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

Abstract

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 R ₂ ²(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,

• a = 10.176 (1) Å

• b = 15.629 (2) Å

• c = 11.282 (1) Å

• β = 115.463 (1)°

• V = 1619.9 (3) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) .

supplementary crystallographic information

Experimental

(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

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 U_iso(H) set to 1.2U_eq(C). The amino H-atom was located in a difference Fourier map, and was freely refined without any restraint.

Figures

Fig. 1.

Displacement ellipsoid plot (Barbour, 2001) of C18H14ClNO3 at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

Crystal data

C18H14ClNO3	F(000) = 680
Mr = 327.75	Dx = 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

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

Refinement

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(Fo2) + (0.0664P)2 + 0.4015P] where P = (Fo2 + 2Fc2)/3
3699 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O2iv	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.