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

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

doi:10.1107/S1600536809045425

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o2987

doi:10.1107/S1600536809045425

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

F. Nawaz Khan,^a Suganya Mittal,^a Soheil Anjum,^a Venkatesha R. Hathwar ^b and Seik Weng Ng ^c ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 October 2009; accepted 29 October 2009; online 4 November 2009)

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

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

Experimental

Crystal data

C₁₈H₁₄ClNO₃
M_r = 327.75
Monoclinic, P 2₁ /c
a = 10.176 (1) Å
b = 15.629 (2) Å
c = 11.282 (1) Å
β = 115.463 (1)°
V = 1619.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 290 K
0.35 × 0.31 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.918, T_max = 0.945
13600 measured reflections
3699 independent reflections
2906 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 1.00
3699 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88 (2)	1.89 (2)	2.763 (2)	178 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045425/ci2958sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045425/ci2958Isup2.hkl

checkCIF report

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.

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

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

C₁₈H₁₄ClNO₃	F(000) = 680
M_r = 327.75	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1123 reflections
a = 10.176 (1) Å	θ = 2.9–20.7°
b = 15.629 (2) Å	µ = 0.25 mm⁻¹
c = 11.282 (1) Å	T = 290 K
β = 115.463 (1)°	Block, colourless
V = 1619.9 (3) Å³	0.35 × 0.31 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3699 independent reflections
Radiation source: fine-focus sealed tube	2906 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.918, T_max = 0.945	k = −20→19
13600 measured reflections	l = −14→14

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0664P)² + 0.4015P] where P = (F_o² + 2F_c²)/3
3699 reflections	(Δ/σ)_max = 0.001
213 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₈H₁₄ClNO₃	V = 1619.9 (3) Å³
M_r = 327.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.176 (1) Å	µ = 0.25 mm⁻¹
b = 15.629 (2) Å	T = 290 K
c = 11.282 (1) Å	0.35 × 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)
T_min = 0.918, T_max = 0.945	R_int = 0.022
13600 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.23 e Å⁻³
3699 reflections	Δρ_min = −0.20 e Å⁻³
213 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.54343 (6)	0.02895 (3)	0.68514 (6)	0.0743 (2)
N1	0.46268 (16)	0.38491 (9)	0.50054 (15)	0.0526 (4)
H1	0.527 (2)	0.4235 (14)	0.546 (2)	0.066 (6)*
O1	0.33674 (13)	0.49099 (7)	0.36051 (13)	0.0569 (3)
O2	0.13633 (14)	0.40486 (9)	0.08985 (13)	0.0605 (4)
O3	0.00732 (12)	0.38779 (8)	0.20662 (11)	0.0487 (3)
C1	0.35167 (17)	0.41406 (10)	0.38896 (17)	0.0454 (4)
C2	0.25139 (17)	0.34892 (10)	0.30798 (15)	0.0404 (3)
C3	0.26581 (16)	0.26477 (10)	0.34062 (15)	0.0384 (3)
C4	0.38454 (16)	0.23795 (10)	0.46323 (16)	0.0405 (4)
C5	0.40613 (18)	0.15305 (11)	0.50898 (16)	0.0450 (4)
H5	0.3452	0.1098	0.4580	0.054*
C6	0.5166 (2)	0.13411 (12)	0.62836 (19)	0.0530 (4)
C7	0.6110 (2)	0.19671 (14)	0.7067 (2)	0.0648 (5)
H7	0.6853	0.1826	0.7880	0.078*
C8	0.5932 (2)	0.27920 (13)	0.6629 (2)	0.0634 (5)
H8	0.6566	0.3213	0.7144	0.076*
C9	0.48116 (18)	0.30096 (11)	0.54190 (17)	0.0465 (4)
C10	0.12728 (17)	0.38317 (10)	0.18746 (15)	0.0411 (4)
C11	−0.1227 (2)	0.42135 (14)	0.09932 (19)	0.0620 (5)
H11A	−0.0961	0.4681	0.0573	0.074*
H11B	−0.1882	0.4437	0.1338	0.074*
C12	−0.1985 (2)	0.3536 (2)	0.0004 (2)	0.0894 (8)
H12A	−0.2907	0.3749	−0.0625	0.134*
H12B	−0.2140	0.3044	0.0438	0.134*
H12C	−0.1398	0.3378	−0.0437	0.134*
C13	0.15864 (17)	0.20196 (10)	0.25160 (15)	0.0400 (3)
C14	0.1482 (2)	0.18833 (13)	0.12633 (19)	0.0605 (5)
H14	0.2126	0.2156	0.1001	0.073*
C15	0.0423 (3)	0.13422 (15)	0.0401 (2)	0.0782 (7)
H15	0.0358	0.1254	−0.0438	0.094*
C16	−0.0525 (3)	0.09389 (13)	0.0781 (2)	0.0717 (6)
H16	−0.1231	0.0574	0.0202	0.086*
C17	−0.0437 (2)	0.10699 (12)	0.2011 (2)	0.0619 (5)
H17	−0.1087	0.0796	0.2264	0.074*
C18	0.06135 (19)	0.16075 (11)	0.28790 (17)	0.0499 (4)
H18	0.0667	0.1693	0.3714	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0758 (4)	0.0599 (3)	0.0810 (4)	0.0093 (2)	0.0277 (3)	0.0260 (3)
N1	0.0408 (8)	0.0370 (8)	0.0583 (9)	−0.0040 (6)	0.0007 (7)	−0.0097 (7)
O1	0.0437 (7)	0.0348 (6)	0.0701 (8)	−0.0018 (5)	0.0034 (6)	−0.0062 (6)
O2	0.0600 (8)	0.0724 (9)	0.0500 (7)	0.0001 (7)	0.0246 (6)	0.0108 (6)
O3	0.0396 (6)	0.0591 (7)	0.0424 (6)	0.0039 (5)	0.0127 (5)	0.0059 (5)
C1	0.0350 (8)	0.0384 (9)	0.0528 (9)	−0.0012 (6)	0.0095 (7)	−0.0072 (7)
C2	0.0370 (8)	0.0392 (8)	0.0407 (8)	−0.0041 (6)	0.0126 (7)	−0.0051 (6)
C3	0.0355 (8)	0.0392 (8)	0.0395 (8)	−0.0040 (6)	0.0152 (7)	−0.0057 (6)
C4	0.0362 (8)	0.0400 (8)	0.0427 (8)	−0.0010 (6)	0.0145 (7)	−0.0050 (7)
C5	0.0426 (9)	0.0419 (9)	0.0486 (9)	−0.0011 (7)	0.0178 (7)	−0.0018 (7)
C6	0.0515 (10)	0.0491 (10)	0.0568 (10)	0.0070 (8)	0.0218 (9)	0.0085 (8)
C7	0.0559 (11)	0.0654 (13)	0.0508 (10)	0.0066 (9)	0.0018 (9)	0.0056 (9)
C8	0.0521 (11)	0.0556 (11)	0.0571 (11)	−0.0020 (9)	−0.0007 (9)	−0.0076 (9)
C9	0.0382 (8)	0.0423 (9)	0.0477 (9)	0.0008 (7)	0.0079 (7)	−0.0049 (7)
C10	0.0413 (8)	0.0349 (8)	0.0405 (8)	−0.0062 (6)	0.0115 (7)	−0.0048 (6)
C11	0.0442 (10)	0.0760 (14)	0.0559 (11)	0.0132 (9)	0.0121 (9)	0.0111 (10)
C12	0.0518 (13)	0.133 (2)	0.0645 (14)	−0.0043 (14)	0.0072 (11)	−0.0217 (15)
C13	0.0406 (8)	0.0347 (8)	0.0398 (8)	−0.0046 (6)	0.0127 (7)	−0.0029 (6)
C14	0.0770 (13)	0.0589 (12)	0.0531 (10)	−0.0188 (10)	0.0352 (10)	−0.0146 (9)
C15	0.1034 (18)	0.0738 (15)	0.0521 (12)	−0.0204 (13)	0.0283 (12)	−0.0255 (10)
C16	0.0731 (14)	0.0518 (12)	0.0663 (13)	−0.0210 (10)	0.0073 (11)	−0.0175 (10)
C17	0.0506 (11)	0.0514 (11)	0.0736 (13)	−0.0162 (8)	0.0171 (10)	0.0005 (9)
C18	0.0511 (10)	0.0508 (10)	0.0450 (9)	−0.0105 (8)	0.0181 (8)	−0.0008 (7)

Geometric parameters (Å, º) top

Cl1—C6	1.7424 (19)	C8—C9	1.393 (2)
N1—C1	1.359 (2)	C8—H8	0.93
N1—C9	1.378 (2)	C11—C12	1.490 (3)
N1—H1	0.88 (2)	C11—H11A	0.97
O1—C1	1.237 (2)	C11—H11B	0.97
O2—C10	1.193 (2)	C12—H12A	0.96
O3—C10	1.330 (2)	C12—H12B	0.96
O3—C11	1.454 (2)	C12—H12C	0.96
C1—C2	1.453 (2)	C13—C18	1.382 (2)
C2—C3	1.357 (2)	C13—C14	1.388 (2)
C2—C10	1.501 (2)	C14—C15	1.386 (3)
C3—C4	1.453 (2)	C14—H14	0.93
C3—C13	1.490 (2)	C15—C16	1.367 (3)
C4—C9	1.405 (2)	C15—H15	0.93
C4—C5	1.406 (2)	C16—C17	1.367 (3)
C5—C6	1.365 (2)	C16—H16	0.93
C5—H5	0.93	C17—C18	1.381 (3)
C6—C7	1.389 (3)	C17—H17	0.93
C7—C8	1.365 (3)	C18—H18	0.93
C7—H7	0.93

