[μ-2,3,5,6-Tetrakis(2-pyridyl)­pyrazine]­bis­[chloro­platinum(II)] bis­[tri­chloro­(di­methyl sulfoxide-κS)­platinate(II)]

Sakai, K.; Kurashima, M.

doi:10.1107/S1600536803011541

[μ-2,3,5,6-Tetrakis(2-pyridyl)pyrazine]bis[chloroplatinum(II)] bis[trichloro(dimethyl sulfoxide-κS)platinate(II)]

A reaction of cis-PtCl₂(DMSO)₂ (DMSO = dimethyl sulfoxide, C₂H₆OS) with 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tpp, C₂₄H₁₆N₆) gave the title salt, [Pt₂Cl₂(μ-tpp)][PtCl₃(DMSO)]₂. The compound consists of a dinuclear Pt cation, [Pt₂Cl₂(μ-tpp)]²⁺, and two [PtCl₃(DMSO)]⁻ anions. The two Pt atoms within the cation are separated by a distance of 6.4792 (17) Å, and their coordination planes are canted at an angle of 19.6 (9)°. The shortest intermolecular Pt

Pt distance is 4.5726 (16) Å. Metal–metal interactions are unimportant in the crystal structure, and the packing is stabilized by extensive π–π interactions between the tpp moieties, in addition to ionic interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011541/lh6065sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011541/lh6065Isup2.hkl Contains datablock I

CCDC reference: 217354

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.040 Å
R factor = 0.079
wR factor = 0.117
Data-to-parameter ratio = 12.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



THETM_01  Alert B The value of sine(theta_max)/wavelength is less than 0.575
          Calculated sin(theta_max)/wavelength =    0.5559

Author response: See Experimental


 Alert Level C:



PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C(5)   -   C(6)   =       1.56 Ang.


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Attempts have been made thus far to develop new types of one-dimensional platinum compounds in our laboratory (Sakai et al., 2002). We were hoping to obtain systems involving relatively large aromatic systems and recently started exploring the coordination chemistry of platinum and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tpp). The title compound was obtained during efforts to synthesize tetravalent dimer cations of hexadentate tpp, such as [Pt₂(NH₃)₂(µ-tpp)]⁴⁺, even though the preparation of such compounds have been unsuccessful so far. Here we report on the crystal structure of an unprecedented double salt obtained for the Pt-tpp family, [Pt₂Cl₂(µ-tpp)][PtCl₃(DMSO)]₂, (I).

Up until now, at least 34 tpp complexes have been structurally analyzed by X-ray diffraction (see CCDC), and at least eight kinds of coordination modes have been characterized. These compounds involve mono-, di-, and trinuclear complexes, but there have been no structures of mixed-metal complexes determined. Among them, 12 complexes possess a structure in which tpp bridges two metal centers with two tridentate moieties in a mer fashion. As for Pt, only one compound, namely [Pt₂(PEt₃)₂Cl₂(µ-tpp)][Pt(SnCl₃)₄(PEt₃)] (Teles et al., 2000), has been structurally characterized, where tpp binds to two Pt atoms with two bidentate moieties while the two N donors of the pyrazine ring do not take part in the coordination. In this context, this is the first example of a Pt–tpp complex in which tpp bridges two Pt centers in a fully ligated form with two chelates in a mer fashion.

As shown in Fig. 1, a dinuclear cation and two mononuclear anions are found in the asymmetric unit of (I). Displacement parameters of DMSO C and O atoms are relatively large, reflecting the rotational flexibility about the Pt—S axes. The tpp ligand is largely distorted from the planarity in order to avoid the steric contacts between the protons at the 3-position of pyridyl moieties. The twist originated at the tpp ligand is estimated to be ω(tpp) = 26.7 (2)° based on the best-plane calculations performed for two halves of the ligand (see Fig. 2), where 15-atom r.m.s. deviations are 0.102 and 0.117 Å. The twist angle estimated based on the dihedral cant between two Pt coordination planes is ω(Pt1/Pt2) = 19.6 (9)°, where four-atom r.m.s. deviations are 0.008 and 0.014 Å. These values are quite similar to those reported for [Pd₂(NO₃)₂(µ-tpp)](NO₃)₂·0.5H₂O [ω(tpp) = 29.1° and ω(Pd1/Pd2) = 21.9°; Yamada et al., 2000]. On the other hand, Ni complexes are reported to have relatively large twists compared to those discussed above [ω(tpp) = 38.3° and ω(Ni1/Ni2) = 31.9° for [Ni₂(acetato)₄(H₂O)₂(µ-tpp)]·CH₂O (Koman et al., 1998), and ω(tpp) = 34.6° and ω(Ni1/Ni2) = 25.1° for [Ni₂(H₂O)₆(µ-tpp)](NO₃)₄·2.5H₂O (Graf et al., 1997)].

Shifts of Pt1 and Pt2 atoms from their coordination planes are estimated as 0.020 and 0.003 Å, respectively. The former is clearly relevant to the effective d–π interaction achieved between the Pt atom and the neighbouring tpp moiety [Pt1—C24ⁱⁱ = 3.40 (3) Å; symmetry code: (ii) −x, 1 − y, 1 − z]. However, face-to-face interactions between the tpp ligands appear to dominate the stabilization of crystal packing of (I). The intermolecular Pt···Pt distances listed in Table 1 indicate that Pt···Pt interactions are not enhanced in this system.

Finally, it should be noted that the Pt—Cl distances within the dimer unit [2.278 (7) and 2.268 (7) Å] are effectively shorter than those in [PtCl₃(DMSO)]⁻ [2.294 (8)–2.320 (7) Å], presumably due to the relatively strong back-donation promoted by the tpp ligand.

