2-(4-Methyl­phen­yl)quinoline-4-carb­oxy­lic acid

Raed A Al-Qawasmeh; Monther A Khanfar; Musa H Abu Zarga; Murad A AlDamen

doi:10.1107/S160053681203797X

. 2012 Sep 8;68(Pt 10):o2892. doi: 10.1107/S160053681203797X

2-(4-Methylphenyl)quinoline-4-carboxylic acid

Raed A Al-Qawasmeh ^a,^*, Monther A Khanfar ^a, Musa H Abu Zarga ^a, Murad A AlDamen ^a

PMCID: PMC3470244 PMID: 23125688

Abstract

In the title compound, C₁₇H₁₃NO₂, the dihedral angle between the plane of the carboxy group and the quinoline mean plane is 45.05 (13)°, and that between the toluene ring mean plane and the quinoline mean plane is 25.29 (7)°. In the crystal, molecules are linked via O—H⋯.N hydrogen bonds, forming chains propagating along the b-axis direction. These chain are linked via C—H⋯O interactions, forming two-dimensional networks lying parallel to the ab plane.

Related literature

For the importance of the quinoline carboxylic acid analogues in the synthesis of various compounds with pharmacological properties, see: Deady et al. (1999 ▶, 2011 ▶); Kalluraya & Sreenivasa (1998 ▶); Tseng et al. (2008 ▶); Kravchenko et al. (2005 ▶). The structure of the related compound 2-phenylquinoline-4-carboxlic acid is described by Blackburn et al. (1996 ▶). For a description of puckering analysis, see: Cremer & Pople (1975 ▶). For synthetic preparation, see: Pfitzinger (1886 ▶).

Experimental

Crystal data

C₁₇H₁₃NO₂
M _r = 263.28
Monoclinic,
a = 4.1001 (6) Å
b = 15.3464 (11) Å
c = 20.3037 (17) Å
β = 90.859 (9)°
V = 1277.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.70 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 ▶), based on expressions derived from Clark & Reid (1995 ▶)] T _min = 0.992, T _max = 0.999
4867 measured reflections
2238 independent reflections
1747 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.126
S = 1.04
2238 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681203797X/go2066sup1.cif

e-68-o2892-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203797X/go2066Isup2.hkl

e-68-o2892-Isup2.hkl^{(110KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681203797X/go2066Isup3.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
O1—H1⋯N1ⁱ	0.89 (3)	1.89 (3)	2.763 (2)	168 (2)
C3—H3⋯O1ⁱⁱ	0.93	2.51	3.233 (2)	135

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was carried out during sabbatical leave granted to MAK during the academic year 2011–2012.

supplementary crystallographic information

Comment

Quinoline derivatives are widely used as synthons for biologically important compounds (Tseng et al., 2008), (Kravchenko et al., 2005). In our group this moiety was used to synthesize new antitumor as well as antibacterial agents. The title molecule is shown in Fig. 1 with the numbering scheme. The dihedral angle between the plane of the carboxyl group and the quinoline mean plane is 45.05 (13)° and that between the toluene ring mean plane and the quinoline mean plane is 25.29 (7)°. The total puckering amplitude, Q, (Cremer & Pople, 1975) for the quinoline ring in the title compound is 0.044 (2)Å in the title compound as compared with the value of 0.080 (3) Å in the closely related compound 2-phenylquinoline-4-carboxlic acid (Blackburn et al., 1996). There is a hydrogen bond between the carboxylic acid oxygen atom, O1 and N1 in the quinoline ring, Table 1, Figure 2. In addition the molecules are linked by a weak C-H..O interaction between C3 and O1, Table 1. There is π–π stacking between molecules Molecules are stacked above and below one another with unit translation along the a-axis so that rings containing N1 stack above those containing N1, the same applies to the rings containing C1 and C12. This results in π–π stacking between the molecules: i) between rings containing N1 (centroid Cg1) [Cg1···Cg1(-1+x, y, z), centroid to centroid distance: 4.1001 (13) Å, perpendicular distance between rings: 3.7681 (8) Å slippage: 1.616Å] and ii) between rings containing C1, (centroid Cg2), [Cg2···Cg2(-1+x ,y, z), centroid to centroid distance 4.1000 (14) Å, perpendicular distance between rings 3.3521 (8) Å, slippage 2.361Å] and iii) between rings containing C12 (centroid Cg3) Cg3···Cg3 (-1+x, y, z), [centroid to centroid) distance 4.1003 (17) Å, perpendicular distance between rings 3.7411 (11)Å, slippage 1.678Å].

Experimental

The title compound was synthesized according to Pfitzinger reaction (Pfitzinger, 1886). Herein, we use the microwave technology for this synthesis, in a typical procedure: a mixture of isatin (1 mmole), acetophenone (1.05 equivalents) and potassium hydroxide (10 equivalents) in aqueous ethanol (10 ml) was placed in a closed vessel and irradiated with MW for 12 minutes at 140°C. The reaction mixture was acidified with acetic acid and the product was recrystallized from ethanol to produce white crystals with a melting point of 214–216 °C. Crystal with two different morphologies were found, cubic crystals which did not produce good diffraction and needle-shaped crystals. A large needle crystal was selected since the others were too small to provide good diffraction data.