Experimental and theoretical spectroscopic studies, HOMO–LUMO, NBO analyses and thione–thiol tautomerism of a new hybrid of 1,3,4-oxadiazole-thione with quinazolin-4-one

• Synthesis and spectral characterization of new oxadiazole derivative are presented.
• The compound exists as thione-(T2) tautomer rather than thiol-(T1) one.
• The calculated NMR spectra of T2 correlated well with the experimental data than T1.
• The NBO analysis is used to explain the intramolecular charge transfer interactions.

The hybrid 3-(4-chlorophenyl)-2-[(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)methylthio]quinazolin-4(3H)-one has been synthesized and characterized using elemental analysis, FTIR and NMR spectroscopy. The thione–thiol tautomeric equilibria has been studied using both DFT/B3LYP and HF methods at different basis sets. The results of calculations showed predominance of the thione form. The molecular structure and vibrational spectra of the stable tautomer are predicted using the same level of theory. The complete assignments of the vibrational modes were performed on the basis of potential energy distribution (PED). The 6-311++G(d,p) gave the best results compared to the experimental data. The chemical shift values of the two tautomers are calculated using GIAO method. The NH proton of the thione tautomer have chemical shift value closer to the experimental data compared to the SH proton of the thiol one. The electronic transitions are predicted using the TD-DFT calculations at B3LYP/6-311++G(d,p) level of theory. The calculated polarizability and first hyperpolarizability showed that the studied compound has better NLO properties than urea. The molecular electrostatic potential (MEP) analysis reveals the sites for electrophilic and nucleophilic attack in the molecule. NBO analysis is carried out to investigate the stabilization energy of various intramolecular charge transfer interactions within the studied molecule.

Optimized molecular structure and molecular electrostatic potential (MEP) calculated at B3LYP/6-311G++(d,p) method of hybrid 3-(4-chlorophenyl)-2-[(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)methylthio]quinazolin-4(3H)-one 2.Figure optionsDownload as PowerPoint slide