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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2340.
Published online 2010 August 18. doi:  10.1107/S1600536810032253
PMCID: PMC3008027

2-Fluoro-4-(meth­oxy­carbon­yl)benzoic acid

Abstract

In the crystal of the title compound, C9H7FO4, classical carboxylate inversion dimers are linked by pairs of O—H(...)O hydrogen bonds. The packing is consolidated by C—H(...)F and C—H(...)O interactions. The benzene ring and the methoxycarbonyl group are nearly coplanar, with a dihedral angle of 1.5 (3)° between them, whereas the carboxyl group has a dihedral angle of 20.2 (4)° with respect to the benzene ring.

Related literature

For background to the applications of the title compound, see: Jiang et al. (2008 [triangle]); Sakaki et al. (2007 [triangle]). For related structures, see: Wagner et al. (2009 [triangle]).

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Object name is e-66-o2340-scheme1.jpg

Experimental

Crystal data

  • C9H7FO4
  • M r = 198.15
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2340-efi1.jpg
  • a = 7.536 (7) Å
  • b = 7.591 (7) Å
  • c = 8.523 (8) Å
  • α = 99.480 (14)°
  • β = 108.748 (13)°
  • γ = 99.240 (14)°
  • V = 443.3 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 296 K
  • 0.25 × 0.19 × 0.08 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.969, T max = 0.990
  • 2526 measured reflections
  • 1535 independent reflections
  • 1025 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.190
  • S = 1.02
  • 1535 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT-Plus (Bruker, 2008 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XSHELL (Bruker, 2004 [triangle]); software used to prepare material for publication: APEX2.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032253/pb2036sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032253/pb2036Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Chemistry Division of the National Science Foundation for financial support of this work (Grant CHE-0741978).

supplementary crystallographic information

Comment

The title compound, 4-(methoxycarbonyl)-2-fluorobenzoic acid, has recently been used to prepare novel diazepinylbenzoic acid retinoid-X-receptor antagonists (Jiang et al., 2008; Sakaki et al., 2007) as potential oral anti-obesity and anti-diabetic treatments as well as novel retinoid-X-receptor agonists with potential to treat various human cancers. Thus, the X-ray diffraction data of the present study confirms the fluorine locus for 4-(methoxycarbonyl)-2-fluorobenzoic acid.

The structure consists of sheets parallel to (212) stabilized by six intermolecular hydrogen interactions per molecule as shown in Table 1. The benzene ring and the methoxycarbonyl group are essentially coplanar as shown by the 1.51 (25)° dihedral angle between the two planes. However, the carboxylic acid is not coplanar with the benzene ring, as shown by the 20.18 (36)° dihedral angle between those two planes.

Experimental

The method of Sakaki and co-workers (Sakaki et al., 2007) was followed to synthesize (1). To a flask containing 3-fluoro-4-formylmethylbenzoate (Wagner et al., 2009) (9.22 g, 50.5 mmol) and sulfamic acid (5.40 g, 55.6 mmol) in water (21 ml) and ACN (42 ml) was slowly added a solution of 80% NaClO2 (4.92 g, 53.8 mmol) in water (21 ml) at room temperature. After being stirred for 1 h, the reaction solution was added to a saturated, aqueous solution of Na2SO3 (75 ml) and 1 N HCl (150 ml), and the resulting solution was extracted with ethyl acetate (75 ml) three times. The combined organic extracts were washed with brine, dried over sodium sulfate, and the solvents were removed in vacuo to give crude (1) (7.56 g, 75%) as a white solid. A small sample was crystallized from hot ethyl acetate to give pure (1) as white crystals, m.p. 154–155 °C: 1H NMR (400 MHz, CDCl3) δ 10.5 (br s, 1H), 8.10 (t, J = 7.8, 1H), 7.89 (d, J = 8.2, 1H), 7.82 (d, J = 11.0, 1H), 3.97 (s, 3H); 13C NMR (100.6 MHz, CDCl3) δ 168.6, 168.5, 165.0, 164.9, 163.4, 160.8, 136.7, 136.6, 132.8, 124.9, 124.8, 121.3, 121.2, 118,4, 118.1, 52.8; LC-APCI-MS (M+) calcd for C9H7O4F 198.0328, found 198.0331.

