Samaderin B, or (1R,2S,5R,5aR,7aS,11S,11aS,11bR,14S)-1,7,7a,11,11a,11b-hexahydro-1,11-dihydroxy-8,11a,14-trimethyl-2H-5a,2,5-(methanoxymetheno)naphth[1,2-d]oxepine-4,6,10(5H)-trione, C19H22O7, and samaderin C, or (1R,2S,5R,5aR,7aS,10S,11S,11aS,11bR,14S)-7,7a,10,11,11a,11b-hexahydro-1,10,11-trihydroxy-8,11a,14-trimethyl-2H-5a,2,5-(methanoxymetheno)naphth[1,2-d]oxepine-4,6(1H,5H)-dione, C19H24O7, were isolated from the seed kernels of Samadera indica and were shown to exhibit antifeedant activity against Spodoptera litura third-instar larvae. The replacement of the carbonyl group in samaderin B by a hydroxy group in samaderin C causes conformational changes at the substitution site, but the overall conformation is not affected; however, the compounds pack differently in the crystal lattice.
Supporting information
CCDC references: 159666; 159667
Compounds (I) and (II) were isolated from the seed kernels of Samadera indica according to the procedure described by Govindachari et al. (2001).
In the absence of suitable anomalous scatters, Friedel equivalents could not be used to determine the absolute structure. Refinement of the Flack (1983) parameter led to inconclusive values (Flack & Bernadinelli, 2000) for this parameter [0.9 (8) for (I) and −0.2 (3) for (II)]. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of quassinoids (Polonsky, 1985). The methyl and hydroxyl H atoms were constrained to an ideal geometry [C—H = 0.96 and O—H = 0.82 Å, with Uiso(H) = 1.5Ueq(parent atom)] but were 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 atoms with Uiso(H) values equal to 1.2Ueq(C).
For both compounds, 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: 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 and PARST (Nardelli, 1995).
Crystal data top
C19H22O7 | F(000) = 768 |
Mr = 362.37 | Dx = 1.460 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 10.342 (4) Å | θ = 15–30° |
b = 13.328 (7) Å | µ = 0.94 mm−1 |
c = 11.956 (9) Å | T = 293 K |
V = 1648.0 (16) Å3 | Rod shaped, colourless |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.060 |
Radiation source: fine-focus sealed tube | θmax = 72.0°, θmin = 5.4° |
Graphite monochromator | h = −12→12 |
non–profiled ω/2θ scans | k = 0→16 |
1807 measured reflections | l = 0→14 |
1741 independent reflections | 3 standard reflections every 200 reflections |
1203 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.208 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1269P)2 + 0.1667P] where P = (Fo2 + 2Fc2)/3 |
1741 reflections | (Δ/σ)max < 0.001 |
238 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
C19H22O7 | V = 1648.0 (16) Å3 |
Mr = 362.37 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 10.342 (4) Å | µ = 0.94 mm−1 |
b = 13.328 (7) Å | T = 293 K |
c = 11.956 (9) Å | 0.30 × 0.20 × 0.10 mm |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.060 |
1807 measured reflections | 3 standard reflections every 200 reflections |
1741 independent reflections | intensity decay: 1% |
1203 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.208 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.37 e Å−3 |
1741 reflections | Δρmin = −0.42 e Å−3 |
238 parameters | |
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 | 0.1276 (5) | 0.6090 (5) | 0.4430 (4) | 0.0507 (14) | |
H1 | 0.1621 | 0.6359 | 0.3891 | 0.076* | |
O2 | 0.3732 (5) | 0.6576 (5) | 0.4484 (4) | 0.0539 (15) | |
O7 | −0.0455 (6) | 0.6100 (6) | 0.9624 (5) | 0.085 (2) | |
O11 | −0.0691 (5) | 0.4558 (4) | 0.5223 (4) | 0.0519 (14) | |
H11 | −0.0966 | 0.4130 | 0.5654 | 0.078* | |
O12 | −0.2826 (4) | 0.6563 (4) | 0.6204 (5) | 0.0441 (13) | |
O13 | −0.1924 (4) | 0.4116 (3) | 0.7216 (4) | 0.0429 (12) | |
O15 | −0.2725 (5) | 0.7577 (4) | 0.7677 (5) | 0.0638 (16) | |
C1 | 0.1712 (6) | 0.6544 (5) | 0.5418 (6) | 0.0367 (15) | |
H1A | 0.1311 | 0.7209 | 0.5468 | 0.044* | |
C2 | 0.3205 (7) | 0.6694 (5) | 0.5369 (6) | 0.0423 (17) | |
C3 | 0.3821 (7) | 0.6936 (5) | 0.6399 (6) | 0.0414 (16) | |
H3 | 0.4668 | 0.7168 | 0.6371 | 0.050* | |
C4 | 0.3266 (7) | 0.6853 (5) | 0.7397 (6) | 0.0427 (17) | |
C5 | 0.1846 (7) | 0.6565 (5) | 0.7482 (6) | 0.0364 (15) | |
