Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017050/sk1651sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017050/sk1651Isup2.hkl |
CCDC reference: 205654
The shade-dried powdered aerial parts (8.4 kg) of Teucrium tomentosum were exhaustively percolated with acetone (3 x 35 l). The extract was then dried in a rotary evaporator to yield a residue (146 g), 55 g of which were subjected to column chromatography using Silica gel (70–325) and eluted with chloroform–methanol (1:100), thus yielding 69 fractions in total. Fractions 28–38 were further chromatographed over Silica gel (70–325) and eluted with n-hexane–ethyl acetate (1:100) to yield Teuctosin (75 mg). Needle-shaped crystals of the compound were obtained from a mixture of methanol and chloroform at room temperature (293 K).
In the absence of suitable anomalous scatters, Friedel equivalents could not be used to determine the absolute structure. Refinement of the Flack parameter (Flack, 1983) led to inconclusive values (Flack & Bernadinelli, 2000) for this parameter [0.1 (8)]. Therefore, the 1990 Friedel equivalents were merged before the final refinement. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of diterpenes (Rogers et al., 1979; De la Torre et al., 1994; Rodriguez et al., 1994). The CH, CH2 and OH H atoms were constrained to an ideal geometry [C—H = 0.98 Å, C—H2 = 0.97 Å and O—H = 0.82 Å, with Uiso(H) = 1.5Ueq(parent atom)], but where allowed to rotate freely about the C—C and C—O bonds, respectively. All remaining H atoms were placed in idealized positions (C—H = 0.97—0.98 Å) and constrained to ride on their parent atom with Uiso(H) values of 1.2 Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST97 (Nardelli, 1995).
C22H28O8 | F(000) = 896 |
Mr = 420.44 | Dx = 1.366 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5722 reflections |
a = 7.7235 (5) Å | θ = 2.6–27.8° |
b = 19.0625 (9) Å | µ = 0.10 mm−1 |
c = 13.8907 (13) Å | T = 293 K |
V = 2045.1 (3) Å3 | Needle, colourless |
Z = 4 | 0.25 × 0.19 × 0.15 mm |
CCD area-detector diffractometer | 2526 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 28.0°, θmin = 1.8° |
ω scan | h = −9→10 |
12937 measured reflections | k = −25→14 |
2759 independent reflections | l = −18→17 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0779P)2 + 0.2384P] where P = (Fo2 + 2Fc2)/3 |
2759 reflections | (Δ/σ)max < 0.001 |
273 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C22H28O8 | V = 2045.1 (3) Å3 |
Mr = 420.44 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.7235 (5) Å | µ = 0.10 mm−1 |
b = 19.0625 (9) Å | T = 293 K |
c = 13.8907 (13) Å | 0.25 × 0.19 × 0.15 mm |
CCD area-detector diffractometer | 2526 reflections with I > 2σ(I) |
