Bis([mu]-pyridine-2-thiol­ato)-[kappa]⁴S:N;N:S-bis­[(pyridine-2-thiol­ato-[kappa]S)(2-pyridyl­phen­yl-[kappa]²N,C²)platinum(III)](Pt-Pt): the non-solvated and acetonitrile-solvated forms

The title dinuclear platinum(III) complex, [Pt₂(C₁₁H₈N)₂(C₅H₄NS)₄], forms two crystal structures, viz. the non-solvated and acetonitrile-solvated (C₂H₃N) forms. For both forms, two (2-pyridylphenyl)platinum units are bridged by two pyridine-2-thiol­ate (pyt) anions in a head-to-tail configuration, and the other two pyridine-2-thiol­ate anions occupy the axial position, coordinated through their S atoms. The most remarkable difference between the two forms is the orientation of the axial monodentate ligands. Those for the solvated form are located over the 2-pyridylphenyl ligands, being related by a twofold axis which lies through the centre of the Pt-Pt bond, while the axial pyt ligands for the non-solvated form are oriented irregularly, which is attributable to the dimeric arrangement in the crystal.

S1. Comment

We recently reported a luminescent dinuclear platinum(II) complex, [Pt₂(ppy)₂(pyt)₂] (where Hppy is 2-phenylpyridine and Hpyt is pyridine-2-thiol; Koshiyama et al., 2004). Because of the strong ligand field of the ppy ligand, this platinum complex was found to have a short Pt···Pt distance [2.8491 (4) Å] for the divalent state of platinum and could be oxidized easily. For example, the divalent complex formed the trivalent complex [Pt₂Cl₂(ppy)₂(pyt)₂] immediately on dissolution in chloroform. We then investigated the redox properties of [Pt₂(ppy)₂(pyt)₂] and the possibility of the formation of trivalent complexes with various axial ligands. In the course of the study, the pyt ligand itself was found to act as an axial ligand. This compound is remarkable for containing such an asymmetric ligand as both bridging and terminal ligands, although various dinuclear platinum(III) complexes with bridging ligands have been reported (Umakoshi & Sasaki, 1993; Roundhill et al., 1989; Lippard, 1982). We report here the title trivalent complex, [Pt₂(ppy)₂(pyt)₄], which was produced either by heating the reaction solution at 343 K or in the presence of an excess of pyt ligand. Two crystal structures, a nonsolvated form, (I), and an acetonitrile solvated form, (II), were found.

Fig. 1 shows the molecular structure of (I). As in the case of the [Pt₂(ppy)₂(pyt)₂] and [Pt₂Cl₂(ppy)₂(pyt)₂] complexes, only the anti form, with a head-to-tail configuration of the bridging pyt ligands, was produced for this dinuclear complex, because the strong trans influence of the deprotonated C atom in ppy prefers the N atom to the S atom of the pyt ligand at the trans position (Koshiyama et al., 2004).

The Pt—C bond distances of (I) are comparable with those reported for other cyclometalated platinum complexes containing ppy (1.98–2.03 Å; Chassot et al., 1984; Mdleleni et al., 1995; Yamaguchi et al., 2004). The pyt ligands at the axial sites are coordinated to the respective Pt cations by the S⁻ anions. The orientation is likely to be regulated by a dimeric interaction, as shown in Fig. 2. Two complexes related by an inversion centre form a π–π stack of pyt ligands, with an interplanar spacing of 3.52 (1) Å.

There are hydrogen bonds (Table 2) between C—H in the aromatic rings and S or N atoms in the axial pyt ligands. As a result, the pyt ligand containing atom S4 is oriented in the opposite direction to the π–π stack, whereas the pyt ligand at the other axial site is located over the ppy ligand. The large displacements for the axial pyridine rings indicate that the monodentate ligands fluctuate easily.

For compound (II), on the other hand, a completely different orientation of the axial pyt ligands was found, as shown in Fig. 3. In this case, both axial pyt ligands are located over the ppy ligands. The complex molecule in (II) has a twofold axis passing through the centre of the Pt—Pt bond. A molecule of solvated acetonitrile was found to be disordered, forming hydrogen bonds (Table 4) with the ppy ligands.

Some geometric characteristics for (II) can be seen in connection with the arrangement of the axial pyt ligands. The dihedral angle between two ppy ligands for (II) is much smaller than that for (I) [21.0 (2)° for (I), cf. 11.7 (1)° for (II)]. The interplanar spacings, defined as the average distance of the atoms in one ppy from the least-squares plane of the other, are similar [3.4 (1) Å for (I) and 3.30 (7) Å for (II)]. These values indicate that the axial pyt ligands in (II) effectively stabilize the stacking of the ppy ligands. In fact, the dihedral angle and the interplanar spacing between the ppy ligand and the adjacent axial pyt ligand in (II) are 17.3 (1)° and 3.3 (1) Å, respectively, suggesting π–π interactions through pyt–ppy–ppy–pyt ligands. The smaller Pt—S—C angle at the axial positions for (II) [103.7 (2)°] compared with those for (I) [110(s.u.)-120(s.u.)° Please provide s.u.s] also supports these interactions.

For (I) and (II), the Pt—Pt distances of 2.6514 (5) and 2.6650 (2) Å, respectively, are normal for a Pt^III—Pt^III single bond but slightly longer than those for [Pt₂Cl₂(pyt)₄] and its analogues held by four bridging pyt ligands: Pt—Pt = 2.532 (1) Å in cis-[Pt₂Cl₂(pyt)₄], 2.539 (1) Å in trans-[Pt₂I₂(4-mpyt)₄] (4-mpyt is the 4-methylpyridine-2-thiolate anion), and 2.566 (2) Å in cis-[Pt₂(CN)₂(pyt)₄] (Umakoshi & Sasaki, 1993). In addition, it is interesting to note that the Pt—Pt distances for (I) and (II) are also slightly longer than that for [Pt₂Cl₂(ppy)₂(pyt)₂] [Pt—Pt 2.615 (1) Å; Koshiyama et al., 2004]. The coordination geometries of the equatorial planes for (I) and (II) are very similar to that for [Pt₂Cl₂(ppy)₂(pyt)₂]. Thus, the difference in the Pt—Pt distances could be attributed to the trans influence of the axial ligands, with the pyt ligand stronger than Cl⁻.

