Ethyl 6-chloro-2-methyl-4-phenyl­quinoline-3-carboxyl­ate

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

doi:10.1107/S160053680904536X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o2986

doi:10.1107/S160053680904536X

Open

access

Ethyl 6-chloro-2-methyl-4-phenylquinoline-3-carboxylate

R. Subashini,^a F. Nawaz Khan,^a Suganya Mittal,^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, C₁₉H₁₆ClNO₂, the quinoline ring system is planar (r.m.s. deviation = 0.008 Å). The phenyl group and the –CO₂ fragment of the ester unit form dihedral angles of 60.0 (1) and 60.5 (1)°, respectively, with the quinoline ring system.

Related literature

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

Experimental

Crystal data

C₁₉H₁₆ClNO₂
M_r = 325.78
Triclinic, $[P \overline 1]$
a = 8.3622 (3) Å
b = 10.1971 (3) Å
c = 10.7052 (3) Å
α = 110.440 (2)°
β = 101.588 (2)°
γ = 94.860 (2)°
V = 825.91 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 290 K
0.24 × 0.18 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.945, T_max = 0.970
15008 measured reflections
3775 independent reflections
2854 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.147
S = 1.04
3775 reflections
210 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.38 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904536X/ci2957sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680904536X/ci2957Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

2-Amino-5-chlorobenzophenone (0.5 mmol), ethyl acetoacete (0.6 mmol, 1.2 equiv.) and iodine (1 mol %) in ethanol (1 ml) were stirred until the reaction was completed, as indicated by TLC. The reaction was quenched with water (15 ml). The organic product was extracted with ethyl acetate. Evaporation of the solvent gave a solid that was recrystallized from DMSO.

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 C₁₉H₁₆ClNO₂ at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

Ethyl 6-chloro-2-methyl-4-phenylquinoline-3-carboxylate top

Crystal data top

C₁₉H₁₆ClNO₂	Z = 2
M_r = 325.78	F(000) = 340
Triclinic, P1	D_x = 1.310 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3622 (3) Å	Cell parameters from 1153 reflections
b = 10.1971 (3) Å	θ = 1.7–24.3°
c = 10.7052 (3) Å	µ = 0.24 mm⁻¹
α = 110.440 (2)°	T = 290 K
β = 101.588 (2)°	Block, colourless
γ = 94.860 (2)°	0.24 × 0.18 × 0.13 mm
V = 825.91 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3775 independent reflections
Radiation source: fine-focus sealed tube	2854 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.945, T_max = 0.970	k = −12→13
15008 measured reflections	l = −13→10

