Crystal structure of ethyl 2-chloro-6-methyl­quinoline-3-carboxyl­ate

Hayour, H.; Bouraiou, A.; Bouacida, S.; Benzerka, S.; Belfaitah, A.

doi:10.1107/S1600536814016900

organic compounds

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Volume 70| Part 9| September 2014| Page o941

doi:10.1107/S1600536814016900

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Crystal structure of ethyl 2-chloro-6-methylquinoline-3-carboxylate

Hasna Hayour,^a Abdelmalek Bouraiou,^a Sofiane Bouacida,^b,^c ^* Saida Benzerka ^b and Ali Belfaitah ^a

^aLaboratoire des Produits Naturels d'Origine Végétale et de Synthèse Organique, PHYSYNOR, Université Constantine 1, 25000 Constantine, Algeria, ^bUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine 1, 25000 , Algeria, and ^cDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 22 July 2014; accepted 22 July 2014; online 1 August 2014)

In the title compound, C₁₃H₁₂ClNO₂, the dihedral angle between the planes of the quinoline ring system (r.m.s. deviation = 0.029 Å) and the ester group is 54.97 (6)°. The C—O—C—C_m (m = methyl) torsion angle is −140.62 (16)°. In the crystal, molecules interact via aromatic π–π stacking [shortest centroid–centroid separation = 3.6774 (9) Å] generating (010) sheets.

Keywords: crystal structure; 2-chloro-3-formylquinoline; ethyl ester; π–π stacking.

CCDC reference: 1015360

1. Related literature

For background to 2-chloro-3-formylquinolines, see: Michael (2004 ); Abdel-Wahab et al. (2012 ). For our previous work in this area, see: Benzerka et al. (2012 , 2013 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₂ClNO₂
M_r = 249.69
Triclinic, $[P \overline 1]$
a = 6.0391 (5) Å
b = 7.2986 (6) Å
c = 13.4323 (12) Å
α = 98.238 (6)°
β = 90.123 (5)°
γ = 96.429 (6)°
V = 582.16 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 150 K
0.18 × 0.14 × 0.12 mm

2.2. Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.690, T_max = 0.747
5190 measured reflections
2061 independent reflections
1872 reflections with I > 2σ(I)
R_int = 0.016

2.3. Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.078
S = 1.06
2061 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1015360

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814016900/hb7259sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016900/hb7259Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016900/hb7259Isup3.cml

checkCIF report

Comment top

The 2-chloro-3-formylquinolines occupy a prominent position as key intermediates for further annelation and various functional group inter-conversions (Abdel-Wahab et al., 2012; Michael, 2004). As part of our ongoing studies in this area (Benzerka et al., 2012, 2013), we now describe the synthesis and single-crystal X-ray structure of the title compound, (I).

The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. In the asymmetric unit of title compound the quinoline ring is three times substituted by two methyl, one chlore and one ethyl carboxylate. The crystal packing can be described as double layers parallel to (010) plane (Fig. 2). It features π···π stacking, distances controid-controid between aromatic rings are from 3.6774 (9) to 4.2262 (9) Å.

Related literature top

For background to 2-chloro-3-formylquinolines, see: Michael (2004); Abdel-Wahab et al. (2012). For our previous work in this area, see: Benzerka et al. (2012, 2013).

Experimental top

Into a solution of NaCN (3 mmol) in absolute ethanol (15 ml), was added, in portion and at 0 °C,a mixture of 1 mmol of 2-chloro-3-formyl-6-methylquinoline and activated manganese dioxide (6.7 mmol). The reaction mixture was stirred for 3 h at rt. Purification of the corresponding compound was carried out by diluting the reaction mixture with CH₂Cl₂ and filtering through a small column packed with 4 cm of celite and 3 cm of silica gel. The pure compound was recovered after evaporation of solvents. Colourless blocks of (I) were obtained by dissolving the pure compound in EtOH and allowing the solution to slowly evaporate at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A diagram of the layered crystal packing of (I) viewed down the a axis.

