Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040755/wk2073sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040755/wk2073Isup2.hkl |
CCDC reference: 663667
The synthesis of (I) was carried out by heating C70 in a stream of CF3I at 420 °C as previously described (Popov et al., 2007). Crystals of the HPLC-purified compound were grown by slow evaporation of a saturated deuterochloroform solution.
The maximum (0.52 e/Å3) and minimum (-0.53 e/Å3) residual electron density peaks were located 1.07 Å from F422 and 0.58 Å from F391. The H atoms were geometrically placed (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C)
Recently reported high-temperature reactions of C70 with CF3I have yielded twenty-five C70(CF3)n derivatives (n = 2–18), most with relatively stable addition patterns that are chiral as well as unprecedented in fullerene(X)n chemistry (Kareev et al., 2005; Kareev et al., 2006a; Kareev et al., 2006b; Avdoshenko et al., 2006; Goryunkov et al., 2006; Ignat'eva et al., 2006; Popov et al., 2007). A member of the n = 14 set of five isomers, the title compound, (I), has been crystallized from p-xylene and we report its crystal structure here. A much lower-quality structure (C—C su's 0.015–0.019 Å, R1 = 0.186, wR2 = 0.41) of the same fullerene molecule as a hexane solvate has recently been reported (Goryunkov et al., 2006).
The structure of (I), Figs. 1 and 2, comprises an idealized D5 h C70 core with fourteen sp3 carbon atoms at positions 1, 4, 7, 11, 18, 21, 24, 31, 35, 39, 51, 58, 61, and 64 (Powell et al., 2002), each of which is attached to a CF3 group. The molecule has crystallographic C2 symmetry; symmetry related atoms have the letter a after the atom number. The core sp3 carbon atoms are not adjacent to one another. The CF3 groups are arranged on a para-para-para-para-para-para-para- meta-para (p7mp) ribbon and a para-meta-para (pmp) ribbon of edge-sharing C6(CF3)2 hexagons such that the two ribbons connect to one another, forming two 1,3-C5(CF3)2 pentagons (see Schlegel diagram in Fig. 2). The shared edges in each ribbon of hexagons are C(sp3)-C(sp2) bonds (e.g., C16—C17, C4—C18, etc.), not C(sp2)-C(sp2) bonds. Thus, any pair of adjacent hexagons along the two ribbons have a common CF3 group. As in all other published structures of fullerene(CF3)n compounds, there are F···F intramolecular contacts between pairs of neighboring CF3 groups that range from 2.560 (3) to 2.876 (3) Å.
The four shortest cage C—C bonds (two pairs) in (I) are C1—C6a/C1a—C6, at 1.347 (3) Å, and C3—C4/C3a—C4a, at 1.356 (3) Å. All four are significantly shorter than the shortest C—C bond in the most precise structure of empty C60 reported to date (C60.Pt(octaethylporphyrin)), which is 1.379 (3) Å (Olmstead et al., 2003). More importantly, the C1—C6a and C1a—C6 bonds are pentagon-hexagon junctions, and the shortest pent-hex junction in C60.Pt(OEP) is 1.440 (3) Å (the longest pent-hex junction in C60.Pt(OEP) is 1.461 (3) Å); OEP is octaethylporphyrin).
For related literature, see: Avdoshenko et al. (2006); Goryunkov et al. (2006); Ignat'eva et al. (2006); Kareev et al. (2005, 2006a,b); Olmstead et al. (2003); Popov et al. (2007); Powell et al. (2002).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
C84F42·3C8H10 | F(000) = 4224 |
Mr = 2125.32 | Dx = 1.811 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.4423 (16) Å | Cell parameters from 999 reflections |
b = 14.1495 (7) Å | θ = 1.7–27.9° |
c = 22.6519 (11) Å | µ = 0.18 mm−1 |
β = 107.070 (5)° | T = 100 K |
