Ethyl 2,6-dichloro-4-phenyl­quinoline-3-carboxyl­ate

Roopan, S.M.; Khan, F.N.; Vijetha, M.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809045334

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o2982

doi:10.1107/S1600536809045334

Open

access

Ethyl 2,6-dichloro-4-phenylquinoline-3-carboxylate

S. Mohana Roopan,^a F. Nawaz Khan,^a M. Vijetha,^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, C₁₈H₁₃Cl₂NO₂, the quinoline ring system is almost planar (r.m.s. deviation 0.009 Å), and the phenyl and carboxylate planes are twisted away from it by 59.2 (1) and 65.9 (2)°, respectively.

Related literature

The title compound is a 6-chloro analouge of ethyl 2-chloro-4-phenylquinoline-3-carboxylate, which has been examined for endothelin binding affinity; for details, see: Anzini et al. (1991 , 1992 , 2001 ); Cappelli et al. (2008 ); Pittala et al. (2008 ).

Experimental

Crystal data

C₁₈H₁₃Cl₂NO₂
M_r = 346.19
Triclinic, $[P \overline 1]$
a = 8.3553 (3) Å
b = 10.1861 (5) Å
c = 10.6731 (6) Å
α = 110.537 (5)°
β = 101.421 (4)°
γ = 95.980 (4)°
V = 818.73 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 295 K
0.34 × 0.26 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.875, T_max = 0.906
18102 measured reflections
3700 independent reflections
2537 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.144
S = 1.02
3700 reflections
209 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.36 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/S1600536809045334/ci2954sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045334/ci2954Isup2.hkl

checkCIF report

Related literature top

The title compound is a 6-chloro analouge of ethyl 2-chloro-4-phenylquinoline-3-carboxylate, which has been examined for endothelin binding affinity; for details, see: Anzini et al. (1991, 1992, 2001); Cappelli et al. (2008); Pittala et al. (2008).

Experimental top

An excess of phosphorus oxychloride (0.9 ml, 10 mmol) and 6-chloro-1,2-dihydro-2-oxo-4-phenylquinoline-3-carboxylate (0.33 g, 1 mmol) were heated for 1 h. The mixture was then added to crushed ice. The solid that formed was collected and recrystallized from methanol.

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 C₁₈H₁₃Cl₂NO₂ at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

Ethyl 2,6-dichloro-4-phenylquinoline-3-carboxylate top

Crystal data top

C₁₈H₁₃Cl₂NO₂	Z = 2
M_r = 346.19	F(000) = 356
Triclinic, P1	D_x = 1.404 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3553 (3) Å	Cell parameters from 1235 reflections
b = 10.1861 (5) Å	θ = 1.7–21.3°
c = 10.6731 (6) Å	µ = 0.40 mm⁻¹
α = 110.537 (5)°	T = 295 K
β = 101.421 (4)°	Block, colourless
γ = 95.980 (4)°	0.34 × 0.26 × 0.25 mm
V = 818.73 (7) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3700 independent reflections
Radiation source: fine-focus sealed tube	2537 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.875, T_max = 0.906	k = −13→12
18102 measured reflections	l = −13→13

