Experimental evidence for the amino-group non-planarity in nitroanilines: neutron diffraction study of 2-methyl-5-nitroaniline at 100 K

Acta Crystallogr B. 1999 Apr 1;55(Pt 2):209-215. doi: 10.1107/s0108768198010349.

Abstract

An appreciable degree of pyramidalization of the amine N atom is observed in the title compound. The existence of polar chains, induced by N-H.O synthons, is confirmed. C-H.O interactions, not noted in a previous X-ray study, were found to stabilize further the known head-to-tail assembling of the chains. The structure can be described as non-polar (101) layers, embodying chains interlinked by centrosymmetric dimers, connected by C(aryl)-H.pi interactions. The latter are not present in m-nitroaniline, 2-methyl-4-nitroaniline and other related compounds with chains built from similar N-H.O synthons and assembled head-to-head. This finding implies that an obvious relationship between molecular recognition patterns and crystal structures should not be assumed.