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Acta Cryst. (2010). E66, o2767    [ doi:10.1107/S1600536810039760 ]

Methyl 4-(4-methoxyphenyl)-2-methyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

X.-H. Yang, Y.-H. Zhou, M. Zhang and X. Song

Abstract top

In the title compound, C19H21NO4, the dihydropyridine ring adopts a distorted screw-boat conformation. The fused cyclohexenone ring forms a slightly distorted envelope conformation. The dihedral angle between the mean planes of the benzene and heterocyclic rings is 86.1 (7)°. An intramolecular C-H...O interaction occurs. In the crystal, molecules are linked by intermolecular N-H...O hydrogen bonds, forming an infinite chain along the c axis.

Comment top

The development of new methods for the synthesis of 1,4-dihydropyridine derivatives is a motive for the current study. 1,4-dihydropyridine derivatives attract interest because of their presence in numerous natural products. In addition, they exhibit calcium modulatory properties (Rose & Draeger, 1992), antibacterial (Davies et al., 2005) and fungicidal activity (Warrior et al., 2005).

In the title compound the heterocyclic ring adopts a distorted screw-boat conformation (Fig. 1). Atoms C7 and N deviate from the mean plane of C1/C6/C8/C9 by 0.177 (3)Å and 0.067 (7)Å, respectively. The fused cyclohexene ring displays a slightly distorted envelope conformation, with atom C3 out of the plane of the atoms by -0.314 (5)°. The dihedral angle between the mean planes of the benzene and heterocyclic rings is 86.1 (7)°. The methoxy group is nearly coplanar with the attached benzene ring with a C19/O4/C16/C17 torsion angle of -4.1 (6)°. Crystal packing is stabilized by an intermolecular N—H···O hydrogen bond forming an infinite chain of molecules along the c axis (Table 1, Fig. 2).

Related literature top

For the physiological activity of 1,4-dihydropyridine derivatives, see: Davies et al. (2005); Rose & Draeger (1992); Warrior et al. (2005).

Experimental top

A mixture of 4-methoxybenzaldehyde (2 mmol), methyl 3-oxobutanoate (4 mmol), cyclohexane-1,3-dione (2 mmol) and NH4CO3 (2 mmol) was stirred in water (2 ml) at 353 K. After completion of the reaction (TLC monitoring),the mixture was diluted with cold water (20 ml) and filtered to obtain the precipitated product which was further purified by recrystallization. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.

Refinement top

Atom H0A was located in a difference map and refined isotropically. All other H atoms were positioned geometrically and treated as riding, with C—H distances in the range 0.93–0.98 Å and Uiso(H) = 1.2 or 1.5 times Ueq(C). In the absence of significant anomalous dispersion effects, Friedel pairs were merged.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing of the title compound, viewed along the a axis. Dashed lines indicate N—H···O hydrogen bonds.
Methyl 4-(4-methoxyphenyl)-2-methyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top
Crystal data top
C19H21NO4F(000) = 696
Mr = 327.37Dx = 1.282 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 13.628 (3) Åθ = 9–12°
b = 8.6300 (17) ŵ = 0.09 mm−1
c = 14.577 (3) ÅT = 293 K
β = 98.39 (3)°Block, colourless
V = 1696.0 (6) Å30.20 × 0.20 × 0.05 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1300 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.078
graphiteθmax = 25.3°, θmin = 1.5°
ω/2θ scansh = 0→16
Absorption correction: ψ scan
(North et al., 1968)		k = 0→10
Tmin = 0.982, Tmax = 0.996l = −17→17
3232 measured reflections3 standard reflections every 200 reflections
3040 independent reflections intensity decay: 1%
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)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.030P)2]
where P = (Fo2 + 2Fc2)/3
3040 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.16 e Å−3
1 restraintΔρmin = −0.19 e Å−3
Crystal data top
C19H21NO4V = 1696.0 (6) Å3
Mr = 327.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.628 (3) ŵ = 0.09 mm−1
b = 8.6300 (17) ÅT = 293 K
c = 14.577 (3) Å0.20 × 0.20 × 0.05 mm
β = 98.39 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1300 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.078
Tmin = 0.982, Tmax = 0.996θmax = 25.3°
3232 measured reflections3 standard reflections every 200 reflections
3040 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.070H-atom parameters constrained
wR(F2) = 0.128Δρmax = 0.16 e Å−3
S = 1.00Δρmin = −0.19 e Å−3
3040 reflectionsAbsolute structure: ?
217 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Experimental. Absorption correction: semi-empirical absorption based on psi-scan (North et al., 1968)

