Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047381/rk2041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047381/rk2041Isup2.hkl |
CCDC reference: 667384
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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).
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.
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).
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).
C14H10O5 | Z = 2 |
Mr = 258.22 | F(000) = 268 |
Triclinic, P1 | Dx = 1.487 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.544 (3) Å | Cell parameters from 993 reflections |
b = 8.974 (2) Å | θ = 4.7–48.1° |
c = 9.291 (3) Å | µ = 0.11 mm−1 |
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 |
Bruker SMART CCD area-detector diffractometer | 2273 independent reflections |
Radiation source: fine–focus sealed tube | 1496 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.138 |
φ and ω scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.968, Tmax = 0.984 | k = −11→6 |
3184 measured reflections | l = −10→11 |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-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 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
C14H10O5 | γ = 100.735 (7)° |
Mr = 258.22 | V = 576.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.544 (3) Å | Mo Kα radiation |
b = 8.974 (2) Å | µ = 0.11 mm−1 |
c = 9.291 (3) Å | T = 293 K |
α = 107.509 (7)° | 0.48 × 0.24 × 0.15 mm |
β = 97.844 (6)° |
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 = 0.984 | Rint = 0.138 |
3184 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.33 e Å−3 |
2235 reflections | Δρmin = −0.42 e Å−3 |
174 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 > 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.0229 (2) | 1.1646 (3) | 0.3963 (2) | 0.0690 (7) | |
O2 | 0.8629 (2) | 1.2740 (2) | 0.2522 (2) | 0.0562 (5) | |
O3 | 0.1254 (2) | 1.1304 (2) | 0.0008 (2) | 0.0559 (5) | |
H3 | 0.0779 | 1.0385 | −0.0045 | 0.084* | |
O4 | 0.3470 (2) | 0.82265 (19) | 0.29896 (18) | 0.0419 (5) | |
O5 | −0.0173 (3) | 0.6380 (2) | 0.0900 (2) | 0.0612 (6) | |
H5A | −0.0237 | 0.7203 | 0.0705 | 0.092* | |
C1 | 0.8761 (3) | 1.1658 (3) | 0.3283 (3) | 0.0484 (7) | |
C2 | 0.6891 (3) | 1.0621 (3) | 0.3073 (3) | 0.0400 (6) | |
C3 | 0.5654 (3) | 1.1226 (3) | 0.2156 (3) | 0.0374 (6) | |
C4 | 0.6769 (3) | 1.2464 (3) | 0.1850 (3) | 0.0433 (6) | |
C5 | 0.6139 (3) | 1.3299 (3) | 0.0957 (3) | 0.0520 (7) | |
H5 | 0.6933 | 1.4105 | 0.0758 | 0.062* | |
C6 | 0.4262 (3) | 1.2883 (3) | 0.0363 (3) | 0.0475 (7) | |
H6 | 0.3774 | 1.3424 | −0.0245 | 0.057* | |
C7 | 0.3106 (3) | 1.1680 (3) | 0.0659 (3) | 0.0397 (6) | |
C8 | 0.3757 (3) | 1.0833 (3) | 0.1552 (3) | 0.0390 (6) | |
H8 | 0.2959 | 1.0027 | 0.1746 | 0.047* | |
C9 | 0.6754 (3) | 0.9416 (3) | 0.3666 (3) | 0.0431 (6) | |
H9 | 0.7862 | 0.9379 | 0.4215 | 0.052* | |
C10 | 0.5221 (3) | 0.8192 (3) | 0.3603 (3) | 0.0428 (6) | |
C11 | 0.5126 (4) | 0.6904 (4) | 0.4072 (3) | 0.0577 (8) | |
H11 | 0.6112 | 0.6619 | 0.4551 | 0.069* | |
C12 | 0.3258 (4) | 0.6066 (3) | 0.3705 (3) | 0.0588 (8) | |
H12 | 0.2783 | 0.5112 | 0.3870 | 0.071* | |
C13 | 0.2293 (3) | 0.6913 (3) | 0.3069 (3) | 0.0436 (6) | |
C14 | 0.0307 (3) | 0.6752 (3) | 0.2518 (3) | 0.0524 (7) | |
H14A | −0.0409 | 0.5911 | 0.2804 | 0.063* | |
H14B | −0.0009 | 0.7752 | 0.3026 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0256 (10) | 0.0971 (18) | 0.0869 (15) | 0.0081 (10) | −0.0017 (9) | 0.0446 (13) |
O2 | 0.0245 (9) | 0.0618 (13) | 0.0823 (13) | 0.0000 (8) | 0.0010 (8) | 0.0348 (11) |
O3 | 0.0269 (9) | 0.0512 (12) | 0.0931 (14) | 0.0015 (8) | −0.0062 (8) | 0.0419 (11) |
O4 | 0.0319 (9) | 0.0408 (10) | 0.0556 (11) | 0.0072 (7) | 0.0019 (7) | 0.0236 (8) |
O5 | 0.0495 (11) | 0.0631 (13) | 0.0757 (14) | 0.0095 (10) | −0.0044 (9) | 0.0401 (11) |
C1 | 0.0290 (13) | 0.0597 (18) | 0.0572 (16) | 0.0077 (11) | 0.0028 (11) | 0.0249 (14) |
C2 | 0.0252 (12) | 0.0488 (15) | 0.0460 (14) | 0.0083 (10) | 0.0035 (10) | 0.0182 (11) |
C3 | 0.0280 (11) | 0.0384 (13) | 0.0449 (13) | 0.0071 (10) | 0.0053 (9) | 0.0140 (11) |
C4 | 0.0259 (12) | 0.0415 (14) | 0.0584 (16) | 0.0022 (10) | 0.0013 (10) | 0.0176 (12) |
C5 | 0.0340 (13) | 0.0443 (16) | 0.0788 (19) | −0.0013 (11) | 0.0058 (12) | 0.0309 (14) |
C6 | 0.0357 (13) | 0.0399 (15) | 0.0717 (18) | 0.0061 (11) | 0.0037 (12) | 0.0308 (13) |
C7 | 0.0270 (12) | 0.0360 (13) | 0.0558 (15) | 0.0041 (10) | 0.0019 (10) | 0.0199 (11) |
C8 | 0.0265 (11) | 0.0398 (14) | 0.0530 (15) | 0.0054 (10) | 0.0045 (10) | 0.0222 (11) |
C9 | 0.0285 (12) | 0.0535 (16) | 0.0503 (15) | 0.0149 (11) | 0.0038 (10) | 0.0207 (12) |
C10 | 0.0373 (13) | 0.0472 (15) | 0.0478 (14) | 0.0163 (11) | 0.0021 (10) | 0.0206 (12) |
C11 | 0.0500 (16) | 0.0614 (19) | 0.0741 (19) | 0.0226 (14) | 0.0044 (14) | 0.0386 (16) |
C12 | 0.0574 (17) | 0.0461 (16) | 0.079 (2) | 0.0089 (13) | 0.0034 (14) | 0.0360 (15) |
C13 | 0.0414 (13) | 0.0366 (14) | 0.0520 (15) | 0.0030 (11) | 0.0061 (11) | 0.0189 (11) |
C14 | 0.0419 (14) | 0.0464 (16) | 0.0674 (18) | 0.0021 (12) | 0.0052 (12) | 0.0245 (14) |
O1—C1 | 1.201 (3) | C5—H5 | 0.9300 |
O2—C1 | 1.373 (3) | C6—C7 | 1.377 (3) |
O2—C4 | 1.400 (3) | C6—H6 | 0.9300 |
O3—C7 | 1.380 (3) | C7—C8 | 1.383 (3) |
O3—H3 | 0.8200 | C8—H8 | 0.9300 |
O4—C13 | 1.365 (3) | C9—C10 | 1.420 (4) |
O4—C10 | 1.375 (3) | C9—H9 | 0.9300 |
O5—C14 | 1.417 (3) | C10—C11 | 1.346 (4) |
O5—H5A | 0.8200 | C11—C12 | 1.410 (4) |
C1—C2 | 1.490 (3) | C11—H11 | 0.9300 |
C2—C9 | 1.348 (4) | C12—C13 | 1.348 (4) |
C2—C3 | 1.464 (3) | C12—H12 | 0.9300 |
C3—C4 | 1.389 (3) | C13—C14 | 1.481 (3) |
C3—C8 | 1.400 (3) | C14—H14A | 0.9700 |
C4—C5 | 1.370 (3) | C14—H14B | 0.9700 |
C5—C6 | 1.384 (3) | ||
C1—O2—C4 | 107.42 (19) | C7—C8—C3 | 118.1 (2) |
C7—O3—H3 | 109.5 | C7—C8—H8 | 121.0 |
C13—O4—C10 | 107.05 (18) | C3—C8—H8 | 121.0 |
C14—O5—H5A | 109.5 | C2—C9—C10 | 131.6 (2) |
O1—C1—O2 | 120.6 (2) | C2—C9—H9 | 114.2 |
