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ISSN: 2056-9890

2-Amino-5-fluoro­benzoic acid

aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, bDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, cDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, and dCentre of Advanced Study in Crystallography and Biophysics, University of Madras Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: drsreenivasa@yahoo.co.in

(Received 10 February 2013; accepted 11 February 2013; online 16 February 2013)

In the title compound, C7H6FNO2, the mol­ecule is almost planar (r.m.s. deviation for the non-H atoms = 0.015 Å) and an intra­molecular N—H⋯O hydrogen bond closes an S(6) ring. In the crystal, inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R22(8) loops. Weak N—H⋯F hydrogen bonds, short F⋯F contacts [2.763 (2) Å] and aromatic ππ stacking inter­actions [centroid–centroid separation = 3.5570 (11) Å] are also observed in the crystal structure.

Related literature

For the applications of the title compound in the field of genetics, see: Toyn et al. (2000[Toyn, J. H., Gunyuzlu, P. L., White, W. H., Thompson, L. A. & Hollis, G. F. (2000). Yeast. 16, 553-560.]).

[Scheme 1]

Experimental

Crystal data
  • C7H6FNO2

  • Mr = 155.13

  • Monoclinic, P 21 /c

  • a = 4.9346 (2) Å

  • b = 11.7542 (6) Å

  • c = 11.9727 (5) Å

  • β = 96.782 (3)°

  • V = 689.58 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 293 K

  • 0.43 × 0.37 × 0.25 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.947, Tmax = 0.969

  • 5184 measured reflections

  • 1207 independent reflections

  • 1057 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.100

  • S = 1.09

  • 1207 reflections

  • 108 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.11 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯O1 0.901 (19) 2.044 (19) 2.6959 (17) 128.2 (16)
N1—H1A⋯F1i 0.91 (2) 2.55 (2) 3.3646 (17) 149.8 (14)
O2—H2⋯O1ii 0.82 1.81 2.6279 (12) 175
Symmetry codes: (i) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]);; cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

2-Amino-5-fluorobenzoic acid is used for the counterselection of TRP1, a commonly used genetic marker in the yeast Saccharomyces cerevisiae (Toyn et al., 2000). The ability to counterselect, as well as to select for, a genetic marker has numerous applications in microbial genetics. Keeping this in mind, the structure of the title compound is discussed here.

In the crystal structure of the title compound, C7H6FNO2, the molecules are linked through O2—H2···O1 hydrogen bonds into inversion related dimers. N1—H1A···F1 hydrogen bonds and short F1···F1 contacts [2.763 (2) Å] are also observed in the crystal structure. Further, the structure features an intra molecular hydrogen bond between the amino proton and the adjacent carboxylic oxygen atom.

Related literature top

For the applications of the title compound in the field of genetics, see: Toyn et al. (2000).

Experimental top

4-Fluoroaniline (0.01 mmol), aluminium chloride (0.05 mmol) and trichloroacetyl chloride(0.03 mmol) were taken in dichloro methane (DCM) (20 ml) at 00 C under nitrogen atmosphere. The reaction mixture was refluxed for 16 h. The mixture was poured into ice-water carefully and the pH was adjusted to 2. The organic layer was separated and the aqueous layer was extracted with DCM. The combined extract was concentrated to get dark oily 1-(2-amino-5-fluorophenyl)-2,2,2-trichloroethanone. This compound (0.01 mmol) was dissolved in methanol. To this solution sodium methoxide (25% w/t in methanol) was added at 0 °C. The mixture was stirred for 1 h, the pH was adjusted to 6. The resulting solution was extracted with DCM and concentrated to get a brown solid methyl-2-amino-5-fluorobenzoate. To a solution of methyl-2-amino-5-fluorobenzoate (0.01 mmol) in tetrahydrofuran (10 ml),1 N Lithium hydroxide (0.03 mmol) was added at room temperature and stirred at 60 °C for 6 h. The reaction mixture was cooled to 0 °C and pH was adjusted to 5, the precipitate obtained was collected and dried in vacuum to get the title compound. Colourless prisms were obtained by slow evaporation of the solution of the compound in a mixture of DCM and methanol.