Experimental top

A solution of tpp (0.050 mmol, 0.020 g; Goodwin & Lions, 1959) and cis-PtCl₂(DMSO)₂ (0.10 mmol, 0.042 g; Price et al., 1972) in methanol (15 ml) was reacted within a pressure-resistant sealed tube at 393 K for 12 h. After the solution was cooled down to room temperature, orange prisms of (I) were collected by filtration.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: KENX (Sakai, 2002); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 1999), KENX and ORTEPII (Johnson, 1976).

Figures top

	Fig. 1. The structures of the three independent complex ions in (I), showing the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A view along the Cl1—Pt1···Pt2—Cl2 axis, showing a twist of the tpp ligand.

[µ-2,3,5,6-Tetrakis(2-pyridyl)pyrazine]bis[chloroplatinum(II)] bis[trichloro(dimethylsulfoxide-κS)platinate(II)] top

Crystal data top

[Pt₂Cl₂(C₂₄H₁₆N₆)][PtCl₃(C₂H₆OS)]₂	Z = 2
M_r = 1608.64	F(000) = 1468
Triclinic, P1	D_x = 2.639 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0868 (11) Å	Cell parameters from 818 reflections
b = 12.9476 (14) Å	θ = 2.5–19.1°
c = 16.5057 (19) Å	µ = 14.45 mm⁻¹
α = 94.085 (2)°	T = 296 K
β = 105.321 (2)°	Plate, orange
γ = 100.954 (2)°	0.08 × 0.04 × 0.02 mm
V = 2024.3 (4) Å³

Data collection top

Bruker SMART APEX CCD-detector diffractometer	5638 independent reflections
Radiation source: fine-focus sealed tube	3198 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
Detector resolution: 8.366 pixels mm^-1	θ_max = 23.3°, θ_min = 1.3°
ω scans	h = −11→11
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001)	k = −14→14
T_min = 0.511, T_max = 0.868	l = −18→18
9820 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²)]
5638 reflections	(Δ/σ)_max < 0.001
455 parameters	Δρ_max = 1.55 e Å⁻³
516 restraints	Δρ_min = −1.15 e Å⁻³

Crystal data top

[Pt₂Cl₂(C₂₄H₁₆N₆)][PtCl₃(C₂H₆OS)]₂	γ = 100.954 (2)°
M_r = 1608.64	V = 2024.3 (4) Å³
Triclinic, P1	Z = 2
a = 10.0868 (11) Å	Mo Kα radiation
b = 12.9476 (14) Å	µ = 14.45 mm⁻¹
c = 16.5057 (19) Å	T = 296 K
α = 94.085 (2)°	0.08 × 0.04 × 0.02 mm
β = 105.321 (2)°

Data collection top

Bruker SMART APEX CCD-detector diffractometer	5638 independent reflections
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001)	3198 reflections with I > 2σ(I)
T_min = 0.511, T_max = 0.868	R_int = 0.088
9820 measured reflections	θ_max = 23.3°

Refinement top

R[F² > 2σ(F²)] = 0.079	516 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 0.91	Δρ_max = 1.55 e Å⁻³
5638 reflections	Δρ_min = −1.15 e Å⁻³
455 parameters

Special details top

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.8512 (0.0614) x + 10.7782 (0.0468) y − 4.6091 (0.0679) z = 4.7019 (0.0552)

* −0.0096 (0.0106) N1 * 0.0078 (0.0089) N3 * 0.0081 (0.0090) N6 * −0.0063 (0.0071) Cl1 − 0.0196 (0.0083) Pt1

Rms deviation of fitted atoms = 0.0080

6.7517 (0.0537) x + 7.7647 (0.0739) y − 5.4038 (0.0664) z = 2.2118 (0.0535)

Angle to previous plane (with approximate e.s.d.) = 19.58 (0.85)

* −0.0174 (0.0110) N2 * 0.0141 (0.0090) N4 * 0.0143 (0.0091) N5 * −0.0110 (0.0070) Cl2 0.0027 (0.0085) Pt2

Rms deviation of fitted atoms = 0.0144

3.3898 (0.0167) x + 11.0993 (0.0136) y − 4.6873 (0.0827) z = 4.9330 (0.0381)

Angle to previous plane (with approximate e.s.d.) = 22.38 (0.64)

* −0.0105 (0.0183) N1 * 0.0871 (0.0181) N3 * −0.1101 (0.0188) N6 * 0.0365 (0.0205) C1 * −0.0240 (0.0214) C2 * −0.0626 (0.0226) C3 * −0.0518 (0.0214) C4 * 0.1188 (0.0233) C5 * 0.1497 (0.0199) C6 * −0.1659 (0.0210) C19 * −0.1668 (0.0232) C20 * 0.0856 (0.0214) C21 * 0.1365 (0.0223) C22 * 0.0584 (0.0219) C23 * −0.0808 (0.0216) C24 − 0.0425 (0.0072) Pt1 − 0.0572 (0.0194) Cl1

Rms deviation of fitted atoms = 0.1020

7.2953 (0.0133) x + 6.9817 (0.0221) y − 5.2481 (0.0901) z = 1.7046 (0.0209)

Angle to previous plane (with approximate e.s.d.) = 26.71 (0.23)

* −0.0382 (0.0178) N2 * −0.1742 (0.0199) N4 * 0.1241 (0.0197) N5 * −0.1906 (0.0205) C7 * −0.1263 (0.0230) C8 * 0.1002 (0.0215) C9 * 0.1777 (0.0233) C10 * 0.0254 (0.0231) C11 * −0.0830 (0.0220) C12 * 0.0913 (0.0226) C13 * −0.0244 (0.0215) C14 * −0.0999 (0.0221) C15 * −0.0354 (0.0210) C16 * 0.0798 (0.0224) C17 * 0.1734 (0.0208) C18 − 0.0395 (0.0082) Pt2 − 0.0770 (0.0212) Cl2