S2. Experimental

(Bu₄N)[PtCl₂(ppy)] was prepared according to the literature method of Mdleleni et al. (1995). The preparation of the dinuclear Pt^II complex, [Pt₂(ppy)₂(pyt)₂], was reported in a previous paper (Koshiyama et al., 2004). The trivalent complex, [Pt₂(ppy)₂(pyt)₄], was prepared in two different ways. The brown powder of (I) was produced by stirring an acetonitrile–ethanol solution (8:2 (v/v), 100 ml) of [Pt₂(ppy)₂(pyt)₂] (92 mg, 0.1 mmol) and Hpyt (22 mg, 0.2 mmol) at room temperature for 2 d (yield 81 mg). The crude product contained ca. 25% of unoxidized complex, [Pt₂(ppy)₂(pyt)₂], according to the ¹H NMR spectrum. Brown needle crystals of (I) were obtained by recrystallization from an acetonitrile solution. The dark-red–purple powder of (II) was precipitated by the reaction of (Bu₄N)[PtCl₂(ppy)] (342 mg, 0.52 mmol) and Hpyt (58 mg, 0.52 mmol) in water (60 ml) at 343 K for 3 d (yield 77 mg, 26%). Recrystallization from acetonitrile gave dark-red prismatic crystals of (II). Both (I) and (II) exhibited essentially the same ¹H NMR spectra (DMSO-d₆, δ, p.p.m.): 6.33 (t, 2 H), 6.65 (t, 2 H), 6.89 (t, 2 H), 7.02 (d, 2 H), 7.11 (t, 2 H), 7.18 (d, 2 H), 7.29 (br, 4 H), 7.40 (t, 4 H), 7.61 (d, 4 H), 7.73 (t, 2 H), 7.80 (t, 2 H), 8.47 (d, 2 H), 8.50 (br, 2 H).

S3. Refinement

For both (I) and (II), large ratios of U_eq(max)/U_eq(min) for C and N were observed, because of the fluctuation of the axial pyt ligands. The possibility of rotational disorder of the axial pyt ligands was rejected because of the steric factor for the packing. Other assignments of the N atoms would cause steric hindrance of the C—H moiety. The acetonitrile solvent molecule in (II) was found to be disordered, with the two components related by a twofold axis. The two possible sites share the terminal C23 atom, which lies on the twofold axis. The non-H atoms of the solvent molecule were refined isotropically. The H atoms of the methyl group (C23) of the acetonitrile were positioned geometrically as two disordered sites without further refinement Occupancies? All other H atoms were treated as riding, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. For (I), the deepest hole of residual density (−1.52 e Å⁻³) was found 0.86 Å from Pt1. For (II), the peaks of 3.15 and 2.24 e Å⁻³ and the hole of −1.59 e Å⁻³ were observed 0.78, 1.23 and 0.73 Å from atoms C5, N4 and Pt1, respectively.

Computing details

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004). Program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1992) for (I); SHELXS97 (Sheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The dimeric arrangement of (I). Atoms labelled with a prime are at the symmetry position (1 − x, 1 − y, −z).
	Fig. 3. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level, except those for the solvated acetonitrile, which are drawn as ideal spheres of arbitrary radii. H atoms are also shown as small spheres of arbitrary radii. The disordered atoms of the acetonitrile are shown as open circles. [Symmetry code: (i) −x, y, 1/2 − z.]

(I) Bis(µ-pyridine-2-thiolato)-κ⁴S:N;N:S-bis[(pyridine-2-thiolato- κS)(2-pyridylphenyl-κ²N,C²)platinum(III)](Pt—Pt)

Crystal data

[Pt2(C11H8N)2(C5H4NS)4]	Z = 2
Mr = 1139.18	F(000) = 1092.00
Triclinic, P1	Dx = 2.036 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 11.3534 (2) Å	Cell parameters from 5557 reflections
b = 12.3455 (2) Å	θ = 3.1–27.5°
c = 15.3328 (4) Å	µ = 7.76 mm^−1
α = 67.918 (9)°	T = 173 K
β = 84.242 (13)°	Needle, brown
γ = 69.034 (10)°	0.22 × 0.04 × 0.04 mm
V = 1858.1 (2) Å^3

