Abstract
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
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
Δρmax = 0.28 e Å−3
Δρmin = −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
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014061/hb7469Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015014061/hb7469Isup3.cml
. DOI: 10.1107/S2056989015014061/hb7469fig1.tif
The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.
. 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 |
Symmetry codes: (i) ; (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.
S3. Refinement
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.
Figures
Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.
Fig. 2.
The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.
Crystal data
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 |
Data collection
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
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 |
Special details
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)
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)* |
Atomic displacement parameters (Å2)
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) |
Geometric parameters (Å, º)
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) |
Hydrogen-bond geometry (Å, º)
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.
Footnotes
Supporting information for this paper is available from the IUCr electronic archives (Reference: HB7469).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014061/hb7469sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014061/hb7469Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015014061/hb7469Isup3.cml
. DOI: 10.1107/S2056989015014061/hb7469fig1.tif
The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.
. 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