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

Song, X.-Q.

doi:10.1107/S1600536808035733

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2282

doi:10.1107/S1600536808035733

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

Xiao-Qing Song ^a ^*

^aSchool of Chemical and Material Engineering, Jiangnan University, Lihu Road No. 1800 Wuxi, Wuxi 214122, People's Republic of China
^*Correspondence e-mail: owengoal13@163.com

(Received 28 October 2008; accepted 31 October 2008; online 8 November 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₄H₁₁FO₃
M_r = 246.23
Monoclinic, P 2₁ /c
a = 8.1640 (16) Å
b = 5.9120 (12) Å
c = 24.946 (6) Å
β = 105.33 (3)°
V = 1161.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.28 × 0.25 × 0.17 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.970, T_max = 0.982
2229 measured reflections
2072 independent reflections
1452 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.145
S = 1.04
2072 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82	2.28	2.690 (2)	111
O1—H1A⋯O2ⁱ	0.82	2.16	2.876 (3)	146
O2—H2B⋯O3ⁱⁱ	0.82	1.92	2.744 (2)	178
Symmetry codes: (i) -x, -y, -z; (ii) x-1, y, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035733/hb2831sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035733/hb2831Isup2.hkl

checkCIF report

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.

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

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

C₁₄H₁₁FO₃	F(000) = 512
M_r = 246.23	D_x = 1.408 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.1640 (16) Å	θ = 9–12°
b = 5.9120 (12) Å	µ = 0.11 mm⁻¹
c = 24.946 (6) Å	T = 293 K
β = 105.33 (3)°	Block, colorless
V = 1161.2 (4) Å³	0.28 × 0.25 × 0.17 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2072 independent reflections
Radiation source: fine-focus sealed tube	1452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω/2θ scans	θ_max = 25.2°, θ_min = 1.7°
Absorption correction: ψ scan (North et al., 1968)	h = −9→0
T_min = 0.970, T_max = 0.982	k = −7→0
2229 measured reflections	l = −28→29

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.0627P)² + 0.5485P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2072 reflections	Δρ_max = 0.18 e Å⁻³
164 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.019 (3)

