Molecular structure and conformations of 2-nitrobenzenesulfonyl fluoride: Gas-phase electron diffraction and quantum chemical calculations study

作者：Petrov Vjacheslav M; Girichev Georgiy V^*; Oberhammer Heinz; Giricheva Nina I; Bardina Anna V; Petrova Valentina N; Ivanov Sergey N

来源：Journal of Molecular Structure, 2010, 978(1-3): 97-103.

DOI：10.1016/j.molstruc.2009.12.005

• 2-Nitrobenzenesulfonyl fluoride
• Geometric structure
• Conformer
• Gas-phase electron diffraction
• Mass-spectrometry
• Quantum chemical calculations

The molecular structure and conformational properties of 2-nitrobenzenesulfonyl fluoride, 2-NO(2)-C(6)H(4)SO(2)F, have been studied by gas-phase electron diffraction (GED) and quantum chemical methods (B3LYP/6-311+G** and MP2/6-31G**). Quantum chemical calculations predict the existence of three conformers for 2-NO(2)-C(6)H(4)SO(2)F each of them possesses C(1) symmetry. Conformer I. in which the S-F bond of the SO(2)F group is nearly perpendicular to the plane of benzene ring, is predicted to be most favored. Conformer II, in which the S-F bond is situated in opposite direction with reference to the NO(2) group, possesses intermediate energy (Delta E(1-2) = 0.73 kcal/mol (B3LYP), or 0.71 kcal/mol (MP2)), and conformer III with the S-F bond tilted to the NO(2) group possesses the higher energy (Delta E(1-3) = 1.58 kcal/mol (B3LYP), or 1.47 kcal/mol (MP2)).
The analysis of the GED intensities was carried out assuming the vapour consists of three conformers. In was obtained the conformer I dominates in vapour over solid 2-NO(2)-C(6)H(4)SO(2)F at T = 383(5) K. The conformer III concentration was found to be negligible. In dominant conformer I the S-F bond is bent slightly towards the nitro group (phi(C-C-S-F) = 84(8)), and the torsional angle of the nitro group with respect to the benzene ring phi(C-C-S-F) equals 125(4)degrees.
The conformation properties were determined by the potential energy surface analysis. The relative stability of conformers is discussed.

• 出版日期2010-8-20