Ethyl (E)-3-(6-methyl-4-oxo-4H-chromen-3-yl)prop-2-enoate

Sammer Yousuf; Asma Mukhtar; Nida Ambreen; Syed Muhammad Saad; Khalid M Khan

doi:10.1107/S1600536812038585

. 2012 Sep 19;68(Pt 10):o2948. doi: 10.1107/S1600536812038585

Ethyl (E)-3-(6-methyl-4-oxo-4H-chromen-3-yl)prop-2-enoate

Sammer Yousuf ^a,^*, Asma Mukhtar ^a, Nida Ambreen ^a, Syed Muhammad Saad ^a, Khalid M Khan ^a

PMCID: PMC3470320 PMID: 23125733

Abstract

In the title compound, C₁₅H₁₄O₄, the chromone ring system is close to being planar [maximum deviation = 0.015 (2) Å]. The double bond of the ethyl prop-2-enoate chain adopts an E conformation and an intramolecular C—H⋯O hydrogen bond generates an S6 ring. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R ₂ ²(14) loops. Weak π–π interactions [centroid–centroid distance = 3.8493 (12) Å] also occur.

Related literature

For the biological activity of chromones, see: Patel et al. (2011 ▶); Khan et al. (2010 ▶); Gautam et al. (2010 ▶). For a related structure, see: Wang & Kong (2007 ▶).

Experimental

Crystal data

C₁₅H₁₄O₄
M _r = 258.26
Monoclinic,
a = 13.8663 (12) Å
b = 12.3512 (10) Å
c = 7.6947 (6) Å
β = 96.390 (2)°
V = 1309.65 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.34 × 0.25 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.968, T _max = 0.985
7621 measured reflections
2431 independent reflections
1650 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.04
2431 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812038585/hb6950sup1.cif

e-68-o2948-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038585/hb6950Isup2.hkl

e-68-o2948-Isup2.hkl^{(119.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812038585/hb6950Isup3.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
C11—H11A⋯O2	0.93	2.28	2.908 (2)	124
C9—H9A⋯O3ⁱ	0.93	2.37	3.276 (3)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to OPCW, Netherlands, and the Higher Education Commission (HEC) Pakistan (project No. 1910) for their financial support.

supplementary crystallographic information

Comment

Chromone is a group of naturally occurring oxygen containing heterocyclic compounds having a benzene ring fused with pyran ring. They are widely distributed in plant kingdom and form the basic nucleus of important compounds such as anthocyanin and flavonoids. The chromone moiety forms an important component of pharmacophores of a number of biologically active molecules of synthetic as well as natural origin and therefore responsible for various biological activities (e.g. Patel et al. (2011); Gautam et al. (2010); Khan et al. (2010). The title compound is a chromone derivative obtained as a part of our ongoing project to synthesize libraries of chromone derivatives in order to study their different biological activities. The structure of title compound (Fig. 1) is composed of almost planner chromone moiety (O1/C1–C9) with maximum deviation of 0.015 (2) Å for C7 atom from the root mean square plane. The C11–C12 (1.462 (3) Å) olefinic bond of ethyl prop-2-enoate chain (O3–O4/C10–C14) attached to chromone moiety adopt an E configuartion. The shorter bond lengths of C11–C12 = 1.462 (3) Å than the expected C–C single bond length is due to the conjugation effects of the olefinc bond (C11–C12, 1.462 (3) Å) with carbonyl carbon (O3/C12) of ethyl prop-2-enoate chain (O3–O4/C10–C14). The bond lengths and angle were found to be similar as in structurally realted compound (Wang & Kong, 2007). The E conformation of olefinic bound further stabilized by an intramolecular C11–C11A···O2 intramolecular hydrogen bond. In the crystal inversion-related molecules are consolidated by C9–C9A···O3 hydrogen bond and found stacked along the a-axis. The crystal structure also features weak π–π interaction between pyrane (Cg(1)= O1/C6–C9) and benzene (Cg(2)= C1–C6) of chromone moeity ((Cg(1)to Cg(2) distance = 3.8493 (12) Å;X,1/2-Y,-1/2+Z)

Experimental

A mixture of 3-formyl chromone (10 mmol) and malonic acid (20 mmol), using pyridine (15 ml) as solvent was refluxed in 500 mL round-bottomed flask for 30–45 minutes with vigorous stirring. After completion of reaction (monitored by TLC), the reaction mixture was cooled to room temperature, acidified by concntrated hydrochloric acid (pH 1.0) and stirred again for 30 minutes at room temprature. The yellow colored solid (1.02 g) obtained was filtered and washed with water. The crude residue was dried, dissolved in ethanol (50 ml) along with few drops of H₂SO₄ and refluxed for 24 h (progress of the reaction was monitored by TLC). After completion of reaction the solvent was evaporated under vacuum followed by addition of saturated solution of NaHCO₃ and extracted with ethyl acetate, washed with water. The organic phase was dried over Na₂SO₄. The solvent was evaporated under reduced pressure to obtain crude product which was further recrystallized in ethanol to obtain yellow blocks in 82% yield (0.94 g).