(Z)-3-[(2-Fluoro­anilino)carbon­yl]prop-2-enoic acid

Abstract

In the title mol­ecule, C₁₀H₈FNO₃, the dihedral angle between the fluoro­phenyl group and the essentially planar [within 0.064 (3) Å] COC=CCOOH unit, which has a Z configuration, is 19.99 (14)°. There is an intra­molecular O—H⋯O bond in the mol­ecule involving the acid –OH group and the adjacent carbonyl O atom. In the crystal, inter­molecular N—H⋯O bonds lead to the formation of polymer chains propagating along [011].

Related literature

For the use of carb­oxy­lic acids containing N atoms as anti­biotics, see: Gould et al. (1980 ▶). For the biological properties of compounds containing keto, ester, imide and carboxylc acid groups, see: Chen & Njoroge (2009 ▶); Shen & Walford (1972 ▶; 1980 ▶). For the structure of 3-[(4-bromo­anilino)carbon­yl]prop-2-enoic acid, see Parvez, Shahid et al. (2004 ▶). For the structure of 3-[(2,4,6-tricholoroanilino)carbon­yl]prop-2-enoic acid, see Parvez, Shahzadi et al.(2004 ▶).

Experimental

Crystal data

• C₁₀H₈FNO₃

• M _r = 209.17

• Orthorhombic,

• a = 20.282 (2) Å

• b = 3.8025 (4) Å

• c = 11.8183 (8) Å

• V = 911.45 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.13 mm⁻¹

• T = 299 K

• 0.57 × 0.21 × 0.06 mm

Data collection

• Bruker–Nonius KappaCCD diffractometer

• 7575 measured reflections

• 1075 independent reflections

• 799 reflections with I > 2σ(I)

• R _int = 0.066

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.121

• S = 1.09

• 1075 reflections

• 132 parameters

• 1 restraint

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

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DIRAX (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1	0.92 (8)	1.60 (8)	2.506 (4)	170 (7)
N1—H1A⋯O2i	0.83 (5)	2.10 (5)	2.929 (5)	175 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Carboxylic acids are good reducing agents and applied as an antioxidant agent and a precursor for the prevention of cancer. Carboxylic acids are used for therapeutic purposes and for other biological applications as well. Those carboxylic acids which contain N atoms are widely used as antibiotics (Gould et al., 1980). Compounds containing NH and carboxyl groups are of great interest for the synthesis of drugs due to their coordination to biological systems. Compounds containing keto, ester and imide are good anti-HCV agents (Chen et al., 2009). Carboxylic acids are also used as anti-inflammatories (Shen & Walford, 1980) and enzymetic inhibitors (Shen & Walford, 1972). We therefore used maleic anhydride to synthesize the title compound, by condensation with 2-fluoroaniline.

The molecular structure of the title compound is illustrated in Fig. 1. The bond distances and angles are close to those observed in simlar compounds; 3-[(4-bromoanilino)carbonyl]prop-2-enoic acid (Parvez, Shahid et al., 2004) and 3-[(2,4,6-Tricholoroanilino)carbonyl]prop-2-enoic acid (Parvez, Shahzadi et al., 2004). In the molecule there is an intramolecular O—H···O hydrogen bond involving the acid OH group and the adjacent carbonyl O-atom (Table 1). The COC=CCOOH moiety is essentially planar [atoms O1,C7—C10, O2,O3 planar to within 0.064 (3) Å], and has a Z configuration. It makes a dihedral angle of 19.99 (14) Å with the phenyl ring.

In the crystal there are intermolecular N–H···.O hydrogen bonds connecting symmetry related molecules yielding chains propagating along [011] (Table 1 and Fig. 2).

Experimental

A solution of maleic anhydride (5 g, 1 mmol) in (300 ml glacial acetic acid) was added to a solution of 2-fluoroaniline (5 ml, 1 mmol) (150 ml glacial acetic acid) in 500 ml beaker at room temperature and the mixture was stirred in fuming hood at room temperature overnight. The light yellow precipitates formed were filtered off, washed with cold distilled H₂O (200 ml) and air dried. The yellow crystals, suitable for X-ray diffraction analysis, were obtained by recrystallization in acetone:n-hexane (1:1).

