Acta Cryst. (2009). E65, o252 [ doi:10.1107/S1600536809000129 ]
In the title compound, C13H9FO3, the dihedral angle between the two benzene rings is 59.86 (4)°. In the crystal, intermolecular O-H
H hydrogen bonds lead to molecular chains propagating in [010].
Hydroquinone and 4-fluorobenzoyl chloride were purchased from Sigma Chemical Co. and used without further purification. The title compound was prepared from the reaction of 4-fluorobenzoyl chloride (0.159 g, 1 mmol) and hydroquinone (0.132 g, 1.2 mmol) in TEA (8.0 ml). After being stirred for 8 h at 333 K, the mixture was quenched and worked up with ethyl acetate. The mixture was chromatographed on silica gel (2/1 = dichloromethane / ethylacetate) to give the title compound as colorless solid (60%, m.p. 454 K). Single crystals were obtained by slow evaporation of a solution of the title compound in ethyl alcohol and methyl alcohol at room temperature.
Atom H16 of the OH group was located in a difference map and refined freely. Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(carrier C).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./bh2214fig1thm.gif)
| Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids. |
| C13H9FO3 | F(000) = 480 |
| Mr = 232.2 | Dx = 1.472 Mg m−3 |
| Monoclinic, P21/c | Melting point: 454 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 24.938 (5) Å | Cell parameters from 3698 reflections |
| b = 5.4789 (11) Å | θ = 2.5–28.0° |
| c = 7.6858 (15) Å | µ = 0.12 mm−1 |
| β = 93.59 (3)° | T = 174 K |
| V = 1048.1 (4) Å3 | Block, colourless |
| Z = 4 | 0.12 × 0.09 × 0.06 mm |
| Bruker SMART CCD area-detector diffractometer | Rint = 0.027 |
| φ and ω scans | θmax = 28.3°, θmin = 0.8° |
| 10972 measured reflections | h = −31→33 |
| 2597 independent reflections | k = −6→7 |
| 2054 reflections with I > 2σ(I) | l = −10→10 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | 0 constraints |
| R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0431P)2 + 0.436P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2597 reflections | Δρmax = 0.31 e Å−3 |
| 158 parameters | Δρmin = −0.24 e Å−3 |
| C13H9FO3 | V = 1048.1 (4) Å3 |
| Mr = 232.2 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 24.938 (5) Å | µ = 0.12 mm−1 |
| b = 5.4789 (11) Å | T = 174 K |
| c = 7.6858 (15) Å | 0.12 × 0.09 × 0.06 mm |
| β = 93.59 (3)° |
| Bruker SMART CCD area-detector diffractometer | 2054 reflections with I > 2σ(I) |
| 10972 measured reflections | Rint = 0.027 |
| 2597 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.105 | Δρmax = 0.31 e Å−3 |
| S = 1.05 | Δρmin = −0.24 e Å−3 |
| 2597 reflections | Absolute structure: ? |
| 158 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.17529 (5) | 0.4464 (2) | 0.47353 (17) | 0.0219 (3) | |
| C2 | 0.13428 (5) | 0.2841 (3) | 0.50782 (18) | 0.0249 (3) | |
| H2 | 0.1423 | 0.1423 | 0.5708 | 0.03* | |
| C3 | 0.08163 (6) | 0.3318 (3) | 0.44905 (19) | 0.0275 (3) | |
| H3 | 0.0541 | 0.224 | 0.4711 | 0.033* | |
| C4 | 0.07154 (5) | 0.5443 (3) | 0.35679 (18) | 0.0270 (3) | |
| C5 | 0.11101 (6) | 0.7093 (3) | 0.32085 (18) | 0.0278 (3) | |
| H5 | 0.1026 | 0.8508 | 0.2581 | 0.033* | |
