trans-Di­chlorido­bis­­(4,8-di­methyl-2-phenyl-2-phosphabi­cyclo­[3.3.1]nonane-κP)platinum(II)

The crystal structure of the title compound, trans-[PtCl₂(C₁₆H₂₃P)₂], has been determined at 100 K. The Pt atom is located on a twofold axis and adopts a distorted square-planar coordination geometry. The structure is only the second example of a coordination complex containing a derivative of the 4,8-dimethyl-2-phosphabicyclo­[3.3.1]nona­ne (Lim) phosphine ligand family. The ligand contains four chiral C atoms, with the stereochemistry at three of these fixed during synthesis, therefore resulting in two possible ligand stereoisomers. The compound crystallizes in the chiral space group P4₃2₁2 but is racemic, comprising an equimolar mixture of both stereoisomers disordered on a single ligand site. The effective cone angles for both isomers are the same at 146°.

Comment

Lim ligands (2-Q-4,8-dimethyl-2-phosphabicyclo­[3.3.1]non­ane) are derived from the radical addition reaction of the monoterpene R-(+)-limonene with a QPH₂ mol­ecule, where Q = H or some other suitable monoanionic group such as alkyl or aryl, resulting in a racemic mixture of ligands being obtained. Although the phosphine Lim backbone contains four chiral C atoms, the stereochemistry at three of these sites is fixed, viz. C1 (R), C5 (R) and C8 (S), while C4 can have either an R or S configuration. This stereochemistry is a consequence of performing the synthesis with the optically pure terpene and the mechanism of addition to the P atom (Robertson et al., 2001).

Chiral phosphine ligands are of general inter­est in coordination chemistry and catalysis, and ligands of the Lim family have been shown to display exceptional qualities in the modified cobalt hydro­formyl­ation of alkenes to give alcohols directly (Steynberg et al., 2002; Crause et al., 2003; Dwyer et al., 2004). The only other crystal structure in the open literature of a coordination compound containing a member of the Lim ligand family, [Co(CO)₃(Lim-C18)]₂ (Lim-C18 is the 4R isomer of 2-octa­decyl-4,8-dimethyl-2-phosphabicyclo­[3.3.1]non­a­ne), was obtained during such a study (Polas et al., 2003).

In order to investigate further the coordination mode of these ligands, we prepared [PtCl₂(Lim-Ph)₂] by reaction of [PtCl₂(COD)] (COD is cis,cis-cyclo­octa-1,5-diene) with two molar equivalents of a solution containing a mixture of both Lim-Ph isomers. Recrystallization as described in the Experimental section resulted in crystals of (I) being obtained.

Compound (I) crystallizes with a distorted square-planar coordination geometry, with a twofold rotation axis passing through the Pt metal centre and bis­ecting the P2—Pt1—P2ⁱ and Cl1—Pt1—Cl1ⁱ angles [symmetry code: (i) y, x, −z] (Fig. 1). The Lim-Ph ligands adopt a trans orientation, suggesting significant steric bulk, although cis isomers have been observed in solution using ³¹P NMR (vide infra). The coordination geometry deviates significantly from ideal square planar, with P2—Pt1—P2ⁱ and Cl1—Pt1—Cl1ⁱ angles of 170.97 (9) and 175.49 (8)°, respectively. Inter­estingly, the C11 methyl groups, which contribute significantly to the overall steric bulk of the Lim-Ph ligands, occupy the same side of the equatorial plane, with a closest contact of only 3.655 (13) Å between C11 and C11ⁱ. This inter­action manifests itself in the deviation of the P atoms below the equatorial plane. In addition, the presence of these two methyl substituents effectively blocks one apical position of the Pt atom, with Pt1⋯C11 contacts of only 3.563 (6) Å. The Pt1—P2 bond distance of 2.3088 (14) Å is within the expected range, while the Pt1—Cl1 distance of 2.3320 (13) Å is quite long. This elongation is probably a consequence of the steric repulsion of the two bulky phosphine ligands and the resulting distortion from square planarity. The deviations in the bond angles from the ideal value of 180° would impact negatively on the efficiency of the relevant orbital overlap between the atoms involved. Table 1 presents a comparison with related structures, also containing bulky ligands, taken from the open literature, to illustrate this effect.

