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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o489.
Published online 2008 January 23. doi:  10.1107/S160053680800175X
PMCID: PMC2960401

(E)-Ethyl 3-(2-fluoro­anilino)-2-(4-methoxy­phen­yl)acrylate

Abstract

The title compound, C18H18FNO3, consists of three individually planar subunits, namely two substituted benzene rings and one amino­acrylate group. The dihedral angle between the two benzene rings is 47.48 (8)°. The amino­acrylate group forms dihedral angles of 57.95 (7) and 11.27 (6)° with the methoxy­phenyl and fluorophenyl rings, respectively.

Related literature

For related literature, see: Xiao et al. (2007 [triangle], 2008 [triangle]).

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Object name is e-64-0o489-scheme1.jpg

Experimental

Crystal data

  • C18H18FNO3
  • M r = 315.33
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o489-efi1.jpg
  • a = 6.3630 (13) Å
  • b = 9.4700 (19) Å
  • c = 13.981 (3) Å
  • α = 97.68 (3)°
  • β = 97.38 (3)°
  • γ = 95.40 (3)°
  • V = 822.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 (2) K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.963, T max = 0.981
  • 3273 measured reflections
  • 2980 independent reflections
  • 1922 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.175
  • S = 1.09
  • 2980 reflections
  • 209 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800175X/pv2066sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800175X/pv2066Isup2.hkl

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

Acknowledgments

This work was financed by the National Natural Science Foundation of China (grant No. 30772627).

supplementary crystallographic information

Comment

An enamine, a tautomer of a Schiff base, shows a high similarity to the corresponding Schiff base in chemical structure which shows diverse biological activities. Our recent work affirmed that enamine, like Schiff base, exhibited high antibacterial activity (Xiao et al., 2007; Xiao et al., 2008). We herein report the crystal structure of the title compound, (I), an enamine.

As shown in Fig. 1, (I) is structurally divided into three subunits, and each moiety forms a plane, namely, C1 to C6 forms a plane with the mean deviation of 0.0037 Å, defined as plane I; C7 to C12 forms a plane with the mean deviation of 0.0028 Å, defined as plane II; N1, C13, C14, C15, O1 and O2 is nearly coplanar with the mean deviation of 0.0119 Å, defined as plane III. Plane II and plane III make a dihedral angle with plane I of 47.48 (8) and 11.27 (6) °, and the dihedral angle between plane II and plane III is 57.95 (7) °. The bond distance C13—C14 (1.351 (4) Å) falls in the range of a typical double bond, and C13—N1 bond (1.340 (4) Å) is shorter than the standard C—N single bond (1.48 Å), but longer than a C—N double bond (1.28 Å). This clearly indicates that the p orbital of N1 seems to be conjugated with the π molecular orbital of C13—C14 double bond. All other double bonds and single bonds in the molecule fall in normal range of bond lengths. The structure is stabilized by intramolecular interactions involving rather weak hydrogen bonds of the types N—H···O and C—H···0 as well as intermolecular interactions amino-H···F and C13—H···O2; details of hydrogen-bond geometry are given in Table 1.

Experimental

Equimolar quantities (6 mmol) of ethyl 2-(4-methoxyphenyl)-3- oxopropanoate (1.33 g) and 2-fluorobenzenamine (0.67 g) in absolute alcohol (18 ml) were heated at 344–354 K for 2 h. The excess solvent was removed under reduced pressure. The residue was purified by a flash chromatography with EtOAc-petrolum ether to afford two fractions. The first fraction gave a Z-isomer, and the second fraction, after partial solvent evaporated, furnished colorless blocks of (I) suitable for single-crystal structure determination.

Refinement

The H atom bonded to N1 was located in a difference Fourier map. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.93, 0.96 and 0.97 Å for the aromatic, CH3 and CH2 type H atoms, respectively. Uiso = 1.2Ueq(parent atoms) were assigned for amino, aromatic and CH2 type H-atoms and 1.5Ueq(parent atoms) for CH3 type H-atoms.