V = 7795.4 (7) Å3 | Rhombic, orange |
Z = 4 | 0.40 × 0.23 × 0.09 mm |
Bruker Kappa APEX II diffractometer | 9305 independent reflections |
Radiation source: fine-focus sealed tube | 6651 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
φ and ω scans | θmax = 27.9°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS, Bruker, 2000) | h = −33→33 |
Tmin = 0.933, Tmax = 0.984 | k = −18→18 |
130931 measured reflections | l = −29→29 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0719P)2 + 26.7468P] where P = (Fo2 + 2Fc2)/3 |
9305 reflections | (Δ/σ)max = 0.001 |
679 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
C84F42·3C8H10 | V = 7795.4 (7) Å3 |
Mr = 2125.32 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.4423 (16) Å | µ = 0.18 mm−1 |
b = 14.1495 (7) Å | T = 100 K |
c = 22.6519 (11) Å | 0.40 × 0.23 × 0.09 mm |
β = 107.070 (5)° |
Bruker Kappa APEX II diffractometer | 9305 independent reflections |
Absorption correction: multi-scan (SADABS, Bruker, 2000) | 6651 reflections with I > 2σ(I) |
Tmin = 0.933, Tmax = 0.984 | Rint = 0.066 |
130931 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0719P)2 + 26.7468P] where P = (Fo2 + 2Fc2)/3 |
9305 reflections | Δρmax = 0.53 e Å−3 |
679 parameters | Δρmin = −0.53 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.08268 (11) | 0.48440 (17) | 0.79209 (11) | 0.0160 (5) | |
C2 | −0.03691 (10) | 0.46569 (17) | 0.85024 (11) | 0.0155 (5) | |
C3 | 0.01826 (10) | 0.46278 (16) | 0.83587 (11) | 0.0154 (5) | |
C4 | 0.02365 (10) | 0.44834 (16) | 0.77873 (11) | 0.0147 (5) | |
C5 | 0.08103 (11) | 0.45187 (17) | 0.77182 (11) | 0.0160 (5) | |
C6 | 0.12112 (10) | 0.55193 (17) | 0.71344 (11) | 0.0160 (5) | |
C7 | −0.15208 (10) | 0.74444 (18) | 0.75467 (11) | 0.0169 (5) | |
C8 | −0.13424 (10) | 0.71890 (17) | 0.81628 (11) | 0.0166 (5) | |
C9 | −0.12683 (10) | 0.61496 (17) | 0.83788 (11) | 0.0163 (5) | |
C10 | −0.07032 (10) | 0.61925 (18) | 0.88728 (11) | 0.0157 (5) | |
C11 | −0.02992 (11) | 0.55333 (17) | 0.89099 (11) | 0.0152 (5) | |
C12 | 0.02623 (10) | 0.57981 (17) | 0.91181 (10) | 0.0147 (5) | |
C13 | 0.06281 (11) | 0.51229 (17) | 0.88946 (11) | 0.0171 (5) | |
C14 | 0.10346 (10) | 0.56652 (17) | 0.86427 (11) | 0.0145 (5) | |
C15 | 0.11537 (10) | 0.52832 (17) | 0.81343 (11) | 0.0155 (5) | |
C16 | 0.14151 (10) | 0.58187 (18) | 0.77804 (11) | 0.0166 (5) | |
C17 | 0.15683 (10) | 0.67436 (18) | 0.79395 (11) | 0.0166 (5) | |
C18 | −0.07696 (11) | 0.85962 (17) | 0.83726 (11) | 0.0170 (5) | |
C19 | −0.09497 (11) | 0.77643 (18) | 0.85807 (11) | 0.0166 (5) | |
C20 | −0.05573 (10) | 0.71536 (17) | 0.90126 (10) | 0.0154 (5) | |
C21 | −0.00067 (11) | 0.74112 (17) | 0.92113 (10) | 0.0157 (5) | |
C22 | 0.04088 (10) | 0.67163 (17) | 0.92801 (10) | 0.0152 (5) | |
C23 | 0.09401 (10) | 0.71747 (17) | 0.92343 (11) | 0.0157 (5) | |
C24 | 0.11795 (10) | 0.66342 (17) | 0.87978 (11) | 0.0148 (5) | |
C25 | 0.14403 (10) | 0.71565 (17) | 0.84463 (11) | 0.0157 (5) | |
C26 | 0.13972 (11) | 0.82482 (17) | 0.83513 (11) | 0.0167 (5) | |
C27 | 0.13535 (10) | 0.83146 (17) | 0.76627 (11) | 0.0164 (5) | |
C28 | 0.09857 (11) | 0.88846 (17) | 0.72555 (11) | 0.0169 (5) | |
C29 | 0.05705 (11) | 0.95174 (17) | 0.74390 (12) | 0.0177 (5) | |
C30 | 0.04806 (11) | 0.91925 (17) | 0.80457 (11) | 0.0168 (5) | |
C31 | −0.00411 (11) | 0.93096 (16) | 0.81014 (11) | 0.0176 (5) | |
C32 | −0.01942 (11) | 0.88503 (16) | 0.85809 (11) | 0.0162 (5) | |
C33 | 0.01818 (11) | 0.82719 (17) | 0.89960 (11) | 0.0160 (5) | |
C34 | 0.07156 (11) | 0.81482 (17) | 0.89430 (11) | 0.0164 (5) | |