Refinement

H atoms were placed geometrically and allowed to refine as atoms riding on their bonding partners. The hydrogen was placed on the carboxylic acid based on the longer of the carboxylic acid carbon-oxygen bonds.

Figures

Fig. 1.
Labeled thermal ellipsoid plot of (1) shown at the 50% probability level for all non-H atoms.
Fig. 2.
Molecular pair of (1) shown at the 50% probability level for all non-H atoms illustrating classical intermolecular centrosymmetric carboxylic acid hydrogen bonding interactions.
Fig. 3.
Packing diagram of (1) shown at the 50% probability level for all non-H atoms showing the alternating molecular orientations in two adjacent layers.

Crystal data

C9H7FO4Z = 2
Mr = 198.15F(000) = 204
Triclinic, P1Dx = 1.484 Mg m3
Hall symbol: -P 1Melting point: 427 K
a = 7.536 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.591 (7) ÅCell parameters from 51 reflections
c = 8.523 (8) Åθ = 4.5–11.9°
α = 99.480 (14)°µ = 0.13 mm1
β = 108.748 (13)°T = 296 K
γ = 99.240 (14)°Plate, colourless
V = 443.3 (7) Å30.25 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer1535 independent reflections
Radiation source: sealed tube1025 reflections with I > 2σ(I)
graphiteRint = 0.025
ω and [var phi] scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −8→8
Tmin = 0.969, Tmax = 0.990k = −9→8
2526 measured reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.P)2 + 0.1145P] where P = (Fo2 + 2Fc2)/3
1535 reflections(Δ/σ)max = 0.001
128 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.22 e Å3

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.H atoms were placed geometrically and allowed to refine as atoms riding on their bonding partners. The hydrogen was placed on the carboxylic acid based on the longer of the carboxylic acid carbon-oxygen bonds.

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

xyzUiso*/Ueq
F10.4739 (2)1.3542 (2)0.6014 (2)0.0629 (5)
O10.8299 (2)1.4232 (4)0.5841 (2)0.0672 (7)
O20.8296 (2)1.3413 (2)0.3192 (2)0.0716 (8)
H2A0.93261.41710.36030.107*
O3−0.1230 (4)0.8633 (4)0.2593 (2)0.0798 (9)
O4−0.0485 (2)0.7256 (2)0.0437 (2)0.0582 (7)
C10.5568 (4)1.2070 (4)0.3734 (2)0.0453 (7)
C20.4248 (4)1.2212 (4)0.4562 (2)0.0464 (7)
C30.2443 (4)1.1083 (4)0.3967 (2)0.0479 (8)
H3A0.16071.12270.45530.057*
C40.1871 (4)0.9720 (4)0.2478 (2)0.0437 (7)
C50.3166 (4)0.9507 (4)0.1625 (2)0.0495 (8)
H5A0.28070.85840.06420.059*
C60.4976 (5)1.0670 (4)0.2248 (4)0.0527 (8)
H6A0.58191.05230.16690.063*
C70.7527 (4)1.3333 (4)0.4321 (4)0.0503 (8)
C8−0.0112 (4)0.8498 (4)0.1877 (4)0.0491 (8)
C9−0.2360 (5)0.5972 (5)−0.0216 (4)0.0692 (10)
H9A−0.24820.5131−0.12380.104*
H9B−0.33590.6639−0.04620.104*
H9C−0.24740.53030.06230.104*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0579 (11)0.0628 (13)0.0540 (10)−0.0020 (9)0.0211 (9)−0.0111 (8)
O10.0526 (15)0.0782 (17)0.0532 (13)−0.0072 (11)0.0119 (10)0.0038 (11)
O20.0590 (16)0.0765 (18)0.0690 (15)−0.0133 (11)0.0303 (11)0.0019 (11)
O30.0532 (16)0.088 (2)0.0828 (17)−0.0110 (13)0.0346 (13)−0.0154 (14)
O40.0485 (14)0.0591 (14)0.0525 (11)−0.0015 (10)0.0137 (10)−0.0038 (10)
C10.0435 (17)0.0453 (17)0.0477 (15)0.0102 (14)0.0161 (13)0.0123 (13)
C20.0485 (18)0.0445 (17)0.0414 (14)0.0071 (13)0.0153 (13)0.0026 (11)
C30.0447 (18)0.051 (2)0.0470 (15)0.0086 (14)0.0202 (13)0.0045 (13)
C40.0431 (17)0.0430 (16)0.0434 (15)0.0074 (13)0.0149 (13)0.0091 (11)
C50.050 (2)0.0467 (18)0.0490 (16)0.0076 (14)0.0208 (14)0.0017 (13)
C60.050 (2)0.056 (2)0.0535 (17)0.0099 (15)0.0243 (14)0.0063 (14)
C70.049 (2)0.0493 (18)0.0510 (17)0.0095 (14)0.0168 (15)0.0105 (14)
C80.0432 (18)0.0511 (18)0.0490 (16)0.0079 (14)0.0156 (14)0.0055 (13)
C90.052 (2)0.062 (2)0.069 (2)−0.0055 (17)0.0060 (16)−0.0018 (17)

