Pendant orientation and its influence on the formation of hydrogen-bonded thiacalixarene nanotubes

Abstract

Five 1,3-alternatethiacalix[4]arene derivatives bearing carboxylic acid and/or urea hydrogen-bonding groups were prepared and their crystal structures were determined by single-crystal X-ray diffraction methods. In compound 1, where the pendant arms are all adorned with carboxylic acid groups, the pendants all orientate along the base of the molecular axis. An interesting three-dimensional network of “endo-inclusion” aquatubes is formed by stacking the water contained cavities of 1 up and down. While concerning to the other four compounds to which the urea groups are introduced, their pendant arms either orientate towards the inner side of the cavities, or orientate towards the outside, depending on the types of hydrogen-bonding groups and the position of these groups. When the urea groups are in the same side (compounds 2, 4 and 5), the opposite chains in the molecule will locate away from each other which may be due to the steric repulsions. But when the urea group and carboxylic acid group are in the same side (compounds 3 and 4), the opposite chains all orientate inwards because of the intramolecular, inter-chain hydrogen bonds between the opposite chains. Although these four compounds can also self-assemble through the cavity stacking motif, the inwardly orientated pendant arms which protrude into the thiacalixarene cavity obstruct the channels.