Rms deviation of fitted atoms = 0.1170

5.4325 (0.0793) x + 9.3310 (0.0831) y − 5.4008 (0.1234) z = 3.3613 (0.0742)

Angle to previous plane (with approximate e.s.d.) = 13.84 (0.93)

* −0.0112 (0.0158) N1 * −0.0151 (0.0154) N2 * −0.0994 (0.0160) C6 * 0.1107 (0.0159) C7 * −0.0912 (0.0166) C18 * 0.1063 (0.0168) C19

Rms deviation of fitted atoms = 0.0838

6.2140 (0.0183) x + 8.4965 (0.0225) y − 4.4550 (0.0398) z = 6.4807 (0.0222)

Angle to previous plane (with approximate e.s.d.) = 6.82 (1.00)

* 0.0294 (0.0039) Cl3 * −0.0294 (0.0039) Cl4 * 0.0297 (0.0039) Cl5 * −0.0297 (0.0040) S1 0.0232 (0.0041) Pt3

Rms deviation of fitted atoms = 0.0296

3.4853 (0.0242) x − 4.1967 (0.0373) y + 13.2509 (0.0260) z = 0.6451 (0.0234)

Angle to previous plane (with approximate e.s.d.) = 89.79 (0.21)

* 0.0537 (0.0045) Cl6 * −0.0548 (0.0046) Cl7 * 0.0560 (0.0047) Cl8 * −0.0550 (0.0046) S2 0.0046 (0.0050) Pt4

Rms deviation of fitted atoms = 0.0549

0.2069 (0.0242) x + 3.4467 (0.0613) y + 14.5238 (0.0262) z = 8.8818 (0.0304)

Angle to previous plane (with approximate e.s.d.) = 36.83 (0.23)

* 0.4305 (0.0215) C1 * 0.0729 (0.0195) C2 * 0.1073 (0.0209) C23 * 0.3803 (0.0229) C24 * −0.4378 (0.0186) N3 * −0.5121 (0.0190) N6 * −0.4305 (0.0215) C1_$1 * −0.0729 (0.0195) C2_$1 * −0.1073 (0.0209) C23_$1 * −0.3803 (0.0229) C24_$1 * 0.4378 (0.0185) N3_$1 * 0.5121 (0.0189) N6_$1

