Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101001858/sx1121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101001858/sx1121IIIsup2.hkl |
CCDC reference: 164655
For related literature, see: Greenhow et al. (1953); Meyers et al. (2000, 2001); Miller & Bachman (1935); Naik et al. (1988); Robinson et al. (2000); Rouzaud et al. (1965); Scherf & Brown (1961); Sheldrick (1997); Von & Wagner (1944).
Compound (III) was isolated by flash chromatography as one of the byproducts in our preparation of (I) from the reaction of 9-fluorenyllithium with acetyl chloride in THF under argon (Meyers et al., 2000; Meyers et al., 2001; Robinson et al., 2000). It was also prepared directly from (II) via treatment with acetic anhydride and DMAP, or acetyl chloride and pyridine. Chromatographically (TLC and column) it was slightly less polar than (II); m.p. 441.5–443 K (corr.). 1H NMR: δ 1.67 (s, 3 H), 2.25 (s, 3 H), 4.87 (s, 2 H), 7.01 (m, 4 H), 7.16 (ddd, 2 H, J = 7.5, 1.2 Hz), 7.26 (dd, 2 H, J = 7.5 Hz), 7.35 (dd, 2 H, J = 7.5 Hz), 7.59 (d, 2 H, J = 7.5 Hz), 7.64 (d, 2 H, J = 7.5 Hz), 7.68 (d, 2H, J = 7.5 Hz); 13C NMR: δ 20.92, 22.82, 54.52, 89.53, 119.53, 119.57, 126.24, 126.40, 126.80, 126.85, 127.29, 127.43, 141.93, 142.02, 142.66, 143.52, 169.89. Von & Wagner (1944) reported m.p. 520–521 K for `dimeric 9-acetylfluorene', same m.w. and elemental analysis as (III).
The rotational orientations of the methyl groups were refined by the circular Fourier methods available in SHELXL97 (Sheldrick, 1997). All H atoms were riding.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: PROCESS in TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: MITHRIL (Gilmore, 1984); program(s) used to refine structure: TEXSAN and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON (Spek, 2000).
C30H24O2 | F(000) = 880 |
Mr = 416.49 | Dx = 1.260 Mg m−3 |
Triclinic, P1 | Melting point = 441.5–443 K |
a = 13.211 (3) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 19.044 (3) Å | Cell parameters from 25 reflections |
c = 9.5505 (12) Å | θ = 10.0–11.3° |
α = 98.852 (11)° | µ = 0.08 mm−1 |
β = 108.115 (14)° | T = 296 K |
γ = 74.565 (14)° | Irregular fragment, colorless |
V = 2194.7 (6) Å3 | 0.43 × 0.41 × 0.27 mm |
Z = 4 |
Rigaku AFC-5S diffractometer | Rint = 0.033 |
Radiation source: sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = 0→15 |
ω scans | k = −21→22 |
8103 measured reflections | l = −11→10 |
7737 independent reflections | 3 standard reflections every 100 reflections |
2792 reflections with I > 2σ(I) | intensity decay: 0.5% |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.046P)2] where P = (Fo2 + 2Fc2)/3 |
7737 reflections | (Δ/σ)max < 0.001 |
581 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C30H24O2 | γ = 74.565 (14)° |
Mr = 416.49 | V = 2194.7 (6) Å3 |
Triclinic, P1 | Z = 4 |
a = 13.211 (3) Å | Mo Kα radiation |
b = 19.044 (3) Å | µ = 0.08 mm−1 |
c = 9.5505 (12) Å | T = 296 K |
α = 98.852 (11)° | 0.43 × 0.41 × 0.27 mm |
β = 108.115 (14)° |
Rigaku AFC-5S diffractometer | Rint = 0.033 |
8103 measured reflections | 3 standard reflections every 100 reflections |
7737 independent reflections | intensity decay: 0.5% |
2792 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.17 e Å−3 |
7737 reflections | Δρmin = −0.17 e Å−3 |
581 parameters |
Geometry. SELECTED LEAST SQUARES PLANES Definitions: Sigref - R·M·S-Error of the Contributing Atoms Sigpln - Sqrt(Sum(j=1:N)(D(j)**2/(N-3)) Chisq - Chi-Squared = Sum(j=1:N)(D(j)**2)/Sigref**2 ——-Plane 1———- Atoms Distance From Defining Plane (Angstroms) Plane with s.u. C1 0.047 (4) C2 0.072 (4) C3 0.009 (4) C4 - 0.042 (4) C4a -0.054 (4) C4b -0.047 (4) C5 0.014 (4) C6 0.042 (4) C7 0.045 (4) C8 0.005 (4) C8a -0.037 (4) C9 - 0.012 (3) C9a -0.042 (4) Sigref 0.004 Sigpln 0.046 Chisq 1516.9 =========================== ——-Plane 2———- Atoms Distance From Defining Plane (Angstroms) Plane with s.u. C1X -0.023 (4) C2X -0.082 (4) C3X -0.075 (4) C4X -0.007 (4) C4aX 0.075 (3) C4bX 0.075 (3) C5X 0.076 (4) C6X 0.004 (4) C7X -0.109 (4) C8X -0.107 (4) C8aX 0.012 (3) C9X 0.089 (3) C9aX 0.071 (3) Sigref 0.004 Sigpln 0.081 Chisq 4810.9 Plane 1 - Plane 2 A ngle: 58.45 (9) °. =========================== ——-Plane 3———- Atoms Distance From Defining Plane (Angstroms) Plane with s.u. C1Y -0.025 (4) C2Y -0.052 (4) C3Y -0.023 (4) C4Y 0.014 (4) C4aY 0.038 (4) C4bY 0.027 (4) C5Y 0.015 (4) C6Y -0.011 (4) C7Y -0.038 (6) C8Y -0.039 (4) C8aY 0.013 (4) C9Y 0.031 (4) C9aY 0.049 (4) Sigref 0.004 Sigpln 0.036 Chisq 753.0 =========================== ——-Plane 4———- Atoms Distance From Defining Plane (Angstroms) Plane with s.u. C1Z 0.121 (4) C2Z 0.147 (4) C3Z 0.031 (4) C4Z -0.083 (4) C4AZ -0.105 (4) C4BZ -0.107 (4) C5Z -0.037 (4) C6Z 0.083 (5) C7Z 0.143 (5) C8Z 0.056 (4) C8aZ -0.081 (4) C9Z -0.127 (3) C9aZ -0.040 (4) Sigref 0.004 Sigpln 0.111 Chisq 7415.0 Plane 3 - Plane 4 A ngle: 60.95 (10) °. =========================== |