Crystal data top

C₁₄H₁₁FO₃	V = 1161.2 (4) Å³
M_r = 246.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1640 (16) Å	µ = 0.11 mm⁻¹
b = 5.9120 (12) Å	T = 293 K
c = 24.946 (6) Å	0.28 × 0.25 × 0.17 mm
β = 105.33 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2072 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1452 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.982	R_int = 0.030
2229 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
2072 reflections	Δρ_min = −0.17 e Å⁻³
164 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.5159 (3)	0.4835 (4)	0.08518 (10)	0.0502 (6)
C2	0.4714 (3)	0.2980 (4)	0.04986 (10)	0.0536 (7)
H2A	0.5544	0.2229	0.0374	0.064*
C3	0.3067 (3)	0.2257 (4)	0.03341 (11)	0.0533 (6)
C4	0.1810 (3)	0.3396 (4)	0.05140 (10)	0.0496 (6)
C5	0.2243 (3)	0.5232 (5)	0.08571 (11)	0.0609 (7)
H5A	0.1406	0.5990	0.0977	0.073*
C6	0.3901 (3)	0.5969 (5)	0.10269 (12)	0.0622 (8)
H6A	0.4177	0.7224	0.1258	0.075*
C7	0.6960 (3)	0.5566 (4)	0.10307 (10)	0.0502 (6)
C8	0.7428 (3)	0.7480 (5)	0.14453 (12)	0.0636 (8)
H8A	0.6923	0.8862	0.1266	0.076*
H8B	0.6923	0.7179	0.1749	0.076*
C9	0.9297 (3)	0.7876 (4)	0.16843 (10)	0.0496 (6)
C10	1.0273 (3)	0.6323 (4)	0.20441 (11)	0.0543 (7)
H10A	0.9768	0.5008	0.2129	0.065*
C11	1.1974 (3)	0.6678 (5)	0.22796 (12)	0.0614 (7)
H11A	1.2620	0.5620	0.2522	0.074*
C12	1.2691 (3)	0.8598 (5)	0.21518 (13)	0.0640 (8)
C13	1.1793 (4)	1.0184 (5)	0.17977 (13)	0.0693 (8)
H13A	1.2317	1.1486	0.1715	0.083*
C14	1.0083 (4)	0.9806 (5)	0.15645 (12)	0.0624 (7)
H14A	0.9450	1.0872	0.1322	0.075*
F1	1.4375 (2)	0.8958 (4)	0.23816 (10)	0.1039 (7)
O1	0.2648 (2)	0.0477 (4)	−0.00250 (10)	0.0813 (7)
H1A	0.1726	−0.0035	−0.0012	0.122*
O2	0.0199 (2)	0.2558 (3)	0.03311 (8)	0.0615 (5)
H2B	−0.0421	0.3199	0.0493	0.092*
O3	0.8048 (2)	0.4626 (3)	0.08579 (8)	0.0650 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0430 (13)	0.0574 (15)	0.0503 (14)	0.0101 (11)	0.0126 (10)	−0.0043 (12)
C2	0.0470 (14)	0.0553 (15)	0.0637 (16)	0.0095 (12)	0.0240 (12)	−0.0087 (13)
C3	0.0513 (14)	0.0511 (15)	0.0610 (15)	0.0044 (12)	0.0208 (12)	−0.0110 (13)
C4	0.0426 (13)	0.0552 (15)	0.0528 (14)	0.0084 (11)	0.0157 (11)	0.0012 (12)
C5	0.0429 (14)	0.0747 (19)	0.0676 (17)	0.0135 (13)	0.0190 (12)	−0.0202 (15)
C6	0.0477 (14)	0.0707 (18)	0.0689 (17)	0.0087 (13)	0.0169 (12)	−0.0199 (15)
C7	0.0424 (12)	0.0580 (16)	0.0503 (14)	0.0099 (12)	0.0127 (11)	−0.0033 (12)
C8	0.0495 (14)	0.0680 (18)	0.0720 (18)	0.0114 (13)	0.0139 (13)	−0.0164 (15)
C9	0.0475 (13)	0.0477 (14)	0.0550 (15)	0.0049 (11)	0.0163 (11)	−0.0086 (12)
C10	0.0524 (14)	0.0447 (14)	0.0690 (17)	−0.0029 (12)	0.0216 (12)	0.0032 (13)
C11	0.0513 (15)	0.0593 (17)	0.0721 (18)	0.0063 (13)	0.0137 (13)	0.0068 (14)
C12	0.0458 (14)	0.0609 (17)	0.087 (2)	−0.0100 (13)	0.0207 (14)	−0.0153 (16)
C13	0.075 (2)	0.0485 (16)	0.093 (2)	−0.0114 (15)	0.0380 (17)	−0.0034 (16)
C14	0.0721 (18)	0.0514 (16)	0.0657 (18)	0.0113 (14)	0.0216 (14)	0.0065 (14)
F1	0.0526 (10)	0.0961 (14)	0.157 (2)	−0.0212 (10)	0.0171 (11)	−0.0227 (14)
O1	0.0564 (11)	0.0761 (14)	0.1190 (18)	−0.0081 (10)	0.0364 (11)	−0.0460 (13)
O2	0.0454 (9)	0.0655 (12)	0.0780 (12)	0.0031 (9)	0.0241 (8)	−0.0133 (10)
O3	0.0458 (10)	0.0736 (13)	0.0791 (13)	0.0107 (9)	0.0226 (9)	−0.0201 (10)

Geometric parameters (Å, º) top

C1—C6	1.391 (3)	C8—H8A	0.9700
C1—C2	1.393 (3)	C8—H8B	0.9700
C1—C7	1.483 (3)	C9—C14	1.380 (4)
C2—C3	1.366 (3)	C9—C10	1.380 (3)
C2—H2A	0.9300	C10—C11	1.374 (3)
C3—O1	1.365 (3)	C10—H10A	0.9300
C3—C4	1.397 (3)	C11—C12	1.354 (4)
C4—O2	1.366 (3)	C11—H11A	0.9300
C4—C5	1.369 (4)	C12—F1	1.359 (3)
C5—C6	1.378 (3)	C12—C13	1.362 (4)
C5—H5A	0.9300	C13—C14	1.381 (4)
C6—H6A	0.9300	C13—H13A	0.9300
C7—O3	1.219 (3)	C14—H14A	0.9300
C7—C8	1.512 (4)	O1—H1A	0.8200
C8—C9	1.503 (3)	O2—H2B	0.8200

