Molecular structure and conformations of para-methylbenzene sulfonamide and ortho-methylbenzene sulfonamide: Gas electron diffraction and quantum chemical calculations study

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

来源：Journal of Physical Chemistry A, 2008, 112(13): 2969-2976.

DOI：10.1021/jp710532z

The molecular structure and conformational properties of para-methylbenzene sulfonamide (4-MBSA) and ortho-methylbenzene sulfonamide (2-MBSA) have been studied by gas electron diffraction (GED) and quantum chemical methods (B3LYP/6-311+G** and MP2/6-31G**). Quantum chemical calculations predict the existence of two conformers for 4-MBSA with the S-N bond perpendicular to the benzene plane and the NH2 group either eclipsing or staggering the S-O bonds. of the SO2 group. Both conformers possess C-S symmetry. The eclipsed form is predicted to be favored by Delta E = 0.63 kcal/mol (B3LYP) or 1.00 kcal/mol (MP2). According to the calculations, the S-N bond in 2-MBSA can possess planar direction opposite the methyl group (phi C2C1SN) = 180 degrees) or nonplanar direction (phi(C2C1SN) approximate to 60 degrees). In both cases, the NH2 group can'adopt eclipsed or staggered orientation, resulting in a total of four stable conformers. The nonplanar eclipsed conformer (C-1 symmetry) and the planar eclipsed form (C-S symmetry) are predicted to be favored. According to the GED analysis, the saturated vapor over solid 4-MBSA at T = 151(3) degrees C consists as mixture of the eclipsed (78(19) %) and staggered (22(19) %) forms. The saturated vapor over solid 2-MBSA at T = 157(3) degrees C consists as a mixture of the nonplanar eclipsed (69(11) %) and planar eclipsed (31(11) %) forms.

• 出版日期2008-4-3