O1—C1—C2 | 130.4 (3) | C10—C9—H9 | 114.2 |
O2—C1—C2 | 109.03 (19) | C11—C10—O4 | 109.0 (2) |
C9—C2—C3 | 137.1 (2) | C11—C10—C9 | 131.1 (2) |
C9—C2—C1 | 117.8 (2) | O4—C10—C9 | 119.9 (2) |
C3—C2—C1 | 105.0 (2) | C10—C11—C12 | 107.4 (2) |
C4—C3—C8 | 118.2 (2) | C10—C11—H11 | 126.3 |
C4—C3—C2 | 105.99 (19) | C12—C11—H11 | 126.3 |
C8—C3—C2 | 135.8 (2) | C13—C12—C11 | 106.8 (2) |
C5—C4—C3 | 124.1 (2) | C13—C12—H12 | 126.6 |
C5—C4—O2 | 123.3 (2) | C11—C12—H12 | 126.6 |
C3—C4—O2 | 112.5 (2) | C12—C13—O4 | 109.6 (2) |
C4—C5—C6 | 116.7 (2) | C12—C13—C14 | 134.4 (2) |
C4—C5—H5 | 121.7 | O4—C13—C14 | 116.0 (2) |
C6—C5—H5 | 121.7 | O5—C14—C13 | 112.6 (2) |
C7—C6—C5 | 120.9 (2) | O5—C14—H14A | 109.1 |
C7—C6—H6 | 119.5 | C13—C14—H14A | 109.1 |
C5—C6—H6 | 119.5 | O5—C14—H14B | 109.1 |
C6—C7—O3 | 118.0 (2) | C13—C14—H14B | 109.1 |
C6—C7—C8 | 122.0 (2) | H14A—C14—H14B | 107.8 |
O3—C7—C8 | 120.0 (2) | ||
C4—O2—C1—O1 | −179.9 (2) | C5—C6—C7—C8 | −0.2 (4) |
C4—O2—C1—C2 | 0.7 (3) | C6—C7—C8—C3 | −0.3 (4) |
O1—C1—C2—C9 | −3.0 (4) | O3—C7—C8—C3 | 178.3 (2) |
O2—C1—C2—C9 | 176.3 (2) | C4—C3—C8—C7 | 1.3 (3) |
O1—C1—C2—C3 | 179.2 (3) | C2—C3—C8—C7 | −177.2 (3) |
O2—C1—C2—C3 | −1.4 (3) | C3—C2—C9—C10 | 0.2 (5) |
C9—C2—C3—C4 | −175.4 (3) | C1—C2—C9—C10 | −176.6 (2) |
C1—C2—C3—C4 | 1.6 (3) | C13—O4—C10—C11 | −0.9 (3) |
C9—C2—C3—C8 | 3.2 (5) | C13—O4—C10—C9 | 179.5 (2) |
C1—C2—C3—C8 | −179.8 (3) | C2—C9—C10—C11 | 172.7 (3) |
C8—C3—C4—C5 | −2.0 (4) | C2—C9—C10—O4 | −7.8 (4) |
C2—C3—C4—C5 | 176.9 (3) | O4—C10—C11—C12 | 1.7 (3) |
C8—C3—C4—O2 | 179.79 (19) | C9—C10—C11—C12 | −178.9 (3) |
C2—C3—C4—O2 | −1.3 (3) | C10—C11—C12—C13 | −1.8 (3) |
C1—O2—C4—C5 | −177.9 (3) | C11—C12—C13—O4 | 1.3 (3) |
C1—O2—C4—C3 | 0.4 (3) | C11—C12—C13—C14 | −176.1 (3) |
C3—C4—C5—C6 | 1.5 (4) | C10—O4—C13—C12 | −0.2 (3) |
O2—C4—C5—C6 | 179.6 (2) | C10—O4—C13—C14 | 177.7 (2) |
C4—C5—C6—C7 | −0.4 (4) | C12—C13—C14—O5 | −113.2 (3) |
C5—C6—C7—O3 | −178.8 (2) | O4—C13—C14—O5 | 69.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3i | 0.82 | 1.90 | 2.682 (3) | 160 |
O3—H3···O3i | 0.82 | 1.96 | 2.717 (3) | 154 |
C9—H9···O1ii | 0.93 | 2.56 | 3.414 (3) | 153 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H10O5 |
Mr | 258.22 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 576.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.48 × 0.24 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.968, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3184, 2273, 1496 |
Rint | 0.138 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.164, 0.97 |
No. of reflections | 2235 |
No. of parameters | 174 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.42 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3i | 0.82 | 1.90 | 2.682 (3) | 160.0 |
O3—H3···O3i | 0.82 | 1.96 | 2.717 (3) | 153.7 |
C9—H9···O1ii | 0.93 | 2.56 | 3.414 (3) | 152.8 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+2, −y+2, −z+1. |
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.