ChemInform Abstract The three related pentaazamacrocyclic ligands (VII) are prepared as shown. The metal complexes (IX)-(XII) are obtained from the 1:1 reactions of the appropriate ligand and the DMSO solvates of each metal perchlorate in ethanol. They are characterized by UV, mass, and 13C NMR spectroscopy and magnetic moment measurements. The Ni complexes are high-spin and six-coordinate, and the Cu complexes five-coordinate. The complex (IXb) is a 2:1 mixture of two species, one sym. and the other asymmetric. In (XIIb) only ca. 10% of the asym. species is present in solution. X-ray crystallography is used to determine the structure of the sym. isomer of (XIIb). This trigonal-bipyramidal species crystallizes in the space group P21/n with Z=4.