trans-Chloridobis[(Z)-1-imino-1-meth­oxy­ethane-κN](triphenyl­phosphane-κP)platinum(II) chloride monohydrate

The title compound, [PtCl(C₃H₇NO)₂(C₁₈H₁₅P)]Cl·H₂O or trans-[PtCl{Z-HN=C(Me)OMe}₂(PPh₃)]Cl·H₂O, crystallizes from an acetone solution of isomeric trans-[PtCl{E-HN=C(Me)OMe}₂(PPh₃)]Cl. The two HN=C(Me)OMe ligands show typical π-bond delocalization over the N—C—O group [Cini, Caputo, Intini & Natile (1995). Inorg. Chem. 34, 1130–1137] and have the unprecedented Z–anti configuration. The relative orientation of the imino ether ligands is head-to-tail.

S1. Comment

The development of new platinum drugs is ongoing, in order to provide agents which are less toxic than cisplatin, cis-[PtCl₂(NH₃)₂] (cis-DDP), and active against different types of tumours (Fuertes et al., 2003). Moreover, since the ultimate target appears to be nuclear DNA, the interaction of platinum complexes in the oxidation states II and IV (Hall & Hambley, 2002) with model nucleosides and nucleotides has been investigated in great detail (Ali et al., 2005; Shen & Lippert, 2008; Suzuky et al., 1998; Yamanari et al., 2003; Messere et al., 2007; Mikola et al., 2000).

Apart from amines, other neutral ligands such as phosphines have been exploited and one phosphine compound, the cisplatin analogue cis-Pt(PR₃)₂Cl₂ [R = what?], has also been widely investigated in relation to its reactivity with nucleobases (Longato et al., 2006). In particular, the mixed phosphine/nucleobase complex cis-bis(triphenylphosphine)-[N-(1-methyl-2-oxo-2,3-1H-pyrimidin-4-ylidene)benzamidine]platinum(II) nitrate exhibits high antitumour activity (Montagner et al., 2011).

Although early structure–activity relationships suggested that a cis geometry was required for antitumour activity of platinum complexes, more recently some platinum compounds with a trans geometry have been found to possess remarkable antitumour properties (Kalinowska-Lis et al., 2008; Coluccia & Natile, 2007). Among these, the trans-[PtCl₂(iminoether)₂] complexes were the first for which significant in vivo antitumour activity was reported (Coluccia et al., 1995; Leng et al., 2000). Iminoether ligands can have either an E or a Z configuration, depending on the positions of the substituents with respect to the C═N double bond (Scheme 2). The thermodynamic stability depends on the size of the alkyl substituents. In the case of methyl substituents, the E configuration is the most stable.

In an investigation aimed at the synthesis of mixed iminoether/phosphine complexes, we synthesized the complex trans-[PtCl{E-HN═ C(Me)OMe}₂(PPh₃)].Cl.H₂O. However, on crystallization from acetone, a complex in which the iminoether ligands had switched to the less stable Z configuration was obtained, the title compound, (I) (Scheme 1). The structural characterization of this compound has been undertaken to clarify the reason for such an isomerization.

Complex (I) has a square-planar coordination geometry (Fig. 1). The trans Pt—P and Pt—Cl bond distances (Table 1) fall in the range previously observed in cis-dichloridobis(triphenylphosphine)platinum(II), cis-chlorido(1,2,3,6-tetrahydro-3,7-dimethylpurine-2,6-dionato-κN¹)bis(triphenylphosphine-κP)platinum(II) and cis-chlorido(3-hydroxypicolinato-N)bis(triphenylphosphine)platinum(II), where the Pt—Cl and Pt—P bond distances are ca 2.35 (1) and 2.25 (1) Å, respectively (Anderson et al., 1982; Dubler et al., 2002; Quintal et al., 2000). The two iminoether ligands have similar geometric parameters. The N—C, Csp²—O and Csp³—O bond distances [average values 1.27 (1), 1.33 (1) and 1.45 (1) Å, respectively] and the Pt—N—C and N—C—C angles [average values 128.5 (3) and 123.0 (4)°, respectively] are similar to those previously observed in cis- and trans-bis(E-1-imino-1-methoxyethane)dichloridoplatinum(II) (Cini et al., 1995), in tetrakis(E-1-ethoxy-1-iminopropane)platinum bis(trifluoromethanesulfonate) (Prenzler et al., 1997) and in trans-dichloridobis(Z-1-imino-1-methoxy-2,2'-dimethylpropane)platinum(II) (Gonzalez et al., 2002), and are in accord with a π-bond delocalized over the N—C—O group.

