Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Mar 22;16(1):18.
doi: 10.1186/s13065-022-00805-1.

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

Muhammad Haroon  1   2 , Tashfeen Akhtar  3 , Muhammad Yousuf  4 , Muhammad Nawaz Tahir  5 , Lubna Rasheed  6 , Syeda Saniya Zahra  7 , Ihsan Ul Haq  7 , Muhammad Ashfaq  5   8
Affiliations

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

Muhammad Haroon et al. BMC Chem. .

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.

Keywords: Anti-oxidant; DFT calculations; Spectroscopy; Thiazole; XRD.

PubMed Disclaimer

Conflict of interest statement

No competing interests.

Figures

Scheme 1
Scheme 1
Synthesis of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate
Fig. 1
Fig. 1
The ORTEP diagram drawn at probability level of 50% for (1). H-atoms are displayed by tiny circles of arbitrary radii
Fig. 2
Fig. 2
Packing diagram showing 2D sheet formed by N–H…O, C–H…N and C–H…O bonding for (1)
Fig. 3
Fig. 3
Graphical view of π–π stacking interaction for (1). Distance shown is measured in Å. H-atoms are omitted for clarity
Fig. 4
Fig. 4
HS plotted over dnorm in the range − 0.5540 to 1.4207 a.u. for (1)
Fig. 5
Fig. 5
HS plotted over shape index in the range − 1 to 1a.u. for (1)
Fig. 6
Fig. 6
2D plots for (1), a for overall interaction, b–f for major contributor in crystal packing
Fig. 7
Fig. 7
a–j 2D plots for minor contributor in crystal packing for (1)
Fig. 8
Fig. 8
Percentage contribution of interaction of an atom located inside HS to atoms of molecules located in the surrounding of HS
Fig. 9
Fig. 9
Optimized structure of compound (a) 6-311G(d,p) (b) ccPVTZ
Fig. 10
Fig. 10
Overlay structure of compound optimized by 6-311G (d,p) and cc-pVTZ method
Fig. 11
Fig. 11
Comparison of FT-IR spectra with experiment and calculated values (DFT/B3LYP method with the 6-311G(d,p) and cc-pVTZ basis sets)
Fig. 12
Fig. 12
Correlation graphics of calculated and experimental chemical shifts of compound (a) 1H–NMR (b) 13C–NMR by B3LYP/6-311G(d,p)
Fig. 13
Fig. 13
Correlation graphics of calculated and experimental chemical shifts of compound (a) 1H–NMR (b) 13C–NMR by B3LYP/cc-pVTZ
Fig. 14
Fig. 14
FMOs at B3LYP/cc-pVTZ level
Fig. 15
Fig. 15
MEP map of compound in gas phase usingB3LYP/cc-pVTZ
Fig. 16
Fig. 16
The Mullikan charges diagram of compound (a) B3LYP/6-311G(d,p) (b) B3LYP/ccPVTZ
Fig. 17
Fig. 17
Thermodynamic properties of compound (a) B3LYP/6-311G(d,p) (b) B3LYP/cc-pVTZ
See this image and copyright information in PMC

References

    1. Siddiqui N, Arshad MF, Ahsan W, Alam MS. Thiazoles: A valuable insight into the recent advances and biological activities. Int J Pharm Sci Drug Res. 2009;1(3):136–143.
    1. Hudson BM, Nguyen E, Tantillo DJ. The influence of intramolecular sulfur–lone pair interactions on small-molecule drug design and receptor binding. Org Biomol Chem. 2016;14:3975–3980. - PubMed
    1. Cunico W, Gomes CRB, Vellasco WTJ. Chemistry and Biological Activities of 1,3-Thiazolidin-4-ones. Mini Rev Org Chem. 2008;5:336–344.
    1. Verma A, Saraf SK. 4-thiazolidinone–a biologically active scaffold. Eur J Med Chem. 2008;43:897–905. - PubMed
    1. Hamama WS, Ismail MA, Shaaban S, Zoorob HHJ. Progress in the chemistry of 4- thiazolidinones. Heterocycl Chem. 2008;45(4):939–956.