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
N0.7089 (2)−0.1346 (4)1.10531 (19)0.0561 (9)
H0A0.7239−0.16171.16240.067*
O10.7167 (2)−0.2573 (3)0.79342 (17)0.0675 (8)
C10.7348 (2)−0.2312 (4)1.0380 (2)0.0437 (9)
O30.5828 (3)0.3072 (4)1.0342 (2)0.1228 (14)
O20.5564 (2)0.2194 (3)0.8893 (2)0.0691 (8)
C20.7719 (3)−0.3882 (4)1.0694 (2)0.0579 (11)
H2A0.7161−0.45451.07640.069*
H2B0.8130−0.37951.12940.069*
C30.8315 (3)−0.4604 (5)1.0013 (3)0.0783 (14)
H3A0.8450−0.56801.01780.094*
H3B0.8944−0.40691.00400.094*
O41.0127 (2)0.2744 (3)0.7949 (2)0.0800 (9)
C40.7756 (3)−0.4514 (5)0.9038 (3)0.0713 (13)
H4A0.8194−0.48410.86060.086*
H4B0.7204−0.52340.89830.086*
C50.7367 (3)−0.2935 (5)0.8765 (3)0.0571 (11)
C60.7201 (3)−0.1864 (4)0.9470 (2)0.0444 (9)
C70.6864 (3)−0.0254 (4)0.9202 (2)0.0488 (10)
H7A0.6318−0.03430.86860.059*
C80.6458 (3)0.0595 (4)0.9990 (3)0.0477 (9)
C90.6599 (3)0.0044 (4)1.0854 (3)0.0486 (10)
C100.6220 (3)0.0715 (4)1.1683 (2)0.0673 (12)
H10A0.58840.16731.15140.101*
H10B0.67670.09031.21650.101*
H10C0.57670.00001.19020.101*
C110.5931 (3)0.2038 (5)0.9799 (3)0.0648 (12)
C120.5003 (4)0.3605 (5)0.8655 (3)0.1003 (17)
H12A0.47850.36310.79980.151*
H12B0.54160.44870.88320.151*
H12C0.44370.36280.89770.151*
C130.7696 (3)0.0644 (4)0.8845 (2)0.0432 (9)
C140.8566 (3)0.0938 (4)0.9442 (2)0.0570 (11)
H14A0.86190.06461.00610.068*
C150.9360 (3)0.1667 (5)0.9120 (3)0.0635 (12)
H15A0.99370.18680.95270.076*
C160.9296 (3)0.2093 (5)0.8199 (3)0.0577 (11)
C170.8445 (3)0.1823 (4)0.7607 (2)0.0519 (10)
H17A0.83930.21150.69880.062*
C180.7645 (3)0.1101 (4)0.7942 (2)0.0500 (10)
H18A0.70630.09270.75370.060*
C191.0128 (3)0.3077 (6)0.6991 (3)0.0961 (17)
H19A1.07520.35310.69080.144*
H19B0.96020.37880.67810.144*
H19C1.00320.21350.66380.144*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N0.080 (2)0.055 (2)0.0358 (17)0.0012 (18)0.0164 (16)−0.0055 (16)
O10.096 (2)0.071 (2)0.0380 (14)−0.0014 (16)0.0202 (15)−0.0075 (15)
C10.047 (2)0.039 (2)0.046 (2)−0.0057 (18)0.0089 (17)−0.0011 (18)
O30.212 (4)0.069 (2)0.091 (3)0.048 (3)0.033 (3)−0.015 (2)
O20.076 (2)0.0566 (19)0.074 (2)0.0125 (16)0.0078 (16)0.0084 (16)
C20.072 (3)0.047 (3)0.055 (2)−0.002 (2)0.008 (2)0.002 (2)
C30.113 (4)0.055 (3)0.066 (3)0.012 (3)0.012 (3)−0.005 (2)
O40.072 (2)0.092 (2)0.079 (2)−0.0276 (18)0.0220 (16)0.0123 (18)
C40.096 (4)0.060 (3)0.061 (3)0.001 (3)0.022 (3)−0.008 (2)
C50.071 (3)0.043 (2)0.060 (3)−0.010 (2)0.018 (2)−0.013 (2)
C60.052 (2)0.044 (2)0.038 (2)−0.0081 (19)0.0100 (17)−0.0026 (18)
