Effect of Intra- and Intermolecular Interactions on the Properties of para-Substituted Nitrobenzene Derivatives

Halina Szatyłowicz , Olga A. Stasyuk , Celia Fonseca Guerra , Tadeusz Marek Krygowski

Abstract

To study the influence of intra- and intermolecular interactions on properties of the nitro group in para-substituted nitrobenzene derivatives, two sources of data were used: (i) Cambridge Structural Database and (ii) quantum chemistry modeling. In the latter case, “pure” intramolecular interactions were simulated by gradual rotation of the nitro group in para-nitroaniline, whereas H-bond formation at the amino group allowed the intermolecular interactions to be accounted for. BLYP functional with dispersion correction and TZ2P basis set (ADF program) were used to perform all calculations. It was found that properties of the nitro group dramatically depend on both its orientation with respect to the benzene ring as well as on the substituent in the para-position. The nitro group lies in the plane of the benzene ring for only a small number of molecules, whereas the mean value of the twist angle is 7.3 deg, mostly due to intermolecular interactions in the crystals. This distortion from planarity and the nature of para-substituent influence the aromaticity of the ring (described by HOMA index) and properties of the nitro group due to electronic effects. The results obtained by QM calculations fully coincide with observations found for the data set of crystal structures.
Author Halina Szatyłowicz ZChF
Halina Szatyłowicz,,
- Department Of Physical Chemistry
, Olga A. Stasyuk ZChF
Olga A. Stasyuk,,
- Department Of Physical Chemistry
, Celia Fonseca Guerra
Celia Fonseca Guerra,,
-
, Tadeusz Marek Krygowski
Tadeusz Marek Krygowski,,
-
Journal seriesCrystals, ISSN 2073-4352
Issue year2016
Vol6
No29
Pages1-17
Publication size in sheets1.45
Keywords in Englishnitro group; crystal structures; hydrogen bond; Voronoi deformation density; energy decomposition analysis (EDA)
DOIDOI:10.3390/cryst6030029
URL http://www.mdpi.com/2073-4352/6/3/29
Languageen angielski
File
crystals-06-00029.pdf (file archived - login or check accessibility on faculty) crystals-06-00029.pdf 4.02 MB
Score (nominal)20
ScoreMinisterial score = 20.0, 28-11-2017, ArticleFromJournal
Ministerial score (2013-2016) = 20.0, 28-11-2017, ArticleFromJournal
Publication indicators WoS Impact Factor: 2016 = 1.566 (2) - 2016=1.394 (5)
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