Copper(II) and (VO)-O-IV complexes of an open chain (1:2) Schiff-base ligand (H(2)L1), derivied by the template condensation of diaminomaleonitrile (DMN) and salicylaldehyde, and dicopper(II) complexes of (2:2) macrocyclic Schiff-base ligands derived by template condensation of diformylphenols and diaminomaleonitrile, have been synthesized and studied. Structures have been established for the first time for mononuclear Cu(II) and (VO)-O-IV derivatives of the open chain ligand H(2)L1 (1:2), a dinuclear macrocyclic Cu(II) complex derived from a 2:2 macrocyclic ligand (H(2)M1), and the half-condensed 1:1 salicylaldehyde ligand (H(2)L2). [Cu(L1)] (1) (L1 = C18H10N4O2) crystallized in the monoclinic system, space group P2(l)/n (No. 14), with a = 11.753(6) Angstrom, b = 7.708(5) Angstrom, c = 16.820(1) Angstrom , and Z = 4. [VO(L1)(DMSO] (2) crystallized in the orthorhombic system, space group Pbca (No. 61), with a = 22.534(9) Angstrom, b = 23.31(1) Angstrom, c = 7.694(5) Angstrom, and Z = 8. H(2)L2 (C18H8N4O) (3) crystallized in the monoclinic system, space group P2(l)/c (No. 14), with a = 13.004(6) Angstrom, b = 11.441(7) Angstrom, c= 7.030(4) Angstrom, and Z = 4. [Cu-2(M3)](CH3COCH3) (4) (M3 = C32H24N8O4) crystallized in the monoclinic system, space group C2/c (No. 15), with a = 38.33(2) Angstrom, b = 8.059(4) Angstrom, c = 22.67(2) Angstrom, and Z = 8. [Cu(L3)(DMSO)] (5) (L3 = C20H14N2O4) crystallized in the triclinic system, space group P1 (No. 2), with a = 10.236(4) Angstrom, b = 13.514(4) Angstrom, c = 9.655(4) Angstrom, and Z =2. 4 results from the unique addition of two acetone molecules to two imine sites in [Cu-2(M1)](ClO4)(2) (M1 = 2:2 macrocyclic ligand derived from template condensation of DMN and 2,6-diformyl-4-methylphenol). 4 has extremely small Cu-OPh-Cu bridge angles (92.0, 92.8 degrees), well below the expected lower limit for antiferromagnetic behavior, but is still antiferromagnetically coupled (-2J = 25.2 cm(-1)). This behavior is associated with a possible antiferromagnetic exchange term that involves the conjugated framework of the macrocyclic ligand itself. The ligand L3 in 5 results from hydrolysis of M1 on recrystallization of[Cu-2(M1)](ClO4)(2) from undried dimethyl sulfoxide.