Competition between Polar and Centrosymmetric Packings in Molecular Crystals: Analysis of Actual and Virtual Structures

Imines obtained by condensation of 4-hydroxybenzohydrazide with aliphatic ketones are a rare example of a class of compounds showing a remarkable tendency to crystallize in acentric polar space groups (Pna21 or Cc). In fact, all of the (seven) compounds studied up to now show at least one polar polymorph. In some cases, polymorphism was detected, and a nonpolar centrosymmetric phase was also identified (P21/c or P21/n space group). With the aim to disclose the conditions that can favor the formation of acentric structures in molecular crystals, we report, in this paper, a theoretical analysis (ab initio density functional theory with periodic boundary) of the lattice energy and density of all the packing modes observed in the whole set of imines. The computational analysis has been performed by optimizing each compound in its own experimental packings (actual crystal structures) and also in the packings of the other compounds of the class (virtual structures). The experimental crystallographic data and the theoretical analysis suggest that two conformers, basically differing for the orientation of the phenolic H atom in the plane of the phenyl ring, compete, in solution, for the formation of polar or centrosymmetric packings. The transitions between polar and centrosymmetric polymorphs are of diffusive type, and single crystals are not preserved, while the transitions between different polar polymorphs can be of single-crystal-to-single-crystal type