3-Fluoro-4-(4-hy­droxy­phen­oxy)benzonitrile

Zheng, M.; Wang, J.; Zhang, J.; Luo, S.

doi:10.1107/S1600536810024360

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1856

doi:10.1107/S1600536810024360

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3-Fluoro-4-(4-hydroxyphenoxy)benzonitrile

Mei Zheng,^a Jianfeng Wang,^b Jixu Zhang ^b and Shuping Luo ^b ^*

^aHangzhou Huadong Medicine Group Biotechnology Institute Co. Ltd, Hangzhou 310015, People's Republic of China, and ^bState Key Laboratory Breeding Base of Green Chemistry–Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zhangjixu123@163.com

(Received 12 May 2010; accepted 23 June 2010; online 30 June 2010)

The title compound, C₁₃H₈FNO₂, was synthesized from 3,4-difluorobenzonitrile and hydroquinone. The dihedral angle between the two aromatic rings is 70.9 (2)°. In the crystal structure, molecules are linked by O—H⋯N hydrogen bonds, forming zigzag chains.

Related literature

For the herbicidal actvity of hydroquinone derivatives, see: Bao et al. (2007 ); Liu (2002 ). For related structures, see: Sørensen et al. (2009 ); Luo et al. (2009 ); Zhang et al. (2009 ).

Experimental

Crystal data

C₁₃H₈FNO₂
M_r = 229.20
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1932 (4) Å
b = 8.8109 (5) Å
c = 20.5269 (12) Å
V = 1120.11 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.39 × 0.31 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.959, T_max = 0.976
10999 measured reflections
1498 independent reflections
928 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.117
S = 1.01
1498 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H201⋯N1ⁱ	0.82	2.03	2.839 (4)	168
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ); 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 I, global. DOI: 10.1107/S1600536810024360/im2202sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024360/im2202Isup2.hkl

checkCIF report

Comment top

Hydroquinone derivatives are important intermediates of herbicide synthesis and have therefore received growing attention recently (Liu, 2002; Bao et al., 2007). Several hydroquinone derivatives were synthesized and investigated by X-ray diffraction in our laboratory. 4-(4-Cyano-2-fluoro-phenoxy)-phenol was obtained reacting hydroquinone and 3,4-difluorobenzonitrile and it's molecular structure is shown in Fig.1.

As it is expected substituents at both aromatic rings are coplanar with repect to the aromatic planes. The dihedral angle between the two planes is 70.66°. The molecule is bent with a C6—O1—C7 angle of 118.0 (2)°. The crystal structure is determined by intermolecular O—H···N interactions. The resulting supramolecular chains of the title compound showing H-bridge interactions is shown in Fig.2.

Related literature top

For the herbicidal actvity of hydroquinone derivatives, see: Bao et al. (2007); Liu (2002). For related structures, see: Sørensen et al. (2009); Luo et al. (2009); Zhang et al. (2009).

Experimental top

A DMSO (10 ml) solution of hydroquinone (0.0012 mol) and NaOH (0.0024 mol) was stirred at room temperature for 5 h. Then the mixture was heated to 80°C and 3,4-difluorobenzonitrile (0.001 mol) was added dropwise and stirred for 10 h. Then the mixture was washed with water (30 ml) and extracted with ethyl acetate (three times). The organic solvent was removed under reduced pressure and the resulting crude product was purified by silica gel chromatography (pentane: ethyl acetate mixtures, yield 86%). Single crystals were obtained by slow evaporation of ethyl acetate at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2007); 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 title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of title compound. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x+1/2, -y+2, z+1/2].

3-Fluoro-4-(4-hydroxyphenoxy)benzonitrile top

Crystal data top

C₁₃H₈FNO₂	F(000) = 472
M_r = 229.20	D_x = 1.359 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6842 reflections
a = 6.1932 (4) Å	θ = 3.0–27.4°
b = 8.8109 (5) Å	µ = 0.10 mm⁻¹
c = 20.5269 (12) Å	T = 295 K
V = 1120.11 (12) Å³	Chunk, colorless
Z = 4	0.39 × 0.31 × 0.22 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1498 independent reflections
Radiation source: rolling anode	928 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
T_min = 0.959, T_max = 0.976	l = −26→26
10999 measured reflections

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0487P)² + 0.2503P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1498 reflections	Δρ_max = 0.17 e Å⁻³
156 parameters	Δρ_min = −0.15 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: 0.031 (5)

