supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, o672    [ doi:10.1107/S1600536809007089 ]

(E)-2-(4-Methoxyphenyl)-N-(2-pyridyl)-3-(2-pyridylamino)acrylamide

Z.-P. Xiao, X.-C. Peng and Y.-C. Wang

Abstract top

In the title compound, C20H18N4O2, the aminoacrylamide group makes a dihedral angles of 4.0 (1)° with the amino-bound pyridyl ring and 15.66 (12)° with the amide-bound pyridyl ring. The dihedral angle between the aminoacrylamide group and the pendant 4-methoxyphenyl group is 71.22 (9)°. In the crystal structure, N-H...N hydrogen bonds and C-H...O and C-H...N interactions help to establish the packing. Intramolecular C-H...O and C-H...(N,O) contacts also occur.

Comment top

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, 2008). We herein report the crystal structure of the title compound, (I).

As shown in Fig. 1, the title compound is an enamine containing a functional group of amide moiety. The title compound consists of an aminoacrylamide moiety and three aromatic ring fragments. The aminoacrylamide moiety, C8, C9, C15, N1, N3 and O2, is nearly coplanar with a mean deviation of 0.023 Å, defined as plane I; C10 to C14 and N2 forms a plane with a mean deviation of 0.005 Å, defined as plane II; C16 to C20 and N4 forms a plane with a mean deviation of 0.008 Å, defined as plane III; C2 to C7 forms the fourth plane with a mean deviation of 0.005 Å, defined as plane IV. Plane II, plane III and plane IV make a dihedral angle of 4.018 (8), 15.66 (12) and 71.22 (9) ° with plane I, respectively. The bond distance C8—C9 [1.359 (5) Å] falls in the range of a typical double bond, and C9—N1 bond [1.352 (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 is conjugated with the π molecular orbital of C8—C9 double bond. For the same reason, we speculate that the p orbital of N1 is also conjugated with pyridyl group (plane II) and the p orbital of N3 is conjugated with both pyridyl group (plane III) and carboxyl group (C15=O2). All other double bonds and single bonds in the molecule fall in normal range of bond lengths.

In the crystal of (I), the structure is stabilized by intermolecular interactions including hydrogen bond N1—H1A···N4, C11—H11A···N4 and C14—H14A···O2; details of hydrogen-bond geometry are given in Table 1.

Related literature top

For background to the antibacteriological activy of enamines, see: Xiao et al. (2007, 2008).

Experimental top

Equimolar quantities (6 mmol) of 2-(4-methoxyphenyl)-3-oxo-N-(pyridin-2-yl)propanamide (1.62 g) and 2-aminobenzenamine (0.56 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 evaporation, furnished colourless blocks of (I) suitable for single-crystal structure determination.

