organic compounds
H-chromen-4-yl)acetate
of methyl 2-(7-hydroxy-2-oxo-2aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, bDepartment of Chemistry, Karakoram International University, Gilgit, Pakistan, and cPCSIR Laboratories, Karachi, Pakistan
*Correspondence e-mail: dr.sammer.yousuf@gmail.com
In the title coumarin derivative, C12H10O5, the fused ring system is almost planar (r.m.s deviation = 0.016 Å). The Car—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.
CCDC reference: 1415274
1. 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 of a related compound, see: Subramanian et al. (1990).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: SMART (Bruker, 2000); cell 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).
Supporting information
CCDC reference: 1415274
https://doi.org/10.1107/S2056989015014061/hb7469sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014061/hb7469Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015014061/hb7469Isup3.cml
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.
H atoms on methyl, methylene and phenyl were positioned geometrically with C—H = 0.96 Å (CH3), 0.97 Å (CH2) and 0.93 Å (CH phenyl) and constrained to ride on their parent atoms with Uiso(H)=1.5Ueq(CH3) and 1.2Ueq(CH and CH2). The H atoms on the oxygen (O–H= 0.96 (2) Å) was located in difference Fourier map and refined isotropically.
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
features O3—H3···O1, and C7—H7A···O4 interactions to form (001) sheets (symmetry codes as in Table 2 and Fig. 2).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
of a related compound, see: Subramanian et al. (1990).Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).C12H10O5 | Dx = 1.477 Mg m−3 |
Mr = 234.20 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 4477 reflections |
a = 13.0780 (12) Å | θ = 2.4–28.3° |
b = 7.2354 (7) Å | µ = 0.12 mm−1 |
c = 22.262 (2) Å | T = 273 K |
V = 2106.5 (3) Å3 | Plate, yellow |
Z = 8 | 0.62 × 0.35 × 0.07 mm |
F(000) = 976 |
Bruker SMART APEX CCD diffractometer | 1958 independent reflections |
Radiation source: fine-focus sealed tube | 1669 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scan | θmax = 25.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −15→14 |
Tmin = 0.932, Tmax = 0.992 | k = −8→8 |
11536 measured reflections | l = −26→26 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0523P)2 + 0.6817P] where P = (Fo2 + 2Fc2)/3 |
1958 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C12H10O5 | V = 2106.5 (3) Å3 |
Mr = 234.20 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.0780 (12) Å | µ = 0.12 mm−1 |
b = 7.2354 (7) Å | T = 273 K |
c = 22.262 (2) Å | 0.62 × 0.35 × 0.07 mm |
Bruker SMART APEX CCD diffractometer | 1958 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1669 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.992 | Rint = 0.021 |
11536 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.28 e Å−3 |
1958 reflections | Δρmin = −0.19 e Å−3 |
158 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.42044 (8) | 0.1647 (2) | 0.43882 (5) | 0.0591 (4) | |
