	−0.006 (2)	0.001 (2)
C16	0.019 (2)	0.024 (2)	0.022 (3)	−0.009 (2)	−0.004 (2)	0.003 (2)
C21	0.022 (3)	0.017 (2)	0.017 (3)	−0.008 (2)	−0.006 (2)	−0.0039 (19)
C22	0.023 (3)	0.020 (2)	0.022 (3)	−0.002 (2)	−0.007 (2)	0.003 (2)
C23	0.033 (3)	0.025 (3)	0.019 (3)	−0.007 (2)	−0.001 (2)	0.005 (2)
C24	0.022 (3)	0.027 (3)	0.023 (3)	−0.011 (2)	0.001 (2)	−0.004 (2)
C25	0.017 (2)	0.024 (2)	0.026 (3)	−0.007 (2)	−0.005 (2)	−0.003 (2)
C26	0.022 (3)	0.022 (2)	0.020 (3)	−0.009 (2)	−0.010 (2)	0.002 (2)
C31	0.018 (2)	0.020 (2)	0.026 (3)	−0.004 (2)	−0.008 (2)	0.000 (2)
C32	0.021 (3)	0.024 (3)	0.039 (3)	−0.005 (2)	−0.011 (2)	0.001 (2)
C33	0.032 (3)	0.021 (3)	0.055 (4)	−0.002 (2)	−0.013 (3)	−0.005 (3)
C34	0.041 (4)	0.030 (3)	0.057 (4)	0.008 (3)	−0.015 (3)	−0.024 (3)
C35	0.032 (3)	0.052 (4)	0.027 (3)	0.007 (3)	−0.005 (3)	−0.013 (3)
C36	0.033 (3)	0.028 (3)	0.032 (3)	−0.001 (2)	−0.011 (3)	−0.003 (2)
C41	0.027 (3)	0.018 (2)	0.024 (3)	−0.004 (2)	−0.015 (2)	−0.002 (2)
C42	0.035 (3)	0.041 (3)	0.033 (3)	−0.014 (3)	−0.018 (3)	0.005 (3)
C43	0.036 (3)	0.056 (4)	0.025 (3)	−0.020 (3)	−0.002 (3)	0.008 (3)
C44	0.039 (3)	0.044 (3)	0.019 (3)	−0.004 (3)	−0.007 (3)	0.003 (2)
C45	0.040 (3)	0.038 (3)	0.021 (3)	0.003 (3)	−0.015 (3)	−0.003 (2)
C46	0.025 (3)	0.027 (3)	0.029 (3)	−0.001 (2)	−0.011 (2)	−0.006 (2)
C51	0.018 (2)	0.024 (2)	0.020 (3)	−0.010 (2)	−0.007 (2)	0.008 (2)
C52	0.033 (3)	0.026 (3)	0.048 (4)	−0.017 (2)	−0.024 (3)	0.014 (2)
C53	0.032 (3)	0.042 (3)	0.041 (4)	−0.022 (3)	−0.021 (3)	0.020 (3)
C54	0.021 (3)	0.058 (4)	0.023 (3)	−0.013 (3)	−0.004 (2)	0.004 (3)
C55	0.023 (3)	0.042 (3)	0.033 (3)	−0.001 (2)	−0.011 (3)	−0.012 (3)
C56	0.027 (3)	0.037 (3)	0.025 (3)	−0.016 (2)	−0.011 (2)	−0.001 (2)
C61	0.026 (3)	0.024 (3)	0.040 (3)	−0.011 (2)	−0.024 (3)	0.008 (2)
C62	0.043 (3)	0.027 (3)	0.045 (4)	−0.020 (3)	−0.027 (3)	0.011 (3)
C63	0.072 (5)	0.035 (3)	0.074 (5)	−0.036 (3)	−0.052 (4)	0.031 (3)
C64	0.066 (5)	0.024 (3)	0.107 (7)	−0.022 (3)	−0.056 (5)	0.019 (4)
C65	0.051 (4)	0.024 (3)	0.083 (5)	−0.008 (3)	−0.023 (4)	−0.004 (3)
C66	0.038 (3)	0.024 (3)	0.058 (4)	−0.011 (2)	−0.019 (3)	0.005 (3)