H5 | 0.1368 | 0.7200 | 0.7466 | 0.044* | |
C6 | 0.1507 (7) | 0.6073 (6) | 0.8611 (6) | 0.0424 (17) | |
H6A | 0.1929 | 0.5425 | 0.8659 | 0.051* | |
H6B | 0.1836 | 0.6489 | 0.9214 | 0.051* | |
C7 | 0.0071 (7) | 0.5937 (6) | 0.8756 (5) | 0.0428 (17) | |
C8 | −0.0682 (7) | 0.5538 (5) | 0.7748 (6) | 0.0352 (14) | |
C9 | −0.0187 (6) | 0.5945 (5) | 0.6608 (6) | 0.0322 (14) | |
H9 | −0.0417 | 0.6658 | 0.6630 | 0.039* | |
C10 | 0.1344 (6) | 0.5957 (5) | 0.6472 (6) | 0.0321 (13) | |
C11 | −0.1018 (7) | 0.5526 (6) | 0.5633 (5) | 0.0375 (16) | |
H11A | −0.0924 | 0.5994 | 0.5006 | 0.045* | |
C12 | −0.2456 (6) | 0.5538 (5) | 0.5971 (6) | 0.0357 (15) | |
H12 | −0.2993 | 0.5257 | 0.5373 | 0.043* | |
C13 | −0.2714 (6) | 0.4996 (5) | 0.7083 (5) | 0.0356 (15) | |
C14 | −0.2157 (6) | 0.5786 (5) | 0.7861 (6) | 0.0362 (16) | |
H14 | −0.2474 | 0.5722 | 0.8630 | 0.043* | |
C15 | −0.2586 (6) | 0.6751 (5) | 0.7305 (7) | 0.0430 (17) | |
C16 | −0.0777 (6) | 0.4399 (5) | 0.7815 (6) | 0.0406 (16) | |
H16A | −0.0021 | 0.4092 | 0.7479 | 0.049* | |
H16B | −0.0834 | 0.4185 | 0.8589 | 0.049* | |
C17 | −0.4116 (7) | 0.4726 (6) | 0.7257 (7) | 0.0463 (18) | |
H17A | −0.4367 | 0.4226 | 0.6721 | 0.070* | |
H17B | −0.4642 | 0.5313 | 0.7161 | 0.070* | |
H17C | −0.4232 | 0.4466 | 0.7999 | 0.070* | |
C19 | 0.1961 (6) | 0.4899 (5) | 0.6419 (6) | 0.0410 (16) | |
H19A | 0.1733 | 0.4528 | 0.7078 | 0.062* | |
H19B | 0.2884 | 0.4961 | 0.6375 | 0.062* | |
H19C | 0.1647 | 0.4552 | 0.5769 | 0.062* | |
C20 | 0.3979 (7) | 0.7058 (7) | 0.8466 (7) | 0.055 (2) | |
H20A | 0.4110 | 0.6440 | 0.8862 | 0.082* | |
H20B | 0.3482 | 0.7509 | 0.8920 | 0.082* | |
H20C | 0.4801 | 0.7356 | 0.8298 | 0.082* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.042 (3) | 0.078 (4) | 0.032 (2) | −0.002 (3) | 0.004 (2) | 0.005 (3) |
O2 | 0.036 (3) | 0.083 (4) | 0.043 (3) | 0.005 (3) | 0.012 (2) | 0.008 (3) |
O7 | 0.061 (4) | 0.158 (7) | 0.037 (3) | −0.032 (4) | 0.011 (3) | −0.027 (4) |
O11 | 0.041 (3) | 0.064 (3) | 0.050 (3) | −0.002 (3) | 0.006 (3) | −0.020 (3) |
O12 | 0.028 (3) | 0.047 (3) | 0.058 (3) | −0.003 (2) | 0.004 (2) | 0.017 (2) |
O13 | 0.035 (2) | 0.039 (2) | 0.055 (3) | −0.004 (2) | −0.007 (2) | 0.005 (2) |
O15 | 0.050 (3) | 0.045 (3) | 0.096 (4) | 0.002 (3) | 0.025 (3) | −0.007 (3) |
C1 | 0.035 (4) | 0.040 (3) | 0.035 (3) | 0.007 (3) | 0.001 (3) | 0.005 (3) |
C2 | 0.037 (4) | 0.044 (4) | 0.047 (4) | 0.006 (3) | 0.006 (3) | 0.009 (3) |
C3 | 0.026 (3) | 0.046 (4) | 0.052 (4) | 0.001 (3) | 0.001 (3) | 0.001 (4) |
C4 | 0.037 (4) | 0.048 (4) | 0.043 (4) | 0.006 (3) | 0.002 (3) | 0.009 (3) |
C5 | 0.031 (3) | 0.038 (3) | 0.041 (4) | 0.004 (3) | −0.001 (3) | −0.002 (3) |
C6 | 0.035 (4) | 0.059 (4) | 0.033 (3) | −0.010 (3) | −0.008 (3) | 0.002 (3) |
C7 | 0.048 (4) | 0.061 (4) | 0.019 (3) | −0.007 (4) | −0.001 (3) | −0.005 (3) |
C8 | 0.031 (3) | 0.044 (3) | 0.030 (3) | −0.005 (3) | −0.002 (3) | −0.005 (3) |
C9 | 0.025 (3) | 0.031 (3) | 0.040 (3) | −0.001 (3) | 0.007 (3) | −0.002 (3) |
C10 | 0.024 (3) | 0.036 (3) | 0.036 (3) | 0.003 (3) | 0.000 (3) | −0.001 (3) |
C11 | 0.026 (3) | 0.055 (4) | 0.031 (3) | 0.005 (3) | −0.007 (3) | 0.004 (3) |
C12 | 0.023 (3) | 0.044 (4) | 0.040 (4) | −0.002 (3) | −0.003 (3) | 0.006 (3) |
C13 | 0.033 (4) | 0.036 (3) | 0.038 (3) | −0.004 (3) | 0.000 (3) | −0.002 (3) |
C14 | 0.028 (3) | 0.046 (4) | 0.034 (3) | −0.009 (3) | 0.000 (3) | −0.001 (3) |
C15 | 0.022 (3) | 0.046 (4) | 0.061 (4) | 0.001 (3) | 0.017 (4) | −0.001 (4) |
C16 | 0.030 (3) | 0.044 (4) | 0.048 (4) | −0.003 (3) | −0.010 (3) | 0.015 (3) |
C17 | 0.030 (4) | 0.060 (5) | 0.049 (4) | −0.004 (3) | 0.008 (4) | 0.006 (4) |
C19 | 0.026 (3) | 0.040 (3) | 0.058 (4) | 0.005 (3) | 0.004 (3) | −0.002 (3) |
C20 | 0.034 (4) | 0.074 (5) | 0.057 (5) | −0.005 (4) | −0.005 (4) | 0.001 (4) |
Geometric parameters (Å, º) top
O1—C1 | 1.401 (8) | C8—C16 | 1.523 (9) |
O1—H1 | 0.8200 | C8—C9 | 1.554 (9) |
O2—C2 | 1.200 (8) | C8—C14 | 1.567 (10) |
O7—C7 | 1.192 (8) | C9—C11 | 1.552 (9) |
O11—C11 | 1.421 (9) | C9—C10 | 1.591 (9) |
O11—H11 | 0.8200 | C9—H9 | 0.9800 |
O12—C15 | 1.363 (10) | C10—C19 | 1.549 (8) |
O12—C12 | 1.446 (8) | C11—C12 | 1.540 (9) |
