Interestingly, host-guest interaction led to a conspicuous capsule-like complex in the crystalline state. Two large-rim-to-large-rim aligned belt molecules are interdigitated due to the steric effect between N-alkyl substituents on pyrrole moieties. The resulting spherical cavity encompassed by two belts accommodated a Buckyball nicely at the center owing to the perfect concaveconvex complementarity between host and guest. Substantiated by short atomic distances between belt and C60 (Fig. ) and noncovalent interaction