O2 | 0.58807 (7) | 0.16062 (15) | 0.44081 (4) | 0.0403 (3) | |
O3 | 0.94960 (9) | 0.1761 (2) | 0.45283 (6) | 0.0597 (4) | |
O4 | 0.64831 (11) | 0.23456 (17) | 0.22259 (5) | 0.0633 (4) | |
O5 | 0.64257 (9) | −0.01095 (16) | 0.16271 (5) | 0.0525 (3) | |
C1 | 0.50365 (12) | 0.0564 (2) | 0.35141 (6) | 0.0440 (4) | |
H1A | 0.4432 | 0.0350 | 0.3305 | 0.053* | |
C2 | 0.49845 (11) | 0.1288 (2) | 0.41145 (7) | 0.0432 (4) | |
C3 | 0.68119 (11) | 0.12502 (18) | 0.41444 (6) | 0.0338 (3) | |
C4 | 0.76625 (11) | 0.1663 (2) | 0.44865 (6) | 0.0365 (3) | |
H4A | 0.7595 | 0.2141 | 0.4872 | 0.044* | |
C5 | 0.86154 (11) | 0.1347 (2) | 0.42403 (6) | 0.0397 (4) | |
C6 | 0.87047 (12) | 0.0581 (2) | 0.36677 (7) | 0.0414 (4) | |
H6A | 0.9349 | 0.0341 | 0.3509 | 0.050* | |
C7 | 0.78507 (11) | 0.01819 (19) | 0.33383 (6) | 0.0376 (3) | |
H7A | 0.7923 | −0.0328 | 0.2957 | 0.045* | |
C8 | 0.68705 (11) | 0.05257 (18) | 0.35637 (6) | 0.0336 (3) | |
C9 | 0.59328 (12) | 0.01865 (19) | 0.32448 (6) | 0.0375 (3) | |
C10 | 0.59598 (12) | −0.0602 (2) | 0.26187 (6) | 0.0426 (4) | |
H10A | 0.6403 | −0.1677 | 0.2617 | 0.051* | |
H10B | 0.5278 | −0.1013 | 0.2512 | 0.051* | |
C11 | 0.63285 (11) | 0.0736 (2) | 0.21485 (6) | 0.0379 (3) | |
C12 | 0.67778 (15) | 0.1002 (3) | 0.11240 (8) | 0.0640 (5) | |
H12A | 0.6822 | 0.0244 | 0.0771 | 0.096* | |
H12B | 0.7440 | 0.1503 | 0.1214 | 0.096* | |
H12C | 0.6304 | 0.1993 | 0.1054 | 0.096* | |
H3 | 0.9369 (17) | 0.231 (3) | 0.4915 (11) | 0.091 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0375 (6) | 0.0935 (10) | 0.0463 (7) | 0.0056 (6) | 0.0053 (5) | −0.0091 (6) |
O2 | 0.0358 (6) | 0.0533 (6) | 0.0318 (5) | 0.0014 (5) | 0.0024 (4) | −0.0043 (4) |
O3 | 0.0379 (7) | 0.0923 (10) | 0.0489 (7) | −0.0035 (6) | −0.0062 (5) | −0.0117 (6) |
O4 | 0.1002 (11) | 0.0475 (7) | 0.0424 (6) | −0.0102 (7) | −0.0047 (6) | −0.0019 (5) |
O5 | 0.0647 (8) | 0.0582 (7) | 0.0345 (6) | −0.0042 (6) | 0.0086 (5) | −0.0083 (5) |
C1 | 0.0401 (9) | 0.0549 (9) | 0.0371 (8) | −0.0024 (7) | −0.0052 (6) | −0.0016 (7) |
C2 | 0.0390 (8) | 0.0527 (9) | 0.0379 (8) | 0.0009 (7) | 0.0006 (6) | 0.0009 (7) |
C3 | 0.0375 (8) | 0.0340 (7) | 0.0298 (7) | 0.0035 (6) | 0.0027 (6) | 0.0018 (5) |
C4 | 0.0420 (9) | 0.0400 (7) | 0.0276 (6) | 0.0000 (6) | −0.0010 (6) | −0.0025 (5) |
C5 | 0.0387 (8) | 0.0436 (8) | 0.0368 (8) | −0.0002 (6) | −0.0041 (6) | 0.0017 (6) |
C6 | 0.0391 (8) | 0.0451 (8) | 0.0401 (8) | 0.0053 (7) | 0.0056 (6) | −0.0003 (6) |
C7 | 0.0455 (9) | 0.0360 (7) | 0.0314 (7) | 0.0038 (6) | 0.0032 (6) | −0.0024 (6) |
C8 | 0.0399 (8) | 0.0310 (7) | 0.0300 (7) | 0.0009 (6) | −0.0003 (6) | −0.0001 (5) |
C9 | 0.0451 (9) | 0.0360 (7) | 0.0314 (7) | −0.0023 (6) | −0.0024 (6) | 0.0007 (6) |
C10 | 0.0486 (9) | 0.0446 (8) | 0.0345 (8) | −0.0049 (7) | −0.0046 (6) | −0.0055 (6) |
C11 | 0.0346 (8) | 0.0464 (8) | 0.0327 (7) | 0.0005 (6) | −0.0059 (6) | −0.0049 (6) |
C12 | 0.0679 (12) | 0.0845 (14) | 0.0394 (9) | −0.0071 (10) | 0.0132 (8) | 0.0016 (9) |
O1—C2 | 1.2165 (18) | C4—H4A | 0.9300 |
