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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1765.
Published online 2008 August 16. doi:  10.1107/S1600536808025737
PMCID: PMC2960644

(3aS,7S,9aS,9bR)-3a,6,6,9a-Tetra­methyl-2-oxoperhydro­naphtho[2,1-b]furan-7-yl acetate

Abstract

The title compound (common name: 3β-acet­oxy-8-epi-sclareolide), C18H28O4, is a sclareolide derivative, which was synthesized from 9(11)-en-3β-acet­oxy-8-epi-sclareolide. In the mol­ecular structure, the two six-membered rings display chair conformations and the five-membered ring displays an envelope conformation. Weak inter­molecular C—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

For general background, see: Choudhary et al. (2004 [triangle]); Quideau et al. (2002 [triangle]). For related structures, see: Devi et al. (2004 [triangle]); Bhattacharyya et al. (2006 [triangle]). For synthesis, see: Yang et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1765-scheme1.jpg

Experimental

Crystal data

  • C18H28O4
  • M r = 308.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1765-efi1.jpg
  • a = 10.1935 (5) Å
  • b = 7.3226 (3) Å
  • c = 11.3056 (4) Å
  • β = 99.2940 (1)°
  • V = 832.81 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 153 (2) K
  • 0.60 × 0.54 × 0.47 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: none
  • 8195 measured reflections
  • 2046 independent reflections
  • 1943 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.086
  • S = 0.99
  • 2046 reflections
  • 205 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025737/xu2447sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025737/xu2447Isup2.hkl

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

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (grant No. 20572107) and by Chengdu Municipal Bureau of Science and Technology.

supplementary crystallographic information

Comment

Sclareolide has exhibited phytotoxic activity and cytotoxicity against human cancer cell lines (Choudhary et al., 2004). It also be important pharmaceutical intermediates (Quideau et al., 2002). Here we report the synthesis and crystal structure of the title compound which is a 8-epi-sclareolide type compound.

The molecular structure is shown in Fig. 1. The molecule contains two six-membered rings, A (atoms C1–C5/C10) and B (atoms C5–C10), and one five-membered lactone rings C (C8/C9/O1/C11/C12). The cyclohexane ring A and the cyclohexane ring B exist both in chair conformation. The γ-lactone rings C adopt envelope conformations with C9 at the flap (Devi et al., 2004; Bhattacharyya et al., 2006). The rings A/B are trans fused and the rings B/C are cis fused. The C1/C2/C4/C5, C6/C7/C9/C10, C8/C11/C12/O1 form least square plane D, E and F, respectively. The dihedral angels between planes D and E is 15.50 (8)°, between planes E and F is 59.03 (7)°, between planes D and F is 43.54 (7)°. The C3 and C10 deviate from plane D by 0.634 (2)and 0.644 (2) Å, respectively. The C5 and C8 deviate from plane E by 0.765 (2) and 0.382 (3) Å, respectively. The C9 deviates from plane F by 0.566 (3) Å.

The intermolacular weak C—H···O hydrogen bonding presents in the crystal structure (Table 1).

Experimental

To a methanol solution (10 ml) of 9(11)-en-3β-Acetoxy-8-epi-sclareolide (1 mmol) (Yang et al., 2006) was added NiCl2.6H2O (1 mmol), and the mixture was cooled to 273 K with an ice bath, then NaBH4 (4 mmol) was added in small portions over 30 min. The ice bath was removed and the reaction mixture was left stirred for 4 h at room temperature. Then the suspension was filtered, and after usual workup, the residue was purified by flash chromatography eluted with petroleum ether–ethyl acetate (10:1) to afford the title compound. Yield (97%).

Refinement

H atoms were placed in calculated positions with C—H = 0.98–1.00 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C). The absolute configuration has been assigned by reference to an unchanging chiral centre in the synthetic procedure; Friedel pairs were merged.

Figures

Fig. 1.
The molecular structure of the title compound, displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C18H28O4F000 = 336
Mr = 308.40Dx = 1.230 Mg m3
Monoclinic, P21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 7613 reflections
a = 10.1935 (5) Åθ = 3.3–27.5º
b = 7.3226 (3) ŵ = 0.09 mm1
c = 11.3056 (4) ÅT = 153 (2) K
β = 99.2940 (1)ºBlock, colourless
V = 832.81 (6) Å30.60 × 0.54 × 0.47 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID IP diffractometer1943 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.018
Monochromator: graphiteθmax = 27.5º
T = 153(2) Kθmin = 3.3º
ω scansh = −13→13
Absorption correction: nonek = −9→9
8195 measured reflectionsl = −14→12
2046 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.0526P)2 + 0.1209P] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
2046 reflectionsΔρmax = 0.20 e Å3
205 parametersΔρmin = −0.14 e Å3
1 restraintExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.065 (6)

