Six analogue compounds with the general formula [Fe2( xL)5(NCS)4]· yMeOH ( x = o-Cl, y = 3 for compound 1; x = m-Cl, y = 5 for 2; x = p-Cl, y = 1 for 3; x = o-Me, y = 2 for 4; x = m-Me, y = 2 for 5; x = p-Me, y = 3 for 6; L = N-phenylmethylene-4-amino-1,2,4-triazole) were synthesized. The two Fe(II) ions are triply bridged by the triazole groups of three xL ligands and each Fe(II) is further capped with two NCS- groups and one more xL ligand. These compounds show regular patterns in their magnetic properties that depend on the positions the substituent groups (-Cl or -Me) ride, i.e., ortho-substituted compounds 1 and 4 undergo complete one-step spin crossover (SCO), while meta-substituted compounds 2 and 5 display incomplete one-step SCO with lower transition temperatures, and para-substituted compounds 3 and 6 are in the high-spin states in all temperature ranges. Structural analyses reveal that the molecular geometry and intermolecular interactions of these compounds, which should account for the differences in magnetic properties, are obviously depend on the positions of substituent groups (steric effect), despite them being electron-withdrawing chlorine or electron-donating methyl, whereas theoretical calculations confirm that the electronic effects of substituent groups exert no effect on the magnetic properties.