Rms deviation of fitted atoms = 0.3653

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pt1	−0.07386 (12)	0.65039 (8)	0.44332 (7)	0.0288 (3)
Pt2	−0.25499 (12)	0.53161 (9)	0.03547 (7)	0.0334 (3)
Pt3	0.05194 (13)	0.85989 (9)	0.25251 (8)	0.0382 (3)
Pt4	−0.49029 (12)	0.25699 (9)	0.25938 (7)	0.0322 (3)
Cl1	−0.0098 (8)	0.6901 (5)	0.5869 (4)	0.045 (2)
Cl2	−0.3209 (8)	0.4879 (6)	−0.1071 (4)	0.056 (2)
Cl3	−0.0695 (8)	0.8785 (7)	0.1172 (5)	0.062 (3)
Cl4	0.1616 (8)	0.7434 (6)	0.1950 (5)	0.053 (2)
Cl5	0.1785 (9)	0.8377 (6)	0.3852 (5)	0.059 (2)
Cl6	−0.6873 (9)	0.2354 (6)	0.3081 (6)	0.066 (3)
Cl7	−0.4423 (9)	0.4365 (6)	0.2991 (5)	0.058 (2)
Cl8	−0.2887 (7)	0.2848 (6)	0.2190 (5)	0.050 (2)
S1	−0.0597 (8)	0.9645 (5)	0.3081 (5)	0.043 (2)
S2	−0.5377 (10)	0.0878 (7)	0.2138 (7)	0.071 (3)
O1	−0.184 (2)	0.9102 (14)	0.3277 (13)	0.062 (6)
O2	−0.453 (2)	0.0460 (16)	0.1631 (16)	0.084 (7)
N1	−0.124 (2)	0.6167 (15)	0.3204 (13)	0.023 (4)
N2	−0.201 (2)	0.5659 (15)	0.1562 (13)	0.023 (5)
N3	−0.252 (2)	0.7057 (14)	0.4175 (13)	0.025 (5)
N4	−0.372 (2)	0.6385 (16)	0.0414 (14)	0.040 (5)
N5	−0.120 (2)	0.4377 (16)	0.0674 (14)	0.037 (5)
N6	0.092 (2)	0.5901 (15)	0.4349 (13)	0.026 (5)
C1	−0.316 (3)	0.7424 (18)	0.4695 (16)	0.030 (5)
H1	−0.2704	0.7535	0.5273	0.036*
C2	−0.446 (3)	0.7649 (19)	0.4414 (17)	0.036 (6)
H2	−0.4863	0.7924	0.4804	0.043*
C3	−0.516 (3)	0.749 (2)	0.3603 (18)	0.042 (6)
H3	−0.6043	0.7650	0.3426	0.050*
C4	−0.458 (3)	0.7067 (19)	0.3010 (18)	0.036 (6)
H4	−0.5072	0.6890	0.2440	0.044*
C5	−0.317 (3)	0.6929 (19)	0.3338 (17)	0.032 (5)
C6	−0.235 (3)	0.6468 (18)	0.2775 (16)	0.025 (5)
C7	−0.265 (3)	0.6354 (18)	0.1881 (17)	0.029 (5)
C8	−0.352 (3)	0.685 (2)	0.1205 (17)	0.032 (5)
C9	−0.400 (3)	0.7773 (19)	0.1339 (17)	0.036 (6)
H9	−0.3788	0.8109	0.1889	0.043*
C10	−0.477 (3)	0.820 (2)	0.0688 (18)	0.043 (6)
H10	−0.5089	0.8815	0.0785	0.051*
C11	−0.507 (3)	0.767 (2)	−0.0129 (19)	0.051 (7)
H11	−0.5647	0.7895	−0.0591	0.061*
C12	−0.447 (3)	0.682 (2)	−0.0228 (18)	0.044 (6)
H12	−0.4592	0.6519	−0.0779	0.052*
C13	−0.097 (3)	0.369 (2)	0.014 (2)	0.053 (7)
H13	−0.1319	0.3697	−0.0438	0.064*
C14	−0.018 (3)	0.292 (2)	0.0439 (18)	0.044 (6)
H14	−0.0014	0.2432	0.0058	0.053*
C15	0.032 (3)	0.292 (2)	0.1270 (18)	0.041 (6)
H15	0.0821	0.2408	0.1471	0.049*
C16	0.011 (3)	0.3649 (19)	0.1822 (18)	0.038 (6)
H16	0.0472	0.3657	0.2403	0.046*
C17	−0.066 (3)	0.4385 (19)	0.1512 (17)	0.030 (5)
C18	−0.101 (3)	0.5257 (19)	0.2015 (17)	0.029 (5)
C19	−0.045 (3)	0.5659 (19)	0.2905 (17)	0.029 (5)
C20	0.086 (3)	0.552 (2)	0.3533 (18)	0.035 (5)
C21	0.204 (3)	0.5319 (19)	0.3366 (18)	0.038 (6)
H21	0.2069	0.5200	0.2809	0.045*
C22	0.318 (3)	0.529 (2)	0.4010 (19)	0.043 (6)
H22	0.3953	0.5085	0.3893	0.052*
C23	0.321 (3)	0.555 (2)	0.4825 (19)	0.043 (6)
H23	0.3991	0.5542	0.5272	0.052*
C24	0.207 (3)	0.5835 (19)	0.4963 (17)	0.034 (6)
H24	0.2076	0.5995	0.5522	0.040*
C25	0.049 (3)	1.041 (2)	0.403 (2)	0.082 (11)
H25A	0.0024	1.0924	0.4208	0.122*
H25B	0.1359	1.0766	0.3939	0.122*
H25C	0.0696	0.9954	0.4460	0.122*
C26	−0.098 (3)	1.069 (2)	0.248 (2)	0.066 (10)
H26A	−0.1883	1.0460	0.2064	0.099*
H26B	−0.0269	1.0891	0.2196	0.099*
H26C	−0.1000	1.1294	0.2847	0.099*
C27	−0.717 (3)	0.040 (3)	0.148 (2)	0.084 (11)
H27A	−0.7412	0.0899	0.1090	0.125*
H27B	−0.7797	0.0330	0.1831	0.125*
H27C	−0.7255	−0.0274	0.1169	0.125*
C28	−0.549 (5)	0.017 (3)	0.297 (3)	0.147 (18)
H28A	−0.6187	0.0372	0.3212	0.221*
H28B	−0.4595	0.0324	0.3389	0.221*