O2—C2 | 1.3617 (18) | C5—C6 | 1.395 (2) |
O2—C3 | 1.3764 (17) | C6—C7 | 1.367 (2) |
O3—C5 | 1.3515 (18) | C6—H6A | 0.9300 |
O3—H3 | 0.96 (2) | C7—C8 | 1.399 (2) |
O4—C11 | 1.1944 (19) | C7—H7A | 0.9300 |
O5—C11 | 1.3183 (17) | C8—C9 | 1.438 (2) |
O5—C12 | 1.454 (2) | C9—C10 | 1.5064 (19) |
C1—C9 | 1.345 (2) | C10—C11 | 1.505 (2) |
C1—C2 | 1.437 (2) | C10—H10A | 0.9700 |
C1—H1A | 0.9300 | C10—H10B | 0.9700 |
C3—C4 | 1.381 (2) | C12—H12A | 0.9600 |
C3—C8 | 1.3971 (19) | C12—H12B | 0.9600 |
C4—C5 | 1.380 (2) | C12—H12C | 0.9600 |
C2—O2—C3 | 121.67 (11) | C8—C7—H7A | 119.4 |
C5—O3—H3 | 111.6 (14) | C3—C8—C7 | 116.67 (12) |
C11—O5—C12 | 116.88 (13) | C3—C8—C9 | 118.30 (13) |
C9—C1—C2 | 122.00 (13) | C7—C8—C9 | 125.03 (12) |
C9—C1—H1A | 119.0 | C1—C9—C8 | 119.25 (13) |
C2—C1—H1A | 119.0 | C1—C9—C10 | 120.65 (13) |
O1—C2—O2 | 116.43 (13) | C8—C9—C10 | 120.09 (13) |
O1—C2—C1 | 125.70 (14) | C11—C10—C9 | 114.04 (12) |
O2—C2—C1 | 117.87 (13) | C11—C10—H10A | 108.7 |
O2—C3—C4 | 115.91 (12) | C9—C10—H10A | 108.7 |
O2—C3—C8 | 120.90 (12) | C11—C10—H10B | 108.7 |
C4—C3—C8 | 123.19 (13) | C9—C10—H10B | 108.7 |
C5—C4—C3 | 118.19 (13) | H10A—C10—H10B | 107.6 |
C5—C4—H4A | 120.9 | O4—C11—O5 | 124.29 (14) |
C3—C4—H4A | 120.9 | O4—C11—C10 | 125.51 (13) |
O3—C5—C4 | 122.97 (13) | O5—C11—C10 | 110.16 (13) |
O3—C5—C6 | 116.74 (14) | O5—C12—H12A | 109.5 |
C4—C5—C6 | 120.28 (13) | O5—C12—H12B | 109.5 |
C7—C6—C5 | 120.38 (14) | H12A—C12—H12B | 109.5 |
C7—C6—H6A | 119.8 | O5—C12—H12C | 109.5 |
C5—C6—H6A | 119.8 | H12A—C12—H12C | 109.5 |
C6—C7—C8 | 121.25 (13) | H12B—C12—H12C | 109.5 |
C6—C7—H7A | 119.4 | ||
C3—O2—C2—O1 | 179.92 (13) | C4—C3—C8—C9 | −178.69 (13) |
C3—O2—C2—C1 | −0.1 (2) | C6—C7—C8—C3 | −1.5 (2) |
C9—C1—C2—O1 | −179.37 (16) | C6—C7—C8—C9 | 178.62 (13) |
C9—C1—C2—O2 | 0.7 (2) | C2—C1—C9—C8 | −0.4 (2) |
C2—O2—C3—C4 | 178.95 (12) | C2—C1—C9—C10 | 178.94 (14) |
C2—O2—C3—C8 | −0.7 (2) | C3—C8—C9—C1 | −0.4 (2) |
O2—C3—C4—C5 | −179.42 (12) | C7—C8—C9—C1 | 179.48 (14) |
C8—C3—C4—C5 | 0.2 (2) | C3—C8—C9—C10 | −179.72 (13) |
C3—C4—C5—O3 | 177.69 (14) | C7—C8—C9—C10 | 0.1 (2) |
C3—C4—C5—C6 | −1.8 (2) | C1—C9—C10—C11 | 108.63 (16) |
O3—C5—C6—C7 | −177.79 (14) | C8—C9—C10—C11 | −72.02 (18) |
C4—C5—C6—C7 | 1.8 (2) | C12—O5—C11—O4 | 2.1 (2) |
C5—C6—C7—C8 | 0.0 (2) | C12—O5—C11—C10 | −179.98 (14) |
O2—C3—C8—C7 | −178.95 (12) | C9—C10—C11—O4 | −8.4 (2) |
C4—C3—C8—C7 | 1.5 (2) | C9—C10—C11—O5 | 173.79 (13) |
O2—C3—C8—C9 | 0.91 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.96 (2) | 1.74 (2) | 2.7002 (17) | 177 (2) |
C7—H7A···O4ii | 0.93 | 2.47 | 3.3320 (18) | 155 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+3/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.96 (2) | 1.74 (2) | 2.7002 (17) | 177 (2) |
C7—H7A···O4ii | 0.93 | 2.47 | 3.3320 (18) | 155 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+3/2, y−1/2, z. |
Acknowledgements
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.
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.
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).