Temperature-induced order-disorder structural phase transitions of two-dimensional isostructural hexamethylenetetramine co-crystals

Hexamethylenetetramine-benzoic acid (1/2) (HBA) and hexamethylenetetramine-4-methylbenzoic acid (1/2) (HMBA) co-crystals undergo order-disorder structural phase transition from a low-temperature monoclinic crystal structure to a high-temperature orthorhombic crystal structure at the transition temperatures of 257.5 (5) K (Pn ↔ Fmm2) and 265.5 (5) K (P21/n ↔ Cmcm), respectively, using variable-temperature single-crystal X-ray diffraction analysis. The observed phase transitions were confirmed to be reversible first-order transitions as indicated by the sharp endothermic and exothermic peaks in the differential scanning calorimetry measurement. The three-molecule aggregate of HBA and HMBA consists of a hexamethylenetetramine molecule and two benzoic acid or two 4-methylbenzoic acid molecules, respectively. The acid molecules are ordered at the low-temperature phase and are equally disordered over two positions, which are related by a mirror symmetry, at the high-temperature phase. The two-dimensional supramolecular constructs common to both co-crystals are formed by three-molecule aggregates via weak intermolecular C-H...O and C-H...π interactions into molecular trilayers parallel to the ac plane with small XPac dissimilarity indices and parameters. The PIXEL interaction energies of all corresponding molecular contacts were calculated and the results are comparable between HBA and HMBA co-crystals, resulting in similar lattice energies and transition temperatures despite their two-dimensional isostructural relationship. The observed phase transitions of these two energetically similar co-crystals are triggered by similar mechanisms, i.e. the molecular rotator ordering and structural order-disorder transformation, which induced non-merohedral twinning with similar twin matrices in the low-temperature crystal form of both co-crystals.