Two mononuclear copper(II) complexes [Cu(L)(NO 2 )](ClO 4 ) (1) and [Cu(L)(MO 4 )] 2 AE 5H 2 O (2) (L ¼ 1, 3,10, 12,16,19-hexaazatetracyclo[17,3,1,1 12.16 ,0 4.9 ]tetracosane) have been synthesized and their structures determined. Both compounds show a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one ligand coordinated at the axial position. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.