Utilization of mixtures of differently coordinating aromatic N-donor ligands leads to the formation of the two new compounds {[Ni(phen)₂]₂Sn₂S₆}·4,4′-bipy·½H₂O I and {[Ni(phen)₂]₂Sn₂S₆}·2,2′-bipy II that could be prepared under solvothermal conditions (4,4′-bipy = 4,4′-bipyridine, C₁₀H₈N₂; phen = 1,10-phenanthroline, C₁₂H₈N₂; 2,2′-bipy = 2,2′-bipyridine, C₁₀H₈N₂). In the structures of both compounds Ni–S bond formation is observed which is highly unusual when only bidentate N-donor ligands are applied in the reaction mixture. The detailed analysis of the crystal structure indicates that the presence of 4,4′-bipy and 2,2′-bipy molecules are essential for the stabilization of the arrangement of the constituents. The main structural motif {[Ni(phen)₂]₂Sn₂S₆} is arranged generating off center parallel stacking of the phen ligands. The empty spaces between the {[Ni(phen)₂]₂Sn₂S₆} moieties are occupied by either 2,2′-bipy (I) or 4,4′-bipy (II) molecules which are oriented towards the phen ligands to form intermolecular π–π interactions.