The iminoether ligands of (I) have the unprecedented Z-anti configuration (Scheme 2). A Z configuration was observed in our previous paper reporting the X-ray structure of the complex trans-[PtCl₂{Z-HN═C(^tBu)OMe}₂] (Gonzalez et al., 2002), but the conformation was syn and not anti as in the present case. In the previously reported Z-iminoether complex there was a ^tBu substituent on the C atom of the N≐C≐O group and the steric bulkiness of ^tBu was considered responsible for stabilization of the Z configuration (^tBu trans to the metal core with respect to the C═N double bond) over the E configuration (^tBu cis to the metal core). In that case the bulkiness of ^tBu could also be responsible for the stabilization of the syn conformation (the Me on the O atom cis to Pt with respect to the N≐C≐O group and trans to ^tBu with respect to the C≐O quasi-double bond). However, in the present case of a small Me on the C atom of the N≐C≐O group, there is no steric interaction which can account for the stabilization of the Z configuration, as also witnessed by the anti conformation of the O—Me (O—Me cis to C—Me with respect to the C≐O quasi-double bond and trans to Pt with respect to the planar N≐C≐O group). Why, then, does the presence of a PPh₃ group in the coordination environment of Pt stabilize the Z configuration of the iminoether, accompanied by the anti conformation of the O—Me group? Our hypothesis is that replacement of a chloride anion by a phosphine ligand has the effect of increasing the net positive charge on Pt and possibly of decreasing the dieletric constant around the metal core, so favouring electrostatic interactions. Among these is the interaction between the lone pair of electrons on the O atom and the positively charged metal core. This obviously requires the iminoether to assume a Z-anti configuration. This hypothesis appears to be supported by the observation that the Cl^- counterion is the acceptor of three hydrogen bonds involving the iminic N atom of two adjacent complex molecules and the solvent water molecule, which bridges the Cl^- counterion with the chloride ligand. Such a hydrogen-bond network would be favoured by a local decrease in the dieletric constant.

The relative orientations of the imino ether ligands can be head-to-head (HH) or head-to-tail (HT) (Scheme 2). In (I), the relative orientation of the imino ether ligands is HT. The two imino ether ligands are almost coplanar [dihedral angle 8.9 (2)°] and the dihedral angles between their planes and the coordination plane are 74.9 (2) and 69.0 (2)°.

Fig. 2 shows the chloride anion interacting with the N—H groups of two iminoether ligands from two adjacent complex molecules and a water molecule as a trifurcated acceptor, Cl···H—X, with Cl···X distances of 3.293 (3), 3.264 (4) and 3.338 (5) Å for X = N, N and O, respectively, and Cl···H—X angles in the range 166 (2)–169 (2)°. Weaker C—H···Cl hydrogen bonds (Table 2) are apparent between aryl or methyl C—H groups and the chloride anion.

Related literature

For related literature, see: Ali et al. (2005); Anderson et al. (1982); Cini et al. (1995); Coluccia & Natile (2007); Coluccia et al. (1995); Dubler et al. (2002); Fuertes et al. (2003); Gonzalez et al. (2002); Hall & Hambley (2002); Kalinowska-Lis, Ochocki & Matlawska-Wasowska (2008); Leng et al. (2000); Longato et al. (2006); Messere et al. (2007); Mikola et al. (2000); Montagner et al. (2011); Prenzler et al. (1997); Quintal et al. (2000); Sheldrick (2008); Shen & Lippert (2008); Suzuky et al. (1998); Yamanari et al. (2003).

