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Acta Cryst. (2008). E64, o2282    [ doi:10.1107/S1600536808035733 ]

1-(3,4-Dihydroxyphenyl)-2-(4-fluorophenyl)ethanone

X.-Q. Song

Abstract top

In the title compound, C14H11FO3, the dihedral angle between the aromatic rings is 69.11 (8)°. An intramolecular O-H...O hydrogen bond is present. Intermolecular O-H...O interactions help to establish the packing.

Comment top

Doxybenzion derivatives play an important role in organic chemistry (Li et al., 2007; Li et al., 2008). In the title compound, (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the least-squares planes of the two benzene rings is 69.11 (8) °. In the crystal, O—H···O hydrogen bonds (Table 1) help to establish the packing.

Related literature top

For bond-length data, see: Allen et al. (1987). For background on deoxybenzoins, see: Li et al. (2007, 2008).

Experimental top

Pyrocatechol (0.050 mol) and 2-(4-fluorophenyl)acetic acid (0.050 mol) were dissolved into freshly distilled BF3Et2O under argon. The mixture was stirred at room temperature and then poured in an ice bath. The resulting mixture was extracted with ethyl acetate, and the organic layer was washed with aq. dried (Na2S1O4), and evaporated. The white deposits precipitated were separated from the solvents by filtration. They were washed with aqueous saturated Na1H1C1O3 twice. The solid was dissolved in acetone (15 ml) and stirred for about 10 min to give a clear solution. After keeping the solution in air for 10 d, colorless blocks of (I) were formed at the bottom of the vesssl on slow evaporation of the solvent.They were collected, washed three times with acetone and dried in a vacuum desiccator using CaCl2. The compound was isolated in 90% yield.

