Controlling the confinement and alignment of fullerene C(70) in para-substituted calix[5]arenes

In toluene fullerene C(70) forms 2:1 complexes with p-benzylcalix5]arene (1) and p-phenylcalix5]arene (2), C(70) subset1(2)].6(C(7)H(8)) and C(70) subset2(2)].7(C(7)H(8)). The fullerene molecules are completely shrouded by two calix5]arenes in addition to terminal benzyl groups from other supermolecules, C(70) subset1(2)], and solvent. Within the capsule-like supermolecules the calixarenes have distinctly different arrangements relative to the principal axis of the fullerene; for C(70) subset1(2)].6(C(7)H(8)) the oxygen planes of the two calixarenes are skewed by 37.0 and 47.5 degrees , whereas in C(70) subset2(2)].7(C(7)H(8)) the principal axes of the fullerene and the two encapsulating calixarenes are more closely aligned with the corresponding angles at 9.7 and 8.6 degrees , and features a pentaphenyl inter-calixarene embrace. The Hirshfeld surfaces of these two complexes have been investigated for a detailed understanding of the orientation and nature of interactions of C(70) with the cavitand-type molecules and toluene.