4-[(E)-(4-Fluoro­benzyl­idene)amino]­benzoic acid

Muñoz-Flores, B.M.; Pérez, V.M.J.; Santillan, R.L.; Ochoa, M.E.; Waksman, N.

doi:10.1107/S1600536811052275

organic compounds

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Volume 68| Part 1| January 2012| Page o175

doi:10.1107/S1600536811052275

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4-[(E)-(4-Fluorobenzylidene)amino]benzoic acid

Blanca M. Muñoz-Flores,^a ^* Víctor M. Jiménez Pérez,^a Rosa L. Santillan,^b Maria Eugenia Ochoa ^b and Noemi Waksman ^c

^aFacultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, San Nicolás de los Garza, 66451 Nuevo León, Mexico, ^bDepartamento de Química, Centro de Investigación y de Estudios Avanzados, del Instituto Politécnico Nacional, Apartado Postal 14-740, 07000 México, DF, Mexico, and ^cDepartamento de Química Analítica Facultad de Medicina, Universidad Autónoma de Nuevo León, León PO Box 2316, 64841 Nuevo León, Mexico
^*Correspondence e-mail: blanca.munozfl@uanl.edu.mx

(Received 16 November 2011; accepted 4 December 2011; online 21 December 2011)

In the title compound, C₁₄H₁₀FNO₂, the benzene rings make a dihedral angle of 57.50 (13)°, and the molecule has an E configuration about the C=N bond. In the crystal, molecules are linked via pairs of O—H⋯O hydrogen bonds, forming inversion dimers.

Related literature

For the synthesis, properties and uses of 4-(benzylideneamino)benzoic acid, see: Borisova et al. (2007 ); Schiff (1864 ); Innocenzi & Lebeau (2005 ); Muñoz-Flores et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₀FNO₂
M_r = 243.24
Monoclinic, P 2₁ /n
a = 12.2787 (5) Å
b = 5.6264 (2) Å
c = 17.2874 (8) Å
β = 105.833 (2)°
V = 1148.99 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.23 × 0.2 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
9975 measured reflections
2002 independent reflections
1226 reflections with I > 2σ(I)
R_int = 0.186

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.191
S = 1.04
2002 reflections
166 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 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
O2—H⋯O1ⁱ	0.85 (1)	1.79 (2)	2.601 (3)	159 (4)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: XSCANS (Bruker, 2000 ); data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052275/fj2486sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052275/fj2486Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052275/fj2486Isup3.cml

checkCIF report

Comment top

Hugo Josef Schiff discovered the condensation a primary amine and a carbonyl compounds (Schiff 1864) afford the corresponding azomethine group. This organic compounds show an important synthetic advantages such as: high yields, simple synthetic route, short-time reactions, and easy isolation. Schiff base compounds have been of great importance in coordination chemistry (Borisova et al. 2007) due to the lone pair of electrons in an sp² hybridized orbital of nitrogen atom of the azomethine group. On the other hand, it has been reported that organic compounds containing donor and acceptor groups linked through to pi-system delocalized exhibit promising nonlinear optical properties (Innocenzi & Lebeau 2005). We have been focused our attention on synthesis of push-pull organic molecules with no linear optical potential properties (Muñoz-Flores et al. 2008). In continuous with our research, we synthesized the title compound (E)-4-(4-fluorobenzylideneamino)benzoic acid by condensation of 4-fluorobenzaldehyde and 4-aminobenzoic acid. In the present article, the crystal structure of (I) is being reported as shown in Fig 1. The compound, (E)-4-(4-fluorbenzylideneamino)benzoic acid (C₁₄H₁₀N₂O₂F), displays C₁ symmetry. The aromatic rings are not in the same plane, with a dihedral angle of 15.59° between mean planes. The carboxylic group represents a delocalized system with C(14)—O(1) and C(14)—O(2) bond lengths are 1.275 (4) and 1.293 (4) Å, respectively. The azomethine group are in the same plane as the monofluorated ring, probably because the short contact between the C(5)—H(5)···N(1) 2.633 (4) Å, [〈 C—H···N: 96.8°]. The intermolecular O(2)—H(2)···O(1) [2.621 (5)Å (angleO-H···O: 156.30°], hydrogen bond form a dimer with a inversion center as shown in Fig 2.

Related literature top

For the synthesis, properties and uses of 4-(benzylideneamino)benzoic acid, see: Borisova et al. (2007); Schiff (1864); Innocenzi & Lebeau (2005); Muñoz-Flores et al. (2008).

Experimental top

A solution of 4-fluorobenzaldehyde (0.5 g, 4 mmol) and 4-aminobenzoic acid (0.55 g, 4 mmol) in benzene (50 ml) was heated under reflux for 6 h, with a Dean-Stark apparatus used for the azeotropic removal of water and allowed to cool to room temperature. Removal of solvent yielded a pale yellow solid, which was recrystallized from hot benzene (10 ml). Yield: 0.74 g 76%. M. p. 191 °C. 1H NMR (400.13 MHz, MeOD): δ = 4.9 (bs, 1H, OH), 6.62 (d, ³J = 8.4 Hz, 2H, H-11/H-12), 6.80 (d, ³J = 8.4 Hz, 2H, H-9/H-13), 7.10 (t, ³J = 8.4 Hz, 2H, H-2/H-4), 8.05 (d, ³J = 78.4 Hz, 2H, H-1/H-5), 8.53 (s, 1H, H-7). MS (DIP 20 eV) for C₁₄H₁₀N₂O₂F (f. w: 243.24 g/mol) m/z (%): 243 (100) [M⁺], 226 (3) [M⁺—H₂O], 198 (3) [M⁺—CO₂], 137 (4) [M⁺—FC₆H₈], 121 [M⁺—C₇H₆O₂].

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: XSCANS (Bruker, 2000); data reduction: XSCANS (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: 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 atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Intermolecular interaction via hydrogen bonds.

4-[(E)-(4-Fluorobenzylidene)amino]benzoic acid top

Crystal data top

C₁₄H₁₀FNO₂	F(000) = 504
M_r = 243.24	D_x = 1.406 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 464 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.2787 (5) Å	Cell parameters from 4962 reflections
b = 5.6264 (2) Å	θ = 2.9–27.5°
c = 17.2874 (8) Å	µ = 0.11 mm⁻¹
β = 105.833 (2)°	T = 293 K
V = 1148.99 (8) Å³	Prism, yellow
Z = 4	0.23 × 0.2 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	1226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.186
Graphite monochromator	θ_max = 25.0°, θ_min = 3.7°
CCD rotation images, thick slices scans	h = −14→14
9975 measured reflections	k = −6→6
2002 independent reflections	l = −17→20

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0979P)² + 0.0699P] where P = (F_o² + 2F_c²)/3
2002 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₀FNO₂	V = 1148.99 (8) Å³
M_r = 243.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.2787 (5) Å	µ = 0.11 mm⁻¹
b = 5.6264 (2) Å	T = 293 K
c = 17.2874 (8) Å	0.23 × 0.2 × 0.15 mm
β = 105.833 (2)°

