3-[3-(3-Fluoro­phen­yl)-1,2,4-oxadiazol-5-yl]propionic acid

Santos, S.K.M.; Neves Filho, R.A.W.; Bortoluzzi, A.J.; Srivastava, R.M.

doi:10.1107/S1600536808042001

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o146

doi:10.1107/S1600536808042001

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3-[3-(3-Fluorophenyl)-1,2,4-oxadiazol-5-yl]propionic acid

Suseanne K. M. Santos,^a Ricardo A. W. Neves Filho,^a Adailton J. Bortoluzzi ^b and Rajendra M. Srivastava ^a ^*

^aDepto. de Química Fundamental, Universidade Federal de Pernambuco, 50740-540 Recife, Pernambuco, Brazil, and ^bDepto. de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, Santa Catarina, Brazil
^*Correspondence e-mail: rms_indu@yahoo.com

(Received 18 November 2008; accepted 10 December 2008; online 17 December 2008)

In the title compound, C₁₁H₉FN₂O₃, the benzene ring is almost coplanar with the heterocyclic ring, making a dihedral angle of 14.0 (1)°. The plane of the carboxyl group is rotated by 14.7 (3)° with respect to the 1,2,4-oxadiazole ring plane. The aliphatic chain exhibits a standard zigzag arrangement. Two intermolecular O—H⋯O hydrogen bonds between the carboxyl groups related by an inversion centre promote a dimeric structure formation. The dimers are stacked along the crystallographic a axis.

Related literature

For general background, see: Gallardo et al. (2008 ); Jakopin & Dolenc (2008 ). For related structures, see: Wang et al. (2006 , 2007 ); Yan, Xing et al. (2006 ); Yan et al. (2006a ,b ). For the method of preparation, see: Sindkhedkar et al. (2008 ); Srivastava & Seabra (1997 ).

Experimental

Crystal data

C₁₁H₉FN₂O₃
M_r = 236.20
Triclinic, $[P \overline 1]$
a = 5.055 (1) Å
b = 5.905 (1) Å
c = 17.967 (1) Å
α = 85.769 (5)°
β = 87.965 (7)°
γ = 81.252 (7)°
V = 528.47 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.50 × 0.33 × 0.07 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2136 measured reflections
2066 independent reflections
1557 reflections with I > 2σ(I)
R_int = 0.010
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.112
S = 1.06
2066 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10⋯O9ⁱ	0.97 (3)	1.68 (3)	2.650 (2)	179 (3)
Symmetry code: (i) -x-2, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1996 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2003 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042001/is2367sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042001/is2367Isup2.hkl

checkCIF report

Comment top

1,2,4-Oxadiazoles are well known compounds, which exhibit a large number of biological activities (Jakopin & Dolenc, 2008). Recently, the use of this heterocycle as core for luminescent liquid crystals has also been described (Gallardo et al., 2008).

In the title compound (Fig. 1), the bond lengths and angles are in agreement with the values previously reported for 1,2,4-oxadiazole-containing molecules (Wang et al., 2006, 2007; Yan, Xing et al., 2006; Yan et al., 2006a,b). The torsion angle N2—C3—C11—C16 between the benzene ring attached to C-3 of the 1,2,4-oxadiazole system is -13.6 (2)°, thus, both rings are almost coplanar. The C-5 side-chain containing a carboxylic acid group shows a zigzag arrangement, having the torsion angle C5—C6—C7—C8 of -179.4 (1)°. In addition, the plane of the carboxylic group is also rotated by 14.7 (3)° with respect to the mean plane of the 1,2,4-oxadiazole five-membered ring, but in opposite direction of deviation of the fluoro-phenyl ring. This makes the molecular structure to be slightly twisted. Carboxylic groups are involved in centrosymmetric intermolecular hydrogen-bonding forming a dimeric structure (Fig. 2). The dimmers are perfectly stacked along the crystallographic a axis (Fig. 3).

Related literature top

For general background, see: Gallardo et al. (2008); Jakopin & Dolenc (2008). For related structures, see: Wang et al. (2006, 2007); Yan, Xing et al. (2006); Yan et al. (2006a,b). For the preparation method, see: Sindkhedkar et al. (2008); Srivastava & Seabra (1997).