O13—C16 | 1.436 (8) | C11—H11A | 0.9800 |
O13—C13 | 1.438 (8) | C12—C13 | 1.537 (9) |
O15—C15 | 1.196 (8) | C12—H12 | 0.9800 |
C1—C10 | 1.532 (9) | C13—C17 | 1.509 (9) |
C1—C2 | 1.558 (10) | C13—C14 | 1.518 (9) |
C1—H1A | 0.9800 | C14—C15 | 1.514 (10) |
C2—C3 | 1.423 (10) | C14—H14 | 0.9800 |
C3—C4 | 1.329 (10) | C16—H16A | 0.9700 |
C3—H3 | 0.9300 | C16—H16B | 0.9700 |
C4—C20 | 1.501 (10) | C17—H17A | 0.9600 |
C4—C5 | 1.521 (10) | C17—H17B | 0.9600 |
C5—C6 | 1.542 (9) | C17—H17C | 0.9600 |
C5—C10 | 1.544 (9) | C19—H19A | 0.9600 |
C5—H5 | 0.9800 | C19—H19B | 0.9600 |
C6—C7 | 1.507 (10) | C19—H19C | 0.9600 |
C6—H6A | 0.9700 | C20—H20A | 0.9600 |
C6—H6B | 0.9700 | C20—H20B | 0.9600 |
C7—C8 | 1.530 (9) | C20—H20C | 0.9600 |
| | | |
C1—O1—H1 | 109.5 | O11—C11—C12 | 109.2 (6) |
C11—O11—H11 | 109.5 | O11—C11—C9 | 117.0 (6) |
C15—O12—C12 | 108.2 (5) | C12—C11—C9 | 109.5 (5) |
C16—O13—C13 | 108.0 (5) | O11—C11—H11A | 106.9 |
O1—C1—C10 | 113.1 (5) | C12—C11—H11A | 106.9 |
O1—C1—C2 | 110.1 (6) | C9—C11—H11A | 106.9 |
C10—C1—C2 | 110.1 (5) | O12—C12—C13 | 103.3 (5) |
O1—C1—H1A | 107.8 | O12—C12—C11 | 108.4 (5) |
C10—C1—H1A | 107.8 | C13—C12—C11 | 112.9 (5) |
C2—C1—H1A | 107.8 | O12—C12—H12 | 110.6 |
O2—C2—C3 | 126.1 (7) | C13—C12—H12 | 110.6 |
O2—C2—C1 | 117.8 (7) | C11—C12—H12 | 110.6 |
C3—C2—C1 | 116.1 (6) | O13—C13—C17 | 109.6 (6) |
C4—C3—C2 | 124.4 (6) | O13—C13—C14 | 106.4 (5) |
C4—C3—H3 | 117.8 | C17—C13—C14 | 116.5 (6) |
C2—C3—H3 | 117.8 | O13—C13—C12 | 112.4 (5) |
C3—C4—C20 | 122.5 (6) | C17—C13—C12 | 113.5 (6) |
C3—C4—C5 | 119.9 (7) | C14—C13—C12 | 98.0 (5) |
C20—C4—C5 | 117.6 (6) | C15—C14—C13 | 102.0 (6) |
C4—C5—C6 | 112.6 (6) | C15—C14—C8 | 115.2 (5) |
C4—C5—C10 | 113.9 (6) | C13—C14—C8 | 99.8 (5) |
C6—C5—C10 | 112.7 (5) | C15—C14—H14 | 112.8 |
C4—C5—H5 | 105.6 | C13—C14—H14 | 112.8 |
C6—C5—H5 | 105.6 | C8—C14—H14 | 112.8 |
C10—C5—H5 | 105.6 | O15—C15—O12 | 120.4 (7) |
C7—C6—C5 | 112.1 (6) | O15—C15—C14 | 130.9 (8) |
C7—C6—H6A | 109.2 | O12—C15—C14 | 108.7 (6) |
C5—C6—H6A | 109.2 | O13—C16—C8 | 106.8 (5) |
C7—C6—H6B | 109.2 | O13—C16—H16A | 110.4 |
C5—C6—H6B | 109.2 | C8—C16—H16A | 110.4 |
H6A—C6—H6B | 107.9 | O13—C16—H16B | 110.4 |
O7—C7—C6 | 121.9 (7) | C8—C16—H16B | 110.4 |
O7—C7—C8 | 121.2 (7) | H16A—C16—H16B | 108.6 |
C6—C7—C8 | 116.9 (6) | C13—C17—H17A | 109.5 |
C16—C8—C7 | 109.7 (6) | C13—C17—H17B | 109.5 |
C16—C8—C9 | 114.5 (6) | H17A—C17—H17B | 109.5 |
C7—C8—C9 | 113.7 (5) | C13—C17—H17C | 109.5 |
C16—C8—C14 | 98.2 (5) | H17A—C17—H17C | 109.5 |
C7—C8—C14 | 110.8 (6) | H17B—C17—H17C | 109.5 |
C9—C8—C14 | 108.9 (5) | C10—C19—H19A | 109.5 |
C8—C9—C11 | 110.5 (5) | C10—C19—H19B | 109.5 |
C8—C9—C10 | 114.9 (6) | H19A—C19—H19B | 109.5 |
C11—C9—C10 | 118.6 (6) | C10—C19—H19C | 109.5 |
C8—C9—H9 | 103.6 | H19A—C19—H19C | 109.5 |
C11—C9—H9 | 103.6 | H19B—C19—H19C | 109.5 |
C10—C9—H9 | 103.6 | C4—C20—H20A | 109.5 |
C1—C10—C5 | 106.9 (5) | C4—C20—H20B | 109.5 |
C1—C10—C19 | 109.2 (5) | H20A—C20—H20B | 109.5 |
C5—C10—C19 | 111.8 (5) | C4—C20—H20C | 109.5 |
C1—C10—C9 | 109.7 (5) | H20A—C20—H20C | 109.5 |
C5—C10—C9 | 105.1 (5) | H20B—C20—H20C | 109.5 |
C19—C10—C9 | 113.9 (5) | | |
| | | |
O1—C1—C2—O2 | 12.0 (9) | C8—C9—C10—C19 | 67.6 (8) |
C10—C1—C2—O2 | 137.3 (7) | C11—C9—C10—C19 | −66.2 (8) |
O1—C1—C2—C3 | −166.4 (6) | C8—C9—C11—O11 | −83.5 (7) |
C10—C1—C2—C3 | −41.1 (8) | C10—C9—C11—O11 | 52.2 (8) |
O2—C2—C3—C4 | −164.9 (8) | C8—C9—C11—C12 | 41.4 (7) |
C1—C2—C3—C4 | 13.4 (10) | C10—C9—C11—C12 | 177.1 (5) |
C2—C3—C4—C20 | 176.2 (7) | C15—O12—C12—C13 | 31.3 (6) |
C2—C3—C4—C5 | −5.3 (11) | C15—O12—C12—C11 | −88.8 (6) |
C3—C4—C5—C6 | 155.6 (7) | O11—C11—C12—O12 | −170.5 (5) |
C20—C4—C5—C6 | −25.9 (9) | C9—C11—C12—O12 | 60.3 (7) |
C3—C4—C5—C10 | 25.7 (9) | O11—C11—C12—C13 | 75.7 (7) |
C20—C4—C5—C10 | −155.8 (6) | C9—C11—C12—C13 | −53.6 (8) |
C4—C5—C6—C7 | 171.3 (6) | C16—O13—C13—C17 | −139.8 (6) |
C10—C5—C6—C7 | −58.2 (8) | C16—O13—C13—C14 | −13.1 (7) |
C5—C6—C7—O7 | −138.6 (8) | C16—O13—C13—C12 | 93.0 (6) |
C5—C6—C7—C8 | 43.7 (10) | O12—C12—C13—O13 | −154.4 (5) |
O7—C7—C8—C16 | −85.2 (10) | C11—C12—C13—O13 | −37.5 (8) |
C6—C7—C8—C16 | 92.6 (8) | O12—C12—C13—C17 | 80.5 (7) |