Data collection

Rigaku MercuryCCD diffractometer	6772 reflections with F^2 > 2σ(F^2)
Detector resolution: 14.62 pixels mm^-1	Rint = 0.036
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −14→13
Tmin = 0.284, Tmax = 0.733	k = −16→16
14354 measured reflections	l = −19→18
8029 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.048	w = 1/[σ^2(Fo^2) + (0.0141P)^2 + 9.3496P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.085	(Δ/σ)max = 0.001
S = 1.17	Δρmax = 0.90 e Å^−3
8029 reflections	Δρmin = −1.52 e Å^−3
488 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Pt1	0.18638 (2)	0.19317 (2)	0.25034 (2)	0.01592 (7)
Pt2	0.32693 (3)	0.32639 (3)	0.24599 (2)	0.01711 (8)
S1	0.0148 (2)	0.3746 (2)	0.22181 (13)	0.0211 (4)
S2	0.3968 (2)	0.1905 (2)	0.39734 (13)	0.0239 (4)
S3	0.0166 (2)	0.1120 (2)	0.2480 (1)	0.0254 (4)
S4	0.4406 (2)	0.4655 (2)	0.2406 (2)	0.0269 (4)
N1	0.3315 (6)	0.0268 (5)	0.2668 (4)	0.0197 (13)
N2	0.2806 (6)	0.4466 (5)	0.1078 (4)	0.0183 (13)
N3	0.1714 (5)	0.1609 (5)	0.4009 (4)	0.0163 (12)
N4	0.1679 (6)	0.4326 (6)	0.3077 (5)	0.023 (1)
N5	0.1681 (7)	−0.1221 (6)	0.2819 (5)	0.036 (2)
N6	0.5425 (9)	0.4671 (9)	0.3848 (7)	0.064 (3)
C1	0.2104 (7)	0.2101 (7)	0.1143 (5)	0.020 (2)
C2	0.1468 (7)	0.3105 (7)	0.0351 (5)	0.023 (2)
C3	0.1701 (7)	0.3038 (8)	−0.0537 (6)	0.029 (2)
C4	0.2574 (8)	0.1991 (8)	−0.0650 (6)	0.030 (2)
C5	0.3226 (8)	0.0994 (8)	0.0120 (6)	0.030 (2)
C6	0.3005 (7)	0.1037 (7)	0.1031 (6)	0.024 (2)
C7	0.3668 (6)	0.0033 (7)	0.1874 (6)	0.021 (2)
C8	0.4548 (8)	−0.1110 (7)	0.1923 (6)	0.029 (2)
C9	0.5080 (8)	−0.2008 (7)	0.2766 (7)	0.036 (2)
C10	0.4727 (8)	−0.1755 (7)	0.3582 (6)	0.034 (2)
C11	0.3839 (7)	−0.0608 (7)	0.3505 (6)	0.023 (2)
C12	0.4688 (7)	0.2357 (7)	0.1824 (5)	0.021 (2)
C13	0.5667 (7)	0.1227 (7)	0.2228 (6)	0.029 (2)
C14	0.6599 (8)	0.0746 (8)	0.1682 (7)	0.035 (2)
C15	0.6582 (8)	0.1375 (9)	0.0724 (7)	0.038 (2)
C16	0.5631 (7)	0.2494 (8)	0.0289 (6)	0.030 (2)
C17	0.4681 (7)	0.2983 (7)	0.0838 (6)	0.024 (2)
C18	0.3644 (7)	0.4173 (7)	0.0437 (5)	0.022 (2)
C19	0.3481 (8)	0.4964 (8)	−0.0494 (6)	0.032 (2)
C20	0.2481 (8)	0.6070 (8)	−0.0799 (6)	0.033 (2)
C21	0.1626 (8)	0.6355 (7)	−0.0143 (6)	0.029 (2)
C22	0.1809 (7)	0.5545 (7)	0.0777 (6)	0.026 (2)
C23	0.2644 (7)	0.1568 (7)	0.4509 (5)	0.020 (2)
C24	0.2570 (8)	0.1251 (8)	0.5482 (5)	0.030 (2)
C25	0.1538 (8)	0.1007 (8)	0.5933 (6)	0.034 (2)
C26	0.0548 (8)	0.1116 (8)	0.5402 (6)	0.030 (2)
C27	0.0681 (7)	0.1410 (7)	0.4442 (5)	0.025 (2)
C28	0.0466 (7)	0.4494 (7)	0.2884 (5)	0.020 (2)
C29	−0.0564 (8)	0.5269 (7)	0.3215 (6)	0.029 (2)
C30	−0.0337 (9)	0.5857 (8)	0.3747 (7)	0.039 (2)
C31	0.0895 (9)	0.5629 (8)	0.3995 (6)	0.035 (2)
C32	0.1851 (8)	0.4876 (7)	0.3636 (6)	0.029 (2)
C33	0.0790 (8)	−0.0226 (8)	0.2222 (6)	0.029 (2)
C34	0.0315 (10)	−0.0278 (9)	0.1447 (7)	0.043 (2)
C35	0.0845 (12)	−0.1364 (10)	0.1239 (8)	0.063 (3)
C36	0.1814 (11)	−0.2336 (9)	0.1809 (8)	0.053 (3)
C37	0.2175 (9)	−0.2225 (8)	0.2574 (7)	0.044 (3)
C38	0.5521 (9)	0.3987 (8)	0.3309 (6)	0.036 (2)
C39	0.6455 (9)	0.2825 (9)	0.3495 (8)	0.049 (3)
C40	0.7297 (9)	0.2363 (10)	0.4221 (8)	0.052 (3)
C41	0.7221 (10)	0.3030 (11)	0.4761 (8)	0.058 (3)
C42	0.6369 (13)	0.4194 (12)	0.4516 (9)	0.085 (5)
H2	0.0886	0.3822	0.0417	0.028*
H3	0.1263	0.3708	−0.1063	0.034*
H4	0.2721	0.1958	−0.1249	0.036*
H5	0.3815	0.0289	0.0041	0.036*
H8	0.4780	−0.1268	0.1372	0.035*
H9	0.5668	−0.2774	0.2793	0.044*
H10	0.5079	−0.2342	0.4166	0.041*
H11	0.3594	−0.0434	0.4049	0.028*
H13	0.5695	0.0789	0.2874	0.034*
H14	0.7244	−0.0010	0.1965	0.042*
H15	0.7218	0.1043	0.0368	0.046*
H16	0.5620	0.2918	−0.0358	0.036*
H19	0.4060	0.4745	−0.0926	0.039*
H20	0.2384	0.6608	−0.1425	0.039*
H21	0.0931	0.7090	−0.0323	0.035*
H22	0.1224	0.5746	0.1211	0.031*
H24	0.3227	0.1206	0.5827	0.036*
H25	0.1499	0.0772	0.6584	0.041*
H26	−0.0182	0.0995	0.5684	0.035*
H27	0.0030	0.1473	0.4083	0.029*
H29	−0.1387	0.5380	0.3074	0.034*
H30	−0.1007	0.6406	0.3941	0.046*
H31	0.1067	0.5974	0.4390	0.042*
H32	0.2676	0.4738	0.3792	0.034*