C1—N1—C9	124.83 (14)	O2—C10—C2	124.65 (15)
C1—N1—H1	115.4 (14)	O3—C10—C2	110.23 (13)
C9—N1—H1	119.8 (14)	O3—C11—C12	111.10 (18)
C10—O3—C11	117.05 (13)	O3—C11—H11A	109.4
O1—C1—N1	121.80 (15)	C12—C11—H11A	109.4
O1—C1—C2	122.91 (15)	O3—C11—H11B	109.4
N1—C1—C2	115.28 (15)	C12—C11—H11B	109.4
C3—C2—C1	122.95 (15)	H11A—C11—H11B	108.0
C3—C2—C10	122.83 (14)	C11—C12—H12A	109.5
C1—C2—C10	114.18 (14)	C11—C12—H12B	109.5
C2—C3—C4	119.12 (14)	H12A—C12—H12B	109.5
C2—C3—C13	119.56 (14)	C11—C12—H12C	109.5
C4—C3—C13	121.31 (14)	H12A—C12—H12C	109.5
C9—C4—C5	118.23 (15)	H12B—C12—H12C	109.5
C9—C4—C3	117.95 (14)	C18—C13—C14	118.65 (15)
C5—C4—C3	123.80 (14)	C18—C13—C3	121.14 (14)
C6—C5—C4	119.94 (16)	C14—C13—C3	120.06 (14)
C6—C5—H5	120.0	C15—C14—C13	120.29 (18)
C4—C5—H5	120.0	C15—C14—H14	119.9
C5—C6—C7	121.72 (17)	C13—C14—H14	119.9
C5—C6—Cl1	119.97 (15)	C16—C15—C14	120.11 (19)
C7—C6—Cl1	118.31 (15)	C16—C15—H15	119.9
C8—C7—C6	119.16 (18)	C14—C15—H15	119.9
C8—C7—H7	120.4	C15—C16—C17	120.18 (18)
C6—C7—H7	120.4	C15—C16—H16	119.9
C7—C8—C9	120.70 (18)	C17—C16—H16	119.9
C7—C8—H8	119.6	C16—C17—C18	120.24 (19)
C9—C8—H8	119.6	C16—C17—H17	119.9
N1—C9—C8	119.95 (16)	C18—C17—H17	119.9
N1—C9—C4	119.80 (15)	C17—C18—C13	120.53 (17)
C8—C9—C4	120.24 (16)	C17—C18—H18	119.7
O2—C10—O3	125.10 (15)	C13—C18—H18	119.7

C9—N1—C1—O1	176.16 (17)	C7—C8—C9—C4	0.1 (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—C3	0.3 (2)	C5—C4—C9—C8	−1.2 (3)
O1—C1—C2—C10	−0.6 (2)	C3—C4—C9—C8	177.35 (16)
N1—C1—C2—C10	178.23 (15)	C11—O3—C10—O2	0.5 (2)
C1—C2—C3—C4	1.4 (2)	C11—O3—C10—C2	178.93 (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—O2	77.4 (2)
C10—C2—C3—C13	2.7 (2)	C3—C2—C10—O3	76.87 (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—C12	82.5 (2)
C2—C3—C4—C5	177.38 (15)	C2—C3—C13—C18	−111.20 (19)
C13—C3—C4—C5	−1.6 (2)	C4—C3—C13—C18	67.7 (2)
C9—C4—C5—C6	1.5 (2)	C2—C3—C13—C14	64.3 (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—Cl1	179.98 (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—C8	178.89 (17)	C14—C15—C16—C17	0.3 (4)
C6—C7—C8—C9	0.7 (3)	C15—C16—C17—C18	−0.3 (4)
C1—N1—C9—C8	−175.35 (18)	C16—C17—C18—C13	0.1 (3)
C1—N1—C9—C4	3.1 (3)	C14—C13—C18—C17	0.2 (3)
C7—C8—C9—N1	178.5 (2)	C3—C13—C18—C17	175.69 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (2)	1.89 (2)	2.763 (2)	178 (2)
C11—H11A···O2ⁱⁱ	0.97	2.51	3.420 (3)	157
C17—H17···O1ⁱⁱⁱ	0.93	2.51	3.299 (3)	143
C18—H18···O2^iv	0.93	2.53	3.317 (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.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄ClNO₃
M_r	327.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	10.176 (1), 15.629 (2), 11.282 (1)
β (°)	115.463 (1)
V (Å³)	1619.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.35 × 0.31 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.918, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	13600, 3699, 2906
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 1.00
No. of reflections	3699
No. of parameters	213
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (2)	1.89 (2)	2.763 (2)	178 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Baumer, V. N., Shishkin, O. V., Ukrainets, I. V., Taran, S. G. & Amin, J. N. (2001). Acta Cryst. E57, o254–o255. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subashini, R., Hathwar, V. R., Manivel, P., Prabakaran, K. & Khan, F. N. (2009). Acta Cryst. E65, o370. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar