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The title compound, C30H20F2O4, 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016994/lh6094sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016994/lh6094Isup2.hkl
Contains datablock I

CCDC reference: 209590

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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 ππ 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).

Experimental top

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).

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I), showing 50% displacement ellipsoids for non-H atoms. [Symmetry code: (*) 1/2 − x, 1/2 − y, z.]
[Figure 2] Fig. 2. The crystal structure of (I), projected along a. H atoms have been omitted for clarity.
(I) top
Crystal data top
C30H20F2O4Dx = 1.405 Mg m3
Mr = 482.48Melting point = 482–485 K
Orthorhombic, PccnMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ab 2acCell parameters from 20 reflections
a = 8.303 (2) Åθ = 13.0–14.5°
b = 12.011 (3) ŵ = 0.10 mm1
c = 22.868 (6) ÅT = 298 K
V = 2280.6 (10) Å3Plate, colourless
Z = 40.5 × 0.4 × 0.3 mm
F(000) = 1000
Data collection top
Rigaku AFC-7R
diffractometer
θmax = 27.5°
ω scansh = 410
3523 measured reflectionsk = 156
2622 independent reflectionsl = 029
1644 reflections with I > 2σ(I)3 standard reflections every 150 reflections
Rint = 0.010 intensity decay: 0.0%
Refinement top
Refinement on F2H-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 = 1.03Δρmax = 0.27 e Å3
2622 reflectionsΔρmin = 0.46 e Å3
164 parameters
Crystal data top
C30H20F2O4V = 2280.6 (10) Å3
Mr = 482.48Z = 4
Orthorhombic, PccnMo Kα radiation
a = 8.303 (2) ŵ = 0.10 mm1
b = 12.011 (3) ÅT = 298 K
c = 22.868 (6) Å0.5 × 0.4 × 0.3 mm
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.010
3523 measured reflections3 standard reflections every 150 reflections
2622 independent reflections intensity decay: 0.0%
1644 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.054164 parameters
wR(F2) = 0.190H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
2622 reflectionsΔρmin = 0.46 e Å3
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
xyzUiso*/Ueq
F10.4415 (3)0.0510 (2)0.89344 (7)0.0927 (7)
O20.5500 (3)0.1968 (2)0.6373 (1)0.0705 (6)
O30.0841 (3)0.1728 (2)0.55028 (9)0.0690 (6)
C40.4411 (4)0.0666 (3)0.8346 (1)0.0616 (8)
C50.5116 (4)0.1600 (3)0.8129 (1)0.0675 (9)
C60.5067 (4)0.1783 (2)0.7532 (1)0.0561 (7)
C70.4312 (3)0.1027 (2)0.7161 (1)0.0412 (5)
C80.3631 (3)0.0083 (2)0.7402 (1)0.0494 (6)
C90.3682 (4)0.0102 (3)0.8003 (1)0.0589 (7)
C100.4146 (3)0.1284 (2)0.6514 (1)0.0404 (5)
C110.2498 (3)0.1860 (2)0.6380 (1)0.0413 (5)
C120.1918 (3)0.1352 (2)0.5803 (1)0.0481 (6)
C130.2881 (3)0.0355 (2)0.5696 (1)0.0445 (6)
C140.2695 (4)0.0434 (2)0.5252 (1)0.0543 (7)
C150.3778 (4)0.1298 (2)0.5231 (1)0.0586 (7)
C160.5006 (4)0.1384 (2)0.5640 (1)0.0595 (7)
C170.5177 (4)0.0607 (2)0.6085 (1)0.0527 (7)
C180.4101 (3)0.0277 (2)0.6105 (1)0.0414 (5)
H20.53260.22980.60650.0705*
H50.56270.21160.83830.0819*
H60.55510.24350.73720.0672*
H80.31200.04450.71550.0594*
H90.32140.07530.81670.0708*
H110.17480.17120.66840.0502*
H140.18500.03750.49740.0659*
H150.36760.18480.49340.0704*
H160.57490.19850.56140.0720*
H170.60070.06760.63690.0635*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.098 (2)0.140 (2)0.0400 (9)0.019 (1)0.0071 (9)0.008 (1)
O20.076 (1)0.065 (1)0.070 (1)0.009 (1)0.003 (1)0.001 (1)
O30.091 (2)0.055 (1)0.061 (1)0.016 (1)0.032 (1)0.0066 (10)