Crystal data top

C₁₃H₈FNO₂	V = 1120.11 (12) Å³
M_r = 229.20	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1932 (4) Å	µ = 0.10 mm⁻¹
b = 8.8109 (5) Å	T = 295 K
c = 20.5269 (12) Å	0.39 × 0.31 × 0.22 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1498 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	928 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.976	R_int = 0.032
10999 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
1498 reflections	Δρ_min = −0.15 e Å⁻³
156 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.8260 (4)	0.8262 (3)	0.91021 (10)	0.0842 (7)
F1	0.7477 (4)	0.5751 (2)	0.84401 (10)	0.0994 (7)
C3	0.2965 (5)	0.7967 (4)	0.78841 (13)	0.0647 (8)
C13	0.1155 (6)	0.7849 (4)	0.74589 (16)	0.0797 (10)
C7	0.8277 (5)	0.9255 (4)	0.96363 (13)	0.0662 (8)
O2	0.8846 (4)	1.2010 (3)	1.12504 (11)	0.0890 (8)
H201	0.7775	1.1944	1.1484	0.134*
C4	0.3341 (5)	0.9302 (4)	0.82157 (14)	0.0706 (8)
H4	0.2411	1.0120	0.8158	0.085*
C10	0.8605 (5)	1.1076 (3)	1.07184 (13)	0.0647 (8)
C1	0.6082 (5)	0.6918 (4)	0.83712 (14)	0.0689 (8)
C8	0.6707 (5)	0.9204 (4)	1.01045 (14)	0.0720 (8)
H8	0.5543	0.8546	1.0059	0.086*
C6	0.6460 (5)	0.8233 (4)	0.87182 (13)	0.0648 (8)
C2	0.4369 (5)	0.6748 (4)	0.79642 (14)	0.0712 (8)
H2	0.4141	0.5839	0.7744	0.085*
C9	0.6853 (5)	1.0130 (4)	1.06440 (14)	0.0718 (9)
H9	0.5769	1.0115	1.0958	0.086*
C11	1.0188 (6)	1.1111 (4)	1.02514 (15)	0.0789 (10)
H11	1.1376	1.1745	1.0301	0.095*
C12	1.0011 (6)	1.0202 (4)	0.97087 (15)	0.0805 (10)
H12	1.1076	1.0231	0.9390	0.097*
C5	0.5080 (6)	0.9438 (4)	0.86314 (14)	0.0710 (9)
H5	0.5319	1.0344	0.8853	0.085*
N1	−0.0310 (6)	0.7800 (4)	0.71268 (15)	0.1078 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0678 (14)	0.1042 (16)	0.0805 (13)	0.0258 (14)	−0.0173 (12)	−0.0286 (13)
F1	0.0986 (16)	0.0867 (12)	0.1129 (14)	0.0398 (13)	−0.0214 (12)	−0.0218 (12)
C3	0.0581 (18)	0.083 (2)	0.0534 (14)	−0.0009 (17)	−0.0006 (13)	0.0069 (16)
C13	0.076 (2)	0.092 (2)	0.0710 (19)	−0.009 (2)	−0.0057 (19)	0.0122 (18)
C7	0.0610 (18)	0.0736 (17)	0.0642 (15)	0.0089 (17)	−0.0031 (16)	−0.0066 (15)
O2	0.0893 (19)	0.0916 (15)	0.0861 (15)	−0.0181 (15)	0.0185 (13)	−0.0244 (14)
C4	0.069 (2)	0.0754 (19)	0.0671 (16)	0.0133 (18)	−0.0032 (17)	0.0033 (16)
C10	0.066 (2)	0.0648 (17)	0.0632 (15)	−0.0042 (16)	0.0052 (16)	−0.0025 (14)
C1	0.068 (2)	0.0692 (18)	0.0697 (17)	0.0159 (17)	0.0009 (16)	−0.0051 (17)
C8	0.065 (2)	0.0776 (18)	0.0733 (17)	−0.0135 (18)	0.0016 (17)	−0.0006 (17)
C6	0.0592 (19)	0.0778 (18)	0.0572 (15)	0.0090 (17)	0.0002 (14)	−0.0069 (15)
C2	0.072 (2)	0.0751 (19)	0.0665 (17)	0.0011 (18)	−0.0016 (16)	−0.0044 (17)
C9	0.068 (2)	0.084 (2)	0.0632 (16)	−0.0165 (19)	0.0125 (16)	−0.0001 (16)
C11	0.063 (2)	0.094 (2)	0.0801 (19)	−0.0177 (19)	0.0167 (18)	−0.0068 (19)
C12	0.066 (2)	0.107 (2)	0.0689 (17)	−0.004 (2)	0.0148 (18)	−0.0094 (19)
C5	0.072 (2)	0.0706 (18)	0.0706 (17)	0.0124 (17)	−0.0058 (17)	−0.0094 (17)
N1	0.094 (2)	0.128 (3)	0.101 (2)	−0.030 (2)	−0.031 (2)	0.034 (2)