Ethyl 2-chloro-6-methylquinoline-3-carboxylate top

Crystal data top

C₁₃H₁₂ClNO₂	Z = 2
M_r = 249.69	F(000) = 260
Triclinic, P1	D_x = 1.424 Mg m⁻³
a = 6.0391 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2986 (6) Å	Cell parameters from 2875 reflections
c = 13.4323 (12) Å	θ = 2.8–25.0°
α = 98.238 (6)°	µ = 0.32 mm⁻¹
β = 90.123 (5)°	T = 150 K
γ = 96.429 (6)°	BLOCK, colourless
V = 582.16 (9) Å³	0.18 × 0.14 × 0.12 mm

Data collection top

Bruker APEXII diffractometer	1872 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
CCD rotation images, thin slices scans	θ_max = 25.1°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −7→7
T_min = 0.690, T_max = 0.747	k = −8→8
5190 measured reflections	l = −16→15
2061 independent reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0383P)² + 0.2333P] where P = (F_o² + 2F_c²)/3
2061 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₂ClNO₂	γ = 96.429 (6)°
M_r = 249.69	V = 582.16 (9) Å³
Triclinic, P1	Z = 2
a = 6.0391 (5) Å	Mo Kα radiation
b = 7.2986 (6) Å	µ = 0.32 mm⁻¹
c = 13.4323 (12) Å	T = 150 K
α = 98.238 (6)°	0.18 × 0.14 × 0.12 mm
β = 90.123 (5)°

