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Acta Cryst. (2008). E64, o1661    [ doi:10.1107/S1600536808024082 ]

4-[(2-Fluorophenyl)amino]-4-oxobutanoic acid

F. A. Shah, M. N. Tahir and S. Ali

Abstract top

The crystal structure of the title compound, C10H10FNO3, contains dimers of the asymmetric unit, with R22(8) rings arising from intermolecular O-H...O hydrogen bonding through the carboxylate groups. Adjacent dimeric units are connected to each other through one N-H...O and two C-H...O intermolecular hydrogen bonds. C-H...O hydrogen bonds involving the aromatic ring and the O atoms of two carboxylate groups form an R33(7) ring. The crystal structure is further stabilized by C-H...F interactions, giving rise to a three-dimensional network.

Comment top

The title compound (I) results from our continuing studies into the synthesis of carboxylic acids having the possibility of coordination with more donor atoms (Shah, et al., 2008). The purpose of synthesizing (I) was to make complexes with various metals and to study the biological activity at large.

The structures of (II) 3-(3,5-dichloroanilinocarbonyl)propionic acid (Shah, et al., 2008) is the best example for comparison of geometry. In (I) the C=O bond distances for carboxylate and carbonyl group have values of (C1=O2: 1.215 (2) Å) and (C4=O3: 1.223 (2) Å) in comparison to 1.219 (3) Å and 1.225 (2) Å, respectively. The C—N bond distances are compareable within experimental errors. The crystal structure of (I) consists of cetro-symmetric dimers forming R22(8) ring (Bernstein, et al., 1995), through intermolecular H-bonding (Table 1). The adjacent dimers are connected to each other through two C—H···O intermolecular H-bonds forming R33(7) ring [O—H···O···H—C—C—H···O] as shown in Fig 2. In (I) and (II), there is similarity of H-bonding between the amino and carbonyl group. There are C—H···F interaction also (Table 1) which stabilize the title molecule. The dihedral angle between the aromatic ring (C5—C10) and (C1,C2,C3,O1,O2) have a value of 58.87 (6)°, whereas with (N1,C3,C4,O3) its value is 51.09 (16)°. The value of dihedral angle between (C1,C2,C3,O1,O2) and (N1,C3,C4,O3) is 74.17 (13)°.

Related literature top

For related literature, see: Bernstein et al. (1995); Shah et al. (2008).

Experimental top

2-Fluoroaniline (0.1 mole, 9.56 ml) was dissolved in 30 ml of glacial acetic acid. A solution of succinic anhydride (10 g, 0.1 mole) in 50 ml glacial acetic acid was added and the mixture was stirred overnight. The precipitate which appeared was filtered, washed with distilled water and dried at 313–315 K. The acid was recrystallized from acetone. (Yield: 85%, m.p: 435 K)

