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-1 H -benzimidazole-2-thiol-ato)-κ 2 N 3 : S ;κ 2 S : N 3 -bis-[cyanido(tri-phenyl-phosphine-κ P )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-1 H -imidazole-2-thiol-ato)-κ 2 N 3 : S ;κ 2 S : N 3 -bis-[cyanido(tri-phenyl-phosphine-κ P )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.