Refinement top

All the H atoms were positioned geometrically (C—H = 0.93–0.96 Å, O—H = 0.82Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
1-(3,4-Dihydroxyphenyl)-2-(4-fluorophenyl)ethanone top
Crystal data top
C14H11FO3F(000) = 512
Mr = 246.23Dx = 1.408 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.1640 (16) Åθ = 9–12°
b = 5.9120 (12) ŵ = 0.11 mm−1
c = 24.946 (6) ÅT = 293 K
β = 105.33 (3)°Block, colorless
V = 1161.2 (4) Å30.28 × 0.25 × 0.17 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		2072 independent reflections
Radiation source: fine-focus sealed tube1452 reflections with I > 2σ(I)
graphiteRint = 0.030
ω/2θ scansθmax = 25.2°, θmin = 1.7°
Absorption correction: ψ scan
(North et al., 1968)		h = −9→0
Tmin = 0.970, Tmax = 0.982k = −7→0
2229 measured reflectionsl = −28→29
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.145 w = 1/[σ2(Fo2) + (0.0627P)2 + 0.5485P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2072 reflectionsΔρmax = 0.18 e Å−3
164 parametersΔρmin = −0.17 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.019 (3)
Crystal data top
C14H11FO3V = 1161.2 (4) Å3
Mr = 246.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1640 (16) ŵ = 0.11 mm−1
b = 5.9120 (12) ÅT = 293 K
c = 24.946 (6) Å0.28 × 0.25 × 0.17 mm
β = 105.33 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1452 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.030
Tmin = 0.970, Tmax = 0.982θmax = 25.2°
2229 measured reflectionsStandard reflections: 0
2072 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.145Δρmax = 0.18 e Å−3
S = 1.04Δρmin = −0.17 e Å−3
2072 reflectionsAbsolute structure: ?
164 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5159 (3)0.4835 (4)0.08518 (10)0.0502 (6)
C20.4714 (3)0.2980 (4)0.04986 (10)0.0536 (7)
H2A0.55440.22290.03740.064*
C30.3067 (3)0.2257 (4)0.03341 (11)0.0533 (6)
C40.1810 (3)0.3396 (4)0.05140 (10)0.0496 (6)
C50.2243 (3)0.5232 (5)0.08571 (11)0.0609 (7)
H5A0.14060.59900.09770.073*
C60.3901 (3)0.5969 (5)0.10269 (12)0.0622 (8)
H6A0.41770.72240.12580.075*
C70.6960 (3)0.5566 (4)0.10307 (10)0.0502 (6)
C80.7428 (3)0.7480 (5)0.14453 (12)0.0636 (8)
H8A0.69230.88620.12660.076*
H8B0.69230.71790.17490.076*
C90.9297 (3)0.7876 (4)0.16843 (10)0.0496 (6)
C101.0273 (3)0.6323 (4)0.20441 (11)0.0543 (7)
H10A0.97680.50080.21290.065*
C111.1974 (3)0.6678 (5)0.22796 (12)0.0614 (7)
H11A1.26200.56200.25220.074*
C121.2691 (3)0.8598 (5)0.21518 (13)0.0640 (8)
C131.1793 (4)1.0184 (5)0.17977 (13)0.0693 (8)
H13A1.23171.14860.17150.083*
C141.0083 (4)0.9806 (5)0.15645 (12)0.0624 (7)
H14A0.94501.08720.13220.075*
F11.4375 (2)0.8958 (4)0.23816 (10)0.1039 (7)
O10.2648 (2)0.0477 (4)−0.00250 (10)0.0813 (7)
H1A0.1726−0.0035−0.00120.122*
O20.0199 (2)0.2558 (3)0.03311 (8)0.0615 (5)
H2B−0.04210.31990.04930.092*
O30.8048 (2)0.4626 (3)0.08579 (8)0.0650 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0430 (13)0.0574 (15)0.0503 (14)0.0101 (11)0.0126 (10)−0.0043 (12)
C20.0470 (14)0.0553 (15)0.0637 (16)0.0095 (12)0.0240 (12)−0.0087 (13)
C30.0513 (14)0.0511 (15)0.0610 (15)0.0044 (12)0.0208 (12)−0.0110 (13)
C40.0426 (13)0.0552 (15)0.0528 (14)0.0084 (11)0.0157 (11)0.0012 (12)
C50.0429 (14)0.0747 (19)0.0676 (17)0.0135 (13)0.0190 (12)−0.0202 (15)
C60.0477 (14)0.0707 (18)0.0689 (17)0.0087 (13)0.0169 (12)−0.0199 (15)
C70.0424 (12)0.0580 (16)0.0503 (14)0.0099 (12)0.0127 (11)−0.0033 (12)
C80.0495 (14)0.0680 (18)0.0720 (18)0.0114 (13)0.0139 (13)−0.0164 (15)
C90.0475 (13)0.0477 (14)0.0550 (15)0.0049 (11)0.0163 (11)−0.0086 (12)
C100.0524 (14)0.0447 (14)0.0690 (17)−0.0029 (12)0.0216 (12)0.0032 (13)
C110.0513 (15)0.0593 (17)0.0721 (18)0.0063 (13)0.0137 (13)0.0068 (14)
C120.0458 (14)0.0609 (17)0.087 (2)−0.0100 (13)0.0207 (14)−0.0153 (16)
C130.075 (2)0.0485 (16)0.093 (2)−0.0114 (15)0.0380 (17)−0.0034 (16)
C140.0721 (18)0.0514 (16)0.0657 (18)0.0113 (14)0.0216 (14)0.0065 (14)
F10.0526 (10)0.0961 (14)0.157 (2)−0.0212 (10)0.0171 (11)−0.0227 (14)
O10.0564 (11)0.0761 (14)0.1190 (18)−0.0081 (10)0.0364 (11)−0.0460 (13)
O20.0454 (9)0.0655 (12)0.0780 (12)0.0031 (9)0.0241 (8)−0.0133 (10)
O30.0458 (10)0.0736 (13)0.0791 (13)0.0107 (9)0.0226 (9)−0.0201 (10)
Geometric parameters (Å, °) top
C1—C61.391 (3)C8—H8A0.9700
C1—C21.393 (3)C8—H8B0.9700
C1—C71.483 (3)C9—C141.380 (4)
C2—C31.366 (3)C9—C101.380 (3)
C2—H2A0.9300C10—C111.374 (3)
C3—O11.365 (3)C10—H10A0.9300
C3—C41.397 (3)C11—C121.354 (4)
C4—O21.366 (3)C11—H11A0.9300
C4—C51.369 (4)C12—F11.359 (3)
C5—C61.378 (3)C12—C131.362 (4)
C5—H5A0.9300C13—C141.381 (4)
C6—H6A0.9300C13—H13A0.9300
C7—O31.219 (3)C14—H14A0.9300
C7—C81.512 (4)O1—H1A0.8200
C8—C91.503 (3)O2—H2B0.8200
C6—C1—C2119.2 (2)C9—C8—H8B108.3
C6—C1—C7121.4 (2)C7—C8—H8B108.3
C2—C1—C7119.4 (2)H8A—C8—H8B107.4
C3—C2—C1120.5 (2)C14—C9—C10118.0 (2)
C3—C2—H2A119.8C14—C9—C8121.6 (2)
C1—C2—H2A119.8C10—C9—C8120.3 (2)
O1—C3—C2119.6 (2)C11—C10—C9121.4 (2)
O1—C3—C4120.3 (2)C11—C10—H10A119.3
C2—C3—C4120.1 (2)C9—C10—H10A119.3
O2—C4—C5124.3 (2)C12—C11—C10118.6 (3)
O2—C4—C3116.2 (2)C12—C11—H11A120.7
C5—C4—C3119.5 (2)C10—C11—H11A120.7
C4—C5—C6120.9 (2)C11—C12—F1119.0 (3)
C4—C5—H5A119.6C11—C12—C13122.6 (3)
C6—C5—H5A119.6F1—C12—C13118.5 (3)
C5—C6—C1119.9 (3)C12—C13—C14118.2 (3)
C5—C6—H6A120.1C12—C13—H13A120.9
C1—C6—H6A120.1C14—C13—H13A120.9
O3—C7—C1121.2 (2)C9—C14—C13121.2 (3)
O3—C7—C8120.5 (2)C9—C14—H14A119.4
C1—C7—C8118.3 (2)C13—C14—H14A119.4
C9—C8—C7115.7 (2)C3—O1—H1A109.5
C9—C8—H8A108.3C4—O2—H2B109.5
C7—C8—H8A108.3
C6—C1—C2—C3−1.2 (4)C2—C1—C7—C8−175.8 (2)
C7—C1—C2—C3179.1 (2)O3—C7—C8—C9−8.8 (4)
C1—C2—C3—O1178.1 (2)C1—C7—C8—C9169.9 (2)
C1—C2—C3—C40.9 (4)C7—C8—C9—C14112.3 (3)
O1—C3—C4—O22.9 (4)C7—C8—C9—C10−69.3 (3)
C2—C3—C4—O2−179.9 (2)C14—C9—C10—C110.3 (4)
O1—C3—C4—C5−177.5 (3)C8—C9—C10—C11−178.2 (2)
C2—C3—C4—C5−0.3 (4)C9—C10—C11—C12−0.1 (4)
O2—C4—C5—C6179.6 (3)C10—C11—C12—F1−179.8 (3)
C3—C4—C5—C60.0 (4)C10—C11—C12—C13−0.3 (4)
C4—C5—C6—C1−0.4 (4)C11—C12—C13—C140.3 (5)
C2—C1—C6—C51.0 (4)F1—C12—C13—C14179.9 (3)
C7—C1—C6—C5−179.4 (3)C10—C9—C14—C13−0.2 (4)
C6—C1—C7—O3−176.9 (3)C8—C9—C14—C13178.3 (2)
C2—C1—C7—O32.8 (4)C12—C13—C14—C9−0.1 (4)
C6—C1—C7—C84.5 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.822.282.690 (2)111
O1—H1A···O2i0.822.162.876 (3)146
O2—H2B···O3ii0.821.922.744 (2)178
Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.822.282.690 (2)111
O1—H1A···O2i0.822.162.876 (3)146
O2—H2B···O3ii0.821.922.744 (2)178
Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Li, H.-Q., Xu, C., Li, H.-S., Xiao, Z.-P., Shi, L. & Zhu, H.-L. (2007). ChemMedChem, 2, 1361–1369.

Li, H.-Q., Xue, J.-Y., Shi, L., Gui, S.-Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, 662–667.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.