(η³-Allyl-2κ³C)(chloro-1κCl)(μ-N,N′-diethyldithioxamidato-1:2κ⁴S,S′:N,N′)[diphenyl(2-pyridyl)phosphine-1κP]palladium(II)platinum(II) chloroform solvate

The title compound, [PdPtCl(C₃H₅)(C₆H₁₀N₂S₂)(C₁₇H₁₄NP)]·CHCl₃, was obtained by deprotonation of the initial platinum(II) complex of the di­thio­xamide and subsequent reaction with [Pd(η³-C₃H₅)(μ-Cl)]₂. Both metal atoms exhibit a square-planar coordination geometry, with the two planes forming a dihedral angle of 21.7 (2)°. The di­thio­xamide bis-chelating bridge is flat.

S1. Comment

Secondary dithioxamides, H₂R₂C₂N₂S₂ (R is an alkyl group) are effective chelating ligands and readily afford S,S'-coordinated metal complexes, such as (I) in Scheme 1 (Antolini et al., 1987; Desseyn et al., 1978; Rosace et al., 1993). One of the two amidic H atoms in (I) can easily be removed and monometallic complexes, such as (II), are obtained, in which the dithioxamide (DTO) chelate is in an imidothiolic form (Lanza et al., 1994). Removal of the residual amidic H atom in (II) transforms the coordinated dithioxamide to a diimidothiolic binucleating ligand, as in (III). \sch

As a consequence of these reaction possibilities, secondary dithioxamides can be exploited as binucleating ligands suitable for the sterically and typologically controlled synthesis of oligonuclear metal complexes (Lanza et al., 1996, 2000). We have evidence that steric hindrance on N and nitrogen basicity in complexes like (II) are important factors in determining the reactivity of N—H···N frame. For this reason, it is useful to collect structural information on R substituents, on both their steric congestion and their electronic influence over the N—C—S fragment. Hence the title compound, (IV), has been crystallized and its structure is presented here.

Compound (IV) is a palladium-platinum example of (III), and was obtained through the deprotonation of the corresponding Pt^II form of (I). In the solid state, the complex is packed with solvate chloroform molecules in the ratio 1:1. We have attempted to obtain crystals without solvent, but the X-ray diffraction data were not of sufficient quality to obtain an acceptable refined model [orthorhombic Pbcm, a = 11.689 (3), b = 22.362 (6) and c = 12.771 (6) Å, refined up to R₁(obs/all) = 0.0614/0.1033, with S(obs/all) = 0.896/0.895], mainly due to strong pseudo-symmetry effects generated by the intersection of the complex unit with a crystallographic mirror plane. Despite the different crystal packing, the two complexes showed no significant differences, so no further efforts were made to obtain better samples of and diffraction data for the unsolvated solid. The accordance of the two binuclear units might be explained by the sufficiently rigid skeleton of the complex and by the absence of significant intermolecular interactions in both crystal packings. The shortest distance from CHCl₃ is represented by the long contact of one DTO ethyl H atom with one Cl atom (H4B···Cl2 2.93 Å), and this is not strong enough to reduce the disorder of the free co-crystallized chloroform, whose geometry refinement thus had to be restrained.

By considering the allyl as a `short bite' chelating ligand, both d⁸ metal atoms exhibit the usual square-planar coordination. The Pd geometry appears quite distorted, as evidenced by the two opposite chelating angles, C—Pd—C and N—Pd—N, being much narrower than the two adjacent N—Pd—C angles, which are much larger than the expected 90° (Table 1). The central allyl atom, C8, is split over two almost symmetrical positions with respect to the coordination mean plane [50% occupancy, deviating 0.48 (4) and -0.53 (4) Å, respectively], as is usually observed in similar complexes, e.g. our previous work on the similar complex [(η³-allyl)Pd(µ-dibenzyl-DTO N,N'-Pd S,S'-Pt)Pt(PN)Cl] [PN is diphenyl(2-pyridyl)phosphine; Lanza et al., 2000].

The large size of the diphenyl(2-pyridyl)phosphine ligand has no significant influence on the Pt^II geometry because it can easily be accommodated in the coordination shell, avoiding significant steric hindrances. The fact that the deformation of the regular arrangement is only slight in (IV) is evidenced by the Pt bond angles being very close to the expected value of 90° and the four Pt-bonds being of very similar length [to within 0.077 (3) Å]. However, there is a noticeable variation of 0.059 (3) Å between the two Pt—S distances, due to the different trans effects of the opposite ligands. This moiety is almost exactly equivalent to the same fragment we have previously reported in the similar dibenzyl Pd—Pt complex and in another analogous compound, [(η⁶-p-cymene)RuCl{µ-bis(2-hydroxypropyl)-DTO N,N'-Ru S,S'-Pt}Pt(PN)Cl] (Lanza et al., 1996).