O7—C7—C8—C9 | 145.1 (8) | C11—C12—C13—C17 | −162.6 (6) |
C6—C7—C8—C9 | −37.2 (9) | O12—C12—C13—C14 | −43.0 (6) |
O7—C7—C8—C14 | 22.1 (11) | C11—C12—C13—C14 | 73.9 (7) |
C6—C7—C8—C14 | −160.1 (6) | O13—C13—C14—C15 | 154.8 (5) |
C16—C8—C9—C11 | 54.1 (7) | C17—C13—C14—C15 | −82.7 (7) |
C7—C8—C9—C11 | −178.7 (6) | C12—C13—C14—C15 | 38.6 (6) |
C14—C8—C9—C11 | −54.7 (7) | O13—C13—C14—C8 | 36.2 (6) |
C16—C8—C9—C10 | −83.4 (7) | C17—C13—C14—C8 | 158.7 (6) |
C7—C8—C9—C10 | 43.9 (8) | C12—C13—C14—C8 | −80.0 (6) |
C14—C8—C9—C10 | 167.9 (5) | C16—C8—C14—C15 | −151.9 (6) |
O1—C1—C10—C5 | −178.1 (6) | C7—C8—C14—C15 | 93.3 (7) |
C2—C1—C10—C5 | 58.4 (6) | C9—C8—C14—C15 | −32.4 (8) |
O1—C1—C10—C19 | 60.7 (7) | C16—C8—C14—C13 | −43.5 (6) |
C2—C1—C10—C19 | −62.8 (7) | C7—C8—C14—C13 | −158.3 (6) |
O1—C1—C10—C9 | −64.7 (7) | C9—C8—C14—C13 | 76.0 (6) |
C2—C1—C10—C9 | 171.8 (6) | C12—O12—C15—O15 | 174.4 (6) |
C4—C5—C10—C1 | −51.7 (7) | C12—O12—C15—C14 | −5.6 (7) |
C6—C5—C10—C1 | 178.4 (6) | C13—C14—C15—O15 | 157.5 (8) |
C4—C5—C10—C19 | 67.7 (7) | C8—C14—C15—O15 | −95.4 (9) |
C6—C5—C10—C19 | −62.1 (7) | C13—C14—C15—O12 | −22.5 (7) |
C4—C5—C10—C9 | −168.2 (6) | C8—C14—C15—O12 | 84.5 (7) |
C6—C5—C10—C9 | 61.9 (7) | C13—O13—C16—C8 | −16.8 (7) |
C8—C9—C10—C1 | −169.7 (5) | C7—C8—C16—O13 | 153.5 (6) |
C11—C9—C10—C1 | 56.4 (8) | C9—C8—C16—O13 | −77.2 (7) |
C8—C9—C10—C5 | −55.1 (7) | C14—C8—C16—O13 | 38.0 (7) |
C11—C9—C10—C5 | 171.0 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O13 | 0.82 | 2.11 | 2.766 (8) | 136 |
O1—H1···O15i | 0.82 | 2.45 | 3.252 (8) | 168 |
C12—H12···O7ii | 0.98 | 2.58 | 3.468 (10) | 151 |
C17—H17A···O7ii | 0.96 | 2.55 | 3.364 (11) | 143 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x−1/2, −y+1, z−1/2. |
Crystal data top
C19H24O7 | F(000) = 776 |
Mr = 364.38 | Dx = 1.435 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 7.5278 (16) Å | θ = 15–30° |
b = 12.418 (3) Å | µ = 0.91 mm−1 |
c = 18.037 (4) Å | T = 293 K |
V = 1686.2 (7) Å3 | Rod shaped, colourless |
Z = 4 | 0.25 × 0.15 × 0.15 mm |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 71.8°, θmin = 4.3° |
Graphite monochromator | h = 0→9 |
non–profiled ω/2θ scans | k = 0→14 |
1846 measured reflections | l = 0→22 |
1846 independent reflections | 3 standard reflections every 200 reflections |
1660 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0713P)2 + 0.2417P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1846 reflections | Δρmax = 0.18 e Å−3 |
240 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0031 (5) |
Crystal data top
C19H24O7 | V = 1686.2 (7) Å3 |
Mr = 364.38 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 7.5278 (16) Å | µ = 0.91 mm−1 |
b = 12.418 (3) Å | T = 293 K |
c = 18.037 (4) Å | 0.25 × 0.15 × 0.15 mm |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.000 |
1846 measured reflections | 3 standard reflections every 200 reflections |
1846 independent reflections | intensity decay: 2% |
1660 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.18 e Å−3 |
1846 reflections | Δρmin = −0.15 e Å−3 |
240 parameters | |
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 | 0.0358 (3) | 0.74913 (15) | 0.12065 (12) | 0.0476 (5) | |
H1 | −0.0288 | 0.6969 | 0.1140 | 0.071* | |
O2 | −0.3420 (3) | 0.77060 (17) | 0.07249 (11) | 0.0505 (5) | |
H2 | −0.3984 | 0.7960 | 0.1072 | 0.076* | |
O7 | 0.1916 (3) | 1.23757 (15) | 0.21800 (11) | 0.0606 (6) | |
O12 | 0.2523 (3) | 0.89710 (14) | 0.34958 (9) | 0.0433 (5) | |
O11 | 0.3663 (2) | 0.79653 (15) | 0.16733 (11) | 0.0448 (4) | |
H11 | 0.3028 | 0.7632 | 0.1384 | 0.067* | |
O13 | 0.5629 (2) | 0.98607 (16) | 0.21140 (10) | 0.0463 (5) | |
O15 | 0.1031 (3) | 1.04339 (16) | 0.38421 (9) | 0.0480 (5) | |
C1 | −0.0686 (3) | 0.84514 (19) | 0.12011 (13) | 0.0346 (5) | |
H1A | −0.1381 | 0.8478 | 0.1660 | 0.041* | |
C2 | −0.1973 (3) | 0.8406 (2) | 0.05457 (13) | 0.0410 (6) | |
H2A | −0.1331 | 0.8076 | 0.0131 | 0.049* | |
C3 | −0.2599 (4) | 0.9492 (2) | 0.02883 (13) | 0.0454 (6) | |
H3 | −0.3486 | 0.9512 | −0.0070 | 0.055* | |
C4 | −0.1978 (3) | 1.0422 (2) | 0.05350 (12) | 0.0422 (6) | |
C5 | −0.0632 (3) | 1.0448 (2) | 0.11609 (12) | 0.0354 (5) | |