x | y | z | Uiso*/Ueq | ||
O1 | 0.71889 (17) | 0.12752 (12) | 0.5857 (2) | 0.0484 (6) | |
O2 | 0.8552 (3) | 0.18119 (14) | 0.7233 (3) | 0.0788 (9) | |
C1 | 1.0024 (3) | −0.06952 (19) | 0.7725 (4) | 0.0525 (10) | |
C2 | 1.0739 (3) | −0.1371 (2) | 0.7933 (4) | 0.0637 (11) | |
C3 | 1.0822 (3) | −0.1876 (2) | 0.6751 (5) | 0.0670 (11) | |
C4 | 1.0216 (3) | −0.1710 (2) | 0.5328 (4) | 0.0590 (10) | |
C4a | 0.9503 (3) | −0.10268 (18) | 0.5114 (4) | 0.0450 (9) | |
C4b | 0.8809 (3) | −0.07008 (19) | 0.3745 (4) | 0.0455 (9) | |
C5 | 0.8694 (3) | −0.0973 (2) | 0.2282 (4) | 0.0544 (10) | |
C6 | 0.8000 (3) | −0.0545 (2) | 0.1186 (4) | 0.0617 (11) | |
C7 | 0.7440 (3) | 0.0152 (2) | 0.1506 (4) | 0.0617 (11) | |
C8 | 0.7561 (3) | 0.0436 (2) | 0.2968 (4) | 0.0511 (9) | |
C8a | 0.8252 (3) | 0.00064 (18) | 0.4090 (3) | 0.0411 (8) | |
C9 | 0.8584 (2) | 0.01863 (17) | 0.5760 (3) | 0.0391 (8) | |
C9a | 0.9385 (3) | −0.05232 (18) | 0.6314 (4) | 0.0435 (9) | |
C10 | 0.7649 (3) | 0.05483 (17) | 0.6474 (3) | 0.0412 (8) | |
C11 | 0.8037 (3) | 0.06241 (18) | 0.8148 (3) | 0.0516 (10) | |
C12 | 0.7692 (4) | 0.1835 (2) | 0.6315 (5) | 0.0611 (11) | |
C13 | 0.7017 (4) | 0.2489 (2) | 0.5500 (5) | 0.0973 (16) | |
C1X | 0.7363 (3) | −0.1196 (2) | 0.6153 (4) | 0.0568 (10) | |
C2X | 0.7298 (3) | −0.1809 (2) | 0.6727 (5) | 0.0672 (11) | |
C3X | 0.6599 (3) | −0.1745 (2) | 0.7585 (4) | 0.0683 (12) | |
C4X | 0.5960 (3) | −0.1071 (2) | 0.7882 (4) | 0.0587 (10) | |
C4aX | 0.6038 (3) | −0.04626 (19) | 0.7336 (3) | 0.0450 (9) | |
C4bX | 0.5413 (3) | 0.02913 (19) | 0.7418 (3) | 0.0448 (9) | |
C5X | 0.4619 (3) | 0.0611 (2) | 0.8141 (4) | 0.0571 (10) | |
C6X | 0.4100 (3) | 0.1334 (2) | 0.7987 (4) | 0.0669 (11) | |
C7X | 0.4338 (3) | 0.1731 (2) | 0.7094 (4) | 0.0641 (11) | |
C8X | 0.5134 (3) | 0.14158 (19) | 0.6369 (4) | 0.0562 (10) | |
C8aX | 0.5690 (3) | 0.06982 (19) | 0.6553 (3) | 0.0438 (9) | |
C9X | 0.6614 (2) | 0.02274 (17) | 0.5945 (3) | 0.0414 (8) | |
C9aX | 0.6741 (3) | −0.05194 (18) | 0.6471 (3) | 0.0426 (8) | |
H1 | 0.9972 | −0.0357 | 0.8528 | 0.063* | |
H2 | 1.1170 | −0.1486 | 0.8880 | 0.076* | |
H3 | 1.1291 | −0.2335 | 0.6913 | 0.080* | |
H4 | 1.0284 | −0.2048 | 0.4530 | 0.071* | |
H5 | 0.9082 | −0.1438 | 0.2053 | 0.065* | |
H6 | 0.7904 | −0.0728 | 0.0204 | 0.074* | |
H7 | 0.6978 | 0.0435 | 0.0741 | 0.074* | |
H8 | 0.7183 | 0.0907 | 0.3187 | 0.061* | |
H9 | 0.9030 | 0.0545 | 0.5937 | 0.047* | |
H11a | 0.0674 | 0.5894 | 0.6345 | 0.075* | |
H11b | 0.1845 | 0.5415 | 0.6373 | 0.075* | |
H11c | 0.1651 | 0.6268 | 0.6626 | 0.075* | |
H13a | −0.0648 | 0.7865 | 0.9222 | 0.100* | |
H13b | 0.0567 | 0.7677 | 1.0218 | 0.100* | |
H13c | −0.0315 | 0.7345 | 1.0494 | 0.100* | |
H1X | 0.7823 | −0.1244 | 0.5561 | 0.068* | |
H2X | 0.7729 | −0.2264 | 0.6533 | 0.081* | |
H3X | 0.6560 | −0.2157 | 0.7960 | 0.082* | |
H4X | 0.5481 | −0.1026 | 0.8444 | 0.070* | |
H5X | 0.4442 | 0.0339 | 0.8723 | 0.069* | |
H6X | 0.3582 | 0.1556 | 0.8490 | 0.080* | |
H7X | 0.3964 | 0.2216 | 0.6974 | 0.077* | |
H8X | 0.5289 | 0.1687 | 0.5764 | 0.067* | |
H9X | 0.6360 | 0.0198 | 0.4863 | 0.050* | |
O1' | 0.12445 (18) | 0.65076 (11) | 0.9159 (2) | 0.0476 (6) | |
O2' | −0.0483 (2) | 0.66597 (13) | 0.7639 (3) | 0.0662 (7) | |
C1Y | 0.1088 (3) | 0.4215 (2) | 0.6675 (4) | 0.0624 (11) | |
C2Y | 0.1275 (3) | 0.3466 (2) | 0.6300 (5) | 0.0731 (12) | |
C3Y | 0.1702 (3) | 0.2975 (2) | 0.7383 (6) | 0.0764 (13) | |
C4Y | 0.1937 (3) | 0.3219 (2) | 0.8857 (5) | 0.0720 (12) | |
C4aY | 0.1750 (3) | 0.3967 (2) | 0.9241 (4) | 0.0541 (10) | |
C4bY | 0.1882 (3) | 0.4373 (2) | 1.0689 (4) | 0.0578 (10) | |
C5Y | 0.2252 (3) | 0.4124 (2) | 1.2094 (5) | 0.0731 (12) | |
C6Y | 0.2286 (4) | 0.4628 (3) | 1.3300 (5) | 0.0902 (15) | |