Both Pd^II and Pt^II centres lie on the corresponding mean plane of the four bonded atoms [respective deviations 0.034 (1) and 0.038 (1) Å], with a dihedral angle of 21.7 (2)°. The two coordination planes form angles of 6.2 (2) and 16.6 (1)° with the DTO bis-chelating bridge, and the metals deviate by 0.110 (1) and 0.430 (1) Å, respectively, on the same side. Therefore, (IV) is not perfectly planar. The Pt moiety is 16.8 (1)° bent at the S···S bite, while the Pd fragment lies almost on the dithioxamidate plane. This difference is confirmed by the puckering analysis (Cremer & People, 1975) of the corresponding five-membered chelation rings, Pd/N1/C1/C2/N2 and Pt/S1/C1/C2/S2 [ϕ 53 (12) and 169 (2)°, respectively, and Q 0.040 (1) and 0.231 (4) Å, respectively], evidencing the significantly flatter coordination of the Pd centre, while both conformations are intermediate between half-chair and envelope.

S2. Experimental

Diethyl dithioxamide was synthesized according to the method of Hurd et al. (1961). The title complex was prepared according to the following three-step procedure.

Step 1: cis-[Pt(Me₂SO)(PN)Cl₂] {1 mmol, prepared in situ by mixing equimolar quantities of cis-[Pt(Me₂SO)₂Cl₂] and PN}, in the minimum amount of chloroform (about 10 ml), was reacted with a stoichiometric amount of H₂Et₂N₂C₂S₂. The solution turned red, and was allowed to stand at room temperature for 30 min. After this time, petroleum ether (313–333 K, about 50 ml) was added to the concentrated solution. The {[(PN)ClPt(H₂Et₂N₂C₂S₂)]⁺·[Cl]^-} salt immediately precipitated as a magenta powder, which was separated from the colourless supernatant and air dried. Yields were higher than 90%.

Step 2: sodium bicarbonate (200 mg) was added to 1 mmol of the above salt dissolved in the minimum amount of chloroform (about 20 ml). The magenta solution immediately turned to orange; after 30 min of stirring, the sodium bicarbonate was removed by filtration and the orange solution was concentrated to a small volume (about 1 ml). [(PN)ClPt(HEt₂N₂C₂S₂ )] precipitated as an orange powder, which was collected and air dried. Yields were higher than 90%.

Step 3: [Pd(η³-C₃H₅)(µ-Cl)]₂ (1 mmol) was dissolved in a 70:30 (v/v) chloroform-methanol mixture (about 30 ml) and reacted with half the molar equivalent of the [(PN)ClPt(HEt₂N₂S₂C₂)] complex. The solution, which turned deep red, was allowed to stand for 2 h. The solvent was removed and the crude products, redissolved in the minimum amount of chloroform (about 10 ml), were placed on an alumina column and equilibrated with light petroleum. The desired product was collected as orange eluate and concentrated to a small volume (about 1 ml). On adding petroleum ether (313–333 K, about 30 ml), the title bimetallic complex, (IV), precipitated as an orange powder. Yields were higher than 80%. The complex was then crystallized from a chloroform solution to obtain samples suitable for X-ray diffraction studies.

Spectorscopic analysis: ¹H NMR (300.13 MHz, CDCl₃, δ, p.p.m): 8.68 (m, 1H, pyr H6), 8.47 (m, 1H, pyr H3), 7.80–7.13, (22H, Ar—H and pyr-H), 5.39 (m, 1H, allyl CH), 4.81 (dq, ²J_HH = 13.8 Hz, ³J_HH = 6.8 Hz, 2H, N—CH₂– cis to P, part AB of ABC₃), 3.38 (dq, ²J_HH = 13.8 Hz, ³J_HH = 6.8 Hz, 2H, N—CH₂– trans to P, part AB of ABC₃), 1.15 (t, ³J_HH = ³J_HH = 6.8 Hz, 3H, N—CH₂CH₃ trans to P, part C3 or C₃? of ABC₃), 0.95 (t, ³J_HH = ³J_HH = 6.8 Hz, 3H, N—CH₂CH₃ cis to P, part C₃ of ABC₃), 5.42 (m, 1H, allyl central CH), 3.52 (m, ³J_HH = 6.9 Hz, 1H, syn-allyl CH H), 3.50 (m, ³J_HH = 6.9 Hz, 1H, syn-allyl CH H), 2.91 (m, ³J_HH = 12.7 Hz, 1H, anti-allyl CH H), 2.89 (m, ³J_HH = 12.7 Hz, 1H, anti-allyl CH H); ¹³C{¹H} NMR (75.47 MHz, CDCl₃, δ, p.p.m.): 190.8 (d, ³J_CP = 11 Hz, 1 C, CS trans to P), 190.3 (d, ³J_CP = 2 Hz, 1 C, CS cis to P), 154.6–124.3 (29 C, Ar—C), 52.8 (1 C, N—CH₂), 52.1 (1 C, N—CH₂), 13.0 (1 C, N—CH₂CH₃), 12.7 (1 C, N—CH₂CH₃), 115.5 (1 C, allyl-central CH), 58.0 (1 C, allyl CH₂), 57.9 (1 C, allyl CH₂); ³¹P{¹H} NMR (121.49 MHz, CDCl₃, δ, p.p.m.): 17.3 (Pt—P, ¹J_PtP = 3267 Hz). Analysis calculated for C₂₆H₂₉N₃PS₂ClPdPt: C 38.33, H 3.59, N 5.16, S 7.83, Cl 4.30%; found: C 38.61, H 3.71, N 5.25, S 8.05, Cl 4.52%.

