organic compounds
5-Methoxy-2-benzofuran-1(3H)-one
aInstituto de Química–UFU, Uberlândia, MG, Brazil, and bDepartamento de Química–UFV, Viçosa, MG, Brazil
*Correspondence e-mail: silvana@ufu.br, robsonr.teixeira@ufv.br
In the title compound, C9H8O3, the molecular skeleton is almost planar, with an r.m.s. deviation of 0.010 (2) Å. In the crystal, weak C—H⋯O hydrogen bonds connect the molecules into a two-dimensional network parallel to the ac plane.
Related literature
For the biological activity of isobenzofuran-1(3H)-one, see: Ma et al. (2012); Huang et al. (2012); Zhao et al. (2012); Arnone et al. (2002). For the synthesis, see: Zhang et al. (2009). For related structures, see: Sun et al. (2009); Mendenhall et al. (2003); Pereira et al. (2012).
Experimental
Crystal data
|
Data collection
|
Refinement
|
Data collection: COLLECT (Nonius, 2000); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536812044789/zs2239sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044789/zs2239Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044789/zs2239Isup3.cml
Starting materials were commercially available from Sigma Aldrich (USA) and were used without further purification. 5-Methoxyisobenzofuran-1(3H)-one was prepared as follows (Zhang et al., 2009). A tube of 40 ml equipped with a magnetic stir bar was charged with palladium(II) acetate (67.3 mg, 0.30 mmol), potassium bicarbonate (750 mg, 7.50 mmol), 4-methoxybenzoic acid (456 mg, 3.00 mmol) and dibromomethane (12 ml). The tube was sealed with a teflon cap and the reaction mixture was stirred at 140 °C for 18 h. After this time, the mixture was filtered through a pad of celite. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel δ 3.89 (s, 3H, H9), 5.25 (s, 2H, H8), 6.91 (d, 1H, J = 0.6 Hz, H6), 7.02 (dd, 1H, J = 8.4, 0.6 Hz, H4), 7.80 (d, 1H, J = 8.4 Hz, H3). 13C NMR (75 MHz, CDCl3): δ 56.1 (C9), 69.3 (C8), 106.2 (C6), 116.7 (C4), 118.2 (C2), 127.4 (C3), 149.6 (C7), 164.9 (C5), 171.1 (C1). HREIMS m/z (M+H+): Calcd for C9H8O3, 165.0552; found: 165.0606.
eluted with hexane: ethyl acetate (2:1 v/v) to afford 5-methoxyisobenzofuran-1(3H)-one in 33% yield (164 mg, 1.00 mmol). The crystals suitable for X-ray crystallographic analysis were obtained by slow evaporation from acetone solution at room temperature as a yellow solid; m.p. 113.4–114.7 °C. IR (selected bands, cm-1): 3032, 2922, 2852, 1736, 1601, 1489, 1452, 1361, 1333, 1261, 1146, 1036, 986, 773. 1H NMR (300 MHz, CDCl3):Hydrogen atoms were included in the
at calculated positions (C—H = 0.93–0.98 Å), with Uiso(H) = 1.2Ueq(C)(aromatic and methylene) or 1.5Ueq(C)(methyl), using a riding-model approximation.Data collection: COLLECT (Nonius, 2000); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C9H8O3 | Dx = 1.396 Mg m−3 |
Mr = 164.15 | Melting point = 386.4–386.7 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1819 (9) Å | Cell parameters from 1685 reflections |
