Two polymorphs of potassium trichloro­[diethyl (methyl­sulfinyl­methyl)phosphonate-[kappa]S]platinum(II) with Z' = 1 and 3 in the space group P2₁2₁2₁

Two new polymorphs of the title compound, K[PtCl₃(C₆H₁₅O₄PS)], already known in the monoclinic form, were obtained by crystallization from acetone-n-pentane solutions of different composition. Both polymorphs are ortho­rhom­bic in the space group P2₁2₁2₁, with Z' = 1 (solvent ratio 1:4) and 3 (solvent ratio 1:9). In both polymorphs, electrostatic inter­actions link K⁺ cations and [PtCl₃(SMP)]^- anions [SMP is diethyl (methyl­sulfinyl­methyl)phosphonate] in infinite chains, while adjacent chains are held together by weak C-H...Cl and C-H...O hydrogen-bond inter­actions.

S1. Comment

Several compounds form different crystalline structures having the same molecular composition. This phenomenon, known as polymorphism, can stem from different possible ways of optimizing the intra and intermolecular interactions within the crystal packing. Several drugs used in clinical medicine show this peculiar behaviour. For instance, chloramfenicol palmitate exists in three crystalline forms and phenylbutazone in as many as five different polymorphic structures. Although the mode of interaction with the biological target(s) does not change, different polymorphic structures of a given drug can show a variety of chemico-physical properties (rate of dissolution in physiological media, bioavailability etc.) which can significantly influence the success of the pharmacological treatment (Aguiar et al., 1967; Foppoli et al., 2003; Kaliszan, 1986). It is generally accepted that, among different polymorphs, the best form is that with the greatest bioavailability, which usually coincides with the least stable crystalline form at room temperature.

Recently, we have proposed new Pt^II compounds containing diethyl[(methylsulfinyl)methyl]phosphonate, SMP (Laforgia et al., 2004), as antitumour drugs which may have a selective tropism for bone tissue (thanks to the phosphonate moiety) and which have shown interesting MMP inhibition activity (MMP is membrane metalloproteinase; Sasanelli et al., 2006). Our investigation has already led to the isolation and characterization of a monoclinic species, (Ia), K[PtCl₃(SMP)] (Laforgia et al., 2005). We now report the crystallographic analysis of two new orthorhombic polymorphs. The monoclinic form (space group P2₁/a, Z' = 1), (Ia) was obtained from a mixture of H₂O–acetone–CHCl₃ (Ratio?). However, if acetone–pentane is used as solvent, two orthorhombic polymorphs, having space group P2₁2₁2₁ and with Z' = 1 for (Ib) (solvent ratio 1:4) or 3 for (Ic) (solvent ratio 1:9), are obtained.

The bond lengths in the orthorhombic polymorphs (Ib) and (Ic) are very similar to those found in the monoclinic polymorph (Ia), and do not require further discussion. In contrast, the patterns of the supramolecular aggregations are very different for (Ia), (Ib) and (Ic), and these will be discussed here.

The simpler orthorhombic polymorph, (Ib) (Fig. 1), has Z' = 1 in space group P2₁2₁2₁. Each complex anion is linked to three K⁺ cations by way of the three Cl⁻ ligands (Cl1, Cl2, and Cl3) and the S═O and P═O O atoms of the SMP ligand (O1 and O2). Similar to the case of (Ia), the P═O O atom interacts with only one K⁺ cation. Atoms Cl1 and Cl2 interact with two K⁺ cations, while atom Cl3 interacts with only one K⁺ cation (Fig. 1). Each K⁺ cation is trapped in an irregular seven-donor cage formed by five Cl and two O atoms of three different anions, namely atoms Cl2, O1, and O2 of one platinum unit (Pt), atoms Cl1 and Cl3 of the second platinum unit (PtA), and atoms Cl1 and Cl2 of the third platinum unit (PtB). The K···O and K···Cl distances are reported in Table 1.

Electrostatic interactions link cations and anions in an infinite chain extending along the a direction (Fig. 2). Adjacent chains are held together by hydrogen-bond interactions of different strengths involving Cl1 atoms of one chain and C2 atoms of an adjacent chain, and atoms O2 and O1 of one chain and atoms C3 and C1 of an adjacent chain (Table 2). A view of the crystal packing along the a direction is shown in Fig. 3. In this polymorph, one ethyl group (C5/C5A and C6) is disordered, probably because it lacks significant intermolecular interactions.

The second orthorhombic polymorph, (Ic), has Z' = 3 in space group P2₁2₁2₁. Each independent anion interacts with three K⁺ cations by way of atoms Cl1, Cl2, O1 and O2 (Fig. 4). In two of the three independent anions (Pt1 and Pt1A), the ester atom O4 is also involved in electrostatic interactions with the K⁺ cations. In particular, two anions (Pt1A and Pt1B) have one K⁺ cation interacting with the S═ O and P═O O atoms of the SMP ligand and the Cl ligand cis to the sulfoxide [as observed in (Ia) and (Ib)], while the third anion (Pt), having the S═O and P═O O atoms more distant [O1···O2 = 3.505 (5) Å, compared with O1A···O2A = 3.323 (5) Å and O1B···O2B = 3.235 (5) Å), has its K⁺ cation interacting with the P═O O atom of the SMP ligand and with the Cl1 and Cl2 ligands which are cis and trans to the coordinated sulfoxide (Fig. 4). In general, atom Cl1 interacts with only one cation and atom Cl2 with two cations (three in the case of Pt). Two independent K⁺ cations are trapped in an irregular eight-donor cage formed by three Cl and five O atoms of three different anions in the case of K1, and by four Cl and four O atoms of three different anions in the case of K1A. The third cation, K1B, is trapped in a seven-donor cage formed by three Cl and four O atoms. The K···O and K···Cl distances for cations K1, K1A and K1B are given in Table 3.

Intra-chain hydrogen-bonding interactions of different strengths are also present. These involve Cl and O atoms on one hand (Cl1, O4B and O3B) and C atoms on the other hand (C1B, C1A, C2A and C5A). Infinite chains of anions and cations extend along the c direction (Fig. 5). Adjacent chains are held together by hydrogen-bond interactions involving atoms Cl1, Cl1A, Cl1B and Cl3A of one chain, and atoms C1, C2B, C3B, C3A, C3 and C5 of adjacent chains (Table 4). A view of the crystal packing along the c direction is shown in Fig. 5.

