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Acta Crystallogr Sect E Struct Rep Online. 2012 April 1; 68(Pt 4): o1208.
Published online 2012 March 28. doi:  10.1107/S1600536812012470
PMCID: PMC3344144

5α-Hy­droxy­eudesm-4(15),11(13)-dien-8β,12-olide

Abstract

The title compound, C15H20O3, a sesquiterpene lactone, was isolated from the aerial parts of Carpesium minus Hemsl. (Compositae). The mol­ecule is composed of three rings, with the two cyclo­hexane rings in chair conformations and the cyclo­pentane ring adopting a twist conformation. The A/B ring junction is trans-fused. The absolute configuration shown has been arbitrarily assigned. In the crystal, mol­ecules are linked into [100] chains by O—H(...)O hydrogen bonds.

Related literature  

For the isolation and biological activity of the title compound, see: Lee et al. (2002 [triangle]); Yang et al. (2002 [triangle]); Li et al. (2011 [triangle]). For conformational analysis, see: Cremer & Pople (1975 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o1208-scheme1.jpg

Experimental  

Crystal data  

  • C15H20O3
  • M r = 248.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o1208-efi1.jpg
  • a = 7.893 (2) Å
  • b = 7.034 (2) Å
  • c = 12.166 (4) Å
  • β = 101.154 (3)°
  • V = 662.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.23 × 0.20 × 0.19 mm

Data collection  

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.981, T max = 0.984
  • 3673 measured reflections
  • 1323 independent reflections
  • 1159 reflections with I > 2σ(I)
  • R int = 0.024

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.084
  • S = 1.08
  • 1323 reflections
  • 165 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812012470/rn2102sup1.cif

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

Acknowledgments

This work was supported by the Ministry of Education of Chongqing (grant No. KJ100719) and the Innovative Research Team Development Program of the University of Chongqing (grant No. KJTD201020).

supplementary crystallographic information

Comment

The title compound, 5α-hydroxyeudesm-4(15),11 (13)-dien-8β,12-olide (Fig.1), was isolated from the medicinal plant Carpesium minus (Compositae). This plant has been used to reduce swelling, relieve pain and as a detoxifying agent. The compound was identified by NMR spectra, which were compared with the previous reports (Lee et al., 2002; Yang et al., 2002; Li et al., 2011). Herewith, we present its crystal structure.

The molecule of the title compound has three fused rings consisting of two six- and one five-membered rings (A/B/C). The A/B ring junction is trans-fused and B/C is cis-fused. The two cyclohexane rings have chair conformations with puckering parameters (Cremer & Pople,1975) Q = 0.571 (2) Å, θ = 175.7 (2)° and [var phi] = 134 (4)° for the A ring and Q = 0.512 (2) Å, θ = 156.4 (2)° and [var phi] = 344.9 (6)° for the B ring; the cyclopentane ring adopts a twist conformation with puckering parameters Q = 0.258 (2) Å and [var phi] = 237.1 (4)°. In the crystal, the molecules are linked into chains by intermolecular O—H···O hydrogen bonds.

Experimental

The air-dried whole plants of Carpesium minus (3.1 g) were pulverized and extracted with 95% EtOH and yielded 439 g of crude extract, which was then suspended in 2 L water. The suspension was partitioned with EtOAc (3×800 ml) to give a EtOAc-soluble portion, and a water-soluble fraction. After removal of the EtOAc under reduced pressure, 356 g of dark residue was obtained, and this was subjected to silica-gel chromatography, eluted with a stepwise gradient solvent system of petroleum/acetone 50: 1 to 0: 1 (v/v), to yield six major fractions (monitored by TLC). The third fraction (68 g) was rechromatographed on silica gel using a chloroform/MeOH (1: 0 to 30: 1) system and three fractions (Fr.A—Fr.C) were collected. Fr.B was further fractionated on a silica gel column using petroleum/EtOAc (3: 1) to give pure the title compound as colorless crystals.

Refinement

All H atoms were placed in geometrically calculated positions, and allowed to ride on their parent atoms with O—H = 0.82 Å and C—H = 0.93–0.98 Å, and with Uiso(H) = xUeq (C), where x = 1.5 for methyl H atoms and hydroxyl group H atoms, and x = 1.2 for all other H atoms. In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration is arbitrary.