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) = 0.144	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.07P)² + 0.2927P] where P = (F_o² + 2F_c²)/3
3700 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.41 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₈H₁₃Cl₂NO₂	γ = 95.980 (4)°
M_r = 346.19	V = 818.73 (7) Å³
Triclinic, P1	Z = 2
a = 8.3553 (3) Å	Mo Kα radiation
b = 10.1861 (5) Å	µ = 0.40 mm⁻¹
c = 10.6731 (6) Å	T = 295 K
α = 110.537 (5)°	0.34 × 0.26 × 0.25 mm
β = 101.421 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3700 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2537 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.906	R_int = 0.031
18102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.144	H-atom parameters constrained
S = 1.02	Δρ_max = 0.41 e Å⁻³
3700 reflections	Δρ_min = −0.36 e Å⁻³
209 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.38082 (9)	0.27696 (7)	0.20007 (7)	0.0656 (2)
Cl2	0.09541 (10)	0.80809 (9)	0.87358 (6)	0.0737 (3)
N1	0.2968 (2)	0.38235 (19)	0.42803 (19)	0.0464 (4)
O1	0.4425 (2)	0.66274 (18)	0.20689 (15)	0.0522 (4)
O2	0.2357 (2)	0.48698 (19)	0.05569 (16)	0.0651 (5)
C1	0.3141 (3)	0.4086 (2)	0.3210 (2)	0.0432 (5)
C2	0.2874 (3)	0.5342 (2)	0.2978 (2)	0.0394 (5)
C3	0.2357 (3)	0.6384 (2)	0.3963 (2)	0.0372 (5)
C4	0.2145 (3)	0.6144 (2)	0.5166 (2)	0.0381 (5)
C5	0.1637 (3)	0.7137 (2)	0.6250 (2)	0.0436 (5)
H5	0.1397	0.7989	0.6195	0.052*
C6	0.1503 (3)	0.6832 (3)	0.7373 (2)	0.0479 (5)
C7	0.1808 (3)	0.5550 (3)	0.7485 (2)	0.0534 (6)
H7	0.1695	0.5368	0.8261	0.064*
C8	0.2271 (3)	0.4575 (3)	0.6448 (2)	0.0509 (6)
H8	0.2459	0.3714	0.6512	0.061*
C9	0.2472 (3)	0.4845 (2)	0.5278 (2)	0.0421 (5)
C10	0.2017 (3)	0.7710 (2)	0.3758 (2)	0.0399 (5)
C11	0.0839 (3)	0.7647 (3)	0.2608 (2)	0.0479 (5)
H11	0.0235	0.6769	0.1963	0.057*
C12	0.0565 (3)	0.8896 (3)	0.2421 (3)	0.0607 (7)
H12	−0.0235	0.8855	0.1659	0.073*
C13	0.1478 (4)	1.0192 (3)	0.3363 (3)	0.0650 (7)
H13	0.1301	1.1024	0.3227	0.078*
C14	0.2633 (4)	1.0268 (3)	0.4490 (3)	0.0641 (7)
H14	0.3240	1.1151	0.5123	0.077*
C15	0.2910 (3)	0.9030 (2)	0.4697 (2)	0.0506 (6)
H15	0.3701	0.9088	0.5472	0.061*
C16	0.3163 (3)	0.5558 (2)	0.1716 (2)	0.0443 (5)
C17	0.4740 (4)	0.7060 (3)	0.0971 (3)	0.0749 (9)
H17A	0.3713	0.6852	0.0267	0.090*
H17B	0.5522	0.6533	0.0547	0.090*
C18	0.5432 (6)	0.8615 (3)	0.1550 (4)	0.1137 (15)
H18A	0.5572	0.8916	0.0815	0.170*
H18B	0.6490	0.8806	0.2195	0.170*
H18C	0.4683	0.9129	0.2016	0.170*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0792 (5)	0.0546 (4)	0.0702 (4)	0.0224 (3)	0.0354 (4)	0.0209 (3)
Cl2	0.0878 (5)	0.1001 (6)	0.0420 (3)	0.0331 (4)	0.0288 (3)	0.0264 (3)
N1	0.0512 (11)	0.0404 (10)	0.0507 (11)	0.0064 (8)	0.0109 (9)	0.0226 (8)
O1	0.0616 (10)	0.0593 (10)	0.0393 (8)	0.0039 (8)	0.0178 (7)	0.0223 (7)
O2	0.0851 (13)	0.0648 (11)	0.0359 (9)	0.0015 (10)	0.0110 (9)	0.0135 (8)
C1	0.0424 (12)	0.0393 (11)	0.0472 (12)	0.0081 (9)	0.0125 (9)	0.0148 (9)
C2	0.0419 (12)	0.0405 (11)	0.0377 (10)	0.0071 (9)	0.0108 (9)	0.0170 (8)
C3	0.0372 (11)	0.0390 (11)	0.0361 (10)	0.0051 (9)	0.0072 (8)	0.0167 (8)
C4	0.0366 (11)	0.0431 (11)	0.0348 (10)	0.0053 (9)	0.0062 (8)	0.0171 (8)
C5	0.0448 (12)	0.0528 (13)	0.0375 (11)	0.0119 (10)	0.0111 (9)	0.0210 (9)
C6	0.0428 (12)	0.0664 (15)	0.0338 (11)	0.0074 (11)	0.0098 (9)	0.0189 (10)
C7	0.0545 (14)	0.0694 (16)	0.0382 (12)	−0.0051 (12)	0.0054 (10)	0.0309 (11)
C8	0.0577 (15)	0.0511 (13)	0.0479 (13)	0.0015 (11)	0.0063 (11)	0.0298 (11)
C9	0.0406 (12)	0.0441 (11)	0.0423 (11)	0.0017 (9)	0.0065 (9)	0.0212 (9)
C10	0.0461 (12)	0.0414 (11)	0.0398 (11)	0.0128 (9)	0.0176 (9)	0.0193 (9)
C11	0.0505 (14)	0.0519 (13)	0.0484 (12)	0.0093 (10)	0.0132 (10)	0.0272 (10)
C12	0.0577 (16)	0.0768 (19)	0.0698 (16)	0.0248 (14)	0.0205 (13)	0.0486 (15)
C13	0.0747 (19)	0.0517 (15)	0.091 (2)	0.0255 (14)	0.0355 (16)	0.0417 (15)
C14	0.0769 (19)	0.0414 (13)	0.0749 (18)	0.0124 (13)	0.0264 (15)	0.0191 (12)
C15	0.0595 (15)	0.0447 (12)	0.0461 (12)	0.0109 (11)	0.0142 (11)	0.0148 (10)
C16	0.0535 (14)	0.0451 (12)	0.0397 (12)	0.0166 (11)	0.0175 (10)	0.0173 (9)
C17	0.115 (2)	0.0674 (17)	0.0481 (14)	−0.0004 (16)	0.0374 (15)	0.0240 (13)
C18	0.189 (4)	0.082 (2)	0.075 (2)	−0.008 (3)	0.052 (3)	0.0349 (18)

