A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL Me-Benz ) reacts with Fe II Cl 2 ·4H 2 O and NaPF 6 at a 3:1:1 molar ratio to yield a tris(2-methylimidazol-4-yl-methylideneaminobenzyl)iron(II) chloride hexafluorophosphate solvate with the formula of [Fe II (HL Me-Benz ) 3 ]Cl·PF 6 ·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe II (HL Me-Benz ) 3 ]Cl·PF 6 ·1.5H 2 O (1·PF 6 ·1.5H 2 O) and fac-[Fe II (HL Me-Benz ) 3 ]Cl·PF 6 ·EtOH·H 2 O (2·PF 6 ·EtOH·H 2 O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe II (HL Me-Benz ) 3 ]Cl·SbF 6 ·H 2 O (2·SbF 6 ·H 2 O) and fac-[Fe II (HL Me-Benz ) 3 ]Cl·ClO 4 ·EtOH·H 2 O (2·ClO 4 ·EtOH·H 2 O) are synthesized in ethanol, using the corresponding anions. Each Fe II ion has an octahedral coordination geometry with N 6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[Fe II (HL Me-Benz ) 3 ] 2+ cations are hydrogen-bonded to neighboring three Cl − ions, and each Cl − ion is hydrogen-bonded to three imidazole groups of three neighboring complex cations; this results in the formation of hydrogen-bonded assembly structures. mer-Complex 1·PF 6 ·1.5H 2 O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[Fe II (HL Me-Benz ) 3 ] 2+ ⋯Cl − } 3 units with an ΔΔΛ or ΛΛΔ configuration; the PF 6 − ions occupy the spaces between the 2D layers. All the fac-complexes have isomorphous cubane-like tetrameric structures, i.e., {fac-[Fe II (HL Me-Benz ) 3 ] 2+ ⋯Cl − } 4 . The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[Fe II (HL Me-Benz ) 3 ] 2+ cations and four Cl − ions interconnected by twelve imidazole-chloride hydrogen bonds to form a chiral cubane supramolecule that encapsulates one counter anion. In the crystal lattice, the cubane-like tetramers with opposite chiralities are alternately arrayed. The temperature dependence of the magnetic susceptibilities and Mössbauer spectra reveal that the fac-complexes show incomplete spin crossover behavior, while the mer-complex shows a gradual spin crossover between high-spin (HS, S=2) and low-spin (LS, S=0) states.