S2. Experimental

For the preparation of trans-[PtCl{E-HN═ C(Me)OMe}₂(PPh₃)]Cl, an Et₂O (5 ml) suspension of trans-[PtCl₂{E-HN═C(Me)OMe}₂] (100 mg, 0.24 mmol) was mixed with 1.2 equivalents of PPh₃ (73.4 mg, 0.29 mmol). After stirring for 12 h at room temperature, the suspension turned from yellow to white. The white solid, trans-[PtCl{E-HN═C(Me)OMe}₂(PPh₃)]Cl, was filtered off, washed with Et₂O (3 × 5 ml) and dried under vacuum (yield 159.9 mg, >98%). Single crystals of trans-[PtCl{Z-HN═ C(Me)OMe}₂(PPh₃)]Cl.H₂O suitable for X-ray diffraction analysis were obtained from trans-[PtCl{E-HN=C(Me)OMe}₂(PPh₃)]Cl (10.0 mg, 0.024 mmol) dissolved in acetone (2 ml), where it isomers to the E,Z and Z,Z species. The latter form, (I), is the less soluble and precipitates preferentially.

S3. Refinement

The H atoms of the imino groups and of the water molecule were found in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(parent). Soft distance restraints were applied to ensure suitable hydrogen-bond geometries for atoms H1W and H2W (Sheldrick, 2008). The other H atoms were included in idealized positions and constrained to ride on their parent atoms, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, and with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for the phenyl H atoms.

Computing details

Data collection: COSMO, APEX2 and BIS (Bruker, 2004); cell refinement: SAINT-IRIX (Bruker, 2004); data reduction: SAINT-IRIX (Bruker, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1983, 1995) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the hydrogen bonding (dashed lines) present in (I).

trans-Chloridobis[(Z)-1-imino-1-methoxyethane- κN](triphenylphosphane-κP)platinum(II) chloride monohydrate

Crystal data

[PtCl(C3H7NO)2(C18H15P)]Cl·H2O	F(000) = 1360
Mr = 692.47	Dx = 1.684 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 30501 reflections
a = 10.7361 (2) Å	θ = 1.8–30.5°
b = 17.1215 (2) Å	µ = 5.42 mm^−1
c = 15.6226 (2) Å	T = 294 K
β = 108.0087 (8)°	Prismatic, white
V = 2731.03 (7) Å^3	0.12 × 0.10 × 0.09 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	8334 independent reflections
Radiation source: fine-focus sealed tube	5675 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ and ω scans	θmax = 30.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.889, Tmax = 1.000	k = −24→24
30501 measured reflections	l = −22→22

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0214P)^2] where P = (Fo^2 + 2Fc^2)/3
8334 reflections	(Δ/σ)max = 0.002
314 parameters	Δρmax = 0.83 e Å^−3
4 restraints	Δρmin = −0.58 e Å^−3

Special details

Experimental. All H atoms (except those of the methyl group) were found in the difference Fourier map and and refined with a global isotropic displacement parameter with isotropic parameters equivalent to 1.2 times those of the atom to which they are attached (except for H1W and H2W). The positions of H1w and H2w atoms were restrained using the DANG instructions of the SHELXL97 program (Sheldrick, 2008). Final X—H distances varied from 0.82 (4) to 1.08 (4) Å. The H atoms of the methyl group have been included in idealized positions and constrained to ride on their parent atoms, with a C—H distance of 0.96 Å and with U_iso(H) = 1.5Ueq(C).