Geometric parameters (Å, °)

F1—C21.364 (3)C3—C41.393 (4)
O1—C71.257 (3)C3—H3A0.93
O2—C71.278 (4)C4—C51.405 (4)
O2—H2A0.82C4—C81.504 (4)
O3—C81.197 (4)C5—C61.384 (4)
O4—C81.336 (4)C5—H5A0.93
O4—C91.460 (4)C6—H6A0.93
C1—C21.400 (4)C9—H9A0.96
C1—C61.405 (4)C9—H9B0.96
C1—C71.504 (4)C9—H9C0.96
C2—C31.372 (4)
C7—O2—H2A109.5C4—C5—H5A120.0
C8—O4—C9115.8 (2)C5—C6—C1121.4 (3)
C2—C1—C6116.8 (3)C5—C6—H6A119.3
C2—C1—C7124.1 (3)C1—C6—H6A119.3
C6—C1—C7119.2 (2)O1—C7—O2124.2 (3)
F1—C2—C3117.5 (2)O1—C7—C1119.9 (3)
F1—C2—C1119.5 (3)O2—C7—C1115.9 (3)
C3—C2—C1122.9 (3)O3—C8—O4124.0 (3)
C2—C3—C4119.5 (3)O3—C8—C4124.0 (3)
C2—C3—H3A120.2O4—C8—C4112.0 (2)
C4—C3—H3A120.2O4—C9—H9A109.5
C3—C4—C5119.4 (3)O4—C9—H9B109.5
C3—C4—C8117.9 (2)H9A—C9—H9B109.5
C5—C4—C8122.7 (3)O4—C9—H9C109.5
C6—C5—C4120.0 (3)H9A—C9—H9C109.5
C6—C5—H5A120.0H9B—C9—H9C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···F1i0.962.543.278 (5)134 (1)
O2ii—H2Aii···O10.821.862.672 (4)170 (1)
C3—H3A···O3iii0.932.533.325 (4)144 (1)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PB2036).

References

  • Bruker (2004). XSHELL Bruker AXS Inc., Madison, Wisconsin, USA
  • Bruker (2008). APEX2, SADABS and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Jiang, X., Lee, G. T., Prasad, K. & Repic, O. (2008). Org. Process Res. Dev.12, 1137–1141.
  • Sakaki, J., Kishida, M., Konishi, K., Gunji, H., Toyao, A., Matsumoto, Y., Kanazawa, T., Uchiyama, H., Fukaya, H., Mitani, H., Arai, Y. & Kimura, M. (2007). Bioorg. Med. Chem. Lett.17, 4804–4807. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wagner, C. E. et al. (2009). J. Med. Chem.52, 5950–5966. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography