Ordered Structures from Crystalline Carbon Disulfide Solvates of the

Article pubs.acs.org/crystal

Ordered Structures from Crystalline Carbon Disulfide Solvates of the Nano-Tubular Fullerenes D5h(1)‑C90 and D5h-C70 Faye L. Bowles,† Brandon Q. Mercado,† Kamran B. Ghiassi,† Susanne Y. Chen,† Marilyn M. Olmstead,*,† Hua Yang,‡ Ziyang Liu,*,‡ and Alan L. Balch*,† †

Department of Chemistry, University of California, Davis, Davis, California 95616, United States College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China

‡

S Supporting Information *

ABSTRACT: 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.

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INTRODUCTION For fullerenes and endohedral fullerenes, structure determination by X-ray diffraction from single crystals has become essential for identifying the cage geometry and dimensions.1−3 This statement is particularly important for higher fullerenes, where the number of potential isomers increases markedly as the cage size increases.4 Thus, for C60 and C70, there is only one isomer that obeys the isolated pentagon rule (IPR), which requires that each of the twelve pentagons in a fullerene be surrounded by five hexagons. However, for a large fullerene such as C90, there are 46 IPR isomers.1 Computational results suggest that D5h(1)-C90 is one of the more thermodynamically and kinetically stable isomers of C90.5 Experimentally, several isomers of C90 have been isolated from the carbon soot prepared by the Krätschmer-Huffman electric arc method.6−8 In addition to nanotubular D5h(1)-C90,9 the asymmetrical isomers, C1(30)-C90 and C1(32)-C90,10 have been characterized crystallographically. Unfortunately, disorder is a common problem that plagues the crystallographic characterization of fullerenes.11 For example, in cubic crystals of pristine C60, the fullerene molecules are completely disordered above 260 K.12 Upon cooling, they experience a phase change where they undergo uniaxial reorientation, and then below 90 K, rotational motion is stopped, although some static disorder is present. © 2013 American Chemical Society

Figure 1. The structure of D5h(1)-C90·CS2 with thermal contours at 50%. The positions of the two disordered carbon disulfide molecules are shown.

Two methods have been widely employed to overcome the issue of disorder in fullerene crystals and to provide detailed Received: July 26, 2013 Revised: August 20, 2013 Published: August 26, 2013 4591

dx.doi.org/10.1021/cg401138g | Cryst. Growth Des. 2013, 13, 4591−4598

Crystal Growth & Design

Article

information of the molecular geometry of these fullerenes. One utilizes external functionalization of the fullerene to lower its symmetry and limit disorder.13,14 This method, however, has the potential to introduce some degree of distortion into the structure, particularly at the sites of functionalization. The other method involves cocrystallization, with a porphyrin such as Ni(OEP) where OEP is the dianion of octaethylporphyrin.15 This method has led to the structural identification of many large fullerenes and endohedral fullerenes including nanotubular D3d(3)-C96,16 La2@D5(450)-C100,17 Sm2@D3d(822)-C104,18 and Sc4(μ3-O)[email protected] The separation and purification of fullerenes and endohedral fullerenes generally employs extensive chromatography that may utilize a variety of solvents. As a result, these carbon cage molecules are frequently obtained in solid form by evaporation of solutions after chromatography. The resulting solids are likely to contain solvated forms of these fullerenes. The formation of such solvates complicates the study of fullerene solubility and is problematic for those seeking to work with pristine fullerene samples.20 Many fullerene solvates have been found in the crystalline form. Unfortunately, obtaining structural information from some of these solvates has been difficult because of problems with disorder,21 poor diffraction,22 twinning, and crystal symmetry.23,24 For example, in regard to disorder, temperature-dependent phase changes have complicated the study of C60·4(C6H6),25−27 but fully ordered fullerene cages are found for data acquired at 93 K.28 Carbon disulfide is an excellent solvent for fullerenes.29 It is used to extract fullerenes and endohedral fullerenes from the raw carbon soot obtained by conventional fullerene generators and can be used during fullerene purification.30 Its high volatility facilitates crystal growth through evaporation. Thus, evaporation of a solution of C60 in carbon disulfide produces brown crystals of 2C60·3CS2.31 At room temperature, these crystals display considerable disorder. However, upon cooling, these crystals undergo a reversible phase change so that at 90 K, the monoclinic phase contains two fully ordered fullerenes and three-ordered molecules of carbon disulfide in the asymmetric unit.32

Figure 2. Drawing of D5h(1)-C90 with each symmetrically distinct type of bond differently colored (top). C−C bond lengths for each of the ten types of C−C bonds in this fullerene (bottom). The error bars show 2 σ.