S3. Refinement

Reflection intensities were evaluated by profile fitting of a 96-step peak scan of 2θ shells (Diamond, 1969). H atoms were located in idealized positions (C—H = 0.93–0.98 Å) and allowed to ride on their parent C atoms, with isotropic displacement parameters related to the refined values of their corresponding parent atoms. The allyl ligand appeared disordered and the middle C atom was split over two positions, each with 50% occupancy. The terminal methyl group of both N-ethyl substituents and the co-crystallized chloroform molecule were affected by a slight disorder, and it was necessary to restrain their displacement parameters during the model refinement.

Computing details

Data collection: P3/V (Siemens, 1989); cell refinement: P3/V; data reduction: SHELXTL-Plus (Siemens, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW in SHELXTL (Siemens, 1996); software used to prepare material for publication: PARST95 (Nardelli, 1995, locally modified) and SHELXL97.

Figures

Fig. 1. A perspective view of (IV) showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines and atoms represent the alternative arrangement of the disordered allyl ligand. The disordered chloroform molecule in the asymmetric unit has been omitted for clarity.

(η³-Allyl-2κ³C)(chloro-1κCl)(µ-N,N'-diethyldithioxamidato- 1:2κ⁴S,S':N,N')[diphenyl(2-pyridyl)phosphine-1κP]palladium(II)platinum(II) chloroform solvate

Crystal data

[PdPt(C3H5)(C6H10N2S2)(C17H14NP)Cl]CHCl3	F(000) = 1808
Mr = 934.92	Dx = 1.861 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybc	Cell parameters from 50 reflections
a = 13.423 (3) Å	θ = 6.3–15.0°
b = 13.561 (3) Å	µ = 5.24 mm^−1
c = 19.156 (4) Å	T = 298 K
β = 106.83 (3)°	Irregular, orange
V = 3337 (1) Å^3	0.33 × 0.25 × 0.15 mm
Z = 4

Data collection

Siemens P4 diffractometer	3944 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.1°, θmin = 1.9°
ω scans	h = 0→17
Absorption correction: ψ scan (Kopfmann & Huber, 1968)	k = 0→17
Tmin = 0.249, Tmax = 0.456	l = −24→23
7636 measured reflections	3 standard reflections every 197 reflections
7328 independent reflections	intensity decay: 10%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 0.80	w = 1/[σ^2(Fo^2) + (0.0424P)^2] where P = (Fo^2 + 2Fc^2)/3
7328 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 1.20 e Å^−3
36 restraints	Δρmin = −0.82 e Å^−3

Special details

Experimental. Crystallized from chloroform solution.

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.