H28C	−0.5761	−0.0572	0.2767	0.221*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.0364 (8)	0.0275 (7)	0.0203 (7)	0.0084 (6)	0.0037 (6)	0.0022 (5)
Pt2	0.0376 (8)	0.0380 (7)	0.0207 (7)	0.0049 (6)	0.0043 (6)	0.0026 (6)
Pt3	0.0414 (8)	0.0322 (7)	0.0433 (9)	0.0066 (6)	0.0171 (7)	0.0030 (6)
Pt4	0.0332 (8)	0.0328 (7)	0.0322 (8)	0.0085 (6)	0.0098 (6)	0.0083 (6)
Cl1	0.059 (5)	0.046 (5)	0.027 (5)	0.017 (4)	0.002 (4)	0.004 (4)
Cl2	0.067 (6)	0.069 (6)	0.018 (4)	0.008 (5)	−0.001 (4)	−0.010 (4)
Cl3	0.054 (6)	0.093 (6)	0.039 (5)	0.027 (5)	0.007 (5)	−0.003 (5)
Cl4	0.069 (6)	0.048 (5)	0.051 (5)	0.029 (4)	0.021 (5)	0.002 (4)
Cl5	0.080 (6)	0.064 (5)	0.046 (5)	0.031 (5)	0.024 (5)	0.017 (4)
Cl6	0.055 (6)	0.076 (6)	0.078 (7)	0.018 (5)	0.036 (5)	0.016 (5)
Cl7	0.072 (6)	0.046 (5)	0.061 (6)	0.014 (4)	0.024 (5)	0.006 (4)
Cl8	0.029 (5)	0.068 (5)	0.050 (5)	−0.002 (4)	0.014 (4)	0.008 (4)
S1	0.043 (5)	0.023 (4)	0.066 (6)	0.002 (4)	0.025 (5)	0.006 (4)
S2	0.070 (7)	0.047 (5)	0.109 (8)	0.016 (5)	0.049 (6)	0.007 (5)
O1	0.049 (11)	0.054 (11)	0.082 (13)	0.000 (9)	0.026 (10)	0.004 (10)
O2	0.082 (13)	0.060 (12)	0.112 (15)	0.024 (10)	0.030 (12)	−0.018 (11)
N1	0.014 (9)	0.030 (9)	0.025 (9)	0.010 (8)	−0.001 (8)	0.007 (8)
N2	0.013 (9)	0.028 (9)	0.023 (9)	0.000 (8)	0.004 (8)	−0.003 (8)
N3	0.028 (9)	0.029 (9)	0.019 (9)	0.012 (8)	0.002 (8)	0.011 (8)
N4	0.048 (10)	0.039 (10)	0.025 (10)	0.000 (9)	0.003 (9)	0.010 (8)
N5	0.045 (10)	0.036 (10)	0.029 (10)	0.006 (8)	0.014 (9)	−0.002 (9)
N6	0.021 (9)	0.034 (9)	0.025 (10)	0.017 (8)	0.002 (8)	−0.001 (8)
C1	0.032 (10)	0.036 (10)	0.022 (10)	0.010 (9)	0.010 (9)	−0.003 (9)
C2	0.035 (11)	0.041 (10)	0.033 (11)	0.006 (9)	0.015 (9)	−0.007 (10)
C3	0.043 (11)	0.037 (10)	0.040 (11)	0.007 (9)	0.003 (10)	0.003 (10)
C4	0.036 (11)	0.035 (10)	0.035 (11)	0.008 (9)	0.006 (9)	−0.003 (9)
C5	0.025 (9)	0.031 (9)	0.034 (10)	0.003 (8)	0.002 (8)	0.001 (9)
C6	0.022 (9)	0.021 (9)	0.026 (9)	−0.008 (8)	0.005 (8)	0.010 (8)
C7	0.028 (9)	0.022 (9)	0.030 (9)	−0.007 (8)	0.002 (8)	0.010 (8)
C8	0.034 (10)	0.027 (9)	0.033 (10)	0.005 (8)	0.003 (9)	0.015 (8)
C9	0.043 (11)	0.031 (10)	0.033 (11)	0.016 (9)	−0.001 (9)	0.019 (9)
C10	0.046 (11)	0.042 (11)	0.037 (11)	0.020 (9)	−0.003 (10)	0.021 (10)
C11	0.056 (12)	0.053 (11)	0.036 (11)	0.011 (10)	−0.001 (10)	0.019 (10)
C12	0.053 (11)	0.046 (11)	0.030 (11)	0.010 (10)	0.007 (10)	0.005 (10)
C13	0.052 (11)	0.057 (12)	0.048 (11)	0.007 (10)	0.014 (10)	0.004 (10)
C14	0.046 (11)	0.044 (11)	0.043 (11)	0.004 (10)	0.019 (10)	0.003 (10)
C15	0.043 (11)	0.042 (11)	0.041 (11)	0.008 (9)	0.018 (10)	0.006 (10)
C16	0.047 (11)	0.035 (11)	0.036 (11)	−0.004 (9)	0.025 (9)	0.002 (9)
C17	0.032 (9)	0.029 (9)	0.031 (9)	0.002 (8)	0.015 (8)	0.000 (9)
C18	0.023 (9)	0.028 (9)	0.032 (9)	−0.003 (8)	0.007 (8)	0.007 (8)
C19	0.024 (9)	0.025 (9)	0.036 (10)	0.006 (8)	0.003 (8)	0.013 (8)
C20	0.029 (9)	0.034 (9)	0.043 (10)	0.006 (8)	0.009 (9)	0.012 (9)
C21	0.030 (11)	0.041 (10)	0.045 (11)	0.005 (9)	0.016 (9)	0.016 (9)
C22	0.034 (11)	0.044 (11)	0.049 (12)	0.015 (9)	0.001 (10)	0.015 (10)
C23	0.043 (11)	0.043 (11)	0.042 (11)	0.015 (9)	0.001 (10)	0.026 (10)
C24	0.037 (11)	0.042 (10)	0.029 (11)	0.020 (9)	0.011 (9)	0.009 (9)
C25	0.097 (19)	0.068 (17)	0.075 (19)	0.036 (15)	0.010 (15)	−0.012 (14)
C26	0.066 (17)	0.065 (16)	0.072 (18)	0.031 (14)	0.011 (14)	0.023 (14)
C27	0.072 (18)	0.081 (17)	0.090 (19)	0.012 (14)	0.016 (15)	0.000 (14)
C28	0.16 (2)	0.13 (2)	0.15 (2)	0.037 (17)	0.042 (18)	0.025 (17)