In conclusion, this work has shown that it is possible to isolate the complex K[PtCl₃(SMP)] in three different crystalline forms, one of which has already been reported (Laforgia et al., 2005). The solvent of crystallization [H₂O–acetone–CHCl₃ (Ratio?) for (Ia), and acetone–n-pentane in the ratios 1:4 and 1:9 for (Ib) and (Ic), respectively] appears to be responsible for the different crystalline packings. In all cases, strong interactions between anions and cations lead to chains extending in one direction. The chains are held together in the crystal structure by weak hydrogen-bond interactions involving Cl or O atoms of one chain and CH atoms of adjacent chains. In the case of (Ic), there are also hydrogen bonds of this type within each chain. The P═O O atom interacts with only one K⁺ cation in (Ia) and (Ib) (the same K⁺ cation also interacts with the S═O O atom and with the Cl⁻ cis to the sulfoxide), and with two K⁺ cations in (Ic) (one K⁺ cation also interacts with atoms Cl1 and Cl2, and the other interacts with atoms Cl2 and O1 in Pt and PtB, and with atoms Cl2 and O4 in PtA). Moreover, in the structures of (Ia) and (Ib), all three Cl atoms of the complex anion are involved in interactions with K⁺ cations, while in the structure of (Ic), one Cl atom (Cl3 of all three independent anions) does not interact with any K⁺ cations. The different mode of interaction of the [PtCl₃(SMP)]⁻ anion with the cations revealed in this investigation can also provide useful information for elucidating the mechanism of the biological activity of this type of compound, particularly the inhibition of MMP activity.

S2. Experimental

K[PtCl₃(SMP)] was prepared as reported by Laforgia et al. (2005). The polymorphs (Ib) and (Ic) were crystallized as follows. For the crystallization of (Ib), K[PtCl₃(SMP)] (15 mg, 2.7 × 10⁻² mmol) was dissolved in acetone (4 ml) and layered under n-pentane (16 ml). After one week at room temperature, crystals suitable for crystallographic analysis were obtained. They were characterized by elemental analysis, IR spectroscopy and X-ray crystallography; C₆H₁₅Cl₃KO₄PPtS (554.75), calculated: C 13.00, H 2.73%; found: C 13.25, H 2.64; IR (Medium?, cm⁻¹): 2913 (ν_CH), 1253 (ν_PO), 1049 (ν_SO), 1013 (ν_POR), 341 (ν_PtCl).

For the crystallization of (Ic), K[PtCl₃(SMP)] (5 mg, 9 × 10⁻³ mmol) was dissolved in acetone (1 ml) and layered under n-pentane (9 ml). After one week at room temperature, crystals suitable for crystallographic analysis were obtained. They were characterized by elemental analysis, IR spectroscopy and X-ray crystallography; C₆H₁₅Cl₃KO₄PPtS (554.75), found C 13.31, H 2.78%; IR (Medium?, cm⁻¹): 2913 (ν_CH), 1253 (ν_PO), 1049 (ν_SO), 1013 (ν_POR), 341 (ν_PtCl).

S3. Refinement

H atoms were placed in calculated positions, with C—H = 0.96–0.97 Å [Please check added text], and refined with U_iso(H) = 1.2 (1.5 for the methyl H atoms) times U_eq(parent). Four restraints were used in the refinement of the structure of (Ib). These were associated with an –OCH₂CH₃ group, which was disordered over two orientations, DFIX 1.5 O4 C5 O4 C5A and DFIX 1.45 C5 C6 C5A C6. The coordinates of the disordered –OCH₂CH₃ group were refined with occupancies tied to sum to unity.

Computing details

For both compounds, data collection: COSMO, APEX2 and BIS (Bruker, 2004); cell refinement: SAINT-IRIX (Bruker, 2004); data reduction: SAINT-IRIX; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); 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 the asymmetric unit of K[PtCl3(SMP)] in polymorph (Ib), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Atoms labelled with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (x − 1/2, 3/2 − y, 1 − z), respectively.
	Fig. 2. Chains of anions and cations extending along the a direction for K[PtCl3(SMP)] in polymorph (Ib). H atoms have been omitted for clarity. Atoms labelled with an asterisk (*), a dollar sign ($) or a hash (#) are at the symmetry positions (x − 1, y, z), (x + 1, y, z) and (x − 1/2, 3/2 − y, 1 − z), respectively.
	Fig. 3. A view of the crystal packing along the a direction for K[PtCl3(SMP)] in polymorph (Ib). H atoms have been omitted for clarity.
	Fig. 4. A view of the three independent anions and corresponding interactions with K^+ cations for K[PtCl3(SMP)] in polymorph (Ic). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Atoms labelled with an asterisk (*), a dollar sign ($) or a hash (#) are at the symmetry positions (x, y, 1 + z), (3/2 − x, 1 − y, −1/2 + z) and (3/2 − x, 1 − y, 1/2 + z), respectively.
	Fig. 5. The chain of anions and cations extending along the c direction for K[PtCl3(SMP)] in polymorph (Ic). H atoms have been omitted for clarity. Atoms labelled with an asterisk (*), an ampersand (&), a dollar sign ($) or a hash (#) are at the symmetry positions (x, y, 1 + z), (x, y, z − 1), (3/2 − x, 1 − y, −1/2 + z) and (3/2 − x, 1 − y, 1/2 + z), respectively.
	Fig. 6. The crystal packing of K[PtCl3(SMP)] in polymorph (Ic). H atoms have been omitted for clarity.

(Ib) potassium trichloro[diethyl (methylsulfinylmethyl)phosphonate-κS]platinum(II)

Crystal data

K[PtCl3(C6H15O4PS)]	F(000) = 1048
Mr = 554.75	Dx = 2.288 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2Ac 2Ab	Cell parameters from 63182 reflections
a = 8.1697 (2) Å	θ = 2.1–36.0°
b = 13.2052 (3) Å	µ = 9.70 mm^−1
c = 14.9286 (4) Å	T = 295 K
V = 1610.54 (7) Å^3	Prism, yellow
Z = 4	0.50 × 0.25 × 0.14 mm

Data collection

Bruker X8 APEX CCD area-detector diffractometer	7591 independent reflections
Radiation source: fine-focus sealed tube	4342 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 36.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.017, Tmax = 0.437	k = −21→21
63182 measured reflections	l = −24→24

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0271P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.065	(Δ/σ)max = 0.005
S = 0.87	Δρmax = 2.63 e Å^−3
7591 reflections	Δρmin = −1.30 e Å^−3
167 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
10 restraints	Extinction coefficient: 0.00146 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 3348 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.002 (6)

Special details

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. Hydrogen atoms were placed at calculated positions and refined given isotropic parameters equivalent to 1.2 (1.5 for the methyl H atoms) times those of the atom to which they were attached. Some 4 restraints were used in the refinement. These were associated with –OCH₂CH₃ group was disordered over two orientations DFIX 1.5 O4 C5 O4 C5A DFIX 1.45 C5 C6 C5A C6. The coordinates of disorder –OCH₂CH₃ group over two orientations were refined with the occupancies tied to sum to unity.

