Crystal structure of methyl 2-(7-hy­droxy-2-oxo-2H-chromen-4-yl)acetate

Sammer Yousuf; Shafqat Hussain; Khalid Mohammed Khan; Muhammad Shabeer; Shahnaz Perveen

doi:10.1107/S2056989015014061

. 2015 Aug 22;71(Pt 9):o677–o678. doi: 10.1107/S2056989015014061

Crystal structure of methyl 2-(7-hydroxy-2-oxo-2H-chromen-4-yl)acetate

Sammer Yousuf ^a,^*, Shafqat Hussain ^b, Khalid Mohammed Khan ^a, Muhammad Shabeer ^a, Shahnaz Perveen ^c

PMCID: PMC4555392 PMID: 26396900

Abstract

In the title coumarin derivative, C₁₂H₁₀O₅, the fused ring system is almost planar (r.m.s deviation = 0.016 Å). The C_ar—C—C=O torsion angle of the side chain is −8.4 (2)° In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating C(8) chains propagating in the [100] direction. The chains are cross-linked by weak C—H⋯O interactions, thereby generating undulating (001) sheets.

Keywords: crystal structure, ester, coumarin, chromene, hydrogen bonding

Related literature

For the applications and biological activities of coumarin derivatives, see: Vukovic et al. (2010 ▸); Basanagouda et al. (2009 ▸); Ahmad et al. (2008 ▸); Abd Elhafez et al. (2003 ▸); Ukhov et al. (2001 ▸); Emmanuel-Giota et al. (2001 ▸). For the crystal structure of a related compound, see: Subramanian et al. (1990 ▸).

Experimental

Crystal data

C₁₂H₁₀O₅
M _r = 234.20
Orthorhombic,
a = 13.0780 (12) Å
b = 7.2354 (7) Å
c = 22.262 (2) Å
V = 2106.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 273 K
0.62 × 0.35 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T _min = 0.932, T _max = 0.992
11536 measured reflections
1958 independent reflections
1669 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.03
1958 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.19 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: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014061/hb7469sup1.cif

e-71-0o677-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014061/hb7469Isup2.hkl

e-71-0o677-Isup2.hkl^{(96.4KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014061/hb7469Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015014061/hb7469fig1.tif

The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.

Click here for additional data file.^{(2.1MB, tif)}

. DOI: 10.1107/S2056989015014061/hb7469fig2.tif

The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.

CCDC reference: 1415274

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O3H3O1ⁱ	0.96(2)	1.74(2)	2.7002(17)	177(2)
C7H7AO4ⁱⁱ	0.93	2.47	3.3320(18)	155

Open in a new tab

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

Acknowledgments

The authors acknowledge the financial support of the Higher Education Commission of Pakistan (HEC) through research projects Nos. 20-2073 and 20-2216 under the National Research Program for Universities.

supplementary crystallographic information

S1. Comment

Coumarin, 2H-chromen-2-ones are naturally occurring aroma containing organic molecules belongs to benzopyrone (Ahmad et al., 2008) class of compounds. Coumarines known to have wide range of biological activities including antibacterial (Abd Elhafez et al., 2003, Ukhov et al., 2001), antitumour and anticoagulant (Emmanuel-Giota et al., 2001), antioxidant (Basanagouda et al., 2009) and antiinflammatory (Vukovic et al., 2010) properties. The literature has disclosed various methodologies to synthesize coumarine and their structural analogues. The title compound was synthesized during our attempts to maintained libraries of structural analogues of bioactive organic molecules.

The structure of title compound is similar to that of previously published Ethyl 7-hydroxy-4-coumarinacetate (Subramanian et al., 1990) with the difference that ethyl acetate moiety is replaced by methyl acetate chain (O4—O5/C10–C12)attached at C9 of central coumarin ring (Fig. 1).

The crystal structure features O3—H3···O1, and C7—H7A···O4 interactions to form (001) sheets (symmetry codes as in Table 2 and Fig. 2).

S2. Experimental

2-(7-Hydroxy-2-oxo-2H-chromen-4-yl) acetic acid (220 mg, 1 mmol) was dissolved in methanol (15 ml), and a few drops of sulfuric acid were added. The resulting reaction mixture was refluxed for 3 h. After the completion of the reaction as indicated by TLC, solvent was evaporated and the resulting reaction mixture was extracted with ethyl acetate, washed with sodium bicarbonate, brine and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to afford crystals of title compound in 215 mg, 91% yield.