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0795P)² + 0.1903P] where P = (F_o² + 2F_c²)/3
3775 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.33 e Å⁻³
1 restraint	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₉H₁₆ClNO₂	γ = 94.860 (2)°
M_r = 325.78	V = 825.91 (4) Å³
Triclinic, P1	Z = 2
a = 8.3622 (3) Å	Mo Kα radiation
b = 10.1971 (3) Å	µ = 0.24 mm⁻¹
c = 10.7052 (3) Å	T = 290 K
α = 110.440 (2)°	0.24 × 0.18 × 0.13 mm
β = 101.588 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3775 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2854 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.970	R_int = 0.025
15008 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
3775 reflections	Δρ_min = −0.38 e Å⁻³
210 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.59565 (8)	0.80991 (7)	0.87661 (5)	0.0711 (2)
N1	0.79494 (19)	0.38099 (15)	0.42954 (15)	0.0465 (4)
O1	0.93549 (17)	0.66715 (14)	0.21071 (12)	0.0523 (3)
O2	0.7449 (2)	0.48238 (16)	0.06011 (14)	0.0690 (4)
C1	0.8150 (2)	0.40465 (18)	0.31986 (18)	0.0433 (4)
C2	0.7883 (2)	0.53430 (18)	0.30236 (17)	0.0407 (4)
C3	0.7375 (2)	0.63972 (17)	0.40021 (16)	0.0387 (4)
C4	0.71546 (19)	0.61552 (17)	0.52007 (16)	0.0387 (4)
C5	0.6644 (2)	0.7151 (2)	0.62823 (17)	0.0451 (4)
H5	0.6412	0.8009	0.6230	0.054*
C6	0.6496 (2)	0.6845 (2)	0.74006 (17)	0.0481 (4)
C7	0.6778 (2)	0.5543 (2)	0.74986 (18)	0.0523 (5)
H7	0.6647	0.5352	0.8264	0.063*
C8	0.7245 (2)	0.4561 (2)	0.64596 (19)	0.0508 (4)
H8	0.7428	0.3696	0.6520	0.061*
C9	0.7459 (2)	0.48359 (18)	0.52871 (17)	0.0422 (4)
C10	0.8700 (3)	0.2882 (2)	0.2144 (2)	0.0569 (5)
H10A	0.8926	0.2145	0.2484	0.085*
H10B	0.9685	0.3259	0.1968	0.085*
H10C	0.7839	0.2500	0.1307	0.085*
C11	0.8176 (2)	0.55604 (19)	0.17664 (18)	0.0465 (4)
C12	0.9625 (4)	0.7067 (2)	0.0980 (2)	0.0733 (7)
H12A	0.8579	0.6918	0.0321	0.088*
H12B	1.0348	0.6487	0.0514	0.088*
C13	1.0409 (5)	0.8617 (3)	0.1562 (3)	0.1064 (11)
H13A	1.0569	0.8904	0.0826	0.160*
H13B	1.1459	0.8749	0.2191	0.160*
H13C	0.9696	0.9181	0.2038	0.160*
C14	0.7035 (2)	0.77328 (18)	0.38081 (17)	0.0408 (4)
C15	0.5843 (2)	0.7689 (2)	0.26713 (19)	0.0492 (4)
H15	0.5239	0.6823	0.2036	0.059*
C16	0.5557 (3)	0.8940 (2)	0.2488 (2)	0.0609 (5)
H16	0.4755	0.8908	0.1733	0.073*
C17	0.6458 (3)	1.0230 (2)	0.3421 (3)	0.0625 (6)
H17	0.6263	1.1064	0.3293	0.075*
C18	0.7641 (3)	1.0279 (2)	0.4538 (2)	0.0629 (5)
H18	0.8251	1.1147	0.5165	0.075*
C19	0.7927 (2)	0.9034 (2)	0.4729 (2)	0.0521 (4)
H19	0.8731	0.9075	0.5487	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0823 (4)	0.0947 (5)	0.0429 (3)	0.0315 (3)	0.0267 (2)	0.0238 (3)
N1	0.0520 (9)	0.0403 (8)	0.0503 (8)	0.0080 (6)	0.0129 (7)	0.0206 (7)
O1	0.0608 (8)	0.0592 (8)	0.0419 (6)	0.0060 (6)	0.0191 (6)	0.0223 (6)
O2	0.0949 (12)	0.0642 (9)	0.0385 (7)	0.0010 (8)	0.0144 (7)	0.0118 (6)
C1	0.0431 (9)	0.0404 (9)	0.0472 (9)	0.0068 (7)	0.0130 (7)	0.0163 (7)
C2	0.0416 (9)	0.0427 (9)	0.0395 (8)	0.0072 (7)	0.0117 (7)	0.0164 (7)
C3	0.0387 (8)	0.0410 (9)	0.0380 (8)	0.0071 (7)	0.0089 (6)	0.0170 (7)
C4	0.0372 (8)	0.0431 (9)	0.0374 (8)	0.0062 (7)	0.0080 (6)	0.0179 (7)
C5	0.0446 (9)	0.0547 (10)	0.0413 (8)	0.0146 (8)	0.0125 (7)	0.0221 (8)
C6	0.0439 (9)	0.0630 (11)	0.0366 (8)	0.0080 (8)	0.0109 (7)	0.0176 (8)
C7	0.0528 (10)	0.0662 (12)	0.0395 (9)	−0.0035 (9)	0.0069 (7)	0.0274 (9)
C8	0.0581 (11)	0.0494 (10)	0.0470 (9)	0.0005 (8)	0.0069 (8)	0.0260 (8)
C9	0.0418 (9)	0.0440 (9)	0.0422 (8)	0.0033 (7)	0.0077 (7)	0.0201 (7)
C10	0.0645 (12)	0.0455 (10)	0.0657 (12)	0.0169 (9)	0.0276 (10)	0.0186 (9)
C11	0.0557 (10)	0.0464 (10)	0.0422 (9)	0.0155 (8)	0.0176 (8)	0.0177 (8)
C12	0.113 (2)	0.0663 (14)	0.0491 (11)	0.0044 (13)	0.0366 (12)	0.0246 (10)
C13	0.165 (3)	0.086 (2)	0.0744 (17)	−0.011 (2)	0.0446 (19)	0.0358 (15)
C14	0.0453 (9)	0.0429 (9)	0.0410 (8)	0.0124 (7)	0.0171 (7)	0.0192 (7)
C15	0.0503 (10)	0.0527 (10)	0.0515 (10)	0.0093 (8)	0.0119 (8)	0.0280 (8)
C16	0.0559 (11)	0.0731 (14)	0.0729 (13)	0.0208 (10)	0.0185 (10)	0.0469 (12)
C17	0.0709 (13)	0.0522 (12)	0.0866 (15)	0.0251 (10)	0.0355 (12)	0.0407 (11)
C18	0.0757 (14)	0.0423 (10)	0.0725 (13)	0.0136 (10)	0.0271 (11)	0.0180 (10)
C19	0.0583 (11)	0.0474 (10)	0.0488 (10)	0.0107 (8)	0.0128 (8)	0.0158 (8)

