Solid-state compounds of stereoisomers: cis and trans isomers of 1,2-cyclohexanediol and 2,3-tetralindiol

Abstract

The phases of 1,2,3,4-tetrahydro-2,3-naphthalenediol (or 2,3-tetralindiol) and of 1,2-cyclohexanediol have been investigated. The structure of a very stable 1:1 compound (or co-crystal) of the cis and trans isomers of 2,3-tetralindiol, the existence of which has been known for nearly a century, has finally been determined. No evidence of any analogous compound between the cis and trans isomers of 1,2-cyclohexanediol has been found. The formation of solid-state compounds of stereoisomers is rare; it probably occurs only if the crystal packing of at least one of the isomers is unfavorable, e.g. if at least one of the melting points is lower than expected. Compound formation is usually unlikely because of the difficulty of simultaneously optimizing the translational spacings for both isomers, but that packing problem is avoided in the cis/trans compound of 2,3-tetralindiol because the two isomers are in very similar environments. In the structures of the individual 2,3-tetralindiol isomers there are clear conflicts between the competing packing requirements of the 1,2-diol moiety and the aromatic ring system; these conflicts are resolved better in the co-crystal than in the structures of the individual isomers.