H5 | −0.1334 | 1.0423 | 0.1618 | 0.042* | |
C6 | 0.0449 (4) | 1.1485 (2) | 0.12090 (14) | 0.0441 (6) | |
H6A | 0.1147 | 1.1559 | 0.0760 | 0.053* | |
H6B | −0.0364 | 1.2091 | 0.1231 | 0.053* | |
C7 | 0.1664 (4) | 1.15376 (19) | 0.18596 (12) | 0.0361 (5) | |
C8 | 0.2667 (3) | 1.05236 (19) | 0.20735 (11) | 0.0320 (5) | |
C9 | 0.1557 (3) | 0.94828 (19) | 0.19535 (11) | 0.0290 (4) | |
H9 | 0.0588 | 0.9550 | 0.2314 | 0.035* | |
C10 | 0.0574 (3) | 0.94349 (19) | 0.11860 (11) | 0.0311 (5) | |
C11 | 0.2590 (3) | 0.84709 (19) | 0.22193 (13) | 0.0354 (5) | |
H11A | 0.1703 | 0.7941 | 0.2377 | 0.043* | |
C12 | 0.3752 (4) | 0.8715 (2) | 0.28933 (13) | 0.0392 (6) | |
H12 | 0.4495 | 0.8094 | 0.3021 | 0.047* | |
C13 | 0.4869 (3) | 0.9741 (2) | 0.28349 (14) | 0.0410 (6) | |
C14 | 0.3357 (3) | 1.0556 (2) | 0.28895 (12) | 0.0353 (5) | |
H14 | 0.3764 | 1.1273 | 0.3040 | 0.042* | |
C15 | 0.2156 (3) | 1.0044 (2) | 0.34504 (12) | 0.0362 (5) | |
C16 | 0.4476 (3) | 1.0501 (2) | 0.16772 (14) | 0.0421 (6) | |
H16A | 0.4352 | 1.0194 | 0.1186 | 0.050* | |
H16B | 0.4945 | 1.1225 | 0.1629 | 0.050* | |
C17 | 0.6331 (4) | 0.9823 (3) | 0.34056 (18) | 0.0587 (8) | |
H17A | 0.6975 | 1.0482 | 0.3334 | 0.088* | |
H17B | 0.7126 | 0.9223 | 0.3352 | 0.088* | |
H17C | 0.5822 | 0.9816 | 0.3894 | 0.088* | |
C19 | 0.1746 (3) | 0.9384 (2) | 0.04852 (12) | 0.0397 (6) | |
H19A | 0.2500 | 0.8762 | 0.0510 | 0.060* | |
H19B | 0.2464 | 1.0022 | 0.0456 | 0.060* | |
H19C | 0.1003 | 0.9337 | 0.0054 | 0.060* | |
C20 | −0.2672 (4) | 1.1469 (3) | 0.02315 (16) | 0.0584 (8) | |
H20A | −0.3640 | 1.1328 | −0.0101 | 0.088* | |
H20B | −0.1739 | 1.1834 | −0.0030 | 0.088* | |
H20C | −0.3080 | 1.1914 | 0.0632 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0401 (10) | 0.0338 (9) | 0.0689 (12) | −0.0033 (8) | −0.0053 (10) | −0.0079 (9) |
O2 | 0.0384 (9) | 0.0578 (12) | 0.0553 (10) | −0.0110 (9) | −0.0008 (9) | −0.0147 (9) |
O7 | 0.0849 (16) | 0.0357 (10) | 0.0612 (11) | 0.0045 (11) | −0.0190 (13) | −0.0097 (9) |
O12 | 0.0528 (11) | 0.0390 (10) | 0.0381 (8) | 0.0069 (9) | 0.0029 (9) | 0.0033 (7) |
O11 | 0.0359 (8) | 0.0437 (10) | 0.0547 (10) | 0.0057 (8) | 0.0008 (9) | −0.0151 (8) |
O13 | 0.0299 (8) | 0.0570 (12) | 0.0518 (10) | 0.0030 (8) | 0.0048 (8) | −0.0042 (9) |
O15 | 0.0525 (11) | 0.0487 (11) | 0.0428 (8) | 0.0097 (10) | 0.0092 (9) | 0.0000 (8) |
C1 | 0.0297 (11) | 0.0368 (13) | 0.0372 (11) | −0.0033 (10) | 0.0027 (10) | −0.0041 (9) |
C2 | 0.0328 (12) | 0.0535 (15) | 0.0366 (11) | −0.0042 (12) | 0.0001 (10) | −0.0104 (11) |
C3 | 0.0370 (12) | 0.0672 (17) | 0.0321 (10) | 0.0000 (15) | −0.0035 (10) | −0.0027 (12) |
C4 | 0.0385 (12) | 0.0551 (15) | 0.0330 (10) | 0.0078 (13) | 0.0016 (10) | 0.0053 (11) |
C5 | 0.0355 (11) | 0.0377 (13) | 0.0328 (10) | 0.0013 (11) | 0.0010 (10) | 0.0016 (9) |
C6 | 0.0526 (15) | 0.0348 (14) | 0.0448 (13) | 0.0038 (13) | −0.0060 (13) | 0.0037 (10) |
C7 | 0.0391 (12) | 0.0334 (13) | 0.0358 (10) | −0.0026 (11) | 0.0072 (10) | 0.0013 (9) |
C8 | 0.0309 (10) | 0.0324 (11) | 0.0328 (9) | −0.0032 (10) | 0.0026 (9) | −0.0014 (9) |
C9 | 0.0270 (10) | 0.0298 (11) | 0.0304 (9) | −0.0009 (10) | 0.0030 (8) | −0.0011 (8) |
C10 | 0.0313 (10) | 0.0316 (12) | 0.0303 (10) | −0.0017 (11) | 0.0029 (9) | −0.0015 (9) |
C11 | 0.0311 (11) | 0.0339 (13) | 0.0413 (11) | 0.0030 (10) | 0.0026 (11) | −0.0015 (9) |
C12 | 0.0375 (12) | 0.0402 (14) | 0.0399 (11) | 0.0105 (11) | −0.0020 (11) | −0.0008 (10) |
C13 | 0.0309 (11) | 0.0476 (15) | 0.0446 (12) | 0.0013 (11) | −0.0029 (11) | −0.0083 (11) |
C14 | 0.0346 (11) | 0.0335 (12) | 0.0377 (10) | −0.0013 (11) | −0.0032 (10) | −0.0037 (10) |
C15 | 0.0378 (13) | 0.0382 (13) | 0.0326 (10) | 0.0055 (11) | −0.0028 (10) | −0.0002 (10) |
C16 | 0.0325 (11) | 0.0464 (14) | 0.0473 (13) | −0.0083 (12) | 0.0063 (11) | −0.0044 (12) |
C17 | 0.0463 (15) | 0.066 (2) | 0.0633 (16) | 0.0063 (15) | −0.0193 (15) | −0.0135 (15) |
C19 | 0.0384 (13) | 0.0452 (14) | 0.0354 (10) | −0.0019 (12) | 0.0063 (10) | −0.0045 (10) |
C20 | 0.0584 (18) | 0.0652 (19) | 0.0515 (15) | 0.0128 (17) | −0.0095 (15) | 0.0131 (14) |
Geometric parameters (Å, º) top
O1—C1 | 1.428 (3) | C7—C8 | 1.518 (3) |
