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

Ali Shah, F.; Ali, S.; Shahzadi, S.; Ahmad, S.; Fischer, A.

doi:10.1107/S1600536811001152

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o393

doi:10.1107/S1600536811001152

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

Farooq Ali Shah,^a Saqib Ali,^a ^* Saira Shahzadi,^b Sajjad Ahmad ^a and Andreas Fischer ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bDepartment of Chemistry, GC University, Faisalabad, Pakistan, and ^cInorganic Chemistry, School of Chemical Science and Engineering, Royal Institute of Technology (KTH), 100 44 Stockholm, Sweden
^*Correspondence e-mail: drsa54@yahoo.com

(Received 20 December 2010; accepted 8 January 2011; online 15 January 2011)

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, P n a 2₁
a = 20.282 (2) Å
b = 3.8025 (4) Å
c = 11.8183 (8) Å
V = 911.45 (15) Å³
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[F² > 2σ(F²)] = 0.046
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001152/su2241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001152/su2241Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For the use 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 et al. (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 top

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).

Computing details top

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 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	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).

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

Crystal data top

C₁₀H₈FNO₃	F(000) = 432
M_r = 209.17	D_x = 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 top

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

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)] = 0.046	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(F_o²) + (0.0562P)² + 0.3218P] where P = (F_o² + 2F_c²)/3
1075 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₀H₈FNO₃	V = 911.45 (15) Å³
M_r = 209.17	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 20.282 (2) Å	µ = 0.13 mm⁻¹
b = 3.8025 (4) Å	T = 299 K
c = 11.8183 (8) Å	0.57 × 0.21 × 0.06 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	799 reflections with I > 2σ(I)
7575 measured reflections	R_int = 0.066
1075 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.27 e Å⁻³
1075 reflections	Δρ_min = −0.27 e Å⁻³
132 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1/2, y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈FNO₃
M_r	209.17
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	299
a, b, c (Å)	20.282 (2), 3.8025 (4), 11.8183 (8)
V (Å³)	911.45 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.57 × 0.21 × 0.06

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7575, 1075, 799
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.121, 1.09
No. of reflections	1075
No. of parameters	132
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.27

Computer programs: COLLECT (Nonius, 1998), DIRAX (Duisenberg, 1992), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2007), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y−1/2, z−1/2.

Acknowledgements

SA is thankful to Quaid-i-Azam University, Islamabad, Pakistan, for financial support. The Swedish Research Council (VR) is acknowledged for providing funding for the single-crystal diffractometer.

References

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