Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide

Tarek A. Mohamed, Ali M. Hassan, Usama A. Soliman, Wajdi M. Zoghaib, John Husband, Mahmoud M. Abdelall

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The Raman and infrared spectra of solid 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide (AMPC, C6H7N5S 2) were measured in the spectral range of 3700-100 cm-1 and 4000-200 cm-1 with a resolution of 4 and 0.5 cm-1, respectively. Aided by normal coordinate analysis and potential energy distributions, a confident vibrational assignment of all fundamentals is proposed herein. As a result of internal rotation around C̄N and/or C̄S bonds, 32 rotational isomers are suggested for AMPC (Cs symmetry). RHF and DFT/B3LYP quantum mechanical calculations including polarization and diffusion functions up to 6-311++G(d,p) basis sets, predict that after complete relaxation of the 32 possible isomers, four structures lie within 1500 cm-1 of the lowest energy conformer. However, vibrational analysis reveals the lowest energy conformer to be the only structure giving all real frequencies. Thus, the only stable conformer of AMPC is shown to have a fully planar skeleton with the NH2 groups trans to one another. The recorded IR and Raman spectral measurements favor the calculated structural parameters which are further supported by spectral simulation. Additional support is given by 1H and 13C NMR spectra recorded with the sample dissolved in DMSO-d6 and by predicted chemical shifts at the B3LYP/6-311+G(2d,p) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). Finally, CH3, CH3S, and NH 2 torsional barriers to internal rotation have been investigated using the optimized structural parameters from the B3LYP method with the 6-31G(d) basis set. The results are discussed herein and compared with similar molecules whenever appropriate.

Original languageEnglish
Pages (from-to)277-291
Number of pages15
JournalJournal of Molecular Structure
Volume985
Issue number2-3
DOIs
Publication statusPublished - Jan 31 2011

Fingerprint

Isomers
Nuclear magnetic resonance
Infrared radiation
Chemical shift
Dimethyl Sulfoxide
Potential energy
Discrete Fourier transforms
Gages
Polarization
Molecules
pyrazole

Keywords

  • Barriers to internal rotation
  • Conformational stability
  • DFT calculations
  • NMR spectra
  • Normal coordinate analysis
  • Vibrational assignment

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide. / Mohamed, Tarek A.; Hassan, Ali M.; Soliman, Usama A.; Zoghaib, Wajdi M.; Husband, John; Abdelall, Mahmoud M.

In: Journal of Molecular Structure, Vol. 985, No. 2-3, 31.01.2011, p. 277-291.

Research output: Contribution to journalArticle

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abstract = "The Raman and infrared spectra of solid 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide (AMPC, C6H7N5S 2) were measured in the spectral range of 3700-100 cm-1 and 4000-200 cm-1 with a resolution of 4 and 0.5 cm-1, respectively. Aided by normal coordinate analysis and potential energy distributions, a confident vibrational assignment of all fundamentals is proposed herein. As a result of internal rotation around C̄N and/or C̄S bonds, 32 rotational isomers are suggested for AMPC (Cs symmetry). RHF and DFT/B3LYP quantum mechanical calculations including polarization and diffusion functions up to 6-311++G(d,p) basis sets, predict that after complete relaxation of the 32 possible isomers, four structures lie within 1500 cm-1 of the lowest energy conformer. However, vibrational analysis reveals the lowest energy conformer to be the only structure giving all real frequencies. Thus, the only stable conformer of AMPC is shown to have a fully planar skeleton with the NH2 groups trans to one another. The recorded IR and Raman spectral measurements favor the calculated structural parameters which are further supported by spectral simulation. Additional support is given by 1H and 13C NMR spectra recorded with the sample dissolved in DMSO-d6 and by predicted chemical shifts at the B3LYP/6-311+G(2d,p) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). Finally, CH3, CH3S, and NH 2 torsional barriers to internal rotation have been investigated using the optimized structural parameters from the B3LYP method with the 6-31G(d) basis set. The results are discussed herein and compared with similar molecules whenever appropriate.",
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AU - Mohamed, Tarek A.

AU - Hassan, Ali M.

AU - Soliman, Usama A.

AU - Zoghaib, Wajdi M.

AU - Husband, John

AU - Abdelall, Mahmoud M.

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N2 - The Raman and infrared spectra of solid 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide (AMPC, C6H7N5S 2) were measured in the spectral range of 3700-100 cm-1 and 4000-200 cm-1 with a resolution of 4 and 0.5 cm-1, respectively. Aided by normal coordinate analysis and potential energy distributions, a confident vibrational assignment of all fundamentals is proposed herein. As a result of internal rotation around C̄N and/or C̄S bonds, 32 rotational isomers are suggested for AMPC (Cs symmetry). RHF and DFT/B3LYP quantum mechanical calculations including polarization and diffusion functions up to 6-311++G(d,p) basis sets, predict that after complete relaxation of the 32 possible isomers, four structures lie within 1500 cm-1 of the lowest energy conformer. However, vibrational analysis reveals the lowest energy conformer to be the only structure giving all real frequencies. Thus, the only stable conformer of AMPC is shown to have a fully planar skeleton with the NH2 groups trans to one another. The recorded IR and Raman spectral measurements favor the calculated structural parameters which are further supported by spectral simulation. Additional support is given by 1H and 13C NMR spectra recorded with the sample dissolved in DMSO-d6 and by predicted chemical shifts at the B3LYP/6-311+G(2d,p) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). Finally, CH3, CH3S, and NH 2 torsional barriers to internal rotation have been investigated using the optimized structural parameters from the B3LYP method with the 6-31G(d) basis set. The results are discussed herein and compared with similar molecules whenever appropriate.

AB - The Raman and infrared spectra of solid 5-amino-4-cyano-3-(methylthio)-1H- pyrazole-1-carbothioamide (AMPC, C6H7N5S 2) were measured in the spectral range of 3700-100 cm-1 and 4000-200 cm-1 with a resolution of 4 and 0.5 cm-1, respectively. Aided by normal coordinate analysis and potential energy distributions, a confident vibrational assignment of all fundamentals is proposed herein. As a result of internal rotation around C̄N and/or C̄S bonds, 32 rotational isomers are suggested for AMPC (Cs symmetry). RHF and DFT/B3LYP quantum mechanical calculations including polarization and diffusion functions up to 6-311++G(d,p) basis sets, predict that after complete relaxation of the 32 possible isomers, four structures lie within 1500 cm-1 of the lowest energy conformer. However, vibrational analysis reveals the lowest energy conformer to be the only structure giving all real frequencies. Thus, the only stable conformer of AMPC is shown to have a fully planar skeleton with the NH2 groups trans to one another. The recorded IR and Raman spectral measurements favor the calculated structural parameters which are further supported by spectral simulation. Additional support is given by 1H and 13C NMR spectra recorded with the sample dissolved in DMSO-d6 and by predicted chemical shifts at the B3LYP/6-311+G(2d,p) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). Finally, CH3, CH3S, and NH 2 torsional barriers to internal rotation have been investigated using the optimized structural parameters from the B3LYP method with the 6-31G(d) basis set. The results are discussed herein and compared with similar molecules whenever appropriate.

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KW - NMR spectra

KW - Normal coordinate analysis

KW - Vibrational assignment

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