The Lim-Ph ligand exhibits disorder in the orientation of the C10 methyl group, with components A and B corresponding to the 4R and 4S isomers, respectively (Fig. 1). Refinement of the site occupancies for C10A and C10B yielded values that did not differ significantly from 0.5 and the occupancies were therefore constrained to 0.5 for subsequent refinement, corresponding to a true racemic mixture. Short inter­molecular contacts [C10A⋯C10Aⁱⁱ = 2.502 (16) Å; symmetry code: (ii) y − 1, x + 1, −z] preclude the simultaneous presence of C10A in neighbouring mol­ecules, but there are no constraints on the presence of C10B.

Describing the steric demand of phosphine ligands has been the topic of many studies and a variety of models have been developed (Bunten et al., 2002). In practice, the Tolman cone angle (Tolman, 1977) is still the most commonly used model, due to its simplicity and ease of calculation. This principle has been further developed (Otto, 2001) into the concept of the `effective cone angle', where the crystallographically determined metal–P bond length is used in the calculations. Using the Pt1—P2 bond distance obtained in this study and calculating the cone to the outermost H atoms (H11A, H19A and H25A) on C11, C19 and C25 results in a value of 146°. In addition, the cone angle is independent of the orientation of C10.

³¹P NMR analysis of the reaction mixture indicated a number of species in solution corresponding to Pt complexes of both cis and trans geometry, as well as containing combinations of the different ligand isomers, i.e. (4R,4R), (4S,4S) and (4R,4S). Aside from the constraint observed for the inter­molecular contacts involving C10A, the refined 50% disorder in the orientation of the C10 Me group is consistent with any of these combinations. Redissolving some of the single crystals obtained and recollecting the ³¹P NMR spectrum confirmed that mixtures of this nature are indeed present in both the solid and solution states.

Based on high-pressure NMR experiments, it was previously shown that the 4R isomer coordinates preferentially during modified Co hydro­formyl­ation (Polas et al., 2003; Dwyer et al., 2004), and this observation was supported by modelling studies (Crause et al., 2003). Considering, however, that the two isomers are electronically and sterically (as shown here) very similar, this behaviour is currently not well understood and may warrant further investigation.

Figure 1 The mol­ecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry code: (i) y, x, −z.]

Experimental

The Lim-Ph ligand (mixture of isomers) was prepared by adapting methods described previously (Bungu & Otto, 2007). All manipulations involving the free ligand were performed using degassed solvents and working under a positive argon atmosphere to prevent oxidation. PtCl₂(COD) (COD is cis,cis-cyclo­octa-1,5-diene) (200 mg, 0.53 mmol) was dissolved in dichloro­methane (10 ml) and a di­chloro­methane solution of the ligand mixture (1.49 ml, 753 mM, 1.12 mmol) was subsequently added. The resulting reaction mixture was stirred overnight and a portion was subjected to ³¹P NMR analysis. The spectra were quite complex, with both cis and trans Pt^II complexes present as mixtures of the two ligand isomers. Crystals of compound (I) suitable for single-crystal diffraction studies were obtained by addition of acetone to the dichloro­methane reaction mixture followed by slow evaporation.

³¹P (CDCl₃): trans-[PtCl₂(4R-Lim-Ph)₂] −8.82 p.p.m. (t, ¹J_Pt—P = 2378 Hz); trans-[PtCl₂(4R-Lim-Ph)(4S-Lim-Ph)] −9.83 (4R, t, ¹J_Pt—P = 2378 Hz) and −12.42 p.p.m. (4S, t, ¹J_Pt—P = 2383 Hz); trans-[PtCl₂(4S-Lim-Ph)₂] −13.58 p.p.m. (t, ¹J_Pt—P = 2384 Hz).

Crystal data

• [PtCl₂(C₁₆H₂₃P)₂]

• M_r = 758.62

• Tetragonal, P 4₃ 2₁ 2

• a = 9.5909 (1) Å

• c = 33.2924 (9) Å

• V = 3062.41 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 4.88 mm⁻¹

• T = 100 K

• 0.37 × 0.24 × 0.22 mm

Data collection

• Bruker X8 APEXII 4K KappaCCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008) T_min = 0.273, T_max = 0.364

• 31409 measured reflections

• 3782 independent reflections

• 3209 reflections with I > 2σ(I)

• R_int = 0.083

Refinement

• R[F² > 2σ(F²)] = 0.042

• wR(F²) = 0.067

• S = 1.15

• 3782 reflections

• 180 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 1.19 e Å⁻³

• Δρ_min = −1.42 e Å⁻³

• Absolute structure: Flack (1983), 1505 Friedel pairs

• Flack parameter: 0.010 (10)

Table 1
Comparative data for trans-[PtCl₂(P)₂] complexes

P	Pt—P (Å)	Pt—Cl (Å)	Reference
PEt3	2.298 (18)	2.294 (9)	(i)
PPh3	2.3164 (11)	2.2997 (11)	(ii)
PBz3	2.3219 (12)	2.3092 (11)	(iii)
	2.3019 (10)	2.3053 (10)	(iii)
PCy3	2.337 (2)	2.317 (2)	(iv)
PPh2Fc	2.318 (2)	2.301 (2)	(v)
s-PhobPBu	2.3121 (11)	2.3059 (11)	(vi)
a7PhobPBu	2.302 (4)	2.307 (4)	(vi)
	2.321 (5)	2.318 (4)	(vi)
1,2,6-tpp	2.3096 (12)	2.3118 (12)	(vii)
References: (i) Messmer & Amma (1966); (ii) Johansson & Otto (2000); (iii) Johansson et al. (2002); (iv) Del Pra & Zanotti (1980); (v) Otto & Roodt (1997); (vi) Carreira et al. (2009); (vii) Doherty et al. (2006).

The disorder of the methyl substituent on C4 of the Lim-Ph ligand was modelled as two orientations with occupancies summing to unity. Occupancies of 0.493 (18) and 0.507 (18) were obtained for C10A and C10B, respectively. Since these values do not differ significantly from 0.5, they were constrained to 0.5 for further refinement. The C4—C10A and C4—C10B distances were tightly restrained to 1.530 (5) Å. H atoms were placed geometrically with C—H distances of 1.00 Å for CH (alk­yl), 0.95 Å for CH (ar­yl), 0.99 Å for CH₂ and 0.98 Å for CH₃, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for CH and CH₂ or 1.5U_eq(C) for CH₃. For the methyl groups, rotation was permitted about the C—C bond.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Lim ligands (2-Q-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane) are derived from the radical addition reaction of the monoterpene R-(+)-limonene with a QPH₂ molecule, where Q = H or some other suitable monoanionic group such as alkyl or aryl, resulting in a racemic mixture of ligands being obtained. Although the phosphine Lim backbone contains four chiral C atoms, the stereochemistry at three of these sites is fixed, viz. C1 (R), C5 (R) and C8 (S), while C4 can have either an R or S configuration. This stereochemistry is a consequence of performing the synthesis with the optically pure terpene and the mechanism of addition to the P atom (Robertson et al., 2001).

Chiral phosphine ligands are of general interest in coordination chemistry and catalysis, and ligands of the Lim family have been shown to display exceptional qualities in the modified cobalt hydroformylation of alkenes to give alcohols directly (Steynberg et al., 2002; Crause et al., 2003; Dwyer et al., 2004). The only other crystal structure in the open literature of a coordination compound containing a member of the Lim ligand family, [Co(CO)₃(Lim-C18)]₂ (Lim-C18 = 4R isomer of 2-octadecyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane), was obtained during such a study (Polas et al., 2003).

In order to investigate further the coordination mode of these ligands, we prepared [PtCl₂(Lim-Ph)₂] by reaction of [PtCl₂(COD)] (COD = 1,5-cyclooctadiene) with two molar equivalents of a solution containing a mixture of both Lim-Ph isomers. Recrystallization as described in the Experimental section resulted in crystals of (I) being obtained.

