The reactions of di-2-pyridyl ketone with Cu(O2CPh)2 in the presence of NaN3 and LiOH have led to an antiferromagnetically coupled (S = 0) Cu(II)6 cluster with a novel core and to (Cu(II)8)n and (Cu(II)2)n coordination polymers (the former 1D and the latter 2D) with interesting structures. The cluster or polymer formation depends on the reaction solvent.