Solvothermal reaction of 2-mercaptonicotinic acid (H L 1) with copper(II) nitrate in DMF/methanol medium leads to the production of a novel hexanuclear complex [Cu( L 2)] 6 · (H 2O) 2 ( 1), in which in situ formation of an anionic ligand 2-thiolate- N, N′-dimethylnicotinamide ( L 2) and reduction of copper(II) to copper(I) are observed. X-ray single-crystal structure of 1 reveals that each copper(I) center adopts a trigonal geometry provided by two thiolate and one pyridyl groups from three separated L 2 ligands. As a result, six copper(I) ions are interconnected by six μ 3– L 2 bridges to afford a hexanuclear cluster, in which the octahedral Cu 6 core is stabilized by significant cuprophilic interactions.