organic compounds
Ethyl 2-[(2-oxo-2H-chromen-7-yl)oxy]acetate
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia, and cDepartment of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711 103, India
*Correspondence e-mail: hkfun@usm.my
In the title compound, C13H12O5, the mean plane of the 2H-chromene ring system (r.m.s deviation = 0.026 Å) forms a dihedral angle of 81.71 (6)° with the mean plane of ethyl 2-hydroxyacetate moiety (r.m.s deviation = 0.034 Å). In the crystal, C—H⋯O hydrogen bonds result in the formation of zigzag layers parallel to the bc plane.
Related literature
For general background to and the high emission et al. (2012); Liu et al. (2012). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). For related structures, see: Arshad et al. (2010a,b).
photo stability and good solubility in common solvents of coumarin derivatives, see: XieExperimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536813005539/rz5046sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813005539/rz5046Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813005539/rz5046Isup3.cml
To a stirred solution of 7-hydroxycoumarin (500 mg, 3 mmol) in dry acetone, potassium carbonate (900 mg, 6 mmol) was added. After stirring for five minutes, ethyl chloroacetate (564 mg, 4.6 mmol) and a catalytic amount of TBAB were added to it. The whole reaction mixture was further stirred for 12 h at room temperature. After evaporation, water was added to it and the reaction mixture was extracted with chloroform thrice. The organic solvents were combined together and dried over anhydrous sodium sulphate and evaporated under reduced pressure. The crude product was purified through
(silica gel, 100-200 mesh size) using 15% ethyl acetate in petroleum ether as to afford a pure colourless crystalline solid. Yield: 98%. M. p. 74-76 °C.All H atoms were positioned geometrically and refined using a riding model with C–H = 0.93–0.97 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating-group model was applied for the methyl group.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C13H12O5 | F(000) = 520 |
Mr = 248.23 | Dx = 1.436 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3372 reflections |
a = 8.1435 (2) Å | θ = 2.5–29.4° |
b = 16.4887 (4) Å | µ = 0.11 mm−1 |
c = 10.5506 (3) Å | T = 100 K |
β = 125.882 (2)° | Block, colourless |
V = 1147.84 (5) Å3 | 0.31 × 0.24 × 0.11 mm |
Z = 4 |
Bruker SMART APEXII CCD area-detector diffractometer | 3344 independent reflections |
Radiation source: fine-focus sealed tube | 2308 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 30.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −9→11 |
Tmin = 0.966, Tmax = 0.988 | k = −23→15 |
12656 measured reflections | l = −14→14 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.040P)2 + 0.4605P] where P = (Fo2 + 2Fc2)/3 |
3344 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C13H12O5 | V = 1147.84 (5) Å3 |
