The solvothermal reaction of two new neutral tetradentate ligands with different bivalent metal salts gave seven metal–organic frameworks (MOFs): [Co2(L1) (trans-chdc)2]·5H2O (1), [Zn2(L1)(trans-chdc)(NO2)2]·DMF (2), [Cd2(L1)(trans-chdc)2]·4H2O (3), [Zn2(L1)(1,4-bdc)2]·(H2O)3 (4), [Cd2(L1)(1,4-bdc)2]·DMF·(solvent)x (5), [Co(L2) (trans-chdc)(H2O)]·1.5H2O (6), [Co(L2) (1,4-bdc) (H2O)] · 2H2O (7), (L1 = 1,1′-oxybis[3,5-diimidazole]-benzene, L2 = 1,1′-oxybis[3,5-dipyridine]-benzene, trans-chdc = trans-1,4-cyclohexanedicarboxylic acid, 1,4-bdc = 1,4-benzenedicarboxylate). These MOFs were prepared to examine the effects of the core metal ion or organic ligand on the topology and interpenetration form. The results show that the imidazole ligand can rotate easily to coordinate to metal ions, while pyridine ligand exhibits the weaker coordinative abilities, which may influence the self-assembly. Compounds 1, 3, and 5 are three-dimensional (3D) frameworks with 2-fold interpenetrated forms, whereas complex 4 shows a...