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
O10.15453 (13)0.2174 (2)0.55280 (13)0.0477 (4)
O20.10361 (18)0.3434 (4)0.37252 (14)0.0809 (6)
O30.78754 (11)0.58869 (17)0.86839 (11)0.0377 (3)
O40.77677 (15)0.8581 (2)0.96045 (15)0.0599 (4)
C10.44238 (16)0.6709 (2)0.70097 (15)0.0344 (3)
H1A0.41040.74640.62950.041*
H1B0.40250.71990.76870.041*
C20.59341 (16)0.6859 (2)0.73086 (15)0.0370 (4)
H2A0.63410.63950.66300.044*
H2B0.61940.81540.74430.044*
C30.64282 (15)0.5757 (2)0.84229 (14)0.0301 (3)
H30.60510.62900.91100.036*
C40.60784 (14)0.3708 (2)0.83267 (13)0.0280 (3)
C50.45489 (14)0.3533 (2)0.78539 (13)0.0259 (3)
H50.41020.39590.85290.031*
C60.40994 (16)0.1550 (2)0.76243 (16)0.0360 (4)
H6A0.43500.11210.68610.043*
H6B0.45510.07620.82770.043*
C70.25934 (17)0.1404 (3)0.75616 (17)0.0427 (4)
H7A0.23100.01750.72570.051*
H7B0.23880.15020.83860.051*
C80.17711 (15)0.2812 (3)0.67859 (15)0.0386 (4)
C90.24142 (15)0.4709 (3)0.66974 (15)0.0345 (3)
H90.21750.55070.73480.041*
C100.39595 (14)0.4729 (2)0.67643 (13)0.0275 (3)
C110.1657 (2)0.5373 (3)0.54912 (19)0.0482 (5)
H11A0.08240.60030.55950.058*
H11B0.22100.62130.50930.058*
C120.13711 (18)0.3637 (4)0.47870 (18)0.0523 (5)
C130.43749 (17)0.4084 (3)0.55821 (14)0.0384 (4)
H13A0.53470.40900.56630.046*
H13B0.40000.49090.49320.046*
H13C0.40430.28440.53990.046*
C140.03976 (18)0.2954 (4)0.7163 (2)0.0566 (6)
H14A−0.00280.17500.71020.068*
H14B−0.01530.38160.66350.068*
H14C0.04940.33880.79930.068*
C150.84029 (17)0.7424 (3)0.92062 (16)0.0399 (4)
C160.98747 (19)0.7482 (3)0.9221 (2)0.0523 (5)
H16A1.02790.83550.98300.063*
H16B1.00560.78640.84320.063*
H16C1.02520.62660.94110.063*
C170.69680 (16)0.2695 (3)0.75667 (16)0.0395 (4)
H17A0.65940.14850.73530.047*
H17B0.78630.25620.80280.047*
H17C0.70140.33930.68350.047*
C180.63524 (17)0.2918 (3)0.96055 (16)0.0410 (4)
H18A0.72520.32550.99870.049*
H18B0.62740.15850.95690.049*
H18C0.57050.34121.00740.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0391 (7)0.0550 (9)0.0468 (7)−0.0076 (6)0.0003 (5)−0.0144 (6)
O20.0773 (11)0.1122 (17)0.0453 (8)−0.0063 (12)−0.0140 (7)−0.0085 (11)
O30.0267 (6)0.0346 (6)0.0499 (7)−0.0043 (5)0.0006 (5)−0.0051 (5)
O40.0517 (8)0.0469 (8)0.0773 (10)−0.0032 (7)−0.0014 (7)−0.0222 (8)
C10.0347 (8)0.0271 (7)0.0390 (8)0.0021 (7)−0.0014 (6)0.0043 (6)
C20.0352 (8)0.0283 (8)0.0455 (9)−0.0064 (7)0.0008 (6)0.0055 (7)
C30.0243 (7)0.0283 (8)0.0365 (8)−0.0006 (6)0.0017 (5)−0.0027 (6)
C40.0223 (6)0.0265 (7)0.0347 (7)0.0003 (6)0.0027 (5)−0.0008 (6)
C50.0233 (6)0.0255 (7)0.0291 (7)0.0001 (5)0.0050 (5)−0.0019 (6)
C60.0320 (8)0.0273 (8)0.0477 (9)−0.0029 (7)0.0039 (7)0.0012 (7)
C70.0347 (9)0.0406 (10)0.0529 (10)−0.0109 (8)0.0072 (7)0.0021 (8)
C80.0267 (7)0.0466 (10)0.0418 (9)−0.0057 (7)0.0039 (6)−0.0079 (8)
C90.0268 (7)0.0371 (9)0.0382 (8)0.0044 (7)0.0006 (6)−0.0045 (7)
C100.0267 (6)0.0274 (7)0.0278 (7)0.0006 (6)0.0026 (5)−0.0010 (6)
C110.0353 (9)0.0544 (12)0.0501 (11)0.0060 (8)−0.0077 (8)0.0034 (9)
C120.0358 (9)0.0719 (14)0.0454 (10)−0.0014 (10)−0.0050 (7)−0.0045 (11)
C130.0367 (8)0.0486 (10)0.0301 (7)−0.0023 (7)0.0060 (6)−0.0045 (7)
C140.0300 (8)0.0750 (15)0.0665 (12)−0.0064 (10)0.0132 (8)−0.0086 (12)
C150.0383 (8)0.0364 (9)0.0415 (8)−0.0063 (7)−0.0041 (7)0.0003 (8)
C160.0373 (9)0.0492 (11)0.0660 (12)−0.0129 (9)−0.0051 (8)−0.0014 (10)
C170.0290 (7)0.0357 (9)0.0551 (10)0.0030 (7)0.0107 (7)−0.0073 (8)
C180.0372 (8)0.0409 (9)0.0419 (9)0.0002 (7)−0.0021 (6)0.0117 (7)

