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The title compound, C14H10O5, was isolated from Senecio cannabifolius Less var. integrifolius aqueous extract. The structure was elucidated on the basis of spectroscopic data, including MS, 1H NMR and 13C NMR, and the relative configuration was confirmed by X-ray crystallographic analysis. The benzofuran ring is almost coplanar with the furan ring [dihedral angle = 10.47 (15)°]. A chain is formed through supra­molecular R22(10) synthons and three-centre hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047381/rk2041sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047381/rk2041Isup2.hkl
Contains datablock I

CCDC reference: 667384

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.064
  • wR factor = 0.164
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H3 .. H3 .. 1.27 Ang.
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.138 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.14 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.15
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (E)-5-hydroxy-3-((5-(hydroxymethyl)furan-2-yl)methylene) benzofuran-2(3H)-one, cannabifolactone was first obtained from Senecio cannabifolius by Wu et al. (2002). Its structure was identified by NMR spectroscopy. But the (Z) or (E) configuration of it was not determined in the literature. We have now isolated the compound from Senecio cannabifolius Less var integrifolius. Here, the molecular structure of (I) is reported (Fig. 1).

The molecule contains a benzyl ring, a fused five-membered lactone ring and a furan ring connected by a congjugated double bonds. Three above rings are almost planar.

On Fig. 2, two molecules at the invert position are linked via supramolecular synthons R22(10) including paired hydrogen bonds C9—H9···O1ii and C9ii—H9ii···O1 (symmetry code ii: 2 - x, 2 - y, 1 - z). The dimer interacted with the other one through tricentered hydrogen bonds including O3—H3···O3i and O5—H5A···O3i (symmetry code i: x, 2 - y, z). A chain was formed through altering of the supramolecular synthons R22(10) and tricentered hydrogen bonds.

Related literature top

The title compound was first isolated by Wu et al. (2002).

Experimental top

Air-dried aerial parts (35 kg) of Senecio cannabifolius Less var integrifolius were powdered and extracted three times with H2O. The extract was concentrated and acidified with 36% HCl to pH 3 and extracted with EtOAc three times. The EtOAc fraction was chromatographed on silica gel column, using a gradient mixture of CHCl3–CH3OH as eluant. The CHCl3–CH3OH (100:3 v/v) fraction, subjected to repeated chromatography over silica gel and Sephadex LH–20 columns, gave compound (I) (yield 0.000057%, m.p. 497–499 K).

Yellow–orange needles crystals suitable for X–ray studies were grown from ethylacetate–methanol by slow evaporation at room temperature. ESI-MS: m/z 259 [M+H]+; 1H NMR (DMSO, 500 MHz, p.p.m.): 4.70(2H, s, H-15), 5.70(1H, s, 15-OH), 6.65(1H, d, J = 3.4 Hz, H-13), 6.79(1H, dd, J = 2.6, 8.6 Hz, H-7), 7.04 (1H, d, J = 8.6 Hz, H-8), 7.31 (1H, d, J = 3.4 Hz, H-12), 7.41 (1H, s, H-10), 7.80 (1H, d, J = 2.6 Hz, H-5), 9.50(1H, s, 6-OH). 13C NMR (CDCl3, 125 MHz, p.p.m.): 57.8 (C-15), 111.8 (C-8), 112.3 (C-13), 112.6 (C-5), 118.2 (C-3), 118.3 (C-7), 124.0 (C-4), 124.0 (C-10), 124.3 (C-12), 148.9 (C-9), 152.1 (C-11), 155.0 (C-6), 161.7 (C-14), 172.3 (C-2).

Refinement top

H atoms were positioned geometrically, with O—H = 0.82 Å, C—H = 0.98 Å (methine H), 0.97 Å (methylene H), 0.96 Å (methyl H) and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for methine and methylene H and x = 1.5 for all other H.

Structure description top

The title compound, (E)-5-hydroxy-3-((5-(hydroxymethyl)furan-2-yl)methylene) benzofuran-2(3H)-one, cannabifolactone was first obtained from Senecio cannabifolius by Wu et al. (2002). Its structure was identified by NMR spectroscopy. But the (Z) or (E) configuration of it was not determined in the literature. We have now isolated the compound from Senecio cannabifolius Less var integrifolius. Here, the molecular structure of (I) is reported (Fig. 1).

