Synthesis and molecular structure of biologically significant bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) complexes with chloride and dichloridoaurate counter-ions.

Diffraction-quality single crystals of two gold(I) complexes, namely bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) chloride benzene monosolvate, [Au(C29H26N2O2)2]Cl·C6H6 or [(NQMes)2Au]Cl·C6H6, 2, and bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) dichloridoaurate(I) dichloromethane disolvate, [Au(C29H26N2O2)2][AuCl2]·2CH2Cl2 or [(NQMes)2Au][AuCl2]·2CH2Cl2, 4, were isolated and studied with the aid of single-crystal X-ray diffraction analysis. Compound 2 crystallizes in a monoclinic space group C2/c with eight molecules in the unit cell, while compound 4 crystallizes in the triclinic space group P-1 with two molecules in the unit cell. The crystal lattice of compound 2 reveals C-H...Cl- interactions that are present throughout the entire structure representing head-to-tail contacts between the aromatic (C-H) hydrogens of naphthoquinone and Cl- counter-ions. Compound 4 stacks with the aid of short interactions between a naphthoquinone O atom of one molecule and the mesityl methyl group of another molecule along the a axis, leading to a one-dimensional strand that is held together by strong π-η2 interactions between the imidazolium backbone and the [AuCl2]- counter-ion. The bond angles defined by the AuI atom and two carbene C atoms [C(carbene)-Au-C(carbene)] in compounds 2 and 4 are nearly rectilinear, with an average value of ∼174.1 [2]°. Though 2 and 4 share the same cation, they differ in their counter-anion, which alters the crystal lattice of the two compounds. The knowledge gleaned from these studies is expected to be useful in understanding the molecular interactions of 2 and 4 under physiological conditions.