Refinement top

All H atoms were placed in geometrically idealized positions (C—H = 0.93–0.96Å, N—H = 0.86Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.
(E)-2-(4-Methoxyphenyl)-N-(2-pyridyl)-3-(2-pyridylamino)acrylamide top
Crystal data top
C20H18N4O2F(000) = 728
Mr = 346.38Dx = 1.279 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 11.546 (2) Åθ = 9–12°
b = 12.148 (2) ŵ = 0.09 mm−1
c = 14.006 (3) ÅT = 293 K
β = 113.74 (3)°Block, colorless
V = 1798.3 (6) Å30.30 × 0.10 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1452 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 26.0°, θmin = 1.9°
ω/2θ scansh = −14→13
Absorption correction: ψ scan
(North et al., 1968)		k = 0→14
Tmin = 0.975, Tmax = 0.992l = 0→17
3523 measured reflections3 standard reflections every 200 reflections
3523 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.083Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.200H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0712P)2]
where P = (Fo2 + 2Fc2)/3
3523 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.16 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C20H18N4O2V = 1798.3 (6) Å3
Mr = 346.38Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.546 (2) ŵ = 0.09 mm−1
b = 12.148 (2) ÅT = 293 K
c = 14.006 (3) Å0.30 × 0.10 × 0.10 mm
β = 113.74 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1452 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.975, Tmax = 0.992θmax = 26.0°
3523 measured reflections3 standard reflections every 200 reflections
3523 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.083H-atom parameters constrained
wR(F2) = 0.200Δρmax = 0.16 e Å−3
S = 1.04Δρmin = −0.16 e Å−3
3523 reflectionsAbsolute structure: ?
235 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
N10.8670 (3)0.3253 (3)0.3474 (3)0.0628 (10)
H1A0.94830.32440.37250.075*
O11.3868 (3)0.5123 (3)0.3652 (3)0.1153 (14)
C11.4551 (5)0.4266 (5)0.3437 (5)0.137 (3)
H1B1.54340.44500.37180.206*
H1C1.42510.41680.26960.206*
H1D1.44320.35960.37500.206*
O20.6560 (2)0.5617 (3)0.1480 (2)0.0756 (9)
N20.6813 (3)0.2469 (3)0.3418 (3)0.0752 (11)
C21.2592 (4)0.5024 (5)0.3320 (4)0.0820 (15)
N30.8252 (3)0.6425 (3)0.1344 (2)0.0591 (9)
H3A0.90630.64710.16480.071*
C31.1876 (4)0.4216 (4)0.2676 (4)0.0764 (13)
H3B1.22540.36820.24200.092*
N40.8483 (3)0.7805 (3)0.0328 (3)0.0635 (9)
C41.0576 (4)0.4195 (3)0.2404 (3)0.0648 (11)
H4B1.00960.36450.19580.078*
C50.9974 (4)0.4961 (3)0.2771 (3)0.0568 (11)
C61.0728 (4)0.5774 (4)0.3409 (3)0.0743 (13)
H6A1.03560.63130.36650.089*
C71.2003 (4)0.5811 (4)0.3678 (4)0.0874 (15)
H7A1.24790.63730.41070.105*
C80.8599 (3)0.4900 (3)0.2477 (3)0.0545 (10)
C90.8061 (4)0.4077 (3)0.2814 (3)0.0583 (11)
H9A0.71830.40810.25660.070*
C100.8054 (4)0.2412 (3)0.3773 (3)0.0602 (11)
C110.8757 (4)0.1591 (4)0.4414 (4)0.0797 (15)
H11A0.96340.15850.46520.096*
C120.8136 (5)0.0787 (4)0.4691 (4)0.1026 (18)
H12A0.85880.02160.51220.123*
C130.6855 (5)0.0816 (4)0.4340 (4)0.0955 (17)
H13A0.64160.02680.45180.115*