C35 | 0.08718 (10) | 0.85996 (17) | 0.84767 (11) | 0.0158 (5) | |
C36 | −0.04668 (12) | 0.37394 (19) | 0.88469 (12) | 0.0224 (6) | |
C37 | 0.10842 (12) | 0.35315 (18) | 0.78534 (12) | 0.0211 (5) | |
C38 | −0.17389 (11) | 0.58456 (19) | 0.86314 (12) | 0.0216 (5) | |
C39 | 0.09405 (11) | 0.44407 (19) | 0.94399 (12) | 0.0214 (6) | |
C40 | 0.13581 (11) | 0.72325 (18) | 0.98796 (11) | 0.0194 (5) | |
C41 | 0.19157 (11) | 0.87962 (19) | 0.87432 (12) | 0.0209 (5) | |
C42 | 0.07547 (12) | 1.05667 (18) | 0.74822 (12) | 0.0223 (6) | |
C43 | 0.21133 (13) | −0.0831 (3) | 0.15373 (16) | 0.0399 (8) | |
C44 | 0.22565 (14) | −0.0842 (3) | 0.09892 (17) | 0.0431 (9) | |
H44 | 0.2274 | −0.1419 | 0.0798 | 0.052* | |
C45 | 0.23724 (14) | −0.0025 (3) | 0.07215 (18) | 0.0452 (9) | |
H45 | 0.2460 | −0.0059 | 0.0351 | 0.054* | |
C46 | 0.23610 (15) | 0.0854 (3) | 0.0997 (2) | 0.0483 (9) | |
C47 | 0.22347 (15) | 0.0864 (3) | 0.1556 (2) | 0.0505 (10) | |
H47 | 0.2231 | 0.1437 | 0.1756 | 0.061* | |
C48 | 0.21147 (15) | 0.0043 (3) | 0.18204 (18) | 0.0452 (9) | |
H48 | 0.2033 | 0.0075 | 0.2194 | 0.054* | |
C49 | 0.19740 (16) | −0.1722 (3) | 0.18156 (19) | 0.0495 (10) | |
H49A | 0.1602 | −0.1901 | 0.1605 | 0.074* | |
H49B | 0.2011 | −0.1619 | 0.2245 | 0.074* | |
H49C | 0.2219 | −0.2217 | 0.1775 | 0.074* | |
C50 | 0.24732 (19) | 0.1753 (3) | 0.0697 (2) | 0.0653 (13) | |
H50A | 0.2131 | 0.2028 | 0.0460 | 0.098* | |
H50B | 0.2694 | 0.1613 | 0.0430 | 0.098* | |
H50C | 0.2665 | 0.2191 | 0.1011 | 0.098* | |
C51 | 0.04232 (15) | 0.0553 (2) | −0.01127 (15) | 0.0338 (7) | |
C52 | 0.05432 (14) | −0.0201 (2) | 0.03007 (14) | 0.0339 (7) | |
H52 | 0.0908 | −0.0345 | 0.0507 | 0.041* | |
C53 | 0.01247 (15) | −0.0740 (2) | 0.04073 (14) | 0.0342 (7) | |
H53 | 0.0215 | −0.1241 | 0.0685 | 0.041* | |
C54 | 0.08786 (19) | 0.1138 (3) | −0.0231 (2) | 0.0563 (11) | |
H54A | 0.0777 | 0.1322 | −0.0658 | 0.084* | |
H54B | 0.1210 | 0.0771 | −0.0136 | 0.084* | |
H54C | 0.0938 | 0.1692 | 0.0024 | 0.084* | |
F361 | −0.10036 (7) | 0.35690 (12) | 0.87384 (8) | 0.0321 (4) | |
F362 | −0.02505 (8) | 0.38325 (12) | 0.94590 (7) | 0.0316 (4) | |
F363 | −0.02429 (7) | 0.29735 (11) | 0.86770 (8) | 0.0287 (4) | |
F371 | 0.11667 (8) | 0.32738 (12) | 0.84394 (8) | 0.0348 (4) | |
F372 | 0.07692 (8) | 0.28743 (11) | 0.74981 (8) | 0.0325 (4) | |
F373 | 0.15695 (7) | 0.35158 (12) | 0.77421 (9) | 0.0330 (4) | |
F381 | −0.16901 (7) | 0.49526 (11) | 0.88247 (7) | 0.0266 (4) | |
F382 | −0.17586 (7) | 0.63905 (12) | 0.91103 (8) | 0.0291 (4) | |
F383 | −0.22224 (7) | 0.59329 (13) | 0.81948 (8) | 0.0302 (4) | |
F391 | 0.07719 (8) | 0.35491 (12) | 0.93486 (8) | 0.0322 (4) | |
F392 | 0.14813 (7) | 0.44451 (13) | 0.95243 (8) | 0.0316 (4) | |
F393 | 0.08619 (7) | 0.47138 (12) | 0.99746 (7) | 0.0284 (4) | |
F401 | 0.14444 (7) | 0.63742 (12) | 1.01375 (7) | 0.0278 (4) | |
F402 | 0.18459 (7) | 0.75489 (14) | 0.98599 (7) | 0.0337 (4) | |
F403 | 0.11813 (7) | 0.77886 (12) | 1.02572 (7) | 0.0266 (4) | |
F411 | 0.23546 (8) | 0.82497 (14) | 0.88972 (11) | 0.0487 (6) | |
F412 | 0.20312 (9) | 0.95185 (15) | 0.84387 (9) | 0.0495 (6) | |
F413 | 0.18514 (9) | 0.91388 (17) | 0.92594 (9) | 0.0493 (6) | |
F421 | 0.05096 (11) | 1.10843 (13) | 0.78088 (12) | 0.0590 (7) | |
F422 | 0.12873 (8) | 1.06442 (13) | 0.77648 (11) | 0.0484 (6) | |
F423 | 0.06605 (9) | 1.09499 (12) | 0.69320 (8) | 0.0439 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0224 (13) | 0.0140 (11) | 0.0110 (11) | −0.0045 (9) | 0.0042 (10) | −0.0001 (9) |
