4-Fluoro-3-phenoxy­benzoic acid

In the title compound, C₁₃H₉FO₃, the dihedral angle between the benzene rings is 82.1 (1)°. The crystal structure is mainly stabilized by carboxylic acid dimers involving O—H...O hydrogen bonds, along with the formation of weak but highly directional inter­molecular C—H...O and C—H...F inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.069
• wR factor = 0.159
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O4
PLAT331_ALERT_2_B Small Average Phenyl C-C Dist.   C7     -C12           1.36 Ang.

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Pesticides are widely used as pyrethroids (insecticides) in agriculture, forestry, horticulture and homes (Heudork & Angerer, 2001, and references therein). The title compund, (I), is one such compound.

Fig. 1 highlights the asymmetric unit of (I). The C5—O4—C7 bond angle is considerably widened and this eliminates the possibility of formation of an intramolecular C—H···π interaction with the H atom bonded to C6. The molecules pack via the formation of classical carboxylic acid dimers involving O—H···O hydrogen bonds (Table 2). In addition, molecules are linked via C—H···O and C—H···F interactions, forming a sheet-like structure (Fig. 2).

S2. Experimental

The compound (I) was supplied by Rallis India Limited. Crystals of suitable size and quality were grown by slow evaporation method from a solution of acetone at 298 K.

S3. Refinement

The H atom of the carboxylic group was positioned assuming an intermolecular hydrogen bond and fixed geometrically (O—H = 0.82 Å). The ring H atoms were placed in idealized position (C—H= 0.93 Å) and constrained to ride on their parent atom, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. Molecular structure of (I), showing 50% ellipsoidal probability.
	Fig. 2. Packing diagram of (I), highlighting O—H···O hydrogen bonds forming dimers, and C—H···O interactions and C—H···F interactions forming molecular sheets. H atoms have been omitted for clarity, except for those involved in hydrogen bonds. Intermolecular interactions are shown as dotted lines.

4-Fluoro-3-phenoxybenzoic acid

Crystal data

C13H9FO3	F(000) = 480
Mr = 232.20	Dx = 1.412 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 565 reflections
a = 16.659 (3) Å	θ = 1.4–25.8°
b = 5.1494 (9) Å	µ = 0.11 mm^−1
c = 13.916 (2) Å	T = 290 K
β = 113.821 (3)°	Plate, colorless
V = 1092.0 (3) Å^3	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1914 independent reflections
Radiation source: fine-focus sealed tube	1695 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
Tmin = 0.940, Tmax = 0.989	k = −6→6
7407 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0566P)^2 + 0.4402P] where P = (Fo^2 + 2Fc^2)/3
1914 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.49290 (12)	−0.3320 (4)	0.59318 (14)	0.0706 (6)
O2	0.40843 (12)	−0.2783 (4)	0.42436 (13)	0.0709 (6)
O4	0.19980 (18)	0.4475 (5)	0.41915 (17)	0.1106 (10)
F1	0.24893 (12)	0.5720 (4)	0.61568 (14)	0.0885 (6)
C1	0.38185 (15)	−0.0121 (5)	0.54593 (18)	0.0516 (6)
C2	0.40555 (18)	0.0644 (6)	0.6491 (2)	0.0663 (8)
C3	0.36053 (18)	0.2614 (6)	0.6725 (2)	0.0698 (8)
C4	0.29289 (18)	0.3780 (6)	0.5937 (2)	0.0636 (7)
C5	0.26728 (18)	0.3068 (6)	0.4897 (2)	0.0661 (7)
C6	0.31261 (17)	0.1106 (5)	0.4661 (2)	0.0601 (7)
C7	0.1610 (2)	0.3685 (6)	0.3147 (2)	0.0715 (8)
C8	0.1761 (2)	0.5100 (7)	0.2420 (3)	0.0793 (9)
C9	0.1315 (2)	0.4551 (7)	0.1379 (3)	0.0879 (10)
C10	0.0726 (2)	0.2621 (7)	0.1068 (3)	0.0887 (10)
C11	0.0573 (2)	0.1162 (8)	0.1797 (4)	0.1008 (12)
C12	0.1023 (3)	0.1682 (7)	0.2856 (3)	0.0955 (11)
C13	0.43256 (15)	−0.2214 (5)	0.52375 (19)	0.0518 (6)
H2	0.4393	−0.3959	0.4185	0.106*
H2A	0.4520	−0.0173	0.7027	0.080*
H3A	0.3764	0.3138	0.7417	0.084*
H6	0.2968	0.0603	0.3966	0.072*
H8	0.2169	0.6445	0.2628	0.095*
H9	0.1421	0.5527	0.0880	0.105*
H10	0.0422	0.2274	0.0356	0.106*
H11	0.0166	−0.0182	0.1580	0.121*
H12	0.0929	0.0690	0.3359	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0684 (11)	0.0768 (13)	0.0561 (11)	0.0219 (10)	0.0144 (9)	−0.0012 (9)
O4	0.136 (2)	0.1072 (19)	0.0707 (14)	0.0697 (17)	0.0232 (14)	−0.0025 (13)
O2	0.0786 (13)	0.0760 (14)	0.0533 (11)	0.0252 (10)	0.0216 (9)	−0.0010 (9)
F1	0.0942 (12)	0.0852 (13)	0.0947 (13)	0.0191 (10)	0.0472 (10)	−0.0193 (10)
C1	0.0513 (13)	0.0518 (14)	0.0539 (14)	−0.0023 (11)	0.0234 (11)	0.0002 (11)
C2	0.0600 (15)	0.079 (2)	0.0570 (16)	0.0071 (14)	0.0205 (13)	−0.0038 (14)
C3	0.0683 (17)	0.086 (2)	0.0567 (16)	−0.0003 (16)	0.0264 (14)	−0.0150 (15)
C4	0.0645 (16)	0.0599 (17)	0.0754 (19)	0.0025 (13)	0.0376 (15)	−0.0098 (14)
C5	0.0717 (17)	0.0605 (17)	0.0658 (18)	0.0146 (14)	0.0273 (14)	0.0025 (14)
C6	0.0711 (16)	0.0570 (16)	0.0529 (14)	0.0083 (13)	0.0257 (13)	0.0009 (12)
C7	0.0723 (18)	0.0664 (19)	0.0692 (19)	0.0301 (16)	0.0218 (15)	0.0032 (15)
C8	0.0730 (19)	0.073 (2)	0.086 (2)	−0.0092 (16)	0.0264 (17)	−0.0059 (18)
C9	0.104 (2)	0.074 (2)	0.082 (2)	−0.009 (2)	0.034 (2)	0.0045 (18)
C10	0.084 (2)	0.082 (2)	0.081 (2)	0.0019 (19)	0.0123 (18)	−0.0033 (19)
C11	0.084 (2)	0.083 (2)	0.136 (4)	−0.023 (2)	0.045 (2)	−0.021 (3)
C12	0.125 (3)	0.073 (2)	0.116 (3)	0.014 (2)	0.077 (3)	0.015 (2)
C13	0.0517 (13)	0.0516 (14)	0.0505 (14)	−0.0036 (11)	0.0190 (11)	0.0001 (11)

