Methyl 2-oxo-2H-chromene-3-carboxyl­ate

Saeed, A.; Ibrar, A.; Arshad, M.; Bolte, M.

doi:10.1107/S1600536812040044

organic compounds

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Volume 68| Part 10| October 2012| Page o3024

https://doi.org/10.1107/S1600536812040044

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Methyl 2-oxo-2H-chromene-3-carboxylate

Aamer Saeed,^a ^* Aalia Ibrar,^a Muhammad Arshad ^b and Michael Bolte ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bChemistry Division, Directorate of Science, PINSTECH, Nilore, Islamabad, Pakistan, and ^cInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany.
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 19 September 2012; accepted 21 September 2012; online 26 September 2012)

The title compound, C₁₁H₈O₄, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). In the crystal, the molecules are linked via C—H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (1-21).

Related literature

For details of the biological activity of coumarins, see: Surya et al. (2006 ); Kostova (2006 ); Reddy et al. (2002 ); Lacy & O'Kennedy (2004 ). For other applications of coumarins, see: Flašík et al. (2009 ); Fonsecaa et al. (2010 ).

Experimental

Crystal data

C₁₁H₈O₄
M_r = 204.17
Triclinic, $[P \overline 1]$
a = 3.8874 (10) Å
b = 9.782 (3) Å
c = 13.078 (3) Å
α = 111.569 (19)°
β = 90.83 (2)°
γ = 95.01 (2)°
V = 460.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.30 × 0.27 × 0.20 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001 ) T_min = 0.967, T_max = 0.978
4851 measured reflections
1725 independent reflections
1378 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.09
1725 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.95	2.54	3.360 (2)	145
C5—H5⋯O3ⁱ	0.95	2.46	3.298 (2)	147
C8—H8⋯O1ⁱⁱ	0.95	2.55	3.454 (2)	160
C11—H11A⋯O2ⁱⁱⁱ	0.98	2.53	3.354 (2)	142
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z; (iii) -x+3, -y+2, -z+1.

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812040044/su2501sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup4.cml

checkCIF report

Comment top

Coumarins (2H-1-benzopyran-2-ones) are natural lactones and amongst the best known oxygen heterocycles, well represented as a structural motif in numerous natural products (Surya et al., 2006). Various coumarin derivatives are known to possess an array of biological activities, including anticancer, anti-HIV, anti acetylcholinesterase, antifungal, antioxidant, antihelmintic, anticoagulant, antibacterial, antiviral and anticlotting activities, and find extensive application in pharmaceuticals, fragrances, agrochemicals, additives in food and cosmetics and insecticides (Kostova, 2006; Reddy et al., 2002; Lacy & O'Kennedy, 2004). Moreover, coumarins find applications as dyes in laser technology, fluorescent indicators, optical brighteners and photosensitizers (Flašík et al., 2009). Ethyl 2-oxo-2H-chromene-3-carboxylate irreversibly inhibits phospholipase A2 (sPLA2) from Crotalus durissus ruruima venom with an IC50 of 3.1 ± 0.06 nmol (Fonsecaa et al., 2010).

The title compound, Fig. 1, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). The maximum deviation from the mean plane being 0.0734 (12) Å for atom O2.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming two-dimensional networks lying parallel to (121); Table 1 and Fig. 2.

Related literature top

For details of the biological activity of coumarins, see: Surya et al. (2006); Kostova (2006); Reddy et al. (2002); Lacy & O'Kennedy (2004). For other applications of coumarins, see: Flašík et al. (2009); Fonsecaa et al. (2010). [Please revise scheme to show correct methyl derivative, not ethyl]

Experimental top

Salicylaldehyde (1.22 g, 0.01 mol) and diethylmalonate (1.6 g, 0.01 mol) were dissolved in ethanol to give a clear solution. Piperidine (2 ml) was added and the mixture was refluxed for 5 h. The content was concentrated to a small volume. The product (3) was poured onto crushed ice, filtered out and crystallized from ethanol to give colourless crystals, m.p. 393–395 K; Yield: 90%. Spectroscopic data for the title compound are available in the archived CIF.

