Conformational properties of <Emphasis Type="Italic">ortho</Emphasis>-nitrobenzenesulfonamide in gas and crystalline phases. Intra- and intermolecular hydrogen bond |
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Authors: | Nina I Giricheva Georgiy V Girichev Yulia S Medvedeva Sergey N Ivanov Anna V Bardina Vyacheslav M Petrov |
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Institution: | (1) Department of Physical Chemistry, Ivanovo State University, Ermak St. 39, Ivanovo, Russia, 153025;(2) Department of Physics, Ivanovo State University of Chemistry and Technology, F.Engels Av., 7, Ivanovo, Russia, 153000 |
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Abstract: | A combined gas-phase electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pvtz, MP2/cc-pvtz) study of molecular
structure of 2-nitrobenzenesulfonamide (2-NBSA) was carried out. Quantum chemical calculations showed that 2-NBSA has four
conformers, two of which are stabilized by intramolecular hydrogen bond. The latter (with the S–N bond in a close to orthogonal
position around the phenyl ring and differing from each other by staggered or eclipsed positions of the N–H and S=O bonds
in the SO2NH2 group) presented in a saturated vapor over 2-NBSA at T = 433 (3) K in commensurable amounts. Experimental internuclear distances (Ǻ) for the staggered conformer are (?): r
h1(C–H)av. = 1.071(9), r
h1(C–C)av. = 1.390(4), r
h1(C–S) = 1.789(8), r
h1(S=O)av. = 1.427(6), r
h1(S–N) = 1.644(6), r
h1(N–O)av. = 1.221(4), r
h1(C′–N) = 1.487(8), r
h1(N–H)av. = 1.014. Calculations at B3LYP/cc-pvtz level were performed to determine the structure and the energies of the transition
states between conformers. It was shown that the conformer structures of free molecule differ from those of a molecule stabilized
by intermolecular hydrogen bonds in a crystal. Influence of a substituent X (X = –CH3, –NO2) on conformational features of the ortho-substituted benzenesulfonamide was established. |
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