Compound (I) crystallizes with a distorted square-planar coordination geometry, with a twofold rotation axis passing through the Pt metal centre and bisecting the P2—Pt1—P2ⁱ and Cl1—Pt1—Cl1ⁱ angles [symmetry code: (i) y, x, -z] (Fig. 1). The Lim-Ph ligands adopt a trans orientation, suggesting significant steric bulk, although cis isomers have been observed in solution using ³¹P NMR (vide infra). The coordination geometry deviates significantly from ideal square planar, with P2—Pt1—P2ⁱ and Cl1—Pt1—Cl1ⁱ angles of 170.97 (9) and 175.49 (8)°, respectively. Interestingly, the C11 methyl groups, which contribute significantly to the overall steric bulk of the Lim-Ph ligands, occupy the same side of the equatorial plane, with a closest contact of only 3.655 (13) Å between C11 and C11ⁱ. This interaction manifests itself in the deviation of the P atoms below the equatorial plane. In addition, the presence of these two methyl substituents effectively blocks one apical position of the Pt atom, with Pt1···C11 contacts of only 3.563 (6) Å. The Pt1—P2 bond distance of 2.3088 (14) Å is within the expected range, while the Pt1—Cl1 distance of 2.3320 (13) Å is quite long. This elongation is probably a consequence of the steric repulsion of the two bulky phosphine ligands and the resulting distortion from square planarity. The deviations in the bond angles from the ideal 180° would negatively impact on the efficiency of the relevant orbital overlap between the atoms involved. Table 1 presents a comparison with related structures, also containing bulky ligands, taken from the open literature, to illustrate this effect.

The Lim-Ph ligand exhibits disorder in the orientation of the C10 methyl group, with components A and B corresponding to the 4R and 4S isomers, respectively (Fig. 1). Refinement of the site occupancies for C10A and C10B yielded values that did not differ significantly from 0.5 and the occupancies were therefore constrained to 0.5 for subsequent refinement, corresponding to a true racemic mixture. Short intermolecular contacts [C10A···C10Aⁱⁱ = 2.502 (16) Å; symmetry code: (ii) -1 + y, 1 + x, -z] preclude the simultaneous presence of C10A in neighbouring molecules, but there are no constraints on the presence of C10B.

Describing the steric demand of phosphine ligands has been the topic of many studies and a variety of models have been developed (Bunten et al., 2002). In practice, the Tolman cone angle (Tolman, 1977) is still the most commonly used model, due to its simplicity and ease of calculation. This principle has been further developed (Otto, 2001) into the concept of the `effective cone angle', where the crystallographically determined metal–P bond length is used in the calculations. Using the Pt1—P2 bond distance obtained in this study and calculating the cone to the outermost H atoms (H11A, H19A and H25A) on C11, C19 and C25 results in a value of 146°. In addition, the cone angle is independent of the orientation of C10.

³¹P NMR analysis of the reaction mixture indicated a number of species in solution corresponding to Pt complexes of both cis and trans geometry as well as containing combinations of the different ligand isomers, i.e. (4R,4R), (4S,4S) and (4R,4S). Aside from the constraint observed for the intermolecular contacts involving C10A, the refined 50% disorder in the orientation of the C10 Me group is consistent with any of these combinations. Redissolving some of the single crystals obtained and recollecting the ³¹P NMR spectrum confirmed that mixtures of this nature are indeed present in both the solid and solution states.

Based on high-pressure NMR experiments it was previously shown that the 4R isomer coordinates preferentially during modified Co hydroformylation (Polas et al. 2003, Dwyer et al. 2004), and this observation was supported by modelling studies (Crause et al., 2003). Considering, however, that the two isomers are electronically and sterically (as shown here) very similar, this behaviour is currently not well understood and may warrant further investigation.

Related literature

For related literature, see: Bungu & Otto (2007); Bunten et al. (2002); Crause et al. (2003); Dwyer et al. (2004); Otto (2001); Polas et al. (2003); Robertson et al. (2001); Steynberg et al. (2002); Tolman (1977).

S2. Experimental

The Lim-Ph ligand (mixture of isomers) was prepared by adapting the methods described previously (Bungu & Otto, 2007). All manipulations involving the free ligand were performed using degassed solvents and working under a positive argon atmosphere to prevent oxidation. PtCl₂(COD) (COD = cis,cis-1,5-cyclooctadiene) (200 mg, 0.53 mmol) was dissolved in dichloromethane (10 ml) and a dichloromethane solution of the ligand mixture (1.49 ml, 753 mM, 1.12 mmol) was subsequently added. The resulting reaction mixture was stirred overnight and a portion was subjected to ³¹P NMR analysis. The spectra could be quite complex with both cis and trans Pt^II complexes present as mixtures of the two ligand isomers. Crystals of compound (I) suitable for single-crystal diffraction studies were obtained by addition of acetone to the dichloromethane reaction mixture followed by slow evaporation.