O1—H1 | 0.8200 | C8—C16 | 1.538 (3) |
O2—C2 | 1.431 (3) | C8—C9 | 1.554 (3) |
O2—H2 | 0.8200 | C8—C14 | 1.561 (3) |
O7—C7 | 1.205 (3) | C9—C11 | 1.554 (3) |
O12—C15 | 1.363 (3) | C9—C10 | 1.571 (3) |
O12—C12 | 1.462 (3) | C9—H9 | 0.9800 |
O11—C11 | 1.420 (3) | C10—C19 | 1.543 (3) |
O11—H11 | 0.8200 | C11—C12 | 1.528 (3) |
O13—C16 | 1.417 (3) | C11—H11A | 0.9800 |
O13—C13 | 1.429 (3) | C12—C13 | 1.529 (4) |
O15—C15 | 1.204 (3) | C12—H12 | 0.9800 |
C1—C2 | 1.529 (3) | C13—C17 | 1.510 (3) |
C1—C10 | 1.547 (3) | C13—C14 | 1.527 (3) |
C1—H1A | 0.9800 | C14—C15 | 1.499 (3) |
C2—C3 | 1.503 (4) | C14—H14 | 0.9800 |
C2—H2A | 0.9800 | C16—H16A | 0.9700 |
C3—C4 | 1.323 (4) | C16—H16B | 0.9700 |
C3—H3 | 0.9300 | C17—H17A | 0.9600 |
C4—C20 | 1.504 (4) | C17—H17B | 0.9600 |
C4—C5 | 1.517 (3) | C17—H17C | 0.9600 |
C5—C6 | 1.526 (4) | C19—H19A | 0.9600 |
C5—C10 | 1.552 (3) | C19—H19B | 0.9600 |
C5—H5 | 0.9800 | C19—H19C | 0.9600 |
C6—C7 | 1.490 (4) | C20—H20A | 0.9600 |
C6—H6A | 0.9700 | C20—H20B | 0.9600 |
C6—H6B | 0.9700 | C20—H20C | 0.9600 |
| | | |
C1—O1—H1 | 109.5 | C1—C10—C9 | 107.65 (17) |
C2—O2—H2 | 109.5 | C5—C10—C9 | 105.71 (17) |
C15—O12—C12 | 107.22 (18) | O11—C11—C12 | 108.30 (19) |
C11—O11—H11 | 109.5 | O11—C11—C9 | 115.36 (18) |
C16—O13—C13 | 108.61 (18) | C12—C11—C9 | 111.8 (2) |
O1—C1—C2 | 108.84 (19) | O11—C11—H11A | 107.0 |
O1—C1—C10 | 108.79 (18) | C12—C11—H11A | 107.0 |
C2—C1—C10 | 113.82 (19) | C9—C11—H11A | 107.0 |
O1—C1—H1A | 108.4 | O12—C12—C11 | 105.8 (2) |
C2—C1—H1A | 108.4 | O12—C12—C13 | 102.60 (19) |
C10—C1—H1A | 108.4 | C11—C12—C13 | 115.2 (2) |
O2—C2—C3 | 112.1 (2) | O12—C12—H12 | 110.9 |
O2—C2—C1 | 109.3 (2) | C11—C12—H12 | 110.9 |
C3—C2—C1 | 113.8 (2) | C13—C12—H12 | 110.9 |
O2—C2—H2A | 107.1 | O13—C13—C17 | 108.7 (2) |
C3—C2—H2A | 107.1 | O13—C13—C14 | 106.7 (2) |
C1—C2—H2A | 107.1 | C17—C13—C14 | 117.0 (2) |
C4—C3—C2 | 124.7 (2) | O13—C13—C12 | 111.7 (2) |
C4—C3—H3 | 117.6 | C17—C13—C12 | 114.2 (2) |
C2—C3—H3 | 117.6 | C14—C13—C12 | 97.95 (19) |
C3—C4—C20 | 120.6 (2) | C15—C14—C13 | 102.23 (19) |
C3—C4—C5 | 120.3 (2) | C15—C14—C8 | 115.1 (2) |
C20—C4—C5 | 119.0 (2) | C13—C14—C8 | 99.79 (18) |
C4—C5—C6 | 114.6 (2) | C15—C14—H14 | 112.8 |
C4—C5—C10 | 113.3 (2) | C13—C14—H14 | 112.8 |
C6—C5—C10 | 111.7 (2) | C8—C14—H14 | 112.8 |
C4—C5—H5 | 105.4 | O15—C15—O12 | 120.0 (2) |
C6—C5—H5 | 105.4 | O15—C15—C14 | 130.5 (2) |
C10—C5—H5 | 105.4 | O12—C15—C14 | 109.5 (2) |
C7—C6—C5 | 114.2 (2) | O13—C16—C8 | 107.13 (19) |
C7—C6—H6A | 108.7 | O13—C16—H16A | 110.3 |
C5—C6—H6A | 108.7 | C8—C16—H16A | 110.3 |
C7—C6—H6B | 108.7 | O13—C16—H16B | 110.3 |
C5—C6—H6B | 108.7 | C8—C16—H16B | 110.3 |
H6A—C6—H6B | 107.6 | H16A—C16—H16B | 108.5 |
O7—C7—C6 | 120.8 (2) | C13—C17—H17A | 109.5 |
O7—C7—C8 | 121.1 (2) | C13—C17—H17B | 109.5 |
C6—C7—C8 | 118.0 (2) | H17A—C17—H17B | 109.5 |
C7—C8—C16 | 109.7 (2) | C13—C17—H17C | 109.5 |
C7—C8—C9 | 112.78 (19) | H17A—C17—H17C | 109.5 |
C16—C8—C9 | 113.33 (19) | H17B—C17—H17C | 109.5 |
C7—C8—C14 | 112.55 (19) | C10—C19—H19A | 109.5 |
C16—C8—C14 | 98.27 (19) | C10—C19—H19B | 109.5 |
C9—C8—C14 | 109.38 (18) | H19A—C19—H19B | 109.5 |
C11—C9—C8 | 111.14 (18) | C10—C19—H19C | 109.5 |
C11—C9—C10 | 118.50 (18) | H19A—C19—H19C | 109.5 |
C8—C9—C10 | 114.04 (17) | H19B—C19—H19C | 109.5 |
C11—C9—H9 | 103.7 | C4—C20—H20A | 109.5 |
C8—C9—H9 | 103.7 | C4—C20—H20B | 109.5 |
C10—C9—H9 | 103.7 | H20A—C20—H20B | 109.5 |
C19—C10—C1 | 109.44 (18) | C4—C20—H20C | 109.5 |
C19—C10—C5 | 110.11 (19) | H20A—C20—H20C | 109.5 |
C1—C10—C5 | 106.37 (19) | H20B—C20—H20C | 109.5 |
C19—C10—C9 | 117.02 (18) | | |
| | | |
O1—C1—C2—O2 | 77.3 (2) | C11—C9—C10—C5 | 168.23 (19) |
C10—C1—C2—O2 | −161.17 (19) | C8—C9—C10—C5 | −58.0 (2) |
O1—C1—C2—C3 | −156.5 (2) | C8—C9—C11—O11 | −90.3 (2) |
C10—C1—C2—C3 | −35.0 (3) | C10—C9—C11—O11 | 44.7 (3) |
O2—C2—C3—C4 | 131.9 (3) | C8—C9—C11—C12 | 34.0 (2) |
C1—C2—C3—C4 | 7.2 (3) | C10—C9—C11—C12 | 169.03 (19) |
C2—C3—C4—C20 | 178.9 (3) | C15—O12—C12—C11 | −86.9 (2) |
C2—C3—C4—C5 | −4.7 (4) | C15—O12—C12—C13 | 34.2 (2) |
C3—C4—C5—C6 | 159.3 (2) | O11—C11—C12—O12 | −165.88 (18) |
C20—C4—C5—C6 | −24.2 (3) | C9—C11—C12—O12 | 65.9 (2) |
