Reaction of 2,4-(2,2'-dipyridylamino)-6-(2-pyridylhydrazino)-1,3,5-trazine, abbreviated dppht (5), with copper(II) chloride in methanol yields a mixed-valent (Cu4CuI)-Cu-II compound (6), also involving the presence of a radical anion. The single-crystal structure determination for [Cu-5(5(M))(5(MR))Cl-8] (6) reveals that the original dppht ligand (5) has been monochlorinated at one of its pyridine rings and oxidized at its hydrazyl moiety, generating the ligand 2,4-(2,2'-dipyridylamino)-6-(2-(5-chloropyridyl)azo)-1,3,5-triazine (5(M)). Moreover, the molecular structure of 6 indicates that one of the two coordinated ligands 5(M) is in a radical-anion state, symbolized as 5(MR), characterized by a typical N-N bond length of about 1.33 angstrom for a one-electron reduced azo group. The nature of this unique [(Cu4CuI)-Cu-II(radical)] assembly is corroborated by X-ray absorption spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements. Density-functional theory calculations are consistent with the unprecedented structural features and support the spectroscopic data.