3-(2-Fluoro­phen­oxy)propanoic acid

Zhou, Y.-Y.; Gu, X.-B.; Jiang, M.-J.; Cai, G.-M.

doi:10.1107/S1600536810049974

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o121

https://doi.org/10.1107/S1600536810049974

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3-(2-Fluorophenoxy)propanoic acid

Yao-Yuan Zhou,^a ^* Xiao-Bo Gu,^a Meng-Jun Jiang ^a and Gang-Ming Cai ^a

^aKey Laboratory of Nuclear Medicine, Ministry of Health, Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: rambo1265@sina.com

(Received 22 November 2010; accepted 30 November 2010; online 15 December 2010)

In the title compound, C₉H₉FO₃, the dihedral angle between the carboxyl group and the benzene ring is 79.4 (3)°. In the crystal, molecules form centrosymmetric dimers through pairs of classical O—H⋯O hydrogen bonds. These are further linked by weaker C—H⋯O interactions, forming a three-dimensional network.

Related literature

For a related structure, see: Potrzebowski & Chruszcz (2007 ). For the synthesis, see: Bäurle et al. (2006 ).

Experimental

Crystal data

C₉H₉FO₃
M_r = 184.16
Monoclinic, P 2₁ /c
a = 13.934 (16) Å
b = 4.974 (5) Å
c = 13.098 (14) Å
β = 110.546 (12)°
V = 850.0 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 153 K
0.45 × 0.30 × 0.08 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.947, T_max = 0.990
5881 measured reflections
1518 independent reflections
1034 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.189
S = 0.98
1518 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H4O⋯O2ⁱ	0.91 (7)	1.77 (7)	2.671 (6)	177 (7)
C4—H4⋯O1	0.95	2.57	3.519 (7)	176
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810049974/sj5066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049974/sj5066Isup2.hkl

checkCIF report

Comment top

The title compound,(I), is an important intermediate in the synthesis of 8-fluorochroman-4-one (Bäurle et al., 2006). We report herein its structure (Fig.1).

The bond lengths and angles in (I) are within normal ranges (Potrzebowski & Chruszcz, 2007). The dihedral angle between the C1—C6 benzene ring and the C9/O2/O3 plane is 79.4 (3) °. In the crystal, molecules form centrosymmetric dimers through classical O3—H4O···O2 hydrogen bonds (Table 1). These are further linked by weaker C4—H4···O1 contacts forming a three-dimensional network.

Related literature top

For a related structure, see: Potrzebowski & Chruszcz (2007). For the synthesis, see: Bäurle et al. (2006).

Experimental top

The title compound was crystallized from dichloromethane and hexane (1:1); colorless block-shaped crystals were obtained after several days.

Structure description top

The title compound,(I), is an important intermediate in the synthesis of 8-fluorochroman-4-one (Bäurle et al., 2006). We report herein its structure (Fig.1).

For a related structure, see: Potrzebowski & Chruszcz (2007). For the synthesis, see: Bäurle et al. (2006).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3-(2-Fluorophenoxy)propanoic acid top

Crystal data top

C₉H₉FO₃	F(000) = 384
M_r = 184.16	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2182 reflections
a = 13.934 (16) Å	θ = 3.1–27.5°
b = 4.974 (5) Å	µ = 0.12 mm⁻¹
c = 13.098 (14) Å	T = 153 K
β = 110.546 (12)°	Block, colorless
V = 850.0 (16) Å³	0.45 × 0.30 × 0.08 mm
Z = 4

