Exploring concomitant/conformational dimorphism in a difluoro‐substituted phosphoramidate derivative

摘要

The concomitant occurrence of dimorphs of diphenyl (3,4‐difluorophenyl)phosphoramidate, C 18 H 14 F 2 NO 3 P, was observed via a solution‐mediated crystallization process with variation in the symmetry‐free molecules ( Z ′). The existence of two forms, i.e. Form I (block, Z ′ = 1) and Form II (needle, Z ′ = 2), was characterized by single‐crystal X‐ray diffraction, differential scanning calorimetry and powder X‐ray diffraction. Furthermore, a quantitative analysis of the energetics of the different intermolecular interactions was carried out via the energy decomposition method ( PIXEL ), which corroborates with inputs from the energy framework and looks at the topology of the various intermolecular interactions present in both forms. The unequivocally distinguished contribution of strong N—H…O hydrogen bonds along with other interactions, such as C—H…O, C—H…F, π–π and C—H…π, mapped on the Hirshfeld surface is depicted by two‐dimensional fingerprint plots. Apart from the major electrostatic contribution from N—H…O hydrogen bonds, the crystal structures are stabilized by contributions from the dispersion energy. The closely related melting points and opposite trends in the calculated lattice energies are interesting to investigate with respect to the thermodynamic stability of the observed dimorphs. The significant variation in the torsion angles in both forms helps in classifying them in the category of conformational polymorphs .