cis-Dichloridobis{dimeth­yl[3-(9-phos­phabicyclo­[3.3.1]non-9-yl)propyl]amine-κP}platinum(II)

The title compound, [PtCl₂(C₁₃H₂₆NP)₂], is a rare example of a sterically bulky ligand adopting a cis geometry in a square-planar complex. It crystallizes on a twofold rotation axis which bisects the Pt centre and the P—Pt—P′ and Cl—Pt—Cl′ angles. The ligand exhibits a random packing disorder in the N,N-dimethyl­propyl­amine substituent, with the two orientations refining to occupancies of 0.404 (15) and 0.596 (15). Weak inter­molecular inter­actions between a Cl and a H atom of the ligand of a neighbouring mol­ecule result in extended chains along the a axis. The effective cone angle for the di­methyl[3-(9-phosphabicyclo­[3.3.1]non-9-yl)propyl]amine (Phoban[3.3.1]-C₃NMe₂) ligand was determined as being in the range 160–181°, depending on the choice of atoms used in the calculations.

S1. Comment

Phoban ligands are derived from the radical addition reaction of cis,cis-1,5-cyclooctadiene with an RPH₂ moiety (R = H or other suitable monoanionic group such as alkyl or aryl). A mixture of symmetrical and unsymmetrical adducts is obtained, 9-R-9-phosphabicyclo[3.3.1]nonane and 9-R-9-phosphabicyclo[4.2.1]nonane, respectively (Van Winkle et al., 1969). It has been shown that the two isomers may be conveniently separated by selective protonation and aqueous extraction of the [3.3.1] isomer, which is substantially more basic than the [4.2.1] isomer (Eberhard et al., 2005). These ligands are of significant industrial importance in a number of homogeneously catalysed processes, most notably modified cobalt hydroformylation, as used by Shell (Van Winkle et al., 1969).

We previously conducted a systematic evaluation of the steric and electronic aspects of these ligands (Bungu & Otto, 2007a) through their respective phosphine selenides. In addition, their catalytic performance was evaluated in phosphine modified cobalt hydroformylation reactions (Bungu & Otto, 2007b). The Phoban-C₃NMe₂ ligand (both isomers) represents an interesting derivative, since it contains a tertiary alkyl amine substituent that could potantially coordinate to metal centres in addition to the P atom. It could also act as a hemilabile pendant group or facilitate intermolecular interactions with substrate molecules in solution.

In order to investigate the coordination mode of these ligands, we reacted PtCl₂(COD) with a solution containing a mixture of both ligand isomers totalling two molar equivalents. Crystals of the the title compound, (I), were obtained from the reaction mixture after slow evaporation of about 60% of the solvent. Even though ³¹P NMR analysis indicated a mixture of species in solution, crystals of (I) suitable for X-ray diffraction were selectively obtained at this point. This is in accordance with our previous work (Bungu & Otto, 2007a,b), where the [3.3.1] isomers of different Phoban derivatives were found to display a higher degree of crystallinity than the corresponding [4.2.1] isomers.

Compound (I) crystallizes with a distorted square-planar geometry on a twofold rotation axis running through the Pt metal centre and bisecting the P1—Pt—P1ⁱ and Cl1—Pt—Cl1ⁱ [symmetry code: (i) x, -y, 1/2 - z] angles (see Fig. 1). The bulky ligands adopt the thermodynamically preferred cis orientation (from a bond energy perspective), as opposed to a sterically governed trans orientation. The ligand exhibits a random packing disorder in the N,N-dimethylpropylamine substituent, with the two orientations refining to occupancies of 0.406 (14) and 0.594 (15) for fragments A and B, respectively (see Fig. 2).

The Pt1—P1 and Pt1—Cl1 bond distances within the coordination polyhedron are within the expected ranges at 2.2571 (11) and 2.3612 (11) Å respectively (Table 2). All bond angles in the coordination environment of the metal centre deviate significantly from what would be expected for a square-planar geometry. The large P1—Pt—P1ⁱ angle of 97.47 (6)° and the small Cl1—Pt—Cl1ⁱ angle of 86.23 (6)° are a reflection of the steric impact of the two bulky phosphine ligands in close proximity. In general, the cis–trans geometry is governed by both the steric and electronic properties of the ligands. Strongly coordinating ligands, such as phosphines, would prefer a cis orientation, but increased steric demand of the ligands may result in a trans geometry being adopted. Compound (I) represents a rare example in which sterically bulky ligands (effective cone angle in the range 160–181°) display a cis geometry. In comparison, the trans isomer was obtained in trans-[PtCl₂(PBz₃)₂] (PBz₃ is tribenzylphosphine) where effective cone angles of 160 and 162° was calculated for two independant molecules in the unit cell (Johansson et al., 2002).All P—C bond distances and C—P—C angles are within normal ranges for molecules such as these (Bungu & Otto, 2007a,b).

