The [Fe(PM-BiA)(2)(NCS)(2)] complex, where PM is N-2-pyridylmethylene and BiA is 4-aminobiphenyl, crystallizes in two polymorphs. The two phases, denoted (I) and (II), undergo a spin-crossover when the sample is cooled and present distinct spin-transition features as (I) shows a very abrupt spin transition, while (II) exhibits a gradual transition. The two forms of the complex are used to investigate the correlations that exist between the spin-transition features and structural features. This article presents the crystal structures of polymorph (II) at room temperature (high spin) and at 120 K (low spin), including a comparison with those of polymorph (I). This study reveals that the packing, in a first approximation, is similar in both forms. In order to look at the crystal structures in more detail, a new angular parameter, denoted theta(NCS), as well as a particular type of intermolecular hydrogen-bond interaction, which involves the S atoms of the NCS ligands, are investigated. Interestingly, this angle and this intermolecular interaction can be directly connected to the cooperativity of the spin transition. Such a result is extended to all the SCO iron(II) complexes belonging to the same family of the general formula [Fe(PM-L)(2)(NCS)(2)].