Geometric parameters (Å, º) top

Cl1—C6	1.7414 (19)	C10—H10A	0.96
N1—C1	1.317 (2)	C10—H10B	0.96
N1—C9	1.364 (2)	C10—H10C	0.96
O1—C11	1.329 (2)	C12—C13	1.513 (2)
O1—C12	1.450 (2)	C12—H12A	0.97
O2—C11	1.206 (2)	C12—H12B	0.97
C1—C2	1.428 (2)	C13—H13A	0.96
C1—C10	1.503 (3)	C13—H13B	0.96
C2—C3	1.380 (2)	C13—H13C	0.96
C2—C11	1.501 (2)	C14—C19	1.383 (3)
C3—C4	1.432 (2)	C14—C15	1.394 (2)
C3—C14	1.489 (2)	C15—C16	1.389 (3)
C4—C5	1.416 (2)	C15—H15	0.93
C4—C9	1.421 (2)	C16—C17	1.381 (3)
C5—C6	1.364 (2)	C16—H16	0.93
C5—H5	0.93	C17—C18	1.373 (3)
C6—C7	1.404 (3)	C17—H17	0.93
C7—C8	1.362 (3)	C18—C19	1.387 (3)
C7—H7	0.93	C18—H18	0.93
C8—C9	1.419 (2)	C19—H19	0.93
C8—H8	0.93

C1—N1—C9	118.67 (14)	H10B—C10—H10C	109.5
C11—O1—C12	115.60 (15)	O2—C11—O1	124.32 (17)
N1—C1—C2	122.09 (16)	O2—C11—C2	124.75 (18)
N1—C1—C10	116.33 (15)	O1—C11—C2	110.93 (14)
C2—C1—C10	121.57 (15)	O1—C12—C13	108.36 (17)
C3—C2—C1	120.68 (15)	O1—C12—H12A	110.0
C3—C2—C11	119.90 (15)	C13—C12—H12A	110.0
C1—C2—C11	119.42 (15)	O1—C12—H12B	110.0
C2—C3—C4	117.83 (14)	C13—C12—H12B	110.0
C2—C3—C14	121.20 (14)	H12A—C12—H12B	108.4
C4—C3—C14	120.96 (14)	C12—C13—H13A	109.5
C5—C4—C9	119.10 (15)	C12—C13—H13B	109.5
C5—C4—C3	123.49 (15)	H13A—C13—H13B	109.5
C9—C4—C3	117.41 (15)	C12—C13—H13C	109.5
C6—C5—C4	119.64 (16)	H13A—C13—H13C	109.5
C6—C5—H5	120.2	H13B—C13—H13C	109.5
C4—C5—H5	120.2	C19—C14—C15	118.78 (16)
C5—C6—C7	122.02 (17)	C19—C14—C3	120.68 (15)
C5—C6—Cl1	119.74 (15)	C15—C14—C3	120.52 (16)
C7—C6—Cl1	118.23 (13)	C16—C15—C14	120.00 (18)
C8—C7—C6	119.22 (16)	C16—C15—H15	120.0
C8—C7—H7	120.4	C14—C15—H15	120.0
C6—C7—H7	120.4	C17—C16—C15	120.37 (19)
C7—C8—C9	121.19 (17)	C17—C16—H16	119.8
C7—C8—H8	119.4	C15—C16—H16	119.8
C9—C8—H8	119.4	C18—C17—C16	119.94 (18)
N1—C9—C8	117.90 (15)	C18—C17—H17	120.0
N1—C9—C4	123.31 (15)	C16—C17—H17	120.0
C8—C9—C4	118.79 (16)	C17—C18—C19	119.9 (2)
C1—C10—H10A	109.5	C17—C18—H18	120.0
C1—C10—H10B	109.5	C19—C18—H18	120.0
H10A—C10—H10B	109.5	C14—C19—C18	120.97 (19)
C1—C10—H10C	109.5	C14—C19—H19	119.5
H10A—C10—H10C	109.5	C18—C19—H19	119.5

