Ethyl 1-(2,4-dichloro­benz­yl)-4-oxo-7-trifluoro­meth­yl-1,4-dihydro­quinoline-3-carboxyl­ate

Hoong-Kun Fun; Chin Wei Ooi; B Garudachari; Arun M Isloor; Gurumurthy Hegde

doi:10.1107/S1600536812001249

. 2012 Jan 18;68(Pt 2):o435–o436. doi: 10.1107/S1600536812001249

Ethyl 1-(2,4-dichlorobenzyl)-4-oxo-7-trifluoromethyl-1,4-dihydroquinoline-3-carboxylate

Hoong-Kun Fun ^a,^*,^‡, Chin Wei Ooi ^a, B Garudachari ^b, Arun M Isloor ^b, Gurumurthy Hegde ^c

PMCID: PMC3275192 PMID: 22347048

Abstract

In the title compound, C₂₀H₁₄Cl₂F₃NO₃, the trifluromethyl group is disordered over two sets of sites in a 0.784 (10):0.216 (10) ratio. The quinoline ring system is essentially planar with a maximum deviation of 0.058 (2) Å for the N atom and forms dihedral angles of 89.23 (11) and 8.13 (17)°, respectively with the mean planes of the benzene ring and the carboxylate group. In the crystal, pairs of weak C—H⋯O and C—H⋯F hydrogen bonds link molecules into centrosymmetric dimers. The crystal structure is further stabilized by weak π–π [centroid–centroid distance = 3.624 (2) Å] interactions.

Related literature

For background to the properties and uses of quinoline derivatives, see: Kaur et al. (2010 ▶); Eswaran et al. (2010 ▶); Chou et al. (2010 ▶); Chen et al. (2004 ▶); Shingalapur et al. (2009 ▶). For a related structure, see: Fun et al. (2011 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₀H₁₄Cl₂F₃NO₃
M _r = 444.22
Triclinic,
a = 8.090 (2) Å
b = 9.547 (3) Å
c = 14.047 (4) Å
α = 77.299 (6)°
β = 76.198 (5)°
γ = 67.488 (4)°
V = 963.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 296 K
0.43 × 0.18 × 0.07 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.852, T _max = 0.972
13916 measured reflections
5071 independent reflections
2759 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.179
S = 1.04
5071 reflections
288 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812001249/lh5400sup1.cif

e-68-0o435-sup1.cif^{(29.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001249/lh5400Isup2.hkl

e-68-0o435-Isup2.hkl^{(248.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812001249/lh5400Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯O3ⁱ	0.93	2.52	3.292 (5)	141
C18—H18A⋯F2ⁱ	0.97	2.50	3.355 (7)	147

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). CWO also thanks the Malaysian Government and USM for the award of the post of research assistant under the Research University Grant (1001/PFIZIK/811151). AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for the Young Scientist award.

supplementary crystallographic information

Comment

The quinoline moiety is of great importance to chemists as well as biologists as it is one of the key building elements for many naturally occurring compounds. Members of this family have wide range of applications as pharmaceuticals as antimalarial (Kaur et al., 2010), anti-tuberculosis (Eswaran et al., 2010), antitumor (Chou et al., 2010), anticancer (Chen et al., 2004) and antiviral (Shingalapur et al., 2009) agents. Some of the present day drugs such as chloroquine, mefloquine, tafenoquine and primaquine contain quinoline as the basic unit in their structures. In view of the biological importance, we have synthesized the title compound to study its crystal structure.

In the molecular structure (Fig. 1), the trifluromethyl group is disordered over two sets of sites in a ratio of 0.784 (10):0.216 (10). The quinoline ring (N1/C1–C9) is essentially planar with a maximum deviation of 0.058 (2) Å at atom N1. The quinoline ring makes dihedral angles of 89.23 (11) and 8.13 (17)°, respectively with the chloro-substituted benzene ring (C11–C16) and the carboxylate group (O1/O2/C17–C19). The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to a related structure (Fun et al., 2011).

In the crystal (Fig. 2), intermolecular C16—H16A···O3ⁱ and C18—H18A···F2ⁱ hydrogen bonds (Table 1) link molecules to form dimers. The crystal is further stabilized by weak π–π interactions between the quinoline (N1/C1–C9) and the benzene ring (C4–C9) [centroid-to-centroid (-x, 1 - y, -z); distance = 3.624 (2) Å].

Experimental

A mixture of ethyl 4-hydroxy-7-(trifluoromethyl)quinoline-3-carboxylate (0.10 g, 0.00035 mol), potassium carbonate (0.053 g, 0.00038 mol) and 1-(bromomethyl)-2,4-dichlorobenzene (0.091 g, 0.00038 mol) in dimethylformamide (5 ml) was stirred at 353K for 3 h. After completion of the reaction, the reaction mixture was poured into ice-cold water. The solid product obtained was filtered, washed with water and recrystallized using ethanol. Yield: 0.150 g, 96.77%. M. p.: 428–429 K.