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The title compound, C
30H
20F
2O
4, has been obtained as a by-product in the preparation of biindenylidene compounds. The molecule has a twofold axis. There are intramolecular O—H
O hydrogen bonds.
Supporting information
CCDC reference: 209590
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.054
- wR factor = 0.190
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for O2 - C10 = 15.48 su
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Compound (I) was obtained in trace amounts as a by-product in the treatment of 3,3'-bis(4-fluorophenyl)-[2,2']biindenyl-1,1'-dione with Zn–ZnCl2 in aqueous tetrahydrofuran to obtain 3,3'-bis(4-fluorophenyl)-3H,3'H-[2,2']biindenylidene-1,1'-dione (22% yield) and 3,1'-bis(4-fluorophenyl)-1'-hydroperoxy-3'-hydroxy-1',3'-dihydro-3H- [2,2']biindenyliden-1-one (7% yield; Tanaka et al., 2003). The reaction mechanism which gave (I) is expected to be similar to that reported by Xu et al. (2002). Colourless crystals of (I) were grown from an ethyl acetate solution by slow evaporation (m.p. 482–485 K).
The hydroxyl H atom was located from a difference synthesis and was allowed to ride on the parent atom. The other H atoms were positioned geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom).
Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C30H20F2O4 | Dx = 1.405 Mg m−3 |
Mr = 482.48 | Melting point = 482–485 K |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 20 reflections |
a = 8.303 (2) Å | θ = 13.0–14.5° |
b = 12.011 (3) Å | µ = 0.10 mm−1 |
c = 22.868 (6) Å | T = 298 K |
V = 2280.6 (10) Å3 | Plate, colourless |
Z = 4 | 0.5 × 0.4 × 0.3 mm |
F(000) = 1000 | |
Data collection top
Rigaku AFC-7R diffractometer | θmax = 27.5° |
ω scans | h = −4→10 |
3523 measured reflections | k = −15→6 |
2622 independent reflections | l = 0→29 |
1644 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.010 | intensity decay: 0.0% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.093P)2 + 1.0454P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.190 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.27 e Å−3 |
2622 reflections | Δρmin = −0.46 e Å−3 |
164 parameters | |
Crystal data top
C30H20F2O4 | V = 2280.6 (10) Å3 |
Mr = 482.48 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 8.303 (2) Å | µ = 0.10 mm−1 |
b = 12.011 (3) Å | T = 298 K |
c = 22.868 (6) Å | 0.5 × 0.4 × 0.3 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.010 |
3523 measured reflections | 3 standard reflections every 150 reflections |
2622 independent reflections | intensity decay: 0.0% |
1644 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 164 parameters |
wR(F2) = 0.190 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
2622 reflections | Δρmin = −0.46 e Å−3 |
Special details top
Refinement. Refinement using all reflection data. The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.4415 (3) | 0.0510 (2) | 0.89344 (7) | 0.0927 (7) | |
O2 | 0.5500 (3) | 0.1968 (2) | 0.6373 (1) | 0.0705 (6) | |
O3 | 0.0841 (3) | 0.1728 (2) | 0.55028 (9) | 0.0690 (6) | |
C4 | 0.4411 (4) | 0.0666 (3) | 0.8346 (1) | 0.0616 (8) | |
C5 | 0.5116 (4) | 0.1600 (3) | 0.8129 (1) | 0.0675 (9) | |
C6 | 0.5067 (4) | 0.1783 (2) | 0.7532 (1) | 0.0561 (7) | |
C7 | 0.4312 (3) | 0.1027 (2) | 0.7161 (1) | 0.0412 (5) | |
C8 | 0.3631 (3) | 0.0083 (2) | 0.7402 (1) | 0.0494 (6) | |
C9 | 0.3682 (4) | −0.0102 (3) | 0.8003 (1) | 0.0589 (7) | |
C10 | 0.4146 (3) | 0.1284 (2) | 0.6514 (1) | 0.0404 (5) | |
