Intra- and intermolecular interactions in substituted dithia[3.3]metacyclophanes

Abstract

The conformational properties of and intramolecular hydrogen-bonding in dithia[3.3]metacyclophanes carrying one or two amino groups on their internal positions were examined by their ¹H-NMR and IR spectra and by X-ray structural analyses. It was suggested that an intramolecular hydrogen-bonding network between the amino protons and bridge sulfur atoms is closely related to the conformations of the cyclophanes. Crystal structural analyses of dithia[3.3]metacyclophanes carrying an amino and a nitro group on their internal positions were also carried out. It has been found that the molecules assemble as one-dimensional array columns in the crystal owing to the intermolecular π–π interaction and this columnar structure is deformed by the occurrence of intermolecular hydrogen-bonding.