12937 measured reflections | Rint = 0.022 |
2759 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.32 e Å−3 |
2759 reflections | Δρmin = −0.15 e Å−3 |
273 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 > 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. |
x | y | z | Uiso*/Ueq | ||
O3 | 0.4325 (2) | 0.25616 (8) | 0.28124 (10) | 0.0429 (4) | |
O4 | 0.7153 (2) | 0.21616 (9) | 0.40739 (13) | 0.0483 (4) | |
O6 | 0.6961 (2) | 0.02574 (8) | 0.38171 (11) | 0.0432 (4) | |
O12 | 0.0473 (2) | −0.02426 (8) | 0.38320 (10) | 0.0399 (3) | |
O16 | −0.1148 (4) | −0.21093 (12) | 0.5596 (2) | 0.0885 (8) | |
O19 | 0.4467 (2) | 0.12295 (9) | 0.64385 (10) | 0.0437 (4) | |
O20 | 0.2883 (2) | 0.04278 (9) | 0.71134 (10) | 0.0459 (4) | |
O21 | 0.4527 (3) | 0.35577 (9) | 0.36679 (13) | 0.0551 (5) | |
C1 | 0.2141 (2) | 0.12334 (11) | 0.43841 (14) | 0.0328 (4) | |
H1A | 0.1973 | 0.1530 | 0.4944 | 0.039* | |
H1B | 0.1095 | 0.0961 | 0.4287 | 0.039* | |
C2 | 0.2481 (3) | 0.16878 (11) | 0.35024 (16) | 0.0384 (5) | |
H2A | 0.2685 | 0.1391 | 0.2947 | 0.046* | |
H2B | 0.1474 | 0.1977 | 0.3371 | 0.046* | |
C3 | 0.4040 (3) | 0.21512 (11) | 0.36734 (14) | 0.0356 (4) | |
H3 | 0.3798 | 0.2468 | 0.4212 | 0.043* | |
C4 | 0.5641 (3) | 0.17236 (11) | 0.39022 (15) | 0.0344 (4) | |
C5 | 0.5384 (2) | 0.11518 (10) | 0.46797 (13) | 0.0291 (4) | |
C6 | 0.6921 (2) | 0.06328 (11) | 0.47095 (15) | 0.0353 (4) | |
H6 | 0.8005 | 0.0894 | 0.4789 | 0.042* | |
C7 | 0.6727 (3) | 0.01107 (12) | 0.55253 (17) | 0.0388 (5) | |
H7A | 0.6795 | 0.0357 | 0.6135 | 0.047* | |
H7B | 0.7671 | −0.0224 | 0.5500 | 0.047* | |
H6A | 0.7907 | 0.0067 | 0.3754 | 0.065* | |
C8 | 0.5006 (2) | −0.02813 (11) | 0.54669 (15) | 0.0336 (4) | |
C9 | 0.3445 (2) | 0.02451 (10) | 0.54306 (13) | 0.0286 (4) | |
H8 | 0.5007 | −0.0533 | 0.4851 | 0.040* | |
C10 | 0.3671 (2) | 0.07403 (9) | 0.45560 (13) | 0.0267 (3) | |
C11 | 0.1691 (2) | −0.01516 (10) | 0.54300 (13) | 0.0306 (4) | |
C12 | 0.1364 (3) | −0.06269 (10) | 0.45693 (14) | 0.0332 (4) | |
C13 | 0.0311 (3) | −0.12697 (11) | 0.48178 (19) | 0.0434 (5) | |
C14 | −0.0427 (6) | −0.17407 (16) | 0.4137 (3) | 0.0803 (10) | |
C15 | −0.1281 (6) | −0.22285 (17) | 0.4640 (4) | 0.0962 (14) | |
C16 | −0.0171 (4) | −0.15182 (14) | 0.5680 (2) | 0.0606 (7) | |
H10 | 0.3792 | 0.0445 | 0.3982 | 0.032* | |
C17 | 0.4918 (3) | −0.08413 (13) | 0.6258 (2) | 0.0527 (6) | |
C18 | 0.7112 (3) | 0.17230 (13) | 0.32312 (18) | 0.0477 (5) | |
H18A | 0.7855 | 0.1313 | 0.3222 | 0.057* | |
H18B | 0.6956 | 0.1949 | 0.2612 | 0.057* | |
C19 | 0.5310 (3) | 0.15653 (11) | 0.56329 (14) | 0.0359 (4) | |
H19A | 0.6487 | 0.1676 | 0.5822 | 0.043* | |
H19B | 0.4723 | 0.2006 | 0.5510 | 0.043* | |
C20 | 0.3534 (3) | 0.06463 (11) | 0.63771 (13) | 0.0338 (4) | |
