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Treatment of 9-fluorenyllithium with acetyl chloride produces 9-acetylfluorene, (I), and several by-products, among which is `diacetylfluorene', now characterized definitively as 9-(1-acetoxyethylidene)fluorene [IUPAC name: (1-fluoren-9-ylidene)ethyl acetate], (II), C17H14O2, derived from acetylation of initially formed (I). Various parameters disclose substantial structural distortion within (II) emanating from A(1,3) strain associated with the 9-(acetoxyethylidenyl)fluorene system.
Supporting information
CCDC reference: 163912
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); molecular graphics: ORTEP in TEXSAN (Johnson, 1965); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON (Spek, 2000).
9-(1-Acetoxyethylidene)fluorene
top
Crystal data top
C17H14O2 | Dx = 1.253 Mg m−3 |
Mr = 250.28 | Melting point = 353–353.5 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 9.8818 (17) Å | θ = 10.9–12.9° |
b = 27.375 (6) Å | µ = 0.08 mm−1 |
c = 9.8110 (12) Å | T = 296 K |
V = 2654.1 (8) Å3 | Ovoid, colorless |
Z = 8 | 0.43 × 0.35 × 0.23 mm |
F(000) = 1056 | |
Data collection top
Rigaku AFC-5S diffractometer | Rint = 0.061 |
Radiation source: sealed tube | θmax = 25.1°, θmin = 2.6° |
Graphite monochromator | h = 0→11 |
ω scans | k = 0→32 |
4542 measured reflections | l = −11→11 |
2350 independent reflections | 3 standard reflections every 100 reflections |
1029 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0455P)2] where P = (Fo2 + 2Fc2)/3 |
2350 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.68430 (16) | 0.12282 (6) | 0.24166 (17) | 0.0658 (5) | |
O2 | 0.83286 (19) | 0.07732 (7) | 0.1259 (2) | 0.0924 (7) | |
C1 | 0.6577 (2) | 0.07450 (9) | 0.5063 (3) | 0.0653 (7) | |
C2 | 0.6299 (3) | 0.04321 (10) | 0.6128 (3) | 0.0737 (8) | |
C3 | 0.7004 (3) | 0.04547 (11) | 0.7338 (3) | 0.0787 (8) | |
C4 | 0.8000 (3) | 0.08011 (10) | 0.7517 (3) | 0.0712 (8) | |
C4a | 0.8296 (2) | 0.11180 (9) | 0.6456 (3) | 0.0572 (6) | |
C4b | 0.9294 (2) | 0.15101 (9) | 0.6369 (3) | 0.0602 (7) | |
C5 | 1.0223 (3) | 0.16682 (10) | 0.7321 (3) | 0.0770 (8) | |
C6 | 1.1085 (3) | 0.20428 (12) | 0.6979 (4) | 0.0892 (10) | |
C7 | 1.1010 (3) | 0.22674 (11) | 0.5725 (4) | 0.0901 (10) | |
C8 | 1.0073 (3) | 0.21081 (10) | 0.4756 (3) | 0.0788 (8) | |
C8a | 0.9214 (2) | 0.17235 (9) | 0.5073 (3) | 0.0596 (6) | |
C9 | 0.8173 (2) | 0.14609 (9) | 0.4279 (3) | 0.0556 (6) | |
C9a | 0.7597 (2) | 0.10910 (8) | 0.5216 (2) | 0.0535 (6) | |
C10 | 0.7905 (2) | 0.15108 (9) | 0.2958 (3) | 0.0613 (7) | |
C11 | 0.7184 (3) | 0.08626 (10) | 0.1550 (3) | 0.0637 (7) | |
C12 | 0.5969 (3) | 0.05945 (11) | 0.1051 (3) | 0.0797 (9) | |
C13 | 0.8557 (3) | 0.18460 (10) | 0.1947 (3) | 0.0832 (9) | |
H1 | 0.6090 | 0.0725 | 0.4254 | 0.078* | |