³¹P (CDCl₃): trans-[PtCl₂(4R-Lim-Ph)₂] -8.82 p.p.m. (t, ¹J_Pt—P = 2378 Hz); trans-[PtCl₂(4R-Lim-Ph)(4S-Lim-Ph)] -9.83 p.p.m. (4R, t, ¹J_Pt—P = 2378 Hz) and -12.42 p.p.m. (4S, t, ¹J_Pt—P = 2383 Hz); trans-[PtCl₂(4S-Lim-Ph)₂] -13.58 p.p.m. (t, ¹J_Pt—P = 2384 Hz).

S3. Refinement

The disorder of the Me substituent on C4 of the Lim-Ph ligand was modelled as two orientations with occupancies summing to unity. Occupancies of 0.493 (18) and 0.507 (18) were obtained for C10A and C10B, respectively. Since these values do not differ significantly from 0.5, they were constrained to 0.5 for further refinement. The C4—C10A and C4—C10B distances were tightly restrained to 1.530 (5) Å. H atoms were placed geometrically with C—H distances of 1.00 Å for CH (alkyl), 0.95 Å for CH (aryl), 0.99 Å for CH₂ or 0.98 Å for CH₃, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) for CH and CH₂ or 1.5U_eq(C) for CH₃. For the methyl groups, rotation was permitted about the C—C bond.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity. Symmetry code: (i) y, x, -z.

trans-Dichloridobis(4,8-dimethyl-2-phenyl-2- phosphabicyclo[3.3.1]nonane-κP)platinum(II)

Crystal data

[PtCl2(C16H23P)2]	Dx = 1.645 Mg m^−3
Mr = 758.62	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 6453 reflections
Hall symbol: P 4nw 2abw	θ = 2.5–23.0°
a = 9.5909 (1) Å	µ = 4.88 mm^−1
c = 33.2924 (9) Å	T = 100 K
V = 3062.41 (9) Å^3	Block, yellow
Z = 4	0.37 × 0.24 × 0.22 mm
F(000) = 1520

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer	3782 independent reflections
Radiation source: fine-focus sealed tube	3209 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
Detector resolution: 8.4 pixels mm^-1	θmax = 28.3°, θmin = 3.5°
ϕ and ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −8→12
Tmin = 0.273, Tmax = 0.364	l = −43→34
31409 measured reflections

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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.P)^2 + 6.9783P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max < 0.001
3782 reflections	Δρmax = 1.19 e Å^−3
180 parameters	Δρmin = −1.42 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1505 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (10)

Special details

Experimental. The intensity data were collected on a Bruker X8 ApexII 4K Kappa CCD diffractometer using an exposure time of 20 s/frame with a frame width of 0.5°, a total of 949 frames were collected.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.02824 (2)	0.02824 (2)	0.0000	0.02014 (9)
Cl1	0.13895 (16)	−0.06895 (16)	0.05573 (4)	0.0277 (4)
P2	−0.11680 (16)	0.14649 (16)	0.04363 (4)	0.0214 (3)
C1	−0.0416 (7)	0.2564 (6)	0.08386 (15)	0.0242 (14)
H1	0.0114	0.1936	0.1023	0.029*
C3	−0.2444 (6)	0.2641 (6)	0.02059 (17)	0.0304 (14)
H3A	−0.1945	0.3256	0.0015	0.036*
H3B	−0.3107	0.2071	0.0048	0.036*
C4	−0.3287 (7)	0.3562 (7)	0.04924 (19)	0.0400 (17)
H4A	−0.3902	0.2883	0.0636	0.048*	0.50
H4B	−0.3592	0.4362	0.0321	0.048*	0.50
C5	−0.2461 (7)	0.4254 (7)	0.0834 (2)	0.0341 (17)
H5	−0.3159	0.4689	0.1018	0.041*
C6	−0.1484 (7)	0.5413 (8)	0.0697 (2)	0.0386 (17)
H6A	−0.2000	0.6030	0.0511	0.046*
H6B	−0.1221	0.5976	0.0934	0.046*
C7	−0.0161 (6)	0.4933 (6)	0.04896 (18)	0.0329 (16)
H7A	0.0485	0.5734	0.0468	0.039*
H7B	−0.0396	0.4630	0.0214	0.039*
C8	0.0588 (7)	0.3739 (7)	0.07044 (18)	0.0283 (17)
H8	0.0976	0.4148	0.0957	0.034*
C9	−0.1633 (7)	0.3203 (7)	0.10820 (18)	0.0305 (16)
H9A	−0.2263	0.2448	0.1173	0.037*
H9B	−0.1256	0.3673	0.1324	0.037*
C10A	−0.4311 (11)	0.4562 (11)	0.0298 (3)	0.041 (3)	0.50
H10A	−0.4948	0.4039	0.0123	0.062*	0.50
H10B	−0.3799	0.5249	0.0137	0.062*	0.50
H10C	−0.4848	0.5042	0.0506	0.062*	0.50
C10B	−0.4639 (11)	0.2847 (15)	0.0608 (4)	0.047 (4)	0.50
H10D	−0.4453	0.2149	0.0817	0.071*	0.50
H10E	−0.5038	0.2388	0.0372	0.071*	0.50
H10F	−0.5298	0.3541	0.0711	0.071*	0.50
C11	0.1822 (7)	0.3252 (7)	0.04652 (18)	0.0326 (16)
H11A	0.1516	0.2976	0.0196	0.049*
H11B	0.2253	0.2453	0.0600	0.049*
H11C	0.2503	0.4011	0.0444	0.049*
C21	−0.2189 (6)	0.0173 (7)	0.07102 (16)	0.0239 (14)
C22	−0.1751 (6)	−0.0430 (7)	0.10688 (16)	0.0237 (13)
H22	−0.0896	−0.0130	0.1185	0.028*
C23	−0.2508 (7)	−0.1438 (7)	0.12603 (18)	0.0288 (15)
H23	−0.2183	−0.1818	0.1507	0.035*
C24	−0.3737 (7)	−0.1902 (7)	0.1098 (2)	0.0307 (16)
H24	−0.4273	−0.2592	0.1232	0.037*
C25	−0.4184 (9)	−0.1361 (8)	0.0740 (2)	0.047 (2)
H25	−0.5029	−0.1683	0.0623	0.057*
C26	−0.3409 (8)	−0.0350 (9)	0.0548 (2)	0.051 (2)
H26	−0.3723	−0.0002	0.0296	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02319 (11)	0.02319 (11)	0.01406 (12)	−0.00274 (14)	−0.00116 (9)	0.00116 (9)
Cl1	0.0303 (9)	0.0402 (11)	0.0127 (6)	0.0100 (7)	0.0031 (6)	0.0069 (6)
P2	0.0231 (10)	0.0261 (10)	0.0151 (7)	−0.0033 (6)	−0.0014 (6)	−0.0018 (6)
C1	0.032 (4)	0.031 (4)	0.010 (3)	−0.002 (3)	−0.001 (3)	−0.003 (2)
C3	0.031 (4)	0.029 (4)	0.031 (3)	−0.003 (3)	−0.007 (3)	−0.001 (3)
C4	0.037 (5)	0.033 (5)	0.051 (4)	0.007 (3)	−0.011 (3)	−0.014 (3)
C5	0.036 (4)	0.025 (4)	0.042 (4)	0.001 (3)	0.003 (3)	−0.009 (3)
C6	0.044 (4)	0.032 (4)	0.040 (4)	−0.008 (4)	−0.007 (3)	−0.002 (4)
C7	0.037 (4)	0.030 (4)	0.031 (3)	−0.011 (3)	−0.006 (3)	0.003 (2)
C8	0.032 (4)	0.030 (4)	0.023 (3)	−0.015 (3)	−0.004 (3)	−0.001 (3)
C9	0.035 (4)	0.027 (4)	0.029 (3)	−0.006 (3)	0.012 (3)	−0.008 (3)
C10A	0.025 (7)	0.037 (8)	0.062 (8)	0.009 (5)	−0.009 (6)	−0.023 (7)
C10B	0.034 (8)	0.072 (11)	0.035 (8)	0.001 (9)	0.010 (8)	−0.016 (7)
C11	0.027 (4)	0.044 (5)	0.027 (3)	−0.010 (3)	−0.003 (3)	−0.002 (3)
C21	0.025 (3)	0.028 (4)	0.019 (3)	−0.003 (3)	0.002 (2)	−0.005 (3)
C22	0.019 (3)	0.027 (4)	0.026 (3)	0.005 (3)	0.008 (2)	0.000 (3)
C23	0.029 (4)	0.027 (4)	0.030 (3)	0.005 (3)	0.008 (3)	0.004 (3)
C24	0.032 (4)	0.023 (4)	0.037 (4)	−0.002 (3)	0.014 (3)	−0.002 (3)
C25	0.043 (5)	0.049 (5)	0.050 (5)	−0.027 (4)	−0.015 (4)	0.007 (4)
C26	0.056 (5)	0.054 (5)	0.043 (4)	−0.029 (5)	−0.018 (4)	0.015 (4)

