Design of crystal packings of styrylheterocycles and [2+2] photocycloaddition reactions in their single crystals 7. Crystal structures of 4-styrylpyridine hydroperchlorates and solid-state [2+2] autophotocycloaddition reactions of these compounds

Abstract

A series of 4-styrylpyridine hydroperchlorates were synthesized, and the [2+2] autophotocycloaddition (PCA) reaction in their polycrystalline films and single crystals resulting in the centrosymmetric rctt isomers of 1,2,3,4-tetrasubstituted cyclobutanes was investigated. Unlike neutral styrylpyridines, their protonated forms are better preorganized for the solid-state PCA reaction. According to the X-ray diffraction data, the cations of these compounds, like related styryl dyes, are mainly stacked in crystals in a head-to-head or head-to-tail fashion with equal probability. Only in the latter type of stacks, the PCA reaction is feasible as a single-crystal-to-single-crystal transformation. The crystal packing is stabilized by hydrogen bonds between organic cations and perchlorate anions, as well as by other weak directional interactions, for example, by S…S interactions, thus preventing the atomic displacements in the course of PCA. The completion of the PCA reaction in single crystals without their degradation was observed only for 15-crown-5-containing 4-styrylpyridine hydroperchlorate. The crystals of the latter compound are stabilized not by hydrogen bonds between the cations and anions but by N+-H…O(macrocycle) hydrogen bonds resulting in the formation of head-to-tail stacked dimers. In the crystals, these dimers are surrounded by a soft shell formed by rotationally and translationally mobile anions and benzene solvent molecules, as well as by conformationally flexible crown-ether moieties of adjacent dimer pairs. This leads to a decrease in the steric strain that occurs in the crystals in the course of PCA and prevents the degradation of single crystals. The PCA reaction is accompanied by the reduction in the crystal symmetry due to the doubling of the unit cell.