The orientation of the phosphine ligands seems to be directed by an intramolecular interaction between the H atom on atom C15 and atom Cl1 [Cl1···C15 = 3.234 (5) Å, Cl1···H15 = 2.72 Å and Cl1···H15—C15 = 114°]. This results in the smaller sections of the ligands facing each other, with the larger C₃NMe₂ substituents occupying opposite sides of the equatorial plane. In addition, weak intermolecular interactions are observed between Cl1 and H11ⁱⁱ [symmetry code: (ii) x - 1/2, -y, z] of a neighboring molecule, creating infinite chains along the a axis (Fig. 3) [Cl1···C11 = 3.562 (5) Å, Cl1···H11 = 2.75 Å and Cl1···H11—C11 = 141°]. No close interactions were found between the amine functional group and a Pt or Cl atom.

Describing the steric demand of phosphine ligands has been the topic of many studies and a variety of models have been developed in this regard (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. According to this model, a cylindical cone is constructed from a point 2.28 Å from P, just touching the van der Waals radii of the outermost atoms of the ligand. In addition, all substituents on P should be adjusted to occupy the smallest possible space; since ball-and-stick models were originally used, this could be done manually. In the case of tri-n-alkyl phosphines, this would thus result in all ligands containing alkyl chains with C > 2 having the same steric demand as PEt₃, since the rest of the chain would fall within the `slipstream' of the ligand. With the development of user-friendly graphics software for crystallography, it has become more common to determine cone angles using the geometry obtained during a crystal structure determination. This principle has been further developed (Otto, 2001) into the concept of the `effective cone angle', where the crystallographically determined metal—P bond distance is used and the cone is determined as that touching the van der Waals radii of the outermost atoms of the ligand. In this regard, using the Pt—P bond distance obtained in this study, but calculating the cone to the outermost H atoms on C22A and C22B (as representative of the N,N-dimethylpropylamine substituent), results in values of 168 and 160° for orientations A and B, respectively. Even though quite a distance removed from Pt (±4.2–4.7 Å), the outermost point on this substituent is, however, an H atom on one of the Me groups on the amine, and using this in the calculations results in values of 179 and 181° for orientations A and B, respectively. These values should be regarded with some caution when interpreting metal reactivities in terms of the steric bulk of the ligands, as they may not reflect the true environment surrounding the metal.

S2. Experimental

The Phoban-C₃NMe₂ ligand (mixture of isomers) was prepared as described previously (Bungu & Otto, 2007a). 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-1,5-cyclooctadiene) (125 mg, 0.33 mmol) was dissolved in dichloromethane (5 ml) and a dichloromethane solution of the ligand mixture (1.08 ml, 618 mM, 0.67 mmol) was subsequently added. The resulting reaction mixture was stirred overnight and a portion was subjected to ³¹P NMR analysis. ³¹P (CDCl₃, δ, p.p.m.): cis-[PtCl₂(Phoban[4.2.1]-C₃NMe₂)₂] -0.40 (t, ¹J_Pt—P = 3536 Hz); cis-[PtCl₂(Phoban[3.3.1]-C₃NMe₂)₂] 29.79 (t, ¹J_Pt—P = 3432 Hz); cis-[PtCl₂(Phoban[3.3.1]-C₃NMe₂)(Phoban[4.2.1]-C₃NMe₂)] 1.76 ([4.2.1]-isomer, td, ¹J_Pt—P = 3524 Hz, ²J_P—P = 15 Hz), 31.31 ([3.3.1]-isomer, td, ¹J_Pt—P = 3443 Hz, ²J_P—P = 15 Hz). Slow evaporation of the solvent (dichloromethane) from the residual reaction mixture resulted in crystals of compound (I) being obtained.

S3. Refinement

The random packing disorder in the N,N-dimethylpropylamine part of the ligand was refined by the use of a free variable in the positions of the two orientations, adding up to unity occupancy over the two sites. Occupancies of 0.406 (14) and 0.594 (15) were obtained for fragments A and B, respectively. No restraints were required to stabilize the refinement. It was, however, noted that the C21—C22A and C21—C22B bond distances differed significantly [0.190 (16)Å] and a similarity restraint was subsequently introduced for these two bonds. The restraint did not have a marked effect on the geometrical parameters within the coordination polyhedron, or on the refinement statistics. All H atoms were placed in geometrically idealized positions, with C—H distances of 0.98 for CH, 0.97 for CH₂ or 0.96 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. The maximum residual electron density of 1.62 e Å^-3 is located 0.83 Å from the Pt atom.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) 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 & Berndt, 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 30% probability level. H atoms and the disorder have been omitted for clarity. [Symmetry code: (i) x, -y, 1/2 - z.]
	Fig. 2. A perspective view illustrating the disorder in the N,N-dimethylpropylamine substituent of (I). The occupancy for orientation A (shaded octants) refined to 0.406 (14) and that for orientation B (open spheres and bonds) to 0.596 [0.594</span><span style=" font-weight:600;">(15) elsewhere - please check]. H atoms and the rest of the molecule have been omitted for clarity.
	Fig. 3. Extended molecular chains in the a-axis direction due to weak intermolecular interactions between atom Cl1 and atom H11^ii of an adjacent molecule [symmetry code: (ii) x-0.5, -y, z]. H atoms not involved in the interactions were removed for clarity.

cis-Dichloridobis{dimethyl[3-(9-phosphabicyclo[3.3.1]non-9- yl)propyl]amine-κP}platinum(II)

Crystal data

[PtCl2(C13H26NP)2]	Dx = 1.614 Mg m^−3
Mr = 720.63	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Ibca	Cell parameters from 6026 reflections
a = 14.9247 (7) Å	θ = 2.7–27.2°
b = 19.0706 (9) Å	µ = 5.04 mm^−1
c = 20.8432 (10) Å	T = 100 K
V = 5932.5 (5) Å^3	Plate, colourless
Z = 8	0.12 × 0.11 × 0.05 mm
F(000) = 2912

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer	3700 independent reflections
Radiation source: fine-focus sealed tube	2384 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 8.4 pixels mm^-1	θmax = 28.3°, θmin = 2.0°
ϕ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −22→25
Tmin = 0.651, Tmax = 0.873	l = −27→22
29798 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0262P)^2 + 29P] where P = (Fo^2 + 2Fc^2)/3
3700 reflections	(Δ/σ)max = 0.002
202 parameters	Δρmax = 1.62 e Å^−3
1 restraint	Δρmin = −0.57 e Å^−3

Special details

Experimental. The intensity data were collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 200 s/frame with a frame width of 0.5°; a total of 1066 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 > 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	0.792227 (14)	0.0000	0.2500	0.02852 (7)
P1	0.89198 (7)	0.07137 (6)	0.20141 (5)	0.0306 (2)
Cl1	0.67673 (7)	0.07303 (7)	0.21088 (6)	0.0429 (3)
C11	0.9907 (3)	0.0316 (3)	0.1630 (2)	0.0417 (12)
H11	1.0248	0.0065	0.1960	0.050*
C12	1.0505 (4)	0.0872 (3)	0.1343 (3)	0.0599 (16)
H12A	1.0734	0.1155	0.1694	0.072*
H12B	1.1015	0.0636	0.1152	0.072*
C13	1.0140 (5)	0.1352 (4)	0.0862 (3)	0.0704 (18)
H13A	1.0099	0.1107	0.0455	0.084*
H13B	1.0552	0.1740	0.0807	0.084*
C14	0.9243 (4)	0.1634 (3)	0.1031 (3)	0.0524 (14)
H14A	0.9006	0.1862	0.0651	0.063*
H14B	0.9331	0.1996	0.1351	0.063*
C15	0.8520 (3)	0.1147 (3)	0.1281 (2)	0.0406 (12)
H15	0.7995	0.1431	0.1391	0.049*
C16	0.8223 (4)	0.0576 (3)	0.0796 (2)	0.0579 (16)
H16A	0.7977	0.0807	0.0421	0.070*
H16B	0.7744	0.0305	0.0989	0.070*
C17	0.8971 (4)	0.0058 (3)	0.0569 (2)	0.0576 (15)
H17A	0.8692	−0.0329	0.0343	0.069*
H17B	0.9359	0.0299	0.0268	0.069*
C18	0.9553 (4)	−0.0242 (3)	0.1123 (3)	0.0580 (17)
H18A	1.0066	−0.0479	0.0937	0.070*
H18B	0.9204	−0.0592	0.1350	0.070*
C21	0.9289 (3)	0.1431 (3)	0.2527 (2)	0.0407 (10)
H21A	0.9743	0.1266	0.2823	0.049*
H21B	0.9545	0.1803	0.2268	0.049*
C22A	0.8480 (10)	0.1706 (11)	0.2897 (9)	0.058 (5)	0.404 (15)
H22A	0.8086	0.1969	0.2616	0.070*	0.404 (15)
H22B	0.8145	0.1322	0.3084	0.070*	0.404 (15)
C23A	0.8856 (12)	0.2177 (9)	0.3417 (9)	0.043 (4)	0.404 (15)
H23A	0.9274	0.1912	0.3678	0.051*	0.404 (15)
H23B	0.9182	0.2561	0.3221	0.051*	0.404 (15)
N1A	0.8161 (9)	0.2453 (7)	0.3818 (5)	0.049 (4)	0.404 (15)
C24A	0.8551 (14)	0.2994 (10)	0.4236 (8)	0.070 (6)	0.404 (15)
H24A	0.8949	0.2777	0.4539	0.106*	0.404 (15)
H24B	0.8081	0.3232	0.4462	0.106*	0.404 (15)
H24C	0.8880	0.3324	0.3981	0.106*	0.404 (15)
C25A	0.7860 (18)	0.1905 (14)	0.4232 (10)	0.093 (8)	0.404 (15)
H25A	0.7608	0.1532	0.3980	0.140*	0.404 (15)
H25B	0.7414	0.2085	0.4520	0.140*	0.404 (15)
H25C	0.8358	0.1728	0.4475	0.140*	0.404 (15)
C22B	0.8536 (7)	0.1974 (6)	0.2644 (6)	0.049 (3)	0.596 (15)