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
Pt1	0.474780 (15)	0.639305 (8)	0.262503 (10)	0.02790 (5)
Cl1	0.66397 (11)	0.66329 (6)	0.38493 (8)	0.0494 (3)
N1	0.5383 (4)	0.72129 (19)	0.1938 (2)	0.0358 (8)
H1	0.495 (4)	0.763 (2)	0.182 (3)	0.043*
N2	0.4236 (4)	0.55760 (17)	0.3381 (2)	0.0335 (8)
H2	0.475 (4)	0.517 (2)	0.354 (3)	0.040*
P1	0.29706 (10)	0.61815 (5)	0.14464 (7)	0.0286 (2)
C1	0.6304 (5)	0.7141 (2)	0.1593 (3)	0.0443 (11)
C2	0.6756 (5)	0.7779 (3)	0.1119 (3)	0.0638 (15)
H2A	0.6203	0.8227	0.1076	0.096*
H2B	0.6716	0.7608	0.0526	0.096*
H2C	0.7642	0.7915	0.1449	0.096*
C3	0.8019 (7)	0.6321 (3)	0.1438 (6)	0.121 (3)
H3A	0.7825	0.6425	0.0806	0.182*
H3B	0.8308	0.5790	0.1560	0.182*
H3C	0.8697	0.6668	0.1773	0.182*
C4	0.3323 (5)	0.5578 (2)	0.3742 (3)	0.0378 (10)
C5	0.3099 (5)	0.4923 (2)	0.4299 (3)	0.0539 (13)
H5A	0.3752	0.4528	0.4349	0.081*
H5B	0.2246	0.4704	0.4020	0.081*
H5C	0.3154	0.5112	0.4888	0.081*
C6	0.1477 (6)	0.6250 (3)	0.3957 (5)	0.084 (2)
H6A	0.0870	0.5830	0.3740	0.126*
H6B	0.1033	0.6740	0.3792	0.126*
H6C	0.1831	0.6219	0.4601	0.126*
O1	0.6863 (3)	0.64405 (18)	0.1698 (3)	0.0639 (10)
O2	0.2535 (3)	0.61922 (16)	0.3561 (2)	0.0535 (9)
C7	0.2200 (4)	0.5243 (2)	0.1507 (3)	0.0332 (9)
C8	0.2947 (4)	0.4569 (2)	0.1648 (3)	0.0425 (11)
H8	0.3832	0.4601	0.1699	0.051*
C9	0.2405 (6)	0.3853 (2)	0.1713 (3)	0.0544 (14)
H9	0.2905	0.3401	0.1770	0.065*
C10	0.1126 (6)	0.3812 (3)	0.1692 (4)	0.0646 (16)
H10	0.0767	0.3330	0.1756	0.078*
C11	0.0367 (5)	0.4464 (3)	0.1580 (4)	0.0699 (17)
H11	−0.0502	0.4429	0.1570	0.084*
C12	0.0913 (5)	0.5187 (3)	0.1480 (3)	0.0534 (13)
H12	0.0399	0.5635	0.1395	0.064*
C13	0.3298 (4)	0.6192 (2)	0.0372 (3)	0.0323 (9)
C14	0.3523 (5)	0.6919 (2)	0.0027 (3)	0.0441 (11)
H14	0.3439	0.7375	0.0328	0.053*
C15	0.3868 (5)	0.6964 (3)	−0.0754 (3)	0.0540 (13)
H15	0.4043	0.7448	−0.0962	0.065*
C16	0.3953 (5)	0.6297 (3)	−0.1223 (3)	0.0597 (14)
H16	0.4172	0.6329	−0.1753	0.072*
C17	0.3711 (5)	0.5583 (3)	−0.0906 (3)	0.0538 (13)
H17	0.3749	0.5133	−0.1230	0.065*
C18	0.3410 (5)	0.5528 (2)	−0.0102 (3)	0.0439 (11)
H18	0.3283	0.5039	0.0117	0.053*
C19	0.1728 (4)	0.6935 (2)	0.1282 (3)	0.0325 (9)
C20	0.1858 (4)	0.7513 (2)	0.1925 (3)	0.0433 (11)
H20	0.2524	0.7488	0.2471	0.052*
C21	0.0974 (5)	0.8131 (3)	0.1738 (4)	0.0651 (16)
H21	0.1056	0.8521	0.2166	0.078*
C22	−0.0006 (5)	0.8179 (3)	0.0945 (4)	0.0653 (17)
H22	−0.0574	0.8603	0.0828	0.078*
C23	−0.0154 (5)	0.7600 (3)	0.0318 (4)	0.0628 (15)
H23	−0.0838	0.7625	−0.0219	0.075*
C24	0.0713 (4)	0.6976 (3)	0.0481 (3)	0.0495 (12)
H24	0.0611	0.6584	0.0052	0.059*
Cl2	0.59138 (13)	0.39386 (6)	0.35942 (9)	0.0528 (3)
O1W	0.8280 (6)	0.5086 (3)	0.3327 (5)	0.151 (3)
H1W	0.795 (6)	0.556 (3)	0.350 (6)	0.182*
H2W	0.774 (5)	0.473 (4)	0.347 (5)	0.182*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02826 (8)	0.02965 (7)	0.02617 (8)	−0.00112 (7)	0.00895 (6)	−0.00012 (7)
Cl1	0.0435 (7)	0.0570 (6)	0.0385 (7)	−0.0102 (5)	−0.0006 (5)	−0.0030 (5)
N1	0.036 (2)	0.0359 (18)	0.036 (2)	−0.0043 (15)	0.0126 (17)	0.0020 (16)
N2	0.041 (2)	0.0306 (17)	0.0274 (19)	0.0016 (15)	0.0089 (16)	0.0047 (14)
P1	0.0282 (5)	0.0299 (5)	0.0275 (6)	0.0009 (4)	0.0082 (4)	0.0010 (4)
C1	0.045 (3)	0.044 (2)	0.045 (3)	−0.009 (2)	0.017 (2)	−0.004 (2)
C2	0.065 (4)	0.076 (3)	0.061 (4)	−0.016 (3)	0.035 (3)	0.013 (3)
C3	0.109 (6)	0.085 (4)	0.219 (10)	0.017 (4)	0.124 (7)	−0.006 (5)
C4	0.051 (3)	0.033 (2)	0.029 (2)	−0.007 (2)	0.012 (2)	−0.0014 (17)
C5	0.072 (4)	0.047 (3)	0.049 (3)	−0.011 (2)	0.027 (3)	0.003 (2)
C6	0.078 (5)	0.093 (4)	0.103 (5)	0.024 (3)	0.059 (4)	0.012 (4)
O1	0.060 (2)	0.0545 (19)	0.095 (3)	0.0013 (18)	0.051 (2)	0.0012 (19)
O2	0.056 (2)	0.0528 (18)	0.063 (2)	0.0092 (16)	0.0343 (19)	0.0105 (16)
C7	0.031 (2)	0.036 (2)	0.030 (2)	−0.0038 (17)	0.0069 (18)	−0.0025 (17)
C8	0.043 (3)	0.042 (2)	0.041 (3)	0.005 (2)	0.011 (2)	0.003 (2)
C9	0.072 (4)	0.035 (2)	0.052 (3)	0.003 (2)	0.012 (3)	0.004 (2)
C10	0.074 (4)	0.041 (3)	0.066 (4)	−0.019 (3)	0.002 (3)	0.006 (2)
C11	0.039 (3)	0.069 (3)	0.098 (5)	−0.021 (3)	0.015 (3)	0.016 (3)
C12	0.039 (3)	0.046 (3)	0.074 (4)	−0.002 (2)	0.016 (3)	0.012 (2)
C13	0.031 (2)	0.039 (2)	0.027 (2)	0.0062 (17)	0.0103 (18)	0.0003 (16)
C14	0.055 (3)	0.042 (2)	0.034 (3)	0.006 (2)	0.013 (2)	0.006 (2)
C15	0.058 (3)	0.065 (3)	0.041 (3)	0.007 (3)	0.018 (3)	0.014 (2)
C16	0.064 (4)	0.085 (4)	0.037 (3)	0.019 (3)	0.025 (3)	0.014 (3)
C17	0.058 (3)	0.063 (3)	0.043 (3)	0.014 (3)	0.019 (3)	−0.008 (2)
C18	0.052 (3)	0.046 (2)	0.038 (3)	0.007 (2)	0.020 (2)	0.001 (2)
C19	0.033 (2)	0.0302 (19)	0.036 (2)	0.0003 (17)	0.0123 (19)	0.0028 (17)
C20	0.040 (3)	0.038 (2)	0.055 (3)	0.002 (2)	0.021 (2)	−0.005 (2)
C21	0.057 (4)	0.041 (3)	0.109 (5)	0.005 (3)	0.042 (4)	−0.013 (3)
C22	0.049 (3)	0.049 (3)	0.113 (5)	0.021 (3)	0.048 (4)	0.021 (3)
C23	0.034 (3)	0.086 (4)	0.067 (4)	0.021 (3)	0.014 (3)	0.023 (3)
C24	0.040 (3)	0.055 (3)	0.051 (3)	0.014 (2)	0.010 (2)	0.004 (2)
Cl2	0.0595 (8)	0.0423 (6)	0.0607 (8)	0.0027 (5)	0.0245 (7)	−0.0072 (5)
O1W	0.146 (5)	0.074 (3)	0.280 (8)	0.008 (3)	0.133 (5)	0.006 (4)