The allyl ligand appeared very disordered and the middle C atom was split on two positions with 50% occupancy. The terminal methyl group of both N-ethyl substituents and the co-crystallized chloroform molecule were affected by a slight disorder and it was necessary to restrain their displacement parameters during the model refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt	0.31771 (2)	0.27755 (2)	0.507707 (15)	0.04267 (10)
Pd	0.42874 (6)	−0.13022 (5)	0.59334 (4)	0.0664 (2)
Cl1	0.32558 (18)	0.42133 (16)	0.57598 (11)	0.0672 (6)
S1	0.31647 (18)	0.13494 (15)	0.44664 (10)	0.0572 (6)
S2	0.42803 (17)	0.20524 (14)	0.61092 (10)	0.0593 (6)
P	0.20184 (15)	0.34915 (14)	0.41166 (10)	0.0412 (5)
N1	0.3727 (5)	−0.0435 (4)	0.5013 (3)	0.0513 (16)
N2	0.4487 (6)	0.0114 (5)	0.6368 (4)	0.091 (3)
C1	0.3712 (6)	0.0487 (5)	0.5126 (4)	0.0438 (18)
C2	0.4185 (6)	0.0819 (6)	0.5901 (4)	0.062 (2)
C3	0.3263 (9)	−0.0840 (6)	0.4284 (5)	0.087 (3)
H3A	0.3661	−0.1408	0.4212	0.104*
H3B	0.3285	−0.0348	0.3921	0.104*
C4	0.2134 (9)	−0.1146 (8)	0.4187 (6)	0.116 (4)
H4A	0.1842	−0.1410	0.3706	0.174*
H4B	0.1739	−0.0581	0.4252	0.174*
H4C	0.2114	−0.1638	0.4543	0.174*
C5	0.4750 (10)	0.0290 (9)	0.7255 (7)	0.123 (5)
H5A	0.4451	0.0895	0.7374	0.148*
H5B	0.4545	−0.0265	0.7502	0.148*
C6	0.5862 (14)	0.0354 (9)	0.7387 (7)	0.166 (7)
H6A	0.6189	0.0471	0.7896	0.249*
H6B	0.6021	0.0886	0.7107	0.249*
H6C	0.6117	−0.0254	0.7246	0.249*
C7	0.4105 (10)	−0.2773 (7)	0.5586 (7)	0.094 (3)
H7A	0.3461	−0.3096	0.5588	0.113*
H7B	0.4344	−0.2942	0.5169	0.113*
C8A	0.488 (3)	−0.2676 (19)	0.627 (2)	0.102 (10)	0.50
H8A	0.5600	−0.2801	0.6274	0.123*	0.50
C8B	0.411 (3)	−0.2761 (19)	0.6245 (17)	0.093 (8)	0.50
H8B	0.3421	−0.2888	0.6308	0.111*	0.50
C9	0.4745 (14)	−0.2261 (8)	0.6811 (7)	0.137 (6)
H9A	0.5368	−0.2083	0.7194	0.164*
H9B	0.4196	−0.2524	0.6994	0.164*
C10	0.1780 (6)	0.2810 (5)	0.3266 (4)	0.0470 (18)
C11	0.1068 (7)	0.2018 (6)	0.3116 (4)	0.063 (2)
H11	0.0652	0.1895	0.3420	0.076*
C12	0.0994 (8)	0.1431 (7)	0.2522 (5)	0.088 (3)
H12	0.0527	0.0908	0.2423	0.105*
C13	0.1605 (9)	0.1611 (7)	0.2069 (5)	0.084 (3)
H13	0.1563	0.1209	0.1669	0.101*
C14	0.2271 (8)	0.2389 (7)	0.2219 (5)	0.083 (3)
H14	0.2674	0.2528	0.1909	0.100*
C15	0.2361 (6)	0.2967 (6)	0.2814 (4)	0.058 (2)
H15	0.2837	0.3484	0.2910	0.070*
C16	0.2430 (6)	0.4702 (5)	0.3891 (4)	0.0440 (18)
C17	0.3480 (7)	0.4905 (6)	0.4034 (5)	0.064 (2)
H17	0.3972	0.4442	0.4274	0.077*
C18	0.3798 (8)	0.5804 (7)	0.3820 (5)	0.080 (3)
H18	0.4502	0.5949	0.3912	0.096*
C19	0.3069 (10)	0.6457 (7)	0.3476 (5)	0.085 (3)
H19	0.3267	0.7062	0.3330	0.102*
C20	0.2051 (9)	0.6240 (7)	0.3342 (6)	0.093 (3)
H20	0.1562	0.6705	0.3100	0.111*
N3	0.1702 (6)	0.5361 (6)	0.3547 (4)	0.086 (2)
C21	0.0750 (6)	0.3634 (5)	0.4253 (5)	0.055 (2)
C22	−0.0092 (7)	0.3918 (6)	0.3682 (6)	0.078 (3)
H22	−0.0013	0.4018	0.3221	0.094*
C23	−0.1061 (8)	0.4053 (8)	0.3799 (8)	0.100 (4)
H23	−0.1635	0.4234	0.3415	0.121*
C24	−0.1159 (9)	0.3915 (8)	0.4487 (8)	0.099 (4)
H24	−0.1797	0.4031	0.4572	0.119*
C25	−0.0344 (10)	0.3613 (8)	0.5040 (7)	0.102 (4)
H25	−0.0428	0.3496	0.5498	0.123*
