The strain energy minimized structures (MM) of a series of copper(II) tetraamines ([Cu((R)-ahaz)((S)-ahaz)](2+), (R)-ahaz (1)= (R)- 3-aminohexahydroazepine, (S)-ahaz (2)= (S)-3 -aminohexahydroazepine; [Cu((S)-ahaz)(2)(OH2)](2+); [CU(mn[13]aneN(4))(OH2)(2)](2+), mn[l3]aneN(4) (3) = 12-methyl-12-nitro-l,4,7,10-tetraazacyclotridecane; [Cu(mn[l3]aneN(4))(OH2)](2+); [Cu(mn[14]aneN(4))(OH2)](2+), mn[l4]aneN(4) (4)= 6-methyl-6-nitro-1,4,8,11-tetraazacyclotetradecane; [Cu(mn[15]aneN(4))(OH2)](2+), mn[ 15]aneN(4) (5)= 10-methyl-10-nitro-1,4,8,12-tetraazacyclopentadecane; [Cu(mn[15]aneN(4))(OH2)(2)](2+); [Cu(mn[16]aneN(4))(OH2)](+), mn[16]ane N-4 (6) = 3-methyl-3-nitro-1,5,9,13-tetraazacyclohexadecane; [Cu(en)(2)(OH2)(2)](2+), en (7) = ethane-1,2-diamine), with square planar, square pyramidal, and distorted octahedral chromophores exhibiting various degrees of tetrahedral distortion of the central coordination plane, are in good agreement with published X-ray structures (where available) and the two crystal structures reported ip this paper. [Cu(2)(2)(ClO)(4)](ClO4) crystallizes in the orthorhombic space group P2(1)2(1)2(1), with a 18.194(4) Angstrom, Z = 4, and R, = 0.061. [Cu(5)(C1)21 2and0 crystallizes in the 6.884(2) W, b = 9.090(3) Angstrom, c = 9.214(2) Angstrom, cc = 105.13(2)0, P = 107.40(2)", y = 107.85(2)0, Z = 1, and R, = 0.022. The spin Hamiltonian parameters and electronic transitions, estimated with the angular overlap model (AOM) based on the strain energy minimized structures of the chromophores, where generally water is used as axial ligand (MM-AOM), are in reasonable agreement with the calculated spectroscopic parameters based on experimental structures (AOM) and with the experimental spectroscopic data (UV-vis-near-IR and EPR spectra ofsingle crystals, powders, glasses, and solutions). The calculated spectroscopic data are based on a constant set of electronic parameters which depend on the degree of substitution of the amine, on the Cu-N bond length, and on the degree of misdirected valences.