Refinement top

The coordinates of H-atom attached with O1 and N1 were refined. The H-atoms attached with C-atoms were positioned geometrically, C—H = 0.93, and 0.97 Å for aromatic and methylene H, and constrained to ride on their parent atoms. The H-atoms were treated as isotropic with Uiso(H) = xUeq(C, N, O), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 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) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. ORTEP-3 for Windows (Farrugia, 1997) drawing of the title compound, C10H10FNO3 with the atom numbering scheme. The thermal ellipsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii.
[Figure 2] Fig. 2. The partial unit cell packing of (I) (Spek, 2003) with only H-atoms which are involved in H-bonding, showing the dimeric nature formig R22(8) ring, forming R33(7) ring through intermolecular H-bonds and the linkage of dimers through H-bonds of N—H···O type.
4-[(2-Fluorophenyl)amino]-4-oxobutanoic acid top
Crystal data top
C10H10FNO3F000 = 440
Mr = 211.19Dx = 1.418 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2550 reflections
a = 4.8054 (3) Åθ = 2.1–28.7º
b = 19.0399 (13) ŵ = 0.12 mm−1
c = 11.0429 (8) ÅT = 296 (2) K
β = 101.821 (3)ºNeedle, colorless
V = 988.94 (12) Å30.25 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD
diffractometer		2550 independent reflections
Radiation source: fine-focus sealed tube1366 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
Detector resolution: 7.4 pixels mm-1θmax = 28.7º
T = 296(2) Kθmin = 2.1º
ω scansh = −6→5
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		k = −25→25
Tmin = 0.975, Tmax = 0.989l = −14→14
11668 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.145  w = 1/[σ2(Fo2) + (0.0685P)2 + 0.1019P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2550 reflectionsΔρmax = 0.26 e Å−3
142 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C10H10FNO3V = 988.94 (12) Å3
Mr = 211.19Z = 4
Monoclinic, P21/cMo Kα
a = 4.8054 (3) ŵ = 0.12 mm−1
b = 19.0399 (13) ÅT = 296 (2) K
c = 11.0429 (8) Å0.25 × 0.15 × 0.10 mm
β = 101.821 (3)º
Data collection top
Bruker Kappa APEXII CCD
diffractometer		2550 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		1366 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.989Rint = 0.038
11668 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050142 parameters
wR(F2) = 0.145H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.26 e Å−3
2550 reflectionsΔρmin = −0.20 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
F11.0488 (3)0.33085 (7)0.62407 (12)0.0777 (5)
O10.0318 (3)0.56812 (8)0.11407 (14)0.0633 (6)
O20.2963 (3)0.47537 (8)0.09700 (14)0.0675 (6)
O30.2983 (3)0.42965 (8)0.37996 (15)0.0638 (6)
N10.7391 (3)0.38295 (8)0.40847 (14)0.0419 (5)
C10.2503 (4)0.52781 (10)0.15251 (18)0.0422 (6)