Data collection top

Nonius KappaCCD diffractometer	1226 reflections with I > 2σ(I)
9975 measured reflections	R_int = 0.186
2002 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	1 restraint
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.18 e Å⁻³
2002 reflections	Δρ_min = −0.21 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.7423 (2)	0.3339 (5)	−0.03261 (18)	0.0515 (8)
H1	0.7623	0.4696	−0.0012	0.062*
C2	0.7740 (2)	0.3115 (5)	−0.10261 (19)	0.0565 (8)
H2	0.8169	0.4284	−0.1185	0.068*
C3	0.7407 (3)	0.1119 (5)	−0.14822 (19)	0.0557 (8)
C4	0.6800 (2)	−0.0683 (5)	−0.12777 (19)	0.0567 (8)
H4	0.6588	−0.2005	−0.1607	0.068*
C5	0.6511 (2)	−0.0474 (5)	−0.05617 (18)	0.0528 (7)
H5	0.6116	−0.1698	−0.0397	0.063*
C6	0.6803 (2)	0.1547 (4)	−0.00823 (17)	0.0479 (7)
C7	0.6428 (2)	0.1789 (5)	0.06460 (17)	0.0506 (7)
H7	0.6186	0.0437	0.0861	0.061*
C8	0.6104 (2)	0.3845 (4)	0.17270 (17)	0.0452 (7)
C9	0.5490 (2)	0.5794 (4)	0.1872 (2)	0.0563 (8)
H9	0.5247	0.6939	0.1474	0.068*
C10	0.5237 (2)	0.6054 (5)	0.25934 (19)	0.0534 (8)
H10	0.4824	0.7367	0.2677	0.064*
C11	0.5597 (2)	0.4361 (4)	0.32045 (17)	0.0482 (7)
C12	0.6204 (2)	0.2400 (5)	0.30522 (19)	0.0554 (8)
H12	0.6446	0.1251	0.3449	0.066*
C13	0.6449 (2)	0.2136 (5)	0.23337 (18)	0.0546 (8)
H13	0.6849	0.0808	0.2246	0.065*
C14	0.5353 (2)	0.4651 (5)	0.39801 (18)	0.0523 (8)
F1	0.77081 (18)	0.0920 (3)	−0.21809 (12)	0.0827 (7)
N1	0.64180 (18)	0.3768 (4)	0.10000 (15)	0.0530 (7)
O1	0.56240 (18)	0.3041 (4)	0.45179 (13)	0.0679 (7)
O2	0.48502 (19)	0.6570 (4)	0.41100 (13)	0.0675 (7)
H	0.487 (3)	0.678 (7)	0.4597 (9)	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0568 (16)	0.0450 (14)	0.0523 (19)	−0.0016 (12)	0.0142 (13)	−0.0017 (12)
C2	0.0623 (17)	0.0512 (15)	0.061 (2)	0.0016 (13)	0.0245 (15)	0.0098 (14)
C3	0.0649 (18)	0.0582 (17)	0.0471 (19)	0.0168 (14)	0.0206 (14)	0.0037 (14)
C4	0.0639 (17)	0.0483 (15)	0.058 (2)	0.0042 (13)	0.0177 (15)	−0.0075 (14)
C5	0.0526 (15)	0.0457 (14)	0.062 (2)	−0.0007 (12)	0.0191 (13)	0.0006 (14)
C6	0.0455 (14)	0.0456 (14)	0.0520 (19)	0.0034 (11)	0.0122 (13)	0.0026 (12)
C7	0.0508 (15)	0.0520 (15)	0.0516 (18)	−0.0003 (12)	0.0185 (13)	0.0061 (13)
C8	0.0433 (14)	0.0493 (15)	0.0436 (17)	−0.0052 (11)	0.0131 (12)	−0.0007 (12)
C9	0.0569 (16)	0.0434 (14)	0.066 (2)	0.0042 (12)	0.0116 (14)	0.0095 (13)
C10	0.0558 (16)	0.0470 (14)	0.058 (2)	0.0056 (12)	0.0165 (14)	0.0001 (13)
C11	0.0478 (14)	0.0478 (14)	0.0477 (18)	0.0006 (11)	0.0106 (12)	0.0016 (13)
C12	0.0628 (17)	0.0532 (16)	0.0474 (18)	0.0097 (13)	0.0106 (14)	0.0066 (13)
C13	0.0551 (16)	0.0503 (15)	0.056 (2)	0.0109 (12)	0.0112 (14)	0.0044 (13)
C14	0.0467 (14)	0.0511 (15)	0.056 (2)	0.0011 (13)	0.0085 (12)	−0.0023 (14)
F1	0.1162 (16)	0.0737 (12)	0.0682 (14)	0.0116 (11)	0.0420 (12)	0.0015 (10)
N1	0.0532 (14)	0.0494 (13)	0.0564 (16)	0.0016 (10)	0.0150 (11)	0.0027 (11)
O1	0.0832 (15)	0.0652 (13)	0.0558 (15)	0.0141 (11)	0.0198 (11)	0.0101 (10)
O2	0.0804 (15)	0.0660 (13)	0.0549 (15)	0.0158 (10)	0.0165 (12)	−0.0040 (11)

Geometric parameters (Å, º) top

C1—C2	1.375 (4)	C8—C13	1.400 (4)
C1—C6	1.396 (4)	C8—N1	1.413 (4)
C1—H1	0.9300	C9—C10	1.372 (4)
C2—C3	1.369 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.402 (4)
C3—C4	1.360 (4)	C10—H10	0.9300
C3—F1	1.361 (4)	C11—C12	1.396 (4)
C4—C5	1.383 (4)	C11—C14	1.460 (4)
C4—H4	0.9300	C12—C13	1.363 (4)
C5—C6	1.395 (4)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.460 (4)	C14—O1	1.275 (4)
C7—N1	1.272 (3)	C14—O2	1.294 (3)
C7—H7	0.9300	O2—H	0.845 (10)
C8—C9	1.392 (4)

