The title compound, (3a
R,4a
S,7a
R,8
S,9a
R)-decahydro-7a-hydroxy-4a,8-dimethyl-3-methyleneazuleno[6,5-
b]furan-2,5-dione, C
15H
20O
4, from
Ambrosia artemisiifolia, has its seven-membered ring in a twist conformation. Molecules form intermolecular O
O hydrogen bonds of length 2.920 (2) Å.
Supporting information
CCDC reference: 193754
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.109
- Data-to-parameter ratio = 13.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 74.90
From the CIF: _reflns_number_total 2400
Count of symmetry unique reflns 1456
Completeness (_total/calc) 164.84%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 944
Fraction of Friedel pairs measured 0.648
Are heavy atom types Z>Si present no
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(3aR,4aS,7aR,8
S,9aR)-decahydro-7a-hydroxy-4a,8-dimethyl-
methylene-azuleno[6,5-
b]furan-2,5-dione
top
Crystal data top
C15H20O4 | F(000) = 284 |
Mr = 264.31 | Dx = 1.300 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 7.0647 (8) Å | θ = 21.1–43.5° |
b = 12.0073 (13) Å | µ = 0.76 mm−1 |
c = 8.1788 (11) Å | T = 120 K |
β = 103.247 (8)° | Prism, colorless |
V = 675.33 (14) Å3 | 0.47 × 0.35 × 0.32 mm |
Z = 2 | |
Data collection top
κ-geometry diffractometer | 2395 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 74.9°, θmin = 5.5° |
ω/2θ scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→15 |
Tmin = 0.757, Tmax = 0.791 | l = −10→0 |
2686 measured reflections | 3 standard reflections every 120 min |
2400 independent reflections | intensity decay: 2.0% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.3022P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.29 e Å−3 |
2400 reflections | Δρmin = −0.21 e Å−3 |
176 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.033 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983); 944 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.1 (2) |
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 >
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) top | x | y | z | Uiso*/Ueq | |
O1 | 0.1259 (2) | 0.07021 (12) | 0.3895 (2) | 0.0255 (4) | |
O2 | 0.5559 (2) | 0.46442 (12) | 0.82734 (17) | 0.0197 (3) | |
O3 | 0.6105 (2) | 0.41006 (13) | 1.09406 (17) | 0.0214 (3) | |
O4 | 0.44796 (19) | 0.29048 (12) | 0.34110 (17) | 0.0176 (3) | |
H4 | 0.5069 | 0.3184 | 0.2727 | 0.026* | |
C1 | 0.2593 (3) | 0.34316 (17) | 0.3211 (3) | 0.0163 (4) | |
C2 | 0.1442 (3) | 0.31596 (18) | 0.1408 (3) | 0.0193 (4) | |
H2A | 0.0194 | 0.3570 | 0.1129 | 0.023* | |
