A complex of composition {[{Cu(NDC)(OH2)(tn)(mu-OH2)}(2)]center dot 2H(2)O}(a) (1) and a mononuclear complex salt [Cu(OH2)(2)(tn)(2)](NDC)center dot 3H(2)O (2), where NDC = 2,6-naphthalenedicarboxylate dianion and tn = 1,3-diaminopropane, were simultaneously crystallized from an aqueous solution of the copper(II) naphthalenedicarboxylate-1,3-diaminopropane-methanol system. The crystal and molecular structures of both complexes were determined by single-crystal X-ray diffraction. Compound (1) consists of a supramolecular coordination complex in which the monomeric unit is assembled from a homodinuclear Cu(II) bridged by two water ligands. The Cu(II) centers exhibit distorted octahedral coordination; the equatorial plane is provided by one chelating tn ligand, one NDC2- ligand, one mu-H2O while the axial positions are occupied by H2O and mu-H2O. Strong intra- and/or intermolecular hydrogen bonds, also involving the crystallization water molecules, together with pi-pi stacking interactions, are involved in building up the supramolecule. The solid structure of compound (2) includes three water molecules of crystallization, the counter ion NDC2-, and a Cu(II) cationic complex in which the metal is six-coordinated in an axially elongated octahedron defined by two chelating tn ligands in the equatorial plane and two water ligands in the axial positions. Thermal analyses of (1) show two significant weight losses corresponding to water molecules (lattice and coordinated), followed by the decomposition of the network.