9-(1-Acetoxy­ethyl­idene)­fluorene (`diacetyl­fluorene'), a by-product from the acetyl­ation of 9-fluorenyl­lithium

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.

Computing details

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

Crystal data

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) Å^3	Ovoid, colorless
Z = 8	0.43 × 0.35 × 0.23 mm
F(000) = 1056

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0455P)^2] where P = (Fo^2 + 2Fc^2)/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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)