The employment of the di-2-pyridyl ketone [(py)2CO]/PhCO2-/N3- ligand combination in copper(II) chemistry has provided access to the hexanuclear cluster [Cu6(O2CPh)4(N3)2{(py)2CO2}2{(py)2C(OH)O}2] (1), and the coordination polymers [Cu4(O2CPh)2(N3)4{(py)2C(OMe)O}2]n (2) and [Cu2(O2CPh)(N3)2{(py)2C(OMe)O}]n (3). The structural type (cluster versus polymer) depends on the reaction solvent. Complex 1 has a [CuII6(μ3-OR′′)2(μ-OR′′)4]6+ core based on a central defective cubane unit and two additional CuII atoms across the missing edges. Complex 2 consists of zig-zag chains and complex 3 consists of extended 2D networks that adopt the herringbone architecture which is not based on T-shaped nodes. Cluster 1 is antiferromagnetically coupled with an S=0 ground state.