Geometric parameters (Å, º) top

Pt1—N1	1.95 (2)	N2—C18	1.31 (3)
Pt1—N6	2.008 (18)	N2—C7	1.36 (3)
Pt1—N3	2.017 (19)	N3—C1	1.31 (3)
Pt1—Cl1	2.278 (7)	N3—C5	1.35 (3)
Pt2—N2	1.92 (2)	N4—C8	1.35 (3)
Pt2—N5	1.99 (2)	N4—C12	1.36 (3)
Pt2—N4	1.99 (2)	N5—C13	1.30 (3)
Pt2—Cl2	2.268 (7)	N5—C17	1.34 (3)
Pt3—S1	2.212 (7)	N6—C24	1.35 (3)
Pt3—Cl5	2.294 (8)	N6—C20	1.38 (3)
Pt3—Cl3	2.300 (8)	C1—C2	1.37 (3)
Pt3—Cl4	2.320 (7)	C2—C3	1.32 (3)
Pt4—S2	2.184 (8)	C3—C4	1.39 (3)
Pt4—Cl8	2.276 (7)	C4—C5	1.43 (3)
Pt4—Cl7	2.292 (7)	C5—C6	1.56 (3)
Pt4—Cl6	2.310 (8)	C6—C7	1.42 (3)
Pt1—Pt2	6.4792 (17)	C7—C8	1.49 (3)
Pt1—Pt3	4.5726 (16)	C8—C9	1.40 (3)
Pt2—Pt2ⁱ	4.662 (2)	C9—C10	1.37 (3)
Pt1—Pt1ⁱⁱ	4.760 (2)	C10—C11	1.40 (4)
Pt2—Pt3	5.2396 (16)	C11—C12	1.37 (3)
Pt2—Pt2ⁱⁱⁱ	5.758 (2)	C13—C14	1.42 (3)
Pt2—Pt4	5.9359 (16)	C14—C15	1.33 (3)
Pt1—Pt4	5.9778 (16)	C15—C16	1.36 (3)
Pt1—C24ⁱⁱ	3.40 (3)	C16—C17	1.38 (3)
S1—O1	1.445 (18)	C17—C18	1.50 (3)
S1—C25	1.76 (3)	C18—C19	1.45 (3)
S1—C26	1.78 (3)	C19—C20	1.50 (3)
S2—O2	1.49 (2)	C20—C21	1.36 (3)
S2—C28	1.72 (4)	C21—C22	1.35 (3)
S2—C27	1.81 (3)	C22—C23	1.36 (3)
N1—C19	1.29 (3)	C23—C24	1.33 (3)
N1—C6	1.30 (3)

N1—Pt1—N6	81.2 (8)	C1—N3—Pt1	129.5 (18)
N1—Pt1—N3	83.4 (8)	C5—N3—Pt1	111.8 (16)
N6—Pt1—N3	164.6 (8)	C8—N4—C12	117 (2)
N1—Pt1—Cl1	178.6 (6)	C8—N4—Pt2	113.7 (18)
N6—Pt1—Cl1	97.6 (6)	C12—N4—Pt2	128.7 (19)
N3—Pt1—Cl1	97.8 (6)	C13—N5—C17	120 (2)
N1—Pt1—Pt1ⁱⁱ	106.0 (6)	C13—N5—Pt2	124 (2)
N6—Pt1—Pt1ⁱⁱ	50.9 (6)	C17—N5—Pt2	114.8 (17)
N3—Pt1—Pt1ⁱⁱ	136.5 (5)	C24—N6—C20	116 (2)
Cl1—Pt1—Pt1ⁱⁱ	73.60 (17)	C24—N6—Pt1	129.5 (17)
N2—Pt2—N5	80.5 (9)	C20—N6—Pt1	114.1 (17)
N2—Pt2—N4	82.1 (9)	N3—C1—C2	122 (3)
N5—Pt2—N4	162.5 (9)	C3—C2—C1	121 (3)
N2—Pt2—Cl2	179.0 (6)	C2—C3—C4	120 (3)
N5—Pt2—Cl2	99.1 (7)	C3—C4—C5	116 (3)
N4—Pt2—Cl2	98.4 (7)	N3—C5—C4	122 (2)
N2—Pt2—Pt2ⁱ	102.7 (6)	N3—C5—C6	114 (2)
N5—Pt2—Pt2ⁱ	132.4 (6)	C4—C5—C6	123 (2)
N4—Pt2—Pt2ⁱ	53.2 (6)	N1—C6—C7	118 (2)
Cl2—Pt2—Pt2ⁱ	76.8 (2)	N1—C6—C5	114 (2)
S1—Pt3—Cl5	90.6 (3)	C7—C6—C5	128 (2)
S1—Pt3—Cl3	91.6 (3)	N2—C7—C6	114 (2)
Cl5—Pt3—Cl3	177.7 (3)	N2—C7—C8	112 (2)
S1—Pt3—Cl4	177.3 (3)	C6—C7—C8	134 (2)
Cl5—Pt3—Cl4	89.0 (3)	N4—C8—C9	121 (2)
Cl3—Pt3—Cl4	88.7 (3)	N4—C8—C7	114 (2)
S2—Pt4—Cl8	91.7 (3)	C9—C8—C7	125 (3)
S2—Pt4—Cl7	176.6 (4)	C10—C9—C8	122 (3)
Cl8—Pt4—Cl7	87.0 (3)	C9—C10—C11	117 (3)
S2—Pt4—Cl6	90.9 (3)	C12—C11—C10	118 (3)
Cl8—Pt4—Cl6	176.5 (3)	N4—C12—C11	125 (3)
Cl7—Pt4—Cl6	90.6 (3)	N5—C13—C14	121 (3)
O1—S1—C25	106.2 (14)	C15—C14—C13	119 (3)
O1—S1—C26	110.3 (13)	C14—C15—C16	120 (3)
C25—S1—C26	98.9 (15)	C15—C16—C17	119 (3)
O1—S1—Pt3	114.9 (8)	N5—C17—C16	121 (2)
C25—S1—Pt3	111.9 (11)	N5—C17—C18	112 (2)
C26—S1—Pt3	113.2 (11)	C16—C17—C18	127 (3)
O2—S2—C28	111.9 (18)	N2—C18—C19	118 (2)
O2—S2—C27	103.5 (16)	N2—C18—C17	112 (2)
C28—S2—C27	98.0 (18)	C19—C18—C17	130 (2)
O2—S2—Pt4	119.8 (10)	N1—C19—C18	114 (2)
C28—S2—Pt4	108.8 (15)	N1—C19—C20	116 (2)
C27—S2—Pt4	112.6 (11)	C18—C19—C20	130 (2)
C19—N1—C6	127 (2)	C21—C20—N6	119 (3)
C19—N1—Pt1	116.8 (18)	C21—C20—C19	127 (3)
C6—N1—Pt1	116.2 (16)	N6—C20—C19	111 (2)
C18—N2—C7	125 (2)	C22—C21—C20	120 (3)
C18—N2—Pt2	118.4 (17)	C21—C22—C23	121 (3)
C7—N2—Pt2	116.9 (17)	C24—C23—C22	118 (3)
C1—N3—C5	118 (2)	C23—C24—N6	125 (3)

