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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3066.
Published online 2010 November 6. doi:  10.1107/S1600536810044417
PMCID: PMC3011800

1,2,4-Trimeth­oxy­dibenzo[b,d]furan-3-ol

Abstract

The title compound, C15H14O5, is a natural product, isolated from Sorbus lanata Syn. Pyrus lanata (D. Don) found in Pakistan. The compound is composed of three spiro-fused rings. The dihedral angle between the mean planes of the benzene rings is 4.81 (13)°. The meth­oxy groups are oriented at dihedral angles of 74.44 (14), 83.0 (2) and 66.3 (2)° with respect to the planes of the benzene rings to which they are attached. The mol­ecule is consolidated by three intra­molecular O—H(...)O and C—H(...)O hydrogen bonds. In the crystal, mol­ecules are linked by inter­molecular O—H(...)O hydrogen bonds, forming infinite chains along the b axis.

Related literature

The title compound was previously reported from a perry pear tree Pyrus communis, see: Kemp et al. (1983 [triangle]). For the structure of dibenzofuran, see: Dideberg et al. (1972 [triangle]).

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Object name is e-66-o3066-scheme1.jpg

Experimental

Crystal data

  • C15H14O5
  • M r = 274.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3066-efi1.jpg
  • a = 10.422 (3) Å
  • b = 9.075 (3) Å
  • c = 15.007 (4) Å
  • β = 106.378 (7)°
  • V = 1361.8 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 K
  • 0.28 × 0.13 × 0.09 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.972, T max = 0.991
  • 7822 measured reflections
  • 2534 independent reflections
  • 1659 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.134
  • S = 1.04
  • 2534 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044417/pv2347sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044417/pv2347Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

LA acknowledges the financial support of the Higher Education Commission (HEC) of Pakistan, through the indigenous PhD scheme.

supplementary crystallographic information

Comment

Sorbus lanata (D. Don) Schauer is an important medicinal plant, commonly found in Pakistan, Nepal and India. The title compound (Fig. 1) is a dibenzofuran derivative which has been previously reported from perry pear tree Pyrus communis (Kemp et al., 1983). It is composed of three spiro fused rings A (C1–C5/C12), B (O1/C5/C6/C11/C12), and C (C6–C11). The dihedral angles between the mean-planes of the rings A/B, B/C and A/C are 2.62 (14), 2.27 (16) and 4.81 (13) °, respectively, reflecting significant deviation from planarity of the fused ring system. The methoxy groups O2/C15, O4/C14 and O/C13 are oriented with respect to the plane of the phenyl ring (C1–C5/C12) at angles 74.44 (14), 82.95 (19) and 66.3 (2)°, respectively. The molecular structure is stabilized by three intramolecular hydrogen bonds O3—H3A···O4, C13—H13B···O4 and C15—H15B···O3. In the crystal structure, the molecules are linked by the O3—H3A···O2 intermolecular hydrogen bonds to form infinite zigzag chains parallel to the b-axis (Fig. 2 and Table 1).

The crystal structure of dibenzofuran has been reported (Dideberg et al., (1972).

Experimental

The dried and crushed wood of Sorbus lanata (12 kg) was subjected to cold extraction with methanol. The methanolic extract (750 g) was suspended in water and successively partitioned with hexane, ethylacetate and butanol. The ethylacetate fraction (180 g) was further defatted with hexane several times. The defatted ethylacetate fraction (150 g) was subjected to column chromatography on silica gel [Merck Silica gel60 (0.063-0.200 mm), 9 x 50 cm]. The column was first eluted with hexane-ethylacetate (100:0 → 0:100) and then with dichloromethane-methanol (98:2 → 90:10) as solvent systems. A total of 11 fractions, LS-4 (1 g), LS-5 (2.7 g), LS-11 (15 g), LS-18 (27 g), LS-25 (45 g), LS-46 (20 g),LS-60 (37 g), LS-62 (40 g), LS-73 (35 g), LS-81 (10 g) and LS-89 (8 g) were obtained according to their TLC profiles. Fraction LS-11 contained a white solid insoluble in methanol. The solid material was filtered and the filtrate was concentrated and further subjected to column chromatography on silica gel [Merck Silica gel 60 (0.063-0.200 mm), 4 x 30 cm] using hexane-dichloromethane (100:0 → 0:100) as solvent system and as a result 10 fractions LS-1102, LS-1105, LS-1111, LS-1126, LS-1158, LS-1167, LS-1177, LS-1187, LS-1189 and LS-1199 were obtained. Fraction LS-1126 contained colourless crystals of various sizes and were separated from the solution by decantation. The crystals were washed with hexane several times. To obtain pure and larger crystals, these crystals were re-grown in a mixture of hexane-acetone (4:1) and afford colorles needles (80 mg).