b = 10.4285 (18) Å | θ = 3.2–26.4° |
c = 9.2965 (9) Å | µ = 0.11 mm−1 |
β = 99.962 (8)° | T = 293 K |
V = 781.26 (18) Å3 | Prism, yellow |
Z = 4 | 0.30 × 0.18 × 0.16 mm |
F(000) = 344 |
Enraf–Nonius KappaCCD diffractometer | 1101 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 X-ray source | Rint = 0.049 |
Graphite monochromator | θmax = 26.4°, θmin = 3.2° |
Detector resolution: 9 pixels mm-1 | h = 0→10 |
CCD rotation images, thick slices scans | k = 0→13 |
14100 measured reflections | l = −11→11 |
1587 independent reflections |
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) = 0.147 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0818P)2 + 0.0576P] where P = (Fo2 + 2Fc2)/3 |
1587 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
C9H8O3 | V = 781.26 (18) Å3 |
Mr = 164.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1819 (9) Å | µ = 0.11 mm−1 |
b = 10.4285 (18) Å | T = 293 K |
c = 9.2965 (9) Å | 0.30 × 0.18 × 0.16 mm |
β = 99.962 (8)° |
Enraf–Nonius KappaCCD diffractometer | 1101 reflections with I > 2σ(I) |
14100 measured reflections | Rint = 0.049 |
1587 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.16 e Å−3 |
1587 reflections | Δρmin = −0.13 e Å−3 |
109 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 | ||
O3 | 0.37522 (15) | −0.24147 (11) | 0.61307 (13) | 0.0781 (4) | |
O1 | 0.05757 (18) | 0.21719 (13) | 0.30246 (15) | 0.0903 (5) | |
C7 | 0.16866 (17) | 0.02605 (15) | 0.40441 (16) | 0.0577 (4) | |
C5 | 0.32245 (19) | −0.12294 (14) | 0.56458 (16) | 0.0591 (4) | |
C3 | 0.3507 (2) | 0.10279 (17) | 0.61788 (19) | 0.0691 (5) | |
H3 | 0.3971 | 0.17 | 0.6769 | 0.083* | |
C6 | 0.20840 (18) | −0.10008 (15) | 0.43826 (16) | 0.0578 (4) | |
H6 | 0.1609 | −0.1669 | 0.3791 | 0.069* | |
O2 | 0.1929 (2) | 0.35524 (13) | 0.46580 (19) | 0.1117 (6) | |
C4 | 0.39278 (19) | −0.02130 (16) | 0.65283 (17) | 0.0662 (4) | |
H4 | 0.4694 | −0.0388 | 0.7367 | 0.079* | |
C2 | 0.2366 (2) | 0.12584 (14) | 0.49162 (18) | 0.0631 (4) | |
C8 | 0.0518 (2) | 0.07991 (17) | 0.27798 (19) | 0.0757 (5) | |
H8A | 0.0874 | 0.0587 | 0.1866 | 0.091* | |
H8B | −0.0595 | 0.0471 | 0.2757 | 0.091* | |
C9 | 0.3066 (3) | −0.34911 (17) | 0.5294 (2) | 0.0956 (7) | |
H9A | 0.3534 | −0.4266 | 0.5748 | 0.143* | |
H9B | 0.3318 | −0.3432 | 0.4325 | 0.143* | |
H9C | 0.1884 | −0.3501 | 0.5244 | 0.143* | |
C1 | 0.1678 (3) | 0.24532 (17) | 0.4269 (2) | 0.0804 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0902 (8) | 0.0618 (7) | 0.0735 (7) | 0.0057 (6) | −0.0102 (6) | 0.0080 (5) |
O1 | 0.1053 (10) | 0.0749 (9) | 0.0911 (9) | 0.0277 (7) | 0.0182 (8) | 0.0207 (7) |
C7 | 0.0555 (8) | 0.0608 (9) | 0.0574 (8) | 0.0033 (6) | 0.0117 (6) | 0.0053 (6) |
C5 | 0.0602 (8) | 0.0573 (10) | 0.0576 (8) | 0.0000 (6) | 0.0046 (7) | 0.0042 (6) |
C3 | 0.0743 (10) | 0.0658 (10) | 0.0678 (10) | −0.0129 (8) | 0.0144 (8) | −0.0104 (8) |
C6 | 0.0582 (8) | 0.0576 (9) | 0.0555 (8) | −0.0025 (6) | 0.0038 (6) | −0.0010 (6) |