C2 | 0.0215 (13) | 0.0143 (11) | 0.0110 (11) | −0.0005 (9) | 0.0053 (10) | −0.0005 (9) |
C3 | 0.0228 (13) | 0.0099 (10) | 0.0128 (11) | 0.0008 (9) | 0.0041 (10) | 0.0033 (9) |
C4 | 0.0228 (13) | 0.0079 (10) | 0.0131 (11) | 0.0004 (9) | 0.0051 (10) | 0.0016 (9) |
C5 | 0.0223 (13) | 0.0145 (11) | 0.0109 (11) | 0.0018 (9) | 0.0044 (10) | −0.0002 (9) |
C6 | 0.0201 (13) | 0.0156 (11) | 0.0128 (11) | 0.0047 (9) | 0.0056 (10) | 0.0000 (9) |
C7 | 0.0173 (12) | 0.0195 (12) | 0.0147 (12) | 0.0039 (9) | 0.0060 (10) | 0.0010 (10) |
C8 | 0.0184 (12) | 0.0176 (12) | 0.0153 (12) | 0.0032 (9) | 0.0074 (10) | 0.0017 (9) |
C9 | 0.0204 (12) | 0.0170 (12) | 0.0124 (11) | −0.0001 (9) | 0.0063 (10) | 0.0005 (9) |
C10 | 0.0208 (13) | 0.0187 (12) | 0.0085 (11) | −0.0019 (9) | 0.0057 (9) | 0.0016 (9) |
C11 | 0.0242 (13) | 0.0135 (11) | 0.0083 (11) | −0.0007 (9) | 0.0055 (9) | 0.0027 (9) |
C12 | 0.0221 (13) | 0.0152 (11) | 0.0064 (10) | 0.0014 (9) | 0.0037 (9) | 0.0027 (9) |
C13 | 0.0227 (13) | 0.0155 (11) | 0.0122 (11) | 0.0027 (10) | 0.0038 (10) | 0.0003 (9) |
C14 | 0.0167 (12) | 0.0154 (11) | 0.0092 (11) | 0.0016 (9) | 0.0004 (9) | 0.0032 (9) |
C15 | 0.0179 (12) | 0.0142 (11) | 0.0125 (11) | 0.0022 (9) | 0.0013 (9) | 0.0010 (9) |
C16 | 0.0192 (12) | 0.0183 (12) | 0.0107 (11) | 0.0034 (9) | 0.0020 (9) | 0.0000 (9) |
C17 | 0.0176 (12) | 0.0195 (12) | 0.0123 (11) | −0.0006 (9) | 0.0038 (9) | −0.0002 (9) |
C18 | 0.0243 (13) | 0.0143 (11) | 0.0132 (12) | 0.0043 (10) | 0.0067 (10) | −0.0029 (9) |
C19 | 0.0211 (13) | 0.0186 (12) | 0.0121 (11) | 0.0037 (10) | 0.0080 (10) | −0.0012 (9) |
C20 | 0.0234 (13) | 0.0179 (12) | 0.0060 (10) | 0.0020 (10) | 0.0060 (9) | 0.0005 (9) |
C21 | 0.0277 (14) | 0.0157 (11) | 0.0041 (10) | 0.0008 (10) | 0.0052 (9) | −0.0021 (8) |
C22 | 0.0207 (12) | 0.0189 (12) | 0.0055 (10) | 0.0002 (9) | 0.0031 (9) | 0.0010 (9) |
C23 | 0.0218 (13) | 0.0156 (11) | 0.0076 (11) | 0.0001 (9) | 0.0008 (9) | −0.0020 (9) |
C24 | 0.0163 (12) | 0.0178 (11) | 0.0080 (11) | 0.0015 (9) | −0.0004 (9) | −0.0002 (9) |
C25 | 0.0166 (12) | 0.0167 (11) | 0.0118 (11) | −0.0001 (9) | 0.0012 (9) | −0.0015 (9) |
C26 | 0.0213 (13) | 0.0150 (11) | 0.0130 (11) | −0.0033 (9) | 0.0039 (10) | −0.0006 (9) |
C27 | 0.0195 (12) | 0.0160 (11) | 0.0140 (12) | −0.0059 (9) | 0.0055 (10) | −0.0015 (9) |
C28 | 0.0238 (13) | 0.0121 (11) | 0.0155 (12) | −0.0065 (9) | 0.0071 (10) | −0.0009 (9) |
C29 | 0.0263 (14) | 0.0104 (11) | 0.0161 (12) | −0.0034 (9) | 0.0057 (10) | 0.0002 (9) |
C30 | 0.0272 (13) | 0.0105 (10) | 0.0120 (11) | −0.0023 (9) | 0.0048 (10) | −0.0028 (9) |
C31 | 0.0295 (14) | 0.0090 (11) | 0.0132 (11) | −0.0001 (9) | 0.0047 (10) | −0.0031 (9) |
C32 | 0.0270 (13) | 0.0106 (10) | 0.0128 (11) | 0.0016 (9) | 0.0084 (10) | −0.0040 (9) |
C33 | 0.0258 (13) | 0.0135 (11) | 0.0084 (11) | −0.0005 (9) | 0.0046 (9) | −0.0037 (9) |
C34 | 0.0245 (13) | 0.0139 (11) | 0.0090 (11) | −0.0015 (9) | 0.0023 (10) | −0.0047 (9) |
C35 | 0.0235 (13) | 0.0115 (11) | 0.0116 (11) | −0.0035 (9) | 0.0041 (10) | −0.0041 (9) |
C36 | 0.0321 (15) | 0.0191 (13) | 0.0156 (12) | −0.0020 (11) | 0.0064 (11) | 0.0012 (10) |
C37 | 0.0288 (14) | 0.0174 (12) | 0.0164 (12) | 0.0039 (10) | 0.0057 (11) | 0.0010 (10) |
C38 | 0.0238 (14) | 0.0245 (13) | 0.0165 (12) | 0.0005 (11) | 0.0060 (10) | 0.0021 (10) |
C39 | 0.0262 (14) | 0.0230 (13) | 0.0144 (12) | 0.0020 (10) | 0.0047 (11) | 0.0030 (10) |
C40 | 0.0246 (14) | 0.0213 (13) | 0.0113 (11) | −0.0010 (10) | 0.0037 (10) | −0.0031 (10) |
C41 | 0.0261 (14) | 0.0202 (13) | 0.0156 (12) | −0.0041 (10) | 0.0050 (11) | −0.0022 (10) |
C42 | 0.0353 (16) | 0.0144 (12) | 0.0177 (13) | −0.0028 (10) | 0.0086 (11) | −0.0003 (10) |
C43 | 0.0211 (15) | 0.056 (2) | 0.0365 (18) | 0.0034 (14) | −0.0006 (13) | −0.0158 (16) |
C44 | 0.0291 (17) | 0.051 (2) | 0.043 (2) | −0.0020 (15) | 0.0020 (15) | −0.0232 (17) |
C45 | 0.0315 (18) | 0.058 (2) | 0.040 (2) | 0.0035 (16) | 0.0015 (15) | −0.0123 (17) |
C46 | 0.0283 (18) | 0.052 (2) | 0.058 (2) | 0.0107 (16) | 0.0031 (16) | −0.0054 (19) |
C47 | 0.0340 (19) | 0.051 (2) | 0.063 (3) | 0.0080 (16) | 0.0097 (18) | −0.023 (2) |
C48 | 0.0332 (19) | 0.055 (2) | 0.046 (2) | 0.0074 (16) | 0.0085 (16) | −0.0174 (18) |
C49 | 0.0344 (19) | 0.060 (2) | 0.053 (2) | −0.0050 (17) | 0.0109 (17) | −0.0171 (19) |
C50 | 0.049 (2) | 0.058 (3) | 0.086 (3) | 0.017 (2) | 0.015 (2) | 0.007 (2) |
C51 | 0.048 (2) | 0.0254 (15) | 0.0297 (16) | 0.0011 (13) | 0.0140 (14) | −0.0090 (12) |
C52 | 0.0391 (18) | 0.0298 (16) | 0.0267 (16) | 0.0115 (13) | 0.0003 (13) | −0.0101 (12) |
C53 | 0.057 (2) | 0.0219 (14) | 0.0213 (14) | 0.0087 (14) | 0.0083 (14) | −0.0019 (11) |
C54 | 0.067 (3) | 0.044 (2) | 0.069 (3) | −0.0063 (19) | 0.037 (2) | −0.009 (2) |
F361 | 0.0343 (10) | 0.0280 (9) | 0.0369 (10) | −0.0051 (7) | 0.0151 (8) | 0.0093 (7) |
F362 | 0.0511 (11) | 0.0265 (9) | 0.0158 (8) | −0.0014 (8) | 0.0077 (7) | 0.0056 (7) |
F363 | 0.0446 (10) | 0.0162 (7) | 0.0276 (9) | 0.0019 (7) | 0.0142 (8) | 0.0027 (6) |
F371 | 0.0533 (12) | 0.0298 (9) | 0.0206 (8) | 0.0159 (8) | 0.0095 (8) | 0.0085 (7) |
F372 | 0.0421 (10) | 0.0163 (8) | 0.0334 (10) | 0.0005 (7) | 0.0024 (8) | −0.0031 (7) |
F373 | 0.0310 (10) | 0.0277 (9) | 0.0425 (11) | 0.0119 (7) | 0.0140 (8) | 0.0057 (8) |
F381 | 0.0309 (9) | 0.0241 (8) | 0.0273 (9) | −0.0027 (7) | 0.0120 (7) | 0.0070 (7) |
F382 | 0.0342 (9) | 0.0347 (9) | 0.0243 (9) | 0.0018 (7) | 0.0178 (7) | −0.0009 (7) |
F383 | 0.0211 (8) | 0.0432 (10) | 0.0247 (9) | −0.0023 (7) | 0.0043 (7) | 0.0092 (7) |
F391 | 0.0465 (11) | 0.0221 (8) | 0.0243 (9) | 0.0002 (7) | 0.0047 (8) | 0.0056 (7) |
F392 | 0.0274 (9) | 0.0383 (10) | 0.0278 (9) | 0.0090 (7) | 0.0062 (7) | 0.0111 (7) |
F393 | 0.0391 (10) | 0.0326 (9) | 0.0126 (7) | 0.0083 (7) | 0.0060 (7) | 0.0034 (6) |
F401 | 0.0351 (9) | 0.0268 (8) | 0.0140 (8) | 0.0043 (7) | −0.0044 (7) | 0.0035 (6) |
F402 | 0.0257 (9) | 0.0562 (12) | 0.0173 (8) | −0.0161 (8) | 0.0033 (7) | −0.0080 (8) |
F403 | 0.0341 (9) | 0.0311 (9) | 0.0115 (7) | 0.0038 (7) | 0.0018 (6) | −0.0074 (6) |
F411 | 0.0236 (10) | 0.0376 (11) | 0.0690 (15) | 0.0009 (8) | −0.0112 (9) | −0.0171 (10) |
F412 | 0.0535 (13) | 0.0463 (12) | 0.0342 (11) | −0.0352 (10) | −0.0097 (9) | 0.0147 (9) |
F413 | 0.0475 (12) | 0.0731 (15) | 0.0312 (10) | −0.0330 (11) | 0.0174 (9) | −0.0349 (10) |
F421 | 0.1002 (19) | 0.0159 (9) | 0.0904 (18) | −0.0115 (10) | 0.0739 (16) | −0.0133 (10) |
F422 | 0.0388 (11) | 0.0223 (9) | 0.0680 (14) | −0.0106 (8) | −0.0094 (10) | −0.0040 (9) |
F423 | 0.0774 (15) | 0.0232 (9) | 0.0219 (9) | −0.0229 (9) | 0.0001 (9) | 0.0078 (7) |
C1—C6i | 1.346 (4) | C29—C42 | 1.551 (3) |
C1—C2 | 1.504 (3) | C29—C31i | 1.559 (4) |
C1—C5i | 1.532 (3) | C30—C31 | 1.380 (4) |
C2—C11 | 1.525 (3) | C30—C35 | 1.441 (3) |
C2—C3 | 1.532 (4) | C31—C32 | 1.415 (4) |
C2—C36 | 1.572 (3) | C31—C29i | 1.559 (4) |
C3—C4 | 1.356 (3) | C32—C33 | 1.393 (3) |
C3—C13 | 1.562 (3) | C33—C34 | 1.409 (4) |
C4—C4i | 1.491 (5) | C34—C35 | 1.388 (4) |
C4—C5 | 1.514 (4) | C36—F363 | 1.333 (3) |
C5—C15 | 1.529 (3) | C36—F361 | 1.337 (3) |
C5—C1i | 1.532 (3) | C36—F362 | 1.340 (3) |
C5—C37 | 1.551 (3) | C37—F373 | 1.331 (3) |
