electronic papers (organic compounds)
The reaction of 9-fluorenyllithium with acetyl chloride (tetrahydrofuran, 213 K, under argon) provided four products which we have isolated and whose structures we have unequivocally identified for the first time. That of the initially formed component, 9-acetylfluorene (C15H12O), described here, shows it to be exclusively the sp rotamer in its crystalline form. The acetyl C-C=O plane is essentially perpendicular to the planar fluorene ring and there is no indication of rotational restriction. In contrast, related 9-pivaloylfluorene, which we reported previously, is rotationally restricted and exists exclusively as its ap rotamer, in which the pivaloyl C-C=O plane is also almost perpendicular to the fluorene ring.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011124/qa0375sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011124/qa0375Isup2.hkl |
CCDC reference: 150751
Computing details top
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: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN, SHELXL97, and PLATON (Spek, 2000).
sp-9-Acetylfluorene top
Crystal data top
C15H12O | Dx = 1.217 Mg m−3 |
Mr = 208.25 | Melting point = 347–348 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 11.253 (4) Å | Cell parameters from 23 reflections |
b = 5.740 (6) Å | θ = 2.3–8.1° |
c = 17.782 (6) Å | µ = 0.08 mm−1 |
β = 98.19 (3)° | T = 296 K |
V = 1136.9 (13) Å3 | Prism, colourless |
Z = 4 | 0.49 × 0.43 × 0.38 mm |
F(000) = 440 |
Data collection top
Rigaku AFC-5S diffractometer | Rint = 0.043 |
Radiation source: sealed tube | θmax = 25.2°, θmin = 2.0° |
Graphite monochromator | h = 0→13 |
ω scans | k = 0→6 |
2109 measured reflections | l = −21→20 |
2001 independent reflections | 3 standard reflections every 100 reflections |
981 reflections with I > 2σ(I) | intensity decay: −0.3% |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0747P)2 + 0.0629P] where P = (Fo2 + 2Fc2)/3 |
2001 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
O1 | −0.0753 (2) | 0.5733 (4) | 0.41839 (14) | 0.0854 (8) | |
C1 | 0.2326 (2) | 0.2426 (5) | 0.43818 (16) | 0.0592 (7) | |
C2 | 0.3244 (2) | 0.0839 (6) | 0.45510 (18) | 0.0666 (9) | |
C3 | 0.3341 (2) | −0.1050 (6) | 0.40848 (19) | 0.0707 (9) | |
C4 | 0.2529 (2) | −0.1404 (5) | 0.34437 (18) | 0.0616 (8) | |
C4a | 0.1596 (2) | 0.0179 (5) | 0.32713 (15) | 0.0484 (7) | |
C4b | 0.0617 (2) | 0.0272 (5) | 0.26332 (15) | 0.0516 (7) | |
C5 | 0.0321 (3) | −0.1187 (6) | 0.20109 (17) | 0.0695 (9) | |
C6 | −0.0669 (3) | −0.0666 (7) | 0.14903 (19) | 0.0833 (11) | |