Experimental top

The title compound was synthesized following the procedure reported earlier for the analogous compounds (Srivastava & Seabra, 1997; Sindkhedkar et al., 2008). A mixture of 3-fluorbenzamidoxime (2.0 mmol) and succinic anhydride (2.2 mmol) was heated in a domestic microwave oven for 10 min. The crude material was purified by column chromatography. Crystallization of pure material from chloroform, from which a suitable crystal was chosen for the X-ray crystallographic experiment.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with labeling scheme. Displacement ellipsoids are shown at the 40% probability level.
	Fig. 2. Dimeric strucuture formed by hydrogen bonding.
	Fig. 3. Molecules of (I) stacked along the a axis.

3-[3-(3-Fluorophenyl)-1,2,4-oxadiazol-5-yl]propionic acid top

Crystal data top

C₁₁H₉FN₂O₃	Z = 2
M_r = 236.20	F(000) = 244
Triclinic, P1	D_x = 1.484 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.055 (1) Å	Cell parameters from 25 reflections
b = 5.905 (1) Å	θ = 5.0–18.8°
c = 17.967 (1) Å	µ = 0.12 mm⁻¹
α = 85.769 (5)°	T = 293 K
β = 87.965 (7)°	Irregular plate, colorless
γ = 81.252 (7)°	0.50 × 0.33 × 0.07 mm
V = 528.47 (14) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.010
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 1.1°
Graphite monochromator	h = −6→6
ω–2θ scans	k = −7→7
2136 measured reflections	l = −22→0
2066 independent reflections	3 standard reflections every 200 reflections
1557 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0583P)² + 0.0868P] where P = (F_o² + 2F_c²)/3
2066 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₉FN₂O₃	γ = 81.252 (7)°
M_r = 236.20	V = 528.47 (14) Å³
Triclinic, P1	Z = 2
a = 5.055 (1) Å	Mo Kα radiation
b = 5.905 (1) Å	µ = 0.12 mm⁻¹
c = 17.967 (1) Å	T = 293 K
α = 85.769 (5)°	0.50 × 0.33 × 0.07 mm
β = 87.965 (7)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.010
2136 measured reflections	3 standard reflections every 200 reflections
2066 independent reflections	intensity decay: 1%
1557 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.21 e Å⁻³
2066 reflections	Δρ_min = −0.21 e Å⁻³
158 parameters