Mr = 248.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1435 (2) Å | µ = 0.11 mm−1 |
b = 16.4887 (4) Å | T = 100 K |
c = 10.5506 (3) Å | 0.31 × 0.24 × 0.11 mm |
β = 125.882 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 3344 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2308 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.988 | Rint = 0.035 |
12656 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.32 e Å−3 |
3344 reflections | Δρmin = −0.24 e Å−3 |
164 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.39589 (16) | 0.81519 (6) | 0.17293 (12) | 0.0225 (2) | |
O2 | 0.48206 (18) | 0.71922 (7) | 0.07680 (13) | 0.0311 (3) | |
O3 | 0.23054 (17) | 1.01606 (6) | 0.40644 (13) | 0.0273 (3) | |
O4 | 0.06112 (16) | 0.85696 (7) | 0.53551 (13) | 0.0284 (3) | |
O5 | −0.09962 (17) | 0.91734 (7) | 0.30015 (13) | 0.0305 (3) | |
C1 | 0.3155 (2) | 0.91211 (9) | 0.29088 (17) | 0.0211 (3) | |
H1A | 0.3389 | 0.8732 | 0.3635 | 0.025* | |
C2 | 0.3385 (2) | 0.89394 (9) | 0.17359 (16) | 0.0193 (3) | |
C3 | 0.4238 (2) | 0.78861 (10) | 0.06252 (18) | 0.0246 (3) | |
C4 | 0.3788 (2) | 0.84577 (10) | −0.05922 (18) | 0.0268 (3) | |
H4A | 0.3890 | 0.8291 | −0.1386 | 0.032* | |
C5 | 0.3227 (2) | 0.92215 (10) | −0.05837 (18) | 0.0270 (3) | |
H5A | 0.2957 | 0.9579 | −0.1367 | 0.032* | |
C6 | 0.3039 (2) | 0.94961 (9) | 0.06176 (17) | 0.0221 (3) | |
C7 | 0.2475 (2) | 1.02864 (10) | 0.07243 (18) | 0.0254 (3) | |
H7A | 0.2248 | 1.0677 | 0.0001 | 0.031* | |
C8 | 0.2255 (2) | 1.04899 (9) | 0.18806 (18) | 0.0243 (3) | |
H8A | 0.1900 | 1.1016 | 0.1947 | 0.029* | |
C9 | 0.2567 (2) | 0.98993 (9) | 0.29621 (17) | 0.0225 (3) | |
C10 | 0.2416 (2) | 0.95782 (10) | 0.51046 (18) | 0.0253 (3) | |
H10A | 0.2669 | 0.9853 | 0.6017 | 0.030* | |
H10B | 0.3541 | 0.9213 | 0.5454 | 0.030* | |
C11 | 0.0474 (2) | 0.90906 (9) | 0.43309 (17) | 0.0232 (3) | |
C12 | −0.1214 (2) | 0.80927 (10) | 0.4789 (2) | 0.0301 (4) | |
H12A | −0.1582 | 0.7776 | 0.3882 | 0.036* | |
H12B | −0.2336 | 0.8449 | 0.4489 | 0.036* | |
C13 | −0.0765 (3) | 0.75434 (11) | 0.6084 (2) | 0.0381 (4) | |
H13A | −0.1945 | 0.7226 | 0.5743 | 0.057* | |
H13B | −0.0400 | 0.7862 | 0.6975 | 0.057* | |
H13C | 0.0337 | 0.7190 | 0.6365 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0289 (6) | 0.0198 (5) | 0.0218 (5) | 0.0002 (4) | 0.0166 (5) | 0.0001 (4) |
O2 | 0.0396 (7) | 0.0241 (6) | 0.0342 (6) | −0.0001 (5) | 0.0243 (6) | −0.0039 (5) |
O3 | 0.0382 (6) | 0.0211 (6) | 0.0293 (6) | −0.0009 (5) | 0.0236 (5) | −0.0021 (5) |
O4 | 0.0249 (6) | 0.0342 (6) | 0.0231 (5) | −0.0025 (5) | 0.0125 (5) | 0.0046 (5) |
O5 | 0.0309 (6) | 0.0332 (7) | 0.0220 (6) | 0.0021 (5) | 0.0125 (5) | 0.0023 (5) |
C1 | 0.0242 (7) | 0.0208 (7) | 0.0189 (7) | −0.0017 (6) | 0.0129 (6) | 0.0021 (6) |
C2 | 0.0181 (7) | 0.0183 (7) | 0.0185 (7) | −0.0015 (5) | 0.0091 (6) | −0.0009 (5) |
C3 | 0.0237 (7) | 0.0282 (9) | 0.0227 (8) | −0.0039 (6) | 0.0140 (7) | −0.0054 (6) |
