The use of the binary "blend" of MeCO2-/pdmH(2) ligands (pdmH(2) = pyridine-2,6-dimethanol) in copper(II) chemistry has provided access to a compound consisting of discrete linear Cu-3(II) and cubane Cu-4(II) clusters. The complicated magnetic behavior of the Cu-3(II) + Cu-4(II) complex was clarified and interpreted through the designed synthesis of the individual Cu-4(II) component; a unique 1 D (Cu-5(II))(n) compound containing a Cu-3(II) subunit, which is structurally similar to the trinuclear cluster in the Cu-3(II) + Cu-4(II) compound, was also isolated and structurally characterized.