Refinement top

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent atom).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing in the title compound. Hydrogen bonds are shown as dashed lines
[Figure 3] Fig. 3. Display of F···F contacts and O–H···O Hydrogen bonds.
2-Amino-5-fluorobenzoic acid top
Crystal data top
C7H6FNO2Prism
Mr = 155.13Dx = 1.494 Mg m3
Monoclinic, P21/cMelting point: 454 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 4.9346 (2) ÅCell parameters from 108 reflections
b = 11.7542 (6) Åθ = 2.4–25.0°
c = 11.9727 (5) ŵ = 0.13 mm1
β = 96.782 (3)°T = 293 K
V = 689.58 (5) Å3Prism, colourless
Z = 40.43 × 0.37 × 0.25 mm
F(000) = 320
Data collection top
Bruker APEXII CCD
diffractometer
1207 independent reflections
Radiation source: fine-focus sealed tube1057 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 55
Tmin = 0.947, Tmax = 0.969k = 1313
5184 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0616P)2 + 0.0629P]
where P = (Fo2 + 2Fc2)/3
1207 reflections(Δ/σ)max < 0.001
108 parametersΔρmax = 0.11 e Å3
0 restraintsΔρmin = 0.18 e Å3
0 constraints
Crystal data top
C7H6FNO2V = 689.58 (5) Å3
Mr = 155.13Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.9346 (2) ŵ = 0.13 mm1
b = 11.7542 (6) ÅT = 293 K
c = 11.9727 (5) Å0.43 × 0.37 × 0.25 mm
β = 96.782 (3)°
Data collection top
Bruker APEXII CCD
diffractometer
1207 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
1057 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.969Rint = 0.025
5184 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.11 e Å3
1207 reflectionsΔρmin = 0.18 e Å3
108 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
xyzUiso*/Ueq
H1B0.443 (4)0.5012 (15)0.2698 (16)0.077 (5)*
H1A0.681 (4)0.4717 (14)0.3630 (16)0.078 (5)*
O10.20891 (18)0.49475 (8)0.11724 (8)0.0572 (3)
C10.5279 (2)0.34252 (10)0.12427 (10)0.0419 (3)
O20.20142 (19)0.37877 (9)0.02978 (7)0.0606 (3)
H20.07570.42090.05410.091*
C20.6596 (2)0.36817 (11)0.23280 (10)0.0458 (3)
C60.6146 (3)0.24937 (12)0.06514 (10)0.0515 (3)
H60.52770.23150.00590.062*
N10.5831 (3)0.45571 (12)0.29601 (11)0.0688 (4)
C70.3008 (2)0.41184 (10)0.07158 (10)0.0430 (3)
C40.9633 (3)0.20846 (12)0.21735 (11)0.0561 (4)
H41.10920.16360.24740.067*
C30.8792 (3)0.29852 (12)0.27596 (11)0.0529 (4)
H30.96990.31450.34680.063*
F10.9117 (2)0.09467 (9)0.05376 (8)0.0924 (4)
C50.8272 (3)0.18517 (12)0.11232 (11)0.0567 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0586 (6)0.0593 (6)0.0492 (6)0.0139 (4)0.0129 (4)0.0088 (4)
C10.0393 (6)0.0479 (7)0.0374 (6)0.0016 (5)0.0000 (5)0.0045 (5)
O20.0619 (6)0.0706 (6)0.0439 (6)0.0196 (5)0.0163 (4)0.0100 (4)
C20.0430 (6)0.0513 (7)0.0413 (7)0.0038 (5)0.0023 (5)0.0027 (5)
C60.0566 (7)0.0593 (7)0.0370 (6)0.0071 (6)0.0017 (5)0.0009 (6)
N10.0719 (8)0.0721 (8)0.0549 (8)0.0145 (7)0.0238 (6)0.0188 (6)
C70.0407 (6)0.0477 (7)0.0387 (6)0.0033 (5)0.0024 (5)0.0009 (5)
C40.0538 (7)0.0674 (9)0.0461 (7)0.0148 (6)0.0018 (6)0.0161 (6)
