Reaction of 4-aminobenzonitrile with different transition metal ions in the presence of chloride provides metal complexes of different dimensionalities. Whereas platinum forms a 0-D mononuclear complex {[PtCl2(4-ABN)2} 1, three new coordination polymers {[Zn(4-ABN)2(H2O)2](ClO4)2} n 2, {[Cu(4-ABN)2(MeOH)2](ClO4)2} n 3, and {Cd(4-ABN)Cl2} n 4 have been synthesized and characterized.Complexes 2 and 3 crystallize in 1-D polymeric chains, whereas 4 forms a 3-D coordination network, based on fused 12-membered rings of cadmium and chloride. A topological analysis of 4 reveals a uninodal five-connected network with the point (Schlafli) symbol of (44 × 66) and the nov (5/4/08) topology. All the isolated complexes were characterized by IR, elemental, and X-ray single crystal structural analyses. Complexes 1, 2, and 4 were additionally characterized by NMR spectroscopy.