Synthesis and structures of dinuclear palladium complexes with 1,3-benzimidazolidine-2-thione and 1,3-imidazoline-2-thione.

The synthesis and structures of dinuclear palladium complexes with 1,3-benz-imidazolidine-2-thione (bzimtH) and 1,3-imidazoline-2-thione (imtH) are reported, namely, bis-(μ-1H-benzimidazole-2-thiol-ato)-κ(2) N (3):S;κ(2) S:N (3)-bis-[cyanido(tri-phenyl-phosphine-κP)palladium(II)], [Pd(2)(C(7)H(5)N(2)S)(2)(CN)(2)(C(18)H(15)P)(2)] or [Pd(2)(μ-N,S-bzimtH)(2)(CN)(2)(PPh(3))(2)] (1), and bis-(μ-1H-imidazole-2-thiol-ato)-κ(2) N (3):S;κ(2) S:N (3)-bis-[cyanido(tri-phenyl-phosphine-κP)palladium(II)] aceto-nitrile 0.58-solvate, [Pd(2)(C(3)H(3)N(2)S)(2)(CN)(2)(C(18)H(15)P)(2)]·0.58C(2)H(3)N or [Pd(2)(μ-N,S-imtH)(2)(CN)(2)(PPh(3))(2)]·0.58C(2)H(3)N (2). The compound [Pd(2)(μ-N,S-bzimtH)(2)(CN)(2)(PPh(3))(2)] is located on a crystallographic twofold axis while [Pd(2)(μ-N,S-imtH)(2)(CN)(2)(PPh(3))(2)]. 0.58(C(2)H(3)N) contains two partially occupied aceto-nitrile solvent mol-ecules with occupancies of 0.25 and 0.33. In both of these compounds, the anionic bzimtH(-) and imtH(-) ligands coordinate through N,S-donor atoms in a bridging mode, covering four coordination sites of two metal centers and other two sites are occupied by two PPh(3) ligand mol-ecules. Finally, the remaining two sites of two metal centers are occupied by cyano groups, abstracted by the metals from the solvent during reaction. In the packing of the 1,3-benzimidazolidine- 2-thione and 1,3-imidazoline-2-thione complexes, there are intra-molecular π-π inter-actions involving the thione moiety as well as an N-H⋯N hydrogen bond linking the thione and cyano ligands. In addition, in 2, as well as the π-π inter-action involving the thione moieties, there is an additional π-π inter-action involving one of the thione moieties and an adjacent phenyl ring from the tri-phenyl-phosphine ligand. There are also C-H⋯N inter-actions between the imidazoline rings and the aceto-nitrile N atoms.