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)
Pt	0.45308 (2)	0.695750 (14)	0.327866 (12)	0.03397 (6)
Cl1	0.26702 (16)	0.80214 (13)	0.39893 (8)	0.0464 (3)
Cl2	0.65406 (17)	0.81016 (12)	0.36534 (10)	0.0558 (3)
Cl3	0.24153 (17)	0.58728 (12)	0.29386 (11)	0.0583 (4)
S	0.62444 (16)	0.59825 (11)	0.25345 (9)	0.0412 (3)
O1	0.7996 (4)	0.6220 (3)	0.2549 (3)	0.0581 (11)
C1	0.5608 (8)	0.5952 (5)	0.1394 (3)	0.0598 (16)
H1A	0.5520	0.6631	0.1170	0.090*
H1B	0.4563	0.5623	0.1351	0.090*
H1C	0.6398	0.5585	0.1045	0.090*
C2	0.6011 (7)	0.4677 (4)	0.2821 (4)	0.0489 (14)
H2A	0.6559	0.4275	0.2367	0.059*
H2B	0.4855	0.4512	0.2795	0.059*
P	0.6781 (2)	0.42996 (12)	0.39025 (11)	0.0533 (4)
O2	0.7827 (9)	0.5083 (4)	0.4340 (4)	0.0931 (18)
O3	0.7738 (8)	0.3273 (4)	0.3746 (4)	0.0923 (17)
O4	0.5314 (10)	0.3944 (6)	0.4422 (4)	0.127 (2)
C3	0.9367 (9)	0.3322 (7)	0.3282 (6)	0.095 (3)
H3A	0.9475	0.2738	0.2892	0.114*
H3B	0.9400	0.3923	0.2910	0.114*
C4	1.0741 (12)	0.3343 (7)	0.3896 (7)	0.112 (3)
H4A	1.0731	0.3968	0.4225	0.169*
H4B	1.1743	0.3291	0.3564	0.169*
H4C	1.0658	0.2785	0.4305	0.169*
C5	0.454 (2)	0.4853 (16)	0.4960 (11)	0.147 (8)	0.66 (2)
H5A	0.5218	0.5440	0.4840	0.176*	0.66 (2)
H5B	0.3483	0.4988	0.4689	0.176*	0.66 (2)
C5A	0.483 (4)	0.4039 (19)	0.5355 (12)	0.099 (10)	0.34 (2)
H51A	0.3978	0.3534	0.5437	0.119*	0.34 (2)
H52A	0.5763	0.3798	0.5694	0.119*	0.34 (2)
C6	0.431 (2)	0.4833 (13)	0.5795 (10)	0.200 (7)
H6A	0.3514	0.4323	0.5937	0.300*	0.66 (2)
H6b	0.3918	0.5482	0.5991	0.300*	0.66 (2)
H6C	0.5321	0.4680	0.6092	0.300*	0.66 (2)
H6D	0.5205	0.5130	0.6118	0.300*	0.34 (2)
H6E	0.3470	0.4633	0.6209	0.300*	0.34 (2)
H6F	0.3873	0.5319	0.5381	0.300*	0.34 (2)
K	0.95429 (17)	0.66900 (10)	0.41928 (8)	0.0561 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.03539 (9)	0.03427 (9)	0.03225 (8)	−0.00041 (9)	−0.00033 (9)	−0.00079 (9)
Cl1	0.0508 (7)	0.0445 (7)	0.0438 (6)	0.0059 (7)	0.0045 (6)	−0.0084 (7)
Cl2	0.0469 (7)	0.0415 (7)	0.0791 (9)	−0.0056 (7)	−0.0158 (7)	−0.0038 (8)
Cl3	0.0403 (7)	0.0571 (9)	0.0776 (10)	−0.0097 (7)	0.0084 (7)	−0.0249 (8)
S	0.0357 (6)	0.0528 (8)	0.0352 (7)	−0.0001 (6)	0.0026 (6)	−0.0062 (6)
O1	0.0356 (19)	0.082 (3)	0.057 (3)	−0.001 (2)	0.0127 (19)	−0.006 (2)
C1	0.057 (3)	0.088 (4)	0.035 (3)	0.005 (4)	−0.003 (3)	−0.011 (3)
C2	0.054 (3)	0.040 (3)	0.053 (3)	0.006 (2)	0.001 (3)	−0.018 (3)
P	0.0712 (11)	0.0413 (9)	0.0474 (9)	0.0008 (8)	0.0036 (8)	−0.0078 (7)
O2	0.152 (6)	0.056 (3)	0.072 (3)	−0.008 (3)	−0.037 (4)	−0.003 (3)
O3	0.126 (5)	0.065 (4)	0.086 (4)	0.015 (3)	−0.004 (3)	−0.002 (3)
O4	0.111 (5)	0.180 (7)	0.091 (4)	−0.026 (6)	0.023 (4)	−0.004 (4)
C3	0.078 (5)	0.128 (7)	0.078 (5)	0.042 (5)	0.023 (5)	−0.008 (5)
C4	0.113 (8)	0.108 (8)	0.117 (8)	0.016 (6)	−0.036 (6)	−0.005 (6)
C5	0.107 (11)	0.24 (2)	0.091 (12)	0.056 (15)	0.000 (11)	0.017 (14)
C5A	0.12 (2)	0.13 (2)	0.052 (14)	0.046 (17)	0.026 (13)	0.011 (13)
C6	0.244 (19)	0.200 (16)	0.157 (14)	0.020 (16)	0.066 (15)	−0.012 (12)
K	0.0384 (5)	0.0750 (9)	0.0549 (7)	−0.0001 (7)	0.0049 (7)	−0.0077 (6)

Geometric parameters (Å, º)

