Molecular and crystal structure of 4-hexylbenzoic acid: Design of the mesophase

The crystal structure of 4-hexylbenzoic acid C6H13-C6H4-COOH, which forms a nematic mesophase upon melting, is determined. The crystal contains three crystallographically independent molecules. Their molecular skeletons are made up of two almost planar fragments: a benzene ring, π-conjugated with the carboxyl group and a planar zigzag aliphatic fragment. One of the independent molecules forms centrosymmetric dimers via pairs of hydrogen bonds between carboxyl groups, whereas the two others are linked via hydrogen bonds. The dimers in the crystal are packed into pseudostacks with a pronounced nonparallel arrangement of conjugated fragments. There is no good mutual projecting of benzene rings in the stacks, which corresponds to efficient π-stacking interaction. The graph describing the mesophase of this compound contains only one structure-forming element (a hydrogen bond) and corresponds to the nematic mesophase.