| C6 | 0.16347 (6) | 0.6597 (3) | 0.38026 (17) | 0.0250 (3) | |
| H6 | 0.1908 | 0.7688 | 0.3579 | 0.03* | |
| C7 | 0.23063 (5) | 0.3826 (3) | 0.54191 (18) | 0.0259 (3) | |
| O8 | 0.24211 (4) | 0.2045 (2) | 0.62716 (18) | 0.0523 (4) | |
| O9 | 0.26681 (4) | 0.55210 (17) | 0.49833 (12) | 0.0243 (2) | |
| C10 | 0.32036 (5) | 0.5229 (2) | 0.56439 (16) | 0.0207 (3) | |
| C11 | 0.35119 (5) | 0.3277 (2) | 0.51648 (16) | 0.0229 (3) | |
| H11 | 0.3364 | 0.2065 | 0.4436 | 0.027* | |
| C12 | 0.40460 (5) | 0.3149 (2) | 0.57859 (17) | 0.0226 (3) | |
| H12 | 0.426 | 0.1849 | 0.5474 | 0.027* | |
| C13 | 0.42597 (5) | 0.4975 (2) | 0.68769 (17) | 0.0215 (3) | |
| C14 | 0.39464 (5) | 0.6938 (2) | 0.73353 (17) | 0.0234 (3) | |
| H14 | 0.4093 | 0.8157 | 0.806 | 0.028* | |
| C15 | 0.34135 (5) | 0.7073 (2) | 0.67088 (17) | 0.0225 (3) | |
| H15 | 0.32 | 0.8385 | 0.7001 | 0.027* | |
| O16 | 0.47887 (4) | 0.4939 (2) | 0.75328 (14) | 0.0302 (3) | |
| H16 | 0.4915 (8) | 0.356 (4) | 0.742 (3) | 0.052 (6)* | |
| F17 | 0.02021 (3) | 0.59316 (18) | 0.29800 (13) | 0.0424 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0203 (6) | 0.0223 (7) | 0.0231 (6) | 0.0016 (5) | 0.0006 (5) | −0.0004 (5) |
| C2 | 0.0238 (7) | 0.0220 (7) | 0.0289 (7) | 0.0006 (5) | 0.0015 (5) | 0.0022 (5) |
| C3 | 0.0209 (7) | 0.0267 (7) | 0.0349 (7) | −0.0026 (6) | 0.0016 (5) | −0.0021 (6) |
| C4 | 0.0198 (7) | 0.0289 (7) | 0.0317 (7) | 0.0047 (6) | −0.0043 (5) | −0.0060 (6) |
| C5 | 0.0295 (7) | 0.0230 (7) | 0.0302 (7) | 0.0045 (6) | −0.0035 (5) | 0.0010 (5) |
| C6 | 0.0249 (7) | 0.0227 (7) | 0.0273 (7) | −0.0019 (5) | 0.0005 (5) | 0.0011 (5) |
| C7 | 0.0208 (7) | 0.0285 (7) | 0.0284 (7) | 0.0003 (6) | 0.0017 (5) | 0.0061 (6) |
| O8 | 0.0238 (6) | 0.0539 (8) | 0.0787 (9) | 0.0006 (5) | −0.0009 (6) | 0.0418 (7) |
| O9 | 0.0185 (5) | 0.0237 (5) | 0.0300 (5) | −0.0015 (4) | −0.0038 (4) | 0.0041 (4) |
| C10 | 0.0169 (6) | 0.0239 (7) | 0.0210 (6) | −0.0009 (5) | −0.0015 (5) | 0.0036 (5) |
| C11 | 0.0255 (7) | 0.0206 (7) | 0.0224 (6) | −0.0028 (5) | −0.0003 (5) | −0.0013 (5) |
| C12 | 0.0225 (7) | 0.0202 (6) | 0.0252 (6) | 0.0020 (5) | 0.0024 (5) | −0.0001 (5) |
| C13 | 0.0174 (6) | 0.0231 (7) | 0.0237 (6) | −0.0021 (5) | 0.0003 (5) | 0.0038 (5) |
| C14 | 0.0242 (7) | 0.0209 (7) | 0.0248 (6) | −0.0032 (5) | −0.0013 (5) | −0.0034 (5) |
| C15 | 0.0225 (7) | 0.0206 (6) | 0.0245 (6) | 0.0019 (5) | 0.0027 (5) | −0.0012 (5) |
| O16 | 0.0186 (5) | 0.0288 (6) | 0.0423 (6) | 0.0007 (4) | −0.0052 (4) | −0.0018 (4) |
| F17 | 0.0223 (5) | 0.0426 (6) | 0.0605 (6) | 0.0056 (4) | −0.0106 (4) | 0.0019 (5) |
| C1—C2 | 1.3928 (19) | O9—C10 | 1.4078 (15) |
| C1—C6 | 1.3932 (18) | C10—C11 | 1.3806 (19) |
| C1—C7 | 1.4872 (18) | C10—C15 | 1.3824 (18) |
| C2—C3 | 1.3863 (19) | C11—C12 | 1.3881 (18) |
| C2—H2 | 0.93 | C11—H11 | 0.93 |
| C3—C4 | 1.378 (2) | C12—C13 | 1.3900 (18) |
| C3—H3 | 0.93 | C12—H12 | 0.93 |
| C4—F17 | 1.3572 (15) | C13—O16 | 1.3826 (16) |
| C4—C5 | 1.377 (2) | C13—C14 | 1.3874 (19) |
| C5—C6 | 1.3854 (19) | C14—C15 | 1.3869 (18) |
| C5—H5 | 0.93 | C14—H14 | 0.93 |
| C6—H6 | 0.93 | C15—H15 | 0.93 |
| C7—O8 | 1.2000 (17) | O16—H16 | 0.82 (2) |
| C7—O9 | 1.3514 (17) | ||
