organic compounds
4-[(E)-(4-Fluorobenzylidene)amino]benzoic acid
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
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
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Data collection
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Refinement
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Data collection: COLLECT (Nonius, 1998); cell 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
10.1107/S1600536811052275/fj2486sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811052275/fj2486Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811052275/fj2486Isup3.cml
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].
All C-bonded H atoms were placed in calculated positions and refined as riding to their carrier atoms, with bond lengths fixed to 0.93 (aromatic CH). Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.5Ueq(carrier atom.
Data collection: COLLECT (Nonius, 1998); cell
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).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. |
C14H10FNO2 | F(000) = 504 |
Mr = 243.24 | Dx = 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 |
Nonius KappaCCD diffractometer | 1226 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.186 |
Graphite monochromator | θmax = 25.0°, θmin = 3.7° |
CCD rotation images, thick slices scans | h = −14→14 |
9975 measured reflections | k = −6→6 |
2002 independent reflections | l = −17→20 |
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(Fo2) + (0.0979P)2 + 0.0699P] where P = (Fo2 + 2Fc2)/3 |
2002 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.18 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C14H10FNO2 | V = 1148.99 (8) Å3 |
Mr = 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)° |
Nonius KappaCCD diffractometer | 1226 reflections with I > 2σ(I) |
9975 measured reflections | Rint = 0.186 |
2002 independent reflections |
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 | Δρmax = 0.18 e Å−3 |
2002 reflections | Δρmin = −0.21 e Å−3 |
166 parameters |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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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.