Crystal-to-crystal structural transformation of hydrogen-bonding molecular crystals of (imidazolium)(3-hydroxy-2-quinoxalinecarboxylate) through H2O adsorption–desorption

Abstract

The Brønsted acid–base reaction between 3-hydroxy-2-quinoxalinecarboxylic acid (Hhqxc) and imidazole (Im) in acetone–H₂O yielded two 1 : 1 salts: anhydrous (HIm⁺)(hqxc⁻) (1) and hydrated (HIm⁺)(hqxc⁻)·(H₂O) (2), where HIm⁺ and hqxc⁻ are imidazolium and 3-hydroxy-2-quinoxalinecarboxylate, respectively. Single-crystal X-ray structural analyses and vibrational spectra were consistent with the lactam tautomer of the hqxc⁻ anion, which formed π-dimers in both 1 and 2. Each π-dimer in crystal 1 was connected by intermolecular N–H⋯O hydrogen-bonding interactions to form a linear hqxc⁻ chain, whereas the π-dimers in crystal 2 formed an intermolecular N–H⋯O hydrogen-bonding zigzag chain. The HIm⁺ cations existed in the crystalline space between the hydrogen-bonding hqxc⁻ anionic chains. A reversible crystal-to-crystal structural transformation between crystals 1 and 2 was observed following H₂O adsorption–desorption, which was confirmed by powder X-ray diffraction measurements, single-crystal X-ray structural analyses, and H₂O adsorption–desorption isotherms at 323 K. The structural rearrangement of the hqxc⁻ anions was achieved through changes in the intermolecular hydrogen-bonding interactions. The temperature- and frequency-dependent dielectric constants of crystal 2 revealed a dielectric peak at ~330 K owing to thermal fluctuations of H₂O molecules within the crystal.