The reaction of [Cr(CO) 6 ] with a series of heterocyclic bidentate (N,S) ligands in refluxing mesitylene afforded the homoleptic trischelate complexes [Cr(3-Me 3 SipyS) 3 ] (2), [Cr(3-CF 3 pyS) 3 ] (3) and [Cr(5-CF 3 pyS) 3 ] (4), where R-pyS stands for the anion of the corresponding substituted pyridine-2-thione ligand. Studies in the solid state by X-ray diffraction showed that the reaction with the unsubstituted ligand HpyS yielded the compound [Cr(pyS) 3 ]/[Cr(pyS) 2 (pySS)] (1), which is a two-component co-crystal comprising the homoleptic species [Cr(pyS) 3 ] (1a) and the heteroleptic species [Cr(pyS) 2 (pySS)] (1b), in a 1:1 ratio. While the structure of the species [Cr(pyS) 3 ] (1a) is analogous to that of other homoleptic compounds, [Cr(RpyS) 3 ], the species [Cr(pyS) 2 (pySS)] (1b) is an unusual heteroleptic complex containing both pyridine-2-thionate and pyridine-2-dithionate ligands. All of the compounds obtained were characterized by microanalysis and FAB spectrometry, and by IR and UV–Vis spectroscopies. X-ray studies showed that in all cases the metal is in a distorted octahedral environment with the heterocyclic ligand acting as a bidentate (N,S) chelate system. The supramolecular organization in complexes (1) and (2) through hydrogen bonding, weak C–H⋯π and π–π interactions was analyzed.