4-Chloro­phenyl quinoline-2-carboxyl­ate

Fazal, E.; Kaur, M.; Sudha, B.S.; Nagarajan, S.; Jasinski, J.P.

doi:10.1107/S1600536813032054

organic compounds

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Volume 69| Part 12| December 2013| Page o1841

doi:10.1107/S1600536813032054

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4-Chlorophenyl quinoline-2-carboxylate

E. Fazal,^a Manpreet Kaur,^b B. S. Sudha,^a S. Nagarajan ^c and Jerry P. Jasinski ^d ^*

^aDepartment of Chemistry, Yuvaraja's College, Mysore 570 005, India, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^cP.P.S.F.T. Department, Central Food Technplogy Research institute, Mysore 570 005, India, and ^dDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 24 November 2013; accepted 24 November 2013; online 30 November 2013)

In the title compound, C₁₆H₁₀ClNO₂, the dihedral angle between the quinoline ring system and the benzene ring is 14.7 (5)°. The carboxylate group is twisted from the mean planes of the quinoline ring system and the benzene ring by 17.7 (5) and 32.1 (4)°, respectively. In the crystal, inversion dimers are formed with the molecules linked by pairs of weak C—H⋯O interactions arising from an activated aromatic C atom adjacent to the C—Cl bond, generating R₂²(14) loops.

CCDC reference: 973445

Related literature

For related structures, see: Fazal et al. (2012 ); Butcher et al. (2007 ); Jing & Qin (2008 ); Jasinski et al. (2010 ).

Experimental

Crystal data

C₁₆H₁₀ClNO₂
M_r = 283.70
Monoclinic, P 2₁ /n
a = 6.38693 (18) Å
b = 16.8893 (5) Å
c = 12.2649 (4) Å
β = 103.527 (3)°
V = 1286.33 (6) Å³
Z = 4
Cu Kα radiation
μ = 2.63 mm⁻¹
T = 173 K
0.34 × 0.18 × 0.12 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.611, T_max = 1.000
7778 measured reflections
2502 independent reflections
2168 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 1.05
2502 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1ⁱ	0.93	2.42	3.250 (2)	148
Symmetry code: (i) -x+2, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 973445

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813032054/hb7166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813032054/hb7166Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813032054/hb7166Isup3.cml

checkCIF report

Comment top

The crystal structures of 4-methylphenyl quinoline-2-carboxylate (Fazal et al.,2012), 1-(quinolin-2-yl)ethanone (Butcher et al., 2007) and methyl quinoline-2-carboxylate (Jing & Qin, 2008) and the synthesis, crystal structures and theoretical studies of four Schiff bases derived from 4-hydrazinyl-8-(trifluoromethyl) quinoline (Jasinski et al., 2010) have been reported. As part of our studies in this area, we now report the crystal structure of the title compound, (I), C₁₆H₁₀ClNO₂.

The dihedral angle between the mean planes of the quinoline ring and the phenyl ring is 14.7 (5)8° (Fig. 1). The mean plane of the carboxylate group is twisted from the mean planes of the quinoline ring and phenyl ring by 17.7 (5)ånd 32.1 (4)°, respectively. In the crystal, weak C13—H13···O1 intermolecular interactions link the molecules into dimers forming R₂²(14) graph set motifs (Fig. 2).

Related literature top

For related structures, see: Fazal et al. (2012); Butcher et al. (2007); Jing & Qin (2008); Jasinski et al. (2010).

Experimental top

To a mixture of 1.73 g (10 mmole) of quinaldic acid and 1.28 g (10 mmole) of 4-chlorophenol in a round-bottomed flask fitted with a reflex condenser with a drying tube was added 0.75 g (5 mmole) of phosphorous oxychloride. The mixture was heated with occasional swirling, and temperature maintained at 353-363 K. At the end of eight hours the reaction mixture was poured in to a solution of 2 g of sodium bicarbonate in 25 ml of water. The precipitated ester was collected on a filter and washed with water (yield = 2.70 g (90%). Irregula colourless crystals were obtained by recrystallization from absolute ethanol solution ( M.P.: 386 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. ORTEP drawing of (I) showing 50% probability displacement ellipsoids.
	Fig. 2. Molecular packing for (I) viewed along the a axis. Dashed lines indicate weak C13—H13···O1 interactions linking the molecules into dimers forming R₂²(14) loops. The remaining H atoms have been removed for clarity.