C20.4378 (4)0.55192 (10)0.26901 (19)0.0484 (6)
C30.6657 (4)0.49982 (10)0.32502 (19)0.0469 (6)
C40.5482 (3)0.43475 (10)0.37282 (16)0.0400 (6)
C50.6718 (4)0.31736 (9)0.45548 (17)0.0381 (6)
C60.8291 (4)0.29162 (10)0.56401 (18)0.0470 (6)
C70.7714 (5)0.22849 (12)0.6121 (2)0.0671 (8)
C80.5497 (5)0.18915 (12)0.5515 (2)0.0681 (9)
C90.3881 (5)0.21314 (11)0.4428 (2)0.0643 (8)
C100.4499 (4)0.27661 (11)0.39432 (19)0.0542 (7)
H1−0.070 (5)0.5532 (12)0.046 (2)0.0759*
H1A0.916 (4)0.3921 (10)0.4045 (18)0.0503*
H2A0.321390.561960.329030.0581*
H2B0.528670.595430.252770.0581*
H3A0.772410.486550.262940.0563*
H3B0.796320.522300.392500.0563*
H70.882850.212480.685920.0805*
H80.508240.146200.583830.0817*
H90.235820.186500.401360.0771*
H100.340850.292090.319620.0650*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0646 (8)0.0765 (9)0.0763 (9)−0.0227 (7)−0.0221 (7)0.0104 (7)
O10.0610 (10)0.0615 (10)0.0597 (10)0.0270 (8)−0.0055 (7)−0.0027 (7)
O20.0655 (10)0.0638 (10)0.0645 (10)0.0308 (8)−0.0073 (8)−0.0113 (8)
O30.0265 (7)0.0653 (10)0.1013 (12)0.0009 (6)0.0170 (7)0.0277 (8)
N10.0247 (7)0.0430 (9)0.0571 (10)−0.0037 (7)0.0065 (7)0.0100 (7)
C10.0396 (10)0.0384 (11)0.0494 (11)0.0076 (9)0.0113 (9)0.0120 (9)
C20.0434 (10)0.0409 (10)0.0591 (12)−0.0036 (9)0.0060 (9)0.0057 (9)
C30.0335 (9)0.0497 (11)0.0552 (12)−0.0062 (8)0.0034 (9)0.0103 (9)
C40.0278 (8)0.0474 (11)0.0433 (10)−0.0045 (8)0.0038 (7)0.0057 (8)
C50.0311 (9)0.0373 (10)0.0465 (10)−0.0036 (8)0.0094 (8)0.0014 (8)
C60.0396 (10)0.0451 (11)0.0525 (11)−0.0081 (9)0.0007 (9)0.0020 (9)
C70.0680 (15)0.0628 (15)0.0654 (14)−0.0041 (13)0.0018 (12)0.0211 (12)
C80.0742 (16)0.0465 (12)0.0866 (18)−0.0138 (12)0.0233 (14)0.0113 (12)
C90.0606 (13)0.0506 (13)0.0804 (16)−0.0227 (11)0.0114 (12)−0.0102 (12)
C100.0496 (12)0.0540 (13)0.0551 (12)−0.0146 (10)0.0014 (9)0.0000 (10)
Geometric parameters (Å, °) top
F1—C61.351 (2)C6—C71.365 (3)
O1—C11.300 (2)C7—C81.361 (3)
O2—C11.215 (2)C8—C91.368 (3)
O3—C41.223 (2)C9—C101.379 (3)
O1—H10.86 (2)C2—H2A0.9700
N1—C41.350 (2)C2—H2B0.9700
N1—C51.415 (2)C3—H3A0.9700
N1—H1A0.88 (2)C3—H3B0.9700
C1—C21.484 (3)C7—H70.9300
C2—C31.513 (3)C8—H80.9300
C3—C41.502 (3)C9—H90.9300
C5—C101.378 (3)C10—H100.9300
C5—C61.370 (3)
F1···N12.723 (2)C6···C9vii3.566 (3)
F1···C2i3.357 (2)C9···O1viii3.402 (3)
F1···H1A2.648 (19)C9···C6v3.566 (3)
F1···H2Aii2.8200C10···O33.000 (3)
F1···H2Bi2.6100C1···H1iii2.68 (2)
O1···O2iii2.664 (2)C1···H3Av2.9200
O1···C9iv3.402 (3)C4···H102.9100
O2···C1iii3.396 (2)H1···O2iii1.81 (2)
O2···C43.135 (2)H1···C1iii2.68 (2)
O2···O1iii2.664 (2)H1···H1iii2.42 (3)
O3···C3v3.262 (2)H1A···F12.648 (19)
O3···C13.101 (3)H1A···O3vii2.04 (2)
O3···N1v2.908 (2)H1A···H3A2.3900
O3···C103.000 (3)H1A···H3B2.5400
O1···H9iv2.5800H2A···O32.5900
O1···H3Av2.7400H2A···F1ii2.8200
O2···H8vi2.5400H2B···F1i2.6100
O2···H1iii1.81 (2)H3A···O1vii2.7400