C1A	0.061 (12)	0.039 (10)	0.025 (11)	−0.001 (8)	−0.010 (8)	0.001 (6)
C1B	0.072 (12)	0.051 (10)	0.060 (15)	−0.032 (9)	−0.035 (11)	0.001 (10)
C2B	0.14 (2)	0.16 (3)	0.084 (19)	−0.082 (19)	−0.029 (15)	−0.035 (16)
C3B	0.075 (10)	0.066 (9)	0.057 (10)	−0.048 (8)	−0.044 (9)	0.032 (8)
C4B	0.061 (10)	0.052 (8)	0.132 (16)	0.018 (8)	−0.069 (11)	0.007 (10)
C5B	0.048 (9)	0.126 (15)	0.055 (11)	0.014 (10)	−0.023 (8)	0.014 (10)
C6B	0.060 (13)	0.125 (18)	0.037 (11)	−0.041 (12)	−0.024 (11)	0.018 (10)

Geometric parameters (Å, º)

Pt1—O1	2.045 (3)	C36—H36	0.9500
Pt1—O2	2.063 (3)	C41—C42	1.388 (7)
Pt1—P1	2.2324 (11)	C41—C46	1.392 (6)
Pt1—P2	2.2533 (12)	C42—C43	1.396 (7)
Pt1—C1	2.501 (5)	C42—H42	0.9500
Cl1A—C1A	1.741 (9)	C43—C44	1.367 (7)
Cl2A—C1A	1.733 (9)	C43—H43	0.9500
P1—C31	1.815 (4)	C44—C45	1.381 (7)
P1—C21	1.815 (5)	C44—H44	0.9500
P1—C11	1.826 (4)	C45—C46	1.382 (7)
P2—C41	1.811 (5)	C45—H45	0.9500
P2—C61	1.813 (5)	C46—H46	0.9500
P2—C51	1.824 (4)	C51—C56	1.389 (6)
O1—C1	1.348 (5)	C51—C52	1.393 (6)
O2—C1	1.349 (5)	C52—C53	1.374 (7)
O3—C1	1.208 (5)	C52—H52	0.9500
C11—C12	1.394 (6)	C53—C54	1.361 (7)
C11—C16	1.395 (6)	C53—H53	0.9500
C12—C13	1.391 (6)	C54—C55	1.382 (7)
C12—H12	0.9500	C54—H54	0.9500
C13—C14	1.369 (7)	C55—C56	1.392 (6)
C13—H13	0.9500	C55—H55	0.9500
C14—C15	1.382 (6)	C56—H56	0.9500
C14—H14	0.9500	C61—C66	1.382 (7)
C15—C16	1.381 (6)	C61—C62	1.398 (7)
C15—H15	0.9500	C62—C63	1.380 (7)
C16—H16	0.9500	C62—H62	0.9500
C21—C22	1.398 (6)	C63—C64	1.382 (9)
C21—C26	1.404 (6)	C63—H63	0.9500
C22—C23	1.384 (6)	C64—C65	1.374 (9)
C22—H22	0.9500	C64—H64	0.9500
C23—C24	1.391 (6)	C65—C66	1.385 (7)
C23—H23	0.9500	C65—H65	0.9500
C24—C25	1.377 (6)	C66—H66	0.9500
C24—H24	0.9500	C1A—H1A1	0.9900
C25—C26	1.381 (6)	C1A—H1A2	0.9900
C25—H25	0.9500	C1B—C2B	1.3900
C26—H26	0.9500	C1B—C6B	1.3900
C31—C32	1.389 (6)	C1B—H1B	0.9500
C31—C36	1.391 (7)	C2B—C3B	1.3900
C32—C33	1.404 (6)	C2B—H2B	0.9500
C32—H32	0.9500	C3B—C4B	1.3900
C33—C34	1.369 (8)	C3B—H3B	0.9500
C33—H33	0.9500	C4B—C5B	1.3900
C34—C35	1.378 (8)	C4B—H4B	0.9500
C34—H34	0.9500	C5B—C6B	1.3900
C35—C36	1.388 (7)	C5B—H5B	0.9500