4-Chlorophenyl quinoline-2-carboxylate top

Crystal data top

C₁₆H₁₀ClNO₂	F(000) = 584
M_r = 283.70	D_x = 1.465 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 6.38693 (18) Å	Cell parameters from 3028 reflections
b = 16.8893 (5) Å	θ = 3.7–72.3°
c = 12.2649 (4) Å	µ = 2.63 mm⁻¹
β = 103.527 (3)°	T = 173 K
V = 1286.33 (6) Å³	Irregular, colourless
Z = 4	0.34 × 0.18 × 0.12 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	2502 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2168 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 72.5°, θ_min = 4.5°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −5→7
T_min = 0.611, T_max = 1.000	k = −20→20
7778 measured reflections	l = −15→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0544P)² + 0.3P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2502 reflections	Δρ_max = 0.21 e Å⁻³
181 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

Crystal data top

C₁₆H₁₀ClNO₂	V = 1286.33 (6) Å³
M_r = 283.70	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 6.38693 (18) Å	µ = 2.63 mm⁻¹
b = 16.8893 (5) Å	T = 173 K
c = 12.2649 (4) Å	0.34 × 0.18 × 0.12 mm
β = 103.527 (3)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	2502 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	2168 reflections with I > 2σ(I)
T_min = 0.611, T_max = 1.000	R_int = 0.032
7778 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
2502 reflections	Δρ_min = −0.25 e Å⁻³
181 parameters