Figures

Fig. 1.
Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C18H18FNO3Z = 2
Mr = 315.33F000 = 332
Triclinic, P1Dx = 1.273 Mg m3
a = 6.3630 (13) ÅMo Kα radiation λ = 0.71073 Å
b = 9.4700 (19) ÅCell parameters from 1625 reflections
c = 13.981 (3) Åθ = 1.5–25.0º
α = 97.68 (3)ºµ = 0.09 mm1
β = 97.38 (3)ºT = 298 (2) K
γ = 95.40 (3)ºBlock, colorless
V = 822.7 (3) Å30.40 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer2980 independent reflections
Radiation source: fine-focus sealed tube1922 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
T = 298(2) Kθmax = 25.3º
ω/2θ scansθmin = 1.5º
Absorption correction: ψ scan(North et al., 1968)h = 0→7
Tmin = 0.963, Tmax = 0.981k = −11→11
3273 measured reflectionsl = −16→16

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.058  w = 1/[σ2(Fo2) + (0.0677P)2 + 0.314P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.175(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.26 e Å3
2980 reflectionsΔρmin = −0.21 e Å3
209 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.107 (9)
Secondary atom site location: difference Fourier map

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
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)

xyzUiso*/Ueq
O30.4465 (3)0.2358 (2)0.49646 (15)0.0698 (6)
O2−0.0514 (3)0.6582 (2)0.10142 (15)0.0714 (6)
O1−0.1278 (3)0.4580 (2)0.16366 (17)0.0771 (7)
F10.9092 (3)0.8076 (2)0.36459 (16)0.090
C140.2001 (4)0.6001 (3)0.2237 (2)0.0519 (7)
C70.2661 (4)0.5043 (3)0.29442 (19)0.0490 (6)
C120.4551 (4)0.4418 (3)0.2923 (2)0.0555 (7)
H120.53950.46040.24480.067*
N10.5153 (4)0.7686 (3)0.26886 (18)0.0571 (6)
C90.2078 (4)0.3844 (3)0.4321 (2)0.0566 (7)
H90.12440.36560.47990.068*
C15−0.0076 (4)0.5629 (3)0.1627 (2)0.0557 (7)
C10.6532 (4)0.8864 (3)0.25557 (19)0.0508 (7)
C100.3977 (4)0.3237 (3)0.4281 (2)0.0507 (7)
C80.1423 (4)0.4720 (3)0.3660 (2)0.0533 (7)
H80.01370.51050.36890.064*
C130.3239 (4)0.7195 (3)0.2132 (2)0.0543 (7)
H130.27520.77170.16460.065*
C51.0048 (5)1.0171 (3)0.2990 (3)0.0709 (9)
H51.14001.02670.33510.085*
C110.5217 (4)0.3533 (3)0.3579 (2)0.0589 (8)
H110.64960.31390.35490.071*
C60.8571 (4)0.9063 (3)0.3057 (2)0.0580 (7)
C20.6015 (5)0.9858 (3)0.1961 (2)0.0691 (9)