Geometric parameters (Å, º)

Pt1—N1	2.010 (3)	C8—H8	0.93
Pt1—N2	2.014 (3)	C9—C10	1.366 (7)
Pt1—P1	2.2338 (11)	C9—H9	0.93
Pt1—Cl1	2.3559 (11)	C10—C11	1.361 (7)
N1—C1	1.270 (5)	C10—H10	0.93
N1—H1	0.85 (4)	C11—C12	1.399 (6)
N2—C4	1.273 (5)	C11—H11	0.93
N2—H2	0.87 (4)	C12—H12	0.93
P1—C19	1.816 (4)	C13—C18	1.382 (5)
P1—C13	1.819 (4)	C13—C14	1.407 (5)
P1—C7	1.823 (4)	C14—C15	1.381 (6)
C1—O1	1.328 (5)	C14—H14	0.93
C1—C2	1.484 (6)	C15—C16	1.376 (6)
C2—H2A	0.96	C15—H15	0.93
C2—H2B	0.96	C16—C17	1.374 (6)
C2—H2C	0.96	C16—H16	0.93
C3—O1	1.435 (6)	C17—C18	1.393 (6)
C3—H3A	0.96	C17—H17	0.93
C3—H3B	0.96	C18—H18	0.93
C3—H3C	0.96	C19—C24	1.384 (6)
C4—O2	1.324 (5)	C19—C20	1.386 (5)
C4—C5	1.485 (5)	C20—C21	1.391 (6)
C5—H5A	0.96	C20—H20	0.93
C5—H5B	0.96	C21—C22	1.357 (7)
C5—H5C	0.96	C21—H21	0.93
C6—O2	1.455 (6)	C22—C23	1.367 (7)
C6—H6A	0.96	C22—H22	0.93
C6—H6B	0.96	C23—C24	1.389 (6)
C6—H6C	0.96	C23—H23	0.93
C7—C12	1.372 (6)	C24—H24	0.93
C7—C8	1.384 (5)	O1W—H1W	0.953 (16)
C8—C9	1.373 (6)	O1W—H2W	0.921 (16)
N1—Pt1—N2	175.94 (14)	C9—C8—C7	121.2 (4)
N1—Pt1—P1	90.99 (10)	C9—C8—H8	119.4
N2—Pt1—P1	93.01 (10)	C7—C8—H8	119.4
N1—Pt1—Cl1	87.84 (10)	C10—C9—C8	119.3 (4)
N2—Pt1—Cl1	88.16 (10)	C10—C9—H9	120.3
P1—Pt1—Cl1	178.81 (4)	C8—C9—H9	120.3
C1—N1—Pt1	126.6 (3)	C11—C10—C9	121.2 (4)
C1—N1—H1	116 (3)	C11—C10—H10	119.4
Pt1—N1—H1	117 (3)	C9—C10—H10	119.4
C4—N2—Pt1	130.2 (3)	C10—C11—C12	119.0 (5)
C4—N2—H2	113 (3)	C10—C11—H11	120.5
Pt1—N2—H2	117 (3)	C12—C11—H11	120.5
C19—P1—C13	101.86 (18)	C7—C12—C11	120.7 (4)
C19—P1—C7	107.93 (18)	C7—C12—H12	119.6
C13—P1—C7	106.09 (18)	C11—C12—H12	119.6
C19—P1—Pt1	113.85 (13)	C18—C13—C14	118.0 (4)
C13—P1—Pt1	113.57 (14)	C18—C13—P1	124.0 (3)
C7—P1—Pt1	112.69 (13)	C14—C13—P1	117.9 (3)