O2 | 0.1675 (16) | 0.0565 (9) | 0.1221 (12) | 0.0114 (8) | 0.0560 (12) | 0.0022 (7) |
C4 | 0.0636 (9) | 0.0742 (11) | 0.0575 (8) | −0.0091 (7) | 0.0008 (7) | −0.0032 (7) |
C2 | 0.0676 (9) | 0.0564 (10) | 0.0687 (10) | −0.0011 (6) | 0.0210 (8) | −0.0008 (7) |
C8 | 0.0778 (11) | 0.0768 (12) | 0.0706 (10) | 0.0153 (9) | 0.0074 (8) | 0.0127 (8) |
C9 | 0.1225 (17) | 0.0552 (11) | 0.0988 (14) | 0.0070 (10) | −0.0099 (12) | −0.0016 (9) |
C1 | 0.1003 (14) | 0.0612 (11) | 0.0877 (13) | 0.0118 (9) | 0.0391 (11) | 0.0066 (9) |
O3—C5 | 1.3603 (18) | C3—H3 | 0.93 |
O3—C9 | 1.425 (2) | C6—H6 | 0.93 |
O1—C1 | 1.370 (3) | O2—C1 | 1.209 (2) |
O1—C8 | 1.449 (2) | C4—H4 | 0.93 |
C7—C2 | 1.376 (2) | C2—C1 | 1.454 (2) |
C7—C6 | 1.378 (2) | C8—H8A | 0.97 |
C7—C8 | 1.491 (2) | C8—H8B | 0.97 |
C5—C6 | 1.388 (2) | C9—H9A | 0.96 |
C5—C4 | 1.402 (2) | C9—H9B | 0.96 |
C3—C4 | 1.364 (2) | C9—H9C | 0.96 |
C3—C2 | 1.388 (2) | ||
C5—O3—C9 | 117.55 (14) | C7—C2—C1 | 108.43 (16) |
C1—O1—C8 | 110.05 (13) | C3—C2—C1 | 130.82 (16) |
C2—C7—C6 | 122.13 (14) | O1—C8—C7 | 104.45 (14) |
C2—C7—C8 | 108.56 (14) | O1—C8—H8A | 110.9 |
C6—C7—C8 | 129.31 (14) | C7—C8—H8A | 110.9 |
O3—C5—C6 | 124.38 (14) | O1—C8—H8B | 110.9 |
O3—C5—C4 | 114.75 (14) | C7—C8—H8B | 110.9 |
C6—C5—C4 | 120.87 (15) | H8A—C8—H8B | 108.9 |
C4—C3—C2 | 118.08 (15) | O3—C9—H9A | 109.5 |
C4—C3—H3 | 121 | O3—C9—H9B | 109.5 |
C2—C3—H3 | 121 | H9A—C9—H9B | 109.5 |
C7—C6—C5 | 117.03 (14) | O3—C9—H9C | 109.5 |
C7—C6—H6 | 121.5 | H9A—C9—H9C | 109.5 |
C5—C6—H6 | 121.5 | H9B—C9—H9C | 109.5 |
C3—C4—C5 | 121.14 (15) | O2—C1—O1 | 120.56 (18) |
C3—C4—H4 | 119.4 | O2—C1—C2 | 131.0 (2) |
C5—C4—H4 | 119.4 | O1—C1—C2 | 108.49 (15) |
C7—C2—C3 | 120.75 (15) | ||
C9—O3—C5—C6 | −1.0 (2) | C8—C7—C2—C1 | 0.17 (17) |
C9—O3—C5—C4 | 179.11 (15) | C4—C3—C2—C7 | −0.2 (2) |
C2—C7—C6—C5 | −0.6 (2) | C4—C3—C2—C1 | 179.72 (15) |
C8—C7—C6—C5 | −179.90 (15) | C1—O1—C8—C7 | 1.42 (18) |
O3—C5—C6—C7 | −179.79 (13) | C2—C7—C8—O1 | −0.95 (16) |
C4—C5—C6—C7 | 0.1 (2) | C6—C7—C8—O1 | 178.38 (14) |
C2—C3—C4—C5 | −0.3 (2) | C8—O1—C1—O2 | 178.93 (16) |
O3—C5—C4—C3 | −179.70 (13) | C8—O1—C1—C2 | −1.36 (19) |
C6—C5—C4—C3 | 0.4 (2) | C7—C2—C1—O2 | −179.60 (18) |
C6—C7—C2—C3 | 0.7 (2) | C3—C2—C1—O2 | 0.5 (3) |
C8—C7—C2—C3 | −179.91 (15) | C7—C2—C1—O1 | 0.73 (19) |
C6—C7—C2—C1 | −179.22 (13) | C3—C2—C1—O1 | −179.17 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.93 | 2.54 | 3.419 (2) | 157 |
C8—H8A···O2ii | 0.97 | 2.52 | 3.372 (2) | 146 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H8O3 |
Mr | 164.15 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.1819 (9), 10.4285 (18), 9.2965 (9) |
β (°) | 99.962 (8) |
V (Å3) | 781.26 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Enraf–Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14100, 1587, 1101 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.147, 1.06 |
