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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 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 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).graphic file with name e-71-0o677-scheme1.jpg

Experimental  

Crystal data  

  • C12H10O5

  • M r = 234.20

  • Orthorhombic, Inline graphic

  • 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

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)

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) Inline graphic; (ii) Inline graphic.

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.

Fig. 1.

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

Fig. 2.

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 m3
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 mm1
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 Å3
0 restraints Δρmin = −0.19 e Å3

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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  2. Ahmad, H. B., Malana, M. A., Rama, N. H., Ilyas, S., Yousuf, M. & Khan, K. M. (2008). J. Chem. Soc. Pakistan, 30, 834–844.
  3. Basanagouda, M., Kulkarni, M. V., Sharma, D., Gupta, V. K., Pranesha, Sandhyarani, P. & Rasal, V. P. (2009). J. Chem. Sci. 121, 485–495.
  4. Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
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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

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)

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


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