Geometric parameters (Å, º)

Pt1—P2^i	2.3088 (14)	C7—H7B	0.990
Pt1—P2	2.3088 (14)	C8—C11	1.501 (9)
Pt1—Cl1^i	2.3320 (13)	C8—H8	1.000
Pt1—Cl1	2.3320 (13)	C9—H9A	0.990
P2—C21	1.824 (6)	C9—H9B	0.990
P2—C3	1.833 (5)	C10A—H10A	0.980
P2—C1	1.851 (6)	C10A—H10B	0.980
C1—C9	1.548 (8)	C10A—H10C	0.980
C1—C8	1.548 (8)	C10B—H10D	0.980
C1—H1	1.000	C10B—H10E	0.980
C3—C4	1.530 (8)	C10B—H10F	0.980
C3—H3A	0.990	C11—H11A	0.980
C3—H3B	0.990	C11—H11B	0.980
C4—C10B	1.517 (5)	C11—H11C	0.980
C4—C10A	1.519 (5)	C21—C26	1.383 (8)
C4—C5	1.535 (9)	C21—C22	1.391 (8)
C4—H4A	1.000	C22—C23	1.368 (8)
C4—H4B	1.000	C22—H22	0.950
C5—C6	1.524 (9)	C23—C24	1.371 (9)
C5—C9	1.526 (9)	C23—H23	0.950
C5—H5	1.000	C24—C25	1.368 (10)
C6—C7	1.515 (9)	C24—H24	0.950
C6—H6A	0.990	C25—C26	1.379 (10)
C6—H6B	0.990	C25—H25	0.950
C7—C8	1.529 (8)	C26—H26	0.950
C7—H7A	0.990
P2^i—Pt1—P2	170.97 (9)	C8—C7—H7A	108.7
P2^i—Pt1—Cl1^i	88.29 (5)	C6—C7—H7B	108.7
P2—Pt1—Cl1^i	92.06 (5)	C8—C7—H7B	108.7
P2^i—Pt1—Cl1	92.06 (5)	H7A—C7—H7B	107.6
P2—Pt1—Cl1	88.29 (5)	C11—C8—C7	110.8 (5)
Cl1^i—Pt1—Cl1	175.49 (8)	C11—C8—C1	114.7 (5)
C21—P2—C3	105.6 (3)	C7—C8—C1	112.8 (5)
C21—P2—C1	103.6 (3)	C11—C8—H8	105.9
C3—P2—C1	102.3 (3)	C7—C8—H8	105.9
C21—P2—Pt1	107.7 (2)	C1—C8—H8	105.9
C3—P2—Pt1	116.20 (19)	C5—C9—C1	111.7 (5)
C1—P2—Pt1	120.0 (2)	C5—C9—H9A	109.3
C9—C1—C8	109.4 (5)	C1—C9—H9A	109.3
C9—C1—P2	108.1 (4)	C5—C9—H9B	109.3
C8—C1—P2	116.6 (4)	C1—C9—H9B	109.3
C9—C1—H1	107.5	H9A—C9—H9B	107.9
C8—C1—H1	107.5	C4—C10A—H10A	109.5
P2—C1—H1	107.5	C4—C10A—H10B	109.5
C4—C3—P2	116.5 (4)	C4—C10A—H10C	109.5
C4—C3—H3A	108.2	C4—C10B—H10D	109.5
P2—C3—H3A	108.2	C4—C10B—H10E	109.5
C4—C3—H3B	108.2	H10D—C10B—H10E	109.5
P2—C3—H3B	108.2	C4—C10B—H10F	109.5
H3A—C3—H3B	107.3	H10D—C10B—H10F	109.5
C10B—C4—C3	110.4 (7)	H10E—C10B—H10F	109.5
C10A—C4—C3	116.1 (6)	C8—C11—H11A	109.5
C10B—C4—C5	116.6 (7)	C8—C11—H11B	109.5
C10A—C4—C5	112.1 (6)	H11A—C11—H11B	109.5
C3—C4—C5	116.0 (5)	C8—C11—H11C	109.5
C10A—C4—H4A	103.5	H11A—C11—H11C	109.5