Cl5—Pt3—S1—O1	−87.0 (11)	Pt1—N1—C6—C5	−7 (3)
Cl3—Pt3—S1—O1	93.3 (11)	N3—C5—C6—N1	7 (3)
Cl5—Pt3—S1—C25	34.2 (12)	C4—C5—C6—N1	−164 (2)
Cl3—Pt3—S1—C25	−145.6 (12)	N3—C5—C6—C7	−172 (2)
Cl5—Pt3—S1—C26	144.9 (12)	C4—C5—C6—C7	16 (4)
Cl3—Pt3—S1—C26	−34.8 (12)	C18—N2—C7—C6	−11 (3)
Cl8—Pt4—S2—O2	−9.2 (13)	Pt2—N2—C7—C6	172.1 (15)
Cl6—Pt4—S2—O2	173.2 (13)	C18—N2—C7—C8	168 (2)
Cl8—Pt4—S2—C28	121.2 (16)	Pt2—N2—C7—C8	−9 (3)
Cl6—Pt4—S2—C28	−56.3 (16)	N1—C6—C7—N2	19 (3)
Cl8—Pt4—S2—C27	−131.3 (14)	C5—C6—C7—N2	−162 (2)
Cl6—Pt4—S2—C27	51.2 (14)	N1—C6—C7—C8	−160 (3)
N6—Pt1—N1—C19	6.1 (18)	C5—C6—C7—C8	19 (4)
N3—Pt1—N1—C19	−175.4 (19)	C12—N4—C8—C9	−4 (4)
Pt1ⁱⁱ—Pt1—N1—C19	−38.8 (19)	Pt2—N4—C8—C9	165.2 (19)
N6—Pt1—N1—C6	−174.7 (18)	C12—N4—C8—C7	−178 (2)
N3—Pt1—N1—C6	3.8 (17)	Pt2—N4—C8—C7	−9 (3)
Pt1ⁱⁱ—Pt1—N1—C6	140.4 (16)	N2—C7—C8—N4	11 (3)
N5—Pt2—N2—C18	5.8 (18)	C6—C7—C8—N4	−170 (3)
N4—Pt2—N2—C18	−173.3 (19)	N2—C7—C8—C9	−162 (2)
Pt2ⁱ—Pt2—N2—C18	137.4 (17)	C6—C7—C8—C9	17 (4)
N5—Pt2—N2—C7	−177.5 (18)	N4—C8—C9—C10	5 (4)
N4—Pt2—N2—C7	3.3 (17)	C7—C8—C9—C10	179 (2)
Pt2ⁱ—Pt2—N2—C7	−46.0 (17)	C8—C9—C10—C11	0 (4)
N1—Pt1—N3—C1	175 (2)	C9—C10—C11—C12	−5 (4)
N6—Pt1—N3—C1	−180 (3)	C8—N4—C12—C11	−1 (4)
Cl1—Pt1—N3—C1	−6 (2)	Pt2—N4—C12—C11	−169 (2)
Pt1ⁱⁱ—Pt1—N3—C1	68 (2)	C10—C11—C12—N4	6 (4)
N1—Pt1—N3—C5	0.5 (17)	C17—N5—C13—C14	2 (4)
N6—Pt1—N3—C5	6 (4)	Pt2—N5—C13—C14	−168.7 (18)
Cl1—Pt1—N3—C5	179.9 (16)	N5—C13—C14—C15	0 (4)
Pt1ⁱⁱ—Pt1—N3—C5	−105.8 (16)	C13—C14—C15—C16	−2 (4)
N2—Pt2—N4—C8	3.4 (18)	C14—C15—C16—C17	1 (4)
N5—Pt2—N4—C8	1 (4)	C13—N5—C17—C16	−2 (4)
Cl2—Pt2—N4—C8	−177.6 (17)	Pt2—N5—C17—C16	169.5 (18)
Pt2ⁱ—Pt2—N4—C8	115.9 (19)	C13—N5—C17—C18	178 (2)
N2—Pt2—N4—C12	171 (2)	Pt2—N5—C17—C18	−11 (3)
N5—Pt2—N4—C12	169 (2)	C15—C16—C17—N5	0 (4)
Cl2—Pt2—N4—C12	−10 (2)	C15—C16—C17—C18	−180 (2)
Pt2ⁱ—Pt2—N4—C12	−76 (2)	C7—N2—C18—C19	−7 (4)
N2—Pt2—N5—C13	174 (2)	Pt2—N2—C18—C19	169.9 (16)
N4—Pt2—N5—C13	177 (2)	C7—N2—C18—C17	171 (2)
Cl2—Pt2—N5—C13	−5 (2)	Pt2—N2—C18—C17	−13 (3)
Pt2ⁱ—Pt2—N5—C13	76 (2)	N5—C17—C18—N2	15 (3)
N2—Pt2—N5—C17	3.5 (17)	C16—C17—C18—N2	−165 (2)
N4—Pt2—N5—C17	6 (4)	N5—C17—C18—C19	−168 (2)
Cl2—Pt2—N5—C17	−175.5 (17)	C16—C17—C18—C19	12 (4)
Pt2ⁱ—Pt2—N5—C17	−95.1 (18)	C6—N1—C19—C18	−10 (4)
N1—Pt1—N6—C24	176 (2)	Pt1—N1—C19—C18	169.0 (16)
N3—Pt1—N6—C24	170 (2)	C6—N1—C19—C20	173 (2)
Cl1—Pt1—N6—C24	−4 (2)	Pt1—N1—C19—C20	−8 (3)
Pt1ⁱⁱ—Pt1—N6—C24	−65 (2)	N2—C18—C19—N1	17 (3)
N1—Pt1—N6—C20	−3.0 (17)	C17—C18—C19—N1	−159 (2)
N3—Pt1—N6—C20	−9 (4)	N2—C18—C19—C20	−166 (2)
Cl1—Pt1—N6—C20	177.7 (16)	C17—C18—C19—C20	17 (4)
Pt1ⁱⁱ—Pt1—N6—C20	116.0 (19)	C24—N6—C20—C21	−13 (4)
C5—N3—C1—C2	2 (4)	Pt1—N6—C20—C21	165.2 (19)
Pt1—N3—C1—C2	−171.8 (18)	C24—N6—C20—C19	−179 (2)
N3—C1—C2—C3	1 (4)	Pt1—N6—C20—C19	0 (3)
C1—C2—C3—C4	0 (4)	N1—C19—C20—C21	−159 (3)
C2—C3—C4—C5	−5 (4)	C18—C19—C20—C21	25 (4)
C1—N3—C5—C4	−7 (4)	N1—C19—C20—N6	5 (3)
Pt1—N3—C5—C4	167.6 (19)	C18—C19—C20—N6	−171 (2)
C1—N3—C5—C6	−179 (2)	N6—C20—C21—C22	13 (4)
Pt1—N3—C5—C6	−4 (3)	C19—C20—C21—C22	175 (2)
C3—C4—C5—N3	9 (4)	C20—C21—C22—C23	−6 (4)
C3—C4—C5—C6	180 (2)	C21—C22—C23—C24	1 (4)
C19—N1—C6—C7	−8 (4)	C22—C23—C24—N6	−2 (4)
Pt1—N1—C6—C7	172.6 (16)	C20—N6—C24—C23	8 (4)
C19—N1—C6—C5	172 (2)	Pt1—N6—C24—C23	−170 (2)

