Temperature-induced first-order displacive phase transition of isonicotinamide-4-methoxybenzoic acid co-crystal

Abstract

Isonicotinamide–4-methoxybenzoic acid co-crystal (1), C6H6N2O·C8H8O3, is formed through slow evaporation from methanol solution and it undergoes a first-order isosymmetry (monoclinicI2/a↔ monoclinicI2/a) structural phase transition atTc= 142.5 (5) K, which has been confirmed by an abrupt jump of crystallographic interaxial angle β from variable-temperature single-crystal XRD and small heat hysteresis (6.25 K) in differential scanning calorimetry measurement. The three-dimensional X-ray crystal structures of (1) at the low-temperature phase (LTP) (100, 140 and 142 K) and the high-temperature phase (HTP) (143, 150, 200, 250 and 300 K) were solved and refined as a simple non-disordered model with finalR[F2> 2σ(F2)] ≃ 0.05. The asymmetric unit of (1) consists of crystallographically independent 4-methoxybenzoic acid (A) and isonicotinamide (B) molecules in both enantiotropic phases. MoleculeAadopts a `near-hydroxyl' conformation in which the hydroxyl and methoxy groups are positioned on the same side. Both `near-hydroxyl' and `near-carbonyl' molecular conformations possess minimum conformational energies with an energy difference of < 0.15 kJ mol−1from a potential energy surface scan. In the crystal, molecules are joined into linearABBAarrays by intermolecular N—H...O and O—H...N hydrogen bonds which were preserved in both phases. However, theseABBAarrays are displaced from planarity upon LTP-to-HTP transition and the changes in inter-array interactions are observed in two-dimensional fingerprint plots of their Hirshfeld surfaces. ThePIXELenergies of each molecular pair in both phases were calculated to investigate the difference in intermolecular interaction energies before and after the displacement ofABBAarrays from planarity, which directly leads to the single-crystal-to-single-crystal phase transition of (1).