H34	−0.0344	0.0396	0.1071	0.052*
H35	0.0544	−0.1423	0.0722	0.075*
H36	0.2212	−0.3053	0.1673	0.063*
H37	0.2820	−0.2900	0.2963	0.053*
H39	0.6501	0.2367	0.3122	0.059*
H40	0.7928	0.1587	0.4349	0.062*
H41	0.7748	0.2692	0.5294	0.070*
H42	0.6429	0.4700	0.4819	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0173 (1)	0.0153 (1)	0.0151 (2)	−0.0071 (1)	0.0007 (1)	−0.0041 (1)
Pt2	0.0188 (1)	0.0188 (1)	0.0148 (2)	−0.0097 (1)	0.0014 (1)	−0.0046 (1)
S1	0.0204 (9)	0.0204 (9)	0.0216 (10)	−0.0062 (7)	0.0000 (7)	−0.0074 (8)
S2	0.0237 (9)	0.0297 (10)	0.0171 (10)	−0.0141 (8)	−0.0014 (8)	−0.0023 (8)
S3	0.0265 (10)	0.0274 (10)	0.0252 (11)	−0.0154 (8)	0.0017 (8)	−0.0073 (8)
S4	0.0298 (10)	0.0307 (11)	0.0270 (11)	−0.0194 (9)	0.0050 (9)	−0.0105 (9)
N1	0.019 (3)	0.020 (3)	0.021 (4)	−0.008 (3)	0.001 (3)	−0.006 (3)
N2	0.026 (3)	0.024 (3)	0.007 (3)	−0.018 (3)	0.004 (3)	−0.001 (2)
N3	0.021 (3)	0.016 (3)	0.010 (3)	−0.009 (2)	−0.000 (2)	0.001 (2)
N4	0.026 (3)	0.024 (3)	0.023 (4)	−0.015 (3)	0.007 (3)	−0.009 (3)
N5	0.049 (5)	0.022 (4)	0.038 (5)	−0.015 (3)	−0.008 (4)	−0.005 (3)
N6	0.069 (7)	0.058 (6)	0.071 (7)	−0.010 (5)	−0.016 (5)	−0.037 (5)
C1	0.021 (4)	0.023 (4)	0.018 (4)	−0.013 (3)	0.004 (3)	−0.007 (3)
C2	0.023 (4)	0.018 (4)	0.026 (5)	−0.006 (3)	−0.002 (3)	−0.006 (3)
C3	0.028 (4)	0.038 (5)	0.019 (5)	−0.016 (4)	0.000 (3)	−0.004 (4)
C4	0.036 (5)	0.042 (5)	0.012 (4)	−0.016 (4)	0.012 (4)	−0.011 (4)
C5	0.031 (4)	0.038 (5)	0.027 (5)	−0.012 (4)	0.001 (4)	−0.018 (4)
C6	0.020 (4)	0.019 (4)	0.031 (5)	−0.006 (3)	−0.002 (3)	−0.006 (3)
C7	0.013 (3)	0.023 (4)	0.028 (5)	−0.008 (3)	0.001 (3)	−0.008 (3)
C8	0.033 (4)	0.025 (4)	0.025 (5)	−0.006 (4)	0.004 (4)	−0.010 (4)
C9	0.036 (5)	0.019 (4)	0.049 (6)	−0.002 (4)	−0.000 (4)	−0.015 (4)
C10	0.030 (4)	0.021 (4)	0.036 (5)	0.002 (3)	−0.012 (4)	0.001 (4)
C11	0.021 (4)	0.024 (4)	0.023 (4)	−0.009 (3)	−0.002 (3)	−0.004 (3)
C12	0.023 (4)	0.025 (4)	0.024 (4)	−0.019 (3)	0.005 (3)	−0.009 (3)
C13	0.025 (4)	0.029 (4)	0.030 (5)	−0.009 (3)	0.005 (4)	−0.010 (4)
C14	0.025 (4)	0.035 (5)	0.045 (6)	−0.008 (4)	0.004 (4)	−0.019 (4)
C15	0.032 (5)	0.048 (6)	0.052 (7)	−0.019 (4)	0.012 (4)	−0.033 (5)
C16	0.027 (4)	0.049 (5)	0.026 (5)	−0.024 (4)	0.013 (4)	−0.018 (4)
C17	0.023 (4)	0.027 (4)	0.028 (5)	−0.017 (3)	0.006 (3)	−0.010 (3)
C18	0.029 (4)	0.030 (4)	0.013 (4)	−0.023 (4)	0.005 (3)	−0.004 (3)
C19	0.037 (5)	0.050 (5)	0.020 (5)	−0.030 (4)	0.011 (4)	−0.011 (4)
C20	0.040 (5)	0.034 (5)	0.021 (5)	−0.021 (4)	−0.003 (4)	0.000 (4)
C21	0.032 (4)	0.022 (4)	0.026 (5)	−0.011 (4)	−0.010 (4)	0.004 (3)
C22	0.023 (4)	0.027 (4)	0.030 (5)	−0.013 (3)	0.000 (3)	−0.008 (4)
C23	0.023 (4)	0.021 (4)	0.015 (4)	−0.009 (3)	−0.003 (3)	−0.003 (3)
C24	0.041 (5)	0.040 (5)	0.011 (4)	−0.023 (4)	−0.002 (4)	−0.003 (4)
C25	0.045 (5)	0.037 (5)	0.021 (5)	−0.020 (4)	0.005 (4)	−0.008 (4)
C26	0.034 (5)	0.034 (5)	0.027 (5)	−0.018 (4)	0.004 (4)	−0.012 (4)
C27	0.029 (4)	0.022 (4)	0.023 (4)	−0.012 (3)	0.002 (3)	−0.006 (3)
C28	0.027 (4)	0.023 (4)	0.009 (4)	−0.010 (3)	0.007 (3)	−0.005 (3)
C29	0.031 (4)	0.028 (4)	0.024 (5)	−0.008 (4)	0.006 (4)	−0.010 (4)
C30	0.044 (5)	0.036 (5)	0.040 (6)	−0.013 (4)	0.013 (4)	−0.021 (4)
C31	0.047 (5)	0.038 (5)	0.036 (5)	−0.026 (4)	0.019 (4)	−0.025 (4)
C32	0.040 (5)	0.028 (4)	0.023 (5)	−0.019 (4)	0.005 (4)	−0.009 (4)
C33	0.035 (5)	0.031 (4)	0.023 (5)	−0.024 (4)	0.010 (4)	−0.004 (4)
C34	0.054 (6)	0.035 (5)	0.036 (6)	−0.007 (5)	−0.009 (5)	−0.014 (4)
C35	0.097 (10)	0.048 (7)	0.049 (7)	−0.014 (6)	−0.015 (7)	−0.031 (6)
C36	0.063 (7)	0.037 (6)	0.066 (8)	−0.017 (5)	0.008 (6)	−0.028 (5)
C37	0.049 (6)	0.024 (5)	0.064 (7)	−0.017 (4)	−0.006 (5)	−0.014 (5)
C38	0.044 (5)	0.032 (5)	0.035 (5)	−0.016 (4)	0.003 (4)	−0.013 (4)
C39	0.032 (5)	0.045 (6)	0.080 (8)	−0.013 (5)	−0.002 (5)	−0.033 (6)
C40	0.036 (5)	0.057 (7)	0.072 (8)	−0.023 (5)	−0.002 (5)	−0.025 (6)
C41	0.049 (7)	0.063 (7)	0.063 (8)	−0.014 (6)	−0.013 (6)	−0.025 (6)
C42	0.093 (10)	0.068 (8)	0.085 (10)	0.018 (7)	−0.066 (8)	−0.045 (8)