H11A | 0.1627 | −0.0434 | 0.6010 | 0.037* | |
H11B | 0.0766 | 0.0192 | 0.5461 | 0.037* | |
H12 | 0.2484 | −0.0780 | 0.4313 | 0.040* | |
H16 | 0.0126 | −0.1312 | 0.6264 | 0.073* | |
H12A | 0.0903 | −0.0333 | 0.3307 | 0.060* | |
H15 | −0.1887 | −0.2601 | 0.4368 | 0.115* | |
H14 | −0.0334 | −0.1714 | 0.3470 | 0.096* | |
C21 | 0.4566 (3) | 0.32605 (12) | 0.29086 (16) | 0.0399 (5) | |
C22 | 0.4886 (5) | 0.35890 (15) | 0.1954 (2) | 0.0643 (8) | |
H22A | 0.4840 | 0.3236 | 0.1462 | 0.096* | |
H22B | 0.6008 | 0.3806 | 0.1952 | 0.096* | |
H22C | 0.4016 | 0.3938 | 0.1831 | 0.096* | |
H17A | 0.3840 | −0.1090 | 0.6212 | 0.079* | |
H17B | 0.4998 | −0.0620 | 0.6878 | 0.079* | |
H17C | 0.5860 | −0.1165 | 0.6181 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0571 (10) | 0.0368 (7) | 0.0347 (7) | −0.0080 (7) | −0.0012 (7) | 0.0047 (6) |
O4 | 0.0390 (8) | 0.0464 (9) | 0.0596 (9) | −0.0156 (7) | 0.0009 (8) | 0.0003 (8) |
O6 | 0.0346 (8) | 0.0465 (8) | 0.0486 (8) | 0.0053 (7) | 0.0060 (7) | −0.0110 (7) |
O12 | 0.0411 (8) | 0.0492 (8) | 0.0294 (6) | 0.0040 (7) | 0.0020 (6) | −0.0005 (6) |
O16 | 0.0793 (16) | 0.0546 (12) | 0.132 (2) | −0.0257 (12) | −0.0133 (17) | 0.0301 (14) |
O19 | 0.0528 (9) | 0.0474 (8) | 0.0307 (7) | −0.0072 (8) | −0.0006 (7) | −0.0093 (6) |
O20 | 0.0456 (9) | 0.0653 (10) | 0.0268 (6) | −0.0021 (8) | 0.0009 (7) | 0.0010 (7) |
O21 | 0.0708 (12) | 0.0404 (8) | 0.0542 (10) | −0.0084 (9) | 0.0162 (10) | −0.0038 (8) |
C1 | 0.0255 (8) | 0.0346 (9) | 0.0384 (9) | 0.0025 (8) | 0.0018 (8) | 0.0019 (8) |
C2 | 0.0339 (10) | 0.0384 (10) | 0.0430 (10) | −0.0003 (9) | −0.0059 (8) | 0.0059 (9) |
C3 | 0.0405 (11) | 0.0323 (9) | 0.0341 (9) | −0.0019 (8) | 0.0017 (8) | 0.0036 (8) |
C4 | 0.0328 (10) | 0.0344 (9) | 0.0361 (9) | −0.0074 (8) | 0.0024 (8) | −0.0038 (8) |
C5 | 0.0247 (8) | 0.0312 (9) | 0.0313 (8) | −0.0010 (7) | 0.0003 (7) | −0.0044 (7) |
C6 | 0.0221 (8) | 0.0407 (10) | 0.0432 (10) | 0.0000 (8) | −0.0003 (8) | −0.0054 (9) |
C7 | 0.0269 (9) | 0.0416 (11) | 0.0480 (11) | 0.0054 (8) | −0.0050 (8) | −0.0007 (9) |
C8 | 0.0274 (9) | 0.0339 (9) | 0.0396 (10) | 0.0037 (7) | 0.0001 (8) | 0.0016 (8) |
C9 | 0.0256 (8) | 0.0327 (9) | 0.0275 (8) | 0.0024 (7) | 0.0010 (7) | −0.0017 (7) |
C10 | 0.0241 (7) | 0.0291 (8) | 0.0270 (8) | 0.0008 (7) | 0.0005 (7) | −0.0024 (7) |
C11 | 0.0270 (9) | 0.0355 (9) | 0.0294 (8) | −0.0005 (7) | 0.0028 (7) | 0.0014 (8) |
C12 | 0.0269 (8) | 0.0358 (9) | 0.0370 (9) | 0.0027 (8) | 0.0022 (8) | −0.0025 (8) |
C13 | 0.0359 (10) | 0.0325 (9) | 0.0617 (13) | 0.0031 (9) | −0.0082 (11) | −0.0023 (10) |
C14 | 0.095 (3) | 0.0558 (16) | 0.090 (2) | −0.0234 (19) | −0.025 (2) | −0.0132 (16) |
C16 | 0.0591 (16) | 0.0479 (13) | 0.0747 (17) | −0.0159 (12) | −0.0020 (15) | 0.0153 (13) |
