Three copper(II) complexes, [Cu2L2(μ 1,1-NCO)(NCO)] (1), [Cu2L2(μ1,3- NCS)(NCS)] (2) and [CuL(μ1,5-dca)]n- ·nH 2O (3), where HL = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol, have been prepared and characterized by elemental analysis, IR and UV-Vis spectroscopy, single crystal X-ray diffraction studies and by cyclic voltammetry. Complexes 1 and 3 crystallize in monoclinic space group P2 1/n and complex 2 in monoclinic P21/c. In complex 1, OCN- shows μ1,1 bridging mode; in complex 2, SCN - shows μ1,3 bridging mode whereas in complex 3, N(CN)-2 shows μ1,5 bridging mode. The tridentate Schiff base ligand reacts with copper(II) to occupy its three equatorial positions. The coordination polyhedra around one of the copper center in compounds 1 and 2 are best described as an elongated (4 + 1) square pyramid, whereas the coordination polyhedra around other copper center is square planer. The copper atom in compound 3 has a slightly distorted square pyramidal environment. Significant C-H/π interactions are observed in both complexes 1 and 2. Complex 3 is an example of MOFs containing penta-cordinated Cu(II) ions linked together by N(CN)-2 to yield 1D infinite P and M-helical chains. © 2012 Elsevier B.V. All rights reserved.