Data collection top

Bruker APEXII diffractometer	2061 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1872 reflections with I > 2σ(I)
T_min = 0.690, T_max = 0.747	R_int = 0.016
5190 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
2061 reflections	Δρ_min = −0.20 e Å⁻³
156 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C10	0.6109 (2)	0.4100 (2)	0.31856 (11)	0.0233 (3)
C11	0.7716 (3)	0.2270 (2)	−0.23686 (11)	0.0281 (4)
H11A	0.7218	0.3141	−0.2768	0.042*
H11B	0.7582	0.105	−0.2757	0.042*
H11C	0.9246	0.2644	−0.2169	0.042*
C12	0.7931 (3)	0.6667 (2)	0.42998 (12)	0.0356 (4)
H12A	0.9531	0.6636	0.4327	0.043*
H12B	0.7258	0.5967	0.4805	0.043*
C13	0.7400 (4)	0.8609 (3)	0.44891 (14)	0.0491 (5)
H13A	0.8105	0.9297	0.3995	0.074*
H13B	0.7934	0.9171	0.5149	0.074*
H13C	0.5815	0.8625	0.4447	0.074*
O1	0.70435 (19)	0.58589 (15)	0.33028 (8)	0.0290 (3)
O2	0.6007 (2)	0.31046 (17)	0.38231 (9)	0.0374 (3)
C1	0.3008 (2)	0.27029 (19)	0.19204 (11)	0.0204 (3)
C2	0.5237 (2)	0.35132 (19)	0.21333 (11)	0.0203 (3)
C3	0.6587 (2)	0.36577 (19)	0.13282 (11)	0.0209 (3)
H3	0.804	0.4231	0.1429	0.025*
C4	0.5801 (2)	0.29487 (19)	0.03486 (11)	0.0193 (3)
C5	0.7131 (2)	0.29932 (19)	−0.05125 (11)	0.0216 (3)
H5	0.8595	0.3552	−0.0441	0.026*
C6	0.6313 (2)	0.22322 (19)	−0.14494 (11)	0.0217 (3)
C7	0.4081 (3)	0.1369 (2)	−0.15399 (11)	0.0242 (3)
H7	0.3517	0.083	−0.2172	0.029*
C8	0.2740 (2)	0.1305 (2)	−0.07286 (11)	0.0231 (3)
H8	0.1283	0.0733	−0.0812	0.028*
C9	0.3560 (2)	0.21049 (19)	0.02358 (11)	0.0198 (3)
Cl1	0.11327 (6)	0.26599 (5)	0.29105 (3)	0.02749 (13)
N1	0.2174 (2)	0.20436 (16)	0.10369 (9)	0.0218 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C10	0.0187 (7)	0.0291 (8)	0.0229 (8)	0.0065 (6)	0.0032 (6)	0.0034 (6)
C11	0.0327 (9)	0.0288 (8)	0.0235 (8)	0.0071 (7)	0.0035 (7)	0.0039 (6)
C12	0.0407 (10)	0.0442 (10)	0.0191 (8)	0.0002 (8)	−0.0072 (7)	−0.0014 (7)
C13	0.0723 (14)	0.0412 (11)	0.0298 (10)	0.0039 (10)	−0.0100 (9)	−0.0065 (8)
O1	0.0382 (6)	0.0265 (6)	0.0204 (5)	−0.0006 (5)	−0.0049 (5)	0.0009 (4)
O2	0.0440 (7)	0.0414 (7)	0.0278 (6)	−0.0020 (5)	−0.0028 (5)	0.0144 (5)
C1	0.0213 (7)	0.0180 (7)	0.0237 (8)	0.0053 (6)	0.0043 (6)	0.0061 (6)
C2	0.0212 (7)	0.0177 (7)	0.0231 (7)	0.0056 (6)	0.0015 (6)	0.0040 (6)
C3	0.0185 (7)	0.0188 (7)	0.0253 (8)	0.0014 (6)	−0.0005 (6)	0.0034 (6)
C4	0.0202 (7)	0.0144 (7)	0.0240 (7)	0.0040 (5)	0.0008 (6)	0.0039 (6)
C5	0.0190 (7)	0.0195 (7)	0.0270 (8)	0.0029 (6)	0.0014 (6)	0.0052 (6)
C6	0.0266 (8)	0.0169 (7)	0.0235 (7)	0.0070 (6)	0.0022 (6)	0.0058 (6)
C7	0.0306 (8)	0.0202 (7)	0.0218 (8)	0.0044 (6)	−0.0045 (6)	0.0023 (6)
C8	0.0217 (7)	0.0193 (7)	0.0279 (8)	0.0002 (6)	−0.0031 (6)	0.0043 (6)
C9	0.0209 (7)	0.0155 (7)	0.0241 (7)	0.0043 (5)	0.0005 (6)	0.0053 (6)
Cl1	0.0230 (2)	0.0336 (2)	0.0276 (2)	0.00604 (15)	0.00824 (15)	0.00777 (16)
N1	0.0200 (6)	0.0194 (6)	0.0267 (7)	0.0027 (5)	0.0020 (5)	0.0052 (5)

Geometric parameters (Å, º) top

C10—O2	1.1971 (18)	C1—C2	1.419 (2)
C10—O1	1.3308 (18)	C1—Cl1	1.7501 (14)
C10—C2	1.494 (2)	C2—C3	1.365 (2)
C11—C6	1.501 (2)	C3—C4	1.404 (2)
C11—H11A	0.96	C3—H3	0.93
C11—H11B	0.96	C4—C5	1.411 (2)
C11—H11C	0.96	C4—C9	1.421 (2)
C12—O1	1.4588 (19)	C5—C6	1.368 (2)
C12—C13	1.475 (3)	C5—H5	0.93
C12—H12A	0.97	C6—C7	1.420 (2)
C12—H12B	0.97	C7—C8	1.362 (2)
C13—H13A	0.96	C7—H7	0.93
C13—H13B	0.96	C8—C9	1.407 (2)
C13—H13C	0.96	C8—H8	0.93
C1—N1	1.2935 (19)	C9—N1	1.3673 (19)