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

	x	y	z	U_iso*/U_eq
C3	0.1073 (3)	−0.0359 (3)	0.24108 (9)	0.0403 (4)
C5	−0.1973 (3)	0.0022 (3)	0.32245 (9)	0.0412 (4)
C6	−0.4105 (3)	0.0731 (3)	0.37879 (10)	0.0463 (4)
H6A	−0.3429	0.0278	0.4284	0.056*
H6B	−0.5616	−0.0064	0.3722	0.056*
C7	−0.5043 (3)	0.3291 (3)	0.37270 (10)	0.0476 (4)
H7A	−0.3529	0.4086	0.3788	0.057*
H7B	−0.5738	0.3741	0.3233	0.057*
C8	−0.7169 (3)	0.4009 (3)	0.42998 (9)	0.0422 (4)
C11	0.3022 (3)	0.0236 (3)	0.18257 (9)	0.0415 (4)
C12	0.2778 (4)	0.2461 (3)	0.15009 (10)	0.0522 (4)
H12	0.1426	0.3584	0.1660	0.063*
C13	0.4575 (4)	0.2996 (4)	0.09349 (11)	0.0618 (5)
H13	0.4413	0.4485	0.0715	0.074*
C14	0.6588 (4)	0.1352 (4)	0.06958 (11)	0.0594 (5)
H14	0.7785	0.1708	0.0316	0.071*
C15	0.6783 (3)	−0.0823 (3)	0.10322 (10)	0.0534 (5)
C16	0.5063 (3)	−0.1432 (3)	0.15924 (10)	0.0483 (4)
H16	0.5256	−0.2923	0.1811	0.058*
N2	0.0849 (3)	−0.2473 (3)	0.26222 (9)	0.0552 (4)
N4	−0.0667 (3)	0.1270 (2)	0.27700 (8)	0.0437 (3)
O1	−0.1230 (2)	−0.2237 (2)	0.31750 (7)	0.0555 (4)
O9	−0.8599 (2)	0.2685 (2)	0.45969 (7)	0.0547 (3)
O10	−0.7395 (3)	0.6168 (2)	0.44456 (8)	0.0551 (3)
F17	0.8776 (2)	−0.2448 (2)	0.07982 (7)	0.0822 (4)
H10	−0.885 (6)	0.660 (5)	0.4800 (16)	0.102 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0353 (8)	0.0424 (8)	0.0424 (8)	−0.0037 (6)	0.0030 (7)	−0.0040 (7)
C5	0.0372 (8)	0.0418 (8)	0.0440 (9)	−0.0059 (6)	0.0037 (7)	−0.0008 (7)
C6	0.0424 (9)	0.0479 (9)	0.0476 (9)	−0.0091 (7)	0.0116 (7)	0.0011 (7)
C7	0.0432 (9)	0.0465 (9)	0.0510 (10)	−0.0062 (7)	0.0137 (7)	0.0019 (7)
C8	0.0359 (8)	0.0454 (9)	0.0442 (9)	−0.0060 (7)	0.0050 (7)	0.0014 (7)
C11	0.0373 (8)	0.0482 (9)	0.0402 (8)	−0.0093 (7)	0.0040 (6)	−0.0076 (7)
C12	0.0533 (10)	0.0504 (10)	0.0511 (10)	−0.0047 (8)	0.0130 (8)	−0.0059 (8)
C13	0.0734 (13)	0.0582 (12)	0.0543 (11)	−0.0167 (10)	0.0160 (9)	−0.0023 (9)
C14	0.0573 (11)	0.0746 (14)	0.0489 (10)	−0.0210 (10)	0.0186 (9)	−0.0092 (9)
C15	0.0414 (9)	0.0669 (12)	0.0518 (10)	−0.0044 (8)	0.0114 (8)	−0.0165 (9)
C16	0.0445 (9)	0.0497 (10)	0.0503 (10)	−0.0057 (7)	0.0045 (8)	−0.0070 (7)
N2	0.0529 (9)	0.0452 (8)	0.0633 (10)	−0.0008 (6)	0.0206 (7)	0.0004 (7)
N4	0.0412 (7)	0.0429 (7)	0.0468 (8)	−0.0076 (6)	0.0108 (6)	−0.0045 (6)
O1	0.0560 (7)	0.0418 (7)	0.0646 (8)	−0.0033 (5)	0.0208 (6)	0.0038 (5)
O9	0.0488 (7)	0.0519 (7)	0.0636 (8)	−0.0129 (5)	0.0229 (6)	−0.0052 (6)
O10	0.0517 (7)	0.0471 (7)	0.0665 (8)	−0.0103 (5)	0.0198 (6)	−0.0077 (6)
F17	0.0635 (7)	0.0919 (10)	0.0841 (9)	0.0081 (6)	0.0308 (6)	−0.0145 (7)

Geometric parameters (Å, º) top

C3—N2	1.298 (2)	C11—C12	1.387 (2)
C3—N4	1.382 (2)	C11—C16	1.389 (2)
C3—C11	1.475 (2)	C12—C13	1.390 (3)
C5—N4	1.291 (2)	C12—H12	0.9300
C5—O1	1.338 (2)	C13—C14	1.376 (3)
C5—C6	1.486 (2)	C13—H13	0.9300
C6—C7	1.511 (2)	C14—C15	1.370 (3)
C6—H6A	0.9700	C14—H14	0.9300
C6—H6B	0.9700	C15—F17	1.359 (2)
C7—C8	1.497 (2)	C15—C16	1.370 (2)
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	N2—O1	1.4183 (19)
C8—O9	1.2252 (19)	O10—H10	0.97 (3)
C8—O10	1.308 (2)

N2—C3—N4	114.80 (14)	C12—C11—C3	119.61 (15)
N2—C3—C11	122.14 (14)	C16—C11—C3	120.18 (15)
N4—C3—C11	123.06 (14)	C11—C12—C13	119.36 (17)
N4—C5—O1	113.59 (14)	C11—C12—H12	120.3
N4—C5—C6	129.61 (15)	C13—C12—H12	120.3
O1—C5—C6	116.79 (13)	C14—C13—C12	120.87 (18)
C5—C6—C7	112.30 (13)	C14—C13—H13	119.6
C5—C6—H6A	109.1	C12—C13—H13	119.6
C7—C6—H6A	109.1	C15—C14—C13	118.25 (17)
C5—C6—H6B	109.1	C15—C14—H14	120.9
C7—C6—H6B	109.1	C13—C14—H14	120.9
H6A—C6—H6B	107.9	F17—C15—C14	118.33 (16)
C8—C7—C6	112.31 (14)	F17—C15—C16	118.68 (18)
C8—C7—H7A	109.1	C14—C15—C16	122.99 (17)
C6—C7—H7A	109.1	C15—C16—C11	118.33 (17)
C8—C7—H7B	109.1	C15—C16—H16	120.8
C6—C7—H7B	109.1	C11—C16—H16	120.8
H7A—C7—H7B	107.9	C3—N2—O1	102.97 (13)
O9—C8—O10	123.07 (15)	C5—N4—C3	102.40 (13)
O9—C8—C7	122.54 (15)	C5—O1—N2	106.23 (12)
O10—C8—C7	114.38 (14)	C8—O10—H10	112.6 (16)
C12—C11—C16	120.20 (15)