Figure 3. The molecular packing in D5h(1)-C90·CS2 looking at the bc plane and down the a axis. Only the positions of major sites of the carbon disulfide molecules are shown. 4592



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Figure 5. Structure of D5h-C70·3CS2 with thermal contours at 50%.

Table 1. Crystal and Experimental Data for Fullerene/ Carbon Disulfide Solvatesa,b chemical formula formula weight radiation source, λ (Å) crystal system space group T (K) a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z dcalc (g cm−3) μ (mm−1) F(000) crystal size (mm3)

Figure 4. Views of the structure of D5h(1)-C90·CS2 that emphasize the locations of the close contact between two D5h(1)-C90 molecules in adjacent columns.

Here, we show that one can obtain crystals of carbon disulfide solvates of higher fullerenes that are well-ordered at low temperature, provide molecular structural information, and show the influence of molecular structure on crystal packing.

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RESULTS Crystals of D5h(1)-C90·CS2 were obtained simply through evaporation of a solution of the purified fullerene in carbon disulfide. Crystals of poor quality also were obtained through evaporation of carbon disulfide solutions of D5h-C70. However, to obtain suitable crystals of D5h-C70 for X-ray diffraction, it was necessary to have diiodine present during the crystallization. Carbon disulfide and diiodine have similar dimensions. The molecular volume of carbon disulfide is 82.9 Å3, while that of diiodine is 85.1 A3.33 The van der Waals lengths of the two are also comparable: 6.70 Å for carbon disulfide and 6.62 Å for diiodine. There is some evidence that molecules of diiodine can substitute for carbon disulfide in crystals of 2C60·3CS2.33 Diiodine has also been found to cocrystallize with C60 and toluene to form C60·I2·MeC6H5.34 Thus, we initially expected that it would

reflections collected, R(int) data/parameters/ restraints R(int) R1 [I > 2σ(I)] wR2 (all data) largest difference peak and hole (e Å−3)

D5h(1)-C90·CS2

D5h-C70·3CS2

2(D5h-C70)·3CS2

C91S2 1157.03 synchrotron, 0.77490 orthorhombic Pbcm 100(2) 14.1354(5) 21.1391(7) 14.2120(5) 90 90 90 4246.7(3) 4 1.810 0.199 2312 0.15 × 0.10 × 0.05 237697

C73S6 1069.09 sealed tube, 1.54178 triclinic P1̅ 90(2) 10.1998(4) 14.2540(6) 14.3062(6) 86.279(3) 73.297(2) 89.643(3) 1987.82(14) 2 1.786 0.441 1068 0.93 × 0.87 × 0.39 23264

C143S6 1909.79 synchrotron, 0.77490 monoclinic P21/c 90(2) 19.2587(11) 19.5039(11) 19.8293(11) 90 106.076(4) 90 7157.0(7) 4 1.772 0.335 3816 0.35 × 0.15 × 0.11 81796

10335/441/3

6886/712/0

16375/1342/0

0.083 0.0873 0.2387 0.765 and −0.779

0.055 0.0815 0.2471 0.651 and −0.811

0.050 0.1055 0.2604 1.938 and −1.322

a For data with I > 2σI, R1 = ∑∥FO| − |FC∥/∑|FO|. bFor all data, wR2 = ((∑[W(FO2 − FC2])/(∑[W(FO2)2]))1/2

be possible to obtain cocrystals of these nanotubular fullerenes with diiodine. To some extent that proposition is true, and we will describe those results elsewhere. For the present work, 4593