C26	0.0605 (7)	0.3480 (7)	0.4927 (5)	0.067 (2)
H26	0.1165	0.3280	0.5313	0.081*
C27	−0.1648 (14)	0.0094 (14)	0.3448 (10)	0.191 (7)
H27	−0.2284	0.0038	0.3040	0.229*
Cl2	−0.0424 (5)	−0.0341 (4)	0.3355 (3)	0.231 (2)
Cl3	−0.1473 (5)	−0.0720 (4)	0.4356 (3)	0.253 (3)
Cl4	−0.1332 (6)	0.1202 (5)	0.3909 (5)	0.318 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.04411 (17)	0.03947 (16)	0.04363 (15)	0.00331 (17)	0.01144 (12)	0.00032 (16)
Pd	0.0730 (5)	0.0442 (4)	0.0755 (5)	0.0028 (4)	0.0112 (4)	0.0154 (3)
Cl1	0.0750 (16)	0.0555 (13)	0.0631 (13)	0.0071 (12)	0.0076 (12)	−0.0171 (11)
S1	0.0844 (17)	0.0434 (11)	0.0417 (11)	0.0111 (12)	0.0152 (11)	0.0007 (9)
S2	0.0701 (15)	0.0436 (13)	0.0515 (11)	0.0008 (11)	−0.0026 (10)	0.0010 (9)
P	0.0396 (11)	0.0381 (11)	0.0455 (11)	0.0010 (9)	0.0116 (9)	−0.0008 (9)
N1	0.062 (4)	0.039 (4)	0.052 (4)	0.006 (3)	0.014 (3)	−0.001 (3)
N2	0.116 (7)	0.047 (5)	0.076 (5)	−0.007 (5)	−0.024 (5)	0.011 (4)
C1	0.039 (4)	0.042 (5)	0.049 (4)	0.003 (4)	0.012 (4)	0.007 (4)
C2	0.059 (6)	0.052 (5)	0.062 (5)	−0.005 (5)	−0.004 (4)	0.015 (4)
C3	0.151 (11)	0.046 (5)	0.076 (7)	0.030 (6)	0.050 (7)	−0.005 (5)
C4	0.104 (7)	0.106 (7)	0.114 (7)	0.011 (6)	−0.006 (6)	−0.032 (6)
C5	0.120 (8)	0.089 (7)	0.130 (8)	0.016 (7)	−0.013 (7)	−0.023 (6)
C6	0.28 (2)	0.097 (10)	0.143 (12)	0.008 (13)	0.098 (14)	0.027 (9)
C7	0.122 (11)	0.044 (6)	0.124 (9)	−0.014 (7)	0.050 (9)	−0.008 (7)
C8A	0.12 (2)	0.035 (14)	0.15 (3)	0.034 (17)	0.03 (3)	−0.003 (15)
C8B	0.12 (2)	0.049 (13)	0.10 (2)	−0.022 (18)	0.015 (19)	0.022 (16)
C9	0.205 (16)	0.053 (7)	0.117 (10)	−0.018 (10)	−0.010 (12)	0.051 (7)
C10	0.055 (5)	0.037 (4)	0.044 (4)	0.004 (4)	0.007 (4)	−0.003 (4)
C11	0.072 (6)	0.063 (6)	0.054 (5)	−0.009 (5)	0.018 (4)	−0.012 (4)
C12	0.110 (9)	0.077 (7)	0.063 (6)	−0.030 (6)	0.004 (6)	−0.022 (6)
C13	0.129 (10)	0.064 (7)	0.054 (6)	0.003 (7)	0.020 (6)	−0.018 (5)
C14	0.105 (8)	0.082 (8)	0.073 (6)	0.005 (6)	0.045 (6)	−0.001 (6)
C15	0.072 (6)	0.051 (6)	0.055 (5)	−0.007 (4)	0.025 (5)	−0.010 (4)
C16	0.045 (5)	0.042 (4)	0.044 (4)	−0.004 (4)	0.011 (4)	−0.001 (3)
C17	0.052 (6)	0.046 (5)	0.096 (7)	−0.007 (4)	0.025 (5)	0.003 (5)
C18	0.085 (8)	0.070 (7)	0.090 (7)	−0.024 (6)	0.034 (6)	−0.011 (6)
C19	0.118 (10)	0.048 (6)	0.096 (8)	−0.019 (7)	0.040 (7)	0.000 (5)
C20	0.086 (8)	0.046 (6)	0.147 (10)	0.006 (6)	0.035 (8)	0.025 (6)
N3	0.082 (6)	0.064 (5)	0.101 (6)	0.003 (5)	0.009 (5)	0.010 (5)
C21	0.041 (5)	0.040 (4)	0.081 (6)	−0.003 (4)	0.015 (5)	0.005 (4)
C22	0.050 (6)	0.060 (6)	0.119 (8)	0.012 (5)	0.017 (6)	0.035 (6)
C23	0.056 (7)	0.074 (7)	0.165 (12)	0.010 (6)	0.022 (8)	0.032 (8)
C24	0.062 (8)	0.062 (7)	0.190 (14)	−0.004 (6)	0.064 (9)	−0.022 (8)
C25	0.092 (9)	0.100 (9)	0.134 (10)	−0.005 (8)	0.063 (8)	−0.032 (8)
C26	0.055 (6)	0.079 (7)	0.074 (6)	−0.010 (5)	0.028 (5)	−0.010 (5)
C27	0.182 (10)	0.184 (10)	0.220 (11)	−0.030 (9)	0.079 (9)	−0.020 (9)
Cl2	0.226 (5)	0.263 (6)	0.218 (5)	−0.022 (4)	0.085 (4)	0.009 (4)
Cl3	0.310 (6)	0.215 (5)	0.297 (6)	−0.037 (5)	0.191 (5)	0.004 (5)
Cl4	0.333 (7)	0.250 (6)	0.437 (8)	0.000 (5)	0.215 (6)	−0.007 (6)

Geometric parameters (Å, º)

Pt—P	2.256 (2)	C8B—H8B	0.9800
Pt—S1	2.258 (2)	C9—H9A	0.9700
Pt—S2	2.317 (2)	C9—H9B	0.9700
Pt—Cl1	2.333 (2)	C10—C15	1.340 (10)
Pd—N1	2.071 (6)	C10—C11	1.410 (10)
Pd—N2	2.079 (7)	C11—C12	1.369 (11)
Pd—C7	2.094 (10)	C11—H11	0.9300
Pd—C8A	2.05 (2)	C12—C13	1.378 (12)
Pd—C8B	2.10 (2)	C12—H12	0.9300
Pd—C9	2.073 (10)	C13—C14	1.358 (12)
S1—C1	1.722 (7)	C13—H13	0.9300
S2—C2	1.716 (9)	C14—C15	1.360 (11)
P—C21	1.805 (8)	C14—H14	0.9300
P—C10	1.819 (7)	C15—H15	0.9300
P—C16	1.824 (7)	C16—N3	1.347 (9)
N1—C1	1.270 (8)	C16—C17	1.383 (10)
N1—C3	1.461 (10)	C17—C18	1.393 (11)
N2—C2	1.291 (9)	C17—H17	0.9300
N2—C5	1.650 (13)	C18—C19	1.343 (12)
C1—C2	1.505 (10)	C18—H18	0.9300
C3—C4	1.529 (13)	C19—C20	1.347 (13)
C3—H3A	0.9700	C19—H19	0.9300
C3—H3B	0.9700	C20—N3	1.380 (11)
C4—H4A	0.9600	C20—H20	0.9300
C4—H4B	0.9600	C21—C26	1.377 (10)
C4—H4C	0.9600	C21—C22	1.380 (11)
C5—C6	1.443 (17)	C22—C23	1.394 (13)
C5—H5A	0.9700	C22—H22	0.9300
C5—H5B	0.9700	C23—C24	1.376 (14)
C6—H6A	0.9600	C23—H23	0.9300
C6—H6B	0.9600	C24—C25	1.346 (15)
C6—H6C	0.9600	C24—H24	0.9300
C7—C8B	1.26 (3)	C25—C26	1.365 (12)
C7—C8A	1.42 (4)	C25—H25	0.9300
C7—H7A	0.9700	C26—H26	0.9300
C7—H7B	0.9700	C27—Cl4	1.731 (17)
C8A—C9	1.24 (3)	C27—Cl2	1.803 (17)
C8A—H8A	0.9800	C27—Cl3	2.015 (17)
C8B—C9	1.35 (3)	C27—H27	0.9800
P—Pt—S1	92.65 (7)	C9—C8A—H8A	116.8
P—Pt—S2	175.90 (8)	C7—C8A—H8A	116.8
S1—Pt—S2	89.23 (7)	Pd—C8A—H8A	116.8
P—Pt—Cl1	90.35 (7)	C7—C8B—C9	129 (3)
S1—Pt—Cl1	177.00 (8)	C7—C8B—Pd	72.2 (12)
S2—Pt—Cl1	87.78 (7)	C9—C8B—Pd	70.0 (11)
C8A—Pd—N1	142.5 (10)	C7—C8B—H8B	112.9
C8A—Pd—C9	34.9 (10)	C9—C8B—H8B	112.9
N1—Pd—C9	174.8 (4)	Pd—C8B—H8B	112.9
C8A—Pd—N2	136.0 (11)	C8A—C9—Pd	71.7 (13)
N1—Pd—N2	77.8 (3)	C8B—C9—Pd	72.2 (12)
C9—Pd—N2	106.3 (4)	C8A—C9—H9A	116.4
C8A—Pd—C7	40.1 (10)	C8B—C9—H9A	159.6
N1—Pd—C7	106.8 (4)	Pd—C9—H9A	116.4
C9—Pd—C7	68.9 (4)	C8A—C9—H9B	116.4
N2—Pd—C7	175.2 (4)	C8B—C9—H9B	74.7
C8A—Pd—C8B	28.6 (9)	Pd—C9—H9B	116.4
N1—Pd—C8B	137.2 (9)	H9A—C9—H9B	113.4
C9—Pd—C8B	37.8 (9)	C15—C10—C11	118.5 (7)
N2—Pd—C8B	140.2 (9)	C15—C10—P	120.9 (6)
C7—Pd—C8B	35.0 (9)	C11—C10—P	120.1 (6)
C1—S1—Pt	105.3 (3)	C12—C11—C10	119.6 (8)
C2—S2—Pt	103.2 (3)	C12—C11—H11	120.2
C21—P—C10	104.8 (4)	C10—C11—H11	120.2
C21—P—C16	107.5 (4)	C11—C12—C13	120.5 (9)
C10—P—C16	103.4 (3)	C11—C12—H12	119.8
C21—P—Pt	112.6 (3)	C13—C12—H12	119.8
C10—P—Pt	114.4 (2)	C14—C13—C12	118.7 (9)
C16—P—Pt	113.3 (2)	C14—C13—H13	120.7
C1—N1—C3	120.6 (6)	C12—C13—H13	120.7
C1—N1—Pd	115.7 (5)	C13—C14—C15	121.2 (9)
C3—N1—Pd	123.4 (5)	C13—C14—H14	119.4
C2—N2—C5	122.5 (8)	C15—C14—H14	119.4
C2—N2—Pd	115.4 (6)	C10—C15—C14	121.5 (8)
C5—N2—Pd	120.6 (6)	C10—C15—H15	119.2
N1—C1—C2	116.1 (7)	C14—C15—H15	119.2
N1—C1—S1	124.6 (6)	N3—C16—C17	121.2 (8)
C2—C1—S1	119.3 (6)	N3—C16—P	119.1 (6)
N2—C2—C1	114.8 (7)	C17—C16—P	119.5 (6)
N2—C2—S2	125.0 (7)	C16—C17—C18	119.8 (9)
C1—C2—S2	120.2 (6)	C16—C17—H17	120.1
N1—C3—C4	110.5 (8)	C18—C17—H17	120.1
N1—C3—H3A	109.5	C19—C18—C17	118.6 (10)
C4—C3—H3A	109.5	C19—C18—H18	120.7
N1—C3—H3B	109.5	C17—C18—H18	120.7
C4—C3—H3B	109.5	C18—C19—C20	120.4 (10)
H3A—C3—H3B	108.1	C18—C19—H19	119.8
C3—C4—H4A	109.5	C20—C19—H19	119.8
C3—C4—H4B	109.5	C19—C20—N3	122.9 (10)
H4A—C4—H4B	109.5	C19—C20—H20	118.5
C3—C4—H4C	109.5	N3—C20—H20	118.5
H4A—C4—H4C	109.5	C16—N3—C20	117.0 (8)
H4B—C4—H4C	109.5	C26—C21—C22	118.6 (8)
C6—C5—N2	95.2 (11)	C26—C21—P	121.0 (7)
C6—C5—H5A	112.7	C22—C21—P	120.4 (7)
N2—C5—H5A	112.7	C21—C22—C23	119.9 (10)
C6—C5—H5B	112.7	C21—C22—H22	120.0
N2—C5—H5B	112.7	C23—C22—H22	120.0
H5A—C5—H5B	110.2	C24—C23—C22	119.2 (11)
C5—C6—H6A	109.5	C24—C23—H23	120.4
C5—C6—H6B	109.5	C22—C23—H23	120.4
H6A—C6—H6B	109.5	C25—C24—C23	120.9 (11)
C5—C6—H6C	109.5	C25—C24—H24	119.6
H6A—C6—H6C	109.5	C23—C24—H24	119.6
H6B—C6—H6C	109.5	C24—C25—C26	119.9 (11)
C8B—C7—Pd	72.8 (13)	C24—C25—H25	120.0
C8A—C7—Pd	68.4 (11)	C26—C25—H25	120.0
C8B—C7—H7A	75.3	C25—C26—C21	121.4 (9)
C8A—C7—H7A	116.8	C25—C26—H26	119.3
Pd—C7—H7A	116.8	C21—C26—H26	119.3
C8B—C7—H7B	156.9	Cl4—C27—Cl2	103.8 (10)
C8A—C7—H7B	116.8	Cl4—C27—Cl3	94.9 (9)
Pd—C7—H7B	116.8	Cl2—C27—Cl3	91.4 (9)
H7A—C7—H7B	113.8	Cl4—C27—H27	120.2
C9—C8A—C7	125 (3)	Cl2—C27—H27	120.2
C9—C8A—Pd	73.4 (12)	Cl3—C27—H27	120.2
C7—C8A—Pd	71.5 (12)
P—Pt—S1—C1	−163.8 (3)	Pd—C7—C8B—C9	−44 (3)
S2—Pt—S1—C1	12.6 (3)	C8A—C7—C8B—Pd	76 (2)
S1—Pt—S2—C2	−14.8 (3)	C8A—Pd—C8B—C7	−80 (4)
Cl1—Pt—S2—C2	165.5 (3)	N1—Pd—C8B—C7	37 (3)
S1—Pt—P—C21	107.9 (3)	C9—Pd—C8B—C7	−145 (3)
Cl1—Pt—P—C21	−72.3 (3)	N2—Pd—C8B—C7	−178.7 (8)
S1—Pt—P—C10	−11.6 (3)	C8A—Pd—C8B—C9	65 (3)
Cl1—Pt—P—C10	168.3 (3)	N1—Pd—C8B—C9	−178.1 (10)
S1—Pt—P—C16	−129.8 (3)	N2—Pd—C8B—C9	−34 (3)
Cl1—Pt—P—C16	50.0 (3)	C7—Pd—C8B—C9	145 (3)
C8A—Pd—N1—C1	−161.3 (18)	C7—C8A—C9—C8B	30 (2)
N2—Pd—N1—C1	−3.1 (6)	Pd—C8A—C9—C8B	83 (2)
C7—Pd—N1—C1	175.5 (7)	C7—C8A—C9—Pd	−52 (3)
C8B—Pd—N1—C1	154.4 (15)	C7—C8B—C9—C8A	−37 (3)
C8A—Pd—N1—C3	25 (2)	Pd—C8B—C9—C8A	−81 (2)
