Incorporation of the Similarly Sized Molecules, Diiodine and Carbon Disulfide, into Cocrystals Formed with the Fullerenes, C₆₀ or C₇₀

Abstract

Cocrystallization of diiodine and carbon disulfide with the two common fullerenes, C60 and C70, has been examined. The binary cocrystal, C70·I2, readily formed when a solution of diiodine in diethyl ether was layered over C70 dissolved in toluene, chlorobenzene, or 1,2-dichlorobenzene, but no binary cocrystal of diiodine and C60 could be obtained despite persistent efforts. The ternary cocrystal, C70·0.85I2·0.15CS2, which was grown from a carbon disulfide solution of C70 and a benzene solution of diiodine, is isostructural with C70·I2 but has 15% of the diiodine sites replaced with carbon disulfide. In contrast, C70·0.68I2·0.32CS2, which was obtained from diffusion of a cyclohexane solution of diiodine into a carbon disulfide solution of C70, is a unique ternary cocrystal that is not related to any binary cocrystal of C70 with diiodine or carbon disulfide. Crystals of 2C60 ·2.46CS2 ·0.54I2 were obtained from a saturated carbon disulfide solution of diiodine and C60. Black crystals of 2C60 ·2.46CS2 ·0.54I2 form in a different space group from those of the solvate 2C60 ·3CS2 but have a very similar structure. Remarkably, diiodine molecules fractionally replace carbon disulfide in only two of the three independent sites within this crystal.

New Insights into the Structural Complexity of C60·2S8: Two Crystal Morphologies, Two Phase Changes, Four Polymorphs

“…Well-ordered crystals of binary combinations of C 60 or C 70 and sulfur can be prepared by carefully layering toluene or benzene solutions of both components. We previously reported that iodine may play a role in crystal formation but not incorporate itself into the lattice. , The effect of iodine is observed here. In studying the crystal growth of S 8 /C 60 cocrystals, we have discovered that introducing iodine into solution does not yield a ternary crystal.…”

“…We previously reported that iodine may play a role in crystal formation but not incorporate itself into the lattice. 12,13 The effect of iodine is observed here. In studying the crystal growth of S 8 /C 60 cocrystals, we have discovered that introducing iodine into solution does not yield a ternary crystal.…”

Single-Crystal X-ray Diffraction Studies of Solvated Crystals of C60 Reveal the Intermolecular Interactions between the Component Molecules

“…In addition to these methods, we discovered that diiodine dissolved in diethyl ether layered over C 60 dissolved in o -xylene, benzene, or toluene resulted in the formation of C 60 ·diethyl ether. This is another case of diiodine playing a directing role in crystal formation without being incorporated into the crystal. , We also found that mercuric chloride, dissolved in diethyl ether, layered over a solution of C 60 dissolved in o -dichlorobenzene, yielded crystals of C 60 ·diethyl ether.…”

“…This is another case of diiodine playing a directing role in crystal formation without being incorporated into the crystal. 40,41 We also found that mercuric chloride, dissolved in diethyl ether, layered over a solution of C 60 dissolved in o-dichlorobenzene, yielded crystals of C 60 •diethyl ether.…”

Waves of Halogen–Halogen Bond Formation in the Cocrystallization of Hexabromobenzene and 1,2,4,5-Tetrabromobenzene with C70

“…A way to circumvent some of these challenges is to cocrystallize fullerenes with other molecules, utilizing intermolecular interactions to help prevent disorder. In the case of C 70 , these cocrystallization agents have ranged from simple diatomic molecules (e.g., I 2 ) or solvent molecules (e.g., toluene and carbon disulfide) , to more shape-complementary curved molecules such as bis­(ethylenedithio)­tetrathiafulvalene or bowl-like corannulenes and other large aromatic species. − Overall, few crystal structures of nonderivatized C 70 have been well-determined. In many cases, however, crystals with halogenated molecules serving as cocrystallizing agents yield ordered structures. − …”