C6—C1i | 1.346 (4) | C37—F371 | 1.333 (3) |
C6—C16 | 1.464 (3) | C37—F372 | 1.333 (3) |
C6—C9i | 1.506 (3) | C38—F381 | 1.331 (3) |
C7—C8 | 1.383 (3) | C38—F383 | 1.339 (3) |
C7—C27i | 1.429 (4) | C38—F382 | 1.344 (3) |
C7—C17i | 1.460 (3) | C39—F391 | 1.329 (3) |
C8—C19 | 1.415 (4) | C39—F392 | 1.332 (3) |
C8—C9 | 1.544 (3) | C39—F393 | 1.341 (3) |
C9—C6i | 1.506 (3) | C40—F402 | 1.332 (3) |
C9—C38 | 1.532 (4) | C40—F403 | 1.334 (3) |
C9—C10 | 1.542 (3) | C40—F401 | 1.338 (3) |
C10—C11 | 1.372 (4) | C41—F412 | 1.314 (3) |
C10—C20 | 1.421 (3) | C41—F411 | 1.318 (3) |
C11—C12 | 1.417 (4) | C41—F413 | 1.319 (3) |
C12—C22 | 1.372 (3) | C42—F423 | 1.315 (3) |
C12—C13 | 1.521 (3) | C42—F421 | 1.321 (3) |
C13—C14 | 1.526 (4) | C42—F422 | 1.322 (3) |
C13—C39 | 1.585 (3) | C43—C44 | 1.393 (5) |
C14—C15 | 1.384 (3) | C43—C48 | 1.393 (5) |
C14—C24 | 1.436 (3) | C43—C49 | 1.498 (6) |
C15—C16 | 1.404 (4) | C44—C45 | 1.378 (6) |
C16—C17 | 1.383 (4) | C44—H44 | 0.9300 |
C17—C25 | 1.409 (3) | C45—C46 | 1.396 (5) |
C17—C7i | 1.460 (3) | C45—H45 | 0.9300 |
C18—C19 | 1.394 (4) | C46—C47 | 1.394 (6) |
C18—C28i | 1.426 (3) | C46—C50 | 1.509 (6) |
C18—C32 | 1.445 (4) | C47—C48 | 1.380 (6) |
C19—C20 | 1.459 (3) | C47—H47 | 0.9300 |
C20—C21 | 1.389 (4) | C48—H48 | 0.9300 |
C21—C22 | 1.418 (3) | C49—H49A | 0.9600 |
C21—C33 | 1.445 (3) | C49—H49B | 0.9600 |
C22—C23 | 1.530 (4) | C49—H49C | 0.9600 |
C23—C24 | 1.513 (3) | C50—H50A | 0.9600 |
C23—C40 | 1.537 (3) | C50—H50B | 0.9600 |
C23—C34 | 1.561 (3) | C50—H50C | 0.9600 |
C24—C25 | 1.389 (4) | C51—C53ii | 1.383 (5) |
C25—C26 | 1.559 (3) | C51—C52 | 1.393 (5) |
C26—C35 | 1.529 (4) | C51—C54 | 1.511 (5) |
C26—C27 | 1.534 (3) | C52—C53 | 1.387 (5) |
C26—C41 | 1.563 (4) | C52—H52 | 0.9300 |
C27—C28 | 1.368 (4) | C53—C51ii | 1.383 (5) |
C27—C7i | 1.429 (4) | C53—H53 | 0.9300 |
C28—C18i | 1.426 (3) | C54—H54A | 0.9600 |
C28—C29 | 1.532 (4) | C54—H54B | 0.9600 |
C29—C30 | 1.529 (3) | C54—H54C | 0.9600 |
C6i—C1—C2 | 124.1 (2) | C42—C29—C31i | 113.9 (2) |
C6i—C1—C5i | 110.2 (2) | C31—C30—C35 | 120.0 (2) |
C2—C1—C5i | 123.1 (2) | C31—C30—C29 | 116.6 (2) |
C1—C2—C11 | 108.1 (2) | C35—C30—C29 | 121.9 (2) |
C1—C2—C3 | 109.9 (2) | C30—C31—C32 | 120.3 (2) |
C11—C2—C3 | 101.5 (2) | C30—C31—C29i | 125.7 (2) |
C1—C2—C36 | 112.7 (2) | C32—C31—C29i | 108.7 (2) |
C11—C2—C36 | 112.2 (2) | C33—C32—C31 | 119.9 (2) |
C3—C2—C36 | 111.8 (2) | C33—C32—C18 | 120.2 (2) |
C4—C3—C2 | 124.2 (2) | C31—C32—C18 | 110.1 (2) |
C4—C3—C13 | 123.7 (2) | C32—C33—C34 | 120.2 (2) |
C2—C3—C13 | 108.9 (2) | C32—C33—C21 | 119.5 (2) |
C3—C4—C4i | 123.5 (3) | C34—C33—C21 | 110.3 (2) |
C3—C4—C5 | 117.7 (2) | C35—C34—C33 | 120.4 (2) |
C4i—C4—C5 | 117.7 (3) | C35—C34—C23 | 125.2 (2) |
C4—C5—C15 | 110.7 (2) | C33—C34—C23 | 108.4 (2) |
C4—C5—C1i | 113.7 (2) | C34—C35—C30 | 119.2 (2) |
C15—C5—C1i | 101.6 (2) | C34—C35—C26 | 116.9 (2) |
C4—C5—C37 | 109.9 (2) | C30—C35—C26 | 122.1 (2) |
C15—C5—C37 | 111.9 (2) | F363—C36—F361 | 107.5 (2) |
C1i—C5—C37 | 108.8 (2) | F363—C36—F362 | 107.4 (2) |
C1i—C6—C16 | 109.4 (2) | F361—C36—F362 | 107.2 (2) |
C1i—C6—C9i | 125.5 (2) | F363—C36—C2 | 112.7 (2) |
C16—C6—C9i | 120.9 (2) | F361—C36—C2 | 111.1 (2) |
C8—C7—C27i | 121.2 (2) | F362—C36—C2 | 110.9 (2) |
C8—C7—C17i | 120.9 (2) | F373—C37—F371 | 107.5 (2) |
C27i—C7—C17i | 107.5 (2) | F373—C37—F372 | 107.5 (2) |
C7—C8—C19 | 118.9 (2) | F371—C37—F372 | 107.5 (2) |
C7—C8—C9 | 122.8 (2) | F373—C37—C5 | 111.5 (2) |
C19—C8—C9 | 109.9 (2) | F371—C37—C5 | 111.9 (2) |
C6i—C9—C38 | 112.7 (2) | F372—C37—C5 | 110.7 (2) |