Pt—S	2.2027 (14)	C3—C4	1.449 (11)
Pt—Cl2	2.3003 (14)	C3—H3A	0.9700
Pt—Cl3	2.3014 (14)	C3—H3B	0.9700
Pt—Cl1	2.3259 (14)	C4—H4A	0.9600
S—O1	1.465 (4)	C4—H4B	0.9600
S—C1	1.781 (5)	C4—H4C	0.9600
S—C2	1.786 (6)	C5—C6	1.260 (14)
C1—H1A	0.9600	C5—H5A	0.9700
C1—H1B	0.9600	C5—H5B	0.9700
C1—H1C	0.9600	C5A—C6	1.308 (16)
C2—P	1.804 (6)	C5A—H51A	0.9700
C2—H2A	0.9700	C5A—H52A	0.9700
C2—H2B	0.9700	C6—H6A	0.9600
P—O2	1.492 (5)	C6—H6b	0.9600
P—O4	1.503 (7)	C6—H6C	0.9600
P—O3	1.582 (5)	C6—H6D	0.9600
O3—C3	1.502 (9)	C6—H6E	0.9600
O4—C5A	1.454 (15)	C6—H6F	0.9600
O4—C5	1.577 (15)
K···O1	2.829 (4)	K···Cl1^ii	3.139 (2)
K···Cl2	3.184 (2)	K···Cl3^i	3.190 (2)
K···O2	2.553 (6)	K···Cl2^ii	3.616 (2)
K···Cl1^i	3.116 (2)
S—Pt—Cl2	93.03 (5)	C4—C3—H3A	108.9
S—Pt—Cl3	90.13 (5)	O3—C3—H3A	108.9
Cl2—Pt—Cl3	176.82 (6)	C4—C3—H3B	108.9
S—Pt—Cl1	176.85 (5)	O3—C3—H3B	108.9
Cl2—Pt—Cl1	87.64 (5)	H3A—C3—H3B	107.7
Cl3—Pt—Cl1	89.19 (5)	C3—C4—H4A	109.5
O1—S—C1	107.7 (3)	C3—C4—H4B	109.5
O1—S—C2	107.9 (3)	H4A—C4—H4B	109.5
C1—S—C2	100.1 (3)	C3—C4—H4C	109.5
O1—S—Pt	119.19 (19)	H4A—C4—H4C	109.5
C1—S—Pt	108.1 (2)	H4B—C4—H4C	109.5
C2—S—Pt	112.06 (19)	C6—C5—O4	123.2 (15)
S—C1—H1A	109.5	C6—C5—H5A	106.6
S—C1—H1B	109.5	O4—C5—H5A	106.6
H1A—C1—H1B	109.5	C6—C5—H5B	106.6
S—C1—H1C	109.5	O4—C5—H5B	106.6
H1A—C1—H1C	109.5	H5A—C5—H5B	106.6
H1B—C1—H1C	109.5	C6—C5A—O4	129.7 (19)
S—C2—P	116.4 (3)	C6—C5A—H51A	105.1
S—C2—H2A	108.2	O4—C5A—H51A	105.1
P—C2—H2A	108.2	C6—C5A—H52A	105.1
S—C2—H2B	108.2	O4—C5A—H52A	105.1
P—C2—H2B	108.2	H51A—C5A—H52A	105.9
H2A—C2—H2B	107.4	C5—C6—H6A	109.5
O2—P—O4	116.6 (4)	C5—C6—H6b	109.5
O2—P—O3	112.1 (3)	H6A—C6—H6b	109.5
O4—P—O3	101.7 (4)	C5—C6—H6C	109.5
O2—P—C2	113.6 (3)	H6A—C6—H6C	109.5
O4—P—C2	105.7 (4)	H6b—C6—H6C	109.5
O3—P—C2	106.1 (3)	C5A—C6—H6D	109.5
C3—O3—P	118.0 (5)	C5A—C6—H6E	109.5
C5A—O4—P	133.3 (13)	H6D—C6—H6E	109.5
C5A—O4—C5	49.0 (11)	C5A—C6—H6F	109.5
P—O4—C5	110.2 (9)	H6D—C6—H6F	109.5
C4—C3—O3	113.3 (7)	H6E—C6—H6F	109.5

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl1^iii	0.97	2.69	3.639 (6)	166
C3—H3A···O1^iv	0.97	2.95	3.726 (9)	138
C1—H1C···O2^v	0.96	2.77	3.592 (8)	144

Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+3/2, −y+1, z−1/2.

(Ic) potassium trichloro[diethyl (methylsulfinylmethyl)phosphonate-κS]platinum(II)

Crystal data

K[PtCl3(C6H15O4PS)]	F(000) = 3144
Mr = 554.76	Dx = 2.228 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2Ac 2Ab	Cell parameters from 169856 reflections
a = 14.2518 (3) Å	θ = 1.6–37.6°
b = 16.6754 (3) Å	µ = 9.44 mm^−1
c = 20.8743 (3) Å	T = 295 K
V = 4960.87 (15) Å^3	Acicular, yellow
Z = 12	1.00 × 0.07 × 0.06 mm

Data collection

Bruker X8 APEX CCD area-detector diffractometer	23275 independent reflections
Radiation source: fine-focus sealed tube	10272 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 37.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.121, Tmax = 0.437	k = −28→27
169856 measured reflections	l = −34→33

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)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0238P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.003
23275 reflections	Δρmax = 3.73 e Å^−3
469 parameters	Δρmin = −1.50 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 10077 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.008 (3)

Special details

Experimental. no

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. Hydrogen atoms were placed at calculated positions and refined given isotropic parameters equivalent to 1.2 (1.5 for the methyl H atoms) times those of the atom to which they were attached.