O2—C10—O1	125.26 (14)	C3—C2—C1	116.71 (13)
O2—C10—C2	124.26 (14)	C3—C2—C10	121.18 (13)
O1—C10—C2	110.47 (12)	C1—C2—C10	122.05 (13)
C6—C11—H11A	109.5	C2—C3—C4	120.61 (13)
C6—C11—H11B	109.5	C2—C3—H3	119.7
H11A—C11—H11B	109.5	C4—C3—H3	119.7
C6—C11—H11C	109.5	C3—C4—C5	123.51 (13)
H11A—C11—H11C	109.5	C3—C4—C9	117.37 (13)
H11B—C11—H11C	109.5	C5—C4—C9	119.10 (13)
O1—C12—C13	107.55 (14)	C6—C5—C4	121.45 (13)
O1—C12—H12A	110.2	C6—C5—H5	119.3
C13—C12—H12A	110.2	C4—C5—H5	119.3
O1—C12—H12B	110.2	C5—C6—C7	118.37 (13)
C13—C12—H12B	110.2	C5—C6—C11	121.79 (13)
H12A—C12—H12B	108.5	C7—C6—C11	119.84 (13)
C12—C13—H13A	109.5	C8—C7—C6	121.99 (14)
C12—C13—H13B	109.5	C8—C7—H7	119
H13A—C13—H13B	109.5	C6—C7—H7	119
C12—C13—H13C	109.5	C7—C8—C9	119.98 (14)
H13A—C13—H13C	109.5	C7—C8—H8	120
H13B—C13—H13C	109.5	C9—C8—H8	120
C10—O1—C12	117.45 (12)	N1—C9—C8	118.90 (13)
N1—C1—C2	125.71 (13)	N1—C9—C4	122.00 (13)
N1—C1—Cl1	115.40 (11)	C8—C9—C4	119.10 (13)
C2—C1—Cl1	118.82 (11)	C1—N1—C9	117.48 (12)

O2—C10—O1—C12	−2.8 (2)	C9—C4—C5—C6	−0.4 (2)
C2—C10—O1—C12	178.41 (12)	C4—C5—C6—C7	−0.6 (2)
C13—C12—O1—C10	−140.62 (16)	C4—C5—C6—C11	−179.88 (13)
N1—C1—C2—C3	2.2 (2)	C5—C6—C7—C8	1.0 (2)
Cl1—C1—C2—C3	−174.62 (10)	C11—C6—C7—C8	−179.76 (13)
N1—C1—C2—C10	−174.93 (13)	C6—C7—C8—C9	−0.2 (2)
Cl1—C1—C2—C10	8.23 (18)	C7—C8—C9—N1	179.20 (12)
O2—C10—C2—C3	−123.43 (17)	C7—C8—C9—C4	−0.9 (2)
O1—C10—C2—C3	55.34 (18)	C3—C4—C9—N1	2.7 (2)
O2—C10—C2—C1	53.6 (2)	C5—C4—C9—N1	−178.89 (12)
O1—C10—C2—C1	−127.63 (14)	C3—C4—C9—C8	−177.25 (12)
C1—C2—C3—C4	−2.9 (2)	C5—C4—C9—C8	1.2 (2)
C10—C2—C3—C4	174.25 (12)	C2—C1—N1—C9	1.0 (2)
C2—C3—C4—C5	−177.71 (13)	Cl1—C1—N1—C9	177.90 (9)
C2—C3—C4—C9	0.7 (2)	C8—C9—N1—C1	176.48 (12)
C3—C4—C5—C6	177.92 (13)	C4—C9—N1—C1	−3.4 (2)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂ClNO₂
M_r	249.69
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	6.0391 (5), 7.2986 (6), 13.4323 (12)
α, β, γ (°)	98.238 (6), 90.123 (5), 96.429 (6)
V (Å³)	582.16 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.690, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	5190, 2061, 1872
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.078, 1.06
No. of reflections	2061
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.20

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 2012).

Acknowledgements

We are grateful to all personel of the PHYSYNOR Laboratory, Université Constantine 1, Algeria, for their assistance. Thanks are due to the MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algérie) for financial support.

References

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