Geometric parameters (Å, º)

Pt1—Pt2	2.6514 (5)	C19—C20	1.37 (1)
Pt1—S1	2.305 (2)	C20—C21	1.38 (1)
Pt1—S3	2.479 (3)	C21—C22	1.37 (1)
Pt1—N1	2.066 (5)	C23—C24	1.40 (1)
Pt1—N3	2.189 (6)	C24—C25	1.37 (1)
Pt1—C1	2.017 (8)	C25—C26	1.39 (1)
Pt2—S2	2.306 (2)	C26—C27	1.38 (1)
Pt2—S4	2.466 (3)	C28—C29	1.41 (1)
Pt2—N2	2.066 (5)	C29—C30	1.37 (2)
Pt2—N4	2.184 (6)	C30—C31	1.39 (1)
Pt2—C12	2.004 (8)	C31—C32	1.37 (1)
S1—C28	1.75 (1)	C33—C34	1.38 (2)
S2—C23	1.746 (8)	C34—C35	1.40 (2)
S3—C33	1.74 (1)	C35—C36	1.37 (1)
S4—C38	1.72 (1)	C36—C37	1.35 (2)
N1—C7	1.35 (1)	C38—C39	1.39 (1)
N1—C11	1.349 (8)	C39—C40	1.35 (2)
N2—C18	1.36 (1)	C40—C41	1.35 (2)
N2—C22	1.354 (8)	C41—C42	1.35 (2)
N3—C23	1.34 (1)	C2—H2	0.9300
N3—C27	1.34 (1)	C3—H3	0.9300
N4—C28	1.36 (1)	C4—H4	0.9299
N4—C32	1.34 (1)	C5—H5	0.9300
N5—C33	1.349 (9)	C8—H8	0.9301
N5—C37	1.34 (1)	C9—H9	0.9301
N6—C38	1.36 (2)	C10—H10	0.9300
N6—C42	1.36 (2)	C11—H11	0.9300
C1—C2	1.391 (9)	C13—H13	0.9300
C1—C6	1.41 (1)	C14—H14	0.9300
C2—C3	1.39 (1)	C15—H15	0.9300
C3—C4	1.38 (1)	C16—H16	0.9299
C4—C5	1.37 (1)	C19—H19	0.9300
C5—C6	1.41 (1)	C20—H20	0.9300
C6—C7	1.447 (9)	C21—H21	0.9301
C7—N1	1.35 (1)	C22—H22	0.9300
C7—C6	1.447 (9)	C24—H24	0.9300
C7—C8	1.39 (1)	C25—H25	0.9301
C8—C7	1.39 (1)	C26—H26	0.9300
C8—C9	1.37 (1)	C27—H27	0.9300
C9—C10	1.39 (1)	C29—H29	0.9300
C10—C11	1.38 (1)	C30—H30	0.9301
C12—C13	1.395 (9)	C31—H31	0.9299
C12—C17	1.41 (1)	C32—H32	0.9300
C13—C14	1.39 (1)	C34—H34	0.9300
C14—C15	1.38 (1)	C35—H35	0.9299
C15—C16	1.38 (1)	C36—H36	0.9301
C16—C17	1.40 (1)	C37—H37	0.9300
C17—C18	1.466 (9)	C39—H39	0.9300
C18—N2	1.36 (1)	C40—H40	0.9300
C18—C17	1.466 (9)	C41—H41	0.9299
C18—C19	1.38 (1)	C42—H42	0.9300
C19—C18	1.38 (1)
S1—Pt1—Pt2	86.69 (6)	C12—C13—C14	120.9 (7)
Pt1—Pt2—S2	87.21 (6)	C12—C17—C18	116.1 (7)
S3—Pt1—Pt2	167.57 (4)	C12—C17—C16	121.3 (6)
N1—Pt1—Pt2	97.7 (2)	C13—C14—C15	120.8 (7)
Pt1—Pt2—N2	96.3 (2)	C14—C15—C16	120.6 (9)
N3—Pt1—Pt2	86.1 (2)	C15—C16—C17	118.9 (8)
Pt1—Pt2—N4	86.2 (2)	C16—C17—C18	122.6 (7)
C1—Pt1—Pt2	94.7 (3)	C17—C18—C19	126.0 (7)
Pt1—Pt2—C12	93.9 (3)	C18—C19—C20	121.5 (8)
Pt1—Pt2—S4	175.06 (4)	C19—C20—C21	117.7 (7)
S3—Pt1—S1	80.88 (7)	C20—C21—C22	119.5 (6)
N1—Pt1—S1	174.3 (2)	C23—C24—C25	120.5 (9)
N3—Pt1—S1	88.5 (1)	C24—C25—C26	119.0 (8)
C1—Pt1—S1	95.8 (2)	C25—C26—C27	118.1 (8)
Pt1—S1—C28	105.2 (2)	C28—C29—C30	119.1 (9)
N1—Pt1—S3	94.7 (2)	C29—C30—C31	119.8 (9)
N3—Pt1—S3	93.5 (2)	C30—C31—C32	117 (1)
C1—Pt1—S3	86.7 (3)	C33—C34—C35	118.9 (8)
Pt1—S3—C33	109.7 (3)	C34—C35—C36	118 (1)
N3—Pt1—N1	95.5 (2)	C35—C36—C37	118 (1)
C1—Pt1—N1	80.2 (2)	C38—C39—C40	119 (1)
Pt1—N1—C7	115.7 (4)	C39—C40—C41	119 (1)
Pt1—N1—C11	124.6 (6)	C40—C41—C42	119 (1)
C1—Pt1—N3	175.7 (2)	N1—C11—H11	118.8359
Pt1—N3—C23	121.5 (5)	N2—C22—H22	118.6330
Pt1—N3—C27	118.8 (6)	N3—C27—H27	118.7221
Pt1—C1—C2	127.6 (6)	N4—C32—H32	117.6445
Pt1—C1—C6	113.0 (5)	N5—C37—H37	117.2986
N2—Pt2—S2	175.0 (2)	N6—C42—H42	118.2164
N4—Pt2—S2	87.5 (2)	C1—C2—H2	119.9751
C12—Pt2—S2	95.7 (2)	H2—C2—C3	119.9818
Pt2—S2—C23	104.8 (2)	C2—C3—H3	119.5924
S4—Pt2—S2	94.98 (8)	H3—C3—C4	119.5845
N2—Pt2—S4	81.8 (2)	C3—C4—H4	119.9109
N4—Pt2—S4	89.5 (2)	C4—C5—H5	119.9227
C12—Pt2—S4	90.3 (3)	H4—C4—C5	119.9050
Pt2—S4—C38	112.1 (4)	H5—C5—C6	119.9153
N4—Pt2—N2	96.3 (2)	C7—C8—H8	119.3695
C12—Pt2—N2	80.5 (2)	H8—C8—C9	119.3804
Pt2—N2—C18	115.6 (4)	C8—C9—H9	120.6893
Pt2—N2—C22	126.0 (5)	C9—C10—H10	120.7940
C12—Pt2—N4	176.9 (2)	H9—C9—C10	120.6761
Pt2—N4—C28	121.3 (6)	C10—C11—H11	118.8441
Pt2—N4—C32	121.5 (6)	H10—C10—C11	120.7864
