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Acta Cryst. (2009). E65, o2987    [ doi:10.1107/S1600536809045425 ]

Ethyl 6-chloro-2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylate

F. N. Khan, S. Mittal, S. Anjum, V. R. Hathwar and S. W. Ng

Abstract top

In the title compound, C18H14ClNO3, the dihydroquinolin-2-one ring system is almost planar (r.m.s. deviation = 0.033 Å). The carboxylate plane and the phenyl group are twisted away from the dihydroquinolin-2-one ring system by 50.3 (1) and 64.9 (1)°, respectively. In the crystal structure, inversion-related molecules form R22(8) dimers via pairs of N-H...O hydrogen bonds.

Related literature top

For crystal structures of related compounds, see: Baumer et al. (2001); Subashini et al. (2009).

Experimental top

(2-Amino-5-chlorophenyl)(phenyl)methanone (1 mmol) and diethyl malonate (1.2 mmol) along with a catalytic amount of piperidine were heated at 453 K; the reaction was monitored by TLC. After completion, the reaction mixture was poured into the water. The organic product was extracted with ethyl acetate. The crude product was then purified by silica-gel column chromatography, with petroleum ether and ethyl acetate as eluant. Single crystals were obtained by recrystallization from ethyl acetate.

Refinement top

C-bound H-atoms were placed in calculated positions (C-H = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C). The amino H-atom was located in a difference Fourier map, and was freely refined without any restraint.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of C18H14ClNO3 at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.
Ethyl 6-chloro-2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylate top
Crystal data top
C18H14ClNO3F(000) = 680
Mr = 327.75Dx = 1.344 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1123 reflections
a = 10.176 (1) Åθ = 2.9–20.7°
b = 15.629 (2) ŵ = 0.25 mm−1
c = 11.282 (1) ÅT = 290 K
β = 115.463 (1)°Block, colourless
V = 1619.9 (3) Å30.35 × 0.31 × 0.23 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3699 independent reflections
Radiation source: fine-focus sealed tube2906 reflections with I > 2σ(I)
graphiteRint = 0.022
φ and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.918, Tmax = 0.945k = −20→19
13600 measured reflectionsl = −14→14
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0664P)2 + 0.4015P]
where P = (Fo2 + 2Fc2)/3
3699 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C18H14ClNO3V = 1619.9 (3) Å3
Mr = 327.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.176 (1) ŵ = 0.25 mm−1
b = 15.629 (2) ÅT = 290 K
c = 11.282 (1) Å0.35 × 0.31 × 0.23 mm
β = 115.463 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3699 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2906 reflections with I > 2σ(I)
Tmin = 0.918, Tmax = 0.945Rint = 0.022
13600 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.129Δρmax = 0.23 e Å−3
S = 1.00Δρmin = −0.20 e Å−3
3699 reflectionsAbsolute structure: ?
213 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.54343 (6)0.02895 (3)0.68514 (6)0.0743 (2)
N10.46268 (16)0.38491 (9)0.50054 (15)0.0526 (4)
H10.527 (2)0.4235 (14)0.546 (2)0.066 (6)*
O10.33674 (13)0.49099 (7)0.36051 (13)0.0569 (3)
O20.13633 (14)0.40486 (9)0.08985 (13)0.0605 (4)