Structure description top

The title compound, Fig. 1, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). The maximum deviation from the mean plane being 0.0734 (12) Å for atom O2.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming two-dimensional networks lying parallel to (121); Table 1 and Fig. 2.

For details of the biological activity of coumarins, see: Surya et al. (2006); Kostova (2006); Reddy et al. (2002); Lacy & O'Kennedy (2004). For other applications of coumarins, see: Flašík et al. (2009); Fonsecaa et al. (2010). [Please revise scheme to show correct methyl derivative, not ethyl]

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title molecule, with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound view along [100]. Hydrogen bonds are drawn as dashed lines.

Methyl 2-oxo-2H-chromene-3-carboxylate top

Crystal data top

C₁₁H₈O₄	Z = 2
M_r = 204.17	F(000) = 212
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8874 (10) Å	Cell parameters from 10306 reflections
b = 9.782 (3) Å	θ = 3.3–26.0°
c = 13.078 (3) Å	µ = 0.11 mm⁻¹
α = 111.569 (19)°	T = 173 K
β = 90.83 (2)°	Block, colourless
γ = 95.01 (2)°	0.30 × 0.27 × 0.20 mm
V = 460.1 (2) Å³

Data collection top

Stoe IPDS II two-circle diffractometer	1725 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	1378 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	R_int = 0.054
ω scans	θ_max = 25.7°, θ_min = 4.2°
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001)	h = −4→4
T_min = 0.967, T_max = 0.978	k = −11→11
4851 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0591P)² + 0.0733P] where P = (F_o² + 2F_c²)/3
1725 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₁H₈O₄	γ = 95.01 (2)°
M_r = 204.17	V = 460.1 (2) Å³
Triclinic, P1	Z = 2
a = 3.8874 (10) Å	Mo Kα radiation
b = 9.782 (3) Å	µ = 0.11 mm⁻¹
c = 13.078 (3) Å	T = 173 K
α = 111.569 (19)°	0.30 × 0.27 × 0.20 mm
β = 90.83 (2)°

Data collection top

Stoe IPDS II two-circle diffractometer	1725 independent reflections
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001)	1378 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.978	R_int = 0.054
4851 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.09	Δρ_max = 0.21 e Å⁻³
1725 reflections	Δρ_min = −0.18 e Å⁻³
136 parameters