C40.063 (2)0.083 (2)0.038 (1)0.021 (2)0.005 (1)0.001 (1)
C50.076 (2)0.074 (2)0.052 (2)0.005 (2)0.012 (2)0.020 (1)
C60.072 (2)0.046 (1)0.050 (1)0.001 (1)0.005 (1)0.009 (1)
C70.044 (1)0.038 (1)0.041 (1)0.007 (1)0.0024 (10)0.0026 (9)
C80.057 (2)0.047 (1)0.044 (1)0.001 (1)0.004 (1)0.000 (1)
C90.064 (2)0.062 (2)0.050 (1)0.007 (1)0.005 (1)0.012 (1)
C100.047 (1)0.033 (1)0.041 (1)0.0015 (10)0.000 (1)0.0008 (9)
C110.052 (1)0.033 (1)0.038 (1)0.000 (1)0.002 (1)0.0010 (9)
C120.062 (2)0.037 (1)0.046 (1)0.003 (1)0.006 (1)0.000 (1)
C130.059 (2)0.035 (1)0.040 (1)0.005 (1)0.003 (1)0.0014 (9)
C140.070 (2)0.049 (1)0.045 (1)0.009 (1)0.000 (1)0.007 (1)
C150.078 (2)0.045 (1)0.053 (1)0.010 (1)0.015 (1)0.013 (1)
C160.071 (2)0.044 (1)0.064 (2)0.005 (1)0.020 (2)0.009 (1)
C170.058 (2)0.045 (1)0.054 (1)0.004 (1)0.006 (1)0.003 (1)
C180.051 (1)0.035 (1)0.039 (1)0.002 (1)0.005 (1)0.0007 (9)
Geometric parameters (Å, º) top
F1—C41.359 (3)C10—C181.529 (3)
O2—C101.430 (3)C11—C11i1.538 (4)
O2—H20.820C11—C121.533 (3)
O3—C121.214 (4)C11—H110.950
C4—C51.358 (5)C12—C131.461 (4)
C4—C91.354 (4)C13—C141.397 (4)
C5—C61.384 (4)C13—C181.382 (4)
C5—H50.948C14—C151.373 (4)
C6—C71.391 (4)C14—H140.949
C6—H60.954C15—C161.388 (4)
C7—C81.381 (4)C15—H150.951
C7—C101.518 (3)C16—C171.388 (4)
C8—C91.393 (4)C16—H160.951
C8—H80.949C17—C181.388 (4)
C9—H90.951C17—H170.950
C10—C111.563 (4)
C10—O2—H2109.5C10—C11—C12105.5 (2)
F1—C4—C5118.3 (3)C10—C11—H11110.3
F1—C4—C9118.7 (3)C11i—C11—C12113.5 (1)
C5—C4—C9123.0 (3)C11i—C11—H11100.9
C4—C5—C6118.5 (3)C12—C11—H11110.5
C4—C5—H5120.6O3—C12—C11124.7 (2)
C6—C5—H5120.9O3—C12—C13127.9 (2)
C5—C6—C7120.8 (3)C11—C12—C13107.3 (2)
C5—C6—H6119.8C12—C13—C14128.1 (2)
C7—C6—H6119.5C12—C13—C18110.1 (2)
C6—C7—C8118.5 (2)C14—C13—C18121.8 (2)
C6—C7—C10120.1 (2)C13—C14—C15117.8 (3)
C8—C7—C10121.2 (2)C13—C14—H14121.1
C7—C8—C9120.8 (2)C15—C14—H14121.1
C7—C8—H8119.7C14—C15—C16120.9 (3)
C9—C8—H8119.6C14—C15—H15119.4
C4—C9—C8118.4 (3)C16—C15—H15119.7
C4—C9—H9120.9C15—C16—C17121.3 (3)
C8—C9—H9120.6C15—C16—H16119.3
O2—C10—C7105.4 (2)C17—C16—H16119.4
O2—C10—C11113.0 (2)C16—C17—C18118.3 (3)
O2—C10—C18109.6 (2)C16—C17—H17121.0
C7—C10—C11111.1 (2)C18—C17—H17120.7
C7—C10—C18115.9 (2)C10—C18—C13112.2 (2)
C11—C10—C18102.1 (2)C10—C18—C17127.6 (2)
C10—C11—C11i116.1 (3)C13—C18—C17120.0 (2)
C10—C11—C11i—C10i154.8 (3)C10—C11—C11i—C12i82.6 (2)
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.821.992.766 (3)158
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC30H20F2O4
Mr482.48
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)298
a, b, c (Å)8.303 (2), 12.011 (3), 22.868 (6)
V3)2280.6 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.5 × 0.4 × 0.3
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3523, 2622, 1644
Rint0.010
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.190, 1.03
No. of reflections2622
No. of parameters164
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.46

Computer programs: WinAFC Diffractometer Control Software (Rigaku, 1999), WinAFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 2001), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.

Selected geometric parameters (Å, º) top
F1—C41.359 (3)C11—C11i1.538 (4)
O2—C101.430 (3)C11—C121.533 (3)
O3—C121.214 (4)C12—C131.461 (4)
C10—C111.563 (4)C13—C181.382 (4)
C10—C181.529 (3)
C10—C11—C11i—C10i154.8 (3)C10—C11—C11i—C12i82.6 (2)
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.821.992.766 (3)158
Symmetry code: (i) x+1/2, y+1/2, z.
 

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