Pt2—C12—C13	128.5 (6)	C12—C13—H13	119.5366
Pt2—C12—C17	114.0 (5)	H13—C13—C14	119.5339
S1—C28—N4	120.6 (6)	C13—C14—H14	119.6172
S1—C28—C29	118.1 (7)	H14—C14—C15	119.6210
S2—C23—N3	121.7 (6)	C14—C15—H15	119.7212
S2—C23—C24	118.2 (7)	C15—C16—H16	120.5278
S3—C33—N5	118.5 (8)	H15—C15—C16	119.7073
S3—C33—C34	119.6 (6)	H16—C16—C17	120.5229
S4—C38—C39	123 (1)	C18—C19—H19	119.2407
S4—C38—N6	115.3 (6)	H19—C19—C20	119.2397
N1—C7—C6	113.6 (6)	C19—C20—H20	121.1575
C11—N1—C7	119.4 (6)	C20—C21—H21	120.2838
N1—C7—C8	119.9 (6)	H20—C20—C21	121.1574
N1—C11—C10	122.3 (8)	C21—C22—H22	118.6285
N2—C18—C17	113.6 (6)	H21—C21—C22	120.2618
C22—N2—C18	118.2 (6)	C23—C24—H24	119.7641
N2—C18—C19	120.4 (6)	H24—C24—C25	119.7679
N2—C22—C21	122.7 (7)	C24—C25—H25	120.5144
C27—N3—C23	119.6 (7)	C25—C26—H26	120.9464
N3—C23—C24	120.1 (7)	H25—C25—C26	120.5169
N3—C27—C26	122.6 (8)	C26—C27—H27	118.7137
C32—N4—C28	117.2 (7)	H26—C26—C27	120.9576
N4—C28—C29	121.3 (9)	C28—C29—H29	120.4363
N4—C32—C31	124.7 (9)	H29—C29—C30	120.4217
N5—C33—C34	121.7 (9)	C29—C30—H30	120.0963
C37—N5—C33	116.6 (9)	C30—C31—H31	121.1645
N5—C37—C36	125.4 (8)	H30—C30—C31	120.0835
N6—C38—C39	121 (1)	C31—C32—H32	117.6467
C42—N6—C38	115.5 (9)	H31—C31—C32	121.1529
N6—C42—C41	123 (1)	C33—C34—H34	120.5472
C6—C1—C2	119.4 (8)	H34—C34—C35	120.5383
C1—C2—C3	120.0 (7)	C34—C35—H35	120.6123
C1—C6—C7	117.3 (8)	C35—C36—H36	120.8817
C1—C6—C5	119.4 (6)	H35—C35—C36	120.6163
C2—C3—C4	120.8 (6)	H36—C36—C37	120.9023
C3—C4—C5	120.2 (8)	C36—C37—H37	117.2820
C4—C5—C6	120.2 (8)	C38—C39—H39	120.2415
C5—C6—C7	123.4 (7)	H39—C39—C40	120.2417
C6—C7—C8	126.4 (8)	C39—C40—H40	120.0853
C7—C8—C9	121.3 (9)	C40—C41—H41	120.4866
C8—C9—C10	118.6 (7)	H40—C40—C41	120.0621
C9—C10—C11	118.4 (7)	H41—C41—C42	120.4767
C17—C12—C13	117.5 (7)	C41—C42—H42	118.2221
S1—Pt1—Pt2—S2	121.33 (5)	C5—C6—C7—N1	179.8 (6)
Pt2—Pt1—S1—C28	−39.0 (3)	N1—C7—C8—C9	0 (1)
Pt2—Pt1—S3—C33	157.6 (3)	C7—C8—C9—C10	0 (1)
Pt2—Pt1—N1—C7	−97.6 (6)	C8—C9—C10—C11	0 (1)
Pt2—Pt1—N3—C23	−30.5 (5)	C9—C10—C11—N1	0 (1)
Pt2—Pt1—C1—C2	−80.9 (8)	Pt2—C12—C13—C14	−178.1 (9)
Pt1—Pt2—S2—C23	−37.6 (3)	Pt2—C12—C17—C16	178.0 (9)
S2—Pt2—S4—C38	13.9 (4)	C12—C13—C14—C15	0 (1)
Pt1—Pt2—N2—C18	−97.3 (7)	C13—C14—C15—C16	0 (1)
Pt1—Pt2—N4—C28	−31.4 (5)	C14—C15—C16—C17	0 (1)
Pt1—Pt2—C12—C13	−83.0 (9)	C15—C16—C17—C12	0 (1)
Pt1—S1—C28—N4	29.0 (6)	C12—C17—C18—N2	−2 (1)
Pt2—S2—C23—N3	28.0 (7)	C16—C17—C18—N2	178.4 (9)
Pt1—S3—C33—N5	61.6 (8)	N2—C18—C19—C20	0 (1)
Pt2—S4—C38—N6	−125.8 (7)	C18—C19—C20—C21	−1 (1)
Pt1—N1—C7—C6	3 (1)	C19—C20—C21—C22	0 (1)
Pt1—N1—C11—C10	173.8 (8)	C20—C21—C22—N2	0 (1)
Pt2—N2—C18—C17	5 (1)	S2—C23—C24—C25	178.5 (7)
Pt2—N2—C22—C21	173.8 (8)	C23—C24—C25—C26	−1 (1)
Pt1—N3—C23—S2	5.8 (8)	C24—C25—C26—C27	3 (1)
Pt1—N3—C27—C26	175.6 (6)	C25—C26—C27—N3	0 (1)
Pt2—N4—C28—S1	5.8 (8)	S1—C28—C29—C30	179.4 (6)
Pt2—N4—C32—C31	175.2 (6)	C28—C29—C30—C31	−3 (1)
C37—N5—C33—S3	−177.4 (7)	C29—C30—C31—C32	4 (1)
C33—N5—C37—C36	−3 (1)	C30—C31—C32—N4	−1 (1)
C42—N6—C38—S4	−174.7 (8)	S3—C33—C34—C35	178.9 (9)
C38—N6—C42—C41	−11 (1)	C33—C34—C35—C36	0 (1)
Pt1—C1—C2—C3	−176.3 (8)	C34—C35—C36—C37	3 (1)
Pt1—C1—C6—C5	176.7 (8)	C35—C36—C37—N5	−1 (1)
C1—C2—C3—C4	0 (1)	S4—C38—C39—C40	−179.8 (7)
C2—C3—C4—C5	0 (1)	C38—C39—C40—C41	0 (1)
C3—C4—C5—C6	0 (1)	C39—C40—C41—C42	−5 (1)
C4—C5—C6—C1	0 (1)	C40—C41—C42—N6	11 (2)
C1—C6—C7—N1	0 (1)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···S4^i	0.93	2.76	3.60 (1)	150
C26—H26···N5^ii	0.93	2.76	3.54 (1)	142

