4-Hydroxy­phenyl 4-fluoro­benzoate

You, H.P.; Lee, Y.-S.; Han, B.H.; Kang, S.K.; Sung, C.K.

doi:10.1107/S1600536809000129

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o252

doi:10.1107/S1600536809000129

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4-Hydroxyphenyl 4-fluorobenzoate

Hyon Pil You,^a You-Soon Lee,^a Byung Hee Han,^a Sung Kwon Kang ^a ^* and Chang Keun Sung ^b

^aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea, and ^bDepartment of Food Science and Technology, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

(Received 16 December 2008; accepted 3 January 2009; online 8 January 2009)

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].

Related literature

For general background to whitening agents, see: Ha et al. (2007 ); Dawley et al. (1993 ); Nerya et al. (2003 ); Hong et al. (2008 ); Lee et al. (2007 ); Hussain et al. (2003 ).

Experimental

Crystal data

C₁₃H₉FO₃
M_r = 232.2
Monoclinic, P 2₁ /c
a = 24.938 (5) Å
b = 5.4789 (11) Å
c = 7.6858 (15) Å
β = 93.59 (3)°
V = 1048.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 174 (2) K
0.12 × 0.09 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
10972 measured reflections
2597 independent reflections
2054 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.105
S = 1.05
2597 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000129/bh2214sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000129/bh2214Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For general background to whitening agents, see: Ha et al. (2007); Dawley et al. (1993); Nerya et al. (2003); Hong et al. (2008); Lee et al. (2007); Hussain et al. (2003).

Experimental top

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.

Computing details top

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).

Figures top

Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids.

4-Hydroxyphenyl 4-fluorobenzoate top

Crystal data top

C₁₃H₉FO₃	F(000) = 480
M_r = 232.2	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	R_int = 0.027
ϕ and ω scans	θ_max = 28.3°, θ_min = 0.8°
10972 measured reflections	h = −31→33
2597 independent reflections	k = −6→7
2054 reflections with I > 2σ(I)	l = −10→10

Refinement top

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(F_o²) + (0.0431P)² + 0.436P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2597 reflections	Δρ_max = 0.31 e Å⁻³
158 parameters	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₃H₉FO₃	V = 1048.1 (4) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2054 reflections with I > 2σ(I)
10972 measured reflections	R_int = 0.027
2597 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.31 e Å⁻³
2597 reflections	Δρ_min = −0.24 e Å⁻³
158 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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 code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉FO₃
M_r	232.2
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	174
a, b, c (Å)	24.938 (5), 5.4789 (11), 7.6858 (15)
β (°)	93.59 (3)
V (Å³)	1048.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.12 × 0.09 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10972, 2597, 2054
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.105, 1.05
No. of reflections	2597
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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 code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

This study was supported financially by the Research Fund of Chungnam National University in 2008

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