N1—C1—O1	114.6 (4)	C15—C14—C13	120.8 (4)
N1—C1—C2	123.9 (4)	C15—C14—H14	119.6
O1—C1—C2	121.4 (4)	C13—C14—H14	119.6
C1—C2—H2A	109.5	C16—C15—C14	120.3 (4)
C1—C2—H2B	109.5	C16—C15—H15	119.9
H2A—C2—H2B	109.5	C14—C15—H15	119.9
C1—C2—H2C	109.5	C17—C16—C15	119.7 (5)
H2A—C2—H2C	109.5	C17—C16—H16	120.2
H2B—C2—H2C	109.5	C15—C16—H16	120.2
O1—C3—H3A	109.5	C16—C17—C18	120.6 (4)
O1—C3—H3B	109.5	C16—C17—H17	119.7
H3A—C3—H3B	109.5	C18—C17—H17	119.7
O1—C3—H3C	109.5	C13—C18—C17	120.6 (4)
H3A—C3—H3C	109.5	C13—C18—H18	119.7
H3B—C3—H3C	109.5	C17—C18—H18	119.7
N2—C4—O2	115.9 (4)	C24—C19—C20	119.6 (4)
N2—C4—C5	122.9 (4)	C24—C19—P1	120.2 (3)
O2—C4—C5	121.1 (4)	C20—C19—P1	120.0 (3)
C4—C5—H5A	109.5	C19—C20—C21	118.8 (5)
C4—C5—H5B	109.5	C19—C20—H20	120.6
H5A—C5—H5B	109.5	C21—C20—H20	120.6
C4—C5—H5C	109.5	C22—C21—C20	121.6 (5)
H5A—C5—H5C	109.5	C22—C21—H21	119.2
H5B—C5—H5C	109.5	C20—C21—H21	119.2
O2—C6—H6A	109.5	C21—C22—C23	119.7 (5)
O2—C6—H6B	109.5	C21—C22—H22	120.1
H6A—C6—H6B	109.5	C23—C22—H22	120.1
O2—C6—H6C	109.5	C22—C23—C24	120.2 (5)
H6A—C6—H6C	109.5	C22—C23—H23	119.9
H6B—C6—H6C	109.5	C24—C23—H23	119.9
C1—O1—C3	119.4 (4)	C19—C24—C23	120.0 (5)
C4—O2—C6	119.7 (4)	C19—C24—H24	120.0
C12—C7—C8	118.4 (4)	C23—C24—H24	120.0
C12—C7—P1	121.9 (3)	H1W—O1W—H2W	100 (7)
C8—C7—P1	119.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···Cl2	0.92 (2)	2.44 (2)	3.337 (5)	167 (6)
N2—H2···Cl2	0.87 (4)	2.45 (4)	3.293 (3)	166 (4)
N1—H1···Cl2^i	0.85 (4)	2.43 (4)	3.262 (4)	168 (4)
C2—H2A···Cl2^i	0.96	2.76	3.627 (5)	150
C5—H5C···Cl2^ii	0.96	2.79	3.688 (5)	156
C16—H16···Cl2^iii	0.93	2.89	3.772 (5)	160
O1W—H1W···Cl1	0.95 (2)	2.48 (2)	3.416 (5)	168 (6)

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