Discovery of a New System Exhibiting Abundant Polymorphism: <i>m</i>-Aminobenzoic Acid

Given the importance of the phenomenon of polymorphism from both fundamental and applied perspectives, there is considerable interest in the discovery of new systems that exhibit abundant polymorphism. In the present article, the preparation strategies and structural properties of three new polymorphs (denoted Forms III, IV, and V) of <i>m</i>-aminobenzoic acid (<i>m</i>-ABA) are reported, elevating this system to the rare class of polymorphic systems with at least five known polymorphs. The crystal structures of the three new polymorphs have been determined directly from powder X-ray diffraction data, using the direct-space genetic algorithm technique for structure solution followed by Rietveld refinement, demonstrating the opportunities that now exist for determining crystal structures when crystals of sufficient size and quality for single-crystal X-ray diffraction are not available. In two of the new polymorphs (Forms III and IV), the <i>m</i>-ABA molecules exist in the zwitterionic form (as in the previously known Form I), while the <i>m</i>-ABA molecules in the other new polymorph (Form V) are nonzwitterionic (as in the previously known Form II). Furthermore, disorder of the molecular orientation, and hence disorder in the intermolecular hydrogen-bonding arrangement, is revealed in Form V. The assignment of the tautomeric form in each polymorph is confirmed by X-ray photoelectron spectroscopy. Issues relating to the relative stabilities of the five polymorphs of <i>m</i>-ABA are discussed