Methyl 2-[(2-chloro­quinolin-3-yl)(hy­droxy)meth­yl]acrylate

T Anuradha; J Srinivasan; P R Seshadri; M Bakthadoss

doi:10.1107/S1600536813014050

. 2013 May 31;69(Pt 6):o990. doi: 10.1107/S1600536813014050

Methyl 2-[(2-chloroquinolin-3-yl)(hydroxy)methyl]acrylate

T Anuradha ^a, J Srinivasan ^b, P R Seshadri ^a,^*, M Bakthadoss ^b

PMCID: PMC3685122 PMID: 23795141

Abstract

There are two independent molecules (A and B) in the asymmetric unit of the title compound, C₁₄H₁₂ClNO₃. The mean planes of the methyl ester unit (C_methyl—O—C=O; r.m.s. deviation = 0.051 Å for molecule A and 0.016 Å for molecule B) and the chloroquilonine ring system (r.m.s. deviation = 0.023 Å for molecule A and 0.014 Å for molecule B) form dihedral angles of 63.5 (1)° in molecule A and 78.1 (1)° in molecule B. The main difference between the two independent molecules is reflected in the (H)O—C—C=C(H₂) torsion angle which is −109.7 (2)° in molecule A and 10.6 (2)° in molecule B. An intramolecular O—H⋯O hydrogen bond is observed in molecule A. In the crystal, molecules A and B are linked into pairs via bifurcated O—H⋯(N,Cl) hydrogen bonds and a weak C—H⋯O hydrogen bond links pairs of molecules into chains along [100].

Related literature

For the biological activity of quilonine compounds, see: Biavatti et al. (2002 ▶); Towers et al. (1981 ▶); Shen et al. (1999 ▶). For their luminescent properties, see: Montes et al. (2006 ▶). For applications of acrylate compounds, see: Bhatia et al. (2007 ▶); Sharma (2011 ▶). For conformational aspects of methyl esters, see: Dunitz & Schweizer (1982 ▶). For resonance effects in acrylates, see: Merlino (1971 ▶); Varghese et al. (1986 ▶). graphic file with name e-69-0o990-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₂ClNO₃
M _r = 277.70
Triclinic,
a = 9.2614 (4) Å
b = 11.0309 (4) Å
c = 13.8161 (6) Å
α = 102.557 (2)°
β = 100.646 (2)°
γ = 103.704 (2)°
V = 1296.29 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII diffractometer
14402 measured reflections
4466 independent reflections
3767 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.093
S = 1.03
4466 reflections
344 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 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 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97, PLATON and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(25.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813014050/lh5607sup1.cif

e-69-0o990-sup1.cif^{(25.1KB, cif)}

Click here for additional data file.^{(214.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014050/lh5607Isup2.hkl

e-69-0o990-Isup2.hkl^{(214.4KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813014050/lh5607Isup3.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
O1A—H1A⋯O2A	0.82	2.24	2.8372 (19)	130
O1B—H1B⋯Cl1A ⁱ	0.82	2.79	3.5040 (12)	147
O1B—H1B⋯N1A ⁱ	0.82	2.16	2.8609 (17)	144
C5A—H5A⋯O1B ⁱⁱ	0.93	2.56	3.451 (2)	162

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

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT-Madras, India, for the data collection.

supplementary crystallographic information

Comment

The quinoline ring is found in compounds with antifungal (Biavatti et al., 2002), antibacterial (Towers et al., 1981) and anticancer (Shen et al., 1999) properties. Quinoline derivatives have been used for their luminescent properties as organic light-emitting diode (OLED) materials (Montes et al., 2006). Methyl acrylate is an ingredient used in many fragrances and decorative cosmetics (Bhatia et al., 2007; Sharma, 2011). In view of the potential importance of the title compound its crystal structure is presented herein.

The asymmetric unit of the title compound contains the two independent molecules, A and B (Fig. 1). The dihedral angle between the mean plane of methyl ester unit (C13/C14/O2/O3, r.m.s deviation = -0.051 Å for A and -0.016 Å for B) and the chloroquilonin ring system (C1—C9/N1/Cl1, r.m.s deviation = 0.023 Å for A and -0.014 Å for B) is 63.5 (1)° in molecule A and 78.6 (1)° in molecule B. The main difference between the two independent molecules is reflected in the O1—C10—C11—C12 torsion angle which is -109.7 (2)° in molecule A and 10.6 (2)° in molecule B.

The methyl ester moiety adopts an extended conformation as reflected by the torsion angles for C11—C13—C14—O3 = 177.7 (2)° in A and 178.4 (1)° in B. The extended conformation is supported by the fact that the bond angles involving the carbonyl O atoms are invariably expanded (Dunitz & Schweizer, 1982). The significant difference in the bond lengths of the C13—O3 = 1.322 (3) Å (A) 1.331 (3) Å (B) versus C14—O3 = 1.447 (3) Å (A) and 1.447 (2) Å (B) can be attributed to a partial contribution from the O^-–C═O⁺–C resonance structure of the O2—C13—O3—C14 group (Merlino, 1971). This feature, commonly observed in the carboxylic ester group of these substituents in various compounds has been shown to give average values of 1.340 Å and 1.447 Å respectively for these bonds (Varghese et al., 1986).

In the crystal molecule A and B are linked into pairs via bifurcated O—H···(N,Cl) hydrogen bonds (Fig. 2) and a weak C—H···O hydrogen bond links pairs of molecules into chains along [100].

Experimental

A mixture of 2-chloroquinoline-3-carbaldehyde (0.1 g, 0.52 mmol), methyl acrylate (0.071 ml, 0.78 mmol), and DABCO (0.017 g, 0.15 mmol), was kept at room temperature for 7 days. After completion of the reaction (indicated by TLC), the reaction mixture was extracted with ethylacetate (3 τimes 15 ml). The combined organic layer subsequently washed with dil.HCl and dried over anhydrous Na₂SO₄. The solvent was evaporated under reduced pressure. The crude product was obtained and purified by column chromatography eluting with 8% ethylacetate in hexane afforded the alcohol methyl 2-((2-chloroquinolin-3-yl)(hydroxy)methyl)acrylate as a colourless solid. X-ray quality crystals were obtained by slow evaporation of a solution of the title compound in ethylacetate.