C4 | 0.0269 (8) | 0.0334 (9) | 0.0218 (8) | −0.0023 (7) | 0.0152 (7) | −0.0011 (7) |
C5 | 0.0268 (8) | 0.0342 (9) | 0.0203 (7) | −0.0013 (7) | 0.0139 (7) | 0.0047 (7) |
C6 | 0.0191 (7) | 0.0263 (8) | 0.0183 (7) | −0.0021 (6) | 0.0095 (6) | 0.0021 (6) |
C7 | 0.0237 (7) | 0.0246 (8) | 0.0255 (8) | −0.0001 (6) | 0.0130 (7) | 0.0067 (6) |
C8 | 0.0242 (8) | 0.0187 (8) | 0.0285 (8) | −0.0008 (6) | 0.0146 (7) | 0.0006 (6) |
C9 | 0.0232 (7) | 0.0237 (8) | 0.0216 (7) | −0.0036 (6) | 0.0136 (6) | −0.0027 (6) |
C10 | 0.0289 (8) | 0.0270 (8) | 0.0219 (7) | −0.0006 (7) | 0.0160 (7) | −0.0016 (6) |
C11 | 0.0280 (8) | 0.0224 (8) | 0.0213 (7) | 0.0038 (6) | 0.0156 (7) | 0.0000 (6) |
C12 | 0.0256 (8) | 0.0314 (9) | 0.0295 (8) | −0.0033 (7) | 0.0142 (7) | −0.0025 (7) |
C13 | 0.0324 (9) | 0.0384 (10) | 0.0474 (11) | 0.0026 (8) | 0.0257 (9) | 0.0110 (9) |
O1—C2 | 1.3814 (17) | C5—H5A | 0.9300 |
O1—C3 | 1.3827 (17) | C6—C7 | 1.408 (2) |
O2—C3 | 1.2136 (19) | C7—C8 | 1.375 (2) |
O3—C9 | 1.3692 (17) | C7—H7A | 0.9300 |
O3—C10 | 1.4211 (18) | C8—C9 | 1.405 (2) |
O4—C11 | 1.3328 (18) | C8—H8A | 0.9300 |
O4—C12 | 1.4642 (19) | C10—C11 | 1.516 (2) |
O5—C11 | 1.2045 (18) | C10—H10A | 0.9700 |
C1—C9 | 1.382 (2) | C10—H10B | 0.9700 |
C1—C2 | 1.389 (2) | C12—C13 | 1.495 (2) |
C1—H1A | 0.9300 | C12—H12A | 0.9700 |
C2—C6 | 1.387 (2) | C12—H12B | 0.9700 |
C3—C4 | 1.456 (2) | C13—H13A | 0.9600 |
C4—C5 | 1.341 (2) | C13—H13B | 0.9600 |
C4—H4A | 0.9300 | C13—H13C | 0.9600 |
C5—C6 | 1.436 (2) | ||
C2—O1—C3 | 121.70 (12) | C9—C8—H8A | 120.1 |
C9—O3—C10 | 118.20 (12) | O3—C9—C1 | 123.83 (13) |
C11—O4—C12 | 115.63 (12) | O3—C9—C8 | 115.29 (13) |
C9—C1—C2 | 117.86 (13) | C1—C9—C8 | 120.85 (14) |
C9—C1—H1A | 121.1 | O3—C10—C11 | 111.63 (12) |
C2—C1—H1A | 121.1 | O3—C10—H10A | 109.3 |
O1—C2—C6 | 121.23 (13) | C11—C10—H10A | 109.3 |
O1—C2—C1 | 115.48 (12) | O3—C10—H10B | 109.3 |
C6—C2—C1 | 123.28 (14) | C11—C10—H10B | 109.3 |
O2—C3—O1 | 116.08 (14) | H10A—C10—H10B | 108.0 |
O2—C3—C4 | 126.72 (14) | O5—C11—O4 | 124.81 (15) |
O1—C3—C4 | 117.20 (14) | O5—C11—C10 | 125.30 (14) |
C5—C4—C3 | 120.84 (14) | O4—C11—C10 | 109.86 (12) |
C5—C4—H4A | 119.6 | O4—C12—C13 | 107.85 (13) |
C3—C4—H4A | 119.6 | O4—C12—H12A | 110.1 |
C4—C5—C6 | 120.98 (14) | C13—C12—H12A | 110.1 |
C4—C5—H5A | 119.5 | O4—C12—H12B | 110.1 |
C6—C5—H5A | 119.5 | C13—C12—H12B | 110.1 |
C2—C6—C7 | 117.25 (14) | H12A—C12—H12B | 108.5 |
C2—C6—C5 | 117.92 (14) | C12—C13—H13A | 109.5 |
C7—C6—C5 | 124.81 (14) | C12—C13—H13B | 109.5 |
C8—C7—C6 | 121.00 (14) | H13A—C13—H13B | 109.5 |
C8—C7—H7A | 119.5 | C12—C13—H13C | 109.5 |
C6—C7—H7A | 119.5 | H13A—C13—H13C | 109.5 |
C7—C8—C9 | 119.71 (14) | H13B—C13—H13C | 109.5 |
C7—C8—H8A | 120.1 | ||
C3—O1—C2—C6 | 0.8 (2) | C2—C6—C7—C8 | −0.8 (2) |
C3—O1—C2—C1 | 179.82 (13) | C5—C6—C7—C8 | 177.46 (15) |
C9—C1—C2—O1 | −179.53 (12) | C6—C7—C8—C9 | −0.9 (2) |
C9—C1—C2—C6 | −0.6 (2) | C10—O3—C9—C1 | −7.5 (2) |
C2—O1—C3—O2 | 177.16 (13) | C10—O3—C9—C8 | 174.34 (13) |
C2—O1—C3—C4 | −3.51 (19) | C2—C1—C9—O3 | −179.32 (13) |
O2—C3—C4—C5 | −177.40 (16) | C2—C1—C9—C8 | −1.3 (2) |
O1—C3—C4—C5 | 3.4 (2) | C7—C8—C9—O3 | −179.80 (13) |
C3—C4—C5—C6 | −0.5 (2) | C7—C8—C9—C1 | 2.0 (2) |
O1—C2—C6—C7 | −179.50 (13) | C9—O3—C10—C11 | −78.32 (16) |
C1—C2—C6—C7 | 1.6 (2) | C12—O4—C11—O5 | −1.9 (2) |
O1—C2—C6—C5 | 2.1 (2) | C12—O4—C11—C10 | 176.37 (12) |
C1—C2—C6—C5 | −176.81 (14) | O3—C10—C11—O5 | 0.2 (2) |
C4—C5—C6—C2 | −2.2 (2) | O3—C10—C11—O4 | −178.06 (12) |
C4—C5—C6—C7 | 179.51 (15) | C11—O4—C12—C13 | 179.49 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O2i | 0.93 | 2.38 | 3.2913 (19) | 166 |
C5—H5A···O5ii | 0.93 | 2.55 | 3.373 (2) | 147 |
C10—H10B···O2i | 0.97 | 2.48 | 3.353 (2) | 149 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C13H12O5 |
Mr | 248.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 8.1435 (2), 16.4887 (4), 10.5506 (3) |
β (°) | 125.882 (2) |
V (Å3) | 1147.84 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.31 × 0.24 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.966, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12656, 3344, 2308 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.114, 1.04 |
No. of reflections | 3344 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.24 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O2i | 0.9300 | 2.3800 | 3.2913 (19) | 166.00 |
C5—H5A···O5ii | 0.9300 | 2.5500 | 3.373 (2) | 147.00 |
C10—H10B···O2i | 0.9700 | 2.4800 | 3.353 (2) | 149.00 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+2, −z. |
Acknowledgements
The authors thank Universiti Sains Malaysia (USM) for the RUC grant (Structure Determination of 50 kDa Outer Membrane Proteins from S. typhi by X-ray Protein Crystallography, No. 1001/PSKBP/8630013) and APEX DE2012 grant (No.1002/PFIZIK/910323). The authors also thank the CSIR and DST, Government of India, for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Coumarins are attractive fluorescent molecules due to their high emission quantum yield, photo stability and good solubility in common solvents. As a consequence of these features, coumarins are widely used as laser dyes (Xie et al., 2012; Liu et al., 2012). Herein, we report the crystal structure of ethyl 2-(2-oxo-2H-chromen-7-yloxy)acetate.
In the title molecule, Fig. 1, the mean plane of 2H-chromene ring system (O1/C1-C9, r.m.s deviation = 0.026 Å) forms a dihedral angle of 81.71 (6)° with the mean plane of ethyl 2-hydroxyacetate moiety (O1/N3/C9/C10, r.m.s deviation = 0.034 Å). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those observed in related structures (Arshad et al., 2010a, 2010b).
In the crystal structure (Fig. 2), molecules are linked via intermolecular C1–H1A···O2, C5–H5A···O5 and C10–H10B···O2 hydrogen bonds (Table 1) into zigzag layers parallel to the bc plane.