The molecule contains a benzyl ring, a fused five-membered lactone ring and a furan ring connected by a congjugated double bonds. Three above rings are almost planar.

On Fig. 2, two molecules at the invert position are linked via supramolecular synthons R22(10) including paired hydrogen bonds C9—H9···O1ii and C9ii—H9ii···O1 (symmetry code ii: 2 - x, 2 - y, 1 - z). The dimer interacted with the other one through tricentered hydrogen bonds including O3—H3···O3i and O5—H5A···O3i (symmetry code i: x, 2 - y, z). A chain was formed through altering of the supramolecular synthons R22(10) and tricentered hydrogen bonds.

The title compound was first isolated by Wu et al. (2002).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. A drawing of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a spheres with arbitrary radius.
[Figure 2] Fig. 2. A packing diagram of (I) showing the formation of a chain via hydrogen bonds.
(3E)-5-Hydroxy-3-[5-(hydroxymethyl)furan-2-ylmethylene]-1-benzofuran-2(3H)-one top
Crystal data top
C14H10O5Z = 2
Mr = 258.22F(000) = 268
Triclinic, P1Dx = 1.487 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.544 (3) ÅCell parameters from 993 reflections
b = 8.974 (2) Åθ = 4.7–48.1°
c = 9.291 (3) ŵ = 0.11 mm1
α = 107.509 (7)°T = 293 K
β = 97.844 (6)°Needle, yellow
γ = 100.735 (7)°0.48 × 0.24 × 0.15 mm
V = 576.8 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2273 independent reflections
Radiation source: fine–focus sealed tube1496 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.138
φ and ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 99
Tmin = 0.968, Tmax = 0.984k = 116
3184 measured reflectionsl = 1011
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0752P)2]
where P = (Fo2 + 2Fc2)/3
2235 reflections(Δ/σ)max = 0.040
174 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
C14H10O5γ = 100.735 (7)°
Mr = 258.22V = 576.8 (3) Å3
Triclinic, P1Z = 2
a = 7.544 (3) ÅMo Kα radiation
b = 8.974 (2) ŵ = 0.11 mm1
c = 9.291 (3) ÅT = 293 K
α = 107.509 (7)°0.48 × 0.24 × 0.15 mm
β = 97.844 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2273 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1496 reflections with I > 2σ(I)
Tmin = 0.968, Tmax = 0.984Rint = 0.138
3184 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.164H-atom parameters constrained
S = 0.97Δρmax = 0.33 e Å3
2235 reflectionsΔρmin = 0.42 e Å3
174 parameters
Special details top

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 > 2σ(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) top
xyzUiso*/Ueq
O11.0229 (2)1.1646 (3)0.3963 (2)0.0690 (7)
O20.8629 (2)1.2740 (2)0.2522 (2)0.0562 (5)
O30.1254 (2)1.1304 (2)0.0008 (2)0.0559 (5)
H30.07791.03850.00450.084*
O40.3470 (2)0.82265 (19)0.29896 (18)0.0419 (5)
O50.0173 (3)0.6380 (2)0.0900 (2)0.0612 (6)
H5A0.02370.72030.07050.092*
C10.8761 (3)1.1658 (3)0.3283 (3)0.0484 (7)
C20.6891 (3)1.0621 (3)0.3073 (3)0.0400 (6)
C30.5654 (3)1.1226 (3)0.2156 (3)0.0374 (6)
C40.6769 (3)1.2464 (3)0.1850 (3)0.0433 (6)
C50.6139 (3)1.3299 (3)0.0957 (3)0.0520 (7)
H50.69331.41050.07580.062*
C60.4262 (3)1.2883 (3)0.0363 (3)0.0475 (7)
H60.37741.34240.02450.057*
C70.3106 (3)1.1680 (3)0.0659 (3)0.0397 (6)
C80.3757 (3)1.0833 (3)0.1552 (3)0.0390 (6)
H80.29591.00270.17460.047*
C90.6754 (3)0.9416 (3)0.3666 (3)0.0431 (6)
H90.78620.93790.42150.052*
C100.5221 (3)0.8192 (3)0.3603 (3)0.0428 (6)
C110.5126 (4)0.6904 (4)0.4072 (3)0.0577 (8)
H110.61120.66190.45510.069*
C120.3258 (4)0.6066 (3)0.3705 (3)0.0588 (8)
H120.27830.51120.38700.071*
C130.2293 (3)0.6913 (3)0.3069 (3)0.0436 (6)
C140.0307 (3)0.6752 (3)0.2518 (3)0.0524 (7)
H14A0.04090.59110.28040.063*
H14B0.00090.77520.30260.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0256 (10)0.0971 (18)0.0869 (15)0.0081 (10)0.0017 (9)0.0446 (13)
O20.0245 (9)0.0618 (13)0.0823 (13)0.0000 (8)0.0010 (8)0.0348 (11)
O30.0269 (9)0.0512 (12)0.0931 (14)0.0015 (8)0.0062 (8)0.0419 (11)
O40.0319 (9)0.0408 (10)0.0556 (11)0.0072 (7)0.0019 (7)0.0236 (8)
O50.0495 (11)0.0631 (13)0.0757 (14)0.0095 (10)0.0044 (9)0.0401 (11)
C10.0290 (13)0.0597 (18)0.0572 (16)0.0077 (11)0.0028 (11)0.0249 (14)
C20.0252 (12)0.0488 (15)0.0460 (14)0.0083 (10)0.0035 (10)0.0182 (11)
C30.0280 (11)0.0384 (13)0.0449 (13)0.0071 (10)0.0053 (9)0.0140 (11)
C40.0259 (12)0.0415 (14)0.0584 (16)0.0022 (10)0.0013 (10)0.0176 (12)
C50.0340 (13)0.0443 (16)0.0788 (19)0.0013 (11)0.0058 (12)0.0309 (14)
C60.0357 (13)0.0399 (15)0.0717 (18)0.0061 (11)0.0037 (12)0.0308 (13)
C70.0270 (12)0.0360 (13)0.0558 (15)0.0041 (10)0.0019 (10)0.0199 (11)
C80.0265 (11)0.0398 (14)0.0530 (15)0.0054 (10)0.0045 (10)0.0222 (11)
C90.0285 (12)0.0535 (16)0.0503 (15)0.0149 (11)0.0038 (10)0.0207 (12)
C100.0373 (13)0.0472 (15)0.0478 (14)0.0163 (11)0.0021 (10)0.0206 (12)
C110.0500 (16)0.0614 (19)0.0741 (19)0.0226 (14)0.0044 (14)0.0386 (16)
C120.0574 (17)0.0461 (16)0.079 (2)0.0089 (13)0.0034 (14)0.0360 (15)
C130.0414 (13)0.0366 (14)0.0520 (15)0.0030 (11)0.0061 (11)0.0189 (11)
C140.0419 (14)0.0464 (16)0.0674 (18)0.0021 (12)0.0052 (12)0.0245 (14)
Geometric parameters (Å, º) top
O1—C11.201 (3)C5—H50.9300
O2—C11.373 (3)C6—C71.377 (3)
O2—C41.400 (3)C6—H60.9300
O3—C71.380 (3)C7—C81.383 (3)
O3—H30.8200C8—H80.9300
O4—C131.365 (3)C9—C101.420 (4)
O4—C101.375 (3)C9—H90.9300
O5—C141.417 (3)C10—C111.346 (4)
O5—H5A0.8200C11—C121.410 (4)