C35—H35	0.9500	C6B—H6B	0.9500
O1—Pt1—O2	65.16 (11)	C35—C36—C31	120.5 (5)
O1—Pt1—P1	98.84 (9)	C35—C36—H36	119.7
O2—Pt1—P1	163.83 (9)	C31—C36—H36	119.7
O1—Pt1—P2	161.52 (8)	C42—C41—C46	118.7 (5)
O2—Pt1—P2	96.43 (9)	C42—C41—P2	119.1 (3)
P1—Pt1—P2	99.48 (4)	C46—C41—P2	122.1 (4)
O1—Pt1—C1	32.57 (12)	C41—C42—C43	120.6 (5)
O2—Pt1—C1	32.62 (12)	C41—C42—H42	119.7
P1—Pt1—C1	131.28 (11)	C43—C42—H42	119.7
P2—Pt1—C1	128.96 (11)	C44—C43—C42	119.8 (5)
C31—P1—C21	110.5 (2)	C44—C43—H43	120.1
C31—P1—C11	102.4 (2)	C42—C43—H43	120.1
C21—P1—C11	102.5 (2)	C43—C44—C45	120.3 (5)
C31—P1—Pt1	117.35 (15)	C43—C44—H44	119.9
C21—P1—Pt1	111.32 (14)	C45—C44—H44	119.9
C11—P1—Pt1	111.45 (14)	C44—C45—C46	120.3 (5)
C41—P2—C61	104.5 (2)	C44—C45—H45	119.9
C41—P2—C51	105.7 (2)	C46—C45—H45	119.9
C61—P2—C51	103.8 (2)	C45—C46—C41	120.3 (5)
C41—P2—Pt1	107.31 (15)	C45—C46—H46	119.8
C61—P2—Pt1	123.70 (14)	C41—C46—H46	119.8
C51—P2—Pt1	110.53 (15)	C56—C51—C52	118.6 (4)
C1—O1—Pt1	92.7 (2)	C56—C51—P2	118.6 (3)
C1—O2—Pt1	91.8 (2)	C52—C51—P2	122.7 (4)
O3—C1—O1	125.0 (4)	C53—C52—C51	120.2 (5)
O3—C1—O2	124.8 (4)	C53—C52—H52	119.9
O1—C1—O2	110.2 (4)	C51—C52—H52	119.9
O3—C1—Pt1	177.0 (4)	C54—C53—C52	121.1 (5)
O1—C1—Pt1	54.7 (2)	C54—C53—H53	119.4
O2—C1—Pt1	55.5 (2)	C52—C53—H53	119.4
C12—C11—C16	118.5 (4)	C53—C54—C55	120.1 (5)
C12—C11—P1	121.8 (3)	C53—C54—H54	120.0
C16—C11—P1	119.7 (3)	C55—C54—H54	120.0
C13—C12—C11	120.2 (4)	C54—C55—C56	119.4 (5)
C13—C12—H12	119.9	C54—C55—H55	120.3
C11—C12—H12	119.9	C56—C55—H55	120.3
C14—C13—C12	120.4 (4)	C51—C56—C55	120.6 (4)
C14—C13—H13	119.8	C51—C56—H56	119.7
C12—C13—H13	119.8	C55—C56—H56	119.7
C13—C14—C15	120.1 (4)	C66—C61—C62	118.3 (5)
C13—C14—H14	119.9	C66—C61—P2	121.7 (4)
C15—C14—H14	119.9	C62—C61—P2	120.0 (4)
C16—C15—C14	120.0 (5)	C63—C62—C61	120.7 (6)
C16—C15—H15	120.0	C63—C62—H62	119.6
C14—C15—H15	120.0	C61—C62—H62	119.6
C15—C16—C11	120.7 (4)	C62—C63—C64	120.0 (6)
C15—C16—H16	119.6	C62—C63—H63	120.0
C11—C16—H16	119.6	C64—C63—H63	120.0
C22—C21—C26	118.1 (4)	C65—C64—C63	120.0 (5)
C22—C21—P1	122.3 (3)	C65—C64—H64	120.0
