4-(Oct­yloxy)phenyl 2-oxo-2H-chromene-3-carboxyl­ate

B S Palakshamurthy; S Sreenivasa; H T Srinivasa; K R Roopashree; H C Devarajegowda

doi:10.1107/S1600536813000214

. 2013 Jan 9;69(Pt 2):o212. doi: 10.1107/S1600536813000214

4-(Octyloxy)phenyl 2-oxo-2H-chromene-3-carboxylate

B S Palakshamurthy ^a, S Sreenivasa ^b, H T Srinivasa ^c, K R Roopashree ^a, H C Devarajegowda ^a,^*

PMCID: PMC3569748 PMID: 23424494

Abstract

In the title compound, C₂₄H₂₆O₅, the 2H-chromene ring system is essentially planar, with a maximum deviation of 0.029 (2) Å from the best-fit mean plane incorporating both rings. The dihedral angle between the 2H-chromene ring system and the benzene ring is 21.00 (1)°. In the crystal, pairs of C—H⋯O hydrogen bonds generate an R ₂ ²(8) ring pattern. These contacts are bolstered by weaker bifurcated C—H⋯O hydrogen bonds.

Related literature

For general background to coumarin derivatives and their biological and technological applications, see: Georgieva et al. (2004 ▶); Creaven et al. (2005 ▶); Morita et al. (2005 ▶); Tian et al. (2003 ▶); Iliopoulos et al. (2010 ▶); Hejchman et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-69-0o212-scheme1.jpg

Experimental

Crystal data

C₂₄H₂₆O₅
M _r = 394.45
Monoclinic,
a = 14.464 (3) Å
b = 6.7548 (15) Å
c = 21.381 (5) Å
β = 91.663 (8)°
V = 2088.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.29 × 0.25 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.975, T _max = 0.982
22609 measured reflections
3615 independent reflections
1926 reflections with I > 2σ(I)
R _int = 0.084

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.146
S = 0.94
3615 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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, 2012 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(29.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000214/sj5291sup1.cif

e-69-0o212-sup1.cif^{(29.7KB, cif)}

Click here for additional data file.^{(173.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000214/sj5291Isup2.hkl

e-69-0o212-Isup2.hkl^{(173.7KB, hkl)}

Click here for additional data file.^{(7.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000214/sj5291Isup3.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
C4—H4⋯O1ⁱ	0.93	2.59	3.513 (4)	174
C9—H9⋯O2ⁱ	0.93	2.51	3.420 (3)	167
C16—H16⋯O2ⁱ	0.93	2.71	3.551 (3)	151
C16—H16⋯O3ⁱ	0.93	2.63	3.338 (3)	133

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Professor T. N. Guru Row, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, and P. A. Suchetan, Department of Studies and Research in Chemistry, U·C.S. Tumkur University, Tumkur, for their help and suggestions.

supplementary crystallographic information

Comment

Coumarin derivatives have been attracted increasing attention due to their extensive biological applications, such as anticancer, anti-inflammatory and anticoagulant agents (Georgieva et al., 2004; Creaven et al., 2005). The coumarin nucleus has been the focus of our recent research concerning the design, synthesis and characterization to investigate their liquid crystal properties together with crystal structure studies (Morita et al., 2005; Tian et al., 2003). Coumarins are interesting class of heterocycles because of their dipolar moment increases by external stimulus such as light, temperature, electric current and chemical reaction (Iliopoulos et al., 2010). The excitation of the coumarin chromophore increases the electron density of its carbonyl groups owing to excited photochemical and photophysical properties such as molecular fluorescent sensors, laser dyes and many industrial applications (Hejchman et al., 2011).

The asymmetric unit of 4-(octyloxy)phenyl 2-oxo-2H-chromene-3 -carboxylate is shown in Fig. 1. The 2H-chromene ring (O1/C1–C9) system is planar, with a maximum deviation of 0.028 (2) Å for atom C8. The dihedral angle between 2H-chromene ring (O1/C1–C9) and benzene ring (C11–C16) is 21.11 (1)°. The crystal structure is characterized by intermolecular C4—H4···O1 and C9—H9···O2 hydrogen bonding generating an R₂²(8) ring pattern (Bernstein et al., 1995). Bifurcated C16—H16···O2 and C16—H16···O3 contacts further strengthen the packing, Fig. 2.

Experimental

A mixture of 2-oxo-2H-chromene-3-carboxylic acid (19 mg,1 mmol), 4-(octyloxy)phenol (22.2 mg,1 mmol), N,N -dicyclohexylcarbodiimide (23 mg,1.2 mmol) and a catalytic quantity of N,N-dimethylaminopyrimidine was stirred in 5 ml of dry dichloromethane for 24 h at room temperature. The residue obtained on removal of solvent was chromatographed on silica gel and eluted with chloroform. Removal of solvent from the eluate afforded a colorless solid, which was re-crystallized from absolute ethanol to obtain needle like crystals of the title compound for X-ray diffraction analysis.