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

Experimental details

Crystal data
Chemical formula	[Pt₂Cl₂(C₂₄H₁₆N₆)][PtCl₃(C₂H₆OS)]₂
M_r	1608.64
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	10.0868 (11), 12.9476 (14), 16.5057 (19)
α, β, γ (°)	94.085 (2), 105.321 (2), 100.954 (2)
V (Å³)	2024.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	14.45
Crystal size (mm)	0.08 × 0.04 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD-detector diffractometer
Absorption correction	Gaussian (XPREP in SAINT; Bruker, 2001)
T_min, T_max	0.511, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	9820, 5638, 3198
R_int	0.088
θ_max (°)	23.3
(sin θ/λ)_max (Å⁻¹)	0.556

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.117, 0.91
No. of reflections	5638
No. of parameters	455
No. of restraints	516
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.55, −1.15

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), KENX (Sakai, 2002), SHELXL97, TEXSAN (Molecular Structure Corporation, 1999), KENX and ORTEPII (Johnson, 1976).

Selected geometric parameters (Å, º) top

Pt1—N1	1.95 (2)	Pt4—Cl8	2.276 (7)
Pt1—N6	2.008 (18)	Pt4—Cl7	2.292 (7)
Pt1—N3	2.017 (19)	Pt4—Cl6	2.310 (8)
Pt1—Cl1	2.278 (7)	Pt1—Pt2	6.4792 (17)
Pt2—N2	1.92 (2)	Pt1—Pt3	4.5726 (16)
Pt2—N5	1.99 (2)	Pt2—Pt2ⁱ	4.662 (2)
Pt2—N4	1.99 (2)	Pt1—Pt1ⁱⁱ	4.760 (2)
Pt2—Cl2	2.268 (7)	Pt2—Pt3	5.2396 (16)
Pt3—S1	2.212 (7)	Pt2—Pt2ⁱⁱⁱ	5.758 (2)
Pt3—Cl5	2.294 (8)	Pt2—Pt4	5.9359 (16)
Pt3—Cl3	2.300 (8)	Pt1—Pt4	5.9778 (16)
Pt3—Cl4	2.320 (7)	Pt1—C24ⁱⁱ	3.40 (3)
Pt4—S2	2.184 (8)

N1—Pt1—N6	81.2 (8)	S1—Pt3—Cl5	90.6 (3)
N1—Pt1—N3	83.4 (8)	S1—Pt3—Cl3	91.6 (3)
N6—Pt1—N3	164.6 (8)	Cl5—Pt3—Cl3	177.7 (3)
N1—Pt1—Cl1	178.6 (6)	S1—Pt3—Cl4	177.3 (3)
N6—Pt1—Cl1	97.6 (6)	Cl5—Pt3—Cl4	89.0 (3)
N3—Pt1—Cl1	97.8 (6)	Cl3—Pt3—Cl4	88.7 (3)
N2—Pt2—N5	80.5 (9)	S2—Pt4—Cl8	91.7 (3)
N2—Pt2—N4	82.1 (9)	S2—Pt4—Cl7	176.6 (4)
N5—Pt2—N4	162.5 (9)	Cl8—Pt4—Cl7	87.0 (3)
N2—Pt2—Cl2	179.0 (6)	S2—Pt4—Cl6	90.9 (3)
N5—Pt2—Cl2	99.1 (7)	Cl8—Pt4—Cl6	176.5 (3)
N4—Pt2—Cl2	98.4 (7)	Cl7—Pt4—Cl6	90.6 (3)