H22C	0.8508	0.2277	0.2271	0.059*	0.596 (15)
H22D	0.7972	0.1721	0.2663	0.059*	0.596 (15)
C23B	0.8592 (10)	0.2443 (7)	0.3241 (7)	0.060 (4)	0.596 (15)
H23C	0.9135	0.2722	0.3219	0.073*	0.596 (15)
H23D	0.8087	0.2763	0.3243	0.073*	0.596 (15)
C24B	0.8762 (10)	0.2511 (11)	0.4359 (6)	0.099 (6)	0.596 (15)
H24D	0.9272	0.2798	0.4261	0.148*	0.596 (15)
H24E	0.8880	0.2243	0.4739	0.148*	0.596 (15)
H24F	0.8248	0.2804	0.4427	0.148*	0.596 (15)
C25B	0.7715 (9)	0.1690 (8)	0.3927 (7)	0.065 (4)	0.596 (15)
H25D	0.7245	0.2034	0.3937	0.098*	0.596 (15)
H25E	0.7721	0.1436	0.4325	0.098*	0.596 (15)
H25F	0.7612	0.1370	0.3580	0.098*	0.596 (15)
N1B	0.8593 (6)	0.2046 (6)	0.3835 (4)	0.054 (3)	0.596 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01746 (11)	0.04199 (13)	0.02612 (11)	0.000	0.000	0.00331 (12)
P1	0.0225 (5)	0.0449 (6)	0.0244 (5)	0.0001 (5)	−0.0020 (4)	0.0049 (5)
Cl1	0.0214 (5)	0.0537 (7)	0.0536 (7)	0.0021 (5)	−0.0024 (5)	0.0118 (6)
C11	0.023 (2)	0.068 (3)	0.035 (2)	0.006 (2)	0.005 (2)	0.018 (2)
C12	0.051 (3)	0.090 (5)	0.039 (3)	−0.021 (3)	0.015 (3)	0.000 (3)
C13	0.074 (5)	0.073 (4)	0.064 (4)	−0.008 (4)	0.007 (3)	0.007 (4)
C14	0.060 (4)	0.054 (3)	0.043 (3)	0.000 (3)	0.008 (3)	0.013 (3)
C15	0.035 (3)	0.057 (3)	0.029 (2)	0.006 (2)	−0.0034 (19)	0.009 (2)
C16	0.047 (3)	0.103 (5)	0.023 (2)	−0.008 (3)	−0.005 (2)	0.005 (3)
C17	0.064 (4)	0.077 (4)	0.031 (2)	−0.023 (4)	0.007 (2)	−0.014 (3)
C18	0.078 (4)	0.049 (3)	0.046 (3)	0.010 (3)	0.034 (3)	0.010 (2)
C21	0.039 (2)	0.051 (3)	0.033 (2)	−0.007 (2)	−0.013 (2)	0.006 (2)
C22A	0.070 (11)	0.074 (12)	0.030 (9)	−0.019 (9)	0.015 (7)	−0.014 (8)
C23A	0.041 (9)	0.040 (10)	0.048 (11)	0.002 (7)	−0.004 (8)	−0.019 (8)
N1A	0.054 (8)	0.054 (8)	0.040 (7)	0.015 (7)	−0.003 (6)	−0.012 (6)
C24A	0.088 (14)	0.070 (12)	0.054 (9)	0.038 (10)	−0.039 (9)	−0.016 (8)
C25A	0.11 (2)	0.109 (18)	0.057 (13)	−0.010 (15)	0.010 (13)	−0.037 (13)
C22B	0.038 (5)	0.070 (7)	0.040 (8)	−0.008 (5)	0.005 (4)	−0.016 (5)
C23B	0.069 (10)	0.046 (8)	0.066 (9)	−0.005 (6)	0.002 (7)	−0.008 (6)
C24B	0.080 (9)	0.155 (16)	0.061 (8)	0.027 (11)	−0.015 (7)	−0.054 (10)
C25B	0.046 (7)	0.083 (9)	0.068 (9)	−0.001 (6)	0.006 (6)	0.009 (7)
N1B	0.052 (6)	0.082 (7)	0.028 (4)	0.018 (5)	−0.001 (4)	−0.005 (4)

