Molecular structure and conformational composition of 1-[(methylthio) methyl]-2-nitrobenzene (MTMNB): A theoretical and experimental study

Olga V. Dorofeeva, Igor F. Shishkov, Lev V. Vilkov, István Hargittai

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The conformational composition of gaseous MTMNB and the molecular structures of the rotational forms have been studied by electron diffraction at 130°C aided by results from ab initio and density functional theory calculations. The conformational potential energy surface has been investigated by using the B3LYP/6-31G(d,p) method. As a result, six minimum-energy conformers have been identified. Geometries of all conformers were optimized using MP2/6-31G(d,p), B3LYP/6-31G(d,p), and B3LYP/cc-pVTZ methods. These calculations resulted in accurate geometries, relative energies, and harmonic vibrational frequencies for all conformers. The B3LYP/cc-pVTZ energies were then used to calculate the Boltzmann distribution of conformers. The best fit of the electron diffraction data to calculated values was obtained for the six conformer model, in agreement with the theoretical predictions. Average parameter values (r a in angstroms, angle α in degrees, and estimated total errors given in parentheses) weighted for the mixture of six conformers are r(C-C) = 1.507(5), r(C-C)ring,av = 1.397(3), r(C-S)av = 1.814(4), r(C-N) = 1.495(4), r(N-O)av = 1.223(3), 〈(C-C-C)ring = 116.0-122.5, 〈C6-C4-C7 = 118.2(4), 〈C-C-S = 113.6(6), 〈C-S-C = 98.5(12), 〈N-C-C4 = 121.9(3), 〈(O-N-C)av = 116.8(3), 〈O-N-O = 127.0(4). Torsional angles could not be refined. Theoretical B3LYP/cc-pVTZ torsional angles for the rotation about C-N bond, φC-N, were found to be 30.5-36.5° for different conformers. As to internal rotation about C-C and C-S bonds, values of φC-C = 68-118° and φC-S = 66-71° were obtained for the three most stable conformers with gauche orientation with respect to these bonds.

Original languageEnglish
Pages (from-to)617-628
Number of pages12
JournalStructural Chemistry
Issue number6
Publication statusPublished - Dec 1 2005



  • 1-[(Methylthio)methyl]-2-nitrobenzene
  • B3LYP/cc-pVTZ calculations
  • Conformational analysis
  • Gas electron diffraction

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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