H2B | 0.2207 | 0.3345 | 0.0571 | 0.023* | |
C3 | 0.1100 (3) | 0.18961 (18) | 0.1472 (3) | 0.0230 (5) | |
H3A | −0.0219 | 0.1699 | 0.0822 | 0.028* | |
H3B | 0.2069 | 0.1483 | 0.1007 | 0.028* | |
C4 | 0.1321 (3) | 0.16266 (18) | 0.3318 (3) | 0.0192 (4) | |
C5 | 0.1552 (3) | 0.27194 (16) | 0.4327 (2) | 0.0164 (4) | |
C6 | 0.2544 (3) | 0.25643 (17) | 0.6197 (2) | 0.0172 (4) | |
H6A | 0.1785 | 0.2989 | 0.6864 | 0.021* | |
H6B | 0.2441 | 0.1767 | 0.6474 | 0.021* | |
C7 | 0.4686 (3) | 0.29067 (17) | 0.6798 (2) | 0.0153 (4) | |
H7 | 0.5512 | 0.2439 | 0.6225 | 0.018* | |
C8 | 0.5102 (3) | 0.41591 (17) | 0.6561 (2) | 0.0164 (4) | |
H8 | 0.6264 | 0.4230 | 0.6063 | 0.020* | |
C9 | 0.3464 (3) | 0.48771 (16) | 0.5566 (2) | 0.0178 (4) | |
H9A | 0.3835 | 0.5669 | 0.5769 | 0.021* | |
H9B | 0.2290 | 0.4749 | 0.6008 | 0.021* | |
C10 | 0.2930 (3) | 0.46744 (17) | 0.3654 (2) | 0.0175 (4) | |
H10 | 0.4086 | 0.4907 | 0.3224 | 0.021* | |
C11 | 0.5323 (3) | 0.27521 (17) | 0.8674 (2) | 0.0170 (4) | |
C12 | 0.5715 (3) | 0.38658 (17) | 0.9463 (2) | 0.0170 (4) | |
C13 | 0.5474 (3) | 0.18233 (18) | 0.9575 (3) | 0.0217 (5) | |
H13A | 0.5844 | 0.1859 | 1.0766 | 0.026* | |
H13B | 0.5212 | 0.1123 | 0.9029 | 0.026* | |
C14 | 0.1257 (3) | 0.54422 (19) | 0.2814 (3) | 0.0229 (5) | |
H14A | 0.1026 | 0.5368 | 0.1591 | 0.034* | |
H14B | 0.1597 | 0.6216 | 0.3135 | 0.034* | |
H14C | 0.0076 | 0.5235 | 0.3178 | 0.034* | |
C15 | −0.0569 (3) | 0.30919 (18) | 0.4219 (3) | 0.0207 (4) | |
H15A | −0.1269 | 0.3131 | 0.3038 | 0.031* | |
H15B | −0.0571 | 0.3827 | 0.4738 | 0.031* | |
H15C | −0.1211 | 0.2553 | 0.4813 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0275 (8) | 0.0174 (8) | 0.0336 (9) | −0.0010 (6) | 0.0115 (6) | −0.0004 (6) |
O2 | 0.0277 (8) | 0.0160 (7) | 0.0147 (7) | −0.0037 (6) | 0.0035 (5) | −0.0001 (6) |
O3 | 0.0273 (8) | 0.0215 (7) | 0.0151 (7) | −0.0002 (6) | 0.0040 (6) | −0.0013 (6) |
O4 | 0.0163 (7) | 0.0202 (7) | 0.0182 (6) | 0.0033 (5) | 0.0079 (5) | 0.0013 (5) |
C1 | 0.0168 (9) | 0.0174 (10) | 0.0159 (9) | 0.0024 (8) | 0.0062 (7) | 0.0001 (7) |
C2 | 0.0184 (9) | 0.0227 (10) | 0.0172 (9) | 0.0011 (8) | 0.0052 (7) | 0.0000 (8) |
C3 | 0.0239 (10) | 0.0222 (11) | 0.0219 (10) | 0.0004 (9) | 0.0031 (8) | −0.0067 (8) |
C4 | 0.0129 (9) | 0.0193 (10) | 0.0265 (10) | −0.0003 (7) | 0.0065 (8) | −0.0036 (8) |
C5 | 0.0169 (9) | 0.0149 (10) | 0.0183 (9) | 0.0003 (7) | 0.0062 (7) | −0.0001 (8) |
C6 | 0.0190 (9) | 0.0159 (9) | 0.0180 (9) | −0.0025 (7) | 0.0069 (7) | 0.0023 (7) |