Refinement

H atoms on the C of methyl, methine and oxygen were positioned geometrically with C—H = 0.96, 0.93 and 0.82 Å, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(CH) and 1.5Ueq(CH3 and OH).

Figures

Fig. 1.
The molecular structure of the title molecule with displacement ellipsoids drawn at 50% probability level. The dashed lines indicate intramolecular hydrogen bonds.
Fig. 2.
A packing diagram of the title compound showing hydrogen bonds as dashed lines; the hydrogen atoms not involved in bonding have been excluded for clarity.

Crystal data

C15H14O5F(000) = 576
Mr = 274.26Dx = 1.338 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1214 reflections
a = 10.422 (3) Åθ = 2.1–25.5°
b = 9.075 (3) ŵ = 0.10 mm1
c = 15.007 (4) ÅT = 298 K
β = 106.378 (7)°Plate, colorless
V = 1361.8 (6) Å30.28 × 0.13 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2534 independent reflections
Radiation source: fine-focus sealed tube1659 reflections with I > 2σ(I)
graphiteRint = 0.038
ω scansθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −12→8
Tmin = 0.972, Tmax = 0.991k = −10→10
7822 measured reflectionsl = −15→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0588P)2 + 0.185P] where P = (Fo2 + 2Fc2)/3
2534 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.23 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)