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agreement among the various bond length measurements for each bond type. Indeed, the agreement here is slightly better than found in the previous structure determination, which involved the Ni(OEP) cocrystal, D5h(1)-C90·Ni(OEP). The shortest C−C bonds are the c−c [av 1.384(2) Å] and a−b [av 1.394(3) Å] bonds at the 6:6 ring junctions that lie between pentagons. These are the only bonds in D5h(1)-C90 that are at the centers of pyracylene fragments. The next shortest bonds involve the d−e [av 1.398(3) Å] bonds, which involve the unique set of 6:6 ring junctions that join a pentagon and a hexagon. Interestingly, the C−C bonds at the 5:6 ring junctions {a−a [av 1.450(3) Å], b−c [av 1.445(2) Å], c−d [av 1.438(2) Å], and d−d [av 1.445(3) Å]} are all rather similar in length, while there are more sizable differences in the lengths of the bonds at the 6:6 ring junctions, including the set that involves the bonds e− e [av 1.457(1) Å], e−f [av 1.440(3) Å], and f−f [av 1.429(2) Å] that lie between two hexagons. These bond length variations parallel those seen in D5h(1)-C90·Ni(OEP). Figure 3 shows the distinctive molecular packing within D5h(1)-C90·CS2. The structure consists of nanotubular arrays of alternating molecules of D5h(1)-C90 and carbon disulfide with the sulfur atoms of the latter positioned above the centers of terminal pentagons of the adjacent fullerenes. These tubes propagate along the b axis. There are four carbon disulfide molecules that surround the central section of each D5h(1)-C90 molecule and two at each end. In a reciprocal fashion, each carbon disulfide molecule is surrounded by six fullerenes, two at the ends and four at the sides. Within D5h(1)-C90·CS2, there are two remarkably short contacts between the fullerenes as shown in Figure 4. The shortest contact, which involves the 2.871(4) Å distance between C9 and C82ii, occurs at the ends of the two fullerenes in adjacent columns. A second short contact at 3.106(4) Å again occurs between fullerenes in neighboring columns and involves carbon atoms C6 and C6iii. Molecular and Supramolecular Structure of D5h-C70· 3CS2. The asymmetric unit in the black blocks of D5h-C70·3CS2 contains one fullerene and three molecules of carbon disulfide, all in general positions. These components are shown in Figure 5. The dimensions of the D5h-C70 are consistent with previous crystallographic studies of this fullerene, as shown in the data in Table 1.13,36 Figure 6 shows the bond distances for the eight different types of C−C bonds in D5h-C70. As the plot shows, there is good agreement between the lengths of bonds of different types. The c−c and a−b bonds, which are at the centers of pyracylene fragments, are the shortest C−C bonds, while the longest C−C bonds are those along the central belt of the molecule (i.e., the e−e bonds). However, these bonds are not nearly as long as the distance reported [1.538(19) Å] for the same bonds in the gas phase at 810−835 °C.37 Figure 7 shows the molecular packing in crystalline D5h-C70· 3CS2. The nanotubular arrays of fullerenes and carbon disulfide molecules that are a prominent feature of the packing in D5h(1)-C90·CS2 are not present in D5h-C70·3CS2. Rather, the carbon disulfide molecules form chains that snake between the fullerenes and along the crystallographic a axis. Molecular and Supramolecular Structure of 2(D5h-C70)· 3CS2. This compound has the most complex structure of the three solvates considered here. The asymmetric unit consists of two independent molecules of D5h-C70 and three carbon disulfide molecules. All of these components reside in general positions and are fully ordered. A drawing showing these five molecules is shown in Figure 8. Notice that in this view,

Figure 6. Drawing of D5h-C70 with each symmetrically distinct type of bond differently colored (top). C−C bond lengths for each of the eight types of C−C bonds in this fullerene (bottom). Error bars show 2 σ.

diiodine simply facilitated growth of crystals without perceptible uptake of the diiodine into the crystals. Two different solvent systems yielded two different solvates. D5h-C70·3CS2 was obtained from ethanol/carbon disulfide, while 2(D5h-C70)· 3CS2 was obtained from cyclohexane/carbon disulfide. In both solvent systems, it is likely that diiodine was acting to modify the nucleation and growth of crystals as has been seen for a number of additives during the crystallization process.35 Molecular and Supramolecular Structure of D5h(1)C90·CS2. Black parallelepipeds of D5h-C90·CS2 crystallize with one-half of a molecule of the fullerene and carbon disulfide in the asymmetric unit. The other half of each molecule is generated by reflection through a crystallographic mirror plane. Figure 1 shows a drawing of the complete molecule. The fullerene is fully ordered, but there is minor disorder with the carbon disulfide. Figure 1 shows both the locations of the major and minor forms, which have fractional occupancies of 0.45 and 0.05, respectively. In D5h(1)-C90, there are ten different types of C−C bonds. Figure 2 shows a drawing with each bond type in different colors and a graph of the bond lengths for each bond type within D5h(1)-C90·CS2. As the plot shows, there is good 4594



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Figure 7. The molecular packing in crystals of D5h-C70·3CS2 looking down the b axis and showing the chains of carbon disulfide molecules snaking between the fullerenes.