| C2—C1—C6 | 119.93 (12) | C7—O9—C10 | 117.74 (10) |
| C2—C1—C7 | 117.35 (12) | C11—C10—C15 | 121.83 (12) |
| C6—C1—C7 | 122.72 (12) | C11—C10—O9 | 121.57 (12) |
| C3—C2—C1 | 120.65 (13) | C15—C10—O9 | 116.47 (12) |
| C3—C2—H2 | 119.7 | C10—C11—C12 | 119.06 (12) |
| C1—C2—H2 | 119.7 | C10—C11—H11 | 120.5 |
| C4—C3—C2 | 117.74 (13) | C12—C11—H11 | 120.5 |
| C4—C3—H3 | 121.1 | C11—C12—C13 | 119.64 (12) |
| C2—C3—H3 | 121.1 | C11—C12—H12 | 120.2 |
| F17—C4—C5 | 118.34 (13) | C13—C12—H12 | 120.2 |
| F17—C4—C3 | 118.43 (13) | O16—C13—C14 | 117.27 (12) |
| C5—C4—C3 | 123.23 (13) | O16—C13—C12 | 122.04 (12) |
| C4—C5—C6 | 118.52 (13) | C14—C13—C12 | 120.68 (12) |
| C4—C5—H5 | 120.7 | C15—C14—C13 | 119.72 (12) |
| C6—C5—H5 | 120.7 | C15—C14—H14 | 120.1 |
| C5—C6—C1 | 119.93 (13) | C13—C14—H14 | 120.1 |
| C5—C6—H6 | 120 | C10—C15—C14 | 119.05 (12) |
| C1—C6—H6 | 120 | C10—C15—H15 | 120.5 |
| O8—C7—O9 | 123.63 (13) | C14—C15—H15 | 120.5 |
| O8—C7—C1 | 124.63 (13) | C13—O16—H16 | 109.7 (14) |
| O9—C7—C1 | 111.73 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O16—H16···O16i | 0.82 (2) | 2.12 (2) | 2.9368 (9) | 172 (2) |
| Symmetry codes: (i) −x+1, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O16—H16···O16i | 0.82 (2) | 2.12 (2) | 2.9368 (9) | 172 (2) |
| Symmetry codes: (i) −x+1, y−1/2, −z+3/2. |
This study was supported financially by the Research Fund of Chungnam National University in 2008
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Melanin is the pigment responsible for the color of human skin and hair. Tyrosinase is the key enzyme (Ha et al., 2007) that converts tyrosine to melanin and its inhibitors are the target molecules to develop and research anti-pigmentation agents for application to skin. Therefore, treatments using potent inhibitory agents on tyrosinase and melanin formation may be cosmetically useful. Most skin whitening agents currently on the market (Dawley et al., 1993; Nerya et al., 2003) are hydroquinone, ascorbic acid, kojic acid, arbutin, azealic acid, and glycyrrhetinic acid. They contain aromatic, methoxy, hydroxyl (Hong et al., 2008; Lee et al., 2007), or carbonyl functional groups in their structures, and act as a specific functional group to make the skin white by inhibiting the production of melanin. However, most skin whitening agents have some problems, due to toxicity, low stability of formulation and poor skin permeation. In the course of our work on the development of new whitening agents, to complement the inadequacy of current whitening agents and maximize the inhibitory effects of melanin creation, we have synthesized the title compound via a general chemical pathway (Hussain et al., 2003) between hydroquinone and 4-fluorobenzoyl chloride.
The 4-fluorobenzoic acid moiety and the 4-hydroxyphenyl ring are essentially planar, with mean deviations of 0.002 and 0.004 Å, respectively, from the corresponding least-squares planes. The dihedral angle between the two benzene rings is 59.86 (4)°. The intermolecular O16—H16···O16i [symmetry code: (i) -x+1, y-1/2, -z+3/2) hydrogen bond allows to form an extensive one-dimensional network, which stabilizes the crystal structure.