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	0.755981 (15)	0.296334 (13)	0.822025 (9)	0.03914 (5)
Cl1	0.88240 (11)	0.28643 (11)	0.75322 (7)	0.0650 (4)
Cl2	0.81917 (11)	0.41394 (9)	0.85986 (7)	0.0568 (4)
Cl3	0.69554 (15)	0.18023 (9)	0.77911 (8)	0.0736 (5)
S1	0.63265 (9)	0.30902 (8)	0.88412 (6)	0.0415 (3)
O1	0.6248 (3)	0.3791 (2)	0.92649 (17)	0.0561 (11)
P1	0.51816 (12)	0.40254 (9)	0.79171 (7)	0.0457 (4)
O2	0.6055 (3)	0.4317 (2)	0.76448 (17)	0.0487 (10)
O3	0.4391 (3)	0.3820 (3)	0.74418 (19)	0.0679 (13)
O4	0.4810 (3)	0.4676 (3)	0.8390 (2)	0.0620 (12)
C1	0.6140 (5)	0.2219 (4)	0.9311 (3)	0.068 (2)
H11	0.6665	0.2140	0.9592	0.102*
H12	0.6074	0.1762	0.9036	0.102*
H13	0.5579	0.2284	0.9561	0.102*
C2	0.5293 (4)	0.3079 (3)	0.8346 (2)	0.0475 (15)
H21	0.4742	0.2994	0.8610	0.057*
H22	0.5333	0.2641	0.8041	0.057*
C5	0.3982 (6)	0.4579 (5)	0.8776 (5)	0.108 (3)
H51	0.3545	0.4228	0.8556	0.129*
H52	0.4151	0.4328	0.9179	0.129*
C6	0.3542 (6)	0.5320 (5)	0.8900 (4)	0.110 (3)
H61	0.3985	0.5681	0.9091	0.164*
H62	0.3026	0.5238	0.9189	0.164*
H63	0.3313	0.5543	0.8506	0.164*
C3	0.4253 (6)	0.4282 (5)	0.6847 (4)	0.109 (3)
H31	0.4792	0.4628	0.6783	0.131*
H32	0.4225	0.3912	0.6489	0.131*
C4	0.3478 (9)	0.4728 (6)	0.6850 (5)	0.172 (6)
H41	0.2939	0.4388	0.6896	0.257*
H42	0.3434	0.5020	0.6455	0.257*
H43	0.3502	0.5099	0.7202	0.257*
K1	0.76815 (10)	0.45058 (7)	0.70206 (5)	0.0490 (3)
Pt1A	0.793078 (15)	0.301575 (14)	0.121016 (9)	0.03959 (5)
Cl1A	0.85894 (12)	0.28429 (11)	0.02110 (7)	0.0726 (5)
Cl2A	0.88278 (12)	0.41522 (10)	0.13265 (8)	0.0658 (5)
Cl3A	0.70552 (13)	0.18738 (9)	0.10550 (7)	0.0681 (4)
S1A	0.72497 (10)	0.32006 (8)	0.21449 (6)	0.0394 (3)
O1A	0.7462 (3)	0.3925 (2)	0.25189 (15)	0.0493 (10)
P1A	0.55790 (11)	0.40902 (10)	0.16849 (8)	0.0491 (4)
O2A	0.6245 (3)	0.4420 (2)	0.12200 (17)	0.0518 (10)
O3A	0.4577 (3)	0.3907 (3)	0.1467 (2)	0.0905 (17)
O4A	0.5446 (3)	0.4705 (3)	0.2246 (2)	0.0663 (13)
C1A	0.7468 (5)	0.2364 (3)	0.2656 (2)	0.0592 (17)
H11A	0.8130	0.2317	0.2731	0.089*
H12A	0.7242	0.1883	0.2455	0.089*
H13A	0.7149	0.2441	0.3056	0.089*
C2A	0.5995 (4)	0.3179 (3)	0.2050 (3)	0.0455 (15)
H21A	0.5820	0.2725	0.1784	0.055*
H22A	0.5700	0.3112	0.2465	0.055*
C3A	0.4276 (6)	0.3724 (6)	0.0847 (4)	0.122 (4)
H31A	0.4113	0.3160	0.0826	0.147*
H32A	0.4787	0.3818	0.0549	0.147*
C4A	0.3482 (7)	0.4193 (6)	0.0656 (4)	0.139 (4)
H41A	0.2979	0.4114	0.0955	0.209*
H42A	0.3282	0.4029	0.0236	0.209*
H43A	0.3652	0.4750	0.0647	0.209*
C5A	0.4784 (7)	0.4602 (6)	0.2768 (4)	0.108 (3)
H51A	0.4440	0.4106	0.2706	0.130*
H52A	0.5126	0.4560	0.3169	0.130*
C6A	0.4160 (8)	0.5231 (7)	0.2806 (5)	0.154 (5)
H61A	0.4427	0.5652	0.3060	0.230*
H62A	0.3588	0.5049	0.3001	0.230*
H63A	0.4030	0.5428	0.2383	0.230*
K1A	0.73604 (10)	0.45737 (7)	0.01396 (5)	0.0545 (4)
Pt1B	0.846264 (16)	0.290004 (14)	0.473729 (10)	0.04572 (6)
Cl1B	0.94678 (12)	0.27236 (12)	0.38719 (8)	0.0800 (6)
Cl2B	0.92146 (11)	0.41035 (10)	0.49244 (7)	0.0594 (4)
Cl3B	0.77868 (13)	0.16744 (10)	0.45425 (9)	0.0796 (6)
S1B	0.74049 (10)	0.31265 (8)	0.54847 (6)	0.0435 (3)
O1B	0.7402 (3)	0.3904 (2)	0.58158 (16)	0.0596 (12)
P1B	0.60752 (11)	0.36321 (10)	0.44389 (7)	0.0466 (4)
O2B	0.6862 (3)	0.4176 (2)	0.43261 (17)	0.0524 (10)
O3B	0.5901 (3)	0.3043 (3)	0.38629 (16)	0.0595 (11)
O4B	0.5101 (3)	0.4020 (3)	0.4532 (2)	0.0683 (13)
C1B	0.7377 (5)	0.2364 (4)	0.6087 (2)	0.072 (2)
H11B	0.7904	0.2428	0.6369	0.108*
H12B	0.7405	0.1846	0.5887	0.108*
H13B	0.6806	0.2408	0.6329	0.108*
C2B	0.6251 (4)	0.2996 (3)	0.5146 (2)	0.0474 (14)
H21B	0.5782	0.3127	0.5466	0.057*
H22B	0.6166	0.2438	0.5026	0.057*
C3B	0.5116 (4)	0.2456 (4)	0.3896 (3)	0.072 (2)
H31B	0.4900	0.2410	0.4335	0.086*
H32B	0.4597	0.2645	0.3636	0.086*
C4B	0.5424 (6)	0.1660 (4)	0.3663 (3)	0.087 (3)
H41B	0.5636	0.1706	0.3227	0.131*
H42B	0.4908	0.1291	0.3683	0.131*
H43B	0.5929	0.1468	0.3926	0.131*
C5B	0.4962 (7)	0.4682 (7)	0.4936 (5)	0.153 (5)
H51B	0.4817	0.4481	0.5360	0.184*
H52B	0.5552	0.4970	0.4967	0.184*
C6b	0.4295 (8)	0.5212 (5)	0.4775 (5)	0.155 (5)
H61B	0.3727	0.4931	0.4671	0.232*
H62B	0.4498	0.5516	0.4410	0.232*
H63B	0.4182	0.5567	0.5129	0.232*
K1B	0.84078 (10)	0.44627 (8)	0.35408 (6)	0.0533 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.04710 (12)	0.03590 (11)	0.03441 (10)	0.00329 (12)	0.00273 (10)	0.00159 (10)
Cl1	0.0594 (10)	0.0802 (12)	0.0553 (8)	0.0171 (10)	0.0183 (7)	0.0020 (9)
Cl2	0.0572 (11)	0.0547 (10)	0.0584 (9)	−0.0121 (8)	0.0010 (8)	−0.0074 (7)
Cl3	0.1045 (15)	0.0470 (10)	0.0693 (10)	−0.0131 (10)	0.0124 (10)	−0.0165 (7)
S1	0.0461 (8)	0.0436 (8)	0.0349 (7)	−0.0027 (7)	0.0026 (6)	0.0012 (7)
O1	0.055 (3)	0.062 (3)	0.052 (2)	0.006 (2)	0.003 (2)	−0.017 (2)
P1	0.0437 (10)	0.0432 (9)	0.0503 (9)	−0.0082 (8)	−0.0053 (7)	0.0035 (7)
O2	0.047 (2)	0.047 (2)	0.052 (2)	−0.009 (2)	0.001 (2)	0.0080 (18)
O3	0.069 (3)	0.074 (3)	0.060 (3)	−0.025 (3)	−0.027 (2)	0.019 (2)
O4	0.052 (3)	0.057 (3)	0.077 (3)	−0.001 (2)	0.009 (2)	−0.002 (2)
C1	0.078 (5)	0.074 (5)	0.051 (4)	−0.001 (4)	0.013 (3)	0.035 (3)
C2	0.052 (4)	0.045 (4)	0.045 (3)	−0.017 (3)	0.001 (3)	0.000 (3)
C5	0.082 (6)	0.082 (6)	0.160 (8)	0.017 (5)	0.073 (6)	−0.005 (6)
C6	0.075 (6)	0.093 (6)	0.160 (9)	0.009 (5)	0.028 (6)	−0.014 (6)
C3	0.096 (7)	0.115 (8)	0.115 (7)	−0.031 (6)	−0.043 (6)	0.021 (6)
C4	0.267 (15)	0.122 (9)	0.125 (8)	0.129 (10)	−0.007 (10)	0.026 (7)
K1	0.0647 (10)	0.0443 (7)	0.0380 (6)	−0.0039 (7)	0.0100 (6)	−0.0019 (5)
Pt1A	0.03777 (11)	0.04160 (12)	0.03939 (10)	0.00312 (11)	−0.00011 (9)	−0.00294 (11)
Cl1A	0.0715 (11)	0.0954 (13)	0.0510 (8)	0.0075 (11)	0.0170 (8)	−0.0149 (9)
Cl2A	0.0584 (11)	0.0694 (11)	0.0697 (11)	−0.0225 (9)	0.0097 (9)	−0.0082 (9)
Cl3A	0.0817 (11)	0.0494 (10)	0.0731 (10)	−0.0115 (9)	−0.0031 (9)	−0.0135 (8)
S1A	0.0425 (9)	0.0391 (8)	0.0365 (7)	0.0001 (6)	0.0022 (6)	0.0018 (6)
O1A	0.062 (3)	0.044 (2)	0.042 (2)	0.004 (2)	0.003 (2)	−0.0072 (17)
P1A	0.0368 (9)	0.0552 (11)	0.0553 (10)	−0.0007 (8)	−0.0027 (8)	0.0083 (8)
O2A	0.049 (2)	0.066 (3)	0.041 (2)	−0.006 (2)	0.0027 (19)	0.014 (2)
O3A	0.061 (3)	0.113 (4)	0.098 (4)	−0.022 (3)	−0.018 (3)	0.031 (3)
O4A	0.068 (3)	0.066 (3)	0.065 (3)	0.011 (3)	0.021 (3)	−0.005 (2)
C1A	0.071 (4)	0.052 (4)	0.054 (3)	0.017 (4)	−0.002 (3)	0.023 (3)
C2A	0.039 (3)	0.051 (4)	0.047 (3)	−0.010 (3)	0.006 (3)	0.007 (3)
C3A	0.084 (7)	0.157 (10)	0.126 (8)	−0.012 (7)	−0.016 (6)	−0.084 (7)
C4A	0.129 (9)	0.158 (10)	0.131 (8)	0.048 (8)	−0.054 (7)	0.009 (7)
C5A	0.133 (9)	0.124 (8)	0.067 (5)	0.048 (7)	0.016 (6)	0.001 (5)
C6A	0.132 (10)	0.186 (12)	0.143 (10)	0.075 (9)	0.049 (8)	0.012 (8)
K1A	0.0718 (10)	0.0519 (8)	0.0397 (7)	−0.0088 (7)	−0.0007 (7)	0.0014 (5)
Pt1B	0.04379 (13)	0.05108 (14)	0.04230 (11)	0.00651 (13)	−0.00938 (10)	0.00077 (12)
Cl1B	0.0610 (11)	0.1163 (16)	0.0626 (10)	0.0274 (10)	0.0060 (9)	−0.0075 (10)
Cl2B	0.0526 (10)	0.0703 (11)	0.0553 (9)	−0.0166 (8)	−0.0126 (8)	0.0118 (8)
Cl3B	0.0803 (14)	0.0518 (10)	0.1067 (14)	0.0030 (9)	−0.0084 (11)	−0.0243 (9)
S1B	0.0525 (9)	0.0429 (9)	0.0351 (6)	−0.0086 (7)	−0.0029 (6)	0.0033 (6)
O1B	0.085 (3)	0.057 (3)	0.037 (2)	−0.019 (2)	0.006 (2)	−0.0096 (18)
P1B	0.0390 (9)	0.0512 (10)	0.0496 (9)	0.0004 (8)	0.0016 (7)	0.0110 (7)
O2B	0.051 (3)	0.052 (2)	0.054 (2)	−0.004 (2)	−0.004 (2)	0.0174 (19)
O3B	0.059 (3)	0.080 (3)	0.039 (2)	−0.012 (3)	0.0105 (19)	0.000 (2)
O4B	0.049 (3)	0.079 (3)	0.077 (3)	0.012 (2)	0.000 (2)	−0.008 (3)
C1B	0.098 (6)	0.076 (5)	0.041 (3)	−0.019 (4)	−0.009 (3)	0.026 (3)
C2B	0.051 (4)	0.054 (3)	0.037 (3)	−0.011 (3)	0.005 (2)	0.007 (3)
C3B	0.049 (4)	0.119 (6)	0.048 (4)	−0.036 (4)	−0.006 (3)	−0.006 (4)
C4B	0.121 (7)	0.083 (6)	0.058 (4)	−0.038 (5)	−0.029 (5)	0.016 (4)
C5B	0.104 (9)	0.203 (12)	0.152 (10)	0.038 (8)	−0.017 (7)	−0.119 (9)
C6b	0.185 (12)	0.095 (7)	0.185 (11)	0.071 (8)	−0.031 (10)	−0.020 (8)
K1B	0.0575 (8)	0.0610 (9)	0.0415 (7)	−0.0114 (7)	−0.0086 (6)	0.0127 (6)

Geometric parameters (Å, º)

Pt1—S1	2.1942 (13)	C1A—H13A	0.9600
Pt1—Cl2	2.2980 (15)	C2A—H21A	0.9700
Pt1—Cl3	2.3007 (15)	C2A—H22A	0.9700
Pt1—Cl1	2.3101 (14)	C3A—C4A	1.432 (11)
S1—O1	1.469 (4)	C3A—H31A	0.9700
S1—C1	1.773 (5)	C3A—H32A	0.9700
S1—C2	1.800 (5)	C4A—H41A	0.9600
P1—O2	1.452 (4)	C4A—H42A	0.9600
P1—O3	1.540 (4)	C4A—H43A	0.9600
P1—O4	1.560 (4)	C5A—C6A	1.377 (11)
P1—C2	1.821 (6)	C5A—H51A	0.9700
O3—C3	1.474 (8)	C5A—H52A	0.9700
O4—C5	1.438 (8)	C6A—H61A	0.9600
C1—H11	0.9600	C6A—H62A	0.9600
C1—H12	0.9600	C6A—H63A	0.9600
C1—H13	0.9600	Pt1B—S1B	2.2021 (14)
C2—H21	0.9700	Pt1B—Cl3B	2.2956 (17)
C2—H22	0.9700	Pt1B—Cl2B	2.3083 (16)
C5—C6	1.409 (9)	Pt1B—Cl1B	2.3243 (16)
C5—H51	0.9700	S1B—O1B	1.469 (4)
C5—H52	0.9700	S1B—C1B	1.789 (5)
C6—H61	0.9600	S1B—C2B	1.804 (5)
C6—H62	0.9600	P1B—O2B	1.461 (4)
C6—H63	0.9600	P1B—O4B	1.544 (4)
C3—C4	1.333 (11)	P1B—O3B	1.572 (4)
C3—H31	0.9700	P1B—C2B	1.834 (5)
C3—H32	0.9700	O3B—C3B	1.488 (7)
C4—H41	0.9600	O4B—C5B	1.404 (9)
C4—H42	0.9600	C1B—H11B	0.9600
C4—H43	0.9600	C1B—H12B	0.9600
Pt1A—S1A	2.2010 (13)	C1B—H13B	0.9600
Pt1A—Cl2A	2.2988 (15)	C2B—H21B	0.9700
Pt1A—Cl3A	2.2997 (15)	C2B—H22B	0.9700
Pt1A—Cl1A	2.3053 (14)	C3B—C4B	1.479 (9)
S1A—O1A	1.470 (4)	C3B—H31B	0.9700
S1A—C1A	1.784 (5)	C3B—H32B	0.9700
S1A—C2A	1.800 (5)	C4B—H41B	0.9600
P1A—O2A	1.465 (4)	C4B—H42B	0.9600
P1A—O3A	1.529 (5)	C4B—H43B	0.9600
P1A—O4A	1.568 (4)	C5B—C6b	1.339 (11)
P1A—C2A	1.800 (5)	C5B—H51B	0.9700
O3A—C3A	1.398 (8)	C5B—H52B	0.9700
O4A—C5A	1.451 (8)	C6b—H61B	0.9600
C1A—H11A	0.9600	C6b—H62B	0.9600
C1A—H12A	0.9600	C6b—H63B	0.9600
K1···O2	2.678 (4)	K1A···O1^ii	2.748 (4)
K1···O1B	2.737 (3)	K1A···O2B^iii	2.909 (4)
K1···Cl1	3.359 (2)	K1A···O1B^iii	2.924 (4)
K1···Cl2	3.428 (2)	K1A···Cl2B^iii	3.179 (2)
K1···Cl2A^i	3.426 (2)	K1B···Cl1B	3.342 (2)
K1···O1A^i	2.823 (4)	K1B···Cl2B	3.166 (2)
K1···O2A^i	2.888 (4)	K1B···O1A	2.678 (4)
K1···O4A^i	3.013 (5)	K1B···O2B	2.787 (4)
K1A···Cl1A	3.379 (2)	K1B···O2^iii	2.868 (4)
K1A···Cl2A	3.317 (2)	K1B···O4^iii	2.934 (4)
K1A···O2A	2.771 (4)	K1B···Cl2^iii	3.263 (2)
K1A···Cl2^ii	3.504 (2)
S1—Pt1—Cl2	91.64 (5)	S1A—C2A—H21A	109.5
S1—Pt1—Cl3	90.64 (6)	P1A—C2A—H22A	109.5
Cl2—Pt1—Cl3	177.11 (6)	S1A—C2A—H22A	109.5
S1—Pt1—Cl1	177.42 (5)	H21A—C2A—H22A	108.1
Cl2—Pt1—Cl1	88.23 (6)	O3A—C3A—C4A	112.5 (8)
Cl3—Pt1—Cl1	89.41 (7)	O3A—C3A—H31A	109.1
O1—S1—C1	107.9 (2)	C4A—C3A—H31A	109.1
O1—S1—C2	107.0 (3)	O3A—C3A—H32A	109.1
C1—S1—C2	100.7 (3)	C4A—C3A—H32A	109.1
O1—S1—Pt1	119.54 (18)	H31A—C3A—H32A	107.8
C1—S1—Pt1	111.6 (2)	C3A—C4A—H41A	109.5
C2—S1—Pt1	108.36 (18)	C3A—C4A—H42A	109.5
O2—P1—O3	116.7 (2)	H41A—C4A—H42A	109.5
O2—P1—O4	107.8 (2)	C3A—C4A—H43A	109.5
O3—P1—O4	108.3 (3)	H41A—C4A—H43A	109.5
O2—P1—C2	114.0 (2)	H42A—C4A—H43A	109.5
O3—P1—C2	100.8 (2)	C6A—C5A—O4A	111.9 (8)
O4—P1—C2	108.8 (2)	C6A—C5A—H51A	109.2
C3—O3—P1	121.6 (4)	O4A—C5A—H51A	109.2
C5—O4—P1	123.7 (4)	C6A—C5A—H52A	109.2
S1—C1—H11	109.5	O4A—C5A—H52A	109.2
S1—C1—H12	109.5	H51A—C5A—H52A	107.9
H11—C1—H12	109.5	C5A—C6A—H61A	109.5
S1—C1—H13	109.5	C5A—C6A—H62A	109.5
