Three new complexes of [Co(H₂biim)₂(1,2-bdc)] (1), [Cd(H₂biim)(1,3-bdc)]₂ (2), and [Cd₃(H ₂biim)₂(1,4-bdc)₃]·2H₂O (3) (bdc = benzenedicarboxylate, H₂biim = 2,2′-biimidazole) have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 exhibits a 2-D herringbone architecture with mononuclear building blocks assembled via a robust hydrogen-bonded synthon R₂²(9). The homo- and heterochiral assemblies were observed in 1 between the H ₂biim ligand and carboxylate group via single and double hydrogen-bonded synthons R₂²(9). Complex 2 is a ribbonlike polymer based on a binuclear unit, and the ribbons are alternately decorated by H₂biim ligands on both sides and further packed through intercalation of the lateral H₂biim ligands and hydrogen bonds between the H₂biim and carboxylate oxygen atoms into 2-D networks. These layers extend into a 3-D architecture via π-π stacking interactions. Complex 3 is a 3-D coordination polymer with a α-Po net topology based on linear trinuclear {Cd₃O₁₄N₄} clusters. The results indicate that isomeric benzenedicarboxylates give structural diversity in the presence of auxiliary ligand H₂biim, providing a potential tool for crystal engineering.