C7Y | 0.1949 (4) | 0.5364 (3) | 1.3113 (4) | 0.0860 (14) | |
C8Y | 0.1567 (3) | 0.5622 (2) | 1.1711 (4) | 0.0718 (12) | |
C8aY | 0.1552 (3) | 0.5115 (2) | 1.0498 (4) | 0.0538 (10) | |
C9Y | 0.1185 (3) | 0.52425 (18) | 0.8858 (3) | 0.0475 (9) | |
C9aY | 0.1348 (3) | 0.44644 (18) | 0.8144 (4) | 0.0500 (9) | |
C10' | 0.1705 (3) | 0.57971 (17) | 0.8445 (3) | 0.0441 (8) | |
C11' | 0.1445 (3) | 0.58480 (17) | 0.6796 (3) | 0.0499 (9) | |
C12' | 0.0178 (3) | 0.68522 (19) | 0.8713 (4) | 0.0512 (9) | |
C13' | −0.0077 (3) | 0.74911 (19) | 0.9754 (4) | 0.0665 (11) | |
C1Z | 0.3819 (3) | 0.4375 (2) | 0.8194 (4) | 0.0645 (11) | |
C2Z | 0.4523 (3) | 0.3959 (2) | 0.7395 (5) | 0.0763 (13) | |
C3Z | 0.5096 (3) | 0.4290 (2) | 0.6825 (5) | 0.0786 (13) | |
C4Z | 0.5003 (3) | 0.5029 (2) | 0.7056 (4) | 0.0662 (11) | |
C4aZ | 0.4307 (3) | 0.54449 (19) | 0.7853 (4) | 0.0486 (9) | |
C4bZ | 0.4127 (3) | 0.62182 (19) | 0.8354 (4) | 0.0537 (10) | |
C5Z | 0.4642 (3) | 0.6745 (2) | 0.8210 (5) | 0.0754 (12) | |
C6Z | 0.4407 (4) | 0.7428 (2) | 0.8911 (6) | 0.0913 (15) | |
C7Z | 0.3686 (4) | 0.7587 (2) | 0.9745 (5) | 0.0866 (14) | |
C8Z | 0.3158 (3) | 0.7073 (2) | 0.9881 (4) | 0.0691 (12) | |
C8aZ | 0.3371 (3) | 0.6379 (2) | 0.9169 (4) | 0.0503 (9) | |
C9Z | 0.2960 (3) | 0.57069 (18) | 0.9191 (3) | 0.0469 (9) | |
C9aZ | 0.3683 (3) | 0.51251 (19) | 0.8398 (4) | 0.0469 (9) | |
H1Y | 0.0792 | 0.4542 | 0.5943 | 0.075* | |
H2Y | 0.1111 | 0.3293 | 0.5309 | 0.088* | |
H3Y | 0.1832 | 0.2475 | 0.7113 | 0.092* | |
H4Y | 0.2216 | 0.2889 | 0.9583 | 0.086* | |
H5Y | 0.2472 | 0.3626 | 1.2219 | 0.088* | |
H6Y | 0.2539 | 0.4469 | 1.4247 | 0.108* | |
H7Y | 0.1978 | 0.5696 | 1.3939 | 0.103* | |
H8Y | 0.1328 | 0.6121 | 1.1592 | 0.086* | |
H9Y | 0.0394 | 0.5450 | 0.8600 | 0.057* | |
H11d | 0.8731 | 0.0756 | 0.8464 | 0.077* | |
H11e | 0.8114 | 0.0168 | 0.8524 | 0.077* | |
H11f | 0.7511 | 0.0997 | 0.8515 | 0.077* | |
H13d | 0.6320 | 0.2637 | 0.5702 | 0.146* | |
H13e | 0.6910 | 0.2369 | 0.4458 | 0.146* | |
H13f | 0.7388 | 0.2881 | 0.5815 | 0.146* | |
H1Z | 0.3441 | 0.4148 | 0.8591 | 0.077* | |
H2Z | 0.4605 | 0.3456 | 0.7247 | 0.092* | |
H3Z | 0.5553 | 0.4009 | 0.6275 | 0.094* | |
H4Z | 0.5403 | 0.5249 | 0.6681 | 0.079* | |
H5Z | 0.5135 | 0.6634 | 0.7650 | 0.091* | |
H6Z | 0.4739 | 0.7785 | 0.8819 | 0.110* | |
H7Z | 0.3548 | 0.8050 | 1.0229 | 0.104* | |
H8Z | 0.2665 | 0.7192 | 1.0444 | 0.083* | |
H9Z | 0.3134 | 0.5590 | 1.0216 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0443 (15) | 0.0496 (15) | 0.0521 (15) | −0.0121 (12) | 0.0156 (12) | 0.0000 (12) |
O2 | 0.080 (2) | 0.076 (2) | 0.083 (2) | −0.0425 (18) | 0.0159 (18) | −0.0143 (16) |
C1 | 0.051 (2) | 0.060 (2) | 0.042 (2) | −0.013 (2) | 0.0079 (19) | −0.0005 (19) |
C2 | 0.053 (3) | 0.075 (3) | 0.059 (3) | −0.011 (2) | 0.010 (2) | 0.016 (2) |
C3 | 0.062 (3) | 0.059 (3) | 0.082 (3) | −0.008 (2) | 0.022 (3) | 0.017 (3) |
C4 | 0.060 (3) | 0.056 (3) | 0.067 (3) | −0.018 (2) | 0.029 (2) | −0.008 (2) |
C4a | 0.039 (2) | 0.051 (2) | 0.050 (2) | −0.0159 (18) | 0.0172 (18) | −0.0005 (19) |
C4b | 0.044 (2) | 0.061 (2) | 0.039 (2) | −0.0227 (19) | 0.0178 (18) | −0.0036 (19) |
C5 | 0.060 (3) | 0.066 (2) | 0.046 (2) | −0.025 (2) | 0.027 (2) | −0.010 (2) |
C6 | 0.073 (3) | 0.088 (3) | 0.037 (2) | −0.038 (3) | 0.023 (2) | −0.007 (2) |
C7 | 0.062 (3) | 0.094 (3) | 0.039 (2) | −0.035 (2) | 0.011 (2) | 0.011 (2) |
C8 | 0.049 (2) | 0.061 (2) | 0.048 (2) | −0.0178 (19) | 0.0159 (19) | 0.006 (2) |
C8a | 0.036 (2) | 0.056 (2) | 0.038 (2) | −0.0174 (18) | 0.0143 (17) | 0.0006 (18) |
C9 | 0.036 (2) | 0.052 (2) | 0.0334 (19) | −0.0169 (17) | 0.0134 (16) | −0.0036 (16) |
C9a | 0.037 (2) | 0.054 (2) | 0.042 (2) | −0.0147 (17) | 0.0136 (18) | −0.0003 (18) |
C10 | 0.043 (2) | 0.045 (2) | 0.038 (2) | −0.0157 (17) | 0.0136 (16) | −0.0009 (16) |
C11 | 0.047 (2) | 0.072 (3) | 0.038 (2) | −0.0183 (19) | 0.0153 (17) | −0.0078 (18) |
C12 | 0.062 (3) | 0.059 (3) | 0.072 (3) | −0.020 (2) | 0.036 (2) | −0.010 (2) |
C13 | 0.096 (4) | 0.048 (3) | 0.159 (5) | −0.009 (3) | 0.056 (3) | 0.013 (3) |
O1' | 0.0439 (15) | 0.0533 (15) | 0.0410 (13) | −0.0074 (12) | 0.0126 (11) | −0.0038 (11) |
O2' | 0.0474 (16) | 0.0666 (18) | 0.0666 (18) | −0.0059 (14) | 0.0021 (14) | −0.0057 (15) |
C1X | 0.042 (2) | 0.064 (3) | 0.069 (3) | −0.020 (2) | 0.021 (2) | −0.007 (2) |
C2X | 0.056 (3) | 0.050 (2) | 0.094 (3) | −0.014 (2) | 0.021 (2) | 0.003 (2) |
C3X | 0.061 (3) | 0.065 (3) | 0.082 (3) | −0.019 (2) | 0.012 (2) | 0.024 (2) |
C4X | 0.055 (3) | 0.069 (3) | 0.057 (2) | −0.019 (2) | 0.016 (2) | 0.012 (2) |
C4aX | 0.040 (2) | 0.057 (2) | 0.040 (2) | −0.0184 (18) | 0.0081 (17) | 0.0035 (18) |
C4bX | 0.035 (2) | 0.063 (2) | 0.038 (2) | −0.0187 (19) | 0.0082 (17) | −0.0023 (18) |
C5X | 0.049 (2) | 0.075 (3) | 0.054 (2) | −0.020 (2) | 0.021 (2) | 0.006 (2) |
C6X | 0.050 (3) | 0.078 (3) | 0.075 (3) | −0.016 (2) | 0.027 (2) | −0.009 (2) |
C7X | 0.042 (2) | 0.060 (3) | 0.086 (3) | −0.008 (2) | 0.018 (2) | 0.001 (2) |
C8X | 0.043 (2) | 0.060 (3) | 0.067 (3) | −0.013 (2) | 0.012 (2) | 0.012 (2) |
C8aX | 0.035 (2) | 0.055 (2) | 0.041 (2) | −0.0147 (18) | 0.0056 (17) | 0.0048 (18) |
C9X | 0.038 (2) | 0.057 (2) | 0.0331 (19) | −0.0185 (17) | 0.0092 (16) | 0.0022 (16) |
C9aX | 0.035 (2) | 0.052 (2) | 0.041 (2) | −0.0149 (18) | 0.0092 (17) | −0.0016 (17) |
C10' | 0.045 (2) | 0.044 (2) | 0.040 (2) | −0.0031 (17) | 0.0148 (17) | 0.0019 (17) |
C11' | 0.057 (2) | 0.052 (2) | 0.036 (2) | −0.0080 (19) | 0.0116 (18) | 0.0023 (17) |
C12' | 0.045 (2) | 0.052 (2) | 0.056 (2) | −0.005 (2) | 0.018 (2) | 0.006 (2) |
C13' | 0.059 (3) | 0.070 (3) | 0.068 (3) | −0.008 (2) | 0.029 (2) | −0.011 (2) |
C1Y | 0.055 (3) | 0.056 (3) | 0.059 (3) | −0.008 (2) | −0.002 (2) | 0.002 (2) |
C2Y | 0.066 (3) | 0.067 (3) | 0.070 (3) | −0.015 (2) | 0.001 (2) | −0.004 (2) |
C3Y | 0.060 (3) | 0.050 (3) | 0.108 (4) | −0.013 (2) | 0.008 (3) | 0.006 (3) |
C4Y | 0.060 (3) | 0.067 (3) | 0.089 (4) | −0.020 (2) | 0.010 (2) | 0.021 (3) |
C4aY | 0.042 (2) | 0.054 (3) | 0.067 (3) | −0.0114 (19) | 0.014 (2) | 0.012 (2) |
C4bY | 0.050 (2) | 0.077 (3) | 0.057 (3) | −0.016 (2) | 0.023 (2) | 0.019 (2) |
C5Y | 0.065 (3) | 0.093 (3) | 0.074 (3) | −0.016 (3) | 0.029 (3) | 0.030 (3) |
C6Y | 0.087 (4) | 0.134 (5) | 0.061 (3) | −0.014 (3) | 0.030 (3) | 0.042 (3) |
C7Y | 0.104 (4) | 0.117 (4) | 0.047 (3) | −0.025 (3) | 0.033 (3) | 0.011 (3) |
C8Y | 0.086 (3) | 0.087 (3) | 0.054 (3) | −0.018 (3) | 0.036 (2) | 0.010 (2) |
C8aY | 0.050 (2) | 0.070 (3) | 0.047 (2) | −0.016 (2) | 0.0191 (19) | 0.008 (2) |
C9Y | 0.041 (2) | 0.055 (2) | 0.042 (2) | −0.0073 (18) | 0.0093 (17) | 0.0056 (18) |
C9aY | 0.044 (2) | 0.051 (2) | 0.051 (2) | −0.0115 (19) | 0.0068 (19) | 0.005 (2) |
C1Z | 0.046 (2) | 0.063 (3) | 0.086 (3) | −0.006 (2) | 0.021 (2) | 0.018 (2) |
C2Z | 0.057 (3) | 0.048 (3) | 0.116 (4) | 0.001 (2) | 0.029 (3) | 0.000 (3) |
C3Z | 0.066 (3) | 0.073 (3) | 0.095 (3) | 0.000 (3) | 0.040 (3) | −0.009 (3) |
C4Z | 0.063 (3) | 0.070 (3) | 0.075 (3) | −0.007 (2) | 0.037 (2) | 0.009 (2) |
C4aZ | 0.043 (2) | 0.054 (2) | 0.047 (2) | −0.0038 (19) | 0.0145 (18) | 0.0077 (19) |
C4bZ | 0.049 (2) | 0.056 (3) | 0.053 (2) | −0.013 (2) | 0.010 (2) | 0.0032 (19) |
C5Z | 0.070 (3) | 0.064 (3) | 0.101 (4) | −0.018 (2) | 0.036 (3) | 0.004 (3) |
C6Z | 0.073 (3) | 0.067 (3) | 0.139 (4) | −0.025 (3) | 0.034 (3) | 0.000 (3) |
C7Z | 0.058 (3) | 0.066 (3) | 0.125 (4) | −0.023 (3) | 0.019 (3) | −0.024 (3) |
C8Z | 0.049 (3) | 0.075 (3) | 0.071 (3) | −0.013 (2) | 0.011 (2) | −0.016 (2) |
C8aZ | 0.044 (2) | 0.061 (2) | 0.042 (2) | −0.0106 (19) | 0.0111 (18) | −0.0025 (19) |
C9Z | 0.041 (2) | 0.063 (2) | 0.034 (2) | −0.0076 (19) | 0.0104 (17) | 0.0065 (17) |
C9aZ | 0.041 (2) | 0.050 (2) | 0.045 (2) | −0.0017 (18) | 0.0090 (17) | 0.0113 (18) |
O1—C12 | 1.350 (4) | C4aZ—C9aZ | 1.397 (4) |
O1'—C12' | 1.349 (4) | C4b—C8a | 1.396 (4) |
O1—C10 | 1.488 (4) | C4bX—C8aX | 1.397 (4) |
O1'—C10' | 1.484 (3) | C4bY—C8aY | 1.386 (5) |
O2—C12 | 1.194 (4) | C4bZ—C8aZ | 1.394 (4) |
O2'—C12' | 1.202 (4) | C9—C10 | 1.546 (4) |
C1—C2 | 1.379 (4) | C9Y—C10' | 1.557 (4) |
C1X—C2X | 1.396 (5) | C9X—C10 | 1.556 (4) |
C1Y—C2Y | 1.390 (5) | C9Z—C10' | 1.561 (4) |
C1Z—C2Z | 1.392 (5) | C10—C11 | 1.515 (4) |
C2—C3 | 1.378 (5) | C10'—C11' | 1.516 (4) |
C2Y—C3Y | 1.385 (5) | C12'—C13' | 1.483 (4) |
C2X—C3X | 1.386 (5) | C12—C13 | 1.492 (5) |
C2Z—C3Z | 1.372 (5) | C11'—H11a | 0.9600 |
C3—C4 | 1.381 (5) | C11'—H11b | 0.9600 |
C3X—C4X | 1.379 (5) | C11'—H11c | 0.9600 |
C3Y—C4Y | 1.377 (5) | C11—H11d | 0.9600 |
C3Z—C4Z | 1.369 (5) | C11—H11e | 0.9600 |
C4—C4a | 1.389 (4) | C11—H11f | 0.9600 |