H2 | 0.5618 | 0.0200 | 0.6027 | 0.088* | |
H3 | 0.6808 | 0.0236 | 0.8035 | 0.094* | |
H4 | 0.8467 | 0.0822 | 0.8338 | 0.085* | |
H5 | 1.0266 | 0.1524 | 0.8178 | 0.092* | |
H6 | 1.1729 | 0.2147 | 0.7606 | 0.107* | |
H7 | 1.1586 | 0.2526 | 0.5522 | 0.108* | |
H8 | 1.0025 | 0.2258 | 0.3907 | 0.095* | |
H12a | 0.5689 | 0.0728 | 0.0191 | 0.120* | |
H12b | 0.5248 | 0.0628 | 0.1700 | 0.120* | |
H12c | 0.6187 | 0.0255 | 0.0940 | 0.120* | |
H13a | 0.8446 | 0.2178 | 0.2240 | 0.125* | |
H13b | 0.8138 | 0.1804 | 0.1072 | 0.125* | |
H13c | 0.9503 | 0.1771 | 0.1881 | 0.125* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0504 (10) | 0.0840 (12) | 0.0629 (11) | 0.0096 (10) | −0.0043 (9) | −0.0072 (11) |
O2 | 0.0573 (11) | 0.1041 (15) | 0.1159 (17) | 0.0108 (12) | 0.0155 (12) | −0.0223 (13) |
C1 | 0.0557 (15) | 0.0813 (17) | 0.0588 (16) | −0.0014 (15) | 0.0021 (15) | −0.0072 (16) |
C2 | 0.0683 (18) | 0.0791 (19) | 0.074 (2) | −0.0133 (16) | 0.0112 (16) | −0.0079 (17) |
C3 | 0.085 (2) | 0.084 (2) | 0.0675 (19) | 0.0046 (19) | 0.0129 (17) | 0.0047 (17) |
C4 | 0.0710 (18) | 0.0829 (19) | 0.0595 (17) | 0.0134 (17) | −0.0059 (15) | −0.0061 (17) |
C4a | 0.0490 (14) | 0.0616 (16) | 0.0609 (16) | 0.0121 (13) | −0.0002 (14) | −0.0090 (14) |
C4b | 0.0478 (15) | 0.0622 (16) | 0.0707 (18) | 0.0139 (14) | −0.0039 (14) | −0.0188 (16) |
C5 | 0.0679 (18) | 0.0753 (19) | 0.088 (2) | 0.0108 (16) | −0.0140 (17) | −0.0187 (18) |
C6 | 0.070 (2) | 0.083 (2) | 0.114 (3) | 0.0040 (19) | −0.019 (2) | −0.037 (2) |
C7 | 0.068 (2) | 0.076 (2) | 0.126 (3) | −0.0135 (17) | 0.006 (2) | −0.028 (2) |
C8 | 0.0730 (18) | 0.0722 (18) | 0.091 (2) | −0.0062 (17) | 0.0079 (18) | −0.0153 (17) |
C8a | 0.0460 (14) | 0.0576 (15) | 0.0752 (19) | 0.0082 (13) | 0.0017 (15) | −0.0114 (15) |
C9 | 0.0439 (14) | 0.0623 (16) | 0.0607 (16) | 0.0101 (13) | 0.0025 (13) | −0.0069 (13) |
C9a | 0.0428 (13) | 0.0619 (15) | 0.0557 (15) | 0.0048 (14) | 0.0028 (13) | −0.0070 (13) |
C10 | 0.0472 (15) | 0.0640 (17) | 0.0726 (18) | 0.0066 (14) | 0.0014 (14) | −0.0037 (14) |
C11 | 0.0613 (18) | 0.0730 (19) | 0.0568 (15) | 0.0109 (15) | −0.0054 (15) | 0.0042 (15) |
C12 | 0.0633 (18) | 0.104 (2) | 0.0719 (19) | 0.0075 (17) | −0.0150 (15) | −0.0083 (16) |
C13 | 0.0814 (19) | 0.087 (2) | 0.081 (2) | 0.0013 (18) | −0.0035 (16) | 0.0187 (16) |
Geometric parameters (Å, º) top
O1—C11 | 1.356 (3) | C9—C9a | 1.481 (3) |
O1—C10 | 1.408 (3) | C10—C13 | 1.497 (3) |
O2—C11 | 1.192 (3) | C11—C12 | 1.490 (3) |
C1—C2 | 1.379 (3) | C1—H1 | 0.9300 |
C1—C9a | 1.391 (3) | C2—H2 | 0.9300 |
C2—C3 | 1.378 (4) | C3—H3 | 0.9300 |
C3—C4 | 1.377 (3) | C4—H4 | 0.9300 |
C4—C4a | 1.386 (3) | C5—H5 | 0.9300 |
C4a—C9a | 1.401 (3) | C6—H6 | 0.9300 |
C4a—C4b | 1.460 (3) | C7—H7 | 0.9300 |
C4b—C5 | 1.380 (3) | C8—H8 | 0.9300 |
C4b—C8a | 1.402 (3) | C12—H12a | 0.9600 |