C6i—C9—C10 | 107.6 (2) | F381—C38—F383 | 107.9 (2) |
C38—C9—C10 | 113.8 (2) | F381—C38—F382 | 107.5 (2) |
C6i—C9—C8 | 110.5 (2) | F383—C38—F382 | 107.4 (2) |
C38—C9—C8 | 110.5 (2) | F381—C38—C9 | 112.4 (2) |
C10—C9—C8 | 101.2 (2) | F383—C38—C9 | 110.3 (2) |
C11—C10—C20 | 119.7 (2) | F382—C38—C9 | 111.0 (2) |
C11—C10—C9 | 122.7 (2) | F391—C39—F392 | 107.4 (2) |
C20—C10—C9 | 109.1 (2) | F391—C39—F393 | 106.7 (2) |
C10—C11—C12 | 120.3 (2) | F392—C39—F393 | 106.9 (2) |
C10—C11—C2 | 124.3 (2) | F391—C39—C13 | 113.1 (2) |
C12—C11—C2 | 110.1 (2) | F392—C39—C13 | 111.7 (2) |
C22—C12—C11 | 120.5 (2) | F393—C39—C13 | 110.8 (2) |
C22—C12—C13 | 122.7 (2) | F402—C40—F403 | 108.4 (2) |
C11—C12—C13 | 112.3 (2) | F402—C40—F401 | 106.5 (2) |
C12—C13—C14 | 110.9 (2) | F403—C40—F401 | 107.4 (2) |
C12—C13—C3 | 99.5 (2) | F402—C40—C23 | 112.2 (2) |
C14—C13—C3 | 110.6 (2) | F403—C40—C23 | 111.8 (2) |
C12—C13—C39 | 109.8 (2) | F401—C40—C23 | 110.3 (2) |
C14—C13—C39 | 111.0 (2) | F412—C41—F411 | 107.0 (2) |
C3—C13—C39 | 114.6 (2) | F412—C41—F413 | 106.5 (2) |
C15—C14—C24 | 118.2 (2) | F411—C41—F413 | 107.3 (2) |
C15—C14—C13 | 116.9 (2) | F412—C41—C26 | 111.7 (2) |
C24—C14—C13 | 122.8 (2) | F411—C41—C26 | 111.6 (2) |
C14—C15—C16 | 121.4 (2) | F413—C41—C26 | 112.5 (2) |
C14—C15—C5 | 124.3 (2) | F423—C42—F421 | 108.5 (2) |
C16—C15—C5 | 108.1 (2) | F423—C42—F422 | 107.5 (2) |
C17—C16—C15 | 120.4 (2) | F421—C42—F422 | 105.6 (2) |
C17—C16—C6 | 121.6 (2) | F423—C42—C29 | 111.5 (2) |
C15—C16—C6 | 109.0 (2) | F421—C42—C29 | 112.5 (2) |
C16—C17—C25 | 119.3 (2) | F422—C42—C29 | 111.0 (2) |
C16—C17—C7i | 119.4 (2) | C44—C43—C48 | 117.1 (4) |
C25—C17—C7i | 110.2 (2) | C44—C43—C49 | 121.4 (3) |
C19—C18—C28i | 120.7 (2) | C48—C43—C49 | 121.5 (3) |
C19—C18—C32 | 120.1 (2) | C45—C44—C43 | 121.9 (3) |
C28i—C18—C32 | 108.1 (2) | C45—C44—H44 | 119.1 |
C18—C19—C8 | 119.8 (2) | C43—C44—H44 | 119.1 |
C18—C19—C20 | 119.9 (2) | C44—C45—C46 | 121.1 (4) |
C8—C19—C20 | 108.5 (2) | C44—C45—H45 | 119.5 |
C21—C20—C10 | 119.8 (2) | C46—C45—H45 | 119.5 |
C21—C20—C19 | 119.3 (2) | C47—C46—C45 | 117.1 (4) |
C10—C20—C19 | 109.6 (2) | C47—C46—C50 | 121.7 (4) |
C20—C21—C22 | 120.1 (2) | C45—C46—C50 | 121.2 (4) |
C20—C21—C33 | 121.0 (2) | C48—C47—C46 | 121.7 (4) |
C22—C21—C33 | 108.1 (2) | C48—C47—H47 | 119.2 |
C12—C22—C21 | 119.5 (2) | C46—C47—H47 | 119.2 |
C12—C22—C23 | 124.0 (2) | C47—C48—C43 | 121.2 (4) |
C21—C22—C23 | 110.1 (2) | C47—C48—H48 | 119.4 |
C24—C23—C22 | 111.3 (2) | C43—C48—H48 | 119.4 |
C24—C23—C40 | 110.5 (2) | C43—C49—H49A | 109.5 |
C22—C23—C40 | 109.7 (2) | C43—C49—H49B | 109.5 |
C24—C23—C34 | 109.71 (19) | H49A—C49—H49B | 109.5 |
C22—C23—C34 | 100.5 (2) | C43—C49—H49C | 109.5 |
C40—C23—C34 | 114.9 (2) | H49A—C49—H49C | 109.5 |
C25—C24—C14 | 119.9 (2) | H49B—C49—H49C | 109.5 |
C25—C24—C23 | 117.2 (2) | C46—C50—H50A | 109.5 |
C14—C24—C23 | 121.3 (2) | C46—C50—H50B | 109.5 |
C24—C25—C17 | 120.7 (2) | H50A—C50—H50B | 109.5 |
C24—C25—C26 | 125.5 (2) | C46—C50—H50C | 109.5 |
C17—C25—C26 | 108.8 (2) | H50A—C50—H50C | 109.5 |
C35—C26—C27 | 111.3 (2) | H50B—C50—H50C | 109.5 |
C35—C26—C25 | 109.1 (2) | C53ii—C51—C52 | 117.5 (3) |
C27—C26—C25 | 100.50 (19) | C53ii—C51—C54 | 121.8 (3) |
C35—C26—C41 | 111.8 (2) | C52—C51—C54 | 120.7 (3) |
C27—C26—C41 | 110.2 (2) | C53—C52—C51 | 120.7 (3) |
C25—C26—C41 | 113.6 (2) | C53—C52—H52 | 119.7 |
C28—C27—C7i | 119.7 (2) | C51—C52—H52 | 119.7 |
C28—C27—C26 | 123.6 (2) | C51ii—C53—C52 | 121.8 (3) |
C7i—C27—C26 | 110.2 (2) | C51ii—C53—H53 | 119.1 |
C27—C28—C18i | 119.4 (2) | C52—C53—H53 | 119.1 |