C4X—C4aX | 1.381 (4) | C13'—H13a | 0.9600 |
C4Y—C4aY | 1.389 (5) | C13'—H13b | 0.9600 |
C4Z—C4aZ | 1.384 (4) | C13'—H13c | 0.9600 |
C4a—C4b | 1.461 (4) | C13—H13d | 0.9600 |
C4aX—C4bX | 1.457 (4) | C13—H13e | 0.9600 |
C4aY—C4bY | 1.461 (5) | C13—H13f | 0.9600 |
C4aZ—C4bZ | 1.457 (4) | C8Z—H8Z | 0.9300 |
C4b—C5 | 1.389 (4) | C1X—H1X | 0.9300 |
C4bX—C5X | 1.389 (4) | C1—H1 | 0.9300 |
C4bY—C5Y | 1.389 (5) | C7Z—H7Z | 0.9300 |
C4bZ—C5Z | 1.396 (5) | C6Z—H6Z | 0.9300 |
C5—C6 | 1.368 (5) | C6Y—H6Y | 0.9300 |
C5X—C6X | 1.372 (5) | C3—H3 | 0.9300 |
C5Y—C6Y | 1.378 (5) | C3X—H3X | 0.9300 |
C5Z—C6Z | 1.372 (5) | C5Z—H5Z | 0.9300 |
C6—C7 | 1.376 (5) | C4Z—H4Z | 0.9300 |
C6X—C7X | 1.376 (5) | C4—H4 | 0.9300 |
C6Y—C7Y | 1.375 (6) | C4X—H4X | 0.9300 |
C6Z—C7Z | 1.370 (6) | C2X—H2X | 0.9300 |
C7—C8 | 1.395 (4) | C2—H2 | 0.9300 |
C7X—C8X | 1.390 (5) | C8Y—H8Y | 0.9300 |
C7Y—C8Y | 1.392 (5) | C7Y—H7Y | 0.9300 |
C7Z—C8Z | 1.386 (5) | C5Y—H5Y | 0.9300 |
C8—C8a | 1.384 (4) | C5—H5 | 0.9300 |
C8X—C8aX | 1.378 (4) | C5X—H5X | 0.9300 |
C8Z—C8aZ | 1.391 (5) | C4Y—H4Y | 0.9300 |
C8Y—C8aY | 1.388 (5) | C6—H6 | 0.9300 |
C8a—C9 | 1.527 (4) | C3Z—H3Z | 0.9300 |
C8aX—C9X | 1.526 (4) | C7—H7 | 0.9300 |
C8aY—C9Y | 1.526 (4) | C8X—H8X | 0.9300 |
C8aZ—C9Z | 1.524 (4) | C1Y—H1Y | 0.9300 |
C9—C9a | 1.528 (4) | C8—H8 | 0.9300 |
C9X—C9aX | 1.531 (4) | C1Z—H1Z | 0.9300 |
C9Y—C9aY | 1.523 (4) | C2Z—H2Z | 0.9300 |
C9Z—C9aZ | 1.531 (4) | C2Y—H2Y | 0.9300 |
C9a—C1 | 1.385 (4) | C6X—H6X | 0.9300 |
C9aX—C1X | 1.378 (4) | C9Y—H9Y | 0.9800 |
C9aY—C1Y | 1.377 (4) | C9—H9 | 0.9800 |
C9aZ—C1Z | 1.381 (5) | C9X—H9X | 0.9800 |
C4a—C9a | 1.397 (4) | C9Z—H9Z | 0.9800 |
C4aX—C9aX | 1.398 (4) | C7X—H7X | 0.9300 |
C4aY—C9aY | 1.404 (4) | C3Y—H3Y | 0.9300 |
C12—O1—C10 | 123.0 (3) | C9—C10—C9X | 116.8 (2) |
C12'—O1'—C10' | 122.6 (3) | C9Y—C10'—C9Z | 115.2 (3) |
C1—C2—C3 | 120.6 (4) | O1—C12—C13 | 109.9 (4) |
C1X—C2X—C3X | 120.7 (4) | O1'—C12'—C13' | 110.6 (3) |
C1Y—C2Y—C3Y | 120.8 (4) | O2—C12—C13 | 124.8 (4) |
C1Z—C2Z—C3Z | 120.2 (4) | O2'—C12'—C13' | 124.5 (3) |
C2—C3—C4 | 120.8 (4) | C6Y—C5Y—H5Y | 120.6 |
C2X—C3X—C4X | 119.9 (4) | C3X—C4X—H4X | 120.3 |
C2Y—C3Y—C4Y | 120.6 (4) | C4aX—C4X—H4X | 120.3 |
C2Z—C3Z—C4Z | 120.7 (4) | C4bY—C5Y—H5Y | 120.6 |
C3—C4—C4a | 118.7 (4) | C3Z—C4Z—H4Z | 120.4 |
C3X—C4X—C4aX | 119.4 (4) | C4aZ—C4Z—H4Z | 120.4 |
C3Y—C4Y—C4aY | 119.0 (4) | C6—C5—H5 | 120.6 |
C3Z—C4Z—C4aZ | 119.2 (4) | C4b—C5—H5 | 120.6 |
C4—C4a—C4b | 130.0 (3) | C6X—C5X—H5X | 120.4 |
C4X—C4aX—C4bX | 129.8 (3) | C4bX—C5X—H5X | 120.4 |
C4Y—C4aY—C4bY | 130.7 (4) | C3Y—C4Y—H4Y | 120.5 |
C4Z—C4aZ—C4bZ | 130.2 (3) | C4aY—C4Y—H4Y | 120.5 |
C4—C4a—C9a | 120.7 (3) | C5—C6—H6 | 119.4 |
C4X—C4aX—C9aX | 121.2 (3) | C7—C6—H6 | 119.4 |
C4Y—C4aY—C9aY | 120.4 (4) | C4Z—C3Z—H3Z | 119.6 |
C4Z—C4aZ—C9aZ | 121.1 (3) | C2Z—C3Z—H3Z | 119.6 |
C9a—C4a—C4b | 109.2 (3) | C5X—C6X—H6X | 119.7 |
C9aX—C4aX—C4bX | 108.8 (3) | C7X—C6X—H6X | 119.7 |
C9aY—C4aY—C4bY | 108.9 (3) | C4Y—C3Y—H3Y | 119.7 |
C9aZ—C4aZ—C4bZ | 108.6 (3) | C2Y—C3Y—H3Y | 119.7 |
C4a—C4b—C5 | 130.3 (3) | C6—C7—H7 | 119.8 |
C4aX—C4bX—C5X | 130.0 (3) | C8—C7—H7 | 119.8 |
C4aY—C4bY—C5Y | 130.2 (4) | C6X—C7X—H7X | 119.7 |
C4aZ—C4bZ—C5Z | 129.7 (4) | C8X—C7X—H7X | 119.7 |
C5—C4b—C8a | 120.6 (3) | C3Z—C2Z—H2Z | 119.9 |
C5X—C4bX—C8aX | 120.8 (3) | C3Y—C2Y—H2Y | 119.6 |
C5Y—C4bY—C8aY | 120.7 (4) | C1Y—C2Y—H2Y | 119.6 |
C5Z—C4bZ—C8aZ | 121.3 (3) | C1Z—C2Z—H2Z | 119.9 |
C8a—C4b—C4a | 109.0 (3) | C8aX—C8X—H8X | 120.2 |
C8aX—C4bX—C4aX | 109.2 (3) | C7X—C8X—H8X | 120.2 |
C8aY—C4bY—C4aY | 109.1 (3) | C9aY—C1Y—H1Y | 120.5 |
C8aZ—C4bZ—C4aZ | 108.9 (3) | C2Y—C1Y—H1Y | 120.5 |
C4b—C5—C6 | 118.9 (4) | C10'—C11'—H11a | 109.5 |
C4bX—C5X—C6X | 119.1 (4) | C10'—C11'—H11b | 109.5 |
C4bY—C5Y—C6Y | 118.9 (4) | H11a—C11'—H11b | 109.5 |
C4bZ—C5Z—C6Z | 118.8 (4) | C10'—C11'—H11c | 109.5 |
C5—C6—C7 | 121.3 (3) | H11a—C11'—H11c | 109.5 |
C5X—C6X—C7X | 120.5 (4) | H11b—C11'—H11c | 109.5 |
C5Y—C6Y—C7Y | 120.5 (4) | C10—C11—H11d | 109.5 |
C5Z—C6Z—C7Z | 120.5 (4) | C10—C11—H11e | 109.5 |
C6—C7—C8 | 120.5 (4) | H11d—C11—H11e | 109.5 |
C6X—C7X—C8X | 120.7 (4) | C10—C11—H11f | 109.5 |
C6Y—C7Y—C8Y | 121.4 (4) | H11d—C11—H11f | 109.5 |
C6Z—C7Z—C8Z | 121.3 (4) | H11e—C11—H11f | 109.5 |
C7—C8—C8a | 118.9 (3) | C12'—C13'—H13a | 109.5 |
C7X—C8X—C8aX | 119.6 (3) | C12'—C13'—H13b | 109.5 |