Geometric parameters (Å, º) top

O1—C6	1.365 (4)	C10—C11	1.371 (4)
O1—C7	1.403 (4)	C10—C9	1.377 (4)
F1—C1	1.350 (3)	C1—C2	1.359 (4)
C3—C4	1.379 (5)	C1—C6	1.380 (4)
C3—C2	1.391 (4)	C8—C9	1.378 (4)
C3—C13	1.425 (4)	C8—H8	0.9300
C13—N1	1.135 (4)	C6—C5	1.375 (4)
C7—C12	1.368 (5)	C2—H2	0.9300
C7—C8	1.368 (4)	C9—H9	0.9300
O2—C10	1.375 (3)	C11—C12	1.376 (4)
O2—H201	0.8200	C11—H11	0.9300
C4—C5	1.379 (4)	C12—H12	0.9300
C4—H4	0.9300	C5—H5	0.9300

C6—O1—C7	118.0 (2)	C9—C8—H8	120.0
C4—C3—C2	119.7 (3)	O1—C6—C5	124.6 (3)
C4—C3—C13	119.8 (3)	O1—C6—C1	116.9 (3)
C2—C3—C13	120.5 (3)	C5—C6—C1	118.4 (3)
N1—C13—C3	177.8 (5)	C1—C2—C3	118.4 (3)
C12—C7—C8	120.1 (3)	C1—C2—H2	120.8
C12—C7—O1	118.1 (3)	C3—C2—H2	120.8
C8—C7—O1	121.6 (3)	C10—C9—C8	119.9 (3)
C10—O2—H201	109.5	C10—C9—H9	120.0
C5—C4—C3	120.7 (3)	C8—C9—H9	120.0
C5—C4—H4	119.6	C10—C11—C12	119.7 (3)
C3—C4—H4	119.6	C10—C11—H11	120.1
C11—C10—O2	117.7 (3)	C12—C11—H11	120.1
C11—C10—C9	119.9 (3)	C7—C12—C11	120.3 (3)
O2—C10—C9	122.4 (3)	C7—C12—H12	119.8
F1—C1—C2	118.7 (3)	C11—C12—H12	119.8
F1—C1—C6	118.5 (3)	C6—C5—C4	119.9 (3)
C2—C1—C6	122.8 (3)	C6—C5—H5	120.0
C7—C8—C9	119.9 (3)	C4—C5—H5	120.0
C7—C8—H8	120.0

C6—O1—C7—C12	−129.3 (3)	C4—C3—C2—C1	0.0 (5)
C6—O1—C7—C8	56.0 (4)	C13—C3—C2—C1	179.5 (3)
C2—C3—C4—C5	−0.7 (5)	C11—C10—C9—C8	0.8 (5)
C13—C3—C4—C5	179.8 (3)	O2—C10—C9—C8	−179.2 (3)
C12—C7—C8—C9	1.2 (5)	C7—C8—C9—C10	−1.6 (5)
O1—C7—C8—C9	175.8 (3)	O2—C10—C11—C12	−179.7 (3)
C7—O1—C6—C5	27.9 (4)	C9—C10—C11—C12	0.3 (5)
C7—O1—C6—C1	−155.4 (3)	C8—C7—C12—C11	−0.1 (5)
F1—C1—C6—O1	1.0 (4)	O1—C7—C12—C11	−174.8 (3)
C2—C1—C6—O1	−179.0 (3)	C10—C11—C12—C7	−0.7 (5)
F1—C1—C6—C5	177.9 (3)	O1—C6—C5—C4	178.0 (3)
C2—C1—C6—C5	−2.1 (5)	C1—C6—C5—C4	1.4 (5)
F1—C1—C2—C3	−178.6 (3)	C3—C4—C5—C6	0.0 (5)
C6—C1—C2—C3	1.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H201···N1ⁱ	0.82	2.03	2.839 (4)	168

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₈FNO₂
M_r	229.20
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.1932 (4), 8.8109 (5), 20.5269 (12)
V (Å³)	1120.11 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.39 × 0.31 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.959, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	10999, 1498, 928
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.117, 1.01
No. of reflections	1498
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku/MSC, 2007), 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
O2—H201···N1ⁱ	0.82	2.03	2.839 (4)	168

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

Acknowledgements

The authors are grateful to Mr Jianming Gu for the crystal structure analysis.

References

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