xyzUiso*/Ueq
O1−0.04296 (15)0.68527 (16)0.05209 (11)0.0506 (4)
O20.21877 (14)0.79638 (16)0.14577 (10)0.0486 (4)
O30.22888 (14)1.06736 (17)0.23002 (11)0.0583 (5)
H3A0.22021.13460.26440.087*
O40.00148 (15)1.21507 (17)0.23400 (11)0.0547 (5)
O5−0.25302 (15)1.08945 (18)0.14506 (11)0.0574 (5)
C10−0.3847 (2)0.7966 (3)0.01571 (18)0.0567 (7)
H1A−0.43120.87380.03310.068*
C9−0.4521 (3)0.6846 (3)−0.04119 (19)0.0657 (8)
H2A−0.54500.6865−0.06180.079*
C8−0.3837 (3)0.5697 (3)−0.06806 (19)0.0673 (8)
H3B−0.43180.4967−0.10690.081*
C7−0.2460 (3)0.5609 (3)−0.03862 (18)0.0599 (7)
H4A−0.19970.4836−0.05600.072*
C6−0.1813 (2)0.6732 (2)0.01794 (16)0.0482 (6)
C5−0.0212 (2)0.8160 (2)0.10136 (15)0.0439 (6)
C40.1037 (2)0.8724 (2)0.14437 (15)0.0431 (5)
C30.1077 (2)1.0079 (2)0.18832 (15)0.0455 (6)
C2−0.0113 (2)1.0811 (2)0.18854 (15)0.0442 (5)
C1−0.1354 (2)1.0187 (2)0.14702 (15)0.0449 (6)
C12−0.1400 (2)0.8844 (2)0.10160 (15)0.0427 (5)
C11−0.2457 (2)0.7908 (2)0.04626 (16)0.0463 (6)
C13−0.2808 (3)1.1053 (5)0.2305 (2)0.1109 (13)
H13A−0.36461.15550.22140.166*
H13B−0.21101.16140.27200.166*
H13C−0.28601.00970.25670.166*
C14−0.0108 (3)1.3386 (3)0.1722 (2)0.0771 (9)
H14A−0.00171.42850.20710.116*
H14B−0.09691.33630.12700.116*
H14C0.05791.33360.14110.116*
C150.2906 (3)0.8538 (3)0.08552 (18)0.0655 (8)
H15A0.36880.79490.09050.098*
H15B0.31680.95360.10280.098*
H15C0.23450.85170.02260.098*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0472 (10)0.0450 (9)0.0594 (10)0.0019 (7)0.0146 (8)−0.0062 (7)
O20.0421 (9)0.0491 (9)0.0562 (10)0.0098 (7)0.0166 (7)0.0073 (7)
O30.0439 (10)0.0597 (10)0.0667 (12)−0.0015 (8)0.0083 (8)−0.0159 (8)
O40.0566 (11)0.0511 (10)0.0555 (10)0.0012 (8)0.0147 (8)−0.0124 (8)
O50.0458 (10)0.0680 (11)0.0609 (11)0.0133 (8)0.0194 (8)−0.0070 (8)
C100.0462 (15)0.0612 (16)0.0641 (17)−0.0034 (12)0.0181 (12)0.0032 (13)
C90.0508 (16)0.0769 (19)0.0667 (18)−0.0146 (14)0.0122 (13)−0.0021 (15)
C80.0666 (19)0.0657 (17)0.0675 (18)−0.0206 (14)0.0153 (14)−0.0127 (14)
C70.0606 (18)0.0550 (15)0.0641 (17)−0.0074 (12)0.0175 (13)−0.0097 (13)
C60.0434 (14)0.0497 (13)0.0511 (14)−0.0022 (10)0.0128 (11)0.0003 (11)
C50.0490 (14)0.0375 (12)0.0450 (13)0.0036 (10)0.0131 (10)0.0008 (10)
C40.0400 (13)0.0441 (12)0.0444 (13)0.0065 (10)0.0107 (10)0.0045 (10)
C30.0417 (14)0.0490 (13)0.0436 (13)0.0002 (10)0.0083 (10)0.0009 (10)
C20.0464 (14)0.0445 (12)0.0406 (13)0.0019 (10)0.0105 (10)−0.0040 (10)
C10.0453 (14)0.0469 (13)0.0436 (13)0.0077 (10)0.0146 (10)0.0028 (10)
C120.0412 (13)0.0440 (12)0.0424 (13)0.0020 (10)0.0112 (10)0.0029 (10)
C110.0454 (14)0.0486 (13)0.0460 (13)−0.0016 (10)0.0148 (10)0.0041 (11)
C130.097 (3)0.164 (4)0.093 (3)0.034 (2)0.062 (2)0.012 (2)
C140.096 (2)0.0492 (16)0.086 (2)0.0019 (14)0.0267 (17)−0.0016 (15)
C150.0640 (18)0.0750 (18)0.0657 (18)0.0167 (14)0.0316 (14)0.0152 (15)

Geometric parameters (Å, °)