C7Y—C8Y—C8aY | 118.1 (4) | H13a—C13'—H13b | 109.5 |
C7Z—C8Z—C8aZ | 119.4 (4) | C12'—C13'—H13c | 109.5 |
C8—C8a—C9 | 130.1 (3) | H13a—C13'—H13c | 109.5 |
C8X—C8aX—C9X | 130.7 (3) | H13b—C13'—H13c | 109.5 |
C8Y—C8aY—C9Y | 129.2 (3) | C12—C13—H13d | 109.5 |
C8Z—C8aZ—C9Z | 130.4 (3) | C12—C13—H13e | 109.5 |
C8—C8a—C4b | 119.9 (3) | H13d—C13—H13e | 109.5 |
C8X—C8aX—C4bX | 119.3 (3) | C12—C13—H13f | 109.5 |
C8Y—C8aY—C4bY | 120.4 (3) | H13d—C13—H13f | 109.5 |
C8Z—C8aZ—C4bZ | 118.7 (4) | H13e—C13—H13f | 109.5 |
C4b—C8a—C9 | 109.9 (3) | C9aX—C1X—H1X | 120.3 |
C4bX—C8aX—C9X | 110.1 (3) | C2X—C1X—H1X | 120.3 |
C4bY—C8aY—C9Y | 110.4 (3) | C8aY—C8Y—H8Y | 120.9 |
C4bZ—C8aZ—C9Z | 110.8 (3) | C7Y—C8Y—H8Y | 120.9 |
C8a—C9—C9a | 102.1 (3) | C7Z—C8Z—H8Z | 120.3 |
C8aX—C9X—C9aX | 101.6 (2) | C8aZ—C8Z—H8Z | 120.3 |
C8aY—C9Y—C9aY | 101.9 (3) | C6Y—C7Y—H7Y | 119.3 |
C8aZ—C9Z—C9aZ | 100.8 (3) | C8Y—C7Y—H7Y | 119.3 |
C9—C9a—C1 | 130.6 (3) | C2—C1—H1 | 120.2 |
C9X—C9aX—C1X | 130.5 (3) | C9a—C1—H1 | 120.2 |
C9Y—C9aY—C1Y | 130.0 (3) | C6Z—C7Z—H7Z | 119.3 |
C9Z—C9aZ—C1Z | 131.0 (3) | C8Z—C7Z—H7Z | 119.3 |
C1—C9a—C4a | 119.4 (3) | C3X—C2X—H2X | 119.6 |
C1X—C9aX—C4aX | 119.3 (3) | C1X—C2X—H2X | 119.6 |
C1Y—C9aY—C4aY | 120.0 (3) | C3—C2—H2 | 119.7 |
C1Z—C9aZ—C4aZ | 118.5 (3) | C1—C2—H2 | 119.7 |
C4a—C9a—C9 | 109.7 (3) | C7Z—C6Z—H6Z | 119.7 |
C4aX—C9aX—C9X | 110.1 (3) | C5Z—C6Z—H6Z | 119.7 |
C4aY—C9aY—C9Y | 109.7 (3) | C2—C3—H3 | 119.6 |
C4aZ—C9aZ—C9Z | 110.5 (3) | C4—C3—H3 | 119.6 |
C8a—C9—C10 | 116.8 (3) | C4X—C3X—H3X | 120.0 |
C8aY—C9Y—C10' | 114.7 (3) | C2X—C3X—H3X | 120.0 |
C8aX—C9X—C10 | 111.7 (3) | C7Y—C6Y—H6Y | 119.7 |
C8aZ—C9Z—C10' | 113.7 (3) | C5Y—C6Y—H6Y | 119.7 |
C9a—C1—C2 | 119.6 (3) | C6Z—C5Z—H5Z | 120.6 |
C9aX—C1X—C2X | 119.5 (3) | C3—C4—H4 | 120.7 |
C9aY—C1Y—C2Y | 119.1 (4) | C4a—C4—H4 | 120.7 |
C9aZ—C1Z—C2Z | 120.1 (4) | C4bZ—C5Z—H5Z | 120.6 |
C9a—C9—C10 | 119.8 (3) | C8a—C8—H8 | 120.6 |
C9aX—C9X—C10 | 116.2 (3) | C7—C8—H8 | 120.6 |
C9aZ—C9Z—C10' | 114.2 (3) | C9aZ—C1Z—H1Z | 120.0 |
C9aY—C9Y—C10' | 119.4 (3) | C2Z—C1Z—H1Z | 120.0 |
O1—C10—C11 | 111.3 (2) | C8aX—C9X—H9X | 109.0 |
O1'—C10'—C11' | 110.3 (2) | C9aX—C9X—H9X | 109.0 |
O2—C12—O1 | 125.2 (4) | C10—C9X—H9X | 109.0 |
O2'—C12'—O1' | 124.8 (3) | C8a—C9—H9 | 105.6 |
O1—C10—C9 | 104.0 (2) | C9a—C9—H9 | 105.6 |
O1—C10—C9X | 100.3 (2) | C10—C9—H9 | 105.6 |
O1'—C10'—C9Z | 101.9 (2) | C9aY—C9Y—H9Y | 106.6 |
O1'—C10'—C9Y | 104.3 (2) | C8aY—C9Y—H9Y | 106.6 |
C11—C10—C9 | 113.3 (3) | C10'—C9Y—H9Y | 106.6 |
C11'—C10'—C9Y | 114.1 (3) | C8aZ—C9Z—H9Z | 109.3 |
C11—C10—C9X | 110.1 (3) | C9aZ—C9Z—H9Z | 109.3 |
C11'—C10'—C9Z | 110.1 (3) | C10'—C9Z—H9Z | 109.3 |
C9aX—C9X—C10—O1 | −175.8 (2) | C7Y—C8Y—C8aY—C4bY | 1.7 (6) |
C9aZ—C9Z—C10'—O1' | −164.6 (3) | C7X—C8X—C8aX—C4bX | 2.6 (5) |
C9aX—C9X—C10—C11 | −58.4 (3) | C7Z—C8Z—C8aZ—C4bZ | 1.0 (6) |
C9aZ—C9Z—C10'—C11' | −47.5 (4) | C5—C4b—C8a—C8 | 1.4 (5) |
C9aX—C9X—C10—C9 | 72.6 (3) | C5Y—C4bY—C8aY—C8Y | −1.2 (6) |
C9aZ—C9Z—C10'—C9Y | 83.3 (3) | C5X—C4bX—C8aX—C8X | −2.8 (5) |
C8aX—C9X—C10—O1 | −59.9 (3) | C5Z—C4bZ—C8aZ—C8Z | −1.9 (5) |
C8aZ—C9Z—C10'—O1' | −49.6 (3) | C4a—C4b—C8a—C8 | 178.4 (3) |
C8aX—C9X—C10—C11 | 57.5 (3) | C4aY—C4bY—C8aY—C8Y | 178.1 (3) |
C8aZ—C9Z—C10'—C11' | 67.4 (3) | C4aX—C4bX—C8aX—C8X | 174.8 (3) |
C8aX—C9X—C10—C9 | −171.5 (3) | C4aZ—C4bZ—C8aZ—C8Z | 173.7 (3) |
C8aZ—C9Z—C10'—C9Y | −161.8 (3) | C5—C4b—C8a—C9 | −176.0 (3) |
C1—C2—C3—C4 | 2.0 (6) | C5Y—C4bY—C8aY—C9Y | −180.0 (3) |
C1X—C2X—C3X—C4X | −0.2 (6) | C5X—C4bX—C8aX—C9X | 177.5 (3) |
C1Y—C2Y—C3Y—C4Y | 0.9 (6) | C5Z—C4bZ—C8aZ—C9Z | −178.2 (3) |
C1Z—C2Z—C3Z—C4Z | 1.3 (7) | C4a—C4b—C8a—C9 | 1.0 (4) |
C2—C3—C4—C4a | −1.3 (6) | C4aY—C4bY—C8aY—C9Y | −0.8 (4) |
C2X—C3X—C4X—C4aX | −1.0 (6) | C4aX—C4bX—C8aX—C9X | −4.9 (4) |
C2Y—C3Y—C4Y—C4aY | −0.7 (6) | C4aZ—C4bZ—C8aZ—C9Z | −2.6 (4) |
C2Z—C3Z—C4Z—C4aZ | −1.1 (6) | C4b—C8a—C9—C9a | −1.3 (3) |
C3—C4—C4a—C4b | 177.1 (3) | C4bY—C8aY—C9Y—C9aY | 0.4 (4) |
C3X—C4X—C4aX—C4bX | 175.8 (3) | C4bX—C8aX—C9X—C9aX | 5.1 (3) |
C3Z—C4Z—C4aZ—C4bZ | 174.3 (4) | C4bZ—C8aZ—C9Z—C9aZ | 5.4 (4) |
C3Y—C4Y—C4aY—C4bY | 177.4 (4) | C8—C8a—C9—C10 | 49.0 (5) |
C4—C4a—C4b—C5 | −2.2 (6) | C8Y—C8aY—C9Y—C10' | 51.1 (5) |
C4Y—C4aY—C4bY—C5Y | 1.2 (7) | C8X—C8aX—C9X—C10 | 60.8 (4) |
C4X—C4aX—C4bX—C5X | 4.5 (6) | C8Z—C8aZ—C9Z—C10' | 66.9 (5) |