Geometric parameters (Å, °)

O1—C121.354 (3)C7—H7B0.9900
O1—C81.479 (2)C8—C141.532 (2)
O2—C121.203 (2)C8—C91.546 (3)
O3—C151.343 (2)C9—C111.534 (2)
O3—C31.4601 (18)C9—C101.565 (2)
O4—C151.197 (3)C9—H91.0000
C1—C21.526 (2)C10—C131.540 (2)
C1—C101.536 (2)C11—C121.504 (3)
C1—H1A0.9900C11—H11A0.9900
C1—H1B0.9900C11—H11B0.9900
C2—C31.512 (2)C13—H13A0.9800
C2—H2A0.9900C13—H13B0.9800
C2—H2B0.9900C13—H13C0.9800
C3—C41.542 (2)C14—H14A0.9800
C3—H31.0000C14—H14B0.9800
C4—C171.537 (2)C14—H14C0.9800
C4—C181.540 (2)C15—C161.498 (2)
C4—C51.5696 (18)C16—H16A0.9800
C5—C61.532 (2)C16—H16B0.9800
C5—C101.551 (2)C16—H16C0.9800
C5—H51.0000C17—H17A0.9800
C6—C71.529 (2)C17—H17B0.9800
C6—H6A0.9900C17—H17C0.9800
C6—H6B0.9900C18—H18A0.9800
C7—C81.516 (3)C18—H18B0.9800
C7—H7A0.9900C18—H18C0.9800
C12—O1—C8109.23 (16)C8—C9—C10116.08 (13)
C15—O3—C3117.60 (13)C11—C9—H9108.8
C2—C1—C10112.21 (13)C8—C9—H9108.8
C2—C1—H1A109.2C10—C9—H9108.8
C10—C1—H1A109.2C1—C10—C13109.04 (14)
C2—C1—H1B109.2C1—C10—C5108.73 (11)
C10—C1—H1B109.2C13—C10—C5112.98 (13)
H1A—C1—H1B107.9C1—C10—C9107.23 (13)
C3—C2—C1109.55 (13)C13—C10—C9111.77 (12)
C3—C2—H2A109.8C5—C10—C9106.90 (12)
C1—C2—H2A109.8C12—C11—C9103.26 (17)
C3—C2—H2B109.8C12—C11—H11A111.1
C1—C2—H2B109.8C9—C11—H11A111.1
H2A—C2—H2B108.2C12—C11—H11B111.1
O3—C3—C2108.86 (13)C9—C11—H11B111.1
O3—C3—C4106.99 (12)H11A—C11—H11B109.1
C2—C3—C4114.73 (13)O2—C12—O1120.5 (2)
O3—C3—H3108.7O2—C12—C11129.2 (3)
C2—C3—H3108.7O1—C12—C11110.28 (15)
C4—C3—H3108.7C10—C13—H13A109.5
C17—C4—C18108.03 (14)C10—C13—H13B109.5
C17—C4—C3111.00 (13)H13A—C13—H13B109.5
C18—C4—C3107.13 (13)C10—C13—H13C109.5
C17—C4—C5114.41 (13)H13A—C13—H13C109.5
C18—C4—C5107.97 (12)H13B—C13—H13C109.5
C3—C4—C5108.02 (12)C8—C14—H14A109.5
C6—C5—C10109.50 (12)C8—C14—H14B109.5
C6—C5—C4112.88 (12)H14A—C14—H14B109.5
C10—C5—C4117.40 (12)C8—C14—H14C109.5
C6—C5—H5105.3H14A—C14—H14C109.5
C10—C5—H5105.3H14B—C14—H14C109.5
C4—C5—H5105.3O4—C15—O3123.78 (16)
C7—C6—C5110.17 (14)O4—C15—C16125.24 (18)
C7—C6—H6A109.6O3—C15—C16110.98 (17)
C5—C6—H6A109.6C15—C16—H16A109.5
C7—C6—H6B109.6C15—C16—H16B109.5