C7 | −0.1356 (3) | 0.1277 (7) | 0.1581 (2) | 0.0848 (11) | |
C8 | −0.1075 (3) | 0.2762 (6) | 0.21952 (18) | 0.0714 (9) | |
C8a | −0.0075 (2) | 0.2243 (5) | 0.27152 (15) | 0.0520 (7) | |
C9 | 0.0418 (2) | 0.3560 (5) | 0.34278 (15) | 0.0529 (7) | |
C9a | 0.1500 (2) | 0.2089 (4) | 0.37388 (15) | 0.0471 (7) | |
C10 | −0.0491 (2) | 0.3829 (5) | 0.39785 (16) | 0.0549 (7) | |
C11 | −0.1065 (3) | 0.1687 (5) | 0.4228 (2) | 0.0787 (10) | |
H1 | 0.2263 | 0.3703 | 0.4696 | 0.071* | |
H2 | 0.3804 | 0.1045 | 0.4984 | 0.080* | |
H3 | 0.3968 | −0.2101 | 0.4207 | 0.085* | |
H4 | 0.2601 | −0.2679 | 0.3131 | 0.074* | |
H5 | 0.0785 | −0.2495 | 0.1947 | 0.083* | |
H6 | −0.0876 | −0.1634 | 0.1073 | 0.100* | |
H7 | −0.2022 | 0.1596 | 0.1223 | 0.102* | |
H8 | −0.1543 | 0.4065 | 0.2256 | 0.086* | |
H9 | 0.0690 | 0.5104 | 0.3289 | 0.063* | |
H11a | −0.1145 | 0.1819 | 0.4757 | 0.118* | |
H11b | −0.0576 | 0.0360 | 0.4154 | 0.118* | |
H11c | −0.1844 | 0.1499 | 0.3936 | 0.118* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0847 (16) | 0.0616 (15) | 0.111 (2) | 0.0168 (12) | 0.0192 (13) | −0.0204 (13) |
C1 | 0.0522 (15) | 0.0620 (18) | 0.0636 (18) | −0.0020 (14) | 0.0089 (14) | −0.0074 (16) |
C2 | 0.0440 (15) | 0.084 (2) | 0.069 (2) | 0.0035 (16) | 0.0007 (14) | 0.0016 (19) |
C3 | 0.0448 (16) | 0.077 (2) | 0.092 (2) | 0.0120 (16) | 0.0142 (17) | 0.007 (2) |
C4 | 0.0510 (15) | 0.0536 (17) | 0.085 (2) | 0.0035 (15) | 0.0253 (15) | −0.0064 (17) |
C4a | 0.0401 (13) | 0.0483 (15) | 0.0591 (15) | −0.0063 (12) | 0.0157 (12) | −0.0017 (14) |
C4b | 0.0483 (15) | 0.0531 (16) | 0.0555 (17) | −0.0133 (13) | 0.0148 (13) | −0.0047 (14) |
C5 | 0.0676 (19) | 0.075 (2) | 0.068 (2) | −0.0221 (17) | 0.0188 (16) | −0.0143 (18) |
C6 | 0.080 (2) | 0.105 (3) | 0.064 (2) | −0.035 (2) | 0.0062 (19) | −0.013 (2) |
C7 | 0.061 (2) | 0.119 (3) | 0.069 (2) | −0.025 (2) | −0.0055 (17) | 0.013 (2) |
C8 | 0.0575 (18) | 0.081 (2) | 0.073 (2) | −0.0030 (17) | 0.0011 (16) | 0.0119 (19) |
C8a | 0.0464 (14) | 0.0549 (17) | 0.0545 (16) | −0.0099 (13) | 0.0063 (13) | 0.0052 (14) |
C9 | 0.0494 (15) | 0.0388 (14) | 0.0703 (18) | 0.0005 (12) | 0.0080 (13) | 0.0036 (14) |
C9a | 0.0398 (14) | 0.0455 (15) | 0.0569 (16) | −0.0016 (11) | 0.0096 (12) | 0.0016 (13) |
C10 | 0.0454 (14) | 0.0515 (17) | 0.0647 (18) | 0.0086 (14) | −0.0022 (13) | −0.0056 (15) |
C11 | 0.068 (2) | 0.073 (2) | 0.101 (3) | 0.0048 (18) | 0.0351 (18) | 0.008 (2) |
Geometric parameters (Å, º) top
O1—C10 | 1.202 (3) | C9—C9a | 1.519 (3) |
C1—C2 | 1.378 (4) | C9—C10 | 1.521 (4) |
C1—C9a | 1.381 (4) | C10—C11 | 1.486 (4) |
C2—C3 | 1.379 (4) | C1—H1 | 0.9300 |
C3—C4 | 1.371 (4) | C2—H2 | 0.9300 |