Figures

Fig. 1.
The molecular structure of the compound, with atom labels and 50% probability displacement ellipsoids.

Crystal data

C15H20O3F(000) = 268
Mr = 248.31Dx = 1.244 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 7.893 (2) ÅCell parameters from 1583 reflections
b = 7.034 (2) Åθ = 2.9–23.8°
c = 12.166 (4) ŵ = 0.09 mm1
β = 101.154 (3)°T = 296 K
V = 662.7 (3) Å3Block, colorless
Z = 20.23 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer1323 independent reflections
Radiation source: fine-focus sealed tube1159 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
[var phi] and ω scansθmax = 25.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −9→9
Tmin = 0.981, Tmax = 0.984k = −8→7
3673 measured reflectionsl = −13→14

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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.046P)2 + 0.026P] where P = (Fo2 + 2Fc2)/3
1323 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.12 e Å3
1 restraintΔρmin = −0.17 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
C10.5831 (3)0.5040 (4)0.2805 (2)0.0451 (6)
H10.58430.64320.28440.054*
C20.6238 (3)0.4471 (4)0.1686 (2)0.0462 (6)
H2A0.70880.53530.15040.055*
H2B0.51970.46180.11200.055*
C30.6920 (3)0.2446 (4)0.16056 (19)0.0404 (6)
C40.7625 (4)0.2265 (4)0.0514 (2)0.0534 (7)
H4A0.66770.2421−0.01180.064*
H4B0.84420.32850.04860.064*
C50.8506 (4)0.0380 (5)0.0400 (2)0.0663 (9)
H5A0.89980.0396−0.02720.080*
H5B0.7660−0.06350.03250.080*
C60.9931 (4)−0.0002 (5)0.1417 (2)0.0619 (8)
H6A1.0384−0.12750.13670.074*
H6B1.08680.08930.14250.074*
C70.9243 (3)0.0189 (4)0.2486 (2)0.0428 (6)
C80.8428 (3)0.2111 (3)0.26178 (18)0.0370 (5)
C90.7793 (3)0.2326 (3)0.37155 (18)0.0364 (5)
H9A0.87530.21090.43320.044*
H9B0.69310.13570.37520.044*
C100.7006 (3)0.4286 (3)0.38653 (18)0.0391 (5)
H100.79210.52080.41420.047*
C110.5786 (3)0.4143 (3)0.46605 (19)0.0397 (5)
C120.4025 (3)0.4029 (3)0.3975 (2)0.0439 (6)
C130.5451 (3)0.0994 (4)0.1587 (2)0.0491 (6)
H13A0.46070.11470.09100.074*
H13B0.49170.12020.22220.074*
H13C0.5915−0.02710.16180.074*
C140.9291 (3)−0.1238 (4)0.3199 (2)0.0514 (6)
H14A0.9759−0.24010.30490.062*
H14B0.8857−0.10790.38520.062*
C150.6070 (3)0.4053 (4)0.5758 (2)0.0516 (7)
H15A0.51490.39130.61270.062*
H15B0.71920.41280.61680.062*
O10.9648 (2)0.3595 (3)0.25349 (15)0.0503 (5)
H1A1.05150.34450.30210.075*
O20.40859 (19)0.4391 (3)0.28997 (13)0.0530 (5)
O30.2681 (2)0.3667 (3)0.42676 (14)0.0585 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0446 (14)0.0397 (13)0.0508 (14)0.0042 (11)0.0082 (11)0.0056 (12)
C20.0434 (13)0.0513 (15)0.0420 (13)0.0031 (12)0.0038 (10)0.0127 (12)
C30.0365 (12)0.0485 (15)0.0358 (12)0.0004 (11)0.0058 (10)0.0046 (11)
C40.0549 (15)0.0681 (19)0.0381 (13)0.0003 (15)0.0112 (11)0.0055 (13)
C50.0695 (19)0.083 (2)0.0496 (16)0.0125 (18)0.0210 (14)−0.0051 (15)
C60.0571 (17)0.072 (2)0.0608 (17)0.0137 (15)0.0213 (14)−0.0028 (15)
C70.0332 (12)0.0468 (14)0.0473 (14)0.0009 (11)0.0050 (10)−0.0027 (12)
C80.0299 (11)0.0393 (12)0.0405 (12)−0.0064 (10)0.0037 (9)0.0032 (10)
C90.0331 (12)0.0388 (13)0.0346 (12)−0.0009 (10)−0.0001 (9)0.0001 (10)
C100.0360 (12)0.0373 (13)0.0421 (12)−0.0046 (11)0.0030 (9)−0.0010 (11)
C110.0380 (12)0.0347 (12)0.0463 (13)−0.0018 (11)0.0077 (10)−0.0058 (10)
C120.0395 (13)0.0425 (14)0.0491 (14)0.0017 (11)0.0076 (10)−0.0060 (11)
C130.0422 (14)0.0570 (16)0.0447 (14)−0.0085 (12)0.0003 (11)−0.0044 (12)
C140.0465 (14)0.0438 (15)0.0634 (16)0.0054 (12)0.0096 (12)−0.0006 (13)
C150.0537 (15)0.0541 (16)0.0471 (15)0.0042 (13)0.0099 (11)−0.0043 (12)
O10.0357 (9)0.0532 (11)0.0608 (11)−0.0118 (8)0.0062 (7)0.0067 (9)
O20.0357 (9)0.0746 (13)0.0470 (10)0.0067 (9)0.0036 (7)0.0005 (9)
O30.0364 (9)0.0772 (13)0.0632 (11)−0.0042 (9)0.0130 (8)−0.0094 (10)

Geometric parameters (Å, º)

C1—O21.476 (3)C7—C81.519 (3)
C1—C21.512 (3)C8—O11.437 (3)
C1—C101.531 (3)C8—C91.522 (3)
C1—H10.9800C9—C101.538 (3)
C2—C31.533 (4)C9—H9A0.9700
C2—H2A0.9700C9—H9B0.9700
C2—H2B0.9700C10—C111.495 (3)
C3—C41.541 (3)C10—H100.9800
C3—C131.542 (3)C11—C151.312 (3)
C3—C81.556 (3)C11—C121.478 (3)
C4—C51.516 (4)C12—O31.210 (3)
C4—H4A0.9700C12—O21.342 (3)
C4—H4B0.9700C13—H13A0.9600
C5—C61.526 (4)C13—H13B0.9600
C5—H5A0.9700C13—H13C0.9600
C5—H5B0.9700C14—H14A0.9300
C6—C71.509 (3)C14—H14B0.9300
C6—H6A0.9700C15—H15A0.9300
C6—H6B0.9700C15—H15B0.9300
C7—C141.323 (4)O1—H1A0.8200
O2—C1—C2110.7 (2)O1—C8—C7109.61 (18)
O2—C1—C10104.44 (17)O1—C8—C9109.18 (19)
C2—C1—C10117.9 (2)C7—C8—C9113.54 (19)
O2—C1—H1107.8O1—C8—C3104.78 (17)
C2—C1—H1107.8C7—C8—C3109.00 (19)
C10—C1—H1107.8C9—C8—C3110.37 (17)
C1—C2—C3116.2 (2)C8—C9—C10113.71 (18)
C1—C2—H2A108.2C8—C9—H9A108.8
C3—C2—H2A108.2C10—C9—H9A108.8
C1—C2—H2B108.2C8—C9—H9B108.8
C3—C2—H2B108.2C10—C9—H9B108.8
H2A—C2—H2B107.4H9A—C9—H9B107.7
C2—C3—C4108.73 (19)C11—C10—C1101.97 (17)
C2—C3—C13110.1 (2)C11—C10—C9109.97 (19)
C4—C3—C13109.2 (2)C1—C10—C9113.80 (19)
C2—C3—C8108.32 (19)C11—C10—H10110.3
C4—C3—C8108.73 (18)C1—C10—H10110.3
C13—C3—C8111.67 (18)C9—C10—H10110.3
C5—C4—C3113.5 (2)C15—C11—C12121.9 (2)
C5—C4—H4A108.9C15—C11—C10131.1 (2)
C3—C4—H4A108.9C12—C11—C10106.96 (19)
C5—C4—H4B108.9O3—C12—O2121.7 (2)
C3—C4—H4B108.9O3—C12—C11128.9 (2)
H4A—C4—H4B107.7O2—C12—C11109.43 (19)
C4—C5—C6111.1 (3)C3—C13—H13A109.5
C4—C5—H5A109.4C3—C13—H13B109.5
C6—C5—H5A109.4H13A—C13—H13B109.5
C4—C5—H5B109.4C3—C13—H13C109.5
C6—C5—H5B109.4H13A—C13—H13C109.5
H5A—C5—H5B108.0H13B—C13—H13C109.5
C7—C6—C5110.5 (2)C7—C14—H14A120.0
C7—C6—H6A109.5C7—C14—H14B120.0
C5—C6—H6A109.5H14A—C14—H14B120.0
C7—C6—H6B109.5C11—C15—H15A120.0
C5—C6—H6B109.5C11—C15—H15B120.0
H6A—C6—H6B108.1H15A—C15—H15B120.0
C14—C7—C6121.9 (2)C8—O1—H1A109.5
C14—C7—C8124.4 (2)C12—O2—C1110.15 (17)
C6—C7—C8113.6 (2)
O2—C1—C2—C3−83.6 (3)C2—C3—C8—C960.6 (2)
C10—C1—C2—C336.5 (3)C4—C3—C8—C9178.6 (2)
C1—C2—C3—C4−168.0 (2)C13—C3—C8—C9−60.9 (2)
C1—C2—C3—C1372.4 (3)O1—C8—C9—C1056.0 (2)
C1—C2—C3—C8−49.9 (3)C7—C8—C9—C10178.61 (18)
C2—C3—C4—C5174.0 (2)C3—C8—C9—C10−58.7 (2)
C13—C3—C4—C5−65.8 (3)O2—C1—C10—C11−26.1 (2)
C8—C3—C4—C556.2 (3)C2—C1—C10—C11−149.3 (2)
C3—C4—C5—C6−54.6 (3)O2—C1—C10—C992.3 (2)
C4—C5—C6—C752.6 (3)C2—C1—C10—C9−31.0 (3)
C5—C6—C7—C14120.5 (3)C8—C9—C10—C11156.08 (18)
C5—C6—C7—C8−56.6 (3)C8—C9—C10—C142.4 (2)
C14—C7—C8—O1127.5 (3)C1—C10—C11—C15−160.4 (3)
C6—C7—C8—O1−55.5 (3)C9—C10—C11—C1578.5 (3)
C14—C7—C8—C95.1 (3)C1—C10—C11—C1222.0 (2)
C6—C7—C8—C9−177.9 (2)C9—C10—C11—C12−99.1 (2)
C14—C7—C8—C3−118.4 (3)C15—C11—C12—O3−7.9 (4)
C6—C7—C8—C358.6 (2)C10—C11—C12—O3170.0 (3)
C2—C3—C8—O1−56.8 (2)C15—C11—C12—O2172.5 (2)
C4—C3—C8—O161.2 (2)C10—C11—C12—O2−9.7 (3)
C13—C3—C8—O1−178.3 (2)O3—C12—O2—C1172.3 (2)
C2—C3—C8—C7−174.07 (19)C11—C12—O2—C1−8.1 (3)
C4—C3—C8—C7−56.1 (2)C2—C1—O2—C12149.8 (2)
C13—C3—C8—C764.5 (2)C10—C1—O2—C1222.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O3i0.822.062.868 (2)168

Symmetry code: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RN2102).

References

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  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
  • Lee, J. S., Min, B. S., Lee, S. M., Na, M. K., Kwon, B. M., Lee, C. O., Kim, Y. H. & Bae, K. H. (2002). Planta Med. 68, 745–747. [PubMed]
  • Li, X. W., Weng, L., Gao, X., Zhao, Y., Pang, F., Liu, J. H., Zhang, H. F. & Hu, J. F. (2011). Bioorg. Med. Chem. Lett. 21, 366–372. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yang, C., Shi, Y. P. & Jia, Z. J. (2002). Planta Med. 68, 626–630. [PubMed]

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