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

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.


Experimental
Crystal data [Pt(C 13 Table 1 Selected geometric parameters (Å , ).  (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···S i [symmetry code: Experimental 2-(Methylsulfanyl)diazenyl-4-chlorobenzene was prepared by coupling 2-(methylsulfanyl)aniline with 4-nitroso-chlorobenzene. The ligand thus obtained was reacted with K 2 PtCl 4 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.

Refinement
H atoms were included at calculated positions as riding atoms with C-H set to 0.93 Å for (aromatic) and 0.96 Å for (CH 3 ) H atoms, with U iso (H) = 1.2U eq (C) [1.5U eq for methyl group].
supplementary materials sup-2 Figures   Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level. Fig. 2. The molecular arrangement of (I) in the unitcell.   Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.