C1—C21.490 (3)C11—H110.9300
C2—C91.348 (4)C12—C131.348 (4)
C2—C31.464 (3)C12—H120.9300
C3—C41.389 (3)C13—C141.481 (3)
C3—C81.400 (3)C14—H14A0.9700
C4—C51.370 (3)C14—H14B0.9700
C5—C61.384 (3)
C1—O2—C4107.42 (19)C7—C8—C3118.1 (2)
C7—O3—H3109.5C7—C8—H8121.0
C13—O4—C10107.05 (18)C3—C8—H8121.0
C14—O5—H5A109.5C2—C9—C10131.6 (2)
O1—C1—O2120.6 (2)C2—C9—H9114.2
O1—C1—C2130.4 (3)C10—C9—H9114.2
O2—C1—C2109.03 (19)C11—C10—O4109.0 (2)
C9—C2—C3137.1 (2)C11—C10—C9131.1 (2)
C9—C2—C1117.8 (2)O4—C10—C9119.9 (2)
C3—C2—C1105.0 (2)C10—C11—C12107.4 (2)
C4—C3—C8118.2 (2)C10—C11—H11126.3
C4—C3—C2105.99 (19)C12—C11—H11126.3
C8—C3—C2135.8 (2)C13—C12—C11106.8 (2)
C5—C4—C3124.1 (2)C13—C12—H12126.6
C5—C4—O2123.3 (2)C11—C12—H12126.6
C3—C4—O2112.5 (2)C12—C13—O4109.6 (2)
C4—C5—C6116.7 (2)C12—C13—C14134.4 (2)
C4—C5—H5121.7O4—C13—C14116.0 (2)
C6—C5—H5121.7O5—C14—C13112.6 (2)
C7—C6—C5120.9 (2)O5—C14—H14A109.1
C7—C6—H6119.5C13—C14—H14A109.1
C5—C6—H6119.5O5—C14—H14B109.1
C6—C7—O3118.0 (2)C13—C14—H14B109.1
C6—C7—C8122.0 (2)H14A—C14—H14B107.8
O3—C7—C8120.0 (2)
C4—O2—C1—O1179.9 (2)C5—C6—C7—C80.2 (4)
C4—O2—C1—C20.7 (3)C6—C7—C8—C30.3 (4)
O1—C1—C2—C93.0 (4)O3—C7—C8—C3178.3 (2)
O2—C1—C2—C9176.3 (2)C4—C3—C8—C71.3 (3)
O1—C1—C2—C3179.2 (3)C2—C3—C8—C7177.2 (3)
O2—C1—C2—C31.4 (3)C3—C2—C9—C100.2 (5)
C9—C2—C3—C4175.4 (3)C1—C2—C9—C10176.6 (2)
C1—C2—C3—C41.6 (3)C13—O4—C10—C110.9 (3)
C9—C2—C3—C83.2 (5)C13—O4—C10—C9179.5 (2)
C1—C2—C3—C8179.8 (3)C2—C9—C10—C11172.7 (3)
C8—C3—C4—C52.0 (4)C2—C9—C10—O47.8 (4)
C2—C3—C4—C5176.9 (3)O4—C10—C11—C121.7 (3)
C8—C3—C4—O2179.79 (19)C9—C10—C11—C12178.9 (3)
C2—C3—C4—O21.3 (3)C10—C11—C12—C131.8 (3)
C1—O2—C4—C5177.9 (3)C11—C12—C13—O41.3 (3)
C1—O2—C4—C30.4 (3)C11—C12—C13—C14176.1 (3)
C3—C4—C5—C61.5 (4)C10—O4—C13—C120.2 (3)
O2—C4—C5—C6179.6 (2)C10—O4—C13—C14177.7 (2)
C4—C5—C6—C70.4 (4)C12—C13—C14—O5113.2 (3)
C5—C6—C7—O3178.8 (2)O4—C13—C14—O569.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O3i0.821.902.682 (3)160
O3—H3···O3i0.821.962.717 (3)154
C9—H9···O1ii0.932.563.414 (3)153
Symmetry codes: (i) x, y+2, z; (ii) x+2, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC14H10O5
Mr258.22
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.544 (3), 8.974 (2), 9.291 (3)
α, β, γ (°)107.509 (7), 97.844 (6), 100.735 (7)
V3)576.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.48 × 0.24 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.968, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
3184, 2273, 1496
Rint0.138
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.164, 0.97
No. of reflections2235
No. of parameters174
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.42

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O3i0.821.902.682 (3)160.0
O3—H3···O3i0.821.962.717 (3)153.7
C9—H9···O1ii0.932.563.414 (3)152.8
Symmetry codes: (i) x, y+2, z; (ii) x+2, y+2, z+1.
 

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