The difference in coordination behavior of one new flexible polytopic ligand H2L (L = C16H14N6O2) has been examined with Cu(II) and Ni(II) acetate. It leads to the formation of a polynuclear pentacoordinated Cu(II) assemblage and a mononuclear four coordinated Ni(II) complex. Both the compounds are characterized spectroscopically and electrochemically. In the complexes 1 and 2 the ligand binds the metal centers in trans- and cis-orientation (exo and endo-fashion), respectively. The polynuclear copper complex exhibits strong antiferromagnetic behavior at low temperature with J = −327 cm−1 and DFT calculation is also carried out for this complex.