C3—C4—H4A	103.5	H11B—C11—H11C	109.5
C5—C4—H4A	103.5	C26—C21—C22	116.1 (6)
C10B—C4—H4B	104.0	C26—C21—P2	120.3 (5)
C3—C4—H4B	104.0	C22—C21—P2	123.3 (4)
C5—C4—H4B	104.0	C23—C22—C21	122.2 (6)
H4A—C4—H4B	126.8	C23—C22—H22	118.9
C6—C5—C9	108.9 (6)	C21—C22—H22	118.9
C6—C5—C4	114.3 (6)	C22—C23—C24	120.1 (6)
C9—C5—C4	112.6 (5)	C22—C23—H23	119.9
C6—C5—H5	106.9	C24—C23—H23	119.9
C9—C5—H5	106.9	C25—C24—C23	119.3 (6)
C4—C5—H5	106.9	C25—C24—H24	120.3
C7—C6—C5	115.4 (6)	C23—C24—H24	120.3
C7—C6—H6A	108.4	C24—C25—C26	120.1 (7)
C5—C6—H6A	108.4	C24—C25—H25	119.9
C7—C6—H6B	108.4	C26—C25—H25	119.9
C5—C6—H6B	108.4	C25—C26—C21	122.0 (7)
H6A—C6—H6B	107.5	C25—C26—H26	119.0
C6—C7—C8	114.1 (5)	C21—C26—H26	119.0
C6—C7—H7A	108.7
Cl1^i—Pt1—P2—C21	120.39 (19)	C5—C6—C7—C8	−46.0 (7)
Cl1—Pt1—P2—C21	−64.10 (19)	C6—C7—C8—C11	175.7 (5)
Cl1^i—Pt1—P2—C3	2.2 (3)	C6—C7—C8—C1	45.6 (7)
Cl1—Pt1—P2—C3	177.8 (3)	C9—C1—C8—C11	179.9 (5)
Cl1^i—Pt1—P2—C1	−121.7 (2)	P2—C1—C8—C11	−57.1 (7)
Cl1—Pt1—P2—C1	53.9 (2)	C9—C1—C8—C7	−52.0 (6)
C21—P2—C1—C9	−59.4 (4)	P2—C1—C8—C7	71.0 (6)
C3—P2—C1—C9	50.2 (4)	C6—C5—C9—C1	−59.1 (7)
Pt1—P2—C1—C9	−179.5 (3)	C4—C5—C9—C1	68.7 (7)
C21—P2—C1—C8	176.9 (5)	C8—C1—C9—C5	60.2 (7)
C3—P2—C1—C8	−73.5 (6)	P2—C1—C9—C5	−67.8 (6)
Pt1—P2—C1—C8	56.9 (6)	C3—P2—C21—C26	39.5 (7)
C21—P2—C3—C4	68.0 (6)	C1—P2—C21—C26	146.6 (6)
C1—P2—C3—C4	−40.1 (6)	Pt1—P2—C21—C26	−85.3 (6)
Pt1—P2—C3—C4	−172.7 (4)	C3—P2—C21—C22	−146.2 (5)
P2—C3—C4—C10B	−92.1 (8)	C1—P2—C21—C22	−39.1 (6)
P2—C3—C4—C10A	178.3 (7)	Pt1—P2—C21—C22	89.0 (5)
P2—C3—C4—C5	43.4 (8)	C26—C21—C22—C23	−2.7 (9)
C10B—C4—C5—C6	−156.6 (8)	P2—C21—C22—C23	−177.3 (5)
C10A—C4—C5—C6	−65.9 (9)	C21—C22—C23—C24	0.8 (9)
C3—C4—C5—C6	70.7 (8)	C22—C23—C24—C25	1.0 (10)
C10B—C4—C5—C9	78.6 (9)	C23—C24—C25—C26	−0.6 (12)
C10A—C4—C5—C9	169.3 (7)	C24—C25—C26—C21	−1.5 (13)
C3—C4—C5—C9	−54.1 (8)	C22—C21—C26—C25	3.1 (11)
C9—C5—C6—C7	51.8 (7)	P2—C21—C26—C25	177.8 (7)
C4—C5—C6—C7	−75.0 (7)

Symmetry code: (i) y, x, −z.