A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N'-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N'-methyl-N'- (2-pyridyl)methyl-l,3-propanediamine (Hpmaap), which provide an N3O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)CI] (A), was obtained by reaction of Hpamap with CuCl2. 2H(2)O. The binuclear copper(II) complexes [Cu(pamap)](2)(BF4)(2) (B) and [Cu(pmaap)](2)(BF4)(2) (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF4- anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni-2(pamap)(2)(NO3)]NO3 (D). The crystal of A (C17H22ClCuN3O) is orthorhombic Pbca (No. 61), a = 11.837(4) Angstrom, b = 15.648(5) Angstrom, c = 11.002(11) Angstrom, Z = 8; that of B (C34H44B2Cu2F8N6O2) is triclinic P (1) over bar (No. 2), a = 9.147(0) Angstrom, b = 10.375(0) Angstrom, c = 10.535(1) Angstrom, alpha = 107.20(0)degrees, beta =91.19(0)degrees, gamma = 105.05(0)degrees, Z = 1; that of C (C34H44B2Cu2F8N6O2) is monoclinic P2(1)/c (No. 14), a = 9.158(2) Angstrom, b = 10.714(2) Angstrom, c = 19.085(4) Angstrom, beta = 90.58(2)degrees, Z = 4; and that of D (C34H44N8NiO8) is monoclinic C2/c (No. 15), a = 13.849(0) Angstrom, b = 13.609(0) Angstrom, c = 19.558(1) Angstrom, beta = 92.34 (0)degrees, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex Ib is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrate oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.