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...π 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.