O30.00732 (12)0.38779 (8)0.20662 (11)0.0487 (3)
C10.35167 (17)0.41406 (10)0.38896 (17)0.0454 (4)
C20.25139 (17)0.34892 (10)0.30798 (15)0.0404 (3)
C30.26581 (16)0.26477 (10)0.34062 (15)0.0384 (3)
C40.38454 (16)0.23795 (10)0.46323 (16)0.0405 (4)
C50.40613 (18)0.15305 (11)0.50898 (16)0.0450 (4)
H50.34520.10980.45800.054*
C60.5166 (2)0.13411 (12)0.62836 (19)0.0530 (4)
C70.6110 (2)0.19671 (14)0.7067 (2)0.0648 (5)
H70.68530.18260.78800.078*
C80.5932 (2)0.27920 (13)0.6629 (2)0.0634 (5)
H80.65660.32130.71440.076*
C90.48116 (18)0.30096 (11)0.54190 (17)0.0465 (4)
C100.12728 (17)0.38317 (10)0.18746 (15)0.0411 (4)
C11−0.1227 (2)0.42135 (14)0.09932 (19)0.0620 (5)
H11A−0.09610.46810.05730.074*
H11B−0.18820.44370.13380.074*
C12−0.1985 (2)0.3536 (2)0.0004 (2)0.0894 (8)
H12A−0.29070.3749−0.06250.134*
H12B−0.21400.30440.04380.134*
H12C−0.13980.3378−0.04370.134*
C130.15864 (17)0.20196 (10)0.25160 (15)0.0400 (3)
C140.1482 (2)0.18833 (13)0.12633 (19)0.0605 (5)
H140.21260.21560.10010.073*
C150.0423 (3)0.13422 (15)0.0401 (2)0.0782 (7)
H150.03580.1254−0.04380.094*
C16−0.0525 (3)0.09389 (13)0.0781 (2)0.0717 (6)
H16−0.12310.05740.02020.086*
C17−0.0437 (2)0.10699 (12)0.2011 (2)0.0619 (5)
H17−0.10870.07960.22640.074*
C180.06135 (19)0.16075 (11)0.28790 (17)0.0499 (4)
H180.06670.16930.37140.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0758 (4)0.0599 (3)0.0810 (4)0.0093 (2)0.0277 (3)0.0260 (3)
N10.0408 (8)0.0370 (8)0.0583 (9)−0.0040 (6)0.0007 (7)−0.0097 (7)
O10.0437 (7)0.0348 (6)0.0701 (8)−0.0018 (5)0.0034 (6)−0.0062 (6)
O20.0600 (8)0.0724 (9)0.0500 (7)0.0001 (7)0.0246 (6)0.0108 (6)
O30.0396 (6)0.0591 (7)0.0424 (6)0.0039 (5)0.0127 (5)0.0059 (5)
C10.0350 (8)0.0384 (9)0.0528 (9)−0.0012 (6)0.0095 (7)−0.0072 (7)
C20.0370 (8)0.0392 (8)0.0407 (8)−0.0041 (6)0.0126 (7)−0.0051 (6)
C30.0355 (8)0.0392 (8)0.0395 (8)−0.0040 (6)0.0152 (7)−0.0057 (6)
C40.0362 (8)0.0400 (8)0.0427 (8)−0.0010 (6)0.0145 (7)−0.0050 (7)
C50.0426 (9)0.0419 (9)0.0486 (9)−0.0011 (7)0.0178 (7)−0.0018 (7)
C60.0515 (10)0.0491 (10)0.0568 (10)0.0070 (8)0.0218 (9)0.0085 (8)
C70.0559 (11)0.0654 (13)0.0508 (10)0.0066 (9)0.0018 (9)0.0056 (9)
C80.0521 (11)0.0556 (11)0.0571 (11)−0.0020 (9)−0.0007 (9)−0.0076 (9)
C90.0382 (8)0.0423 (9)0.0477 (9)0.0008 (7)0.0079 (7)−0.0049 (7)
C100.0413 (8)0.0349 (8)0.0405 (8)−0.0062 (6)0.0115 (7)−0.0048 (6)
C110.0442 (10)0.0760 (14)0.0559 (11)0.0132 (9)0.0121 (9)0.0111 (10)
C120.0518 (13)0.133 (2)0.0645 (14)−0.0043 (14)0.0072 (11)−0.0217 (15)
C130.0406 (8)0.0347 (8)0.0398 (8)−0.0046 (6)0.0127 (7)−0.0029 (6)
C140.0770 (13)0.0589 (12)0.0531 (10)−0.0188 (10)0.0352 (10)−0.0146 (9)
C150.1034 (18)0.0738 (15)0.0521 (12)−0.0204 (13)0.0283 (12)−0.0255 (10)
C160.0731 (14)0.0518 (12)0.0663 (13)−0.0210 (10)0.0073 (11)−0.0175 (10)
C170.0506 (11)0.0514 (11)0.0736 (13)−0.0162 (8)0.0171 (10)0.0005 (9)
C180.0511 (10)0.0508 (10)0.0450 (9)−0.0105 (8)0.0181 (8)−0.0008 (7)
Geometric parameters (Å, °) top
Cl1—C61.7424 (19)C8—C91.393 (2)
N1—C11.359 (2)C8—H80.93
N1—C91.378 (2)C11—C121.490 (3)
N1—H10.88 (2)C11—H11A0.97
O1—C11.237 (2)C11—H11B0.97
O2—C101.193 (2)C12—H12A0.96
O3—C101.330 (2)C12—H12B0.96
O3—C111.454 (2)C12—H12C0.96
C1—C21.453 (2)C13—C181.382 (2)
C2—C31.357 (2)C13—C141.388 (2)
C2—C101.501 (2)C14—C151.386 (3)
C3—C41.453 (2)C14—H140.93
C3—C131.490 (2)C15—C161.367 (3)
C4—C91.405 (2)C15—H150.93
C4—C51.406 (2)C16—C171.367 (3)
C5—C61.365 (2)C16—H160.93
C5—H50.93C17—C181.381 (3)
C6—C71.389 (3)C17—H170.93
C7—C81.365 (3)C18—H180.93
C7—H70.93
C1—N1—C9124.83 (14)O2—C10—C2124.65 (15)
C1—N1—H1115.4 (14)O3—C10—C2110.23 (13)
C9—N1—H1119.8 (14)O3—C11—C12111.10 (18)
C10—O3—C11117.05 (13)O3—C11—H11A109.4
O1—C1—N1121.80 (15)C12—C11—H11A109.4
O1—C1—C2122.91 (15)O3—C11—H11B109.4
N1—C1—C2115.28 (15)C12—C11—H11B109.4
C3—C2—C1122.95 (15)H11A—C11—H11B108.0
C3—C2—C10122.83 (14)C11—C12—H12A109.5
C1—C2—C10114.18 (14)C11—C12—H12B109.5
C2—C3—C4119.12 (14)H12A—C12—H12B109.5
C2—C3—C13119.56 (14)C11—C12—H12C109.5
C4—C3—C13121.31 (14)H12A—C12—H12C109.5
C9—C4—C5118.23 (15)H12B—C12—H12C109.5
C9—C4—C3117.95 (14)C18—C13—C14118.65 (15)
C5—C4—C3123.80 (14)C18—C13—C3121.14 (14)
C6—C5—C4119.94 (16)C14—C13—C3120.06 (14)
C6—C5—H5120.0C15—C14—C13120.29 (18)
C4—C5—H5120.0C15—C14—H14119.9
C5—C6—C7121.72 (17)C13—C14—H14119.9
C5—C6—Cl1119.97 (15)C16—C15—C14120.11 (19)
C7—C6—Cl1118.31 (15)C16—C15—H15119.9
C8—C7—C6119.16 (18)C14—C15—H15119.9
C8—C7—H7120.4C15—C16—C17120.18 (18)
C6—C7—H7120.4C15—C16—H16119.9
C7—C8—C9120.70 (18)C17—C16—H16119.9
C7—C8—H8119.6C16—C17—C18120.24 (19)
C9—C8—H8119.6C16—C17—H17119.9
N1—C9—C8119.95 (16)C18—C17—H17119.9
N1—C9—C4119.80 (15)C17—C18—C13120.53 (17)
C8—C9—C4120.24 (16)C17—C18—H18119.7
O2—C10—O3125.10 (15)C13—C18—H18119.7
C9—N1—C1—O1176.16 (17)C7—C8—C9—C40.1 (3)
C9—N1—C1—C2−2.6 (3)C5—C4—C9—N1−179.57 (16)
O1—C1—C2—C3−178.45 (16)C3—C4—C9—N1−1.1 (2)
N1—C1—C2—C30.3 (2)C5—C4—C9—C8−1.2 (3)
O1—C1—C2—C10−0.6 (2)C3—C4—C9—C8177.35 (16)
N1—C1—C2—C10178.23 (15)C11—O3—C10—O20.5 (2)
C1—C2—C3—C41.4 (2)C11—O3—C10—C2178.93 (14)
C10—C2—C3—C4−176.30 (14)C3—C2—C10—O2−104.7 (2)
C1—C2—C3—C13−179.62 (14)C1—C2—C10—O277.4 (2)
C10—C2—C3—C132.7 (2)C3—C2—C10—O376.87 (19)
C2—C3—C4—C9−1.0 (2)C1—C2—C10—O3−101.02 (16)
C13—C3—C4—C9−179.99 (14)C10—O3—C11—C1282.5 (2)
C2—C3—C4—C5177.38 (15)C2—C3—C13—C18−111.20 (19)
C13—C3—C4—C5−1.6 (2)C4—C3—C13—C1867.7 (2)
C9—C4—C5—C61.5 (2)C2—C3—C13—C1464.3 (2)
C3—C4—C5—C6−176.91 (15)C4—C3—C13—C14−116.78 (19)
C4—C5—C6—C7−0.8 (3)C18—C13—C14—C15−0.2 (3)
C4—C5—C6—Cl1179.98 (13)C3—C13—C14—C15−175.75 (19)
C5—C6—C7—C8−0.4 (3)C13—C14—C15—C16−0.1 (4)
Cl1—C6—C7—C8178.89 (17)C14—C15—C16—C170.3 (4)
C6—C7—C8—C90.7 (3)C15—C16—C17—C18−0.3 (4)
C1—N1—C9—C8−175.35 (18)C16—C17—C18—C130.1 (3)
C1—N1—C9—C43.1 (3)C14—C13—C18—C170.2 (3)
C7—C8—C9—N1178.5 (2)C3—C13—C18—C17175.69 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.88 (2)1.89 (2)2.763 (2)178 (2)
C11—H11A···O2ii0.972.513.420 (3)157
C17—H17···O1iii0.932.513.299 (3)143
C18—H18···O2iv0.932.533.317 (2)142
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.88 (2)1.89 (2)2.763 (2)178 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank the Department of Science and Technology, India, for use of the diffraction facility set up under the IRHPA–DST programme at IISc. FNK thanks the DST for Fast Track Proposal funding. The authors also thank VIT University and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Baumer, V. N., Shishkin, O. V., Ukrainets, I. V., Taran, S. G. & Amin, J. N. (2001). Acta Cryst. E57, o254–o255.

Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Subashini, R., Hathwar, V. R., Manivel, P., Prabakaran, K. & Khan, F. N. (2009). Acta Cryst. E65, o370.

Westrip, S. P. (2009). publCIF. In preparation.