C7 | 0.0166 (9) | 0.0141 (9) | 0.0165 (9) | 0.0002 (7) | 0.0067 (7) | 0.0012 (7) |
C8 | 0.0190 (10) | 0.0170 (10) | 0.0141 (9) | −0.0030 (8) | 0.0054 (7) | −0.0016 (7) |
C9 | 0.0236 (10) | 0.0128 (10) | 0.0180 (9) | 0.0000 (8) | 0.0070 (8) | −0.0002 (7) |
C10 | 0.0214 (10) | 0.0170 (10) | 0.0152 (9) | 0.0003 (9) | 0.0066 (7) | 0.0018 (8) |
C11 | 0.0153 (9) | 0.0182 (10) | 0.0188 (9) | 0.0018 (7) | 0.0064 (7) | −0.0007 (8) |
C12 | 0.0143 (9) | 0.0187 (10) | 0.0186 (10) | 0.0005 (8) | 0.0050 (7) | 0.0017 (8) |
C13 | 0.0307 (11) | 0.0184 (10) | 0.0168 (10) | 0.0017 (9) | 0.0073 (8) | 0.0005 (8) |
C14 | 0.0287 (11) | 0.0194 (10) | 0.0207 (11) | 0.0032 (9) | 0.0057 (8) | 0.0043 (8) |
C15 | 0.0194 (10) | 0.0218 (11) | 0.0223 (10) | 0.0007 (8) | 0.0076 (8) | 0.0018 (8) |
Geometric parameters (Å, º) top
O1—C4 | 1.211 (3) | C7—C11 | 1.508 (3) |
O2—C12 | 1.335 (2) | C7—C8 | 1.553 (3) |
O2—C8 | 1.483 (2) | C7—H7 | 1.0000 |
O3—C12 | 1.210 (3) | C8—C9 | 1.521 (3) |
O4—C1 | 1.450 (2) | C8—H8 | 1.0000 |
O4—H4 | 0.8400 | C9—C10 | 1.542 (3) |
C1—C10 | 1.541 (3) | C9—H9A | 0.9900 |
C1—C2 | 1.547 (3) | C9—H9B | 0.9900 |
C1—C5 | 1.553 (3) | C10—C14 | 1.532 (3) |
C2—C3 | 1.539 (3) | C10—H10 | 1.0000 |
C2—H2A | 0.9900 | C11—C13 | 1.328 (3) |
C2—H2B | 0.9900 | C11—C12 | 1.483 (3) |
C3—C4 | 1.516 (3) | C13—H13A | 0.9500 |
C3—H3A | 0.9900 | C13—H13B | 0.9500 |
C3—H3B | 0.9900 | C14—H14A | 0.9800 |
C4—C5 | 1.539 (3) | C14—H14B | 0.9800 |
C5—C6 | 1.541 (3) | C14—H14C | 0.9800 |
C5—C15 | 1.547 (3) | C15—H15A | 0.9800 |
C6—C7 | 1.536 (3) | C15—H15B | 0.9800 |
C6—H6A | 0.9900 | C15—H15C | 0.9800 |
C6—H6B | 0.9900 | | |
| | | |
C12—O2—C8 | 112.15 (16) | C8—C7—H7 | 109.7 |
C1—O4—H4 | 109.5 | O2—C8—C9 | 104.89 (15) |
O4—C1—C10 | 107.91 (16) | O2—C8—C7 | 105.60 (14) |
O4—C1—C2 | 106.51 (16) | C9—C8—C7 | 118.25 (16) |
C10—C1—C2 | 116.58 (16) | O2—C8—H8 | 109.2 |
O4—C1—C5 | 103.90 (15) | C9—C8—H8 | 109.2 |
C10—C1—C5 | 117.62 (16) | C7—C8—H8 | 109.2 |
C2—C1—C5 | 103.15 (16) | C8—C9—C10 | 115.63 (16) |
C3—C2—C1 | 103.17 (16) | C8—C9—H9A | 108.4 |
C3—C2—H2A | 111.1 | C10—C9—H9A | 108.4 |
C1—C2—H2A | 111.1 | C8—C9—H9B | 108.4 |
C3—C2—H2B | 111.1 | C10—C9—H9B | 108.4 |
C1—C2—H2B | 111.1 | H9A—C9—H9B | 107.4 |
H2A—C2—H2B | 109.1 | C14—C10—C1 | 114.56 (17) |
C4—C3—C2 | 105.27 (17) | C14—C10—C9 | 110.14 (16) |
C4—C3—H3A | 110.7 | C1—C10—C9 | 112.32 (15) |
C2—C3—H3A | 110.7 | C14—C10—H10 | 106.4 |
C4—C3—H3B | 110.7 | C1—C10—H10 | 106.4 |
C2—C3—H3B | 110.7 | C9—C10—H10 | 106.4 |
H3A—C3—H3B | 108.8 | C13—C11—C12 | 122.19 (18) |