C70.056 (2)0.040 (2)0.053 (2)−0.0059 (19)0.016 (2)−0.0072 (18)
C80.049 (2)0.040 (2)0.058 (2)−0.0060 (19)0.0200 (19)−0.007 (2)
C90.066 (3)0.037 (2)0.048 (2)0.0044 (19)0.025 (2)0.0020 (19)
C100.100 (3)0.051 (3)0.057 (2)0.002 (2)0.034 (2)−0.009 (2)
C110.085 (3)0.044 (3)0.069 (3)−0.007 (3)0.022 (3)−0.003 (2)
C120.108 (4)0.072 (3)0.126 (4)0.006 (3)0.032 (3)0.026 (3)
C130.047 (2)0.037 (2)0.044 (2)0.0087 (18)0.0037 (18)−0.0025 (17)
C140.073 (3)0.054 (3)0.042 (2)−0.009 (2)0.002 (2)0.0095 (19)
C150.071 (3)0.063 (3)0.056 (3)−0.001 (2)0.005 (2)−0.002 (2)
C160.061 (3)0.054 (3)0.062 (3)−0.010 (2)0.021 (2)−0.008 (2)
C170.068 (3)0.047 (2)0.042 (2)−0.013 (2)0.014 (2)0.0054 (18)
C180.052 (2)0.053 (3)0.046 (2)−0.002 (2)0.0082 (18)0.004 (2)
C190.086 (4)0.116 (4)0.093 (4)−0.036 (3)0.035 (3)0.007 (3)
Geometric parameters (Å, °) top
N—C11.372 (4)C7—H7A0.9800
N—C91.383 (4)C8—C91.334 (4)
N—H0A0.8600C8—C111.444 (5)
O1—C51.242 (4)C9—C101.498 (4)
C1—C61.367 (4)C10—H10A0.9600
C1—C21.495 (4)C10—H10B0.9600
O3—C111.214 (4)C10—H10C0.9600
O2—C111.349 (4)C12—H12A0.9600
O2—C121.453 (4)C12—H12B0.9600
C2—C31.506 (5)C12—H12C0.9600
C2—H2A0.9700C13—C181.366 (4)
C2—H2B0.9700C13—C141.388 (4)
C3—C41.514 (5)C14—C151.390 (5)
C3—H3A0.9700C14—H14A0.9300
C3—H3B0.9700C15—C161.383 (5)
O4—C161.361 (4)C15—H15A0.9300
O4—C191.426 (4)C16—C171.361 (5)
C4—C51.495 (5)C17—C181.403 (4)
C4—H4A0.9700C17—H17A0.9300
C4—H4B0.9700C18—H18A0.9300
C5—C61.425 (4)C19—H19A0.9600
C6—C71.497 (4)C19—H19B0.9600
C7—C131.527 (4)C19—H19C0.9600
C7—C81.532 (4)
C1—N—C9122.9 (3)C8—C9—C10127.2 (4)
C1—N—H0A118.5N—C9—C10112.3 (3)
C9—N—H0A118.5C9—C10—H10A109.5
C6—C1—N120.4 (3)C9—C10—H10B109.5
C6—C1—C2123.3 (3)H10A—C10—H10B109.5
N—C1—C2116.2 (3)C9—C10—H10C109.5
C11—O2—C12115.1 (3)H10A—C10—H10C109.5
C1—C2—C3111.3 (3)H10B—C10—H10C109.5
C1—C2—H2A109.4O3—C11—O2120.2 (4)
C3—C2—H2A109.4O3—C11—C8127.5 (4)
C1—C2—H2B109.4O2—C11—C8112.2 (4)
C3—C2—H2B109.4O2—C12—H12A109.5
H2A—C2—H2B108.0O2—C12—H12B109.5
C2—C3—C4110.6 (4)H12A—C12—H12B109.5
C2—C3—H3A109.5O2—C12—H12C109.5
C4—C3—H3A109.5H12A—C12—H12C109.5
C2—C3—H3B109.5H12B—C12—H12C109.5
C4—C3—H3B109.5C18—C13—C14118.0 (3)
H3A—C3—H3B108.1C18—C13—C7122.6 (3)
C16—O4—C19117.7 (3)C14—C13—C7119.3 (3)
C5—C4—C3114.0 (3)C13—C14—C15120.4 (3)
C5—C4—H4A108.7C13—C14—H14A119.8
C3—C4—H4A108.7C15—C14—H14A119.8
C5—C4—H4B108.7C16—C15—C14120.4 (4)
C3—C4—H4B108.7C16—C15—H15A119.8
H4A—C4—H4B107.6C14—C15—H15A119.8
O1—C5—C6120.4 (4)C17—C16—O4124.5 (4)