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

(II) Bis(µ-pyridine-2-thiolato)-κ⁴S:N;N:S-bis[(pyridine-2-thiolato- κS)(2-pyridylphenyl-κ²N,C²)platinum(III)](Pt—Pt) acetonitrile solvate

Crystal data

[Pt2(C11H8N)2(C5H4NS)4]·C2H3N	F(000) = 2272.00
Mr = 1180.23	Dx = 1.987 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2yc	Cell parameters from 6621 reflections
a = 16.390 (1) Å	θ = 3.6–27.5°
b = 15.5766 (9) Å	µ = 7.31 mm^−1
c = 17.534 (2) Å	T = 173 K
β = 118.199 (3)°	Prism, dark red
V = 3945.3 (5) Å^3	0.40 × 0.20 × 0.18 mm
Z = 4

Data collection

Rigaku MercuryCCD diffractometer	3887 reflections with F^2 > 2σ(F^2)
Detector resolution: 7.31 pixels mm^-1	Rint = 0.028
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Higashi 1999)	h = −21→21
Tmin = 0.148, Tmax = 0.268	k = −19→20
15006 measured reflections	l = −22→22
4432 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 33.7943P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max = 0.007
S = 1.09	Δρmax = 3.15 e Å^−3
4432 reflections	Δρmin = −1.59 e Å^−3
255 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F² > 3.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.08730 (1)	0.56183 (1)	0.26401 (1)	0.01693 (7)
S1	0.03602 (7)	0.63849 (7)	0.13745 (7)	0.0225 (2)
S2	0.24222 (9)	0.57122 (8)	0.27053 (10)	0.0334 (3)
N1	0.1329 (2)	0.4858 (2)	0.3735 (2)	0.0194 (7)
N2	0.1045 (2)	0.6836 (2)	0.3313 (2)	0.0206 (7)
N3	0.3483 (4)	0.5165 (5)	0.4303 (4)	0.075 (2)
N4	0.070 (2)	0.106 (2)	0.316 (1)	0.118 (6)*	0.50
C1	0.0806 (3)	0.4458 (3)	0.2110 (3)	0.0184 (8)
C2	0.0608 (3)	0.4289 (3)	0.1256 (3)	0.0232 (9)
C3	0.0674 (3)	0.3459 (3)	0.1009 (3)	0.0303 (10)
C4	0.0925 (3)	0.2784 (3)	0.1592 (3)	0.0326 (10)
C5	0.1104 (4)	0.2950 (3)	0.2444 (4)	0.0391 (13)
C6	0.1072 (3)	0.3782 (3)	0.2702 (3)	0.0226 (8)
C7	0.1333 (3)	0.4000 (3)	0.3595 (3)	0.0214 (8)
C8	0.1602 (4)	0.3425 (3)	0.4279 (3)	0.0321 (10)
C9	0.1866 (4)	0.3733 (4)	0.5105 (3)	0.0379 (12)
C10	0.1871 (4)	0.4606 (4)	0.5239 (3)	0.0334 (10)
C11	0.1595 (3)	0.5152 (3)	0.4538 (3)	0.0259 (9)
C12	0.0548 (3)	0.7039 (3)	0.3719 (3)	0.0223 (8)
C13	0.0773 (3)	0.7766 (3)	0.4253 (3)	0.0262 (9)
C14	0.1489 (4)	0.8291 (3)	0.4350 (3)	0.0315 (10)
C15	0.1961 (3)	0.8107 (3)	0.3889 (3)	0.0305 (10)
C16	0.1726 (3)	0.7379 (3)	0.3383 (3)	0.0268 (9)
C17	0.3079 (4)	0.4935 (4)	0.3474 (4)	0.0427 (13)
C18	0.3144 (4)	0.4103 (4)	0.3217 (4)	0.047 (1)
C19	0.3608 (5)	0.3492 (5)	0.3817 (5)	0.063 (2)
C20	0.4004 (5)	0.3697 (7)	0.4675 (6)	0.077 (3)
C21	0.3947 (5)	0.4539 (6)	0.4896 (5)	0.072 (3)
C22	0.0311 (13)	0.0474 (13)	0.2776 (13)	0.083 (5)*	0.50
C23	0.0000	−0.035 (2)	0.2500	0.160 (9)*
H2	0.0433	0.4734	0.0856	0.028*
H3	0.0548	0.3351	0.0442	0.036*
H4	0.0974	0.2229	0.1422	0.039*
H5	0.1244	0.2500	0.2835	0.047*
H8	0.1605	0.2838	0.4184	0.039*
H9	0.2038	0.3354	0.5565	0.045*
H10	0.2058	0.4824	0.5790	0.040*
H11	0.1592	0.5740	0.4625	0.031*
H13	0.0436	0.7893	0.4542	0.031*
H14	0.1654	0.8763	0.4719	0.038*
H15	0.2428	0.8468	0.3920	0.037*
H16	0.2046	0.7254	0.3078	0.032*
H18	0.2868	0.3967	0.2631	0.057*
H19	0.3655	0.2937	0.3646	0.075*
H20	0.4304	0.3282	0.5099	0.093*
H21	0.4241	0.4686	0.5480	0.087*
H23A	0.0340	−0.0591	0.2233	0.192*	0.50
H23B	−0.0647	−0.0332	0.2089	0.192*	0.50
H23C	0.0089	−0.0694	0.2987	0.192*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01574 (9)	0.01707 (10)	0.01982 (10)	−0.00046 (5)	0.00992 (7)	−0.00071 (5)
S1	0.0255 (5)	0.0224 (5)	0.0248 (5)	0.0022 (4)	0.0159 (4)	0.0037 (4)
S2	0.0264 (6)	0.0296 (6)	0.0545 (8)	−0.0053 (4)	0.0278 (6)	−0.0053 (5)
N1	0.013 (2)	0.023 (2)	0.021 (2)	0.0027 (13)	0.0067 (13)	0.004 (1)
N2	0.022 (2)	0.018 (2)	0.022 (2)	−0.0024 (13)	0.011 (1)	−0.002 (1)
N3	0.042 (3)	0.116 (6)	0.055 (4)	0.010 (4)	0.014 (3)	−0.038 (4)
C1	0.013 (2)	0.021 (2)	0.023 (2)	−0.001 (1)	0.010 (2)	−0.002 (2)
C2	0.022 (2)	0.027 (2)	0.024 (2)	0.001 (2)	0.013 (2)	−0.002 (2)
C3	0.030 (2)	0.034 (3)	0.025 (2)	0.003 (2)	0.012 (2)	−0.006 (2)
C4	0.034 (3)	0.023 (2)	0.039 (3)	0.003 (2)	0.016 (2)	−0.008 (2)
C5	0.036 (3)	0.019 (2)	0.037 (3)	−0.007 (2)	−0.004 (2)	0.013 (2)
C6	0.023 (2)	0.016 (2)	0.031 (2)	−0.001 (2)	0.014 (2)	−0.001 (2)
C7	0.018 (2)	0.022 (2)	0.024 (2)	0.003 (2)	0.010 (2)	0.001 (2)
C8	0.037 (3)	0.027 (2)	0.034 (3)	0.010 (2)	0.018 (2)	0.009 (2)
C9	0.040 (3)	0.043 (3)	0.031 (3)	0.016 (2)	0.017 (2)	0.014 (2)
C10	0.030 (3)	0.045 (3)	0.023 (2)	0.008 (2)	0.011 (2)	−0.000 (2)
C11	0.022 (2)	0.030 (2)	0.024 (2)	0.001 (2)	0.009 (2)	−0.003 (2)
C12	0.025 (2)	0.020 (2)	0.021 (2)	0.002 (2)	0.010 (2)	0.001 (2)
C13	0.032 (2)	0.022 (2)	0.027 (2)	0.001 (2)	0.016 (2)	−0.001 (2)
C14	0.037 (3)	0.023 (2)	0.033 (2)	−0.005 (2)	0.015 (2)	−0.008 (2)
C15	0.032 (2)	0.023 (2)	0.036 (3)	−0.010 (2)	0.016 (2)	−0.004 (2)
C16	0.026 (2)	0.028 (2)	0.029 (2)	−0.004 (2)	0.015 (2)	−0.000 (2)
C17	0.024 (2)	0.057 (4)	0.046 (3)	0.005 (2)	0.016 (2)	−0.012 (3)
C18	0.034 (3)	0.050 (3)	0.058 (4)	0.009 (3)	0.022 (3)	−0.013 (3)
C19	0.042 (4)	0.066 (5)	0.075 (5)	0.020 (3)	0.024 (4)	−0.008 (4)
C20	0.052 (4)	0.111 (7)	0.074 (5)	0.039 (5)	0.033 (4)	0.022 (5)
C21	0.047 (4)	0.120 (7)	0.040 (4)	0.038 (4)	0.012 (3)	−0.008 (4)

Geometric parameters (Å, º)