C3—C4—C5—C10 | 29.4 (3) | O11—C11—C12—C13 | 81.6 (3) |
C20—C4—C5—C10 | −154.1 (2) | C9—C11—C12—C13 | −46.6 (3) |
C4—C5—C6—C7 | 175.4 (2) | C16—O13—C13—C17 | −139.8 (2) |
C10—C5—C6—C7 | −54.0 (3) | C16—O13—C13—C14 | −12.7 (3) |
C5—C6—C7—O7 | −143.5 (3) | C16—O13—C13—C12 | 93.3 (2) |
C5—C6—C7—C8 | 40.5 (3) | O12—C12—C13—O13 | −155.75 (19) |
O7—C7—C8—C16 | −84.7 (3) | C11—C12—C13—O13 | −41.3 (3) |
C6—C7—C8—C16 | 91.3 (3) | O12—C12—C13—C17 | 80.3 (2) |
O7—C7—C8—C9 | 148.0 (2) | C11—C12—C13—C17 | −165.3 (2) |
C6—C7—C8—C9 | −36.1 (3) | O12—C12—C13—C14 | −44.1 (2) |
O7—C7—C8—C14 | 23.6 (3) | C11—C12—C13—C14 | 70.3 (2) |
C6—C7—C8—C14 | −160.4 (2) | O13—C13—C14—C15 | 153.77 (19) |
C7—C8—C9—C11 | −176.87 (18) | C17—C13—C14—C15 | −84.2 (3) |
C16—C8—C9—C11 | 57.7 (2) | C12—C13—C14—C15 | 38.2 (2) |
C14—C8—C9—C11 | −50.8 (2) | O13—C13—C14—C8 | 35.2 (2) |
C7—C8—C9—C10 | 46.0 (2) | C17—C13—C14—C8 | 157.2 (2) |
C16—C8—C9—C10 | −79.4 (2) | C12—C13—C14—C8 | −80.4 (2) |
C14—C8—C9—C10 | 172.10 (17) | C7—C8—C14—C15 | 94.2 (2) |
O1—C1—C10—C19 | 59.7 (2) | C16—C8—C14—C15 | −150.4 (2) |
C2—C1—C10—C19 | −61.8 (3) | C9—C8—C14—C15 | −32.0 (3) |
O1—C1—C10—C5 | 178.62 (19) | C7—C8—C14—C13 | −157.3 (2) |
C2—C1—C10—C5 | 57.1 (2) | C16—C8—C14—C13 | −41.9 (2) |
O1—C1—C10—C9 | −68.5 (2) | C9—C8—C14—C13 | 76.5 (2) |
C2—C1—C10—C9 | 170.00 (19) | C12—O12—C15—O15 | 172.6 (2) |
C4—C5—C10—C19 | 65.0 (3) | C12—O12—C15—C14 | −8.9 (3) |
C6—C5—C10—C19 | −66.3 (2) | C13—C14—C15—O15 | 158.4 (3) |
C4—C5—C10—C1 | −53.5 (2) | C8—C14—C15—O15 | −94.5 (3) |
C6—C5—C10—C1 | 175.25 (19) | C13—C14—C15—O12 | −19.9 (2) |
C4—C5—C10—C9 | −167.75 (18) | C8—C14—C15—O12 | 87.1 (2) |
C6—C5—C10—C9 | 61.0 (2) | C13—O13—C16—C8 | −16.2 (3) |
C11—C9—C10—C19 | −68.8 (3) | C7—C8—C16—O13 | 154.6 (2) |
C8—C9—C10—C19 | 65.0 (3) | C9—C8—C16—O13 | −78.4 (2) |
C11—C9—C10—C1 | 54.9 (2) | C14—C8—C16—O13 | 36.9 (2) |
C8—C9—C10—C1 | −171.39 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O1 | 0.82 | 2.04 | 2.692 (3) | 136 |
O1—H1···O15i | 0.82 | 1.99 | 2.762 (3) | 158 |
O2—H2···O11ii | 0.82 | 2.08 | 2.802 (3) | 147 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C19H22O7 | C19H24O7 |
Mr | 362.37 | 364.38 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.342 (4), 13.328 (7), 11.956 (9) | 7.5278 (16), 12.418 (3), 18.037 (4) |
V (Å3) | 1648.0 (16) | 1686.2 (7) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.94 | 0.91 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 | 0.25 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Enraf Nonius CAD4 diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1807, 1741, 1203 | 1846, 1846, 1660 |
Rint | 0.060 | 0.000 |
(sin θ/λ)max (Å−1) | 0.617 | 0.616 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.208, 1.06 | 0.033, 0.103, 1.03 |
No. of reflections | 1741 | 1846 |
No. of parameters | 238 | 240 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.42 | 0.18, −0.15 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O13 | 0.82 | 2.11 | 2.766 (8) | 136 |
O1—H1···O15i | 0.82 | 2.45 | 3.252 (8) | 168 |
C12—H12···O7ii | 0.98 | 2.58 | 3.468 (10) | 151 |
C17—H17A···O7ii | 0.96 | 2.55 | 3.364 (11) | 143 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x−1/2, −y+1, z−1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O1 | 0.82 | 2.04 | 2.692 (3) | 136 |
O1—H1···O15i | 0.82 | 1.99 | 2.762 (3) | 158 |
O2—H2···O11ii | 0.82 | 2.08 | 2.802 (3) | 147 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1, y, z. |
The title compounds, samaderine-B and C, (I) and (II), respectively, were extracted from the seed kernels of Samadera indica. Compounds (I) and (II) belong to the quassinoid class (Polonsky, 1973, 1985), a diverse group of structurally complex and highly oxygenated lactones (δ-lactones in the C20- and γ-lactones in the C19-compounds) that generally exhibit antifeedant and insecticidal (Leskinen et al., 1984) activities similar to those of limonoids from neem. Compounds (I) and (II) exhibit antifeedant activity against Spodoptera litura third instar larvae (Govindachari et al., 2001). We have taken up the crystallographic study of these compounds as part of our work on the structural studies of ecofriendly bioinsecticides. Chemically, (I) and (II) differ in the substitution at the C2-atom position, viz. a carbonyl group on atom C2 in samaderine-B and a hydroxyl group in samaderine-C. The compounds both crystallize in space group P212121 but have different unit-cell parameters.