Refinement

In the final cycles of refinement, in the absence of significant anomalous scattering effects, 719 Friedel pairs were merged and Δf " set to zero. The OH and NH H-atoms were located from a difference Fourier map and were freely refined: O3—H3B = 0.92 (8) Å, N1—H1A = 0.83 (5) Å. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(parent C-atom).

Figures

Fig. 1.

The molecular structure of the title compound. Thermal ellipsoids are drawn at the 50% probability level. The intramolecular O—H···O hydrogen bond is shown as a dashed line.

Fig. 2.

A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed cyan lines (see Table 1 for details).

Crystal data

C10H8FNO3	F(000) = 432
Mr = 209.17	Dx = 1.524 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 49 reflections
a = 20.282 (2) Å	θ = 6.2–19.7°
b = 3.8025 (4) Å	µ = 0.13 mm−1
c = 11.8183 (8) Å	T = 299 K
V = 911.45 (15) Å3	Plate, yellow
Z = 4	0.57 × 0.21 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	799 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
graphite	θmax = 27.5°, θmin = 5.3°
φ and ω scans	h = −24→26
7575 measured reflections	k = −4→4
1075 independent reflections	l = −15→15

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0562P)2 + 0.3218P] where P = (Fo2 + 2Fc2)/3
1075 reflections	(Δ/σ)max < 0.001
132 parameters	Δρmax = 0.27 e Å−3
1 restraint	Δρmin = −0.27 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
F1	0.06487 (13)	0.1290 (8)	0.1972 (2)	0.0682 (9)
O1	0.13208 (13)	0.4940 (9)	0.5666 (2)	0.0568 (9)
O2	0.31277 (15)	1.0159 (9)	0.6674 (3)	0.0608 (10)
O3	0.21896 (15)	0.7409 (10)	0.6947 (3)	0.0609 (12)
N1	0.11309 (15)	0.4479 (9)	0.3789 (3)	0.0380 (10)
C1	0.04662 (8)	0.3316 (7)	0.38017 (19)	0.0339 (10)
C2	0.02363 (10)	0.1799 (7)	0.28070 (18)	0.0440 (12)
C3	−0.04193 (11)	0.0770 (7)	0.2720 (2)	0.0510 (16)
C4	−0.08451 (9)	0.1257 (8)	0.3629 (2)	0.0500 (15)
C5	−0.06152 (10)	0.2773 (8)	0.4623 (2)	0.0491 (15)
C6	0.00405 (11)	0.3803 (7)	0.47100 (17)	0.0436 (11)
C7	0.15083 (18)	0.5352 (10)	0.4677 (3)	0.0376 (11)
C8	0.21585 (19)	0.6799 (11)	0.4379 (3)	0.0418 (11)
C9	0.26209 (19)	0.8086 (11)	0.5039 (3)	0.0426 (11)
C10	0.2656 (2)	0.8609 (12)	0.6285 (3)	0.0433 (14)
H1A	0.132 (2)	0.467 (11)	0.317 (4)	0.040 (12)*
H3	−0.05730	−0.02450	0.20550	0.0610*
H3B	0.190 (4)	0.630 (18)	0.647 (7)	0.11 (2)*
H4	−0.12840	0.05680	0.35710	0.0600*
H5	−0.09000	0.30990	0.52310	0.0590*
H6	0.01940	0.48170	0.53760	0.0520*
H8	0.22570	0.68040	0.36100	0.0500*
H9	0.29970	0.88070	0.46550	0.0510*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
F1	0.0578 (14)	0.107 (2)	0.0399 (13)	−0.0096 (15)	0.0025 (12)	−0.0258 (14)
O1	0.0460 (14)	0.096 (2)	0.0283 (14)	−0.0165 (15)	−0.0017 (13)	0.0017 (16)
O2	0.0468 (16)	0.093 (2)	0.0425 (17)	−0.0111 (16)	−0.0097 (14)	−0.0176 (17)
O3	0.0479 (16)	0.101 (3)	0.0337 (15)	−0.0106 (18)	−0.0026 (14)	−0.0121 (19)
N1	0.0357 (15)	0.050 (2)	0.0284 (16)	0.0003 (14)	−0.0007 (15)	−0.0046 (16)
C1	0.0368 (17)	0.0353 (18)	0.0297 (19)	0.0044 (15)	−0.0042 (16)	0.0032 (16)
C2	0.044 (2)	0.046 (2)	0.042 (2)	0.0008 (18)	−0.003 (2)	0.001 (2)
C3	0.052 (2)	0.049 (3)	0.052 (3)	−0.0084 (19)	−0.017 (2)	0.003 (2)
C4	0.0400 (19)	0.054 (3)	0.056 (3)	−0.0057 (18)	−0.007 (2)	0.017 (2)
C5	0.0363 (18)	0.062 (3)	0.049 (3)	0.0049 (18)	0.0005 (19)	0.015 (2)
C6	0.0417 (19)	0.049 (2)	0.040 (2)	0.0044 (18)	−0.0049 (18)	0.001 (2)
C7	0.0366 (19)	0.046 (2)	0.0302 (19)	0.0001 (16)	0.0000 (17)	−0.0015 (19)
C8	0.043 (2)	0.058 (2)	0.0244 (17)	−0.0028 (19)	0.0019 (16)	−0.0086 (17)
C9	0.0339 (18)	0.059 (2)	0.035 (2)	−0.0034 (18)	0.0026 (16)	−0.0062 (19)
C10	0.037 (2)	0.059 (3)	0.034 (2)	0.0081 (19)	−0.0041 (18)	−0.008 (2)

Geometric parameters (Å, °)

F1—C2	1.308 (3)	C4—C5	1.3892
O1—C7	1.239 (4)	C5—C6	1.3902
O2—C10	1.214 (5)	C7—C8	1.472 (5)
O3—C10	1.310 (5)	C8—C9	1.314 (5)
O3—H3B	0.92 (8)	C9—C10	1.488 (5)
N1—C1	1.419 (4)	C3—H3	0.9300
N1—C7	1.341 (5)	C4—H4	0.9300
N1—H1A	0.83 (5)	C5—H5	0.9300
C1—C6	1.3900	C6—H6	0.9300
C1—C2	1.3900	C8—H8	0.9300
C2—C3	1.3899	C9—H9	0.9300
C3—C4	1.3908
C10—O3—H3B	105 (5)	C7—C8—C9	129.5 (3)
C1—N1—C7	127.7 (3)	C8—C9—C10	132.2 (4)
C1—N1—H1A	118 (3)	O2—C10—O3	120.8 (4)
C7—N1—H1A	114 (3)	O2—C10—C9	118.5 (4)
N1—C1—C2	116.1 (2)	O3—C10—C9	120.7 (4)
N1—C1—C6	123.8 (2)	C2—C3—H3	120.00
C2—C1—C6	120.00	C4—C3—H3	120.00
C1—C2—C3	120.02	C3—C4—H4	120.00
F1—C2—C1	119.0 (2)	C5—C4—H4	120.00
F1—C2—C3	121.0 (2)	C4—C5—H5	120.00
C2—C3—C4	119.96	C6—C5—H5	120.00
C3—C4—C5	120.00	C1—C6—H6	120.00
C4—C5—C6	120.04	C5—C6—H6	120.00
C1—C6—C5	119.97	C7—C8—H8	115.00
O1—C7—N1	122.1 (3)	C9—C8—H8	115.00
O1—C7—C8	123.2 (3)	C8—C9—H9	114.00
N1—C7—C8	114.6 (3)	C10—C9—H9	114.00
C7—N1—C1—C2	−165.3 (3)	F1—C2—C3—C4	178.4 (3)
C7—N1—C1—C6	18.5 (5)	C1—C2—C3—C4	−0.04
C1—N1—C7—O1	6.3 (6)	C2—C3—C4—C5	0.04
C1—N1—C7—C8	−174.2 (3)	C3—C4—C5—C6	−0.02
N1—C1—C2—F1	5.3 (4)	C4—C5—C6—C1	0.00
N1—C1—C2—C3	−176.3 (3)	O1—C7—C8—C9	−5.0 (7)
C6—C1—C2—F1	−178.4 (3)	N1—C7—C8—C9	175.4 (4)
C6—C1—C2—C3	0.03	C7—C8—C9—C10	−1.3 (8)
N1—C1—C6—C5	176.0 (3)	C8—C9—C10—O2	−173.7 (5)
C2—C1—C6—C5	−0.02	C8—C9—C10—O3	6.6 (7)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1	0.92 (8)	1.60 (8)	2.506 (4)	170 (7)
N1—H1A···O2i	0.83 (5)	2.10 (5)	2.929 (5)	175 (4)

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