Geometric parameters (Å, º) top

Cl1—C1	1.732 (2)	C8—C9	1.407 (3)
Cl2—C6	1.742 (2)	C8—H8	0.93
N1—C1	1.292 (3)	C10—C15	1.385 (3)
N1—C9	1.369 (3)	C10—C11	1.390 (3)
O1—C16	1.325 (3)	C11—C12	1.389 (3)
O1—C17	1.448 (3)	C11—H11	0.93
O2—C16	1.199 (3)	C12—C13	1.375 (4)
C1—C2	1.417 (3)	C12—H12	0.93
C2—C3	1.382 (3)	C13—C14	1.358 (4)
C2—C16	1.499 (3)	C13—H13	0.93
C3—C4	1.429 (3)	C14—C15	1.389 (4)
C3—C10	1.488 (3)	C14—H14	0.93
C4—C5	1.416 (3)	C15—H15	0.93
C4—C9	1.419 (3)	C17—C18	1.485 (2)
C5—C6	1.361 (3)	C17—H17A	0.97
C5—H5	0.93	C17—H17B	0.97
C6—C7	1.397 (4)	C18—H18A	0.96
C7—C8	1.356 (4)	C18—H18B	0.96
C7—H7	0.93	C18—H18C	0.96

C1—N1—C9	117.23 (18)	C11—C10—C3	120.90 (19)
C16—O1—C17	116.36 (18)	C12—C11—C10	120.0 (2)
N1—C1—C2	125.8 (2)	C12—C11—H11	120.0
N1—C1—Cl1	115.05 (16)	C10—C11—H11	120.0
C2—C1—Cl1	119.09 (17)	C13—C12—C11	120.0 (2)
C3—C2—C1	118.10 (19)	C13—C12—H12	120.0
C3—C2—C16	120.40 (18)	C11—C12—H12	120.0
C1—C2—C16	121.50 (19)	C14—C13—C12	120.6 (2)
C2—C3—C4	118.21 (18)	C14—C13—H13	119.7
C2—C3—C10	120.49 (18)	C12—C13—H13	119.7
C4—C3—C10	121.30 (18)	C13—C14—C15	120.1 (3)
C5—C4—C9	118.57 (19)	C13—C14—H14	120.0
C5—C4—C3	123.39 (19)	C15—C14—H14	120.0
C9—C4—C3	118.04 (19)	C10—C15—C14	120.5 (2)
C6—C5—C4	119.4 (2)	C10—C15—H15	119.8
C6—C5—H5	120.3	C14—C15—H15	119.8
C4—C5—H5	120.3	O2—C16—O1	125.1 (2)
C5—C6—C7	122.4 (2)	O2—C16—C2	124.8 (2)
C5—C6—Cl2	119.40 (19)	O1—C16—C2	110.14 (18)
C7—C6—Cl2	118.20 (17)	O1—C17—C18	109.4 (2)
C8—C7—C6	119.2 (2)	O1—C17—H17A	109.8
C8—C7—H7	120.4	C18—C17—H17A	109.8
C6—C7—H7	120.4	O1—C17—H17B	109.8
C7—C8—C9	121.1 (2)	C18—C17—H17B	109.8
C7—C8—H8	119.5	H17A—C17—H17B	108.2
C9—C8—H8	119.5	C17—C18—H18A	109.5
N1—C9—C8	118.0 (2)	C17—C18—H18B	109.5
N1—C9—C4	122.57 (19)	H18A—C18—H18B	109.5
C8—C9—C4	119.4 (2)	C17—C18—H18C	109.5
C15—C10—C11	118.9 (2)	H18A—C18—H18C	109.5
C15—C10—C3	120.20 (19)	H18B—C18—H18C	109.5

C9—N1—C1—C2	0.5 (3)	C7—C8—C9—C4	−1.6 (3)
C9—N1—C1—Cl1	178.84 (15)	C5—C4—C9—N1	179.98 (19)
N1—C1—C2—C3	−1.1 (3)	C3—C4—C9—N1	−0.4 (3)
Cl1—C1—C2—C3	−179.37 (16)	C5—C4—C9—C8	0.5 (3)
N1—C1—C2—C16	178.0 (2)	C3—C4—C9—C8	−179.88 (19)
Cl1—C1—C2—C16	−0.3 (3)	C2—C3—C10—C15	−119.8 (2)
C1—C2—C3—C4	0.8 (3)	C4—C3—C10—C15	60.9 (3)
C16—C2—C3—C4	−178.25 (19)	C2—C3—C10—C11	58.2 (3)
C1—C2—C3—C10	−178.5 (2)	C4—C3—C10—C11	−121.1 (2)
C16—C2—C3—C10	2.4 (3)	C15—C10—C11—C12	−0.5 (3)
C2—C3—C4—C5	179.40 (19)	C3—C10—C11—C12	−178.6 (2)
C10—C3—C4—C5	−1.3 (3)	C10—C11—C12—C13	1.0 (4)
C2—C3—C4—C9	−0.2 (3)	C11—C12—C13—C14	−0.9 (4)
C10—C3—C4—C9	179.14 (19)	C12—C13—C14—C15	0.3 (4)
C9—C4—C5—C6	1.1 (3)	C11—C10—C15—C14	−0.1 (4)
C3—C4—C5—C6	−178.5 (2)	C3—C10—C15—C14	178.0 (2)
C4—C5—C6—C7	−1.7 (3)	C13—C14—C15—C10	0.2 (4)
C4—C5—C6—Cl2	177.61 (16)	C17—O1—C16—O2	5.6 (3)
C5—C6—C7—C8	0.7 (4)	C17—O1—C16—C2	−173.7 (2)
Cl2—C6—C7—C8	−178.63 (18)	C3—C2—C16—O2	−114.0 (3)
C6—C7—C8—C9	1.0 (4)	C1—C2—C16—O2	66.9 (3)
C1—N1—C9—C8	179.8 (2)	C3—C2—C16—O1	65.3 (3)
C1—N1—C9—C4	0.3 (3)	C1—C2—C16—O1	−113.8 (2)
C7—C8—C9—N1	179.0 (2)	C16—O1—C17—C18	148.7 (3)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃Cl₂NO₂
M_r	346.19
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.3553 (3), 10.1861 (5), 10.6731 (6)
α, β, γ (°)	110.537 (5), 101.421 (4), 95.980 (4)
V (Å³)	818.73 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.34 × 0.26 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.875, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	18102, 3700, 2537
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.144, 1.02
No. of reflections	3700
No. of parameters	209
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.36

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

Anzini, M., Cappelli, A., Vomero, S., Cagnotto, A. & Skorupska, M. (1992). Il Farm. 47, 191–202. CAS Google Scholar
Anzini, M., Cappelli, A., Vomero, S., Campiani, G., Cagnotto, A. & Skorupska, M. (1991). Il Farm. 46, 1435–1447. CAS Google Scholar
Anzini, M., Cappelli, A., Vomero, S., Seeber, M., Menziani, M. C., Langer, T., Hagen, B., Manzoni, C. & Bourguignon, J.-J. (2001). J. Med. Chem. 44, 1134–1150. Web of Science CrossRef PubMed CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cappelli, A., Giuliani, G., Anzini, M., Riitano, D., Giorgi, G. & Vomero, S. (2008). Bioorg. Med. Chem. 16, 6850–6859. Web of Science CSD CrossRef PubMed CAS Google Scholar
Pittala, V., Modica, M., Salerno, L., Siracusa, M. A., Guerrera, F., Mereghetti, I., Cagnotto, A., Mennini, T. & Romeo, G. (2008). Med. Chem. 4, 129–137. Web of Science CrossRef PubMed CAS 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
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar