4-Methyl­phenyl quinoline-2-carboxyl­ate

E Fazal; Jerry P Jasinski; Shannon T Krauss; B S Sudha; H S Yathirajan

doi:10.1107/S1600536812044030

. 2012 Oct 27;68(Pt 11):o3231–o3232. doi: 10.1107/S1600536812044030

4-Methylphenyl quinoline-2-carboxylate

E Fazal ^a, Jerry P Jasinski ^b,^*, Shannon T Krauss ^b, B S Sudha ^a, H S Yathirajan ^c

PMCID: PMC3515313 PMID: 23284533

Abstract

In the title compound, C₁₇H₁₃NO₂, two molecules crystallize in the asymmetric unit. The dihedral angle between the mean planes of the quinoline and benzene rings are 78.3 (4) and 88.2 (3)°. The carboxylate group is twisted slightly from the quinoline ring by 7.1 (2) and 13.3 (4)°, respectively. In the crystal, weak C—H⋯O interactions are observed. Further stabilization is provided by weak π–π stacking interactions, with centroid–centroid distances of 3.564 (9)/3.689 (2) and 3.830 (1)/3.896 (5)Å, respectively.

Related literature

For heterocycles in natural products, see: Morimoto et al. (1991 ▶); Michael (1997 ▶). For heterocycles in fragrances and dyes, see: Padwa et al. (1999 ▶). For heterocycles in biologically active compounds, see: Markees et al. (1970 ▶); Campbell et al. (1988 ▶). For quinoline alkaloids used as efficient drugs for the treatment of malaria, see: Robert & Meunier, (1998 ▶). For quinoline as a privileged scaffold in cancer drug discovery, see: Solomon & Lee (2011 ▶). For related structures, see: Dobrzyńska & Jerzykiewicz, (2004 ▶); Butcher et al. (2007 ▶); Jing & Qin (2008 ▶); Jasinski et al. (2010 ▶). For bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₃NO₂
M _r = 263.28
Orthorhombic,
a = 11.5421 (2) Å
b = 17.3191 (3) Å
c = 26.6667 (5) Å
V = 5330.65 (16) Å³
Z = 16
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 173 K
0.22 × 0.14 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.726, T _max = 1.000
34626 measured reflections
5265 independent reflections
4303 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.124
S = 1.02
5265 reflections
363 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Bruker, 2000 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(34.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044030/bq2377sup1.cif

e-68-o3231-sup1.cif^{(34.2KB, cif)}

Click here for additional data file.^{(244.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044030/bq2377Isup2.hkl

e-68-o3231-Isup2.hkl^{(244.3KB, hkl)}

Click here for additional data file.^{(5.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812044030/bq2377Isup3.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
C15B—H15B⋯O2A ⁱ	0.93	2.59	3.343 (2)	138

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Symmetry code: (i) Inline graphic .

Acknowledgments

EF thanks Yuvaraja’s college, UOM for providing the research facilities and also to Dr. S. Nagarajan, Senior Scientist at CFTRI for giving valuable suggestions. JPJ acknowledges the NSF–MRI program (grant No·CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Quinoline-2-carboxylic acid derivatives are a class of important materials as anti-tuberculosis agents, as fluorescent reagents, hydrophobic field-detection reagents, visualization reagents, fluorescent labeled peptide probes and as antihyperglycemics. Quinoline derivatives represent a major class of heterocycles and are found in natural products (Morimoto et al., 1991; Michael, 1997), numerous commercial products, including fragrances, dyes (Padwa et al., 1999) and biologically active compounds (Markees et al., 1970; Campbell et al., 1988). Quinoline alkaloids such as quinine, chloroquin, mefloquine and amodiaquine are used as efficient drugs for the treatment of malaria (Robert & Meunier, 1998). Quinoline as a privileged scaffold in cancer drug discovery is published (Solomon & Lee, 2011). The crystal structures of quinoline-2-carboxylic acid (Dobrzyńska & Jerzykiewicz, 2004), 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. In view of the importance of quinolines, the paper reports the crystal structure of the title compound, 4-methylphenyl quinoline-2-carboxylate, (I).

In the title compound, C₁₇H₁₃NO₂, two molecules (A & B) crystallize in the asymmetric unit (Fig. 1). The dihedral angle between the mean planes of the quinoline and benzene rings are 78.3 (4)° (A) and 88.2 (3)° (B). The carboxylate group is twisted slightly from the quinoline ring by 7.1 (2)° (A) and 13.3 (4)° B, respectively. Bond lengths are in normal ranges (Allen et al., (1987). In the crystal weak C—H···O intermolecular interactions are observed (Fig. 2). Further stabilization is provided by weak π–π stacking interactions with centroid to centroid distances of 3.564 (9)Å (Cg2-Cg1], 3.689 (2)Å (Cg2-Cg6), 3.830 (1)Å (Cg1-Cg5) and 3.896 (5)Å (Cg1-Cg1) [where Cg1 = N1A/C1A/C6A/C7A/C8A/C9A; Cg2 = C1A–C6A; Cg5 = N1B/C1B/C6B/C7B/C8B/C9B; C6 = C1B–C6B].

Experimental

To a mixture of (1.73 g, 10 mmole) of quinaldic acid and p-cresol (1.08 g, 10 mmole) in a round-bottomed flask fitted with a reflux condenser with a drying tube, 0.75 g (5 mmole) of phosphorous oxychloride was added. The mixture was heated with occasional swirling, and temperature maintained at 348–353 K. At the end of six hours, the reaction mixture was poured into a solution of 2 g of sodium bicarbonate in 25 mL of water. The precipitated ester was filtered and washed with water. The yield of crude, air dried p-tolyl quinoline-2-carboxylate was 1.75 to 1.85 g (65-70%). X-ray quality crystals were obtained by recrystallization from absolute ethanol (m.p.: 396-398 K).