Figures 9 and 10 show the molecular packing. The type A and type B molecules are segregated into individual layers that are readily apparent in Figure 10. Within each layer, the fullerenes show hexagonal close packing, as seen in Figure 9. The carbon disulfide molecules form chains that snake between the fullerene layers in a zigzag fashion. These solvate molecules are arranged so that they effectively cradle the adjacent D5h-C70 molecules.

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DISCUSSION The present studies demonstrate that crystalline solvates of fullerenes can be well-ordered and can be used to obtain structural information on higher fullerenes. Generally, solvated fullerene crystals have not been utilized for molecular structure determinations of newly obtained higher fullerenes. However, the solvates Lu3N@Ih-C80·0.5(o-xylene) and Sc3N@Ih-C80·0.5(o-xylene) did yield X-ray diffraction data that allowed structure determinations of these endohedral fullerenes.38 Carbon disulfide has some advantages in forming solvated fullerene crystals. Its high volatility facilitates evaporation but also allows crystals to easily decay due to solvate loss. Its rigid rodlike structure limits possibilities for disorder. The presence of diiodine in solution during crystallization of fullerenes from carbon disulfide may prove to be generally beneficial for improving crystal quality. The packing within D5h(1)-C90·CS2, shown in Figure 3, clearly relates to the fullerene’s nanotubular shape. The organization of

Figure 8. Asymmetric unit of 2(D5h-C70)·3CS2 with thermal contours at 50%.

the 5-fold axis of one D5h-C70 molecule (molecule A, which contains carbon atoms 1−70) is nearly perpendicular to the plane of the drawing. In contrast, the 5-fold axis of the other fullerene (molecule B containing carbon atoms 71−140) lies within the plane of the drawing. Table 2. Average Bond Lengths (Å) of C70 in Different Crystals

average bond lengths (Å)

a

crystal

a−a

a−b

b−c

c−c

c−d

d−d

d−e

e−e

THT·C70a C70·3CS2b

1.446(10) 1.450(8)

1.393(8) 1.390(6)

1.443(6) 1.445(8)

1.370(6) 1.381(8)

1.449(6) 1.447(7)

1.418(7) 1.430(8)

1.423(6) 1.418(8)

1.448(7) 1.464(8)

THT is 1,4,7-tribromo-2,3,5,6,8,9-hexachloroazatriquinacene, data from ref 36. bThis article. 4595



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Figure 9. Molecular packing in crystalline of 2(D5h-C70)·3CS2 looking down the a axis. Molecules of type A are green, while molecules of type B are lilac. Only a portion of the top layer of A type molecules is shown and some of those are shown in space filling form, while others are shown with thermal ellipsoids and bonds.

Figure 10. View showing the layered packing of fullerenes in crystalline of 2(D5h-C70)·3CS2 looking down the b axis. Molecules of type A are green, while molecules of type B are lilac. Only a portion of the top layer of type A molecules is shown.

crystalline forms of fullerenes, where hexagonal close packing is found.39−41 Thus, the smaller aspect ratio in D5h-C70 relative to D5h(1)-C90 seems insufficient to produce any extended nanotubular organization in the solvates considered here.

alternating fullerene and carbon disulfide molecules into extended columnar units is a feature that is unique to this crystal. In contrast, the packing of D5h-C70 molecules in the complex solid 2(D5h-C70)·3CS2 is much like that of many 4596