O1—C5—C4120.5 (4)C17—C16—C15119.8 (4)
C6—C5—C4119.1 (3)O4—C16—C15115.6 (4)
C1—C6—C5120.0 (4)C16—C17—C18119.2 (3)
C1—C6—C7120.7 (3)C16—C17—H17A120.4
C5—C6—C7119.2 (3)C18—C17—H17A120.4
C6—C7—C13110.2 (3)C13—C18—C17122.1 (3)
C6—C7—C8112.3 (3)C13—C18—H18A119.0
C13—C7—C8112.3 (3)C17—C18—H18A119.0
C6—C7—H7A107.2O4—C19—H19A109.5
C13—C7—H7A107.2O4—C19—H19B109.5
C8—C7—H7A107.2H19A—C19—H19B109.5
C9—C8—C11119.3 (4)O4—C19—H19C109.5
C9—C8—C7121.3 (4)H19A—C19—H19C109.5
C11—C8—C7119.4 (3)H19B—C19—H19C109.5
C8—C9—N120.4 (3)
C9—N—C1—C65.7 (5)C11—C8—C9—C103.5 (6)
C9—N—C1—C2−170.1 (3)C7—C8—C9—C10−177.9 (3)
C6—C1—C2—C325.1 (5)C1—N—C9—C8−8.0 (5)
N—C1—C2—C3−159.3 (3)C1—N—C9—C10168.2 (3)
C1—C2—C3—C4−49.6 (5)C12—O2—C11—O3−3.8 (6)
C2—C3—C4—C549.9 (5)C12—O2—C11—C8178.5 (3)
C3—C4—C5—O1158.2 (4)C9—C8—C11—O322.9 (7)
C3—C4—C5—C6−23.5 (6)C7—C8—C11—O3−155.7 (4)
N—C1—C6—C5−173.0 (3)C9—C8—C11—O2−159.6 (4)
C2—C1—C6—C52.4 (5)C7—C8—C11—O221.8 (5)
N—C1—C6—C76.9 (5)C6—C7—C13—C18112.6 (4)
C2—C1—C6—C7−177.6 (3)C8—C7—C13—C18−121.4 (4)
O1—C5—C6—C1174.9 (4)C6—C7—C13—C14−63.6 (4)
C4—C5—C6—C1−3.4 (5)C8—C7—C13—C1462.4 (4)
O1—C5—C6—C7−5.1 (5)C18—C13—C14—C15−0.4 (5)
C4—C5—C6—C7176.7 (3)C7—C13—C14—C15175.9 (3)
C1—C6—C7—C13110.8 (4)C13—C14—C15—C16−0.7 (6)
C5—C6—C7—C13−69.3 (4)C19—O4—C16—C17−4.1 (6)
C1—C6—C7—C8−15.3 (5)C19—O4—C16—C15174.6 (4)
C5—C6—C7—C8164.7 (3)C14—C15—C16—C171.2 (6)
C6—C7—C8—C913.1 (5)C14—C15—C16—O4−177.5 (3)
C13—C7—C8—C9−111.8 (4)O4—C16—C17—C18178.0 (4)
C6—C7—C8—C11−168.3 (3)C15—C16—C17—C18−0.6 (6)
C13—C7—C8—C1166.8 (4)C14—C13—C18—C171.1 (5)
C11—C8—C9—N179.2 (3)C7—C13—C18—C17−175.1 (3)
C7—C8—C9—N−2.2 (6)C16—C17—C18—C13−0.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.052.884 (4)163
C10—H10A···O30.962.082.818 (5)132
Symmetry codes: (i) x, −y−1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.052.884 (4)163
C10—H10A···O30.962.082.818 (5)132
Symmetry codes: (i) x, −y−1/2, z+1/2.
Acknowledgements top

This work was supported by the President of the Chinese Academy of Forestry Foundation (CAFYBB2008009).

references
References top

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Davies, D. T., Markwell, R. E., Pearson, N. D. & Takle, A. K. (2005). US Patent 6 911 442.

Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst., A24, 351–359.

Rose, U. & Draeger, M. (1992). J. Med. Chem. A, 35, 2238–2243.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Warrior, P., Heiman, D. F., Fugiel, J. A. & Petracek, P. D. (2005). WO Patent 2005060748.