No. of reflections | 1587 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.13 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.93 | 2.54 | 3.419 (2) | 157 |
C8—H8A···O2ii | 0.97 | 2.52 | 3.372 (2) | 146 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2. |
Acknowledgements
The authors thank Professor Dr Javier Ellena of the IFSC, USP, Brazil, for the X-ray data collection. This work was supported financially by CAPES, CNPq, FUNARBE and FAPEMIG. This work is also a collaboration research project of members of the Rede Mineira de Química (RQ - MG) also supported by FAPEMIG.
References
Arnone, A., Assante, G., Nasini, G., Strada, S. & Vercesi, A. (2002). J. Nat. Prod. 65, 48–50. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Huang, X.-Z., Zhu, Y., Guan, X.-L., Tian, K., Guo, J.-M., Wang, H.-B. & Fu, G.-M. (2012). Molecules, 17, 4219–4224. Web of Science CrossRef CAS PubMed Google Scholar
Ma, F., Gao, Y., Qiao, H., Hu, X. & Chang, J. (2012). J. Thromb. Thrombolysis, 33, 64–73. Web of Science CrossRef PubMed Google Scholar
Mendenhall, G. D., Luck, R. L., Bohn, R. K. & Castejon, H. J. (2003). J. Mol. Struct. 645, 249–258. CSD CrossRef Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pereira, J. L., Teixeira, R. R., Guilardi, S. & Paixão, D. A. (2012). Acta Cryst. E68, o2995. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, M.-X., Li, X., Liu, W.-Y. & Xiao, K. (2009). Acta Cryst. E65, o2146. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, Y.-H., Shi, B.-F. & Yu, J.-Q. (2009). Angew. Chem. Int. Ed. 48, 6097–6100. Web of Science CrossRef CAS Google Scholar
Zhao, N., Ji, M.-X., Xu, L. & Ji, B.-S. (2012). Drug. Dev. Res. 73, 11–17. Web of Science CrossRef CAS Google Scholar
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.
Isobenzofuran-1(3H)-ones (phthalides) are a class of heterocyclic compounds which occur in several natural products and have been investigated for several biological properties, such as antiplatelet (Ma et al., 2012) and antioxidant activities (Huang et al., 2012), inhibition of glutamate induced cytotoxicity in PC12 cells (Zhao et al., 2012) and phytotoxicity (Arnone et al., 2002). The title compound, C9H8O3 was obtained as an intermediate in a synthetic route in the preparation of compounds endowed with phytotoxic activity and we report the crystal structure of it in a continuation of our work on the synthesis of phthalides (Pereira et al., 2012).
The title molecule (Fig. 1) is essentially planar with a mean deviation of 0.010 (2) Å from the least squares plane traced by 12 non-H atoms. All bond distances and angles agree well with those reported in the related compounds (Sun et al., 2009; Mendenhall et al., 2003; Pereira et al., 2012). In the crystal, molecules are linked via weak C6—H6···O1 hydrogen bonds (Table 1) forming chains along the ac plane. These layers are extended by C8—H8A···O2 hydrogen bonds into a two-dimensional network structure (Fig. 2).