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Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives
[Image: see text] In the current research work, unsymmetrical acyl thiourea derivatives, 4-((3-benzoylthioureido)methyl)cyclohexane-1-carboxylic acid (BTCC) and methyl 2-(3-benzoylthioureido)benzoate (MBTB), have been synthesized efficiently. The structures of these crystalline thioureas were unambi...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8613867/ https://www.ncbi.nlm.nih.gov/pubmed/34841164 http://dx.doi.org/10.1021/acsomega.1c04884 |
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author | Ashfaq, Muhammad Tahir, Muhammad Nawaz Muhammad, Shabbir Munawar, Khurram Shahzad Ali, Akbar Bogdanov, Georgii Alarfaji, Saleh S. |
author_facet | Ashfaq, Muhammad Tahir, Muhammad Nawaz Muhammad, Shabbir Munawar, Khurram Shahzad Ali, Akbar Bogdanov, Georgii Alarfaji, Saleh S. |
author_sort | Ashfaq, Muhammad |
collection | PubMed |
description | [Image: see text] In the current research work, unsymmetrical acyl thiourea derivatives, 4-((3-benzoylthioureido)methyl)cyclohexane-1-carboxylic acid (BTCC) and methyl 2-(3-benzoylthioureido)benzoate (MBTB), have been synthesized efficiently. The structures of these crystalline thioureas were unambiguously confirmed by single-crystal diffractional analysis. The crystallographic investigation showed that the molecular configuration of both compounds is stabilized by intramolecular N–H···O bonding. The crystal packing of BTCC is stabilized by strong N–H···O bonding and comparatively weak O–H···S, C–H···O, C–H···π, and C–O···π interactions, whereas strong N–H···O bonding and comparatively weak C–H···O, C–H···S, and C–H···π interactions are responsible for the crystal packing of MBTB. The noncovalent interactions that are responsible for the crystal packing are explored by the Hirshfeld surface analysis for both compounds. The void analysis is performed to find the quantitative strength of crystal packing in both compounds. Additionally, state-of-the-art applied quantum chemical techniques are used to further explore the structure–property relationship in the above-entitled molecules. The optimization of molecular geometries showed a reasonably good correlation with their respective experimental structures. Third-order nonlinear optical (NLO) polarizability calculations were performed to see the advanced functional application of entitled compounds as efficient NLO materials. The average static γ amplitudes are found to be 27.30 × 10(–36) and 102.91 × 10(–36) esu for the compounds BTCC and MBTB, respectively. The γ amplitude of MBTB is calculated to be 3.77 times larger, which is probably due to better charge-transfer characteristics in MBTB. The quantum chemical analysis in the form of 3-D plots was also performed for their frontier molecular orbitals and molecular electrostatic potentials for understanding charge-transfer characteristics. We believe that the current investigation will not only report the new BTCC and MBTB compounds but also evoke the interest of the materials science community in their potential use in NLO applications. |
format | Online Article Text |
id | pubmed-8613867 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-86138672021-11-26 Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives Ashfaq, Muhammad Tahir, Muhammad Nawaz Muhammad, Shabbir Munawar, Khurram Shahzad Ali, Akbar Bogdanov, Georgii Alarfaji, Saleh S. ACS Omega [Image: see text] In the current research work, unsymmetrical acyl thiourea derivatives, 4-((3-benzoylthioureido)methyl)cyclohexane-1-carboxylic acid (BTCC) and methyl 2-(3-benzoylthioureido)benzoate (MBTB), have been synthesized efficiently. The structures of these crystalline thioureas were unambiguously confirmed by single-crystal diffractional analysis. The crystallographic investigation showed that the molecular configuration of both compounds is stabilized by intramolecular N–H···O bonding. The crystal packing of BTCC is stabilized by strong N–H···O bonding and comparatively weak O–H···S, C–H···O, C–H···π, and C–O···π interactions, whereas strong N–H···O bonding and comparatively weak C–H···O, C–H···S, and C–H···π interactions are responsible for the crystal packing of MBTB. The noncovalent interactions that are responsible for the crystal packing are explored by the Hirshfeld surface analysis for both compounds. The void analysis is performed to find the quantitative strength of crystal packing in both compounds. Additionally, state-of-the-art applied quantum chemical techniques are used to further explore the structure–property relationship in the above-entitled molecules. The optimization of molecular geometries showed a reasonably good correlation with their respective experimental structures. Third-order nonlinear optical (NLO) polarizability calculations were performed to see the advanced functional application of entitled compounds as efficient NLO materials. The average static γ amplitudes are found to be 27.30 × 10(–36) and 102.91 × 10(–36) esu for the compounds BTCC and MBTB, respectively. The γ amplitude of MBTB is calculated to be 3.77 times larger, which is probably due to better charge-transfer characteristics in MBTB. The quantum chemical analysis in the form of 3-D plots was also performed for their frontier molecular orbitals and molecular electrostatic potentials for understanding charge-transfer characteristics. We believe that the current investigation will not only report the new BTCC and MBTB compounds but also evoke the interest of the materials science community in their potential use in NLO applications. American Chemical Society 2021-11-12 /pmc/articles/PMC8613867/ /pubmed/34841164 http://dx.doi.org/10.1021/acsomega.1c04884 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Ashfaq, Muhammad Tahir, Muhammad Nawaz Muhammad, Shabbir Munawar, Khurram Shahzad Ali, Akbar Bogdanov, Georgii Alarfaji, Saleh S. Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives |
title | Single-Crystal Investigation, Hirshfeld Surface Analysis,
and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl
Thiourea Derivatives |
title_full | Single-Crystal Investigation, Hirshfeld Surface Analysis,
and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl
Thiourea Derivatives |
title_fullStr | Single-Crystal Investigation, Hirshfeld Surface Analysis,
and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl
Thiourea Derivatives |
title_full_unstemmed | Single-Crystal Investigation, Hirshfeld Surface Analysis,
and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl
Thiourea Derivatives |
title_short | Single-Crystal Investigation, Hirshfeld Surface Analysis,
and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl
Thiourea Derivatives |
title_sort | single-crystal investigation, hirshfeld surface analysis,
and dft study of third-order nlo properties of unsymmetrical acyl
thiourea derivatives |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8613867/ https://www.ncbi.nlm.nih.gov/pubmed/34841164 http://dx.doi.org/10.1021/acsomega.1c04884 |
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