C27—C28—C29 | 123.5 (2) | C51—C54—H54A | 109.5 |
C18i—C28—C29 | 110.1 (2) | C51—C54—H54B | 109.5 |
C30—C29—C28 | 111.4 (2) | H54A—C54—H54B | 109.5 |
C30—C29—C42 | 110.7 (2) | C51—C54—H54C | 109.5 |
C28—C29—C42 | 110.9 (2) | H54A—C54—H54C | 109.5 |
C30—C29—C31i | 109.0 (2) | H54B—C54—H54C | 109.5 |
C28—C29—C31i | 100.51 (19) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C84F42·3C8H10 |
Mr | 2125.32 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 25.4423 (16), 14.1495 (7), 22.6519 (11) |
β (°) | 107.070 (5) |
V (Å3) | 7795.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.40 × 0.23 × 0.09 |
Data collection | |
Diffractometer | Bruker Kappa APEX II |
Absorption correction | Multi-scan (SADABS, Bruker, 2000) |
Tmin, Tmax | 0.933, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 130931, 9305, 6651 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.161, 1.04 |
No. of reflections | 9305 |
No. of parameters | 679 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0719P)2 + 26.7468P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.53, −0.53 |
Computer programs: APEX2 (Bruker, 2005), SHELXTL (Bruker, 2000).
Recently reported high-temperature reactions of C70 with CF3I have yielded twenty-five C70(CF3)n derivatives (n = 2–18), most with relatively stable addition patterns that are chiral as well as unprecedented in fullerene(X)n chemistry (Kareev et al., 2005; Kareev et al., 2006a; Kareev et al., 2006b; Avdoshenko et al., 2006; Goryunkov et al., 2006; Ignat'eva et al., 2006; Popov et al., 2007). A member of the n = 14 set of five isomers, the title compound, (I), has been crystallized from p-xylene and we report its crystal structure here. A much lower-quality structure (C—C su's 0.015–0.019 Å, R1 = 0.186, wR2 = 0.41) of the same fullerene molecule as a hexane solvate has recently been reported (Goryunkov et al., 2006).
The structure of (I), Figs. 1 and 2, comprises an idealized D5 h C70 core with fourteen sp3 carbon atoms at positions 1, 4, 7, 11, 18, 21, 24, 31, 35, 39, 51, 58, 61, and 64 (Powell et al., 2002), each of which is attached to a CF3 group. The molecule has crystallographic C2 symmetry; symmetry related atoms have the letter a after the atom number. The core sp3 carbon atoms are not adjacent to one another. The CF3 groups are arranged on a para-para-para-para-para-para-para- meta-para (p7mp) ribbon and a para-meta-para (pmp) ribbon of edge-sharing C6(CF3)2 hexagons such that the two ribbons connect to one another, forming two 1,3-C5(CF3)2 pentagons (see Schlegel diagram in Fig. 2). The shared edges in each ribbon of hexagons are C(sp3)-C(sp2) bonds (e.g., C16—C17, C4—C18, etc.), not C(sp2)-C(sp2) bonds. Thus, any pair of adjacent hexagons along the two ribbons have a common CF3 group. As in all other published structures of fullerene(CF3)n compounds, there are F···F intramolecular contacts between pairs of neighboring CF3 groups that range from 2.560 (3) to 2.876 (3) Å.
The four shortest cage C—C bonds (two pairs) in (I) are C1—C6a/C1a—C6, at 1.347 (3) Å, and C3—C4/C3a—C4a, at 1.356 (3) Å. All four are significantly shorter than the shortest C—C bond in the most precise structure of empty C60 reported to date (C60.Pt(octaethylporphyrin)), which is 1.379 (3) Å (Olmstead et al., 2003). More importantly, the C1—C6a and C1a—C6 bonds are pentagon-hexagon junctions, and the shortest pent-hex junction in C60.Pt(OEP) is 1.440 (3) Å (the longest pent-hex junction in C60.Pt(OEP) is 1.461 (3) Å); OEP is octaethylporphyrin).