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REFERENCES

(1) Rodrı ́guez-Fortea, A.; Balch, A. L.; Poblet, J. M. Chem. Soc. Rev. 2011, 40, 3551. (2) Chaur, M. N.; Melin, F.; Ortiz, A. L.; Echegoyen, L. Angew. Chem., Int. Ed. 2009, 48, 7514. (3) Yamada, M.; Akasaka, T.; Nagase, S. Acc. Chem. Res. 2010, 43, 92. (4) Fowler, P. W.; Manolopoulos, D. E. An Atlas of Fullerenes; Clarendon: Oxford, 1995. (5) Watanabe, M.; Ishimaru, D.; Mizorogi, N.; Kiuchi, M.; Aihara, J.I. J. Mol. Struct. 2005, 726, 11. (6) Krätschmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. Nature 1990, 347, 354. (7) Yang, H.; Lu, C.; Liu, Z.; Jin, H.; Che, Y.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 2008, 130, 17296. (8) (a) Achiba, Y.; Kikuchi, K.; Aihara, Y.; Wakabayashi, T.; Miyake, Y.; Kainosho, M. Mater. Res. Soc. Symp. Proc. 1995, 359, 3. (b) Achiba, Y.; Kikuchi, K.; Aihara, Y.; Wakabayashi, T.; Miyake, Y.; Kainosho, M. In The Chemical Physics of Fullerenes 10 [and 5] Years Later; Andreoni, W., Ed.; Kluwer: Dordrecht, 1996; p 139. (9) Yang, H.; Beavers, C. M.; Wang, Z.; Jiang, A.; Liu, Z.; Jin, H.; Mercado, B. Q.; Olmstead, M. M.; Balch, A. L. Angew. Chem., Int. Ed. 2010, 49, 886. (10) Yang, H.; Mercado, B. Q.; Jin, H.; Wang, Z.; Jiang, A.; Liu, Z.; Beavers, C. M.; Olmstead, M. M.; Balch, A. L. Chem. Commun. 2011, 47, 2068. (11) Fischer, J. E.; Heiney, P. A. J. Phys. Chem. Solids 1993, 54, 1725. (12) Davis, W. I. F.; Ibberson, R. M.; Dennis, T. J. S.; Hare, J. P.; Prassides, K. Europhys. Lett. 1992, 18, 219. (13) Balch, A. L.; Catalano, V. J.; Lee, J. W.; Olmstead, M. M.; Parkin, S. R. J. Am. Chem. Soc. 1991, 113, 8953. (14) Balch, A. L.; Ginwalla, A. S.; Lee, J. W.; Noll, B. C.; Olmstead, M. M. J. Am. Chem. Soc. 1994, 116, 2227. (15) Olmstead, M. M.; Costa, D. A.; Maitra, K.; Noll, B. C.; Phillips, S. L.; Van Calcar, P. M.; Balch, A. L. J. Am. Chem. Soc. 1999, 121, 7090. (16) Yang, H.; Jin, H.; Che, Y.; Hong, B.; Liu, Z.; Gharamaleki, J. A.; Olmstead, M. M.; Balch, A. L. Chem.Eur. J. 2012, 18, 2792. (17) Beavers, C. M.; Jin, H.; Yang, H.; Wang, Z.; Wang, X.; Ge, H.; Liu, Z.; Mercado, B. Q.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 2011, 133, 15338. (18) Mercado, B. Q.; Jiang, A.; Yang, H.; Wang, Z.; Jin, H.; Liu, Z.; Olmstead, M. M.; Balch, A. L. Angew. Chem., Int. Ed. 2009, 48, 9114. (19) Mercado, B. Q.; Olmstead, M. M.; Beavers, C. M.; Easterling, M. L.; Stevenson, S.; Mackey, M. A.; Coumbe, C. E.; Phillips, J. D.; Phillips, J. P.; Balch, A. L. Chem. Commun. 2010, 46, 279. (20) Marcus, Y.; Smith, A. L.; Korobov, M. V.; Mirakyan, A. L.; Avramenko, N. V.; Stukalin, E. B. J. Phys. Chem. B 2001, 105, 2499. (21) Korobov, M. V.; Stukalina, E. B.; Mirakyana, A. L.; Neretinb, I. S.; Slovokhotovb, Y. L.; Dzyabchenkoc, A. V.; Ancharovd, A. I.; Tolochko, B. P. Carbon 2003, 41, 2743. (22) Park, C.; Yoon, E.; Kawano, M.; Joo, T.; Choi, H. C. Angew. Chem., Int. Ed. 2010, 49, 9670. (23) Fleming, R. M.; Kortan, A. R.; Hessen, B.; Siegrist, T.; Thiel, F. A.; Marsh, P.; Haddon, R. C.; Tycko, R.; Dabbagh, G.; Kaplan, M. L.; Mujsce, A. M. Phys. Rev. B 1991, 44, 888. (24) Michaud, F.; Barrio, M.; Toscani, S.; Lòpez, D. O.; Tamarit, J. Ll.; Agafonov, V.; Szwarc, H.; Céolin, R. Phys. Rev. B 1998, 57, 10351. (25) Meidine, M. F.; Hitchcock, P. B.; Kroto, H. W.; Taylor, R.; Walton, D. R. M. J. Chem. Soc., Chem. Commun. 1992, 1534. (26) Balch, A. L.; Lee, J. W.; Noll, B. C.; Olmstead, M. M. J. Chem. Soc., Chem. Commun. 1993, 56. (27) Bürgi, H. B.; Restori, R.; Schwarzenbach, D.; Balch, A. L.; Lee, J. W.; Noll, B. C.; Olmstead, M. M. Chem. Mater. 1994, 6, 1325. (28) Olmstead, M. M.; Balch, A. L.; Lee, H. M. Acta Crystallogr. 2012, B68, 66. (29) Ruoff, R. S.; Tse, D. S.; Malhotra, R.; Lorents, D. C. J. Phys. Chem. 1993, 97, 3379. (30) Bucsi, I.; Aniszfeld, R.; Shamma, T.; Surya Prakash, G. K.; Olah, G. A. Proc. Natl. Acad. Sci. 1994, 91, 9019.

