Ab initio and density functional calculations were used to study the coordination and thermodynamic properties of mononuclear complexes of dimethylglyoxime (H2M), diaminoglyoxime (H2A), and (1Z,2Z)-N′1,N′2-dihydroxy-N1,N2-dipyridin-2-ylethanediamidediimide (H2L) as well as dinuclear complexes of H2L with zinc(II) at B3LYP/6-31G(d), B3LYP/6-31+G(d), and B3LYP/6-311+G(2d,p)//B3LYP/6-31G(d) computational levels. Theoretical calculation shows that unusual O,O-coordination is a stable model for coordination of H2L to zinc(II) in the gas phase.