Special details top

Experimental. Spectroscopic data for the title compound: IR (KBr, cm^-1) 1710 (C═O, coumarin), 1670 (C═O), 1750 (C═O, ester), 1200 (C—O); ¹HNMR (DMSO-d6, 300MHz, δ p.p.m.): 7.5 (4H, m, Ar—H), 8.1 (1H, s, Ar—H, H-4), 1.83 (3H, t, CH3), 3.20 (2H, q, CH2). Mass m/z (%): 216 M⁺.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.8969 (3)	0.56201 (13)	0.15727 (9)	0.0371 (3)
O2	1.2039 (3)	0.76399 (14)	0.26510 (10)	0.0472 (4)
O3	0.8489 (3)	0.68616 (13)	0.54600 (9)	0.0469 (4)
O4	1.1674 (3)	0.84024 (13)	0.48731 (9)	0.0394 (3)
C1	1.0100 (4)	0.66021 (18)	0.26166 (14)	0.0352 (4)
C2	0.8796 (4)	0.62198 (18)	0.35402 (13)	0.0328 (4)
C3	0.6775 (4)	0.49482 (18)	0.33393 (13)	0.0329 (4)
H3	0.5978	0.4715	0.3945	0.039*
C4	0.5793 (4)	0.39425 (18)	0.22513 (13)	0.0330 (4)
C5	0.3781 (4)	0.25926 (18)	0.20103 (14)	0.0371 (4)
H5	0.2943	0.2314	0.2591	0.045*
C6	0.3016 (4)	0.1670 (2)	0.09335 (15)	0.0408 (4)
H6	0.1695	0.0745	0.0773	0.049*
C7	0.4178 (4)	0.2090 (2)	0.00751 (14)	0.0422 (4)
H7	0.3604	0.1452	−0.0666	0.051*
C8	0.6144 (4)	0.34155 (19)	0.02878 (14)	0.0385 (4)
H8	0.6927	0.3700	−0.0296	0.046*
C9	0.6949 (4)	0.43218 (18)	0.13747 (13)	0.0338 (4)
C10	0.9625 (4)	0.71847 (18)	0.47158 (13)	0.0338 (4)
C11	1.2460 (4)	0.9364 (2)	0.60135 (14)	0.0415 (4)
H11A	1.3986	1.0231	0.6043	0.062*
H11B	1.3614	0.8827	0.6399	0.062*
H11C	1.0311	0.9682	0.6368	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0401 (6)	0.0439 (7)	0.0297 (6)	−0.0047 (5)	0.0051 (5)	0.0184 (5)
O2	0.0525 (7)	0.0500 (7)	0.0411 (7)	−0.0127 (6)	0.0077 (6)	0.0228 (6)
O3	0.0582 (7)	0.0504 (8)	0.0306 (7)	−0.0130 (6)	0.0077 (5)	0.0171 (6)
O4	0.0420 (6)	0.0437 (7)	0.0321 (6)	−0.0096 (5)	−0.0006 (5)	0.0167 (5)
C1	0.0333 (8)	0.0419 (9)	0.0325 (9)	−0.0004 (7)	0.0049 (6)	0.0171 (7)
C2	0.0294 (7)	0.0411 (9)	0.0312 (9)	0.0011 (6)	0.0042 (6)	0.0178 (7)
C3	0.0309 (8)	0.0423 (9)	0.0301 (8)	0.0021 (7)	0.0053 (6)	0.0191 (7)
C4	0.0304 (7)	0.0400 (9)	0.0313 (9)	0.0015 (6)	0.0033 (6)	0.0165 (7)
C5	0.0349 (8)	0.0450 (9)	0.0348 (9)	−0.0009 (7)	0.0024 (7)	0.0198 (8)
C6	0.0395 (8)	0.0422 (9)	0.0401 (10)	−0.0031 (7)	−0.0016 (7)	0.0161 (8)
C7	0.0407 (9)	0.0506 (10)	0.0318 (9)	0.0017 (8)	−0.0016 (7)	0.0120 (8)
C8	0.0372 (8)	0.0505 (10)	0.0318 (9)	0.0043 (7)	0.0044 (7)	0.0199 (8)
C9	0.0300 (7)	0.0407 (9)	0.0339 (9)	0.0018 (6)	0.0034 (6)	0.0179 (7)
C10	0.0319 (8)	0.0390 (9)	0.0333 (9)	−0.0003 (6)	0.0032 (6)	0.0173 (7)
C11	0.0417 (9)	0.0456 (10)	0.0356 (9)	−0.0061 (7)	−0.0029 (7)	0.0158 (8)

Geometric parameters (Å, º) top

O1—C9	1.3691 (19)	C4—C5	1.400 (2)
O1—C1	1.387 (2)	C5—C6	1.376 (2)
O2—C1	1.1970 (19)	C5—H5	0.9500
O3—C10	1.2069 (19)	C6—C7	1.398 (3)
O4—C10	1.3209 (19)	C6—H6	0.9500
O4—C11	1.452 (2)	C7—C8	1.378 (2)
C1—C2	1.474 (2)	C7—H7	0.9500
C2—C3	1.348 (2)	C8—C9	1.384 (2)
C2—C10	1.491 (2)	C8—H8	0.9500
C3—C4	1.424 (2)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C9	1.397 (2)	C11—H11C	0.9800