C4—C4a | 1.389 (4) | C3—H3 | 0.9300 |
C4a—C9a | 1.389 (4) | C4—H4 | 0.9300 |
C4a—C4b | 1.466 (4) | C5—H5 | 0.9300 |
C4b—C5 | 1.390 (4) | C6—H6 | 0.9300 |
C4b—C8a | 1.393 (4) | C7—H7 | 0.9300 |
C5—C6 | 1.376 (4) | C8—H8 | 0.9300 |
C6—C7 | 1.380 (5) | C9—H9 | 0.9800 |
C7—C8 | 1.386 (4) | C11—H11a | 0.9600 |
C8—C8a | 1.383 (4) | C11—H11b | 0.9600 |
C8a—C9 | 1.512 (4) | C11—H11c | 0.9600 |
C2—C1—C9a | 118.9 (3) | C2—C1—H1 | 120.5 |
C1—C2—C3 | 120.6 (3) | C9a—C1—H1 | 120.5 |
C4—C3—C2 | 121.1 (3) | C1—C2—H2 | 119.7 |
C3—C4—C4a | 118.7 (3) | C3—C2—H2 | 119.7 |
C4—C4a—C9a | 120.4 (3) | C4—C3—H3 | 119.5 |
C4—C4a—C4b | 131.0 (3) | C2—C3—H3 | 119.5 |
C9a—C4a—C4b | 108.7 (2) | C3—C4—H4 | 120.7 |
C5—C4b—C8a | 119.9 (3) | C4a—C4—H4 | 120.7 |
C5—C4b—C4a | 131.5 (3) | C6—C5—H5 | 120.5 |
C8a—C4b—C4a | 108.6 (2) | C4b—C5—H5 | 120.5 |
C6—C5—C4b | 118.9 (3) | C5—C6—H6 | 119.6 |
C5—C6—C7 | 120.7 (3) | C7—C6—H6 | 119.6 |
C6—C7—C8 | 121.4 (3) | C6—C7—H7 | 119.3 |
C8a—C8—C7 | 117.8 (3) | C8—C7—H7 | 119.3 |
C8—C8a—C4b | 121.3 (3) | C8a—C8—H8 | 121.1 |
C8—C8a—C9 | 128.3 (3) | C7—C8—H8 | 121.1 |
C4b—C8a—C9 | 110.5 (2) | C8a—C9—H9 | 109.4 |
C8a—C9—C9a | 101.9 (2) | C9a—C9—H9 | 109.4 |
C8a—C9—C10 | 113.0 (2) | C10—C9—H9 | 109.4 |
C9a—C9—C10 | 113.5 (2) | C10—C11—H11a | 109.5 |
C1—C9a—C4a | 120.4 (2) | C10—C11—H11b | 109.5 |
C1—C9a—C9 | 129.3 (3) | H11a—C11—H11b | 109.5 |
C4a—C9a—C9 | 110.4 (2) | C10—C11—H11c | 109.5 |
O1—C10—C11 | 121.7 (3) | H11a—C11—H11c | 109.5 |
O1—C10—C9 | 120.3 (3) | H11b—C11—H11c | 109.5 |
C11—C10—C9 | 118.0 (2) | ||
C9a—C1—C2—C3 | 0.3 (4) | C4a—C4b—C8a—C9 | −0.4 (3) |
C1—C2—C3—C4 | −0.1 (4) | C8—C8a—C9—C9a | 179.5 (3) |
C2—C3—C4—C4a | −0.2 (4) | C4b—C8a—C9—C9a | 0.7 (3) |
C3—C4—C4a—C9a | 0.5 (4) | C8—C8a—C9—C10 | 57.3 (4) |
C3—C4—C4a—C4b | 179.3 (3) | C4b—C8a—C9—C10 | −121.5 (2) |
C4—C4a—C4b—C5 | 0.2 (5) | C2—C1—C9a—C4a | 0.0 (4) |
C9a—C4a—C4b—C5 | 179.1 (3) | C2—C1—C9a—C9 | −179.9 (3) |
C4—C4a—C4b—C8a | −179.0 (3) | C4—C4a—C9a—C1 | −0.3 (4) |
C9a—C4a—C4b—C8a | 0.0 (3) | C4b—C4a—C9a—C1 | −179.4 (2) |
C8a—C4b—C5—C6 | −0.9 (4) | C4—C4a—C9a—C9 | 179.6 (2) |
C4a—C4b—C5—C6 | 179.9 (3) | C4b—C4a—C9a—C9 | 0.5 (3) |
C4b—C5—C6—C7 | 0.2 (5) | C8a—C9—C9a—C1 | 179.2 (3) |
C5—C6—C7—C8 | 0.1 (5) | C10—C9—C9a—C1 | −59.0 (4) |
C6—C7—C8—C8a | 0.3 (5) | C8a—C9—C9a—C4a | −0.7 (3) |
C7—C8—C8a—C4b | −1.1 (4) | C10—C9—C9a—C4a | 121.1 (2) |
C7—C8—C8a—C9 | −179.7 (3) | C8a—C9—C10—O1 | −123.2 (3) |
C5—C4b—C8a—C8 | 1.4 (4) | C9a—C9—C10—O1 | 121.4 (3) |
C4a—C4b—C8a—C8 | −179.3 (2) | C8a—C9—C10—C11 | 54.7 (3) |
C5—C4b—C8a—C9 | −179.7 (2) | C9a—C9—C10—C11 | −60.7 (3) |