C140.6240 (5)0.1666 (4)0.3725 (4)0.0884 (16)
H14A0.53650.16970.34990.106*
C150.7711 (4)0.5672 (3)0.1737 (3)0.0537 (10)
C160.7672 (4)0.7143 (3)0.0506 (3)0.0559 (10)
C170.6370 (4)0.7165 (4)−0.0105 (3)0.0671 (12)
H17A0.58120.67160.00450.080*
C180.5952 (5)0.7878 (4)−0.0932 (4)0.0870 (15)
H18A0.50940.7909−0.13620.104*
C190.6782 (5)0.8542 (4)−0.1129 (4)0.0860 (16)
H19A0.65050.9018−0.16970.103*
C200.8027 (4)0.8489 (4)−0.0471 (4)0.0811 (14)
H20A0.85880.8961−0.05910.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0472 (19)0.066 (2)0.072 (2)0.0045 (18)0.0203 (17)0.011 (2)
O10.056 (2)0.122 (3)0.161 (4)0.003 (2)0.036 (2)0.026 (3)
C10.066 (3)0.138 (6)0.215 (7)0.023 (4)0.064 (4)0.051 (5)
O20.0566 (18)0.090 (2)0.082 (2)0.0110 (16)0.0303 (16)0.0173 (18)
N20.055 (2)0.079 (3)0.086 (3)−0.011 (2)0.023 (2)0.018 (2)
C20.046 (3)0.091 (4)0.100 (4)0.005 (3)0.020 (3)0.032 (3)
N30.0523 (19)0.056 (2)0.059 (2)0.0026 (17)0.0119 (17)0.0122 (18)
C30.070 (3)0.073 (3)0.092 (4)0.011 (3)0.038 (3)0.015 (3)
N40.062 (2)0.070 (2)0.056 (2)0.000 (2)0.0210 (18)0.009 (2)
C40.065 (3)0.056 (3)0.067 (3)0.000 (2)0.020 (2)0.002 (2)
C50.059 (2)0.051 (3)0.054 (3)0.005 (2)0.015 (2)0.005 (2)
C60.064 (3)0.077 (3)0.075 (3)0.009 (3)0.021 (2)−0.004 (3)
C70.066 (3)0.083 (4)0.094 (4)−0.007 (3)0.013 (3)−0.008 (3)
C80.052 (2)0.050 (3)0.057 (3)0.006 (2)0.0169 (19)0.003 (2)
C90.056 (2)0.050 (2)0.059 (3)0.007 (2)0.012 (2)0.000 (2)
C100.057 (3)0.063 (3)0.057 (3)−0.015 (2)0.019 (2)0.004 (2)
C110.066 (3)0.080 (3)0.084 (3)−0.001 (3)0.021 (3)0.034 (3)
C120.093 (4)0.098 (4)0.101 (4)−0.008 (3)0.023 (3)0.040 (4)
C130.095 (4)0.081 (4)0.095 (4)−0.022 (3)0.023 (3)0.031 (3)
C140.067 (3)0.096 (4)0.098 (4)−0.021 (3)0.030 (3)0.014 (3)
C150.055 (2)0.059 (3)0.047 (2)0.004 (2)0.021 (2)−0.003 (2)
C160.057 (2)0.056 (3)0.054 (3)0.010 (2)0.022 (2)0.003 (2)
C170.060 (3)0.073 (3)0.062 (3)0.003 (2)0.017 (2)0.009 (3)
C180.066 (3)0.106 (4)0.068 (3)0.016 (3)0.005 (3)0.017 (3)
C190.074 (3)0.103 (4)0.077 (4)0.017 (3)0.025 (3)0.039 (3)
C200.075 (3)0.097 (4)0.071 (3)0.006 (3)0.029 (3)0.023 (3)
Geometric parameters (Å, °) top
N1—C91.352 (4)C5—C81.472 (5)
N1—C101.402 (5)C6—C71.366 (6)
N1—H1A0.8600C6—H6A0.9300
O1—C21.360 (5)C7—H7A0.9300
O1—C11.409 (6)C8—C91.359 (5)
C1—H1B0.9600C8—C151.466 (5)
C1—H1C0.9600C9—H9A0.9300
C1—H1D0.9600C10—C111.368 (5)
O2—C151.231 (4)C11—C121.358 (6)
N2—C101.315 (5)C11—H11A0.9300
N2—C141.343 (5)C12—C131.358 (6)
C2—C31.365 (6)C12—H12A0.9300
C2—C71.379 (6)C13—C141.348 (6)
N3—C151.344 (5)C13—H13A0.9300
N3—C161.398 (5)C14—H14A0.9300
N3—H3A0.8600C16—C171.400 (5)
C3—C41.393 (5)C17—C181.368 (6)
C3—H3B0.9300C17—H17A0.9300
N4—C201.321 (5)C18—C191.364 (6)
N4—C161.332 (5)C18—H18A0.9300
C4—C51.379 (5)C19—C201.361 (6)
C4—H4B0.9300C19—H19A0.9300
C5—C61.380 (5)C20—H20A0.9300
C9—N1—C10123.8 (3)N1—C9—C8126.7 (4)
C9—N1—H1A118.1N1—C9—H9A116.7
C10—N1—H1A118.1C8—C9—H9A116.7
C2—O1—C1119.0 (5)N2—C10—C11123.7 (4)
O1—C1—H1B109.5N2—C10—N1117.1 (4)
O1—C1—H1C109.5C11—C10—N1119.2 (4)
H1B—C1—H1C109.5C12—C11—C10118.0 (4)
