Chlorido{5-chloro-2-[2-(methyl­sulfanyl)phenyl­diazen­yl]phenyl}­platinum(II)

Vivek Bagchi; Debkumar Bandyopadhyay

doi:10.1107/S1600536808000767

. 2008 Jan 16;64(Pt 2):m359. doi: 10.1107/S1600536808000767

Chlorido{5-chloro-2-[2-(methylsulfanyl)phenyldiazenyl]phenyl}platinum(II)

Vivek Bagchi ^a, Debkumar Bandyopadhyay ^a,^*

PMCID: PMC2960293 PMID: 21201318

Abstract

The title compound, [Pt(C₁₃H₁₀ClN₂S)Cl], contains a Pt atom tetracoordinated by a benzene C, a diazene N, a Cl and an S atom in an approximately square-planar geometry. The molecules dimerize through a nonbonded S⋯S interaction [S⋯S = 3.523 (18) Å]. There are no hydrogen bonds and the crystal packing is stabilized by four intermolecular π–π interactions; the centroid–centroid distances are 3.804 (3), 3.638 (3), 3.804 (3) and 3.638 (3) Å, and the corresponding perpendicular distances are 3.369, 3.448, 3.406 and 3.466 Å.

Related literature

For related literature, see: Bagchi et al. (2007 ▶); Chattopadhyay et al. (1991 ▶); Dupont et al. (2005 ▶); Buraway & Vellins (1954 ▶).

Experimental

Crystal data

[Pt(C₁₃H₁₀ClN₂S)Cl]
M _r = 492.28
Triclinic,
a = 7.424 (2) Å
b = 8.777 (3) Å
c = 11.069 (3) Å
α = 105.428 (4)°
β = 91.798 (4)°
γ = 96.641 (4)°
V = 689.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 10.70 mm⁻¹
T = 273 (2) K
0.42 × 0.28 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.035, T _max = 0.134
6783 measured reflections
2544 independent reflections
2472 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.018
wR(F ²) = 0.043
S = 1.05
2544 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000767/at2531sup1.cif

e-64-0m359-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000767/at2531Isup2.hkl

e-64-0m359-Isup2.hkl^{(124.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pt1—N1	1.959 (3)
Pt1—C12	1.986 (3)
Pt1—Cl1	2.2911 (11)
Pt1—S1	2.3529 (10)

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N1—Pt1—C12	79.26 (14)
C12—Pt1—Cl1	96.84 (11)
N1—Pt1—S1	86.25 (9)
Cl1—Pt1—S1	97.57 (4)

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Acknowledgments

We thank the Department of Science and Technology, India (project No. SR/S1/IC-04/2007), for funding and CSIR for a fellowship to VB. The single-crystal X-ray diffractometer facility provided by IITD is gratefully acknowledged.

supplementary crystallographic information

Comment

Cyclometallated compounds have numerous applications (Dupont et al., 2005) in organic synthesis, catalysis and metallomesogen chemistry. Although a number of cycloplatinated complexes have been reported in the literature, report of platinum complexes with sulfur as auxiliary donor and the existence of C–Pt bond are sparse. Herein we report the crystal structure of (I) having such features.

The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The platinum atom along with donor set of four atoms lie almost in one plane. Selected bond lengths, bond angles are listed in Table 1. The packing arrangement of (I) is shown in Fig. 2. The N?N bond length is similar of other cycloplatinated azoarenes (Chattopadhyay et al., 1991).

The metal carbon bond length, 1.986 (3) Å, is slightly lower than the reported values of other ortho-metallated azoarenes (Chattopadhyay et al., 1991). The molecules are found to dimerize through non-bonded S···S interaction; having S···Sⁱ [symmetry code: (i) -x, 2 - y, -z] distance of 3.523 (18) Å (Bagchi et al. 2007) (Fig.3).The crystal packing is stabilized by four inter-molecular π-π interactions; the Cg3—Cg4ⁱⁱ, Cg3—Cg4ⁱⁱⁱ, Cg4—Cg3ⁱⁱ, Cg4—Cg3ⁱⁱⁱ, [symmetry codes: (ii) -x, 1 - y, -z, (iii) 1 - x, 1 - y, -z. Cg3 and Cg4 are the centroids of C1—C6 and C7—C12 rings, respectively] distances are 3.638 (3), 3.804 (3), 3.638 (3) and 3.804 (3) Å, respectively; the corresponding perpendicular distances are 3.448, 3.369, 3.466 and 3.406 Å, respectively (Fig. 4).

Experimental

2-(Methylsulfanyl)diazenyl-4-chlorobenzene was prepared by coupling 2-(methylsulfanyl)aniline with 4-nitroso-chlorobenzene. The ligand thus obtained was reacted with K₂PtCl₄ following a reported method (Buraway & Vellins, 1954). The product was purified by column chromatographic technique using silica gel column and methanol and dichloromethane (1:9 v/v) mixture as eluent. The solvent was evaporated in vacuum to obtain the pure product (78.3%). Suitable crystals of (I) were grown from a dichloromethane–hexane solution by slow evaporation.