Manifestation of the gauche effect in conformers of benzenesulfonic acid hydrazide

• Published in: Journal of structural chemistry 2017-03, Vol.58 (2), p.236-243
• Main Authors: Fedorov, M. S., Giricheva, N. I.
• Format: Article
• Language: English
• Subjects: Acids; Atomic; Atomic/Molecular Structure and Spectra; Benzenesulfonic acids; Chemical bonds; Chemistry; Chemistry and Materials Science; Crystal structure; Density distribution; Dipole moments; Electron density; Fragments; Inorganic Chemistry; Molecular; Nitrogen atoms; Optical and Plasma Physics; Orbitals; Physical Chemistry; Solid State Physics
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476617020032

Conformational properties of a benzenesulfonic acid hydrazide molecule and its para -nitro and para -methyl derivatives, which have found wide application as porofors and biologically active compounds, are studied. It is found that the benzenesulfonic acid hydrazide molecule has six conformers with relative energies of 0//0 kcal/mol, 0.34//0.98 kcal/mol, 2.51//2.25 kcal/mol, 2.54//2.56 kcal/mol, 2.90//3.28 kcal/mol, 6.64//6.43 kcal/mol (MP2//DFT(B3LYP) with the cc-pVTZ basis set), each conformer has enantiomer. The conformers differ from each other in the relative orientation of the fragments of the–SO2NHNH2 group, the energies of the frontier orbitals, the direction and value of the dipole moments. It is shown that the introduction of a nitro or methyl group into the para -position practically does not affect the conformational properties of the sulfonyl hydrazide group. Change in the structure of benzenesulfonic acid hydrazide during the crystal–gas transition is considered and it is revealed that in the crystal the conformation similar in structure to one of the high-energy conformers of the free molecule is stabilized. The NBO analysis of the electron density distribution is performed and it is shown that the occurrence of the gauche effect in all conformers of the molecules under study can be interpreted by the manifestation of the total action of strong anomeric effects between the lone pairs of nitrogen atoms and antibonding orbitals of S=O, N–H, C–S, and N–S bonds.