Geometric parameters (Å, º)

O2—C13	1.308 (3)	C2—H2A	0.9300
O2—H2	0.8200	O4—C7	1.392 (4)
O1—C13	1.218 (3)	C7—C8	1.351 (4)
C1—C2	1.384 (4)	C7—C12	1.365 (5)
C1—C6	1.389 (3)	C8—C9	1.364 (5)
C1—C13	1.477 (3)	C8—H8	0.9300
F1—C4	1.345 (3)	C11—C10	1.366 (5)
C4—C3	1.355 (4)	C11—C12	1.384 (5)
C4—C5	1.383 (4)	C11—H11	0.9300
C6—C5	1.378 (4)	C9—C10	1.339 (5)
C6—H6	0.9300	C9—H9	0.9300
C5—O4	1.364 (3)	C10—H10	0.9300
C3—C2	1.376 (4)	C12—H12	0.9300
C3—H3A	0.9300
C13—O2—H2	109.5	C1—C2—H2A	120.0
C2—C1—C6	119.8 (2)	C5—O4—C7	119.8 (2)
C2—C1—C13	118.5 (2)	C8—C7—C12	120.9 (3)
C6—C1—C13	121.7 (2)	C8—C7—O4	118.4 (3)
O1—C13—O2	122.5 (2)	C12—C7—O4	120.3 (3)
O1—C13—C1	122.3 (2)	C7—C8—C9	119.8 (3)
O2—C13—C1	115.3 (2)	C7—C8—H8	120.1
F1—C4—C3	119.7 (3)	C9—C8—H8	120.1
F1—C4—C5	118.0 (3)	C10—C11—C12	120.0 (3)
C3—C4—C5	122.3 (3)	C10—C11—H11	120.0
C5—C6—C1	120.1 (2)	C12—C11—H11	120.0
C5—C6—H6	120.0	C10—C9—C8	120.7 (3)
C1—C6—H6	120.0	C10—C9—H9	119.6
O4—C5—C6	126.1 (3)	C8—C9—H9	119.6
O4—C5—C4	115.4 (2)	C9—C10—C11	120.0 (3)
C6—C5—C4	118.5 (3)	C9—C10—H10	120.0
C4—C3—C2	119.3 (3)	C11—C10—H10	120.0
C4—C3—H3A	120.4	C7—C12—C11	118.5 (3)
C2—C3—H3A	120.4	C7—C12—H12	120.7
C3—C2—C1	120.1 (3)	C11—C12—H12	120.7
C3—C2—H2A	120.0
C2—C1—C13—O1	1.7 (4)	C6—C1—C2—C3	0.1 (4)
C6—C1—C13—O1	−179.3 (2)	C13—C1—C2—C3	179.1 (2)
C2—C1—C13—O2	−177.9 (2)	C6—C5—O4—C7	11.2 (5)
C6—C1—C13—O2	1.1 (3)	C4—C5—O4—C7	−171.0 (3)
C2—C1—C6—C5	−0.5 (4)	C5—O4—C7—C8	−108.3 (4)
C13—C1—C6—C5	−179.4 (2)	C5—O4—C7—C12	78.0 (4)
C1—C6—C5—O4	178.2 (3)	C12—C7—C8—C9	0.9 (5)
C1—C6—C5—C4	0.5 (4)	O4—C7—C8—C9	−172.7 (3)
F1—C4—C5—O4	1.2 (4)	C7—C8—C9—C10	0.0 (5)
C3—C4—C5—O4	−178.1 (3)	C8—C9—C10—C11	−0.6 (6)
F1—C4—C5—C6	179.1 (2)	C12—C11—C10—C9	0.2 (6)
C3—C4—C5—C6	−0.2 (5)	C8—C7—C12—C11	−1.2 (5)
F1—C4—C3—C2	−179.5 (2)	O4—C7—C12—C11	172.2 (3)
C5—C4—C3—C2	−0.2 (5)	C10—C11—C12—C7	0.7 (5)
C4—C3—C2—C1	0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1^i	0.82	1.85	2.667 (3)	178
C3—H3A···O1^ii	0.93	2.56	3.224 (3)	129
C9—H9···F1^iii	0.93	2.55	3.216 (4)	129

Symmetry codes: (i) −x+1, −y−1, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2.