H20.46520.97760.16120.083*
C40.9513 (5)1.1144 (3)0.2383 (2)0.0738 (9)
H41.05021.19020.23190.089*
C30.7505 (6)1.0982 (3)0.1874 (3)0.0780 (10)
H30.71301.16380.14610.094*
C180.6409 (5)0.1735 (4)0.4950 (3)0.0800 (10)
H18A0.63840.11530.43300.120*
H18B0.65750.11510.54590.120*
H18C0.75810.24800.50500.120*
C16−0.2489 (5)0.6276 (4)0.0363 (3)0.0823 (10)
H16A−0.36830.62660.07310.099*
H16B−0.25520.5344−0.00310.099*
C17−0.2589 (7)0.7410 (5)−0.0268 (3)0.1111 (15)
H17A−0.25680.83230.01280.167*
H17B−0.38810.7218−0.07240.167*
H17C−0.13840.7425−0.06160.167*
H10.567 (5)0.714 (4)0.313 (3)0.089 (11)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.0550 (12)0.0796 (14)0.0784 (14)0.0045 (10)0.0128 (10)0.0239 (12)
O20.0526 (12)0.0798 (15)0.0765 (14)−0.0031 (10)−0.0079 (10)0.0156 (12)
O10.0451 (12)0.0827 (15)0.0974 (17)−0.0184 (11)0.0068 (11)0.0121 (12)
F10.0540.0960.121−0.007−0.0080.048
C140.0367 (14)0.0573 (16)0.0594 (17)−0.0039 (12)0.0121 (12)0.0024 (13)
C70.0382 (14)0.0497 (15)0.0562 (16)−0.0067 (11)0.0083 (12)0.0041 (12)
C120.0409 (15)0.0671 (18)0.0596 (17)−0.0034 (13)0.0197 (13)0.0080 (15)
N10.0470 (13)0.0586 (15)0.0633 (15)−0.0110 (11)−0.0012 (11)0.0207 (12)
C90.0448 (16)0.0693 (18)0.0545 (17)−0.0053 (13)0.0166 (13)0.0043 (14)
C150.0419 (15)0.0633 (18)0.0626 (18)0.0018 (14)0.0141 (13)0.0089 (15)
C10.0462 (15)0.0485 (15)0.0563 (16)−0.0034 (12)0.0086 (12)0.0084 (13)
C100.0418 (15)0.0516 (15)0.0560 (16)−0.0051 (12)0.0060 (12)0.0072 (13)
C80.0366 (14)0.0622 (17)0.0602 (17)−0.0019 (12)0.0151 (12)0.0037 (14)
C130.0442 (15)0.0602 (17)0.0574 (17)−0.0025 (13)0.0080 (13)0.0098 (13)
C50.0482 (17)0.0658 (19)0.093 (2)−0.0126 (15)0.0047 (16)0.0110 (18)
C110.0365 (14)0.0654 (18)0.074 (2)0.0014 (13)0.0133 (14)0.0038 (15)
C60.0461 (16)0.0542 (16)0.075 (2)0.0027 (13)0.0055 (14)0.0190 (15)
C20.0575 (19)0.068 (2)0.078 (2)−0.0089 (15)−0.0015 (16)0.0184 (17)
C40.070 (2)0.0584 (19)0.088 (2)−0.0192 (16)0.0142 (18)0.0082 (17)
C30.087 (3)0.058 (2)0.088 (2)−0.0072 (17)0.004 (2)0.0278 (18)
C180.063 (2)0.081 (2)0.097 (3)0.0125 (17)0.0042 (18)0.020 (2)
C160.0512 (19)0.113 (3)0.074 (2)0.0140 (18)−0.0053 (16)−0.005 (2)
C170.112 (3)0.133 (4)0.085 (3)0.041 (3)−0.017 (2)0.018 (3)