C6—C1—C2	119.2 (2)	C9—C8—H8B	108.3
C6—C1—C7	121.4 (2)	C7—C8—H8B	108.3
C2—C1—C7	119.4 (2)	H8A—C8—H8B	107.4
C3—C2—C1	120.5 (2)	C14—C9—C10	118.0 (2)
C3—C2—H2A	119.8	C14—C9—C8	121.6 (2)
C1—C2—H2A	119.8	C10—C9—C8	120.3 (2)
O1—C3—C2	119.6 (2)	C11—C10—C9	121.4 (2)
O1—C3—C4	120.3 (2)	C11—C10—H10A	119.3
C2—C3—C4	120.1 (2)	C9—C10—H10A	119.3
O2—C4—C5	124.3 (2)	C12—C11—C10	118.6 (3)
O2—C4—C3	116.2 (2)	C12—C11—H11A	120.7
C5—C4—C3	119.5 (2)	C10—C11—H11A	120.7
C4—C5—C6	120.9 (2)	C11—C12—F1	119.0 (3)
C4—C5—H5A	119.6	C11—C12—C13	122.6 (3)
C6—C5—H5A	119.6	F1—C12—C13	118.5 (3)
C5—C6—C1	119.9 (3)	C12—C13—C14	118.2 (3)
C5—C6—H6A	120.1	C12—C13—H13A	120.9
C1—C6—H6A	120.1	C14—C13—H13A	120.9
O3—C7—C1	121.2 (2)	C9—C14—C13	121.2 (3)
O3—C7—C8	120.5 (2)	C9—C14—H14A	119.4
C1—C7—C8	118.3 (2)	C13—C14—H14A	119.4
C9—C8—C7	115.7 (2)	C3—O1—H1A	109.5
C9—C8—H8A	108.3	C4—O2—H2B	109.5
C7—C8—H8A	108.3

C6—C1—C2—C3	−1.2 (4)	C2—C1—C7—C8	−175.8 (2)
C7—C1—C2—C3	179.1 (2)	O3—C7—C8—C9	−8.8 (4)
C1—C2—C3—O1	178.1 (2)	C1—C7—C8—C9	169.9 (2)
C1—C2—C3—C4	0.9 (4)	C7—C8—C9—C14	112.3 (3)
O1—C3—C4—O2	2.9 (4)	C7—C8—C9—C10	−69.3 (3)
C2—C3—C4—O2	−179.9 (2)	C14—C9—C10—C11	0.3 (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—C6	179.6 (3)	C10—C11—C12—F1	−179.8 (3)
C3—C4—C5—C6	0.0 (4)	C10—C11—C12—C13	−0.3 (4)
C4—C5—C6—C1	−0.4 (4)	C11—C12—C13—C14	0.3 (5)
C2—C1—C6—C5	1.0 (4)	F1—C12—C13—C14	179.9 (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—C13	178.3 (2)
C2—C1—C7—O3	2.8 (4)	C12—C13—C14—C9	−0.1 (4)
C6—C1—C7—C8	4.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.28	2.690 (2)	111
O1—H1A···O2ⁱ	0.82	2.16	2.876 (3)	146
O2—H2B···O3ⁱⁱ	0.82	1.92	2.744 (2)	178

Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁FO₃
M_r	246.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1640 (16), 5.9120 (12), 24.946 (6)
β (°)	105.33 (3)
V (Å³)	1161.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.25 × 0.17

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.970, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	2229, 2072, 1452
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.145, 1.04
No. of reflections	2072
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.28	2.690 (2)	111
O1—H1A···O2ⁱ	0.82	2.16	2.876 (3)	146
O2—H2B···O3ⁱⁱ	0.82	1.92	2.744 (2)	178

Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z.

Acknowledgements

I gratefully acknowledge financial support from the Science Foundation for the Youth of Jiangnan University.

References

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