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	1518 independent reflections
Radiation source: Rotating Anode	1034 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.5°, θ_min = 3.1°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −6→6
T_min = 0.947, T_max = 0.990	l = −15→15
5881 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0106P)² + 5.690P] where P = (F_o² + 2F_c²)/3
1518 reflections	(Δ/σ)_max < 0.001
122 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₉H₉FO₃	V = 850.0 (16) Å³
M_r = 184.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.934 (16) Å	µ = 0.12 mm⁻¹
b = 4.974 (5) Å	T = 153 K
c = 13.098 (14) Å	0.45 × 0.30 × 0.08 mm
β = 110.546 (12)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	1518 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1034 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.990	R_int = 0.070
5881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	0 restraints
wR(F²) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.42 e Å⁻³
1518 reflections	Δρ_min = −0.38 e Å⁻³
122 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
F1	0.1148 (2)	0.0797 (6)	0.0408 (2)	0.0401 (7)
O1	0.2551 (2)	0.4195 (6)	0.1573 (2)	0.0279 (7)
O2	0.4656 (2)	0.4357 (6)	0.1091 (3)	0.0358 (8)
O3	0.4220 (2)	0.7887 (6)	−0.0035 (3)	0.0350 (8)
C8	0.3591 (3)	0.7823 (8)	0.1414 (4)	0.0279 (10)
H8A	0.2946	0.8508	0.0873	0.034*
H8B	0.3981	0.9392	0.1815	0.034*
C6	0.2124 (3)	0.2528 (8)	0.2131 (4)	0.0239 (9)
C5	0.2368 (3)	0.2465 (8)	0.3253 (3)	0.0264 (9)
H5	0.2869	0.3663	0.3705	0.032*
C1	0.1372 (3)	0.0743 (9)	0.1491 (4)	0.0281 (10)
C3	0.1149 (3)	−0.1099 (9)	0.3076 (4)	0.0339 (11)
H3	0.0820	−0.2334	0.3399	0.041*
C9	0.4201 (3)	0.6507 (8)	0.0816 (4)	0.0279 (10)
C7	0.3327 (3)	0.6037 (8)	0.2214 (4)	0.0288 (10)
H7A	0.3941	0.5042	0.2677	0.035*
H7B	0.3064	0.7129	0.2691	0.035*
C4	0.1878 (3)	0.0641 (9)	0.3721 (4)	0.0301 (10)
H4	0.2050	0.0603	0.4490	0.036*
C2	0.0898 (3)	−0.1050 (9)	0.1967 (4)	0.0304 (10)
H2	0.0395	−0.2255	0.1523	0.036*
H4O	0.462 (5)	0.712 (14)	−0.037 (5)	0.08 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0365 (15)	0.0424 (16)	0.0402 (16)	−0.0105 (12)	0.0121 (12)	0.0004 (13)
O1	0.0313 (15)	0.0225 (15)	0.0344 (17)	−0.0050 (12)	0.0170 (13)	0.0010 (13)
O2	0.0391 (18)	0.0272 (16)	0.052 (2)	0.0124 (14)	0.0289 (16)	0.0122 (15)
O3	0.0405 (18)	0.0250 (16)	0.050 (2)	0.0084 (14)	0.0291 (16)	0.0076 (15)
C8	0.029 (2)	0.0163 (19)	0.044 (3)	−0.0018 (17)	0.0197 (19)	−0.0018 (18)
C6	0.024 (2)	0.0166 (19)	0.036 (2)	0.0033 (15)	0.0168 (17)	0.0019 (17)
C5	0.032 (2)	0.019 (2)	0.030 (2)	0.0035 (16)	0.0134 (18)	−0.0005 (17)
C1	0.024 (2)	0.025 (2)	0.037 (3)	0.0029 (17)	0.0131 (18)	0.0024 (19)
C3	0.033 (2)	0.025 (2)	0.057 (3)	0.0042 (18)	0.031 (2)	0.009 (2)
C9	0.027 (2)	0.020 (2)	0.041 (3)	−0.0025 (17)	0.0175 (19)	0.0010 (19)
C7	0.034 (2)	0.017 (2)	0.043 (3)	0.0003 (17)	0.023 (2)	−0.0049 (19)
C4	0.033 (2)	0.026 (2)	0.035 (2)	0.0088 (18)	0.0168 (19)	0.0066 (19)
C2	0.022 (2)	0.025 (2)	0.045 (3)	0.0006 (17)	0.0131 (19)	0.006 (2)

