A strong N-H•••Br vibrational behaviour studied through X-ray, vibrational spectra and quantum chemical studies in an isomorphous crystal: 2-Nitroanilinium bromide

A needle shaped transparent light brown crystals of 2-nitroanilinium bromide were successfully synthesized and crystallized from an aqueous mixture by slow evaporation technique. Single crystal XRD studies confirm the crystalline phase of this isomorphous compound which contains a positively charge 2-nitroanilinium cation and a negatively charged bromide anion. The solid phase FT-IR and FT-Raman spectra of the compound have been recorded in the range of 4000-400 cm(-1). The observed modes are correlated by the factor group theory analysis and different IR and Raman active species were identified. Geometrical optimisations were carried out and harmonic vibrational wave numbers were computed for the minimum energy molecular structure at RHF level invoking 6-311++G(d,p) and SDD basis sets. Optimised molecular geometry was compared with the crystallographic data. The calculated wavenumbers were compared with the experimental values. The N-H vibrational bands are shifted from its normal range and the shifting is associated with the influence of the intermolecular hydrogen bonds in the crystal. A strong intensity peak in theoretical and corresponding band in experimental confirms the presence of N-H center dot center dot center dot Br interaction as predicted in crystalline state. (C) 2014 Elsevier B.V. All rights reserved.