C4Z—C4aZ—C4bZ—C5Z | −2.7 (7) | C4b—C8a—C9—C10 | −134.0 (3) |
C4a—C4b—C5—C6 | −178.2 (3) | C4bY—C8aY—C9Y—C10' | −130.2 (3) |
C4aY—C4bY—C5Y—C6Y | −179.1 (4) | C4bX—C8aX—C9X—C10 | −119.5 (3) |
C4aX—C4bX—C5X—C6X | −176.5 (3) | C4bZ—C8aZ—C9Z—C10' | −117.3 (3) |
C4aZ—C4bZ—C5Z—C6Z | −173.4 (4) | C2—C1—C9a—C4a | −2.4 (5) |
C4b—C5—C6—C7 | 1.6 (5) | C2Y—C1Y—C9aY—C4aY | −2.9 (5) |
C4bY—C5Y—C6Y—C7Y | 0.7 (7) | C2X—C1X—C9aX—C4aX | −1.4 (5) |
C4bX—C5X—C6X—C7X | 1.9 (6) | C2Z—C1Z—C9aZ—C4aZ | −3.3 (5) |
C4bZ—C5Z—C6Z—C7Z | 0.5 (7) | C4b—C4a—C9a—C1 | −175.6 (3) |
C5—C6—C7—C8 | −0.6 (6) | C4bY—C4aY—C9aY—C1Y | −175.9 (3) |
C5Y—C6Y—C7Y—C8Y | −0.1 (7) | C4bX—C4aX—C9aX—C1X | −175.6 (3) |
C5X—C6X—C7X—C8X | −2.1 (6) | C4bZ—C4aZ—C9aZ—C1Z | −173.0 (3) |
C5Z—C6Z—C7Z—C8Z | −1.4 (7) | C4—C4a—C9a—C1 | 3.1 (5) |
C6—C7—C8—C8a | 0.0 (5) | C4Y—C4aY—C9aY—C1Y | 3.1 (5) |
C6Y—C7Y—C8Y—C8aY | −1.2 (7) | C4X—C4aX—C9aX—C1X | 0.3 (5) |
C6X—C7X—C8X—C8aX | −0.2 (6) | C4Z—C4aZ—C9aZ—C1Z | 3.5 (5) |
C6Z—C7Z—C8Z—C8aZ | 0.6 (7) | C4—C4a—C9a—C9 | 178.1 (3) |
C7—C8—C8a—C9 | 176.4 (3) | C4Y—C4aY—C9aY—C9Y | 178.3 (3) |
C7Y—C8Y—C8aY—C9Y | −179.7 (4) | C4X—C4aX—C9aX—C9X | 176.7 (3) |
C7X—C8X—C8aX—C9X | −177.7 (3) | C4Z—C4aZ—C9aZ—C9Z | −178.2 (3) |
C7Z—C8Z—C8aZ—C9Z | 176.5 (4) | C4b—C4a—C9a—C9 | −0.6 (4) |
C8—C8a—C9—C9a | −178.3 (3) | C4bY—C4aY—C9aY—C9Y | −0.7 (4) |
C8Y—C8aY—C9Y—C9aY | −178.4 (4) | C4bX—C4aX—C9aX—C9X | 0.8 (4) |
C8X—C8aX—C9X—C9aX | −174.6 (3) | C4bZ—C4aZ—C9aZ—C9Z | 5.3 (4) |
C8Z—C8aZ—C9Z—C9aZ | −170.4 (3) | C4a—C9a—C9—C8a | 1.1 (3) |
C8a—C9—C9a—C1 | 175.4 (3) | C4aY—C9aY—C9Y—C8aY | 0.2 (4) |
C8aY—C9Y—C9aY—C1Y | 174.8 (4) | C4aX—C9aX—C9X—C8aX | −3.5 (3) |
C8aX—C9X—C9aX—C1X | 172.4 (3) | C4aZ—C9aZ—C9Z—C8aZ | −6.4 (3) |
C8aZ—C9Z—C9aZ—C1Z | 171.6 (4) | C1—C9a—C9—C10 | −53.7 (5) |
C9—C9a—C1—C2 | −176.2 (3) | C1Y—C9aY—C9Y—C10' | −57.6 (5) |
C9Y—C9aY—C1Y—C2Y | −177.0 (4) | C1X—C9aX—C9X—C10 | −66.1 (4) |
C9X—C9aX—C1X—C2X | −177.0 (3) | C1Z—C9aZ—C9Z—C10' | −66.1 (5) |
C9Z—C9aZ—C1Z—C2Z | 178.8 (3) | C4a—C9a—C9—C10 | 132.1 (3) |
C9a—C1—C2—C3 | −0.1 (5) | C4aY—C9aY—C9Y—C10' | 127.8 (3) |
C9aY—C1Y—C2Y—C3Y | 0.9 (6) | C4aX—C9aX—C9X—C10 | 118.0 (3) |
C9aX—C1X—C2X—C3X | 1.4 (5) | C4aZ—C9aZ—C9Z—C10' | 115.9 (3) |
C9aZ—C1Z—C2Z—C3Z | 0.9 (6) | C8a—C9—C10—O1 | −65.9 (3) |
C9a—C4a—C4—C3 | −1.3 (5) | C8aY—C9Y—C10'—O1' | −66.8 (3) |
C9aY—C4aY—C4Y—C3Y | −1.2 (6) | C8a—C9—C10—C11 | 173.1 (3) |
C9aX—C4aX—C4X—C3X | 0.9 (5) | C8aY—C9Y—C10'—C11' | 172.8 (3) |
C9aZ—C4aZ—C4Z—C3Z | −1.3 (6) | C12—O1—C10—C11 | 46.6 (4) |
C9a—C4a—C4b—C8a | −0.2 (4) | C12'—O1'—C10'—C11' | 54.6 (4) |
C9aY—C4aY—C4bY—C8aY | 0.9 (4) | C12—O1—C10—C9 | −75.6 (3) |
C9aX—C4aX—C4bX—C8aX | 2.5 (4) | C12'—O1'—C10'—C9Y | −68.3 (3) |
C9aZ—C4aZ—C4bZ—C8aZ | −1.7 (4) | C12—O1—C10—C9X | 163.1 (3) |
C9a—C4a—C4b—C5 | 176.4 (3) | C12'—O1'—C10'—C9Z | 171.5 (3) |
C9aY—C4aY—C4bY—C5Y | −180.0 (4) | C9a—C9—C10—O1 | 169.9 (2) |
C9aX—C4aX—C4bX—C5X | 179.9 (3) | C9aY—C9Y—C10'—O1' | 171.8 (3) |
C9aZ—C4aZ—C4bZ—C5Z | 173.4 (4) | C9a—C9—C10—C11 | 48.9 (4) |
C4—C4a—C4b—C8a | −178.8 (3) | C9aY—C9Y—C10'—C11' | 51.4 (4) |
C4Y—C4aY—C4bY—C8aY | −177.9 (4) | C10—O1—C12—O2 | 1.1 (5) |
C4X—C4aX—C4bX—C8aX | −172.9 (3) | C10'—O1'—C12'—O2' | −6.4 (5) |
C4Z—C4aZ—C4bZ—C8aZ | −177.8 (4) | C10—O1—C12—C13 | −179.2 (3) |
C8a—C4b—C5—C6 | −2.0 (5) | C10'—O1'—C12'—C13' | 172.0 (3) |
C8aY—C4bY—C5Y—C6Y | −0.1 (6) | C9a—C9—C10—C9X | −80.6 (4) |
C8aX—C4bX—C5X—C6X | 0.6 (5) | C9aY—C9Y—C10'—C9Z | −77.5 (4) |
C8aZ—C4bZ—C5Z—C6Z | 1.2 (6) | C8a—C9—C10—C9X | 43.5 (4) |
C7—C8—C8a—C4b | −0.4 (5) | C8aY—C9Y—C10'—C9Z | 44.0 (4) |
Experimental details
Crystal data | |
Chemical formula | C30H24O2 |
Mr | 416.49 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 13.211 (3), 19.044 (3), 9.5505 (12) |
α, β, γ (°) | 98.852 (11), 108.115 (14), 74.565 (14) |
V (Å3) | 2194.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.43 × 0.41 × 0.27 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8103, 7737, 2792 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.140, 0.97 |
No. of reflections | 7737 |
No. of parameters | 581 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, PROCESS in TEXSAN (Molecular Structure Corporation, 1997), MITHRIL (Gilmore, 1984), TEXSAN and SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1965), TEXSAN, SHELXL97 and PLATON (Spek, 2000).
