Ordered Structures from Crystalline Carbon Disulfide Solvates of the Nano-Tubular Fullerenes D_5h(1)-C₉₀ and D_5h-C₇₀

Abstract

The structures of three crystalline solvates, D 5h (1)-C 90 ·CS 2 , D 5h -C 70 ·3CS 2 , and 2(D 5h -C 70 )·3CS 2 , 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 D 5h (1)-C 90 ·CS 2 and 90 K for the other two crystals. Moreover, the carbon disulfide molecules are also ordered, except for the case of D 5h (1)-C 90 ·CS 2 , where there is a minor disorder in the solvate location. The molecular packing in D 5h (1)-C 90 ·CS 2 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 D 5h -C 70 · 3CS 2 and 2(D 5h -C 70 )·3CS 2 do not show such channels. In D 5h -C 70 ·3CS 2 , the carbon disulfide molecules form chains that snake between the fullerenes and along the crystallographic a axis. In 2(D 5h -C 70 )·3CS 2 , 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 D 5h -C 70 ·3CS 2 and 2(D 5h -C 70 )·3CS 2 that were suitable for structure determination, although no diiodine was incorporated in these crystals.

Formation of a Stable Complex, RuCl2(S2CPPh3)(PPh3)2, Containing an Unstable Zwitterion from the Reaction of RuCl2(PPh3)3 with Carbon Disulfide

“…16 Of these solvents, only benzene is a suitable solvent for fullerenes. We observed that RuCl 2 (PPh 3 ) 3 dissolved in carbon disulfide, a good solvent for fullerenes, 17,18 to give a red solution. However, we also became aware that RuCl 2 (PPh 3 ) 3 was chemically reactive toward carbon disulfide and that there was an extensive and sometimes discombobulating literature on the topic.…”

Regulated Single‐Axis Rotations of a Carbonaceous Guest in a van der Waals Complex with an Entropy Cost

“…When we revealed the C−C contact area of the C 70 guest by the Hirshfeld analysis (Figure and Figure S15), we found that belt regions of the molecule were surrounded by a smoothly curved surface of the [4]CC host . In contrast, the surface of C 70 in its crystal was surrounded by polyhedral faces, because of face‐to‐face contacts between C 70 molecules (Figure ) . As can be seen from the temperature‐dependence of 1/ T 1 values (Figure ), the phase transition observed with naked C 70 molecules is absent with [4]CC⊃C 70 , which can thus be ascribed to the smoothly curved interface of the complex.…”

“…[23] In contrast, the surfaceo fC 70 in its crystal was surrounded by polyhedral faces, because of face-to-face contacts between C 70 molecules ( Figure 5). [28] As can be seen from the temperature-dependence of 1/T 1 values (Figure 3), the phase transitiono bserved with naked C 70 molecules is absent with [4]CC'C 70 , [21,22] which can thus be ascribed to the smoothly curved interface of the complex.A lthough the curvedi nterface between the host and the guest was similarly found with the C 60 guest, [9] the difference in the molecular shapes resulted in different modes of molecular rotations.…”

[2](1,3)Adamantano[2](2,7)pyrenophane: A Hydrocarbon with a Large Dipole Moment

“…The average bend angle α between adjacent planes of carbon atoms over the length of the pyrene unit in 3 is 17.4° (see Figure S3). A similar bend angle of 18.0° exists in the fullerenes D 5 h ‐C 70 and D 5 h ‐C 90 . The side chain bend angles, β , in 3 (13.0° and 14.0°) are larger than those observed in 1,7‐dioxa[7](2,7)pyrenophane (8.2° and 8.7°), but smaller than those in [2]metacyclo[2](2,7)pyrenophane (17.6° and 17.7°), for which θ =96.1° .…”