A family of isostructural, mononuclear Co-II complexes with distorted trigonal bipyramidal coordination environments is reported. The degree of distortion as well as the overall symmetry of the molecules varies among the members of the series. Different experimental procedures resulted in the isolation of solvomorphs (pseudopolymorphs with different solvent content) for some of the family members. Importantly, their disparate packing arrangements lead to very different dynamic magnetic behavior. The results of magnetostructural correlations and ab initio calculations reveal that the deciding factor for SMM behavior is not the degree of distortion which, a priori, would be expected to be the case, but rather the interactions between neighboring molecules in the solid state.