Calculated interactions of a nitro group with aromatic rings of crystalline picryl bromide

Abstract

Several crystalline polymorphs have been discovered for picryl bromide. Among the several forces that control the formation of such polymorphs are the interactions among the nitro groups and phenyl rings of those crystals. Although there are >300 structures to be found in the Cambridge Structural Database displaying the nitro-phenyl interaction, nonetheless this interesting, and apparently important, interaction, seems not to have been discussed within any of the papers reporting the structures. In this article, quantum calculations are reported that assess the strength of these nitro-phenyl interactions within a crystal of picryl bromide. The rather flat molecules of picryl bromide are arranged in layered planes within the crystal, and we examine the attractive interactions that occur within a given plane, and between adjacent planes. Calculations of Hartree Fock and Møller Plesset perturbation theory carried to a second-order expansion are used. Both quantum mechanical approximations are implemented with 6-31G* basis functions. © 2008 by The National Academy of Sciences of the USA.