C15 | 0.097 (3) | 0.0468 (16) | 0.145 (4) | −0.0287 (18) | −0.040 (3) | 0.006 (2) |
C17 | 0.0436 (12) | 0.0462 (12) | 0.0683 (16) | 0.0097 (11) | 0.0019 (12) | 0.0195 (12) |
C18 | 0.0435 (12) | 0.0480 (12) | 0.0516 (12) | −0.0077 (11) | 0.0140 (11) | 0.0026 (10) |
C19 | 0.0363 (10) | 0.0365 (10) | 0.0349 (9) | −0.0036 (8) | −0.0031 (9) | −0.0067 (8) |
C20 | 0.0294 (9) | 0.0442 (11) | 0.0278 (8) | 0.0056 (8) | −0.0029 (7) | −0.0028 (8) |
C21 | 0.0352 (10) | 0.0388 (10) | 0.0456 (11) | −0.0060 (9) | −0.0002 (10) | 0.0053 (9) |
C22 | 0.086 (2) | 0.0544 (15) | 0.0527 (14) | −0.0232 (15) | −0.0048 (15) | 0.0157 (12) |
C1—C10 | 1.529 (2) | C10—H10 | 0.9800 |
C1—C2 | 1.523 (3) | C18—H18A | 0.9700 |
C1—H1A | 0.9700 | C18—H18B | 0.9700 |
C1—H1B | 0.9700 | C19—O19 | 1.444 (3) |
C2—C3 | 1.513 (3) | C19—H19A | 0.9700 |
C2—H2A | 0.9700 | C19—H19B | 0.9700 |
C2—H2B | 0.9700 | O19—C20 | 1.327 (3) |
O3—C21 | 1.352 (3) | C20—O20 | 1.214 (2) |
O3—C3 | 1.446 (2) | C11—C12 | 1.521 (3) |
C3—C4 | 1.514 (3) | C11—H11A | 0.9700 |
C3—H3 | 0.9800 | C11—H11B | 0.9700 |
C4—O4 | 1.455 (2) | C12—O12 | 1.435 (2) |
C4—C18 | 1.470 (3) | C12—C13 | 1.511 (3) |
C4—C5 | 1.547 (3) | C12—H12 | 0.9800 |
O4—C18 | 1.439 (3) | C13—C16 | 1.340 (4) |
C5—C19 | 1.542 (2) | C13—C14 | 1.424 (4) |
C5—C10 | 1.548 (2) | C16—O16 | 1.361 (3) |
C5—C6 | 1.546 (3) | C16—H16 | 0.9300 |
C6—O6 | 1.432 (2) | O12—H12A | 0.8200 |
C6—C7 | 1.516 (3) | O16—C15 | 1.351 (5) |
C6—H6 | 0.9800 | C15—C14 | 1.337 (5) |
C7—C8 | 1.527 (3) | C15—H15 | 0.9300 |
C7—H7A | 0.9700 | C14—H14 | 0.9300 |
C7—H7B | 0.9700 | C21—O21 | 1.198 (3) |
O6—H6A | 0.8200 | C21—C22 | 1.487 (3) |
C9—C20 | 1.523 (2) | C22—H22A | 0.9600 |
C9—C10 | 1.548 (3) | C22—H22B | 0.9600 |
C9—C11 | 1.551 (2) | C22—H22C | 0.9600 |
C9—C8 | 1.570 (3) | C17—H17A | 0.9600 |
C8—C17 | 1.534 (3) | C17—H17B | 0.9600 |
C8—H8 | 0.9800 | C17—H17C | 0.9600 |
C10—C1—C2 | 110.02 (16) | C1—C10—H10 | 107.4 |
C10—C1—H1A | 109.7 | C9—C10—H10 | 107.4 |
C2—C1—H1A | 109.7 | C5—C10—H10 | 107.4 |
C10—C1—H1B | 109.7 | O4—C18—C4 | 60.03 (14) |
C2—C1—H1B | 109.7 | O4—C18—H18A | 117.8 |
H1A—C1—H1B | 108.2 | C4—C18—H18A | 117.8 |
C3—C2—C1 | 110.06 (17) | O4—C18—H18B | 117.8 |
C3—C2—H2A | 109.6 | C4—C18—H18B | 117.8 |
C1—C2—H2A | 109.6 | H18A—C18—H18B | 114.9 |
C3—C2—H2B | 109.6 | O19—C19—C5 | 117.11 (16) |
C1—C2—H2B | 109.6 | O19—C19—H19A | 108.0 |
H2A—C2—H2B | 108.2 | C5—C19—H19A | 108.0 |
C21—O3—C3 | 118.19 (16) | O19—C19—H19B | 108.0 |
O3—C3—C4 | 109.91 (17) | C5—C19—H19B | 108.0 |
O3—C3—C2 | 107.90 (17) | H19A—C19—H19B | 107.3 |
C4—C3—C2 | 111.63 (16) | C20—O19—C19 | 124.47 (15) |
O3—C3—H3 | 109.1 | O20—C20—O19 | 117.28 (18) |
C4—C3—H3 | 109.1 | O20—C20—C9 | 122.44 (19) |
