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Crystals 2016, 6(3), 29; doi:10.3390/cryst6030029

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

1
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
2
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
3
Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
*
Authors to whom correspondence should be addressed.
Academic Editor: Sławomir Grabowski
Received: 30 January 2016 / Revised: 2 March 2016 / Accepted: 11 March 2016 / Published: 18 March 2016
(This article belongs to the Special Issue Analysis of Hydrogen Bonds in Crystals)
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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. View Full-Text
Keywords: nitro group; crystal structures; hydrogen bond; Voronoi deformation density; energy decomposition analysis (EDA) nitro group; crystal structures; hydrogen bond; Voronoi deformation density; energy decomposition analysis (EDA)
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Szatylowicz, H.; Stasyuk, O.A.; Fonseca Guerra, C.; Krygowski, T.M. Effect of Intra- and Intermolecular Interactions on the Properties of para-Substituted Nitrobenzene Derivatives. Crystals 2016, 6, 29.

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