C9—O1—C1	123.86 (12)	C7—C6—H6	119.9
C10—O4—C11	115.67 (12)	C8—C7—C6	120.97 (17)
O2—C1—O1	115.90 (14)	C8—C7—H7	119.5
O2—C1—C2	128.38 (16)	C6—C7—H7	119.5
O1—C1—C2	115.71 (14)	C7—C8—C9	118.30 (15)
C3—C2—C1	120.00 (16)	C7—C8—H8	120.9
C3—C2—C10	117.20 (14)	C9—C8—H8	120.9
C1—C2—C10	122.80 (15)	O1—C9—C8	117.63 (13)
C2—C3—C4	122.29 (14)	O1—C9—C4	120.23 (15)
C2—C3—H3	118.9	C8—C9—C4	122.14 (15)
C4—C3—H3	118.9	O3—C10—O4	123.18 (16)
C9—C4—C5	118.29 (15)	O3—C10—C2	121.75 (15)
C9—C4—C3	117.80 (15)	O4—C10—C2	115.07 (13)
C5—C4—C3	123.90 (14)	O4—C11—H11A	109.5
C6—C5—C4	120.13 (15)	O4—C11—H11B	109.5
C6—C5—H5	119.9	H11A—C11—H11B	109.5
C4—C5—H5	119.9	O4—C11—H11C	109.5
C5—C6—C7	120.15 (16)	H11A—C11—H11C	109.5
C5—C6—H6	119.9	H11B—C11—H11C	109.5

C9—O1—C1—O2	175.14 (13)	C1—O1—C9—C8	−177.09 (13)
C9—O1—C1—C2	−4.0 (2)	C1—O1—C9—C4	2.4 (2)
O2—C1—C2—C3	−175.95 (16)	C7—C8—C9—O1	178.57 (13)
O1—C1—C2—C3	3.1 (2)	C7—C8—C9—C4	−0.9 (2)
O2—C1—C2—C10	3.8 (3)	C5—C4—C9—O1	−178.95 (13)
O1—C1—C2—C10	−177.24 (12)	C3—C4—C9—O1	0.3 (2)
C1—C2—C3—C4	−0.7 (2)	C5—C4—C9—C8	0.6 (2)
C10—C2—C3—C4	179.63 (13)	C3—C4—C9—C8	179.76 (13)
C2—C3—C4—C9	−1.1 (2)	C11—O4—C10—O3	−0.9 (2)
C2—C3—C4—C5	178.10 (14)	C11—O4—C10—C2	179.09 (12)
C9—C4—C5—C6	0.7 (2)	C3—C2—C10—O3	−1.4 (2)
C3—C4—C5—C6	−178.50 (14)	C1—C2—C10—O3	178.88 (14)
C4—C5—C6—C7	−1.4 (2)	C3—C2—C10—O4	178.57 (13)
C5—C6—C7—C8	1.0 (2)	C1—C2—C10—O4	−1.1 (2)
C6—C7—C8—C9	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.95	2.54	3.360 (2)	145
C5—H5···O3ⁱ	0.95	2.46	3.298 (2)	147
C8—H8···O1ⁱⁱ	0.95	2.55	3.454 (2)	160
C11—H11A···O2ⁱⁱⁱ	0.98	2.53	3.354 (2)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₈O₄
M_r	204.17
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	3.8874 (10), 9.782 (3), 13.078 (3)
α, β, γ (°)	111.569 (19), 90.83 (2), 95.01 (2)
V (Å³)	460.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.27 × 0.20

Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	Multi-scan (X-RED32; Stoe & Cie, 2001)
T_min, T_max	0.967, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	4851, 1725, 1378
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.09
No. of reflections	1725
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18

Computer programs: X-AREA (Stoe & Cie, 2001), X-RED32 (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.95	2.54	3.360 (2)	145
C5—H5···O3ⁱ	0.95	2.46	3.298 (2)	147
C8—H8···O1ⁱⁱ	0.95	2.55	3.454 (2)	160
C11—H11A···O2ⁱⁱⁱ	0.98	2.53	3.354 (2)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+2, −z+1.

References

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