C30.0507 (7)0.0664 (8)0.0384 (6)0.0003 (6)0.0077 (5)0.0079 (6)
F10.1194 (8)0.0939 (7)0.0597 (6)0.0593 (6)0.0071 (5)0.0108 (5)
C50.0665 (8)0.0594 (8)0.0442 (7)0.0186 (6)0.0061 (6)0.0048 (6)
Geometric parameters (Å, º) top
O1—C71.2299 (15)C6—H60.9300
C1—C61.3982 (18)N1—H1B0.901 (19)
C1—C21.4150 (17)N1—H1A0.91 (2)
C1—C71.4667 (16)C4—C31.361 (2)
O2—C71.3129 (14)C4—C51.381 (2)
O2—H20.8200C4—H40.9300
C2—N11.3571 (19)C3—H30.9300
C2—C31.4069 (18)F1—C51.3660 (16)
C6—C51.3599 (18)
C6—C1—C2119.80 (11)O1—C7—O2121.90 (10)
C6—C1—C7118.77 (10)O1—C7—C1123.51 (10)
C2—C1—C7121.43 (11)O2—C7—C1114.59 (11)
C7—O2—H2109.5C3—C4—C5118.59 (11)
N1—C2—C3119.29 (11)C3—C4—H4120.7
N1—C2—C1123.08 (11)C5—C4—H4120.7
C3—C2—C1117.63 (12)C4—C3—C2122.10 (11)
C5—C6—C1119.44 (12)C4—C3—H3119.0
C5—C6—H6120.3C2—C3—H3119.0
C1—C6—H6120.3C6—C5—F1119.08 (12)
C2—N1—H1B120.5 (12)C6—C5—C4122.44 (13)
C2—N1—H1A119.8 (11)F1—C5—C4118.48 (12)
H1B—N1—H1A119.5 (17)
C6—C1—C2—N1178.62 (12)C2—C1—C7—O2179.10 (11)
C7—C1—C2—N11.46 (19)C5—C4—C3—C20.1 (2)
C6—C1—C2—C31.17 (18)N1—C2—C3—C4179.06 (13)
C7—C1—C2—C3178.75 (11)C1—C2—C3—C40.74 (19)
C2—C1—C6—C50.75 (19)C1—C6—C5—F1179.65 (12)
C7—C1—C6—C5179.17 (11)C1—C6—C5—C40.1 (2)
C6—C1—C7—O1179.42 (11)C3—C4—C5—C60.6 (2)
C2—C1—C7—O10.66 (18)C3—C4—C5—F1179.91 (12)
C6—C1—C7—O20.82 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O10.901 (19)2.044 (19)2.6959 (17)128.2 (16)
N1—H1A···F1i0.91 (2)2.55 (2)3.3646 (17)149.8 (14)
O2—H2···O1ii0.821.812.6279 (12)175
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC7H6FNO2
Mr155.13
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)4.9346 (2), 11.7542 (6), 11.9727 (5)
β (°) 96.782 (3)
V3)689.58 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.43 × 0.37 × 0.25
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.947, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
5184, 1207, 1057
Rint0.025
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.100, 1.09
No. of reflections1207
No. of parameters108
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.11, 0.18

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O10.901 (19)2.044 (19)2.6959 (17)128.2 (16)
N1—H1A···F1i0.91 (2)2.55 (2)3.3646 (17)149.8 (14)
O2—H2···O1ii0.821.812.6279 (12)175
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1, z.
 

Acknowledgements

The authors thank Dr S. C. Sharma, Vice Chancellor, Tumkur University, Tumkur, for his constant encouragement. BSPM thanks Dr H. C. Devarajegowda, Department of Physics Yuvarajas College (Constituent), University of Mysore, for his guidance.

References

First citationBruker (2004). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationToyn, J. H., Gunyuzlu, P. L., White, W. H., Thompson, L. A. & Hollis, G. F. (2000). Yeast. 16, 553–560.  CrossRef PubMed CAS

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ISSN: 2056-9890
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