O1—C51.383 (2)C7—H4A0.9300
O1—C61.391 (3)C6—C111.390 (3)
O2—C41.379 (3)C5—C41.378 (3)
O2—C151.425 (3)C5—C121.386 (3)
O3—C31.353 (2)C4—C31.390 (3)
O3—H3A0.8200C3—C21.408 (3)
O4—C21.382 (2)C2—C11.389 (3)
O4—C141.438 (3)C1—C121.391 (3)
O5—C11.377 (3)C12—C111.451 (3)
O5—C131.399 (3)C13—H13A0.9600
C10—C91.385 (3)C13—H13B0.9600
C10—C111.391 (3)C13—H13C0.9600
C10—H1A0.9300C14—H14A0.9600
C9—C81.385 (4)C14—H14B0.9600
C9—H2A0.9300C14—H14C0.9600
C8—C71.380 (4)C15—H15A0.9600
C8—H3B0.9300C15—H15B0.9600
C7—C61.375 (3)C15—H15C0.9600
C5—O1—C6105.14 (16)O4—C2—C3117.00 (19)
C4—O2—C15114.67 (17)C1—C2—C3121.1 (2)
C3—O3—H3A109.5O5—C1—C2122.0 (2)
C2—O4—C14112.89 (18)O5—C1—C12119.4 (2)
C1—O5—C13116.2 (2)C2—C1—C12118.5 (2)
C9—C10—C11118.4 (2)C5—C12—C1119.1 (2)
C9—C10—H1A120.8C5—C12—C11105.73 (19)
C11—C10—H1A120.8C1—C12—C11135.1 (2)
C10—C9—C8121.3 (2)C6—C11—C10118.4 (2)
C10—C9—H2A119.4C6—C11—C12105.7 (2)
C8—C9—H2A119.4C10—C11—C12135.9 (2)
C7—C8—C9121.6 (2)O5—C13—H13A109.5
C7—C8—H3B119.2O5—C13—H13B109.5
C9—C8—H3B119.2H13A—C13—H13B109.5
C6—C7—C8116.1 (2)O5—C13—H13C109.5
C6—C7—H4A121.9H13A—C13—H13C109.5
C8—C7—H4A121.9H13B—C13—H13C109.5
C7—C6—C11124.2 (2)O4—C14—H14A109.5
C7—C6—O1124.3 (2)O4—C14—H14B109.5
C11—C6—O1111.48 (19)H14A—C14—H14B109.5
C4—C5—O1124.04 (19)O4—C14—H14C109.5
C4—C5—C12124.0 (2)H14A—C14—H14C109.5
O1—C5—C12111.94 (19)H14B—C14—H14C109.5
C5—C4—O2121.6 (2)O2—C15—H15A109.5
C5—C4—C3116.7 (2)O2—C15—H15B109.5
O2—C4—C3121.7 (2)H15A—C15—H15B109.5
O3—C3—C4118.1 (2)O2—C15—H15C109.5
O3—C3—C2121.2 (2)H15A—C15—H15C109.5
C4—C3—C2120.7 (2)H15B—C15—H15C109.5
O4—C2—C1121.91 (19)
C11—C10—C9—C8−0.5 (4)C13—O5—C1—C2−68.4 (3)
C10—C9—C8—C70.7 (4)C13—O5—C1—C12115.4 (3)
C9—C8—C7—C6−0.6 (4)O4—C2—C1—O53.0 (3)
C8—C7—C6—C110.3 (4)C3—C2—C1—O5−178.87 (19)
C8—C7—C6—O1−178.0 (2)O4—C2—C1—C12179.22 (19)
C5—O1—C6—C7177.2 (2)C3—C2—C1—C12−2.6 (3)
C5—O1—C6—C11−1.3 (2)C4—C5—C12—C10.5 (3)
C6—O1—C5—C4−177.8 (2)O1—C5—C12—C1−178.95 (18)
C6—O1—C5—C121.6 (2)C4—C5—C12—C11178.1 (2)
O1—C5—C4—O2−3.8 (3)O1—C5—C12—C11−1.3 (2)
C12—C5—C4—O2176.8 (2)O5—C1—C12—C5178.0 (2)
O1—C5—C4—C3177.83 (19)C2—C1—C12—C51.6 (3)
C12—C5—C4—C3−1.5 (3)O5—C1—C12—C111.2 (4)
C15—O2—C4—C5106.2 (2)C2—C1—C12—C11−175.2 (2)
C15—O2—C4—C3−75.5 (3)C7—C6—C11—C10−0.1 (4)
C5—C4—C3—O3−179.0 (2)O1—C6—C11—C10178.4 (2)
O2—C4—C3—O32.6 (3)C7—C6—C11—C12−178.0 (2)
C5—C4—C3—C20.5 (3)O1—C6—C11—C120.5 (2)
O2—C4—C3—C2−177.87 (19)C9—C10—C11—C60.2 (3)
C14—O4—C2—C1−84.2 (3)C9—C10—C11—C12177.3 (2)
C14—O4—C2—C397.6 (2)C5—C12—C11—C60.5 (2)
O3—C3—C2—O4−0.7 (3)C1—C12—C11—C6177.5 (2)
C4—C3—C2—O4179.8 (2)C5—C12—C11—C10−176.9 (3)
O3—C3—C2—C1−178.9 (2)C1—C12—C11—C100.2 (5)
C4—C3—C2—C11.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O40.822.322.738 (2)113
C13—H13B···O40.962.493.092 (4)121
C15—H15B···O30.962.563.108 (3)117
O3—H3A···O2i0.821.972.742 (2)156

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2347).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dideberg, O., Dupont, L. & André, J. M. (1972). Acta Cryst B28, 1002–1007.
  • Kemp, M. S., Berden, R. S. & Leoffler, R. S. T. (1983). J. Chem. Soc. Perkin Trans. 1, pp. 2267–2272.
  • Nardelli, M. (1995). J. Appl. Cryst.28, 659.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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