C2—C1—C6	120.6 (3)	C9—C8—N1	118.5 (2)
C2—C1—H1	119.7	C13—C8—N1	123.0 (2)
C6—C1—H1	119.7	C10—C9—C8	121.0 (3)
C3—C2—C1	118.0 (3)	C10—C9—H9	119.5
C3—C2—H2	121.0	C8—C9—H9	119.5
C1—C2—H2	121.0	C9—C10—C11	120.7 (3)
C4—C3—F1	118.0 (3)	C9—C10—H10	119.7
C4—C3—C2	124.1 (3)	C11—C10—H10	119.7
F1—C3—C2	117.9 (3)	C12—C11—C10	118.0 (3)
C3—C4—C5	117.5 (3)	C12—C11—C14	121.0 (2)
C3—C4—H4	121.2	C10—C11—C14	121.0 (2)
C5—C4—H4	121.2	C13—C12—C11	121.3 (3)
C4—C5—C6	120.9 (3)	C13—C12—H12	119.4
C4—C5—H5	119.5	C11—C12—H12	119.4
C6—C5—H5	119.5	C12—C13—C8	120.7 (3)
C5—C6—C1	118.8 (3)	C12—C13—H13	119.6
C5—C6—C7	119.9 (2)	C8—C13—H13	119.6
C1—C6—C7	121.3 (2)	O1—C14—O2	120.6 (3)
N1—C7—C6	122.9 (2)	O1—C14—C11	120.8 (2)
N1—C7—H7	118.5	O2—C14—C11	118.7 (3)
C6—C7—H7	118.5	C7—N1—C8	119.7 (2)
C9—C8—C13	118.3 (3)	C14—O2—H	114 (3)

C6—C1—C2—C3	1.6 (4)	C9—C10—C11—C12	−0.8 (4)
C1—C2—C3—C4	−1.4 (4)	C9—C10—C11—C14	178.6 (2)
C1—C2—C3—F1	179.0 (2)	C10—C11—C12—C13	0.4 (4)
F1—C3—C4—C5	179.2 (2)	C14—C11—C12—C13	−179.0 (3)
C2—C3—C4—C5	−0.3 (4)	C11—C12—C13—C8	0.5 (4)
C3—C4—C5—C6	1.9 (4)	C9—C8—C13—C12	−1.0 (4)
C4—C5—C6—C1	−1.8 (4)	N1—C8—C13—C12	174.3 (2)
C4—C5—C6—C7	176.2 (2)	C12—C11—C14—O1	−4.7 (4)
C2—C1—C6—C5	0.0 (4)	C10—C11—C14—O1	175.9 (2)
C2—C1—C6—C7	−178.0 (2)	C12—C11—C14—O2	175.7 (2)
C5—C6—C7—N1	−162.4 (3)	C10—C11—C14—O2	−3.7 (4)
C1—C6—C7—N1	15.6 (4)	C6—C7—N1—C8	−176.5 (2)
C13—C8—C9—C10	0.6 (4)	C9—C8—N1—C7	−143.9 (3)
N1—C8—C9—C10	−174.9 (2)	C13—C8—N1—C7	40.8 (4)
C8—C9—C10—C11	0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H···O1ⁱ	0.85 (1)	1.79 (2)	2.601 (3)	159 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀FNO₂
M_r	243.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.2787 (5), 5.6264 (2), 17.2874 (8)
β (°)	105.833 (2)
V (Å³)	1148.99 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.23 × 0.2 × 0.15

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9975, 2002, 1226
R_int	0.186
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.191, 1.04
No. of reflections	2002
No. of parameters	166
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)	0.18, −0.21

Computer programs: COLLECT (Nonius, 1998), XSCANS (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H···O1ⁱ	0.845 (10)	1.793 (18)	2.601 (3)	159 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank the Programa de Mejoramiento del Profesorado (PROMEP; grant No. 103.5/11/4330) and the Consejo Nacional de Ciencia y Tecnología (CONACYT; grant No. 82605) for financial support.

References

Borisova, N. E., Reshetova, M. D. & Ustynyuk, Y. A. (2007). Chem. Rev. 107, 46–79. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2000). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Innocenzi, P. & Lebeau, B. (2005). J. Mater. Chem. 15, 3821–3831. 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
Muñoz-Flores, B. M., Santillan, R., Rodríguez, M., Méndez, J. M., Romero, M., Farfán, N., Lacroix, P. G., Nakatani, K., Ramos-Ortíz, G. & Maldonado, J. L. (2008). J. Organomet. Chem. 693, 1321–1334. Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Schiff, H. (1864). Annalen, 131, 118–119. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar