The reaction of fac-[ReX(CH3CN)(2)(CO)(3)] (X = Cl, Br) with N-phenyl-[4-(dimethylamino)benzaldehyde] thiosemicarbazone (HLA) or N-4-methoxybenzyl-[4-(dimethylamino)benzaldehyde] thiosemicarbazone (HLB) under controlled synthetic conditions gave 4 mononuclear [ReX(HL)(CO)(3)] (X = Cl, Br) and 16 dinuclear [Re2L2(CO)(6)] compounds. These complexes were obtained as single crystals, and their structures were established by X-ray diffraction. The structural study of these dimers showed the formation of several solvates, the presence of linkage isomerism, and the stabilization of four- and/or five-membered chelate rings. The different ligand coordination modes (a new mu-kappa(2)-S,N2:kappa-N3 coordination mode for a thiosemicarbazone ligand was observed), the conformation of the thiosemicarbazone chain in each case, the formal symmetry of the dimers, and the role of the synthetic procedure in the stability of the different chelate rings were analyzed and are discussed. Theoretical calculations in the gas phase were performed for the dimers with the HLA ligand in order to identify the thermodynamically most stable species. The behavior and structural stability of dimers in dimethyl sulfoxide and acetone solutions was investigated by H-1 NMR spectroscopy. The strength of the Re-I-L bond in solution was evidenced by the formation of [Re-2(L-NO2)(2)(CO)(6)] and [Re(L-A)(py)(CO)(3)] upon reaction of the corresponding dimer with concentrated nitric acid and pyridine, respectively.