C26—C21—P1	119.4 (3)	C63—C64—H64	120.0
C23—C22—C21	120.4 (4)	C64—C65—C66	120.0 (6)
C23—C22—H22	119.8	C64—C65—H65	120.0
C21—C22—H22	119.8	C66—C65—H65	120.0
C22—C23—C24	120.5 (4)	C61—C66—C65	121.0 (6)
C22—C23—H23	119.7	C61—C66—H66	119.5
C24—C23—H23	119.7	C65—C66—H66	119.5
C25—C24—C23	119.6 (5)	Cl2A—C1A—Cl1A	112.8 (6)
C25—C24—H24	120.2	Cl2A—C1A—H1A1	109.0
C23—C24—H24	120.2	Cl1A—C1A—H1A1	109.0
C24—C25—C26	120.3 (4)	Cl2A—C1A—H1A2	109.0
C24—C25—H25	119.8	Cl1A—C1A—H1A2	109.0
C26—C25—H25	119.8	H1A1—C1A—H1A2	107.8
C25—C26—C21	121.0 (4)	C2B—C1B—C6B	120.0
C25—C26—H26	119.5	C2B—C1B—H1B	120.0
C21—C26—H26	119.5	C6B—C1B—H1B	120.0
C32—C31—C36	119.6 (4)	C3B—C2B—C1B	120.0
C32—C31—P1	123.8 (4)	C3B—C2B—H2B	120.0
C36—C31—P1	116.3 (3)	C1B—C2B—H2B	120.0
C31—C32—C33	119.3 (5)	C2B—C3B—C4B	120.0
C31—C32—H32	120.3	C2B—C3B—H3B	120.0
C33—C32—H32	120.3	C4B—C3B—H3B	120.0
C34—C33—C32	120.3 (5)	C5B—C4B—C3B	120.0
C34—C33—H33	119.9	C5B—C4B—H4B	120.0
C32—C33—H33	119.9	C3B—C4B—H4B	120.0
C33—C34—C35	120.7 (5)	C4B—C5B—C6B	120.0
C33—C34—H34	119.6	C4B—C5B—H5B	120.0
C35—C34—H34	119.6	C6B—C5B—H5B	120.0
C34—C35—C36	119.6 (5)	C5B—C6B—C1B	120.0
C34—C35—H35	120.2	C5B—C6B—H6B	120.0
C36—C35—H35	120.2	C1B—C6B—H6B	120.0
O1—Pt1—P1—C31	135.33 (19)	C22—C23—C24—C25	0.8 (7)
O2—Pt1—P1—C31	143.2 (4)	C23—C24—C25—C26	−1.9 (7)
P2—Pt1—P1—C31	−47.15 (17)	C24—C25—C26—C21	0.9 (7)
C1—Pt1—P1—C31	138.7 (2)	C22—C21—C26—C25	1.2 (6)
O1—Pt1—P1—C21	−96.03 (17)	P1—C21—C26—C25	175.3 (3)
O2—Pt1—P1—C21	−88.2 (4)	C21—P1—C31—C32	17.0 (4)
P2—Pt1—P1—C21	81.48 (15)	C11—P1—C31—C32	−91.6 (4)
C1—Pt1—P1—C21	−92.7 (2)	Pt1—P1—C31—C32	146.0 (3)
O1—Pt1—P1—C11	17.72 (19)	C21—P1—C31—C36	−169.4 (3)
O2—Pt1—P1—C11	25.6 (4)	C11—P1—C31—C36	82.1 (4)
P2—Pt1—P1—C11	−164.77 (16)	Pt1—P1—C31—C36	−40.3 (4)
C1—Pt1—P1—C11	21.0 (2)	C36—C31—C32—C33	0.6 (7)
O1—Pt1—P2—C41	−51.4 (3)	P1—C31—C32—C33	174.1 (4)
O2—Pt1—P2—C41	−46.50 (17)	C31—C32—C33—C34	−2.2 (7)
P1—Pt1—P2—C41	136.39 (15)	C32—C33—C34—C35	2.5 (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—C35	0.6 (7)
P1—Pt1—P2—C61	14.9 (2)	P1—C31—C36—C35	−173.3 (4)
C1—Pt1—P2—C61	−170.7 (2)	C61—P2—C41—C42	99.9 (4)
