Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680202086X/ac6020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680202086X/ac60203sup2.hkl |
CCDC reference: 176188
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.122
- Data-to-parameter ratio = 9.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 2074 Count of symmetry unique reflns 2082 Completeness (_total/calc) 99.62% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 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.
Grandiflorenic acid, (1), was reacted with NaIO4 and catalytic amounts of OsO4 (Castellaro et al., 1990). The product was norketone (2). Under Baeyer–Villiger rearrangement conditions, 2.5 ml of hydrogen peroxide (30%) dissolved in anhydrous dichloromethane (15 ml) and 14 ml of anhydrous t rifluoroacetic acid were added to a solution of 0.66 mmol (200 mg) of ketoacid (2) in anhydrous dicloromethane (10 ml). The reaction was left at room temperature for 1 h. The unexpected novel compound (3) was isolated with 19% yield after column chromatography (hexane–ethyl acetate, 7:3). Colourless well shaped single crystals were obtained by recrystallization from chloroform.
Since the anomalous scattering was not large enough to permit determination of the enantiomer present, the intensities of the Friedel reflections were averaged before refinement. The H atoms were positioned stereochemically and were refined using a riding model with C—H = 0.99 Å. The H atoms of the rings were set isotropically, with displacement parameters 20% greater than the equivalent isotropic displacement parameter of the atom to which each was bonded; this percentage was set to 50% for methoxy H atom.
Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 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: WinGX (Farrugia, 1999).
Fig. 1. ORTEP-3 (Farrugia, 1997) view of the title compound, showing the atom and ring labeling, and 50% probability ellipsoids. |
C19H24O5 | Dx = 1.407 Mg m−3 |
Mr = 332.38 | Melting point: 503-505 K K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2081 reflections |
a = 6.6980 (2) Å | θ = 1.0–27.5° |
b = 13.6063 (3) Å | µ = 0.10 mm−1 |
c = 17.2155 (5) Å | T = 120 K |
V = 1568.85 (7) Å3 | Prism, colorless |
Z = 4 | 0.25 × 0.05 × 0.05 mm |
F(000) = 712 |
Nonius KappaCCD diffractometer | Rint = 0.023 |
CCD scans | θmax = 27.5°, θmin = 3.0° |
3592 measured reflections | h = 0→8 |
2074 independent reflections | k = 0→17 |