Geometric parameters (Å, °)

O3—C101.374 (3)C10—C111.376 (4)
O3—C181.421 (4)C8—H80.9300
O2—C151.349 (3)C13—H130.9300
O2—C161.435 (4)C5—C61.363 (4)
O1—C151.198 (3)C5—C41.370 (4)
F1—C61.362 (3)C5—H50.9300
C14—C131.351 (4)C11—H110.9300
C14—C151.463 (4)C2—C31.386 (4)
C14—C71.478 (4)C2—H20.9300
C7—C121.392 (4)C4—C31.365 (5)
C7—C81.397 (4)C4—H40.9300
C12—C111.377 (4)C3—H30.9300
C12—H120.9300C18—H18A0.9600
N1—C131.364 (3)C18—H18B0.9600
N1—C11.400 (3)C18—H18C0.9600
N1—H10.91 (3)C16—C171.479 (5)
C9—C81.374 (4)C16—H16A0.9700
C9—C101.391 (4)C16—H16B0.9700
C9—H90.9300C17—H17A0.9600
C1—C21.373 (4)C17—H17B0.9600
C1—C61.377 (4)C17—H17C0.9600
C10—O3—C18117.1 (2)C4—C5—H5120.5
C15—O2—C16116.8 (3)C10—C11—C12119.5 (3)
C13—C14—C15119.2 (3)C10—C11—H11120.2
C13—C14—C7122.7 (2)C12—C11—H11120.2
C15—C14—C7118.2 (2)F1—C6—C5119.7 (3)
C12—C7—C8117.1 (3)F1—C6—C1116.6 (2)
C12—C7—C14121.1 (2)C5—C6—C1123.7 (3)
C8—C7—C14121.8 (2)C1—C2—C3120.7 (3)
C11—C12—C7122.4 (2)C1—C2—H2119.7
C11—C12—H12118.8C3—C2—H2119.7
C7—C12—H12118.8C3—C4—C5118.9 (3)
C13—N1—C1125.7 (2)C3—C4—H4120.6
C13—N1—H1117 (2)C5—C4—H4120.6
C1—N1—H1116 (2)C4—C3—C2121.2 (3)
C8—C9—C10120.5 (3)C4—C3—H3119.4
C8—C9—H9119.8C2—C3—H3119.4
C10—C9—H9119.8O3—C18—H18A109.5
O1—C15—O2122.0 (3)O3—C18—H18B109.5
O1—C15—C14125.0 (3)H18A—C18—H18B109.5
O2—C15—C14113.0 (2)O3—C18—H18C109.5
C2—C1—C6116.4 (2)H18A—C18—H18C109.5
C2—C1—N1125.1 (3)H18B—C18—H18C109.5
C6—C1—N1118.5 (2)O2—C16—C17107.6 (3)
O3—C10—C11124.7 (3)O2—C16—H16A110.2
O3—C10—C9115.8 (2)C17—C16—H16A110.2
C11—C10—C9119.5 (3)O2—C16—H16B110.2
C9—C8—C7121.0 (3)C17—C16—H16B110.2
C9—C8—H8119.5H16A—C16—H16B108.5
C7—C8—H8119.5C16—C17—H17A109.5
C14—C13—N1124.4 (3)C16—C17—H17B109.5
C14—C13—H13117.8H17A—C17—H17B109.5
N1—C13—H13117.8C16—C17—H17C109.5
C6—C5—C4119.1 (3)H17A—C17—H17C109.5
C6—C5—H5120.5H17B—C17—H17C109.5
C13—C14—C7—C12−56.8 (4)C14—C7—C8—C9−179.0 (2)
C15—C14—C7—C12122.9 (3)C15—C14—C13—N1176.7 (3)
C13—C14—C7—C8123.3 (3)C7—C14—C13—N1−3.5 (4)
C15—C14—C7—C8−57.0 (3)C1—N1—C13—C14175.6 (3)
C8—C7—C12—C11−0.8 (4)O3—C10—C11—C12179.2 (2)
C14—C7—C12—C11179.3 (2)C9—C10—C11—C12−0.5 (4)
C16—O2—C15—O1−0.6 (4)C7—C12—C11—C100.5 (4)
C16—O2—C15—C14177.9 (2)C4—C5—C6—F1179.0 (3)
C13—C14—C15—O1177.8 (3)C4—C5—C6—C1−0.9 (5)
C7—C14—C15—O1−2.0 (4)C2—C1—C6—F1−179.8 (3)
C13—C14—C15—O2−0.6 (4)N1—C1—C6—F10.4 (4)
C7—C14—C15—O2179.7 (2)C2—C1—C6—C50.1 (5)
C13—N1—C1—C212.3 (5)N1—C1—C6—C5−179.7 (3)
C13—N1—C1—C6−168.0 (3)C6—C1—C2—C30.7 (5)
C18—O3—C10—C111.1 (4)N1—C1—C2—C3−179.5 (3)
C18—O3—C10—C9−179.3 (3)C6—C5—C4—C30.9 (5)
C8—C9—C10—O3−178.9 (2)C5—C4—C3—C2−0.1 (5)
C8—C9—C10—C110.8 (4)C1—C2—C3—C4−0.8 (5)
C10—C9—C8—C7−1.1 (4)C15—O2—C16—C17−177.3 (3)
C12—C7—C8—C91.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.91 (3)2.65 (3)3.256 (3)125 (3)
C12—H12···O1ii0.932.533.394 (3)155
N1—H1···F10.91 (3)2.26 (3)2.654 (3)102 (2)
C13—H13···O293.02.262.649 (3)104

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2066).

References

  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xiao, Z.-P., Fang, R.-Q., Li, H.-Q., Shi, L., Xue, J.-Y., Zheng, Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. In the press. DOI 10.1016/j.ejmech.2007.11.026.
  • Xiao, Z.-P., Xue, J.-Y., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007). Bioorg. Med. Chem.15, 4212–4219. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography