New Zn(II) complexes (1–8) of general formula [Zn(R)2(L')2], where R = cinnamic acid (1–7), L' = 3-pyridine carboxamide (1), 2,2'-bipyridine (2), 3-pyridinecarbonitrile (3), 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole (4), 2-methylimidazole (5), 2-phenylimidazole (6), 2-imidazolidinethione (7) and for (8), R = acetic acid; L' = 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole)2, have been synthesized by a stoichiometric reaction between Zn(II) carboxylate(s) and the respective nitrogen-based ligands. The prepared compounds are analyzed by FTIR, NMR spectroscopy and single crystal X-ray diffraction techniques for their structural manifestations along with elemental analyses. The crystallographic data for 6 and 8 exhibit four-coordinated zinc having distorted tetrahedral molecular geometry. The thermogravimetric data demonstrate high stability of the compounds with gradual loss of acetate and thiadiazol fragments that ultimately lead to zinc oxide as the residual mass of 8. Quantum chemical calculations indicate that 7 is the softest in reactivity having the lowest band gap as determined from the energies of frontier molecular orbitals whereas 8 is highly polar with the highest dipole moment value of 12.61 D. The computational data are a complement to the success of the research.