C9—N1—C1—C2	0.5 (3)	C7—C8—C9—C4	−0.8 (3)
C9—N1—C1—C10	179.69 (16)	C5—C4—C9—N1	179.81 (15)
N1—C1—C2—C3	−1.0 (3)	C3—C4—C9—N1	0.2 (2)
C10—C1—C2—C3	179.86 (16)	C5—C4—C9—C8	−0.2 (2)
N1—C1—C2—C11	178.43 (16)	C3—C4—C9—C8	−179.76 (15)
C10—C1—C2—C11	−0.7 (3)	C12—O1—C11—O2	6.4 (3)
C1—C2—C3—C4	1.1 (2)	C12—O1—C11—C2	−174.03 (17)
C11—C2—C3—C4	−178.39 (15)	C3—C2—C11—O2	−119.9 (2)
C1—C2—C3—C14	−177.78 (15)	C1—C2—C11—O2	60.7 (3)
C11—C2—C3—C14	2.8 (2)	C3—C2—C11—O1	60.5 (2)
C2—C3—C4—C5	179.76 (15)	C1—C2—C11—O1	−118.93 (17)
C14—C3—C4—C5	−1.4 (2)	C11—O1—C12—C13	156.4 (2)
C2—C3—C4—C9	−0.7 (2)	C2—C3—C14—C19	−119.39 (19)
C14—C3—C4—C9	178.17 (15)	C4—C3—C14—C19	61.8 (2)
C9—C4—C5—C6	1.7 (3)	C2—C3—C14—C15	58.7 (2)
C3—C4—C5—C6	−178.74 (16)	C4—C3—C14—C15	−120.12 (18)
C4—C5—C6—C7	−2.3 (3)	C19—C14—C15—C16	−0.7 (3)
C4—C5—C6—Cl1	177.19 (13)	C3—C14—C15—C16	−178.83 (17)
C5—C6—C7—C8	1.3 (3)	C14—C15—C16—C17	0.5 (3)
Cl1—C6—C7—C8	−178.20 (14)	C15—C16—C17—C18	−0.1 (3)
C6—C7—C8—C9	0.3 (3)	C16—C17—C18—C19	−0.2 (3)
C1—N1—C9—C8	179.84 (16)	C15—C14—C19—C18	0.5 (3)
C1—N1—C9—C4	−0.1 (3)	C3—C14—C19—C18	178.57 (18)
C7—C8—C9—N1	179.20 (17)	C17—C18—C19—C14	0.0 (3)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₆ClNO₂
M_r	325.78
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	8.3622 (3), 10.1971 (3), 10.7052 (3)
α, β, γ (°)	110.440 (2), 101.588 (2), 94.860 (2)
V (Å³)	825.91 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.24 × 0.18 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.945, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	15008, 3775, 2854
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.147, 1.04
No. of reflections	3775
No. of parameters	210
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.38

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

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