C2—C3—H3 | 109.1 | O19—C20—C9 | 120.06 (17) |
O4—C4—C18 | 58.93 (15) | C12—C11—C9 | 115.82 (15) |
O4—C4—C3 | 112.37 (16) | C12—C11—H11A | 108.3 |
C18—C4—C3 | 119.90 (19) | C9—C11—H11A | 108.3 |
O4—C4—C5 | 113.11 (17) | C12—C11—H11B | 108.3 |
C18—C4—C5 | 122.76 (19) | C9—C11—H11B | 108.3 |
C3—C4—C5 | 114.91 (16) | H11A—C11—H11B | 107.4 |
C18—O4—C4 | 61.04 (13) | O12—C12—C13 | 108.60 (17) |
C19—C5—C10 | 108.82 (15) | O12—C12—C11 | 109.67 (15) |
C19—C5—C4 | 104.13 (15) | C13—C12—C11 | 113.13 (17) |
C10—C5—C4 | 112.89 (16) | O12—C12—H12 | 108.4 |
C19—C5—C6 | 109.43 (16) | C13—C12—H12 | 108.4 |
C10—C5—C6 | 109.58 (14) | C11—C12—H12 | 108.4 |
C4—C5—C6 | 111.79 (16) | C16—C13—C14 | 105.0 (3) |
O6—C6—C7 | 108.74 (16) | C16—C13—C12 | 129.8 (2) |
O6—C6—C5 | 108.25 (16) | C14—C13—C12 | 125.1 (3) |
C7—C6—C5 | 111.35 (16) | C13—C16—O16 | 111.7 (3) |
O6—C6—H6 | 109.5 | C13—C16—H16 | 124.1 |
C7—C6—H6 | 109.5 | O16—C16—H16 | 124.1 |
C5—C6—H6 | 109.5 | C12—O12—H12A | 109.5 |
C6—C7—C8 | 111.60 (17) | C15—O16—C16 | 105.4 (3) |
C6—C7—H7A | 109.3 | O16—C15—C14 | 111.1 (3) |
C8—C7—H7A | 109.3 | O16—C15—H15 | 124.5 |
C6—C7—H7B | 109.3 | C14—C15—H15 | 124.5 |
C8—C7—H7B | 109.3 | C15—C14—C13 | 106.8 (3) |
H7A—C7—H7B | 108.0 | C15—C14—H14 | 126.6 |
C6—O6—H6A | 109.5 | C13—C14—H14 | 126.6 |
C20—C9—C10 | 111.48 (15) | O21—C21—O3 | 123.3 (2) |
C20—C9—C11 | 106.56 (15) | O21—C21—C22 | 126.2 (2) |
C10—C9—C11 | 113.29 (15) | O3—C21—C22 | 110.5 (2) |
C20—C9—C8 | 104.98 (15) | C21—C22—H22A | 109.5 |
C10—C9—C8 | 109.16 (14) | C21—C22—H22B | 109.5 |
C11—C9—C8 | 111.04 (15) | H22A—C22—H22B | 109.5 |
C17—C8—C7 | 109.95 (17) | C21—C22—H22C | 109.5 |
C17—C8—C9 | 115.71 (17) | H22A—C22—H22C | 109.5 |
C7—C8—C9 | 110.95 (16) | H22B—C22—H22C | 109.5 |
C17—C8—H8 | 106.6 | C8—C17—H17A | 109.5 |
C7—C8—H8 | 106.6 | C8—C17—H17B | 109.5 |
C9—C8—H8 | 106.6 | H17A—C17—H17B | 109.5 |
C1—C10—C9 | 114.22 (15) | C8—C17—H17C | 109.5 |
C1—C10—C5 | 111.50 (14) | H17A—C17—H17C | 109.5 |
C9—C10—C5 | 108.56 (14) | H17B—C17—H17C | 109.5 |
C10—C1—C2—C3 | −63.2 (2) | C8—C9—C10—C1 | 174.39 (15) |
C21—O3—C3—C4 | −106.6 (2) | C20—C9—C10—C5 | 55.01 (18) |
C21—O3—C3—C2 | 131.5 (2) | C11—C9—C10—C5 | 175.20 (14) |
C1—C2—C3—O3 | 179.01 (16) | C8—C9—C10—C5 | −60.51 (18) |
C1—C2—C3—C4 | 58.1 (2) | C19—C5—C10—C1 | 68.20 (19) |
O3—C3—C4—O4 | 60.6 (2) | C4—C5—C10—C1 | −46.9 (2) |
C2—C3—C4—O4 | −179.70 (16) | C6—C5—C10—C1 | −172.19 (16) |
O3—C3—C4—C18 | −5.4 (3) | C19—C5—C10—C9 | −58.49 (18) |
C2—C3—C4—C18 | 114.3 (2) | C4—C5—C10—C9 | −173.56 (15) |
O3—C3—C4—C5 | −168.15 (15) | C6—C5—C10—C9 | 61.13 (18) |
C2—C3—C4—C5 | −48.5 (2) | C3—C4—C18—O4 | 99.6 (2) |
C3—C4—O4—C18 | −112.4 (2) | C5—C4—C18—O4 | −99.0 (2) |
C5—C4—O4—C18 | 115.5 (2) | C10—C5—C19—O19 | 37.2 (2) |
O4—C4—C5—C19 | 55.9 (2) | C4—C5—C19—O19 | 157.86 (18) |
C18—C4—C5—C19 | 122.8 (2) | C6—C5—C19—O19 | −82.5 (2) |
C3—C4—C5—C19 | −75.0 (2) | C5—C19—O19—C20 | −10.8 (3) |
O4—C4—C5—C10 | 173.77 (15) | C19—O19—C20—O20 | −179.1 (2) |
C18—C4—C5—C10 | −119.4 (2) | C19—O19—C20—C9 | 6.2 (3) |
C3—C4—C5—C10 | 42.9 (2) | C10—C9—C20—O20 | 156.6 (2) |
O4—C4—C5—C6 | −62.1 (2) | C11—C9—C20—O20 | 32.5 (3) |
C18—C4—C5—C6 | 4.7 (3) | C8—C9—C20—O20 | −85.3 (2) |
C3—C4—C5—C6 | 166.99 (16) | C10—C9—C20—O19 | −29.0 (2) |
C19—C5—C6—O6 | −179.92 (15) | C11—C9—C20—O19 | −153.03 (18) |
C10—C5—C6—O6 | 60.84 (19) | C8—C9—C20—O19 | 89.1 (2) |
C4—C5—C6—O6 | −65.1 (2) | C20—C9—C11—C12 | −176.55 (16) |
C19—C5—C6—C7 | 60.6 (2) | C10—C9—C11—C12 | 60.5 (2) |
C10—C5—C6—C7 | −58.6 (2) | C8—C9—C11—C12 | −62.8 (2) |
C4—C5—C6—C7 | 175.43 (16) | C9—C11—C12—O12 | −91.59 (19) |
O6—C6—C7—C8 | −63.7 (2) | C9—C11—C12—C13 | 147.02 (17) |
C5—C6—C7—C8 | 55.5 (2) | O12—C12—C13—C16 | −131.3 (3) |
C6—C7—C8—C17 | 175.81 (18) | C11—C12—C13—C16 | −9.3 (3) |
C6—C7—C8—C9 | −54.9 (2) | O12—C12—C13—C14 | 47.1 (3) |
C20—C9—C8—C17 | 64.2 (2) | C11—C12—C13—C14 | 169.1 (3) |
C10—C9—C8—C17 | −176.23 (18) | C14—C13—C16—O16 | 0.2 (3) |
C11—C9—C8—C17 | −50.6 (2) | C12—C13—C16—O16 | 178.9 (2) |
C20—C9—C8—C7 | −62.0 (2) | C13—C16—O16—C15 | −0.3 (4) |
C10—C9—C8—C7 | 57.6 (2) | C16—O16—C15—C14 | 0.3 (5) |
C11—C9—C8—C7 | −176.76 (17) | O16—C15—C14—C13 | −0.1 (5) |
C2—C1—C10—C9 | −179.12 (15) | C16—C13—C14—C15 | 0.0 (4) |
C2—C1—C10—C5 | 57.3 (2) | C12—C13—C14—C15 | −178.8 (3) |
C20—C9—C10—C1 | −70.1 (2) | C3—O3—C21—O21 | −1.2 (4) |
C11—C9—C10—C1 | 50.1 (2) | C3—O3—C21—C22 | 178.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O12i | 0.82 | 2.07 | 2.875 (2) | 166 |
O12—H12A···O20ii | 0.82 | 1.91 | 2.727 (2) | 171 |
C19—H19A···O21iii | 0.97 | 2.49 | 3.407 (3) | 157 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, −y, z−1/2; (iii) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H28O8 |
Mr | 420.44 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.7235 (5), 19.0625 (9), 13.8907 (13) |
V (Å3) | 2045.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.25 × 0.19 × 0.15 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12937, 2759, 2526 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.04 |
No. of reflections | 2759 |
No. of parameters | 273 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.15 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 1997) and PARST97 (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O12i | 0.82 | 2.07 | 2.875 (2) | 166 |
O12—H12A···O20ii | 0.82 | 1.91 | 2.727 (2) | 171 |
C19—H19A···O21iii | 0.97 | 2.49 | 3.407 (3) | 157 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, −y, z−1/2; (iii) x+1/2, −y+1/2, −z+1. |
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A large number of diterpenoids with the clerodane skeleton have been isolated from plants belonging to the genus Teucrium of the family Labiatae, from which a large number of clerodanes have been isolated in the past few years (Merrit & Ley, 1992; Rodriguez et al., 1994; Piozzi et al., 1998). The present study was carried out as part of our ongoing research on the structures of ecofriendly bioinsecticides. Interest in these compounds has been stimulated by their biological activity, particularly as antifeedant agents against lepidopterous pests (De la Torre et al., 1994; Merrit & Ley, 1992). The chemical structure of (I) was obtained from C13 and H1 NMR data and HMBC (Heteronuclear Multiple Bond Correlation) and the three-dimensional structure was obtained via single-crystal X-ray diffraction.
Rings A and B have distorted-chair and chair, respectively [QT =0.553 (2) Å, ϕ2 =-89.7 (7) ° and q2 =0.126 (1) Å for ring A, and QT =0.610 (1) Å, ϕ2 =0.3(1.5) ° and q2 =0.056 (2) Å for ring B; Cremer & Pople, 1975]. The lactone ring, C, adopts a sofa conformation [QT =0.502 (1) Å, ϕ2 =8.94 (2) ° and q2 = 0.367 (1) Å], whereas the ring D is planar (Nardelli, 1995). All interatomic distances and angles have normal values. Rings A/B and B/C are trans fused and ring A/C is cis fused. The furan ring, D, is in a synclinal conformation with respect to ring B [C11—C12—C13—C16 = −9.3 (3) °]. The acetyl group on atom C3 is in an anticlinal conformation as described by the C21—O3—C3—C2 dihedral angle [131.5 (2) °]. The methyl group on atom C8 is in an α configuration, whereas the hydroxyl group on atom C6 is in a β configuration.
The ORTEPIII (Burnett & Johnson, 1996) diagram of the molecule (Fig. 1) shows that the displacement parameters are normal; however, the furan ring is highly distorted, which can be attributed to rotational disorder about the C9—C11 bond, as demonstrated by the steady increase in the value of the thermal parameters from atoms C9 to C15. Similar behaviour is observed in many of the limonoids (Kabaleeswaran et al., 1997; 2000; Narayanan et al., 1980; Malathi et al., 2002).
The packing of the molecules (Fig.2) reveals that the crystal lattice is stabilized by a two-dimensional network (in the ab plane) of hydrogen bonds. The O6···O12 hydrogen bond forms an infinite chain along the [100] direction, forming a graph-set motif (Bernstein et al., 1995) of C(9), and the other O12···O20 bond forms a graph-set motif of C(7). In addition, there is a C—H···O hydrogen bond observed atoms C19 and O21 (Table 1). The two O—H···O hydrogen bonds in the crystal lattice together form an R44(26) ring motif.