Pt1—Pt1^i	2.6650 (2)	C14—C15	1.389 (9)
Pt1—S1	2.301 (1)	C15—C16	1.378 (7)
Pt1—S2	2.492 (2)	C17—C18	1.392 (9)
Pt1—N1	2.072 (4)	C18—C19	1.36 (1)
Pt1—N2	2.180 (4)	C19—C20	1.36 (1)
Pt1—C1	2.011 (4)	C20—C21	1.38 (1)
S1—C12^i	1.746 (5)	C22—C23	1.38 (3)
S2—C17	1.752 (6)	C23—C22^i	1.38 (3)
N1—C7	1.358 (6)	C2—H2	0.9300
N1—C11	1.343 (6)	C3—H3	0.9301
N2—C12	1.349 (7)	C4—H4	0.9299
N2—C16	1.358 (6)	C5—H5	0.9300
N3—C17	1.330 (9)	C8—H8	0.9301
N3—C21	1.37 (1)	C9—H9	0.9301
N4—C22	1.13 (3)	C10—H10	0.9299
C1—C2	1.398 (7)	C11—H11	0.9299
C1—C6	1.396 (6)	C13—H13	0.9302
C2—C3	1.385 (7)	C14—H14	0.9300
C3—C4	1.386 (7)	C15—H15	0.9299
C4—C3	1.386 (7)	C16—H16	0.9300
C4—C5	1.403 (9)	C18—H18	0.9300
C5—C6	1.383 (7)	C19—H19	0.9301
C6—C7	1.454 (7)	C20—H20	0.9301
C7—C8	1.393 (7)	C21—H21	0.9300
C8—C9	1.386 (8)	C23—H23A	0.9588
C9—C10	1.379 (8)	C23—H23A^i	0.9588
C10—C11	1.382 (7)	C23—H23B	0.9604
C12—S1^i	1.746 (5)	C23—H23B^i	0.9604
C12—C13	1.403 (6)	C23—H23C	0.9606
C13—C14	1.372 (8)	C23—H23C^i	0.9606
S1—Pt1—Pt1^i	87.20 (3)	C8—C9—C10	119.6 (5)
S2—Pt1—Pt1^i	172.21 (4)	C9—C10—C11	118.8 (5)
N1—Pt1—Pt1^i	93.3 (1)	C12—S1^i—Pt1^i	107.5 (2)
N2—Pt1—Pt1^i	87.3 (1)	C13—C12—S1^i	118.5 (4)
C1—Pt1—Pt1^i	95.5 (1)	C12—C13—C14	120.3 (6)
S2—Pt1—S1	85.05 (5)	C13—C14—C15	118.9 (5)
N1—Pt1—S1	176.3 (1)	C14—C15—C16	118.7 (5)
N2—Pt1—S1	88.0 (1)	C17—C18—C19	120.2 (7)
C1—Pt1—S1	96.0 (1)	C18—C19—C20	119.5 (8)
Pt1—S1—C12^i	107.5 (2)	C19—C20—C21	118.1 (8)
N1—Pt1—S2	94.4 (1)	N1—C11—H11	118.9920
N2—Pt1—S2	93.2 (1)	N2—C16—H16	118.6779
C1—Pt1—S2	84.6 (1)	N3—C21—H21	118.3026
Pt1—S2—C17	103.7 (2)	C1—C2—H2	120.0770
N2—Pt1—N1	95.7 (1)	H2—C2—C3	120.0851
C1—Pt1—N1	80.3 (2)	C2—C3—H3	119.4159
Pt1—N1—C7	115.2 (3)	H3—C3—C4	119.4016
Pt1—N1—C11	124.9 (3)	C3—C4—H4	120.4885
C1—Pt1—N2	175.2 (1)	C4—C5—H5	120.0006
Pt1—N2—C12	122.3 (3)	H4—C4—C5	120.4891
Pt1—N2—C16	118.8 (4)	H5—C5—C6	120.0095
Pt1—C1—C2	126.7 (3)	C7—C8—H8	120.2619
Pt1—C1—C6	113.8 (3)	H8—C8—C9	120.2451
S1—C12^i—N2^i	120.9 (3)	C8—C9—H9	120.2324
S1—C12^i—C13^i	118.5 (4)	C9—C10—H10	120.6094
S2—C17—N3	117.5 (6)	H9—C9—C10	120.2078
S2—C17—C18	120.5 (5)	C10—C11—H11	118.9836
N1—C7—C6	113.6 (4)	H10—C10—C11	120.6079
C11—N1—C7	119.9 (4)	C12—C13—H13	119.8590
N1—C7—C8	120.2 (4)	H13—C13—C14	119.8529
N1—C11—C10	122.0 (5)	C13—C14—H14	120.5597
N2—C12—S1^i	120.9 (3)	C14—C15—H15	120.6316
C16—N2—C12	118.8 (4)	H14—C14—C15	120.5402
N2—C12—C13	120.5 (4)	C15—C16—H16	118.6632
N2—C16—C15	122.7 (6)	H15—C15—C16	120.6312
N3—C17—C18	122.0 (6)	C17—C18—H18	119.8950
C21—N3—C17	116.8 (8)	H18—C18—C19	119.9006
N3—C21—C20	123.4 (7)	C18—C19—H19	120.2627
N4—C22—C23	164 (1)	C19—C20—H20	120.9564
C6—C1—C2	119.1 (4)	H19—C19—C20	120.2752
C1—C2—C3	119.8 (4)	H20—C20—C21	120.9509
C1—C6—C7	117.0 (4)	C20—C21—H21	118.3073
C1—C6—C5	120.7 (5)	C22—C23—H23A	109.4777
C2—C3—C4	121.2 (5)	C22—C23—H23B	109.4540
C3—C4—C5	119.0 (5)	C22—C23—H23C	109.4639
C4—C5—C6	120.0 (5)	H23B—C23—H23A	109.5426
C5—C6—C7	122.3 (4)	H23C—C23—H23A	109.5054
C6—C7—C8	126.1 (4)	H23C—C23—H23B	109.3836
C7—C8—C9	119.5 (5)
S1—Pt1—S2—C17	−164.5 (2)	C4—C5—C6—C1	4.0 (8)
S2—Pt1—N1—C7	−86.3 (3)	C1—C6—C7—N1	−3.5 (6)
S1—Pt1—N2—C12	115.9 (3)	C5—C6—C7—N1	174.8 (5)
S1—Pt1—C1—C2	6.6 (4)	N1—C7—C8—C9	0.0 (8)
Pt1—S2—C17—N3	−85.1 (6)	C7—C8—C9—C10	−1.0 (9)
Pt1—N1—C7—C6	3.9 (5)	C8—C9—C10—C11	1.3 (9)
Pt1—N1—C11—C10	178.4 (4)	C9—C10—C11—N1	−0.6 (8)
Pt1—N2—C12—C13	170.3 (3)	N2—C12—C13—C14	1.7 (6)
Pt1—N2—C16—C15	−171.5 (3)	C12—C13—C14—C15	2.2 (6)
C21—N3—C17—S2	176.3 (6)	C13—C14—C15—C16	−3.2 (6)
C17—N3—C21—C20	0 (1)	C14—C15—C16—N2	0.5 (6)
Pt1—C1—C2—C3	173.9 (4)	S2—C17—C18—C19	−176.1 (7)
Pt1—C1—C6—C5	−177.0 (4)	C17—C18—C19—C20	0 (1)
C1—C2—C3—C4	0.6 (8)	C18—C19—C20—C21	−2 (1)
C2—C3—C4—C5	0.8 (8)	C19—C20—C21—N3	2 (1)
C3—C4—C5—C6	−3.1 (8)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N4	0.93	2.57	3.38 (3)	146
C14—H14···N3^ii	0.93	2.48	3.36 (1)	157

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