A series of bulky substituted bipyridine-related iron(II) complexes [Fe(H2Bpz2)2(L)] (pz = pyrazoly1) were prepared, where L = 5,5'-dimethy1-2,2'-bipyridine (bipy-CH3, 1), L = dimethy1-2,21-bipyridy1-5,5'-dicarboxylate (MeObpydc, 2), L = diethyl-2,2'-bipyridy1-5,5'-dicarboxylate (EtObpydc, 3), or L = diisopropy1-2,2'-bipyridine-5,5'-dicarboxylate (iPrObpydc, 4). The crystal structures of five new iron(II) complexes were determined by X-ray diffraction: those of 1, 3, and 4 and two modifications of 3 (3B) and 4 (4B). Complexes 1 and 3B display incomplete spin crossover (SCO) behavior because of a freezing -in effect, whereas 3 and 4B undergo gradual and incomplete SCO behaviors. Complexes 2 and 4 show a completely gradual and steep SCO, respectively. Such different SCO behaviors can be attributed to an electronic substituent effect in the bipyridyl ligand conformation and a crystal packing effect. Importantly, the electronic substituent effect of the isopropyl acetate group and C-H center dot center dot center dot O supramolecular interactions in 4 contribute to a highly cooperative behavior, which leads to an abrupt thermally induced spin transition.