Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate

Springer Science and Business Media LLC
Muhammad Haroon1, Tashfeen Akhtar1, Muhammad Yousuf2, Muhammad Nawaz Tahir3, Lubna Rasheed4, Syeda Saniya Zahra5, İhsan Ul Haq5, Muhammad Ashfaq6
1Department of Chemistry, Mirpur University of Science and Technology (MUST), 10250-Mirpur (AJK), Pakistan
2Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, South Korea
3Department of Physics, University of Sargodha, Sargodha, Punjab, Pakistan
4Department of Chemistry, Division of Science and Technology, University of Education, Township, Lahore, Pakistan
5Department of Pharmacy, Quaid-i-Azam University, 45320 Islamabad, Pakistan
6Department of Physics, University of Mianwali, Mianwali, Punjab, Pakistan

Tóm tắt

Abstract

The ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1), a thiazole ester, was synthesized by refluxing 1-(2-nitrobenzylidene)thiosemicarbazide and ethyl bromopyruvate. The compound is characterized by spectrometric, spectroscopic and single crystal (SC-XRD) techniques. Non-covalent interactions that are responsible for crystal packing are explored by Hirshfeld surface analysis. All theoretical calculations were performed by DFT quantum chemical methods using 6-311G(d,p) and cc-pVTZ basis sets and compared. Theoretical harmonic frequencies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) were optimized. Confirmation of hydrogen bonding sites was analyzed by molecular electrostatic potential (MEP) and Mulliken population analysis. The vibrational frequencies of characteristic functional groups and chemical shifts were found in good agreement with experimental assignments. Frontier molecular orbital (FMO) revealed relatively small HOMO–LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gape, which speaks off the nearly planar geometry and extended conjugation, as compared to the substituents with no conjugation possible. It has also been observed that –NO2 substituent plays a vital role for this relatively small HOMO–LUMO gape and overall electronic properties when compared with similar thiazole carboxylates (2–6, Table 6). Ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) was also evaluated for its anti-oxidant and anti-microbial activities.

Graphical Abstract

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Tài liệu tham khảo

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