O2···H3A2.6300H3A···O22.6300
O3···H1Av2.04 (2)H3A···O3vii2.8100
O3···H2A2.5900H3A···C1vii2.9200
O3···H3Av2.8100H3A···H1A2.3900
O3···H102.7200H3B···H1A2.5400
O3···H3Bii2.8000H3B···O3ii2.8000
N1···F12.723 (2)H7···H10ix2.3900
N1···O3vii2.908 (2)H8···O2x2.5400
C1···O33.101 (3)H9···O1viii2.5800
C1···O2iii3.396 (2)H10···O32.7200
C2···F1i3.357 (2)H10···C42.9100
C3···O3vii3.262 (2)H10···H7xi2.3900
C4···O23.135 (2)
C1—O1—H1111.6 (16)C8—C9—C10120.3 (2)
C4—N1—C5124.00 (15)C5—C10—C9120.65 (19)
C4—N1—H1A116.6 (13)C1—C2—H2A109.00
C5—N1—H1A119.3 (13)C1—C2—H2B109.00
O1—C1—O2122.59 (18)C3—C2—H2A109.00
O1—C1—C2114.01 (17)C3—C2—H2B109.00
O2—C1—C2123.40 (18)H2A—C2—H2B108.00
C1—C2—C3114.31 (16)C2—C3—H3A109.00
C2—C3—C4113.08 (16)C2—C3—H3B109.00
N1—C4—C3115.05 (14)C4—C3—H3A109.00
O3—C4—C3122.21 (17)C4—C3—H3B109.00
O3—C4—N1122.74 (17)H3A—C3—H3B108.00
N1—C5—C6120.67 (17)C6—C7—H7120.00
N1—C5—C10121.94 (17)C8—C7—H7120.00
C6—C5—C10117.39 (17)C7—C8—H8120.00
C5—C6—C7122.39 (19)C9—C8—H8120.00
F1—C6—C5117.86 (17)C8—C9—H9120.00
F1—C6—C7119.76 (18)C10—C9—H9120.00
C6—C7—C8119.6 (2)C5—C10—H10120.00
C7—C8—C9119.6 (2)C9—C10—H10120.00
C5—N1—C4—O31.1 (3)N1—C5—C6—C7−179.78 (19)
C5—N1—C4—C3−179.64 (16)C10—C5—C6—F1179.37 (17)
C4—N1—C5—C6−129.3 (2)C10—C5—C6—C7−0.5 (3)
C4—N1—C5—C1051.4 (3)N1—C5—C10—C9−179.55 (19)
O1—C1—C2—C3170.92 (17)C6—C5—C10—C91.2 (3)
O2—C1—C2—C3−9.5 (3)F1—C6—C7—C8179.9 (2)
C1—C2—C3—C4−67.8 (2)C5—C6—C7—C8−0.3 (3)
C2—C3—C4—O3−9.2 (3)C6—C7—C8—C90.3 (4)
C2—C3—C4—N1171.57 (16)C7—C8—C9—C100.4 (4)
N1—C5—C6—F10.1 (3)C8—C9—C10—C5−1.1 (3)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x, y+1/2, −z+1/2; (v) x−1, y, z; (vi) x, −y+1/2, z−1/2; (vii) x+1, y, z; (viii) −x, y−1/2, −z+1/2; (ix) x+1, −y+1/2, z+1/2; (x) x, −y+1/2, z+1/2; (xi) x−1, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2iii0.86 (2)1.81 (2)2.664 (2)178 (2)
N1—H1A···O3vii0.88 (2)2.04 (2)2.908 (2)169.7 (18)
C8—H8···O2x0.932.543.435 (3)160
C9—H9···O1viii0.932.583.402 (3)147
C2—H2B···F1i0.972.613.357 (2)134
C2—H2A···F1ii0.972.823.602 (2)138
Symmetry codes: (iii) −x, −y+1, −z; (vii) x+1, y, z; (x) x, −y+1/2, z+1/2; (viii) −x, y−1/2, −z+1/2; (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.86 (2)1.81 (2)2.664 (2)178 (2)
N1—H1A···O3ii0.88 (2)2.04 (2)2.908 (2)169.7 (18)
C8—H8···O2iii0.932.543.435 (3)160
C9—H9···O1iv0.932.583.402 (3)147
C2—H2B···F1v0.972.613.357 (2)134
C2—H2A···F1vi0.972.823.602 (2)138
Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y, z; (iii) x, −y+1/2, z+1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+2, −y+1, −z+1; (vi) −x+1, −y+1, −z+1.
Acknowledgements top

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore. SA is also thankful to PSF for financial support under project No. PSF/R&D/C-QU/Chem(270).

references
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