C11 | 0.2498 (3) | 0.1860 (2) | 0.6380 (1) | 0.0413 (5) | |
C12 | 0.1918 (3) | 0.1352 (2) | 0.5803 (1) | 0.0481 (6) | |
C13 | 0.2881 (3) | 0.0355 (2) | 0.5696 (1) | 0.0445 (6) | |
C14 | 0.2695 (4) | −0.0434 (2) | 0.5252 (1) | 0.0543 (7) | |
C15 | 0.3778 (4) | −0.1298 (2) | 0.5231 (1) | 0.0586 (7) | |
C16 | 0.5006 (4) | −0.1384 (2) | 0.5640 (1) | 0.0595 (7) | |
C17 | 0.5177 (4) | −0.0607 (2) | 0.6085 (1) | 0.0527 (7) | |
C18 | 0.4101 (3) | 0.0277 (2) | 0.6105 (1) | 0.0414 (5) | |
H2 | 0.5326 | 0.2298 | 0.6065 | 0.0705* | |
H5 | 0.5627 | 0.2116 | 0.8383 | 0.0819* | |
H6 | 0.5551 | 0.2435 | 0.7372 | 0.0672* | |
H8 | 0.3120 | −0.0445 | 0.7155 | 0.0594* | |
H9 | 0.3214 | −0.0753 | 0.8167 | 0.0708* | |
H11 | 0.1748 | 0.1712 | 0.6684 | 0.0502* | |
H14 | 0.1850 | −0.0375 | 0.4974 | 0.0659* | |
H15 | 0.3676 | −0.1848 | 0.4934 | 0.0704* | |
H16 | 0.5749 | −0.1985 | 0.5614 | 0.0720* | |
H17 | 0.6007 | −0.0676 | 0.6369 | 0.0635* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.098 (2) | 0.140 (2) | 0.0400 (9) | 0.019 (1) | −0.0071 (9) | 0.008 (1) |
O2 | 0.076 (1) | 0.065 (1) | 0.070 (1) | −0.009 (1) | 0.003 (1) | 0.001 (1) |
O3 | 0.091 (2) | 0.055 (1) | 0.061 (1) | 0.016 (1) | −0.032 (1) | −0.0066 (10) |
C4 | 0.063 (2) | 0.083 (2) | 0.038 (1) | 0.021 (2) | −0.005 (1) | −0.001 (1) |
C5 | 0.076 (2) | 0.074 (2) | 0.052 (2) | 0.005 (2) | −0.012 (2) | −0.020 (1) |
C6 | 0.072 (2) | 0.046 (1) | 0.050 (1) | −0.001 (1) | −0.005 (1) | −0.009 (1) |
C7 | 0.044 (1) | 0.038 (1) | 0.041 (1) | 0.007 (1) | −0.0024 (10) | −0.0026 (9) |
C8 | 0.057 (2) | 0.047 (1) | 0.044 (1) | 0.001 (1) | −0.004 (1) | 0.000 (1) |
C9 | 0.064 (2) | 0.062 (2) | 0.050 (1) | 0.007 (1) | 0.005 (1) | 0.012 (1) |
C10 | 0.047 (1) | 0.033 (1) | 0.041 (1) | −0.0015 (10) | 0.000 (1) | −0.0008 (9) |
C11 | 0.052 (1) | 0.033 (1) | 0.038 (1) | 0.000 (1) | −0.002 (1) | 0.0010 (9) |
C12 | 0.062 (2) | 0.037 (1) | 0.046 (1) | −0.003 (1) | −0.006 (1) | 0.000 (1) |
C13 | 0.059 (2) | 0.035 (1) | 0.040 (1) | −0.005 (1) | 0.003 (1) | −0.0014 (9) |
C14 | 0.070 (2) | 0.049 (1) | 0.045 (1) | −0.009 (1) | 0.000 (1) | −0.007 (1) |
C15 | 0.078 (2) | 0.045 (1) | 0.053 (1) | −0.010 (1) | 0.015 (1) | −0.013 (1) |
C16 | 0.071 (2) | 0.044 (1) | 0.064 (2) | 0.005 (1) | 0.020 (2) | −0.009 (1) |
C17 | 0.058 (2) | 0.045 (1) | 0.054 (1) | 0.004 (1) | 0.006 (1) | −0.003 (1) |
C18 | 0.051 (1) | 0.035 (1) | 0.039 (1) | −0.002 (1) | 0.005 (1) | −0.0007 (9) |
Geometric parameters (Å, º) top
F1—C4 | 1.359 (3) | C10—C18 | 1.529 (3) |
O2—C10 | 1.430 (3) | C11—C11i | 1.538 (4) |
O2—H2 | 0.820 | C11—C12 | 1.533 (3) |
O3—C12 | 1.214 (4) | C11—H11 | 0.950 |
C4—C5 | 1.358 (5) | C12—C13 | 1.461 (4) |
C4—C9 | 1.354 (4) | C13—C14 | 1.397 (4) |
C5—C6 | 1.384 (4) | C13—C18 | 1.382 (4) |
C5—H5 | 0.948 | C14—C15 | 1.373 (4) |
C6—C7 | 1.391 (4) | C14—H14 | 0.949 |
C6—H6 | 0.954 | C15—C16 | 1.388 (4) |
C7—C8 | 1.381 (4) | C15—H15 | 0.951 |
C7—C10 | 1.518 (3) | C16—C17 | 1.388 (4) |
C8—C9 | 1.393 (4) | C16—H16 | 0.951 |
C8—H8 | 0.949 | C17—C18 | 1.388 (4) |
C9—H9 | 0.951 | C17—H17 | 0.950 |
C10—C11 | 1.563 (4) | | |
| | | |
C10—O2—H2 | 109.5 | C10—C11—C12 | 105.5 (2) |
F1—C4—C5 | 118.3 (3) | C10—C11—H11 | 110.3 |
F1—C4—C9 | 118.7 (3) | C11i—C11—C12 | 113.5 (1) |
C5—C4—C9 | 123.0 (3) | C11i—C11—H11 | 100.9 |
C4—C5—C6 | 118.5 (3) | C12—C11—H11 | 110.5 |
C4—C5—H5 | 120.6 | O3—C12—C11 | 124.7 (2) |
C6—C5—H5 | 120.9 | O3—C12—C13 | 127.9 (2) |
C5—C6—C7 | 120.8 (3) | C11—C12—C13 | 107.3 (2) |
C5—C6—H6 | 119.8 | C12—C13—C14 | 128.1 (2) |
C7—C6—H6 | 119.5 | C12—C13—C18 | 110.1 (2) |
C6—C7—C8 | 118.5 (2) | C14—C13—C18 | 121.8 (2) |
C6—C7—C10 | 120.1 (2) | C13—C14—C15 | 117.8 (3) |
C8—C7—C10 | 121.2 (2) | C13—C14—H14 | 121.1 |
C7—C8—C9 | 120.8 (2) | C15—C14—H14 | 121.1 |
C7—C8—H8 | 119.7 | C14—C15—C16 | 120.9 (3) |
C9—C8—H8 | 119.6 | C14—C15—H15 | 119.4 |
C4—C9—C8 | 118.4 (3) | C16—C15—H15 | 119.7 |
C4—C9—H9 | 120.9 | C15—C16—C17 | 121.3 (3) |
C8—C9—H9 | 120.6 | C15—C16—H16 | 119.3 |
O2—C10—C7 | 105.4 (2) | C17—C16—H16 | 119.4 |
O2—C10—C11 | 113.0 (2) | C16—C17—C18 | 118.3 (3) |
O2—C10—C18 | 109.6 (2) | C16—C17—H17 | 121.0 |
C7—C10—C11 | 111.1 (2) | C18—C17—H17 | 120.7 |
C7—C10—C18 | 115.9 (2) | C10—C18—C13 | 112.2 (2) |
C11—C10—C18 | 102.1 (2) | C10—C18—C17 | 127.6 (2) |
C10—C11—C11i | 116.1 (3) | C13—C18—C17 | 120.0 (2) |
| | | |
C10—C11—C11i—C10i | −154.8 (3) | C10—C11—C11i—C12i | 82.6 (2) |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.99 | 2.766 (3) | 158 |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
Experimental details
Crystal data |
Chemical formula | C30H20F2O4 |
Mr | 482.48 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 298 |
a, b, c (Å) | 8.303 (2), 12.011 (3), 22.868 (6) |
V (Å3) | 2280.6 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3523, 2622, 1644 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.190, 1.03 |
No. of reflections | 2622 |
No. of parameters | 164 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.46 |
Selected geometric parameters (Å, º) topF1—C4 | 1.359 (3) | C11—C11i | 1.538 (4) |
O2—C10 | 1.430 (3) | C11—C12 | 1.533 (3) |
O3—C12 | 1.214 (4) | C12—C13 | 1.461 (4) |
C10—C11 | 1.563 (4) | C13—C18 | 1.382 (4) |
C10—C18 | 1.529 (3) | | |
| | | |
C10—C11—C11i—C10i | −154.8 (3) | C10—C11—C11i—C12i | 82.6 (2) |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.99 | 2.766 (3) | 158 |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
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Photochromism of the inclusion crystals of a hydroperoxybiindenylidene has been reported recently by Tanaka et al. (2003). The title compound, (I), was obtained as a by-product in the preparation of the biindenylidene compounds.
The molecule (I) has a twofold axis, which is parallel to c (Figs. 1 and 2). The central C11—C11i bond [symmetry code: (i) 1/2 − x, 1/2 − y, z] is a single bond (Table 1), which corresponds to no photochromic property of (I), since the photochromism of these crystals seems to be due to the biradical caused by breaking the π-bond at the center of the biindenylidene moiety (Ohba et al., 2003). The indene ring is not planar, as the five-membered ring has an envelope conformation, with atom C11 in the flap position. The angle between the planes composed of atoms C12–C18/C10 and C10–C12 is 14.45 (4)°. The best planes of the two symmetry-related indene rings are twisted by 74.18 (7)°. The angle between the two C—Ph(4-fluorophenyl) bond directions is 25.8 (1)°, and the dihedral angle between the two fluorophenyl rings is 12.15 (10)°. However, the shortest interatomic distance, between the fluorophenyl rings, is 4.597 (6) Å for C6···C6i, and there is no intramolecular π–π interaction.
There are intramolecular O2—H2···O3i hydrogen bonds (Table 2), but no intermolecular hydrogen bonds. This situation contrasts with the crystal structure of the hydroperoxybiindenylidene compound, which forms a ladder structure through the O—H···O intermolecular hydrogen bond to accommodate several guest molecules (Tanaka et al., 2003).