Geometric parameters (Å, º)

Pt1—P1^i	2.2571 (11)	C21—C22A	1.525 (10)
Pt1—P1	2.2571 (11)	C21—C22B	1.547 (9)
Pt1—Cl1^i	2.3614 (11)	C21—H21A	0.9700
Pt1—Cl1	2.3614 (11)	C21—H21B	0.9700
P1—C11	1.840 (5)	C22A—C23A	1.52 (2)
P1—C15	1.837 (4)	C22A—H22A	0.9700
P1—C21	1.821 (5)	C22A—H22B	0.9700
Cl1—H11^ii	2.7454	C23A—N1A	1.43 (2)
Cl1—C11^ii	3.562 (5)	C23A—H23A	0.9700
Cl1—H15	2.7163	C23A—H23B	0.9700
Cl1—C15	3.234 (5)	N1A—C25A	1.43 (3)
C11—C12	1.510 (7)	N1A—C24A	1.471 (19)
C11—C18	1.589 (8)	C24A—H24A	0.9600
C11—H11	0.9800	C24A—H24B	0.9600
C12—C13	1.462 (8)	C24A—H24C	0.9600
C12—H12A	0.9700	C25A—H25A	0.9600
C12—H12B	0.9700	C25A—H25B	0.9600
C13—C14	1.486 (8)	C25A—H25C	0.9600
C13—H13A	0.9700	C22B—C23B	1.536 (17)
C13—H13B	0.9700	C22B—H22C	0.9700
C14—C15	1.515 (7)	C22B—H22D	0.9700
C14—H14A	0.9700	C23B—N1B	1.450 (17)
C14—H14B	0.9700	C23B—H23C	0.9700
C15—C16	1.551 (7)	C23B—H23D	0.9700
C15—H15	0.9800	C24B—N1B	1.429 (14)
C16—C17	1.564 (8)	C24B—H24D	0.9600
C16—H16A	0.9700	C24B—H24E	0.9600
C16—H16B	0.9700	C24B—H24F	0.9600
C17—C18	1.554 (8)	C25B—N1B	1.489 (15)
C17—H17A	0.9700	C25B—H25D	0.9600
C17—H17B	0.9700	C25B—H25E	0.9600
C18—H18A	0.9700	C25B—H25F	0.9600
C18—H18B	0.9700
P1^i—Pt1—P1	97.46 (6)	C16—C17—H17A	108.7
P1^i—Pt1—Cl1^i	88.33 (4)	C18—C17—H17B	108.7
P1—Pt1—Cl1^i	172.79 (4)	C16—C17—H17B	108.7
P1^i—Pt1—Cl1	172.79 (4)	H17A—C17—H17B	107.6
P1—Pt1—Cl1	88.33 (4)	C17—C18—C11	115.7 (4)
Cl1^i—Pt1—Cl1	86.23 (6)	C17—C18—H18A	108.4
C11—P1—C21	108.9 (2)	C11—C18—H18A	108.4
C11—P1—C15	94.8 (2)	C17—C18—H18B	108.4
C15—P1—C21	104.4 (2)	C11—C18—H18B	108.4
C11—P1—Pt1	118.32 (17)	H18A—C18—H18B	107.4
C15—P1—Pt1	115.50 (16)	C22A—C21—P1	108.4 (7)
C21—P1—Pt1	112.89 (16)	C22B—C21—P1	112.1 (5)
Pt1—Cl1—H15	89.3	C22A—C21—H21A	110.0
Pt1—Cl1—H11^ii	108.4	C22B—C21—H21A	128.6
H15—Cl1—H11^ii	140.0	P1—C21—H21A	110.0
Pt1—Cl1—C15	74.85 (9)	C22A—C21—H21B	110.0
H11^ii—Cl1—C15	138.0	C22B—C21—H21B	83.4
Pt1—Cl1—C11^ii	109.61 (10)	P1—C21—H21B	110.0
H11^ii—Cl1—C11^ii	9.9	H21A—C21—H21B	108.4
C15—Cl1—C11^ii	128.24 (12)	C23A—C22A—C21	105.8 (12)
C12—C11—C18	113.8 (4)	C23A—C22A—H22A	110.6
C12—C11—P1	110.8 (4)	C21—C22A—H22A	110.6
C18—C11—P1	107.4 (3)	C23A—C22A—H22B	110.6
C12—C11—H11	108.2	C21—C22A—H22B	110.6
C18—C11—H11	108.2	H22A—C22A—H22B	108.7
P1—C11—H11	108.2	N1A—C23A—C22A	111.5 (13)
C13—C12—C11	119.4 (5)	N1A—C23A—H23A	109.3
C13—C12—H12A	107.5	C22A—C23A—H23A	109.3
C11—C12—H12A	107.5	N1A—C23A—H23B	109.3
C13—C12—H12B	107.5	C22A—C23A—H23B	109.3
C11—C12—H12B	107.5	H23A—C23A—H23B	108.0
H12A—C12—H12B	107.0	C25A—N1A—C23A	108.1 (17)
C12—C13—C14	113.6 (5)	C25A—N1A—C24A	106.2 (13)
C12—C13—H13A	108.8	C23A—N1A—C24A	108.5 (13)
C14—C13—H13A	108.8	C23B—C22B—C21	118.6 (9)
C12—C13—H13B	108.8	C23B—C22B—H22C	107.7
C14—C13—H13B	108.8	C21—C22B—H22C	107.7
H13A—C13—H13B	107.7	C23B—C22B—H22D	107.7
C13—C14—C15	120.1 (5)	C21—C22B—H22D	107.7
C13—C14—H14A	107.3	H22C—C22B—H22D	107.1
C15—C14—H14A	107.3	N1B—C23B—C22B	112.8 (10)
C13—C14—H14B	107.3	N1B—C23B—H23C	109.0
C15—C14—H14B	107.3	C22B—C23B—H23C	109.0
H14A—C14—H14B	106.9	N1B—C23B—H23D	109.0
C14—C15—C16	114.2 (4)	C22B—C23B—H23D	109.0
C14—C15—P1	109.3 (3)	H23C—C23B—H23D	107.8
C16—C15—P1	108.6 (4)	N1B—C24B—H24D	109.5
C14—C15—Cl1	155.5 (4)	N1B—C24B—H24E	109.5
C16—C15—Cl1	86.8 (3)	H24D—C24B—H24E	109.5
P1—C15—Cl1	73.01 (15)	N1B—C24B—H24F	109.5
C14—C15—H15	108.2	H24D—C24B—H24F	109.5
C16—C15—H15	108.2	H24E—C24B—H24F	109.5
P1—C15—H15	108.2	N1B—C25B—H25D	109.5
Cl1—C15—H15	50.4	N1B—C25B—H25E	109.5
C15—C16—C17	115.9 (4)	H25D—C25B—H25E	109.5
C15—C16—H16A	108.3	N1B—C25B—H25F	109.5
C17—C16—H16A	108.3	H25D—C25B—H25F	109.5
C15—C16—H16B	108.3	H25E—C25B—H25F	109.5
C17—C16—H16B	108.3	C24B—N1B—C23B	109.1 (11)
H16A—C16—H16B	107.4	C24B—N1B—C25B	109.9 (10)
C18—C17—C16	114.0 (4)	C23B—N1B—C25B	110.4 (11)
C18—C17—H17A	108.7

Symmetry codes: (i) x, −y, −z+1/2; (ii) x−1/2, −y, z.