O1—C1—H1D109.5C12—C11—H11A121.0
H1B—C1—H1D109.5C10—C11—H11A121.0
H1C—C1—H1D109.5C11—C12—C13120.1 (5)
C10—N2—C14116.3 (4)C11—C12—H12A120.0
O1—C2—C3125.0 (5)C13—C12—H12A120.0
O1—C2—C7116.1 (5)C14—C13—C12117.9 (5)
C3—C2—C7118.8 (4)C14—C13—H13A121.0
C15—N3—C16128.6 (4)C12—C13—H13A121.0
C15—N3—H3A115.7N2—C14—C13124.0 (5)
C16—N3—H3A115.7N2—C14—H14A118.0
C2—C3—C4119.6 (5)C13—C14—H14A118.0
C2—C3—H3B120.2O2—C15—N3122.9 (4)
C4—C3—H3B120.2O2—C15—C8122.5 (4)
C20—N4—C16117.9 (4)N3—C15—C8114.6 (4)
C5—C4—C3122.4 (4)N4—C16—N3113.5 (3)
C5—C4—H4B118.8N4—C16—C17122.5 (4)
C3—C4—H4B118.8N3—C16—C17124.0 (4)
C4—C5—C6116.3 (4)C18—C17—C16117.1 (4)
C4—C5—C8120.7 (4)C18—C17—H17A121.4
C6—C5—C8123.0 (4)C16—C17—H17A121.4
C7—C6—C5122.0 (4)C19—C18—C17120.6 (4)
C7—C6—H6A119.0C19—C18—H18A119.7
C5—C6—H6A119.0C17—C18—H18A119.7
C6—C7—C2120.8 (5)C20—C19—C18118.2 (5)
C6—C7—H7A119.6C20—C19—H19A120.9
C2—C7—H7A119.6C18—C19—H19A120.9
C9—C8—C15115.4 (4)N4—C20—C19123.7 (5)
C9—C8—C5122.2 (4)N4—C20—H20A118.1
C15—C8—C5122.3 (4)C19—C20—H20A118.1
C1—O1—C2—C3−8.5 (8)N2—C10—C11—C120.5 (7)
C1—O1—C2—C7171.2 (5)N1—C10—C11—C12−180.0 (4)
O1—C2—C3—C4179.1 (4)C10—C11—C12—C13−0.4 (8)
C7—C2—C3—C4−0.6 (7)C11—C12—C13—C14−0.6 (9)
C2—C3—C4—C5−0.7 (7)C10—N2—C14—C13−1.6 (7)
C3—C4—C5—C61.5 (6)C12—C13—C14—N21.7 (9)
C3—C4—C5—C8−179.1 (4)C16—N3—C15—O2−10.3 (6)
C4—C5—C6—C7−1.0 (6)C16—N3—C15—C8168.0 (4)
C8—C5—C6—C7179.6 (4)C9—C8—C15—O23.7 (6)
C5—C6—C7—C2−0.3 (7)C5—C8—C15—O2179.2 (4)
O1—C2—C7—C6−178.6 (4)C9—C8—C15—N3−174.7 (3)
C3—C2—C7—C61.2 (7)C5—C8—C15—N30.8 (5)
C4—C5—C8—C968.4 (5)C20—N4—C16—N3177.8 (4)
C6—C5—C8—C9−112.2 (5)C20—N4—C16—C17−1.4 (6)
C4—C5—C8—C15−106.8 (4)C15—N3—C16—N4178.7 (4)
C6—C5—C8—C1572.6 (5)C15—N3—C16—C17−2.1 (6)
C10—N1—C9—C8−178.4 (4)N4—C16—C17—C182.4 (6)
C15—C8—C9—N1178.4 (4)N3—C16—C17—C18−176.8 (4)
C5—C8—C9—N12.9 (6)C16—C17—C18—C19−1.0 (7)
C14—N2—C10—C110.5 (7)C17—C18—C19—C20−1.2 (8)
C14—N2—C10—N1−179.0 (4)C16—N4—C20—C19−1.0 (7)
C9—N1—C10—N2−3.0 (6)C18—C19—C20—N42.3 (8)
C9—N1—C10—C11177.5 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N4i0.862.253.079 (5)163
C9—H9A···O20.932.332.718 (5)104
C9—H9A···N20.932.422.754 (6)101
C17—H17A···O20.932.272.850 (5)120
C11—H11A···N4i0.932.623.396 (6)141
C14—H14A···O2ii0.932.593.378 (5)143
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N4i0.862.253.079 (5)163
C9—H9A···O20.932.332.718 (5)104
C9—H9A···N20.932.422.754 (6)101
C17—H17A···O20.932.272.850 (5)120
C11—H11A···N4i0.932.623.396 (6)141
C14—H14A···O2ii0.932.593.378 (5)143
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
Acknowledgements top

The work was financed by a grant (project No. 30772627) from the National Natural Science Foundation of China.

references
References top

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.

Xiao, Z.-P., Fang, R.-Q., Li, H.-Q., Shi, L., Xue, J.-Y., Zheng, Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, 1828–1836.

Xiao, Z.-P., Xue, J.-Y., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007). Bioorg. Med. Chem. 15, 4212–4219.