1857 reflections with I > 2σ(I) | l = −22→22 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0794P)2 + 0.0434P] where P = (Fo2 + 2Fc2)/3 |
2074 reflections | (Δ/σ)max < 0.001 |
219 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
C19H24O5 | V = 1568.85 (7) Å3 |
Mr = 332.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.6980 (2) Å | µ = 0.10 mm−1 |
b = 13.6063 (3) Å | T = 120 K |
c = 17.2155 (5) Å | 0.25 × 0.05 × 0.05 mm |
Nonius KappaCCD diffractometer | 1857 reflections with I > 2σ(I) |
3592 measured reflections | Rint = 0.023 |
2074 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.43 e Å−3 |
2074 reflections | Δρmin = −0.52 e Å−3 |
219 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9371 (3) | 0.49131 (13) | 0.42067 (9) | 0.0297 (4) | |
O2 | 0.8328 (3) | 0.60085 (11) | 0.50859 (9) | 0.0214 (4) | |
O3 | 0.2973 (3) | 0.74070 (13) | 0.78964 (10) | 0.0304 (4) | |
O4 | 0.4551 (3) | 0.75071 (11) | 0.67530 (9) | 0.0228 (4) | |
O5 | 0.5882 (3) | 0.46932 (11) | 0.66243 (9) | 0.0218 (4) | |
C1 | 0.4906 (4) | 0.61206 (16) | 0.55131 (13) | 0.0214 (5) | |
H1A | 0.399 | 0.6005 | 0.5955 | 0.026* | |
H1B | 0.4717 | 0.6807 | 0.5336 | 0.026* | |
C2 | 0.4365 (4) | 0.54187 (17) | 0.48498 (13) | 0.0257 (5) | |
H2A | 0.2899 | 0.5415 | 0.4779 | 0.031* | |
H2B | 0.4976 | 0.5659 | 0.4362 | 0.031* | |
C3 | 0.5084 (4) | 0.43717 (17) | 0.50089 (13) | 0.0243 (5) | |
H3A | 0.4984 | 0.3979 | 0.4526 | 0.029* | |
H3B | 0.4212 | 0.4064 | 0.5404 | 0.029* | |
C4 | 0.7271 (4) | 0.43615 (16) | 0.53009 (12) | 0.0218 (5) | |
C5 | 0.7401 (4) | 0.49211 (15) | 0.60803 (12) | 0.0195 (4) | |
C6 | 0.9420 (4) | 0.47644 (17) | 0.64873 (13) | 0.0235 (5) | |
H6A | 1.0522 | 0.4956 | 0.6136 | 0.028* | |
H6B | 0.9587 | 0.4062 | 0.6623 | 0.028* | |
C7 | 0.9478 (4) | 0.53995 (16) | 0.72317 (13) | 0.0228 (5) | |
H7A | 0.9384 | 0.4974 | 0.7697 | 0.027* | |
H7B | 1.075 | 0.5769 | 0.7257 | 0.027* | |
C8 | 0.7707 (4) | 0.61175 (14) | 0.72096 (12) | 0.0192 (4) | |
C9 | 0.7818 (4) | 0.67206 (15) | 0.64208 (12) | 0.0182 (4) | |
C10 | 0.7072 (3) | 0.59853 (15) | 0.57885 (12) | 0.0179 (4) | |
C11 | 0.6601 (4) | 0.76832 (15) | 0.64905 (13) | 0.0208 (5) | |
H11 | 0.66 | 0.8044 | 0.5984 | 0.025* | |
C12 | 0.7404 (4) | 0.83416 (15) | 0.71387 (13) | 0.0239 (5) | |
H12A | 0.6855 | 0.9016 | 0.711 | 0.029* | |
H12B | 0.8881 | 0.8368 | 0.7141 | 0.029* | |
C13 | 0.6578 (4) | 0.77688 (16) | 0.78329 (14) | 0.0231 (5) | |
H13 | 0.6573 | 0.817 | 0.8319 | 0.028* | |
C14 | 0.7739 (4) | 0.67928 (15) | 0.79330 (12) | 0.0223 (5) | |
H14A | 0.9145 | 0.6948 | 0.8062 | 0.027* | |
H14B | 0.7165 | 0.6429 | 0.8378 | 0.027* | |
C15 | 0.5856 (4) | 0.54330 (16) | 0.72380 (13) | 0.0217 (5) | |
H15A | 0.5812 | 0.51 | 0.7749 | 0.026* | |
H15B | 0.4632 | 0.5835 | 0.7187 | 0.026* | |
C16 | 0.4497 (4) | 0.75566 (17) | 0.75449 (13) | 0.0236 (5) | |
C18 | 0.8139 (5) | 0.33231 (17) | 0.52817 (13) | 0.0292 (6) | |
H18A | 0.7925 | 0.3035 | 0.4767 | 0.044* | |
H18B | 0.7477 | 0.2917 | 0.5675 | 0.044* | |
H18C | 0.9574 | 0.3351 | 0.5391 | 0.044* | |
C19 | 0.8444 (4) | 0.50782 (17) | 0.47945 (12) | 0.0225 (5) | |
C20 | 0.9974 (4) | 0.70440 (17) | 0.62387 (13) | 0.0229 (5) | |
H20A | 0.9951 | 0.7585 | 0.5863 | 0.034* | |
H20B | 1.0717 | 0.6489 | 0.602 | 0.034* | |
H20C | 1.0626 | 0.7264 | 0.6718 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0297 (10) | 0.0369 (9) | 0.0224 (7) | −0.0032 (8) | 0.0050 (8) | −0.0076 (7) |
O2 | 0.0245 (9) | 0.0232 (7) | 0.0166 (7) | −0.0025 (7) | 0.0026 (7) | −0.0003 (6) |
O3 | 0.0219 (9) | 0.0361 (9) | 0.0333 (9) | −0.0029 (8) | 0.0056 (8) | −0.0097 (8) |
O4 | 0.0190 (8) | 0.0240 (8) | 0.0255 (8) | 0.0012 (7) | −0.0008 (7) | −0.0037 (6) |
O5 | 0.0276 (9) | 0.0183 (7) | 0.0195 (7) | −0.0052 (7) | 0.0040 (7) | −0.0020 (6) |
C1 | 0.0208 (12) | 0.0221 (10) | 0.0214 (10) | −0.0001 (9) | −0.0027 (9) | −0.0004 (8) |
C2 | 0.0250 (12) | 0.0267 (11) | 0.0255 (10) | −0.0028 (10) | −0.0049 (10) | −0.0012 (9) |
C3 | 0.0268 (12) | 0.0239 (10) | 0.0222 (10) | −0.0068 (9) | 0.0005 (10) | −0.0028 (9) |
C4 | 0.0257 (12) | 0.0201 (9) | 0.0196 (10) | −0.0008 (10) | 0.0008 (10) | −0.0016 (8) |
C5 | 0.0227 (11) | 0.0181 (9) | 0.0179 (9) | 0.0003 (9) | 0.0031 (9) | −0.0002 (8) |
C6 | 0.0282 (13) | 0.0212 (10) | 0.0212 (10) | 0.0047 (10) | −0.0026 (10) | −0.0006 (9) |
C7 | 0.0257 (11) | 0.0225 (10) | 0.0201 (10) | 0.0059 (9) | −0.0027 (10) | −0.0005 (9) |
C8 | 0.0200 (11) | 0.0195 (9) | 0.0181 (9) | 0.0005 (9) | −0.0004 (9) | −0.0002 (8) |
C9 | 0.0188 (11) | 0.0169 (9) | 0.0188 (9) | 0.0018 (9) | −0.0010 (9) | 0.0021 (8) |
C10 | 0.0188 (11) | 0.0187 (9) | 0.0161 (9) | −0.0008 (9) | 0.0020 (8) | 0.0023 (7) |
C11 | 0.0205 (11) | 0.0178 (9) | 0.0242 (10) | −0.0010 (10) | 0.0006 (9) | 0.0003 (8) |
C12 | 0.0233 (11) | 0.0185 (9) | 0.0297 (11) | −0.0001 (9) | −0.0002 (10) | −0.0033 (9) |
C13 | 0.0220 (11) | 0.0218 (10) | 0.0255 (10) | −0.0017 (9) | −0.0011 (10) | −0.0053 (9) |
C14 | 0.0236 (12) | 0.0230 (9) | 0.0202 (10) | −0.0001 (10) | −0.0024 (9) | −0.0019 (8) |
C15 | 0.0264 (11) | 0.0199 (9) | 0.0188 (9) | −0.0024 (9) | 0.0036 (10) | −0.0021 (8) |
C16 | 0.0214 (12) | 0.0229 (10) | 0.0266 (11) | 0.0004 (10) | 0.0018 (10) | −0.0071 (9) |
C18 | 0.0403 (15) | 0.0232 (10) | 0.0241 (10) | 0.0023 (11) | 0.0001 (11) | −0.0029 (9) |
C19 | 0.0237 (11) | 0.0241 (10) | 0.0197 (9) | −0.0013 (10) | −0.0012 (9) | −0.0037 (8) |
C20 | 0.0192 (11) | 0.0243 (10) | 0.0253 (10) | −0.0026 (9) | −0.0012 (10) | −0.0008 (9) |
O1—C19 | 1.208 (3) | C7—H7A | 0.99 |
O2—C19 | 1.364 (3) | C7—H7B | 0.99 |
O2—C10 | 1.474 (3) | C8—C14 | 1.548 (3) |
O3—C16 | 1.204 (3) | C8—C15 | 1.551 (3) |
O4—C16 | 1.365 (3) | C8—C9 | 1.588 (3) |
O4—C11 | 1.466 (3) | C9—C20 | 1.542 (3) |
O5—C5 | 1.417 (3) | C9—C11 | 1.547 (3) |
O5—C15 | 1.459 (3) | C9—C10 | 1.561 (3) |
C1—C2 | 1.532 (3) | C11—C12 | 1.529 (3) |
C1—C10 | 1.538 (3) | C11—H11 | 1 |
C1—H1A | 0.99 | C12—C13 | 1.530 (3) |
C1—H1B | 0.99 | C12—H12A | 0.99 |
C2—C3 | 1.529 (3) | C12—H12B | 0.99 |
C2—H2A | 0.99 | C13—C16 | 1.507 (3) |
C2—H2B | 0.99 | C13—C14 | 1.549 (3) |
C3—C4 | 1.548 (4) | C13—H13 | 1 |
C3—H3A | 0.99 | C14—H14A | 0.99 |
C3—H3B | 0.99 | C14—H14B | 0.99 |
C4—C19 | 1.526 (3) | C15—H15A | 0.99 |
C4—C18 | 1.528 (3) | C15—H15B | 0.99 |
C4—C5 | 1.545 (3) | C18—H18A | 0.98 |
C5—C6 | 1.538 (3) | C18—H18B | 0.98 |
C5—C10 | 1.548 (3) | C18—H18C | 0.98 |
C6—C7 | 1.546 (3) | C20—H20A | 0.98 |
C6—H6A | 0.99 | C20—H20B | 0.98 |
C6—H6B | 0.99 | C20—H20C | 0.98 |
C7—C8 | 1.537 (3) | ||
C19—O2—C10 | 108.32 (16) | C10—C9—C8 | 104.49 (15) |
C16—O4—C11 | 108.93 (18) | O2—C10—C1 | 106.45 (16) |
C5—O5—C15 | 109.62 (16) | O2—C10—C5 | 101.84 (16) |
C2—C1—C10 | 112.21 (19) | C1—C10—C5 | 110.25 (19) |
C2—C1—H1A | 109.2 | O2—C10—C9 | 112.09 (18) |
C10—C1—H1A | 109.2 | C1—C10—C9 | 116.12 (18) |
C2—C1—H1B | 109.2 | C5—C10—C9 | 109.13 (16) |
C10—C1—H1B | 109.2 | O4—C11—C12 | 101.57 (18) |
H1A—C1—H1B | 107.9 | O4—C11—C9 | 112.28 (17) |
C3—C2—C1 | 111.91 (19) | C12—C11—C9 | 111.5 (2) |
C3—C2—H2A | 109.2 | O4—C11—H11 | 110.4 |
C1—C2—H2A | 109.2 | C12—C11—H11 | 110.4 |
C3—C2—H2B | 109.2 | C9—C11—H11 | 110.4 |
C1—C2—H2B | 109.2 | C11—C12—C13 | 98.29 (17) |
H2A—C2—H2B | 107.9 | C11—C12—H12A | 112.1 |
C2—C3—C4 | 111.37 (19) | C13—C12—H12A | 112.1 |
C2—C3—H3A | 109.4 | C11—C12—H12B | 112.1 |
C4—C3—H3A | 109.4 | C13—C12—H12B | 112.1 |
C2—C3—H3B | 109.4 | H12A—C12—H12B | 109.7 |
C4—C3—H3B | 109.4 | C16—C13—C12 | 100.1 (2) |
H3A—C3—H3B | 108 | C16—C13—C14 | 109.68 (18) |
C19—C4—C18 | 112.5 (2) | C12—C13—C14 | 110.0 (2) |
C19—C4—C5 | 98.75 (17) | C16—C13—H13 | 112.2 |
C18—C4—C5 | 116.92 (18) | C12—C13—H13 | 112.2 |
C19—C4—C3 | 107.21 (18) | C14—C13—H13 | 112.2 |
C18—C4—C3 | 111.2 (2) | C8—C14—C13 | 114.37 (18) |
C5—C4—C3 | 109.32 (19) | C8—C14—H14A | 108.7 |
O5—C5—C6 | 107.46 (17) | C13—C14—H14A | 108.7 |
O5—C5—C4 | 115.18 (19) | C8—C14—H14B | 108.7 |
C6—C5—C4 | 112.14 (19) | C13—C14—H14B | 108.7 |
O5—C5—C10 | 108.48 (18) | H14A—C14—H14B | 107.6 |
C6—C5—C10 | 113.73 (19) | O5—C15—C8 | 112.46 (18) |
C4—C5—C10 | 99.85 (16) | O5—C15—H15A | 109.1 |
C5—C6—C7 | 108.81 (19) | C8—C15—H15A | 109.1 |
C5—C6—H6A | 109.9 | O5—C15—H15B | 109.1 |
C7—C6—H6A | 109.9 | C8—C15—H15B | 109.1 |
C5—C6—H6B | 109.9 | H15A—C15—H15B | 107.8 |
C7—C6—H6B | 109.9 | O3—C16—O4 | 121.0 (2) |
H6A—C6—H6B | 108.3 | O3—C16—C13 | 130.6 (2) |
C8—C7—C6 | 108.37 (18) | O4—C16—C13 | 108.3 (2) |
C8—C7—H7A | 110 | C4—C18—H18A | 109.5 |
C6—C7—H7A | 110 | C4—C18—H18B | 109.5 |
C8—C7—H7B | 110 | H18A—C18—H18B | 109.5 |
C6—C7—H7B | 110 | C4—C18—H18C | 109.5 |
H7A—C7—H7B | 108.4 | H18A—C18—H18C | 109.5 |
C7—C8—C14 | 110.29 (18) | H18B—C18—H18C | 109.5 |
C7—C8—C15 | 103.55 (17) | O1—C19—O2 | 120.6 (2) |
C14—C8—C15 | 110.00 (18) | O1—C19—C4 | 128.6 (2) |
C7—C8—C9 | 108.28 (17) | O2—C19—C4 | 110.72 (18) |
C14—C8—C9 | 112.37 (16) | C9—C20—H20A | 109.5 |
C15—C8—C9 | 111.98 (18) | C9—C20—H20B | 109.5 |
C20—C9—C11 | 105.52 (17) | H20A—C20—H20B | 109.5 |
C20—C9—C10 | 109.93 (18) | C9—C20—H20C | 109.5 |
C11—C9—C10 | 115.36 (18) | H20A—C20—H20C | 109.5 |
C20—C9—C8 | 111.39 (18) | H20B—C20—H20C | 109.5 |
C11—C9—C8 | 110.27 (17) | ||
C10—C1—C2—C3 | 45.2 (3) | C6—C5—C10—C9 | −42.1 (2) |
C1—C2—C3—C4 | −46.4 (3) | C4—C5—C10—C9 | −161.67 (19) |
C2—C3—C4—C19 | −43.7 (2) | C20—C9—C10—O2 | −16.4 (2) |
C2—C3—C4—C18 | −166.97 (19) | C11—C9—C10—O2 | 102.8 (2) |
C2—C3—C4—C5 | 62.4 (2) | C8—C9—C10—O2 | −135.99 (18) |
C15—O5—C5—C6 | 68.8 (2) | C20—C9—C10—C1 | −139.00 (18) |
C15—O5—C5—C4 | −165.43 (18) | C11—C9—C10—C1 | −19.9 (3) |
C15—O5—C5—C10 | −54.5 (2) | C8—C9—C10—C1 | 101.4 (2) |
C19—C4—C5—O5 | 156.8 (2) | C20—C9—C10—C5 | 95.7 (2) |
C18—C4—C5—O5 | −82.4 (3) | C11—C9—C10—C5 | −145.2 (2) |
C3—C4—C5—O5 | 45.0 (2) | C8—C9—C10—C5 | −23.9 (2) |
C19—C4—C5—C6 | −79.9 (2) | C16—O4—C11—C12 | −28.6 (2) |
C18—C4—C5—C6 | 40.9 (3) | C16—O4—C11—C9 | 90.7 (2) |
C3—C4—C5—C6 | 168.36 (18) | C20—C9—C11—O4 | −173.35 (17) |
C19—C4—C5—C10 | 40.9 (2) | C10—C9—C11—O4 | 65.1 (2) |
C18—C4—C5—C10 | 161.7 (2) | C8—C9—C11—O4 | −52.9 (2) |
C3—C4—C5—C10 | −70.9 (2) | C20—C9—C11—C12 | −60.1 (2) |
O5—C5—C6—C7 | −56.1 (2) | C10—C9—C11—C12 | 178.37 (18) |
C4—C5—C6—C7 | 176.38 (18) | C8—C9—C11—C12 | 60.3 (2) |
C10—C5—C6—C7 | 64.0 (2) | O4—C11—C12—C13 | 44.5 (2) |
C5—C6—C7—C8 | −11.8 (2) | C9—C11—C12—C13 | −75.3 (2) |
C6—C7—C8—C14 | −178.27 (18) | C11—C12—C13—C16 | −43.8 (2) |
C6—C7—C8—C15 | 64.1 (2) | C11—C12—C13—C14 | 71.6 (2) |
C6—C7—C8—C9 | −54.9 (2) | C7—C8—C14—C13 | 158.0 (2) |
C7—C8—C9—C20 | −42.6 (2) | C15—C8—C14—C13 | −88.4 (2) |
C14—C8—C9—C20 | 79.5 (2) | C9—C8—C14—C13 | 37.1 (3) |
C15—C8—C9—C20 | −156.15 (18) | C16—C13—C14—C8 | 51.8 (3) |
C7—C8—C9—C11 | −159.42 (19) | C12—C13—C14—C8 | −57.3 (3) |
C14—C8—C9—C11 | −37.4 (3) | C5—O5—C15—C8 | −11.1 (2) |
C15—C8—C9—C11 | 87.0 (2) | C7—C8—C15—O5 | −54.7 (2) |
C7—C8—C9—C10 | 76.0 (2) | C14—C8—C15—O5 | −172.58 (17) |
C14—C8—C9—C10 | −161.90 (19) | C9—C8—C15—O5 | 61.7 (2) |
C15—C8—C9—C10 | −37.5 (2) | C11—O4—C16—O3 | −177.8 (2) |
C19—O2—C10—C1 | −87.6 (2) | C11—O4—C16—C13 | −0.2 (2) |
C19—O2—C10—C5 | 27.9 (2) | C12—C13—C16—O3 | −153.9 (3) |
C19—O2—C10—C9 | 144.41 (18) | C14—C13—C16—O3 | 90.5 (3) |
C2—C1—C10—O2 | 50.0 (2) | C12—C13—C16—O4 | 28.8 (2) |
C2—C1—C10—C5 | −59.7 (2) | C14—C13—C16—O4 | −86.8 (2) |
C2—C1—C10—C9 | 175.56 (18) | C10—O2—C19—O1 | 178.7 (2) |
O5—C5—C10—O2 | −163.91 (17) | C10—O2—C19—C4 | −0.8 (3) |
C6—C5—C10—O2 | 76.6 (2) | C18—C4—C19—O1 | 30.1 (4) |
C4—C5—C10—O2 | −43.0 (2) | C5—C4—C19—O1 | 154.1 (3) |
O5—C5—C10—C1 | −51.2 (2) | C3—C4—C19—O1 | −92.4 (3) |
C6—C5—C10—C1 | −170.71 (18) | C18—C4—C19—O2 | −150.5 (2) |
C4—C5—C10—C1 | 69.7 (2) | C5—C4—C19—O2 | −26.5 (2) |
O5—C5—C10—C9 | 77.4 (2) | C3—C4—C19—O2 | 87.0 (2) |
Experimental details
Crystal data | |
Chemical formula | C19H24O5 |
Mr | 332.38 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 6.6980 (2), 13.6063 (3), 17.2155 (5) |
V (Å3) | 1568.85 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.25 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3592, 2074, 1857 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.122, 1.19 |
No. of reflections | 2074 |
No. of parameters | 219 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.52 |
Computer programs: COLLECT (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
O1—C19 | 1.208 (3) | C4—C19 | 1.526 (3) |
O2—C19 | 1.364 (3) | C4—C5 | 1.545 (3) |
O2—C10 | 1.474 (3) | C5—C10 | 1.548 (3) |
O3—C16 | 1.204 (3) | C8—C15 | 1.551 (3) |
O4—C16 | 1.365 (3) | C11—C12 | 1.529 (3) |
O4—C11 | 1.466 (3) | C12—C13 | 1.530 (3) |
O5—C5 | 1.417 (3) | C13—C16 | 1.507 (3) |
O5—C15 | 1.459 (3) | ||
C19—O2—C10 | 108.32 (16) | O3—C16—O4 | 121.0 (2) |
C16—O4—C11 | 108.93 (18) | O1—C19—O2 | 120.6 (2) |
C5—O5—C15 | 109.62 (16) |
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Natural and synthetic diterpene lactones show many important biological activities: anti-HIV (Chen et al., 1992), antitumor (Ghisalberti, 1997) and allelopathic (e.g. the phytohormones gibberellins), among others. In an attempt to synthesize novel diterpene lactones from natural sources, for biological screening, the norketone (2), obtained from grandiflorenic acid (1), isolated from Wedelia paludosa (Asteraceae), was submitted to a Baeyer–Villiger oxidation (Anastasia et al., 1985). The product was the very rearranged dilactone (3), whose structure was unambiguously confirmed by X-ray analysis.
Fig. 1 shows an ORTEP-3 (Farrugia, 1997) view of (3). X-ray crystallographic analysis showed that a rearrangement involving C20 occurred, leading to the formation of a lactone in ring A. This rearrangement is common in natural diterpenoids, such as tetrachirin (Zabel et al., 1980; Vieira et al., 2001) and eupatalbin (Herz et al., 1979). Two other changes on the skeleton of (1) occurred: ring D rearrangement leading to the formation of a second lactone moiety, as well as an ether linkage on ring B between C5 and C15 in (3).
The main bond lengths and angles are given in Table 1. The mean value of the C—C single bond distances is 1.54 (2) Å, in good agreement with the expected value for formal single bonds (Orpen et al., 1992). The C—O single-bond lengths are very similar [mean 1.46 (2) Å], except for O2—C19 and O4—C16 ones, whose bond lengths are 1.364 (2) and 1.367 (2) Å, respectively. This decrease in bond length is a consequence of resonance involving the trio O═C—O localized in the two lactones rings. The O1═C19 and O3═C16 bond lengths of the two carbonyl are 1.202 (3) and 1.205 (3) Å, respectively. The three C—O—C angles are also similar [mean 109 (1)°]. The two lactone rings are in envelope conformations, with atoms C5 and C12 in the flap positions (Cremer & Pople, 1975). No intra- or intermolecular hydrogen bonds occur in the structure of (3).