C5—C6—H6B109.6H16A—C16—H16B109.5
H6A—C6—H6B108.1C15—C16—H16C109.5
C8—C7—C6115.88 (15)H16A—C16—H16C109.5
C8—C7—H7A108.3H16B—C16—H16C109.5
C6—C7—H7A108.3C4—C17—H17A109.5
C8—C7—H7B108.3C4—C17—H17B109.5
C6—C7—H7B108.3H17A—C17—H17B109.5
H7A—C7—H7B107.4C4—C17—H17C109.5
O1—C8—C7109.08 (16)H17A—C17—H17C109.5
O1—C8—C14106.37 (14)H17B—C17—H17C109.5
C7—C8—C14109.27 (17)C4—C18—H18A109.5
O1—C8—C9102.92 (14)C4—C18—H18B109.5
C7—C8—C9116.62 (13)H18A—C18—H18B109.5
C14—C8—C9111.92 (17)C4—C18—H18C109.5
C11—C9—C8100.65 (14)H18A—C18—H18C109.5
C11—C9—C10113.45 (15)H18B—C18—H18C109.5
C10—C1—C2—C3−60.61 (18)C14—C8—C9—C11−77.70 (18)
C15—O3—C3—C277.96 (18)O1—C8—C9—C10−86.75 (15)
C15—O3—C3—C4−157.52 (14)C7—C8—C9—C1032.6 (2)
C1—C2—C3—O3178.97 (13)C14—C8—C9—C10159.43 (15)
C1—C2—C3—C459.15 (18)C2—C1—C10—C13−68.69 (16)
O3—C3—C4—C17−45.26 (17)C2—C1—C10—C554.89 (17)
C2—C3—C4—C1775.59 (16)C2—C1—C10—C9170.13 (13)
O3—C3—C4—C1872.47 (15)C6—C5—C10—C1−179.85 (13)
C2—C3—C4—C18−166.68 (13)C4—C5—C10—C1−49.46 (17)
O3—C3—C4—C5−171.45 (11)C6—C5—C10—C13−58.66 (16)
C2—C3—C4—C5−50.60 (17)C4—C5—C10—C1371.73 (17)
C17—C4—C5—C651.22 (18)C6—C5—C10—C964.69 (15)
C18—C4—C5—C6−69.07 (17)C4—C5—C10—C9−164.91 (13)
C3—C4—C5—C6175.39 (13)C11—C9—C10—C179.44 (17)
C17—C4—C5—C10−77.59 (18)C8—C9—C10—C1−164.68 (14)
C18—C4—C5—C10162.11 (14)C11—C9—C10—C13−40.0 (2)
C3—C4—C5—C1046.57 (17)C8—C9—C10—C1375.88 (18)
C10—C5—C6—C7−65.31 (17)C11—C9—C10—C5−164.10 (15)
C4—C5—C6—C7161.90 (13)C8—C9—C10—C5−48.22 (17)
C5—C6—C7—C847.1 (2)C8—C9—C11—C12−31.47 (18)
C12—O1—C8—C7−152.81 (14)C10—C9—C11—C1293.22 (18)
C12—O1—C8—C1489.45 (19)C8—O1—C12—O2−172.27 (18)
C12—O1—C8—C9−28.36 (17)C8—O1—C12—C117.91 (19)
C6—C7—C8—O184.82 (18)C9—C11—C12—O2−163.8 (2)
C6—C7—C8—C14−159.28 (17)C9—C11—C12—O116.0 (2)
C6—C7—C8—C9−31.1 (2)C3—O3—C15—O49.9 (3)
O1—C8—C9—C1136.12 (16)C3—O3—C15—C16−170.25 (14)
C7—C8—C9—C11155.46 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C16—H16B···O2i0.982.553.383 (3)143

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2447).

References

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