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Hydrogen‐bonded complexes of sulfonamides and thioamides with DMF: FT‐IR and DFT study, NBO analysis
Author(s) -
Shainyan B. A.,
Chipani. N.,
Oznobikhina L. P.,
Chernysheva G. N.,
Rozentsveig I. B.
Publication year - 2013
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3094
Subject(s) - thioamide , chemistry , natural bond orbital , intramolecular force , hydrogen bond , intermolecular force , density functional theory , infrared spectroscopy , fourier transform infrared spectroscopy , dimethylformamide , crystallography , sulfonamide , computational chemistry , medicinal chemistry , stereochemistry , molecule , organic chemistry , solvent , physics , quantum mechanics
The structure of H‐complexes of dimethylformamide (DMF) with N‐(2,2,2‐trichloro‐1‐hydroxyethyl)‐ p ‐toluenesulfonamide (1), N‐[1‐(4‐chlorophenylsulfonylamino)‐2,2,2‐trichloro)ethyl]dithiooxamide (2), N,N'‐bis[2,2‐dichloro‐1‐(4‐chlorophenylsulfonylamino)‐2‐phenylethyl]ethanebis(thioamide) (3) and N,N'‐bis[2,2,2‐trichloro‐1‐(phenylsulfonylamino)ethyl]ethanebis(thioamide) (3a) as proton donors was investigated using Fourier transform infrared spectroscopy and Density Functional Theory calculations. According to calculations, the interaction of DMF with the sulfonamide and thioamide NH groups in the complexes strongly affects the intramolecular H‐bonding in 1–3. From the natural bond orbital analysis, complexation with DMF strongly decreases the energy of the intramolecular N−H · · · S = C bonds, up to their rupture. Variation of the strength of the intra‐ and intermolecular H‐bonds in the complexes is consistent with the calculated frequencies of the NH and OH stretching vibrations, and the analysis of the corresponding bands in the IR spectra allows to suggest the preferable structure of the formed H‐complexes. Copyright © 2013 John Wiley & Sons, Ltd.