Four copper(II) complexes, [Cu(L-1)(mu-Cl)](n) (1), [Cu-2(L-2)(2)(mu-Cl)(2)] (2), [Cu(L-1)(mu(1,5)-NCNCN)](n) (3) and [Cu(L-2)(mu(1,5)-NCNCN)](n), (4), where HL1 = 1-[(2-dimethylamino-ethylimino)-methyl]-naphthalen-2-ol and HL2 = 1-[(2-ethylamino-ethylimino)-methyl]-naphthalen-2-ol, acting as tridentate N2O donor ligands, have been prepared and characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. Complexes 1, 3 and 4 show polymeric chain structures, whereas 2 has a double chloride bridged dimeric structure. The existence of C-H center dot center dot center dot pi it interactions between the dimeric units of 2 gives rise to a 2D supramolecular network. Complex 3 shows a zipper structure through pi center dot center dot center dot pi interactions between two polymeric chains. Complex 4 shows hydrogen bonding interactions which produces a 2D hydrogen bonded structure and these 2D layers then show interlayer pi center dot center dot center dot pi interactions. (C) 2013 Elsevier Ltd. All rights reserved.