Two novel mononuclear metal(II) complexes with an asymmetric tridentate Schiff base ligand, and azide/chloride anions, namely [ZnL(N3)2] (1) and [HgL(Cl)2] (2) (L = (pyridin-2yl)methylimino)-2-ethylpyridine), have been synthesized and structurally characterized by elemental analysis, single crystal X-ray crystallography, FT-IR, NMR, UV–vis electronic absorption spectroscopic analysis. The metal in both the complexes displays a pentacoordination environment realized by the tridentate Schiff base and counter anions. The coordination geometry of Zn in complex 1 is in between a trigonal bipyramidal and square pyramidal, whereas Hg in complex 2 shows a distorted square pyramidal. Theoretical DFT/TD-DFT calculation data performed using B3LYP functional with LanL2MB basis set, compared with values of experimental measurements, have shown a reasonable accord. The thermal stability of both complexes has been studied.