A new cocrystal explosive trinitrotoluene (TNT):1-amino-4-bromonaphthalene with reduced sensitivity

Abstract

A 1:1 cocrystal of TNT and 1-amino-4-bromonaphthalene was prepared via solvent evaporation. The structureof the cocrystal was determined via single-crystal and powder X-ray diffraction. Crystal structure determination studiesindicated that the main mechanism of cocrystallization originates from the intermolecular hydrogen bonding (amino–nitro), halogen bonding, and π − π stacking. Investigation of intermolecular interactions by Hirshfeld surface andfingerprint plot analysis revealed that the structures were stabilized by H…H, O…H, C…C (π−π) and Br…O interactions.Hirshfeld surfaces showed that these weak interactions were significant for crystal packing. We analyzed the crystalpacking and showed how this may influence sensitivity to impact. The TNT:1-amino-4-bromonaphthalene cocrystaldisplays significantly reduced impact sensitivity relative to pure TNT, indicating for the first time that a new TNTcocrystal was less sensitive to impact than pure TNT component. This difference in impact sensitivities may arisefrom the considerably different intermolecular interactions seen in the cocrystal structure. The results highlight thatcocrystallization is an effective way to alter the impact sensitivity, detonation performance, decomposition temperature,melting point, oxygen balance, crystal packing, and the density of explosives.