4-Chloro-2,5-dimethyl­quinoline

Prabha, K.; Vennila, K.N.; Prasad, K.J.R.; Velmurugan, D.

doi:10.1107/S1600536810025419

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2020

https://doi.org/10.1107/S1600536810025419

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4-Chloro-2,5-dimethylquinoline

K. Prabha,^a K. N. Vennila,^b K. J. Rajendra Prasad ^a and D. Velmurugan ^b ^*

^aDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, India, and ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: d_velu@yahoo.com

(Received 23 June 2010; accepted 28 June 2010; online 14 July 2010)

Molecules of the title compound, C₁₁H₁₀ClN, are essentially planar (r.m.s. deviation for all non-H atoms = 0.009 Å) and are stacked along the a axis with the centroids of the benzene and pyridine rings alternately separated by 3.649 (1) and 3.778 (1) Å.

Related literature

For the biological activity of quinoline derivatives, see: Miyamoto et al. (1995 ); Milner et al. (2010 ); Li et al. (2008 ); Musiola et al. (2006 ); Muthumani et al. (2010 ). For related chloroquinoline structures, see: Rizvi et al. (2008 ); Bureau et al. (1999 ); de Souza et al. (2010 ); Yathirajan et al. (2007 ).

Experimental

Crystal data

C₁₁H₁₀ClN
M_r = 190.66
Monoclinic, P 2₁ /c
a = 6.9534 (9) Å
b = 13.0762 (14) Å
c = 10.4306 (11) Å
β = 99.239 (8)°
V = 936.09 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.27 × 0.26 × 0.22 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.909, T_max = 0.925
8798 measured reflections
2345 independent reflections
1502 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.147
S = 1.05
2345 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810025419/ci5114sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025419/ci5114Isup2.hkl

checkCIF report

Comment top

This paper presents the first crystal structure of meta isomer of chloro-quinoline derivatives. It was reported earlier that the introduction of methyl group at the 5th position of quinoline nucleus enhanced characteristically the antibacterial activity against Gram-positive bacteria, including Streptococcus pneumonia, which is a major pathogen in the respiratory tract infection (Miyamoto et al., 1995). Also quinoline derivatives are well known to have many biological activities such as antimalarial (Milner et al., 2010), inhibition of melanogenesis (Li et al., 2008), antifungal (Musiola et al., 2006), antibacterial activities etc. (Muthumani et al., 2010).

The non-hydrogen atoms of the title molecule are essentially coplanar (r.m.s. deviation 0.009 Å). The molecules are stacked along the a axis with the centroids of quinoline ring systems alternately separated by 3.649 (1) Å and 3.778 (1) Å (Fig.2).

Related literature top

For the biological activity of quinoline derivatives, see: Miyamoto et al. (1995); Milner et al. (2010); Li et al. (2008); Musiola et al. (2006); Muthumani et al. (2010). For related chloroquinoline structures, see: Rizvi et al. (2008); Bureau et al. (1999); de Souza et al. (2010); Yathirajan et al. (2007).

Experimental top

Ethylacetoacetate (0.25 mol) and m-toluidine (0.25 mol) were mixed. 5–10 drops of dilute hydrochloroacid (1:1) was added, the mixture was shaken well and kept inside a vacuum desiccator over concentrated sulfuric acid for 2 d. A deep yellow oily liquid, (E)-Ethyl-3-(m-tolylamino)but-2-enoate, was formed. It was dried over anhydrous sodium sulfate and was added dropwise from a dropping funnel to diphenyl ether (50 ml) kept at reflux in a two necked flask, one fitted with the dropping funnel and the other with an air condenser to distill off the ethanol formed during the reaction. After the addition, the refluxing was continued for further 10 min and the contents were cooled. 50 ml of petroleum ether was added and the precipitated solid was collected, washed with petroleum ether, dried and recrystallized from ethanol to give (E)-ethyl-3-(m-tolylamino)but-2-enoate as a crystalline white powder.

Phosphorous oxy chloride (100 ml) was added to 2,5-dimethylquinolin-4 (1H)-one (0.1 mol) and kept on a water bath for about 1 h and poured into ice water and neutralized with saturated sodium carbonate solution. The formed precipitate was filtered, dried, purified using silica gel column chromatography and eluted with petrolelum ether (100%) to get a white solid. It was recrystallized using methanol.

Structure description top

For the biological activity of quinoline derivatives, see: Miyamoto et al. (1995); Milner et al. (2010); Li et al. (2008); Musiola et al. (2006); Muthumani et al. (2010). For related chloroquinoline structures, see: Rizvi et al. (2008); Bureau et al. (1999); de Souza et al. (2010); Yathirajan et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis.

4-Chloro-2,5-dimethylquinoline top

Crystal data top

C₁₁H₁₀ClN	F(000) = 400
M_r = 190.66	D_x = 1.353 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2345 reflections
a = 6.9534 (9) Å	θ = 2.5–28.5°
b = 13.0762 (14) Å	µ = 0.35 mm⁻¹
c = 10.4306 (11) Å	T = 293 K
β = 99.239 (8)°	Block, colourless
V = 936.09 (19) Å³	0.27 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	2345 independent reflections
Radiation source: fine-focus sealed tube	1502 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scans	θ_max = 28.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.909, T_max = 0.925	k = −17→12
8798 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0468P)² + 0.6973P] where P = (F_o² + 2F_c²)/3
2345 reflections	(Δ/σ)_max = 0.007
120 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₀ClN	V = 936.09 (19) Å³
M_r = 190.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.9534 (9) Å	µ = 0.35 mm⁻¹
b = 13.0762 (14) Å	T = 293 K
c = 10.4306 (11) Å	0.27 × 0.26 × 0.22 mm
β = 99.239 (8)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2345 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1502 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.925	R_int = 0.027
8798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
2345 reflections	Δρ_min = −0.21 e Å⁻³
120 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
Cl1	0.27505 (13)	0.22264 (5)	0.06695 (7)	0.0680 (3)
N1	0.2186 (3)	−0.08447 (15)	−0.13203 (18)	0.0455 (5)
C5	0.2644 (3)	0.01002 (16)	0.0758 (2)	0.0372 (5)
C8	0.2282 (4)	0.09687 (19)	−0.1312 (2)	0.0461 (6)
H8	0.2218	0.1571	−0.1791	0.055*
C9	0.2550 (4)	0.10065 (17)	0.0003 (2)	0.0410 (5)
C1	0.2513 (4)	−0.17776 (18)	0.0632 (2)	0.0485 (6)
H1	0.2379	−0.2374	0.0140	0.058*
C6	0.2455 (3)	−0.08204 (17)	0.0005 (2)	0.0383 (5)
C3	0.2963 (4)	−0.0945 (2)	0.2683 (2)	0.0504 (6)
H3	0.3140	−0.1002	0.3583	0.060*
C10	0.1806 (5)	−0.0015 (2)	−0.3412 (2)	0.0622 (8)
H10A	0.1524	−0.0705	−0.3697	0.093*
H10B	0.2969	0.0213	−0.3712	0.093*
H10C	0.0738	0.0420	−0.3760	0.093*
C4	0.2913 (4)	0.00173 (18)	0.2147 (2)	0.0426 (5)
C7	0.2103 (4)	0.00246 (19)	−0.1951 (2)	0.0443 (6)
C11	0.3095 (5)	0.0919 (2)	0.3066 (2)	0.0629 (8)
H11A	0.3289	0.0677	0.3946	0.094*
H11B	0.1926	0.1321	0.2905	0.094*
H11C	0.4186	0.1332	0.2931	0.094*
C2	0.2761 (4)	−0.18365 (19)	0.1949 (2)	0.0529 (7)
H2	0.2796	−0.2470	0.2356	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1124 (7)	0.0347 (3)	0.0570 (4)	−0.0066 (4)	0.0141 (4)	−0.0037 (3)
N1	0.0560 (13)	0.0426 (11)	0.0382 (10)	0.0017 (9)	0.0092 (9)	−0.0031 (8)
C5	0.0383 (12)	0.0372 (11)	0.0365 (11)	0.0000 (10)	0.0076 (9)	−0.0003 (9)
C8	0.0556 (16)	0.0430 (13)	0.0403 (13)	−0.0010 (11)	0.0094 (11)	0.0077 (10)
C9	0.0480 (14)	0.0338 (11)	0.0417 (12)	−0.0024 (10)	0.0082 (10)	−0.0006 (9)
C1	0.0601 (17)	0.0341 (11)	0.0520 (14)	0.0037 (11)	0.0106 (12)	0.0004 (10)
C6	0.0406 (13)	0.0375 (11)	0.0370 (11)	0.0026 (9)	0.0068 (9)	−0.0004 (9)
C3	0.0599 (16)	0.0566 (15)	0.0349 (12)	0.0031 (13)	0.0086 (11)	0.0099 (11)
C10	0.077 (2)	0.0737 (19)	0.0356 (13)	−0.0033 (16)	0.0085 (13)	0.0012 (12)
C4	0.0484 (14)	0.0439 (12)	0.0360 (12)	−0.0023 (10)	0.0085 (10)	−0.0012 (9)
C7	0.0497 (15)	0.0483 (13)	0.0349 (12)	−0.0005 (11)	0.0070 (10)	0.0008 (10)
C11	0.094 (2)	0.0591 (16)	0.0353 (13)	−0.0126 (15)	0.0096 (13)	−0.0094 (12)
C2	0.0654 (18)	0.0398 (12)	0.0545 (15)	0.0082 (12)	0.0121 (13)	0.0137 (11)

Geometric parameters (Å, º) top

Cl1—C9	1.737 (2)	C3—C4	1.374 (3)
N1—C7	1.310 (3)	C3—C2	1.390 (4)
N1—C6	1.366 (3)	C3—H3	0.93
C5—C9	1.419 (3)	C10—C7	1.506 (3)
C5—C6	1.432 (3)	C10—H10A	0.96
C5—C4	1.435 (3)	C10—H10B	0.96
C8—C9	1.356 (3)	C10—H10C	0.96
C8—C7	1.399 (3)	C4—C11	1.512 (3)
C8—H8	0.93	C11—H11A	0.96
C1—C2	1.358 (3)	C11—H11B	0.96
C1—C6	1.410 (3)	C11—H11C	0.96
C1—H1	0.93	C2—H2	0.93

C7—N1—C6	118.4 (2)	C7—C10—H10B	109.5
C9—C5—C6	114.0 (2)	H10A—C10—H10B	109.5
C9—C5—C4	127.6 (2)	C7—C10—H10C	109.5
C6—C5—C4	118.4 (2)	H10A—C10—H10C	109.5
C9—C8—C7	120.1 (2)	H10B—C10—H10C	109.5
C9—C8—H8	120.0	C3—C4—C5	118.0 (2)
C7—C8—H8	120.0	C3—C4—C11	117.5 (2)
C8—C9—C5	121.2 (2)	C5—C4—C11	124.4 (2)
C8—C9—Cl1	115.32 (18)	N1—C7—C8	122.2 (2)
C5—C9—Cl1	123.49 (18)	N1—C7—C10	117.8 (2)
C2—C1—C6	120.6 (2)	C8—C7—C10	120.0 (2)
C2—C1—H1	119.7	C4—C11—H11A	109.5
C6—C1—H1	119.7	C4—C11—H11B	109.5
N1—C6—C1	116.0 (2)	H11A—C11—H11B	109.5
N1—C6—C5	124.1 (2)	C4—C11—H11C	109.5
C1—C6—C5	119.9 (2)	H11A—C11—H11C	109.5
C4—C3—C2	123.4 (2)	H11B—C11—H11C	109.5
C4—C3—H3	118.3	C1—C2—C3	119.6 (2)
C2—C3—H3	118.3	C1—C2—H2	120.2
C7—C10—H10A	109.5	C3—C2—H2	120.2

C7—C8—C9—C5	−0.3 (4)	C4—C5—C6—C1	0.8 (3)
C7—C8—C9—Cl1	180.0 (2)	C2—C3—C4—C5	−0.2 (4)
C6—C5—C9—C8	0.7 (3)	C2—C3—C4—C11	178.3 (3)
C4—C5—C9—C8	−179.8 (2)	C9—C5—C4—C3	−179.9 (2)
C6—C5—C9—Cl1	−179.65 (18)	C6—C5—C4—C3	−0.4 (3)
C4—C5—C9—Cl1	−0.1 (4)	C9—C5—C4—C11	1.7 (4)
C7—N1—C6—C1	179.4 (2)	C6—C5—C4—C11	−178.8 (2)
C7—N1—C6—C5	0.4 (3)	C6—N1—C7—C8	0.1 (4)
C2—C1—C6—N1	−179.6 (2)	C6—N1—C7—C10	180.0 (2)
C2—C1—C6—C5	−0.5 (4)	C9—C8—C7—N1	−0.1 (4)
C9—C5—C6—N1	−0.7 (3)	C9—C8—C7—C10	−180.0 (2)
C4—C5—C6—N1	179.7 (2)	C6—C1—C2—C3	−0.1 (4)
C9—C5—C6—C1	−179.7 (2)	C4—C3—C2—C1	0.5 (4)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClN
M_r	190.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.9534 (9), 13.0762 (14), 10.4306 (11)
β (°)	99.239 (8)
V (Å³)	936.09 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.27 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.909, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	8798, 2345, 1502
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.147, 1.05
No. of reflections	2345
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

DV acknowledges the Department of Science and Technology (DST) for providing computing facilities under major research projects and for financial support to the Department under the UGC–SAP.

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