Varying the interplay of calix[5]arenes through chloromethane inclusion

Three inclusion complexes of calix[5]arenes as dichloromethane (DCM) or chloroform solvates have been structurally authenticated, namely, the complexes of p-Bu^t-calix[5]arene, 1, or p-H-calix[5]arene, with DCM, 2, and a new polymorph of the complex of p-phenyl-calix[5]arene with chloroform, 3. Complex 1 has two adjacent ^tbutyl groups of one calixarene embracing the analogous groups from another calixarene. Complex 2 has a slipped head-to-head arrangement of calixarenes with a DCM molecule in the cavity of each calixarene. In complex 3, the calixarenes form dimers through interdigitation, and these dimers are assembled with back-to-back arrangement of calixarenes from adjacent dimers. All solvate complexes were crystallized in the presence of p-carborane, which has complementarity of size of the cavity of the calixarenes yet is not incorporated in the structures.