O1—C4—C3 | 125.37 (19) | C13—C11—C7 | 129.46 (19) |
O1—C4—C5 | 125.57 (19) | C12—C11—C7 | 108.30 (17) |
C3—C4—C5 | 109.02 (17) | O3—C12—O2 | 121.79 (19) |
C4—C5—C6 | 113.42 (17) | O3—C12—C11 | 128.44 (18) |
C4—C5—C15 | 103.52 (16) | O2—C12—C11 | 109.77 (17) |
C6—C5—C15 | 107.82 (16) | C11—C13—H13A | 120.0 |
C4—C5—C1 | 99.24 (15) | C11—C13—H13B | 120.0 |
C6—C5—C1 | 118.74 (16) | H13A—C13—H13B | 120.0 |
C15—C5—C1 | 112.96 (16) | C10—C14—H14A | 109.5 |
C7—C6—C5 | 118.45 (16) | C10—C14—H14B | 109.5 |
C7—C6—H6A | 107.7 | H14A—C14—H14B | 109.5 |
C5—C6—H6A | 107.7 | C10—C14—H14C | 109.5 |
C7—C6—H6B | 107.7 | H14A—C14—H14C | 109.5 |
C5—C6—H6B | 107.7 | H14B—C14—H14C | 109.5 |
H6A—C6—H6B | 107.1 | C5—C15—H15A | 109.5 |
C11—C7—C6 | 109.59 (15) | C5—C15—H15B | 109.5 |
C11—C7—C8 | 103.03 (15) | H15A—C15—H15B | 109.5 |
C6—C7—C8 | 114.82 (16) | C5—C15—H15C | 109.5 |
C11—C7—H7 | 109.7 | H15A—C15—H15C | 109.5 |
C6—C7—H7 | 109.7 | H15B—C15—H15C | 109.5 |
| | | |
O4—C1—C2—C3 | 67.90 (19) | C12—O2—C8—C9 | 133.44 (16) |
C10—C1—C2—C3 | −171.64 (16) | C12—O2—C8—C7 | 7.79 (19) |
C5—C1—C2—C3 | −41.16 (18) | C11—C7—C8—O2 | −10.39 (18) |
C1—C2—C3—C4 | 21.2 (2) | C6—C7—C8—O2 | 108.70 (17) |
C2—C3—C4—O1 | −175.83 (19) | C11—C7—C8—C9 | −127.32 (17) |
C2—C3—C4—C5 | 6.5 (2) | C6—C7—C8—C9 | −8.2 (2) |
O1—C4—C5—C6 | 24.4 (3) | O2—C8—C9—C10 | 170.29 (15) |
C3—C4—C5—C6 | −157.95 (16) | C7—C8—C9—C10 | −72.4 (2) |
O1—C4—C5—C15 | −92.2 (2) | O4—C1—C10—C14 | 154.32 (16) |
C3—C4—C5—C15 | 85.49 (18) | C2—C1—C10—C14 | 34.6 (2) |
O1—C4—C5—C1 | 151.3 (2) | C5—C1—C10—C14 | −88.7 (2) |
C3—C4—C5—C1 | −30.98 (19) | O4—C1—C10—C9 | −79.04 (19) |
O4—C1—C5—C4 | −67.40 (17) | C2—C1—C10—C9 | 161.24 (16) |
C10—C1—C5—C4 | 173.47 (17) | C5—C1—C10—C9 | 38.0 (2) |
C2—C1—C5—C4 | 43.62 (17) | C8—C9—C10—C14 | 179.53 (17) |
O4—C1—C5—C6 | 55.9 (2) | C8—C9—C10—C1 | 50.5 (2) |
C10—C1—C5—C6 | −63.3 (2) | C6—C7—C11—C13 | 64.6 (3) |
C2—C1—C5—C6 | 166.88 (17) | C8—C7—C11—C13 | −172.8 (2) |
O4—C1—C5—C15 | −176.43 (15) | C6—C7—C11—C12 | −112.87 (18) |
C10—C1—C5—C15 | 64.4 (2) | C8—C7—C11—C12 | 9.80 (19) |
C2—C1—C5—C15 | −65.42 (19) | C8—O2—C12—O3 | 179.17 (18) |
C4—C5—C6—C7 | 103.4 (2) | C8—O2—C12—C11 | −1.5 (2) |
C15—C5—C6—C7 | −142.64 (18) | C13—C11—C12—O3 | −4.1 (3) |
C1—C5—C6—C7 | −12.6 (3) | C7—C11—C12—O3 | 173.60 (19) |
C5—C6—C7—C11 | 176.51 (17) | C13—C11—C12—O2 | 176.69 (19) |
C5—C6—C7—C8 | 61.2 (2) | C7—C11—C12—O2 | −5.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.84 | 2.09 | 2.920 (2) | 169 |
Symmetry code: (i) x, y, z−1. |