N2—Pd—N1—C3	−176.3 (7)	C7—C8B—C9—Pd	45 (3)
C7—Pd—N1—C3	2.3 (8)	N2—Pd—C9—C8A	−153 (2)
C8B—Pd—N1—C3	−18.8 (17)	C7—Pd—C9—C8A	28 (2)
C8A—Pd—N2—C2	161.5 (16)	C8B—Pd—C9—C8A	49.0 (16)
N1—Pd—N2—C2	0.5 (7)	C8A—Pd—C9—C8B	−49.0 (16)
C9—Pd—N2—C2	−176.3 (9)	N2—Pd—C9—C8B	158.2 (19)
C8B—Pd—N2—C2	−155.5 (15)	C7—Pd—C9—C8B	−21 (2)
C8A—Pd—N2—C5	−32.1 (18)	C21—P—C10—C15	146.9 (6)
N1—Pd—N2—C5	166.9 (8)	C16—P—C10—C15	34.5 (7)
C9—Pd—N2—C5	−10.0 (10)	Pt—P—C10—C15	−89.3 (7)
C8B—Pd—N2—C5	10.8 (17)	C21—P—C10—C11	−41.3 (7)
C3—N1—C1—C2	178.4 (8)	C16—P—C10—C11	−153.8 (6)
Pd—N1—C1—C2	5.0 (9)	Pt—P—C10—C11	82.5 (6)
C3—N1—C1—S1	0 (1)	C15—C10—C11—C12	0.4 (12)
Pd—N1—C1—S1	−173.2 (4)	P—C10—C11—C12	−171.6 (7)
Pt—S1—C1—N1	170.7 (6)	C10—C11—C12—C13	−0.2 (14)
Pt—S1—C1—C2	−7.4 (7)	C11—C12—C13—C14	−0.9 (15)
C5—N2—C2—C1	−164.3 (8)	C12—C13—C14—C15	1.8 (15)
Pd—N2—C2—C1	1.7 (11)	C11—C10—C15—C14	0.5 (12)
C5—N2—C2—S2	15 (1)	P—C10—C15—C14	172.5 (7)
Pd—N2—C2—S2	−178.9 (5)	C13—C14—C15—C10	−1.7 (14)
N1—C1—C2—N2	−4.5 (12)	C21—P—C16—N3	−29.2 (7)
S1—C1—C2—N2	173.8 (7)	C10—P—C16—N3	81.2 (7)
N1—C1—C2—S2	176.0 (6)	Pt—P—C16—N3	−154.3 (6)
S1—C1—C2—S2	−5.7 (9)	C21—P—C16—C17	154.8 (6)
Pt—S2—C2—N2	−164.4 (8)	C10—P—C16—C17	−94.7 (7)
Pt—S2—C2—C1	15.0 (7)	Pt—P—C16—C17	29.7 (7)
C1—N1—C3—C4	−93.2 (10)	N3—C16—C17—C18	−0.1 (12)
Pd—N1—C3—C4	79.6 (9)	P—C16—C17—C18	175.7 (6)
C2—N2—C5—C6	−98.9 (12)	C16—C17—C18—C19	0.1 (14)
Pd—N2—C5—C6	95.8 (10)	C17—C18—C19—C20	−0.2 (15)
C8A—Pd—C7—C8B	47.1 (16)	C18—C19—C20—N3	0.4 (17)
N1—Pd—C7—C8B	−154.7 (18)	C17—C16—N3—C20	0.3 (13)
C9—Pd—C7—C8B	22 (2)	P—C16—N3—C20	−175.5 (7)
N1—Pd—C7—C8A	158.2 (18)	C19—C20—N3—C16	−0.4 (16)
C9—Pd—C7—C8A	−25 (2)	C10—P—C21—C26	135.9 (7)
C8B—Pd—C7—C8A	−47.1 (16)	C16—P—C21—C26	−114.5 (7)
C8B—C7—C8A—C9	−34 (3)	Pt—P—C21—C26	11.0 (8)
Pd—C7—C8A—C9	53 (3)	C10—P—C21—C22	−45.2 (8)
C8B—C7—C8A—Pd	−87 (2)	C16—P—C21—C22	64.4 (7)
N1—Pd—C8A—C9	−172.4 (10)	Pt—P—C21—C22	−170.1 (6)
N2—Pd—C8A—C9	39 (3)	C26—C21—C22—C23	0.8 (13)
C7—Pd—C8A—C9	−137 (3)	P—C21—C22—C23	−178.2 (7)
C8B—Pd—C8A—C9	−75 (3)	C21—C22—C23—C24	1.0 (15)
N1—Pd—C8A—C7	−36 (3)	C22—C23—C24—C25	−2.8 (17)
C9—Pd—C8A—C7	137 (3)	C23—C24—C25—C26	2.7 (17)
N2—Pd—C8A—C7	175.8 (7)	C24—C25—C26—C21	−0.9 (16)
C8B—Pd—C8A—C7	62 (3)	C22—C21—C26—C25	−0.9 (14)
C8A—C7—C8B—C9	33 (2)	P—C21—C26—C25	178.1 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cl2	0.96	2.93	3.515 (12)	120
C18—H18···Cl1^i	0.93	2.90	3.800 (11)	163

Symmetry code: (i) −x+1, −y+1, −z+1.