Materials. A previously reported procedure was used for the preparation and isolation of D5h(1)-C90.9 C70 was purchased from SES research with 99% purity. No further purification was performed. Carbon disulfide, diiodine, ethanol, and cyclohexane were used as received. Crystal Growth. D5h(1)-C90·CS2. Crystals were grown by slow evaporation of a carbon disulfide solution of the purified fullerene over a period of a week. D5h-C70·3CS2. A 50 mg (0.40 mmol) portion of diiodine was dissolved in 20 mL ethanol and filtered. A 1 mL portion of this solution was layered over a 1 mL portion of a filtered solution of 206 mg (0.255 mmol) of C70 in 20 mL of carbon disulfide. Crystals formed within a week. If diiodine was not present in the ethanol, crystals did not grow. 2(D5h-C70)·3CS2. A 17.6 mg (0.0208 mmol) sample of C70 was dissolved in 9 mL of carbon disulfide and filtered. A 1 mL aliquot of this solution was layered over a 1 mL sample of a filtered solution of 60 mg (0.473 mmol) of diiodine in 8 mL of cyclohexane. Crystals formed within a week. Crystal Structure Determinations. The black crystals of D5h(1)C90·CS2 and 2(D5h-C70)·3CS2 were mounted in the nitrogen cold stream provided by an Oxford Cryostream low temperature apparatus on the goniometer head of a Bruker D8 diffractometer equipped with an ApexII CCD detector at the Advanced Light Source, Berkeley, CA, beamline 11.3.1. Data were collected with the use of silicon(111) monochromated synchrotron radiation (λ = 0.77490 Å). A black block of D5h-C70·3CS2 was selected for data collection on a Bruker D8 DUO diffractometer employing Cu Kα radiation (λ = 1.54178 Å) and a Cryo Industries low-temperature apparatus. All data sets were reduced with the use of Bruker SAINT42 and a multiscan absorption correction applied with the use of SADABS.43 Crystal data are given in Table 1. The structures were solved by direct methods [SIR200844 for D5h(1)C90·CS2 and SHELXS-201343 for the other two] and refined by fullmatrix least-squares on F2 (SHELXL-2013).43 The structure of D5h(1)C90·CS2 was a three component twin. The final refinement was carried out using HKLF 5 with reflection data prepared using TWINROTMAT of PLATON.45 The twin parameters were 0.099(2) and 0.082(2). S Supporting Information *

X-ray crystallographic files in CIF format are available on the Internet only. Access and ordering information is given on any current masthead page. This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the U.S. National Science Foundation [Grants CHE1305125 and CHE-1011760 to A.L.B. and M.M.O.], the U.S. Department of Education for a GAANN fellowship to B.Q.M., the National Natural Science Foundation of China [Grants 21271162, 11274283, and 11179039], Zhejiang Provincial Natural Science Foundation of China [Grant R12B010002], and the Advanced Light Source, Lawrence Berkeley Laboratory, for support and an ALS Predoctoral Fellowship to F.L.B. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231. 4597



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