O1—Pt1—P2—C51	63.4 (3)	C51—P2—C41—C42	−151.0 (4)
O2—Pt1—P2—C51	68.29 (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—C51	65.6 (2)	C51—P2—C41—C46	31.6 (4)
O2—Pt1—O1—C1	−2.2 (2)	Pt1—P2—C41—C46	149.6 (3)
P1—Pt1—O1—C1	175.4 (2)	C46—C41—C42—C43	−0.1 (7)
P2—Pt1—O1—C1	3.1 (5)	P2—C41—C42—C43	−177.7 (4)
O1—Pt1—O2—C1	2.2 (2)	C41—C42—C43—C44	−0.1 (8)
P1—Pt1—O2—C1	−6.4 (5)	C42—C43—C44—C45	0.3 (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—O2	3.3 (4)	C42—C41—C46—C45	0.2 (7)
Pt1—O2—C1—O3	176.3 (4)	P2—C41—C46—C45	177.7 (4)
Pt1—O2—C1—O1	−3.3 (3)	C41—P2—C51—C56	86.8 (4)
O1—Pt1—C1—O3	87 (7)	C61—P2—C51—C56	−163.5 (4)
O2—Pt1—C1—O3	−97 (7)	Pt1—P2—C51—C56	−29.0 (4)
P1—Pt1—C1—O3	81 (7)	C41—P2—C51—C52	−90.6 (4)
P2—Pt1—C1—O3	−92 (7)	C61—P2—C51—C52	19.1 (5)
O2—Pt1—C1—O1	176.3 (4)	Pt1—P2—C51—C52	153.6 (4)
P1—Pt1—C1—O1	−6.1 (3)	C56—C51—C52—C53	1.0 (7)
P2—Pt1—C1—O1	−178.72 (19)	P2—C51—C52—C53	178.4 (4)
O1—Pt1—C1—O2	−176.3 (4)	C51—C52—C53—C54	−1.2 (8)
P1—Pt1—C1—O2	177.65 (18)	C52—C53—C54—C55	0.6 (8)
P2—Pt1—C1—O2	5.0 (3)	C53—C54—C55—C56	0.1 (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—C12	121.5 (3)	C54—C55—C56—C51	−0.2 (7)
C31—P1—C11—C16	173.6 (4)	C41—P2—C61—C66	−16.0 (4)
C21—P1—C11—C16	59.0 (4)	C51—P2—C61—C66	−126.5 (4)
Pt1—P1—C11—C16	−60.1 (4)	Pt1—P2—C61—C66	106.8 (4)
C16—C11—C12—C13	−1.5 (7)	C41—P2—C61—C62	165.9 (4)
P1—C11—C12—C13	176.9 (4)	C51—P2—C61—C62	55.4 (4)
C11—C12—C13—C14	0.4 (7)	Pt1—P2—C61—C62	−71.3 (4)
C12—C13—C14—C15	1.3 (8)	C66—C61—C62—C63	0.4 (7)
C13—C14—C15—C16	−1.8 (7)	P2—C61—C62—C63	178.5 (4)
C14—C15—C16—C11	0.7 (7)	C61—C62—C63—C64	−1.2 (8)
C12—C11—C16—C15	1.0 (7)	C62—C63—C64—C65	1.3 (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—C65	0.3 (7)
C11—P1—C21—C22	45.3 (4)	P2—C61—C66—C65	−177.8 (4)
Pt1—P1—C21—C22	164.5 (3)	C64—C65—C66—C61	−0.2 (8)
C31—P1—C21—C26	122.9 (3)	C6B—C1B—C2B—C3B	0.0
C11—P1—C21—C26	−128.6 (3)	C1B—C2B—C3B—C4B	0.0
Pt1—P1—C21—C26	−9.3 (4)	C2B—C3B—C4B—C5B	0.0
C26—C21—C22—C23	−2.4 (6)	C3B—C4B—C5B—C6B	0.0
P1—C21—C22—C23	−176.3 (4)	C4B—C5B—C6B—C1B	0.0
C21—C22—C23—C24	1.4 (7)	C2B—C1B—C6B—C5B	0.0