H11—C1—H13	109.5	H61A—C6A—H62A	109.5
H12—C1—H13	109.5	C5A—C6A—H63A	109.5
S1—C2—P1	110.1 (3)	H61A—C6A—H63A	109.5
S1—C2—H21	109.6	H62A—C6A—H63A	109.5
P1—C2—H21	109.6	S1B—Pt1B—Cl3B	89.48 (6)
S1—C2—H22	109.6	S1B—Pt1B—Cl2B	92.80 (5)
P1—C2—H22	109.6	Cl3B—Pt1B—Cl2B	177.14 (6)
H21—C2—H22	108.1	S1B—Pt1B—Cl1B	173.88 (6)
C6—C5—O4	111.8 (7)	Cl3B—Pt1B—Cl1B	90.47 (7)
C6—C5—H51	109.3	Cl2B—Pt1B—Cl1B	87.45 (7)
O4—C5—H51	109.3	O1B—S1B—C1B	107.3 (3)
C6—C5—H52	109.3	O1B—S1B—C2B	106.8 (3)
O4—C5—H52	109.3	C1B—S1B—C2B	99.7 (3)
H51—C5—H52	107.9	O1B—S1B—Pt1B	119.11 (18)
C5—C6—H61	109.5	C1B—S1B—Pt1B	113.0 (2)
C5—C6—H62	109.5	C2B—S1B—Pt1B	109.00 (17)
H61—C6—H62	109.5	O2B—P1B—O4B	116.8 (2)
C5—C6—H63	109.5	O2B—P1B—O3B	112.7 (2)
H61—C6—H63	109.5	O4B—P1B—O3B	102.5 (2)
H62—C6—H63	109.5	O2B—P1B—C2B	112.6 (2)
C4—C3—O3	113.5 (9)	O4B—P1B—C2B	105.3 (2)
C4—C3—H31	108.9	O3B—P1B—C2B	105.9 (2)
O3—C3—H31	108.9	C3B—O3B—P1B	119.6 (3)
C4—C3—H32	108.9	C5B—O4B—P1B	122.1 (5)
O3—C3—H32	108.9	S1B—C1B—H11B	109.5
H31—C3—H32	107.7	S1B—C1B—H12B	109.5
C3—C4—H41	109.5	H11B—C1B—H12B	109.5
C3—C4—H42	109.5	S1B—C1B—H13B	109.5
H41—C4—H42	109.5	H11B—C1B—H13B	109.5
C3—C4—H43	109.5	H12B—C1B—H13B	109.5
H41—C4—H43	109.5	S1B—C2B—P1B	111.7 (3)
H42—C4—H43	109.5	S1B—C2B—H21B	109.3
S1A—Pt1A—Cl2A	92.07 (5)	P1B—C2B—H21B	109.3
S1A—Pt1A—Cl3A	90.09 (5)	S1B—C2B—H22B	109.3
Cl2A—Pt1A—Cl3A	177.83 (6)	P1B—C2B—H22B	109.3
S1A—Pt1A—Cl1A	177.63 (6)	H21B—C2B—H22B	107.9
Cl2A—Pt1A—Cl1A	88.41 (6)	C4B—C3B—O3B	110.6 (5)
Cl3A—Pt1A—Cl1A	89.42 (6)	C4B—C3B—H31B	109.5
O1A—S1A—C1A	106.8 (2)	O3B—C3B—H31B	109.5
O1A—S1A—C2A	106.3 (2)	C4B—C3B—H32B	109.5
C1A—S1A—C2A	102.9 (3)	O3B—C3B—H32B	109.5
O1A—S1A—Pt1A	119.68 (16)	H31B—C3B—H32B	108.1
C1A—S1A—Pt1A	110.1 (2)	C3B—C4B—H41B	109.5
C2A—S1A—Pt1A	109.72 (19)	C3B—C4B—H42B	109.5
O2A—P1A—O3A	118.9 (3)	H41B—C4B—H42B	109.5
O2A—P1A—O4A	109.2 (3)	C3B—C4B—H43B	109.5
O3A—P1A—O4A	103.9 (3)	H41B—C4B—H43B	109.5
O2A—P1A—C2A	112.6 (2)	H42B—C4B—H43B	109.5
O3A—P1A—C2A	105.3 (3)	C6B—C5B—O4B	117.9 (9)
O4A—P1A—C2A	106.0 (3)	C6b—C5B—H51B	107.8
C3A—O3A—P1A	127.3 (5)	O4B—C5B—H51B	107.8
C5A—O4A—P1A	124.2 (5)	C6b—C5B—H52B	107.8
S1A—C1A—H11A	109.5	O4B—C5B—H52B	107.8
S1A—C1A—H12A	109.5	H51B—C5B—H52B	107.2
H11A—C1A—H12A	109.5	C5B—C6b—H61B	109.5
S1A—C1A—H13A	109.5	C5B—C6b—H62B	109.5
H11A—C1A—H13A	109.5	H61B—C6b—H62B	109.5
H12A—C1A—H13A	109.5	C5B—C6b—H63B	109.5
P1A—C2A—S1A	110.9 (3)	H61B—C6b—H63B	109.5
P1A—C2A—H21A	109.5	H62B—C6b—H63B	109.5

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x, y, z−1; (iii) −x+3/2, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H13A···O3B	0.96	2.65	3.552 (7)	157
C2A—H22A···O3B	0.97	2.93	3.794 (6)	148
C5A—H52A···O4B	0.97	2.98	3.833 (9)	147
C1—H13···Cl1A^iv	0.96	2.88	3.770 (7)	154
C3B—H32B···Cl1^iv	0.97	2.81	3.544 (6)	133
C3A—H31A···Cl1A^v	0.97	2.83	3.559 (8)	132
C3—H32···Cl1B^iv	0.97	2.85	3.678 (10)	144
C5—H51···Cl3A^iv	0.97	2.92	3.679 (8)	136
C1B—H11B···Cl1	0.96	2.85	3.748 (6)	155
C2B—H21B···Cl1B^iv	0.97	2.73	3.478 (5)	135

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