Ordered Structures from Crystalline Carbon Disulfide Solvates of the Nano-Tubular Fullerenes D5h(1)‑C90 and D5h-C70

The structures of three crystalline solvates, D5h(1)-C90·CS2, D5h-C70·3CS2, and 2­(D5h-C70)·3CS2, of nanotubular fullerenes have been determined by single crystal X-ray diffraction. Despite the marked tendency for fullerenes to disorder, the carbon cages in all three structures are fully ordered at 100(2) K for D5h(1)-C90·CS2 and 90 K for the other two crystals. Moreover, the carbon disulfide molecules are also ordered, except for the case of D5h(1)-C90·CS2, where there is a minor disorder in the solvate location. The molecular packing in D5h(1)-C90·CS2 reflects the nanotubular nature of the fullerene component with channels of alternating fullerenes and carbon disulfide molecules running along the crystallographic b axis. The molecular packing arrangements for D5h-C70·3CS2 and 2­(D5h-C70)·3CS2 do not show such channels. In D5h-C70·3CS2, the carbon disulfide molecules form chains that snake between the fullerenes and along the crystallographic a axis. In 2­(D5h-C70)·3CS2, there are two crystallographically distinct fullerene cages, which are segregated into individual layers. Within each layer, the fullerenes show hexagonal close packing and the carbon disulfide molecules form chains that snake between the fullerene layers in a zigzag fashion. The presence of diiodine in solution was essential for the formation of crystals of D5h-C70·3CS2 and 2­(D5h-C70)·3CS2 that were suitable for structure determination, although no diiodine was incorporated in these crystals.