The phenolic azide bridged dinuclear nickel(II) complex, [Ni(L)(N)(HO)(μ-N)] · EtOH ( I), and the thiocyanate bridged dinuclear copper(II) complex, [Cu(L)(μ-NCS)] ( II), where L and L are the deprotonated forms of 2-mothoxy-6-[(2-piperidin-1-ylethylimino)methyl]phenol and 2,4-dichloro-6-[(2-methylaminoethylimino)methyl]phenol, respectively, were synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal of I is orthorhombic: space group Pbca, a = 12.172(1), b = 20.953(1), c = 29.779(2) Å, V = 7594.8(9) Å, Z = 8. The crystal of II is monoclinic: space group P2/ n, a = 8.7615(11), b = 19.672(2), c = 16.568(2) Å, β = 99.449(2)°, V = 2816.9(6) Å, Z = 4. The Ni atoms in I are in octahedral coordinations, and the Cu atoms in II are in square-pyramidal coordinations. [ABSTRACT FROM AUTHOR]