The reaction of zerovalent copper with cadmium iodide and triethanolamine (H3L) in dimethylformamide (dmf) carried out under open-air conditions afforded a novel heterometallic complex [Cu-3(HL)(3)Cdl(2)](2) center dot 4dmf. The crystal lattice consists of an octanuclear molecule [Cu-3(HL)(3)Cdl(2)](2), which has an inversion center at the midpoint of the central Cu2O2 unit, and of two non-coordinating dmf molecules. Eight metal atoms linked by alkoxide arms of triethanolamine ligands form a zigzag Cd-Cu1-Cu2-Qu3-Cu4-Cu5-Cu6-Cd chain with the separations between bridged Cu atoms in the range 2.935(2)-3.403(2) angstrom. The complex is further stabilized by intramolecular O-H center dot center dot center dot O hydrogen bonds. High-field electron paramagnetic resonance (EPR) spectra of the S = 1 spin state with D-(s=1) = -0.843 cm(-1), E-(s=1) = -0.081 cm(-1) were observed. Fitting the magnetic susceptibility temperature dependence by using the exchange Hamiltonian H-HDVV = J(1)(S1S2 + S5S6) + J(2)(S2S3 + S4S5) + J(3)S(3)S(4), to which terms expressing the zero-field splitting and Zeeman splitting of the ground S = 1 state were added, resulted in J(1) = 68, J(2) = 19, J(3) = -57 cm(-1) "Broken symmetry" DFT calculations correctly predicted the triplet ground state of the hexa-copper system.