The present study shows that the bond lengths and angles in both structures are close to those observed for other quassinoids (Onan et al., 1978; Suong et al., 1982; Chan et al., 1992; Zukerman-Schpector et al., 1994; Kabaleeswaran et al., 2000). In (II), the hydroxyl groups at atoms C1 and C2 are staggered with respect to one another, as described by the O1—C1—C2—O2 dihedral angle of 77.3 (2)°. The hydroxyl group at atom C1 is in a (-)-antiperiplanar conformation (Klyne & Prelog, 1960) with respect to the C2—C3 bond [C3—C2—C1—O1 = −156.5 (2)°], while the hydroxyl group at atom C2 is (+)-anticlinal with respect to the C3—C4 bond [C4—C3—C2—O2 = 131.9 (3)°]. In (I), the hydroxyl and carbonyl groups attached to atoms C1 and C2, respectively, are nearly in an eclipsed conformation [O1—C1—C2—O2 = 12.0 (9)°]. The hydroxyl group on atom C1 assumes a (-)-antiperiplanar conformation with respect to the C2—C3 bond [C3—C2—C1—O1 = −166.4 (6)°]. The hydroxyl groups on atoms C1 and C11 of both molecules are in the β orientation, and the hydroxyl group on atom C2 of (II) is in the α orientation. In both molecules?, the C19 methyl group is in a β orientation, while atom C17 is in an α orientation. The γ lactone ring, E, and the oxymethylene bridge attached to ring C are in α and β orientations, respectively. However, when both molecules are superimposed, the other parts of the molecules show negligible conformational differences.
Ring A of both molecules are in a sofa conformation [Cremer & Pople, 1975; QT = 0.495 (7) Å, θ = 46.5 (9)° and ϕ2 = −43 (1)° in (I), and QT = 0.491 (2) Å, θ = 46.6 (3)° and ϕ2= −54.5 (4)° in (II)]. Ring B is in a highly distorted chair conformation in both molecules [QT = 0.541 (7) Å, θ = 18.9 (8)° and ϕ2 = −32 (2)° in (I), and QT = 0.536 (2) Å, θ = 20.4 (2)° and ϕ2 = −47.2 (7)° in (II)]. Ring C assumes a distorted chair conformation in both molecules [QT = 0.733 (7) Å, θ = 22.5 (5)° and ϕ2 = −84 (1) ° in (I), and QT= 0.718 (2) Å, θ = 28.1 (2)° and ϕ2 = −80.8 (4)° in (II)]. The five-membered ring, D, takes up a half-chair conformation [q2 = 0.452 (7) Å and ϕ2 = −51.9 (8)° in (I), and q2 = 0.439 (2) Å and ϕ2 = 164.0 (3)° in (II)], with atoms C8 and C14 deviating from the least-squares plane of atoms C13, O13 and C16. The γ lactone ring, E, takes up a conformation intermediate between a half-chair and an envelope in both compounds [q2 = 0.434 (6) Å and ϕ2 = 149.7 (7) ° in (I), and q2 = 0.443 (2) Å and ϕ2 = 153.7 (3) ° in (II)]. In both molecules, the A/B, B/C and C/D rings are trans-fused.
The crystal packing is stabilized both by inter- and intramolecular hydrogen bonds. An intramolecular O11—H11···O13 hydrogen bond in (I) forms a ring graph-set motif (Berstein et al., 1995) of S(6), while an intramolecular O11—H11···O1 interaction in (II) forms a ring with the S(7) motif. In (I), an intermolecular O1—H1···O15(1/2 + x, 3/2 − y, 1 − z) hydrogen bond links the molecules into C(9) chains, which run along [100] and are generated by the 21 screw axis along (x, 3/4, 1/2). In addition, there are C—H···O hydrogen bonds involving methine atom H12 and methylene atom H17A, which interact with a common acceptor, namely atom O7 at (−1/2 − x, 1 − y, z − 1/2). This three-centered hydrogen bond generates a graph-set motif of R21(6). Compound (II) is similar to (I) in that an intermolecular O1—H1···O15(-x, y − 1/2, 1/2 − z) hydrogen bond links the molecules into chains, but these run along [010] and are generated by a 21 screw axis along (−1/2, y, 1/4). Another O2—H2···O11(x − 1, y, z) hydrogen bond links the molecules into chains that run along the [100] direction, with a graph-set motif of C(8). These two intermolecular O—H···O hydrogen bonds in combination generate a two-dimensional network in (II), in which the ring graph-set motif of R55(27) can be detected (Figs. 2a and 2 b).