C5—C6 | 1.374 (4) | C12—H12b | 0.9600 |
C6—C7 | 1.378 (4) | C12—H12c | 0.9600 |
C7—C8 | 1.396 (4) | C13—H13a | 0.9600 |
C8—C8a | 1.387 (3) | C13—H13b | 0.9600 |
C8a—C9 | 1.477 (3) | C13—H13c | 0.9600 |
C9—C10 | 1.330 (3) | | |
| | | |
C9—C10—O1 | 117.3 (2) | O1—C11—C12 | 111.7 (2) |
C9—C10—C13 | 128.6 (2) | C2—C1—H1 | 120.4 |
C8a—C9—C10 | 127.0 (2) | C9a—C1—H1 | 120.4 |
C9a—C9—C10 | 126.8 (2) | C3—C2—H2 | 119.2 |
O1—C10—C13 | 114.0 (2) | C1—C2—H2 | 119.2 |
C11—O1—C10 | 117.18 (19) | C4—C3—H3 | 119.9 |
C2—C1—C9a | 119.1 (3) | C2—C3—H3 | 119.9 |
C3—C2—C1 | 121.6 (3) | C3—C4—H4 | 120.5 |
C4—C3—C2 | 120.1 (3) | C4a—C4—H4 | 120.5 |
C3—C4—C4a | 119.1 (3) | C6—C5—H5 | 120.6 |
C4—C4a—C9a | 121.0 (2) | C4b—C5—H5 | 120.6 |
C4—C4a—C4b | 130.3 (3) | C5—C6—H6 | 119.4 |
C9a—C4a—C4b | 108.7 (2) | C7—C6—H6 | 119.4 |
C5—C4b—C8a | 121.4 (3) | C6—C7—H7 | 119.9 |
C5—C4b—C4a | 129.9 (3) | C8—C7—H7 | 119.9 |
C8a—C4b—C4a | 108.8 (2) | C8a—C8—H8 | 120.3 |
C6—C5—C4b | 118.8 (3) | C7—C8—H8 | 120.3 |
C5—C6—C7 | 121.2 (3) | C11—C12—H12a | 109.5 |
C6—C7—C8 | 120.3 (3) | C11—C12—H12b | 109.5 |
C8a—C8—C7 | 119.4 (3) | H12a—C12—H12b | 109.5 |
C8—C8a—C4b | 119.0 (3) | C11—C12—H12c | 109.5 |
C8—C8a—C9 | 132.7 (3) | H12a—C12—H12c | 109.5 |
C4b—C8a—C9 | 108.3 (2) | H12b—C12—H12c | 109.5 |
C8a—C9—C9a | 105.8 (2) | C10—C13—H13a | 109.5 |
C1—C9a—C4a | 119.1 (2) | C10—C13—H13b | 109.5 |
C1—C9a—C9 | 132.6 (2) | H13a—C13—H13b | 109.5 |
C4a—C9a—C9 | 108.3 (2) | C10—C13—H13c | 109.5 |
O2—C11—O1 | 122.5 (3) | H13a—C13—H13c | 109.5 |
O2—C11—C12 | 125.8 (3) | H13b—C13—H13c | 109.5 |
| | | |
C8a—C9—C10—C13 | −1.2 (4) | C6—C7—C8—C8a | 0.4 (4) |
C8a—C9—C10—O1 | −178.79 (19) | C7—C8—C8a—C4b | 1.1 (3) |
C9a—C9—C10—O1 | 8.9 (4) | C7—C8—C8a—C9 | −177.2 (2) |
C9a—C9—C10—C13 | −173.6 (2) | C5—C4b—C8a—C8 | −1.3 (3) |
C8—C8a—C9—C10 | 7.3 (4) | C4a—C4b—C8a—C8 | 179.9 (2) |
C1—C9a—C9—C10 | −7.7 (4) | C5—C4b—C8a—C9 | 177.4 (2) |
C10—C9—C9a—C4a | 171.0 (2) | C4a—C4b—C8a—C9 | −1.4 (2) |
C10—C9—C8a—C4b | −171.2 (2) | C8—C8a—C9—C9a | −179.1 (2) |
C9a—C1—C2—C3 | 0.1 (4) | C4b—C8a—C9—C9a | 2.4 (2) |
C1—C2—C3—C4 | 1.1 (4) | C2—C1—C9a—C4a | −1.2 (3) |
C2—C3—C4—C4a | −1.2 (4) | C2—C1—C9a—C9 | 177.4 (2) |
C3—C4—C4a—C9a | 0.1 (3) | C4—C4a—C9a—C1 | 1.1 (3) |
C3—C4—C4a—C4b | −179.4 (2) | C4b—C4a—C9a—C1 | −179.28 (19) |
C4—C4a—C4b—C5 | 0.7 (4) | C4—C4a—C9a—C9 | −177.9 (2) |
C9a—C4a—C4b—C5 | −179.0 (2) | C4b—C4a—C9a—C9 | 1.8 (2) |
C4—C4a—C4b—C8a | 179.4 (2) | C8a—C9—C9a—C1 | 178.7 (2) |
C9a—C4a—C4b—C8a | −0.2 (3) | C8a—C9—C9a—C4a | −2.6 (2) |
C8a—C4b—C5—C6 | 0.0 (4) | C11—O1—C10—C9 | −110.5 (2) |
C4a—C4b—C5—C6 | 178.6 (2) | C11—O1—C10—C13 | 71.6 (3) |
C4b—C5—C6—C7 | 1.5 (4) | C10—O1—C11—O2 | 1.0 (4) |
C5—C6—C7—C8 | −1.7 (4) | C10—O1—C11—C12 | −179.8 (2) |
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