N4—C5—C6—C7	8.6 (3)	C13—C14—C15—C16	0.2 (3)
O1—C5—C6—C7	−172.42 (15)	F17—C15—C16—C11	−179.68 (16)
C5—C6—C7—C8	−179.36 (14)	C14—C15—C16—C11	0.3 (3)
C6—C7—C8—O9	−23.4 (2)	C12—C11—C16—C15	−0.8 (3)
C6—C7—C8—O10	157.66 (15)	C3—C11—C16—C15	178.08 (15)
N2—C3—C11—C12	165.28 (17)	N4—C3—N2—O1	−0.10 (19)
N4—C3—C11—C12	−14.0 (2)	C11—C3—N2—O1	−179.48 (14)
N2—C3—C11—C16	−13.6 (2)	O1—C5—N4—C3	−0.79 (18)
N4—C3—C11—C16	167.08 (15)	C6—C5—N4—C3	178.25 (16)
C16—C11—C12—C13	0.7 (3)	N2—C3—N4—C5	0.54 (19)
C3—C11—C12—C13	−178.15 (17)	C11—C3—N4—C5	179.91 (15)
C11—C12—C13—C14	−0.2 (3)	N4—C5—O1—N2	0.77 (19)
C12—C13—C14—C15	−0.3 (3)	C6—C5—O1—N2	−178.40 (14)
C13—C14—C15—F17	−179.80 (17)	C3—N2—O1—C5	−0.37 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O9ⁱ	0.97 (3)	1.68 (3)	2.650 (2)	179 (3)

Symmetry code: (i) −x−2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉FN₂O₃
M_r	236.20
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.055 (1), 5.905 (1), 17.967 (1)
α, β, γ (°)	85.769 (5), 87.965 (7), 81.252 (7)
V (Å³)	528.47 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.50 × 0.33 × 0.07

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2136, 2066, 1557
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.112, 1.06
No. of reflections	2066
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O9ⁱ	0.97 (3)	1.68 (3)	2.650 (2)	179 (3)

Symmetry code: (i) −x−2, −y+1, −z+1.

Acknowledgements

The authors are grateful to the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for financial assistance. SKMS thanks the Programa Institucional de Bolsas de Iniciação Científica (PIBIC/CNPq) for an Undergraduate fellowship.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Gallardo, H., Cristiano, R., Vieira, A. A., Neves Filho, R. A. W. & Srivastava, R. M. (2008). Synthesis, pp. 605–609. Web of Science CrossRef Google Scholar
Jakopin, Z. & Dolenc, M. S. (2008). Curr. Org. Chem. 12, 850–898. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sindkhedkar, M. D., Desai, V. N., Loriya, R. M., Patel, M. V., Trivedi, B. K., Bora, R. O., Diwakar, S. D., Jadhav, G. R. & Pawar, S. S. (2008). PCT Int. Patent Appl. 123pp. Google Scholar
Spek, A. L. (1996). HELENA. University of Utrecht, The Netherlands. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Srivastava, R. M. & Seabra, G. M. (1997). J. Braz. Chem. Soc. 8, 397–405. CrossRef CAS Google Scholar
Wang, P., Li, H., Kang, S. & Wang, H. (2007). Acta Cryst. E63, o4411. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, H.-B., Liu, Z.-Q., Wang, H.-B. & Yan, X.-C. (2006). Acta Cryst. E62, o4715–o4716. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yan, X.-C., Wang, H.-B. & Liu, Z.-Q. (2006a). Acta Cryst. E62, o3007–o3008. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yan, X.-C., Wang, H.-B. & Liu, Z.-Q. (2006b). Acta Cryst. E62, o1302–o1303. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yan, X.-C., Xing, Z.-T., Liu, Z.-Q. & Wang, H.-B. (2006). Acta Cryst. E62, o4640–o4641. Web of Science CSD CrossRef IUCr Journals Google Scholar