Synthetic and Structural Exploration of [24]Tetrathiacalix[2]arene[2]pyrimidines

A novel class of two atom bridged meta­cyclo­phanes[24]­thiacalix­[2]­arene­[2]­pyrimidineshas been synthesized via a straightforward SNAr reaction. The conformational properties and intra-annular dimensions of the [24]­thiacalix­[2]­arene­[2]­pyrimidines were evaluated by X-ray structure analysis and compared with known homothia- and thiacalixarenes. Post-macrocyclization oxidation of the bridging sulfur moieties resulted in a [24]­sulfonylcalix­[2]­arene­[2]­pyrimidine, which gave access to an unexplored cavity size among sulfonylcalixarenes.