C2X—C3X | 1.386 (5) | C8X—C8aX | 1.378 (4) |
C2Z—C3Z | 1.372 (5) | C8Z—C8aZ | 1.391 (5) |
C8a—C9—C10 | 116.8 (3) | O1—C10—C11 | 111.3 (2) |
C8aY—C9Y—C10' | 114.7 (3) | O1'—C10'—C11' | 110.3 (2) |
C8aX—C9X—C10 | 111.7 (3) | O1—C10—C9X | 100.3 (2) |
C8aZ—C9Z—C10' | 113.7 (3) | O1'—C10'—C9Z | 101.9 (2) |
C9aX—C9X—C10 | 116.2 (3) | C9—C10—C9X | 116.8 (2) |
C9aZ—C9Z—C10' | 114.2 (3) | C9Y—C10'—C9Z | 115.2 (3) |
C9aX—C9X—C10—O1 | −175.8 (2) | C8aX—C9X—C10—O1 | −59.9 (3) |
C9aZ—C9Z—C10'—O1' | −164.6 (3) | C8aZ—C9Z—C10'—O1' | −49.6 (3) |
C9aX—C9X—C10—C11 | −58.4 (3) | C8aX—C9X—C10—C11 | 57.5 (3) |
C9aZ—C9Z—C10'—C11' | −47.5 (4) | C8aZ—C9Z—C10'—C11' | 67.4 (3) |
C9aX—C9X—C10—C9 | 72.6 (3) | C8aX—C9X—C10—C9 | −171.5 (3) |
C9aZ—C9Z—C10'—C9Y | 83.3 (3) | C8aZ—C9Z—C10'—C9Y | −161.8 (3) |
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Although the acetylation of 9-metalated fluorenes with acetyl chloride and related reagents has received much attention (e.g. Naik et al., 1988; Rouzaud et al., 1965; Scherf & Brown, 1961; Greenhow et al., 1953; Von & Wagner, 1944; Miller & Bachman, 1935), the results have been controversial, mainly because of inadequate structure identification of the products. Moreover, difficulties in their separation and purification also led to discrepancies in the reported melting points. In light of this situation and the important stereochemistry associated with 9-substituted fluorenes, we undertook a re-examination of the reaction of 9-fluorenyllithium with acetyl chloride in tetrahydrofuran. This study afforded the definitive characterization of the major product, sp-9-acetylfluorene, (I) (Meyers et al., 2000), and two byproducts, 9-(1-acetoxyethylidene)fluorene (Robinson et al., 2000), and 1,1-bis(9-fluorenyl)ethanol, (II) (Meyers et al., 2001). A third byproduct, only slightly less polar than (II) and present in very small amounts, was detected by TLC and separated via flash chromatography. There was insufficient material to obtain a definitive NMR spectrum, but the 1H NMR spectrum of the separated material indicated that it contained (II) and another difluorenyl compound similar to (II). A single-crystal was selected from the mass and submitted to X-ray analysis, which indicated this compound to be 1,1-bis(9-fluorenyl)ethyl acetate, (III). Subsequently, larger amounts of (III) were synthesized directly by the acetylation of isolated (II) with acetic anhydride and DMAP as well as with acetyl chloride and pyridine. 1H and 13C NMR as well as an additional X-ray analysis unequivocally confirmed the suggested structure. As illustrated in the Scheme, a reasonable pathway leading to (III) in the acetylation involves nucleophilic attack of the 9-fluorenyllithium on initially formed (I) to provide the oxyanion of (II), which is subsequently either protonated to form (II) or acetylated with residual acetyl chloride to form (III). While, as already noted, (III) has not been previously identified as a product in the acetylation of 9-fluorenyl anion, Von & Wagner (1944) reported that the major product in this reaction, (I), `deteriorated rapidly on storage with conversion to dimeric acetylfluorene.' They suggested no structure for this dimer, and provided only elemental analysis and molecular weight, both of which are identical to those of (III). They noted that their dimer did not react with phenylhydrazine, which also would apply to (III). However, they reported a melting point of 520–521 K (corrected) for their dimer, while (III) melts sharply at 441.5–443 K (corrected). In light of the sharp difference in melting points and mode of formation of the two products, it is reasonable to assume that the Von & Wagner dimer and (III) are not the same. \sch
The X-ray structure of (III) with the atom numbering for the two molecules in the asymmetric unit is illustrated in Fig. 1. The structure reveals two almost identical molecules which differ slightly, but significantly, in conformation and is a not-too-common example of the concurrent co-crystallization of more than one molecular conformation. Differences between the two molecules in the asymmetric unit are manifested in their geometric parameters. Table 1 illustrates the largest differences in the geometric parameters between molecules 1 and 2. Note that equivalent torsion angles about one of the two bonds that join the two fluorene rings of each molecule (the C9X—C10 bond in molecule 1 and the C9Z—C10' bond in molecule 2) generally differ by 7–8 degrees. These significant torsional differences are associated with all of the significant bond-angle variations listed in Table 1 which range from 5 to 8 σ. By contrast, smaller differences are observed between equivalent torsion angles about the C9—C10 and C9Y—C10' bonds, which are the other bonds connecting the two fluorene rings in the respective molecules.
Chemically, compound (III), a di-9-fluorenyl alcohol, differs only slightly from its acetate ester (II). However, significant conformational differences are apparent in their crystal structures. For example, while the two fluorene rings of (II) are normal to each other, those in (III) deviate from perpendicularity by 31.55 (9) (molecule 1) and 29.05 (10)° (molecule 2). In addition, the significant bowing of one of the fluorene rings of (II) has been suggested to emanate from its intermolecular interactions in the packing structure (Meyers et al., 2001). Such bowing is much less obvious in (III). While all of the fluorene rings of (III) are reasonably flat, the two on the right side (Fig. 1) are significantly flatter (χ2 values of 1517 and 753 for molecules 1 and 2, respectively) than those on the left (χ2 values of 4811 and 7415 for molecules 1 and 2, respectively). Complete least-squares plane data for all of the fluorene rings can be found in the CIF.