The three novel heterometallic complexes [(CuCoCo2II)-Co-III(MeDea)(3)Cl-3(CH3OH)(0.55)(H2O)(0.45)](H2O)(0.45) (1), [(CuCoZn2)-Zn-III(MeDea)(3)Cl-3(CH3OH)(0.74)(H2O)(0.26)](H2O)(0.26) (2), and [(CuCoZn2)-Zn-III(MeDea)(3)Cl-3(DMF)] (3) have been prepared using a one-pot reaction of copper powder with cobalt chloride (1) and zinc nitrate (2, 3) in a methanol (1, 2) or dimethylformamide (3) solution of N-methyldiethanolamine. A search of the Cambridge Structural Database shows that the tetranuclear asymmetric cores M-4(mu(3)-X)(mu-X)(5) of 1-3 represent an extremely rare case of M4X6 arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co-II-Cu-II-Co-II exchange fragment with J(Co-Cu)/hc = -4.76 cm(-1), J(Co-Co)/hc = -2.76 cm(-1), and D-Co/hc = +34.3 cm(-1). Compounds 1-3 act as precursors for the mild peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone with overall yields up to 23%. The synthetic and structural features as well as the thermogravimetric behavior and electrospray ionization mass spectrometry data are discussed.