Special details top

Experimental. ¹H NMR(500MHz,DMSO) δ 8.6 (1H,d, J= 8.48Hz), 8.34(1H,d, J= 8.49Hz),8.29(1H,d, J= 8.49Hz), 8.08(1H,d, J= 8.23 Hz),7.91(1H,dt, J1= 8.2Hz, J2=7, J3=1.36Hz), 7.79(1H,t, J= 7.73Hz), 7.51(2H,d, J= 8.78Hz), 7.38(2H,d, J= 8.78Hz)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cl1	1.24130 (8)	0.40648 (3)	0.40342 (4)	0.04923 (18)
O1	0.61750 (19)	0.56656 (7)	−0.05303 (10)	0.0362 (3)
O2	0.57559 (18)	0.60496 (7)	0.11776 (9)	0.0291 (3)
N1	0.2144 (2)	0.68008 (8)	0.02285 (11)	0.0255 (3)
C1	0.5257 (3)	0.60419 (9)	0.00414 (13)	0.0271 (3)
C2	0.3381 (3)	0.65748 (9)	−0.04352 (13)	0.0257 (3)
C3	0.3074 (3)	0.67937 (10)	−0.15754 (13)	0.0299 (4)
H3	0.3984	0.6606	−0.2008	0.036*
C4	0.1399 (3)	0.72894 (10)	−0.20223 (13)	0.0316 (4)
H4	0.1179	0.7457	−0.2763	0.038*
C5	0.0005 (3)	0.75454 (9)	−0.13540 (13)	0.0268 (3)
C6	−0.1776 (3)	0.80535 (10)	−0.17629 (14)	0.0317 (4)
H6	−0.2050	0.8240	−0.2496	0.038*
C7	−0.3082 (3)	0.82679 (10)	−0.10810 (15)	0.0333 (4)
H7	−0.4250	0.8600	−0.1353	0.040*
C8	−0.2682 (3)	0.79909 (10)	0.00373 (14)	0.0313 (4)
H8	−0.3602	0.8138	0.0489	0.038*
C9	−0.0962 (3)	0.75108 (9)	0.04632 (13)	0.0285 (4)
H9	−0.0708	0.7337	0.1202	0.034*
C10	0.0434 (3)	0.72779 (9)	−0.02247 (12)	0.0250 (3)
C11	0.7396 (3)	0.55652 (9)	0.17935 (13)	0.0266 (3)
C12	0.9292 (3)	0.53939 (10)	0.14730 (14)	0.0312 (4)
H12	0.9532	0.5588	0.0803	0.037*
C13	1.0823 (3)	0.49268 (10)	0.21764 (15)	0.0328 (4)
H13	1.2095	0.4797	0.1973	0.039*
C14	1.0458 (3)	0.46548 (10)	0.31740 (15)	0.0314 (4)
C15	0.8591 (3)	0.48398 (10)	0.35058 (14)	0.0314 (4)
H15	0.8375	0.4659	0.4187	0.038*
C16	0.7051 (3)	0.52997 (10)	0.28040 (14)	0.0284 (3)
H16	0.5784	0.5430	0.3012	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0401 (3)	0.0515 (3)	0.0530 (3)	0.0174 (2)	0.0047 (2)	0.0118 (2)
O1	0.0361 (7)	0.0436 (7)	0.0297 (6)	0.0062 (5)	0.0094 (5)	−0.0075 (5)
O2	0.0313 (6)	0.0318 (6)	0.0243 (6)	0.0059 (5)	0.0068 (4)	−0.0011 (4)
N1	0.0294 (7)	0.0249 (6)	0.0221 (6)	−0.0011 (5)	0.0056 (5)	−0.0001 (5)
C1	0.0294 (8)	0.0276 (8)	0.0250 (8)	−0.0035 (6)	0.0076 (6)	−0.0032 (6)
C2	0.0282 (8)	0.0252 (8)	0.0242 (7)	−0.0038 (6)	0.0069 (6)	−0.0025 (6)
C3	0.0339 (9)	0.0343 (9)	0.0236 (8)	−0.0026 (7)	0.0110 (7)	−0.0024 (6)
C4	0.0400 (10)	0.0358 (9)	0.0192 (7)	−0.0041 (7)	0.0075 (7)	0.0021 (6)
C5	0.0305 (8)	0.0254 (8)	0.0230 (7)	−0.0055 (6)	0.0031 (6)	0.0002 (6)
C6	0.0350 (9)	0.0313 (8)	0.0262 (8)	−0.0041 (7)	0.0018 (7)	0.0045 (6)
C7	0.0307 (9)	0.0291 (8)	0.0377 (9)	0.0017 (7)	0.0033 (7)	0.0038 (7)
C8	0.0323 (9)	0.0297 (8)	0.0338 (9)	−0.0002 (7)	0.0116 (7)	−0.0007 (7)
C9	0.0334 (9)	0.0286 (8)	0.0239 (7)	−0.0005 (6)	0.0074 (6)	0.0014 (6)
C10	0.0286 (8)	0.0234 (7)	0.0224 (7)	−0.0038 (6)	0.0047 (6)	−0.0006 (6)
C11	0.0263 (8)	0.0250 (8)	0.0273 (8)	0.0001 (6)	0.0042 (6)	−0.0024 (6)
C12	0.0313 (9)	0.0342 (9)	0.0296 (8)	−0.0022 (7)	0.0104 (7)	−0.0017 (7)
C13	0.0264 (9)	0.0360 (9)	0.0370 (9)	0.0020 (7)	0.0093 (7)	−0.0053 (7)
C14	0.0281 (9)	0.0274 (8)	0.0359 (9)	0.0032 (6)	0.0020 (7)	−0.0009 (7)
C15	0.0318 (9)	0.0316 (8)	0.0305 (8)	−0.0010 (7)	0.0068 (7)	0.0020 (7)
C16	0.0249 (8)	0.0312 (8)	0.0304 (8)	0.0004 (6)	0.0093 (6)	−0.0025 (6)

Geometric parameters (Å, º) top

Cl1—C14	1.7459 (17)	C7—H7	0.9300
O1—C1	1.1963 (19)	C7—C8	1.415 (2)
O2—C1	1.3549 (19)	C8—H8	0.9300
O2—C11	1.4025 (19)	C8—C9	1.367 (2)
N1—C2	1.317 (2)	C9—H9	0.9300
N1—C10	1.366 (2)	C9—C10	1.419 (2)
C1—C2	1.503 (2)	C11—C12	1.388 (2)
C2—C3	1.415 (2)	C11—C16	1.383 (2)
C3—H3	0.9300	C12—H12	0.9300
C3—C4	1.368 (2)	C12—C13	1.388 (2)
C4—H4	0.9300	C13—H13	0.9300
C4—C5	1.411 (2)	C13—C14	1.377 (2)
C5—C6	1.420 (2)	C14—C15	1.383 (2)
C5—C10	1.421 (2)	C15—H15	0.9300
C6—H6	0.9300	C15—C16	1.384 (2)
C6—C7	1.361 (3)	C16—H16	0.9300

C1—O2—C11	120.97 (12)	C9—C8—H8	119.6
C2—N1—C10	117.23 (13)	C8—C9—H9	120.1
O1—C1—O2	125.33 (15)	C8—C9—C10	119.85 (15)
O1—C1—C2	123.05 (15)	C10—C9—H9	120.1
O2—C1—C2	111.61 (13)	N1—C10—C5	122.51 (14)
N1—C2—C1	118.18 (14)	N1—C10—C9	118.37 (14)
N1—C2—C3	124.79 (15)	C9—C10—C5	119.12 (15)
C3—C2—C1	117.03 (14)	C12—C11—O2	124.07 (14)
C2—C3—H3	121.0	C16—C11—O2	114.59 (13)
C4—C3—C2	118.07 (15)	C16—C11—C12	121.23 (15)
C4—C3—H3	121.0	C11—C12—H12	120.8
C3—C4—H4	120.2	C11—C12—C13	118.46 (15)
C3—C4—C5	119.67 (14)	C13—C12—H12	120.8
C5—C4—H4	120.2	C12—C13—H13	120.0
C4—C5—C6	122.82 (15)	C14—C13—C12	120.06 (15)
C4—C5—C10	117.69 (15)	C14—C13—H13	120.0
C6—C5—C10	119.49 (15)	C13—C14—Cl1	118.80 (13)
C5—C6—H6	120.0	C13—C14—C15	121.52 (16)
C7—C6—C5	119.96 (15)	C15—C14—Cl1	119.68 (14)
C7—C6—H6	120.0	C14—C15—H15	120.6
C6—C7—H7	119.7	C14—C15—C16	118.71 (16)
C6—C7—C8	120.66 (16)	C16—C15—H15	120.6
C8—C7—H7	119.7	C11—C16—C15	119.99 (15)
C7—C8—H8	119.6	C11—C16—H16	120.0
C9—C8—C7	120.89 (16)	C15—C16—H16	120.0

Cl1—C14—C15—C16	−179.15 (12)	C5—C6—C7—C8	0.2 (3)
O1—C1—C2—N1	162.83 (16)	C6—C5—C10—N1	−178.71 (14)
O1—C1—C2—C3	−16.9 (2)	C6—C5—C10—C9	1.5 (2)
O2—C1—C2—N1	−17.4 (2)	C6—C7—C8—C9	0.8 (3)
O2—C1—C2—C3	162.86 (14)	C7—C8—C9—C10	−0.7 (2)
O2—C11—C12—C13	177.89 (14)	C8—C9—C10—N1	179.69 (14)
O2—C11—C16—C15	−177.73 (14)	C8—C9—C10—C5	−0.5 (2)
N1—C2—C3—C4	1.4 (2)	C10—N1—C2—C1	−179.29 (13)
C1—O2—C11—C12	36.5 (2)	C10—N1—C2—C3	0.4 (2)
C1—O2—C11—C16	−147.26 (15)	C10—C5—C6—C7	−1.3 (2)
C1—C2—C3—C4	−178.90 (14)	C11—O2—C1—O1	−3.2 (2)
C2—N1—C10—C5	−1.7 (2)	C11—O2—C1—C2	177.06 (13)
C2—N1—C10—C9	178.15 (14)	C11—C12—C13—C14	−1.0 (2)
C2—C3—C4—C5	−1.9 (2)	C12—C11—C16—C15	−1.4 (2)
C3—C4—C5—C6	−179.43 (15)	C12—C13—C14—Cl1	179.69 (13)
C3—C4—C5—C10	0.7 (2)	C12—C13—C14—C15	−0.4 (3)
C4—C5—C6—C7	178.84 (16)	C13—C14—C15—C16	1.0 (3)
C4—C5—C10—N1	1.1 (2)	C14—C15—C16—C11	−0.1 (2)
C4—C5—C10—C9	−178.68 (14)	C16—C11—C12—C13	1.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.93	2.42	3.250 (2)	148

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.93	2.42	3.250 (2)	148

Symmetry code: (i) −x+2, −y+1, −z.

Acknowledgements

EF thanks the CFTRI, Mysore and Yuvaraja's College, UOM, for providing research facilities. EF is grateful to Mr J. R. Manjunatha, PPSFT, CFTRI for the NMR spectra. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

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