Infrared, Raman and temperature-dependent NMR spectra, vibrational assignments, normal coordinate analysis, and DFT calculations of benzoxazoline-2-thione

Tarek A. Mohamed, Ahmed M. Mustafa, Wajdi M. Zoghaib, Mahmoud S. Afifi, Rabei S. Farag, Yehia Badr

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The tautomerism of benzoxazoline-2-thione (BOT; thio-keto) and 2-mercaptobenzoxazole (MBO; thio-enol) has been thoroughly investigated by means of Raman (3600-100 cm-1), infrared (4000-200 cm-1), 1H and 13C NMR spectra and X-ray powder diffraction (XRD). In addition, temperature-dependent 1H NMR spectra from -90 to +90 °C were acquired. To complement experimental results with theoretical predictions, we performed Density Functional Theory (DFT) calculations utilizing B3LYP, B3PW91 and SVWN methods at 6-31G(d) basis set. Both computational and spectral results were in favor of thio-keto BOT structure with no evidence for the existence of thio-enol (MBO) tautomer which firmly eliminates the possibility of an existing equilibrium between keto and enol forms. Moreover the dimerization percentage of thio-keto benzoxazoline-2-thione (BOT) and benzothiazoline-2-thione (BTT) were found to be 11.9% and 2.5%, respectively which favors strong hydrogen bonding interactions in BOT. Aided by normal coordinate analysis, force constants in internal coordinates and potential energy distributions (PEDs), a complete vibrational assignment for all fundamentals was obtained. The results are compared with the sulfur analogue, benzothiazoline-2-thione (BTT) whenever appropriate.

Original languageEnglish
Pages (from-to)128-136
Number of pages9
JournalVibrational Spectroscopy
Volume52
Issue number2
DOIs
Publication statusPublished - Mar 18 2010

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Thiones
Vibrational spectra
Density functional theory
Nuclear magnetic resonance
Infrared radiation
Temperature
Dimerization
Potential energy
Sulfur
X ray powder diffraction
Hydrogen bonds

Keywords

  • Benzoxazoline-2-thione
  • DFT calculations
  • Force constants
  • Infrared
  • Raman
  • Temperature-dependent H NMR

ASJC Scopus subject areas

  • Spectroscopy

Cite this

Infrared, Raman and temperature-dependent NMR spectra, vibrational assignments, normal coordinate analysis, and DFT calculations of benzoxazoline-2-thione. / Mohamed, Tarek A.; Mustafa, Ahmed M.; Zoghaib, Wajdi M.; Afifi, Mahmoud S.; Farag, Rabei S.; Badr, Yehia.

In: Vibrational Spectroscopy, Vol. 52, No. 2, 18.03.2010, p. 128-136.

Research output: Contribution to journalArticle

Mohamed, Tarek A. ; Mustafa, Ahmed M. ; Zoghaib, Wajdi M. ; Afifi, Mahmoud S. ; Farag, Rabei S. ; Badr, Yehia. / Infrared, Raman and temperature-dependent NMR spectra, vibrational assignments, normal coordinate analysis, and DFT calculations of benzoxazoline-2-thione. In: Vibrational Spectroscopy. 2010 ; Vol. 52, No. 2. pp. 128-136.
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AB - The tautomerism of benzoxazoline-2-thione (BOT; thio-keto) and 2-mercaptobenzoxazole (MBO; thio-enol) has been thoroughly investigated by means of Raman (3600-100 cm-1), infrared (4000-200 cm-1), 1H and 13C NMR spectra and X-ray powder diffraction (XRD). In addition, temperature-dependent 1H NMR spectra from -90 to +90 °C were acquired. To complement experimental results with theoretical predictions, we performed Density Functional Theory (DFT) calculations utilizing B3LYP, B3PW91 and SVWN methods at 6-31G(d) basis set. Both computational and spectral results were in favor of thio-keto BOT structure with no evidence for the existence of thio-enol (MBO) tautomer which firmly eliminates the possibility of an existing equilibrium between keto and enol forms. Moreover the dimerization percentage of thio-keto benzoxazoline-2-thione (BOT) and benzothiazoline-2-thione (BTT) were found to be 11.9% and 2.5%, respectively which favors strong hydrogen bonding interactions in BOT. Aided by normal coordinate analysis, force constants in internal coordinates and potential energy distributions (PEDs), a complete vibrational assignment for all fundamentals was obtained. The results are compared with the sulfur analogue, benzothiazoline-2-thione (BTT) whenever appropriate.

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