Geometric parameters (Å, º) top

F1—C1	1.342 (5)	C6—C1	1.405 (6)
O1—C6	1.372 (5)	C5—C4	1.399 (6)
O1—C7	1.441 (5)	C5—H5	0.9500
O2—C9	1.231 (5)	C1—C2	1.381 (6)
O3—C9	1.317 (5)	C3—C2	1.370 (7)
O3—H4O	0.90 (7)	C3—C4	1.376 (7)
C8—C9	1.494 (6)	C3—H3	0.9500
C8—C7	1.515 (6)	C7—H7A	0.9900
C8—H8A	0.9900	C7—H7B	0.9900
C8—H8B	0.9900	C4—H4	0.9500
C6—C5	1.387 (6)	C2—H2	0.9500

C6—O1—C7	116.8 (3)	C2—C3—H3	120.0
C9—O3—H4O	113 (4)	C4—C3—H3	120.0
C9—C8—C7	115.3 (3)	O2—C9—O3	122.7 (4)
C9—C8—H8A	108.4	O2—C9—C8	123.8 (4)
C7—C8—H8A	108.4	O3—C9—C8	113.5 (4)
C9—C8—H8B	108.4	O1—C7—C8	106.5 (4)
C7—C8—H8B	108.4	O1—C7—H7A	110.4
H8A—C8—H8B	107.5	C8—C7—H7A	110.4
O1—C6—C5	126.0 (4)	O1—C7—H7B	110.4
O1—C6—C1	115.9 (4)	C8—C7—H7B	110.4
C5—C6—C1	118.2 (4)	H7A—C7—H7B	108.6
C6—C5—C4	120.2 (4)	C3—C4—C5	120.5 (4)
C6—C5—H5	119.9	C3—C4—H4	119.8
C4—C5—H5	119.9	C5—C4—H4	119.8
F1—C1—C2	121.3 (4)	C3—C2—C1	120.3 (4)
F1—C1—C6	117.8 (4)	C3—C2—H2	119.8
C2—C1—C6	120.9 (4)	C1—C2—H2	119.8
C2—C3—C4	119.9 (4)

C7—O1—C6—C5	0.3 (6)	C7—C8—C9—O3	165.5 (4)
C7—O1—C6—C1	−179.8 (3)	C6—O1—C7—C8	−174.2 (3)
O1—C6—C5—C4	−179.4 (4)	C9—C8—C7—O1	−72.7 (5)
C1—C6—C5—C4	0.7 (6)	C2—C3—C4—C5	−0.1 (6)
O1—C6—C1—F1	0.8 (5)	C6—C5—C4—C3	−0.2 (6)
C5—C6—C1—F1	−179.3 (3)	C4—C3—C2—C1	−0.1 (6)
O1—C6—C1—C2	179.2 (4)	F1—C1—C2—C3	179.0 (4)
C5—C6—C1—C2	−0.9 (6)	C6—C1—C2—C3	0.6 (6)
C7—C8—C9—O2	−15.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4O···O2ⁱ	0.91 (7)	1.77 (7)	2.671 (6)	177 (7)
C4—H4···O1	0.95	2.57	3.519 (7)	176

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₉H₉FO₃
M_r	184.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	13.934 (16), 4.974 (5), 13.098 (14)
β (°)	110.546 (12)
V (Å³)	850.0 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.45 × 0.30 × 0.08

Data collection
Diffractometer	Rigaku AFC10/Saturn724+
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.947, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	5881, 1518, 1034
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.189, 0.98
No. of reflections	1518
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.38

Computer programs: CrystalClear (Rigaku, 2008), 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
O3—H4O···O2ⁱ	0.91 (7)	1.77 (7)	2.671 (6)	177 (7)
C4—H4···O1	0.95	2.57	3.519 (7)	176

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

This work was supported financially by the Key Medical Talents Program of Jiangsu Province (No. RC2007097).

References

Bäurle, S., Berger, M. & Jaroch, S. (2006). WO Patent 2006/027236. Google Scholar
Potrzebowski, W. & Chruszcz, M. (2007). Acta Cryst. E63, o2754. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar