Controlling the Confinement and Alignment of Fullerene C70 in para-Substituted Calix[5]arenes

In toluene fullerene C70 forms 2:1 complexes with p‐benzylcalix[5]arene (1) and p‐phenylcalix[5]arene (2), [C70⊂12]⋅6 (C7H8) and [C70⊂22]⋅7 (C7H8). The fullerene molecules are completely shrouded by two calix[5]arenes in addition to terminal benzyl groups from other supermolecules, [C70⊂12], and solvent. Within the capsule‐like supermolecules the calixarenes have distinctly different arrangements relative to the principal axis of the fullerene; for [C70⊂12]⋅6 (C7H8) the oxygen planes of the two calixarenes are skewed by 37.0 and 47.5°, whereas in [C70⊂22]⋅7 (C7H8) 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°, 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 C70 with the cavitand‐type molecules and toluene. Complexes of fullerene C70 with p‐benzylcalix[5]arene and p‐phenylcalix[5]arene were structurally authenticated. The fullerene molecules are completely shrouded by two calix[5]arenes in a capsular arrangement (see figure). The Hirshfeld surfaces of two complexes have been investigated for a detailed understanding of the orientation and nature of interactions of C70 with the cavitand‐type molecules.