Understanding the origin of cooperativity and the equilibrium temperature of transition (T-1/2) displayed by the spin-crossover (SCO) compounds as well as controlling these parameters are of paramount importance for future applications. For this task, the occurrence of polymorphism, presented by a number of SCO complexes, may provide deep insight into the influence of the supramolecular organization on the SCO behavior. In this context, herein we present a novel family of mononuclear octahedral Fe-II complexes with formula cis-[Fe(bqen)(NCX)(2)], where bqen is the chelating tetradentate ligand N,N'-bis(8-quinolyl)ethane-1,2-diamine and X = S, Se. Depending on the preparation method, these compounds crystallize in either the orthorhombic or the trigonal symmetry systems. While the orthorhombic phase is composed of a racemic mixture of mononuclear complexes (polymorph I), the trigonal phase contains only one of the two possible enantiomers (Delta or Delta), thereby generating a chiral crystal (polymorph II). The four derivatives undergo SCO behavior with well-differentiated T-1/2 values occurring in the interval 90-233 K. On one hand, T-1/2 is about 110 K (polymorph I) and 87 K (polymorph II) higher for the selenocyanate derivatives in comparison to those for their thiocyanate counterparts. These differences in T-1/2 are ascribed not only to the higher ligand field induced by the selenocyanate anion but also to a remarkable difference in the structural reorganization of the [FeN6] coordination core upon SCO. Likewise, the higher cooperativity observed for the thiocyanate derivatives seems to be related to their stronger intermolecular interactions within the crystal. On the other hand, T-1/2 is about 53 K (thiocyanate) and 29 K (selenocyanate) higher for the trigonal polymorph II in comparison to those for the orthorhombic polymorph I. These differences, and the small changes observed in cooperativity, stem from the slightly different hetero- and homochiral crystal packing generated by the cis-[Fe(bqen)(NCX)(2)] molecules, which determines subtle adaptations in the intermolecular contacts and the Feu coordination core.