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The crystal structures of two intact limonoids, nimonol,7α-acetyl-17α-(3-furyl)-6α-hydroxy-4α,4β,8β-trimethyl-5α,18α-androsta-1,14-dien-3-one (C
28H
36O
5), and 6-oxonimonol,7α-acetyl-17α-(3-furyl)-4α,4β,8β-trimethyl-5α,18α-androsta-1,14-diene-3,6-dione (C
28H
34O
5), are reported. The molecular features are mostly the same in the two structures; however the orientations of the acetoxy group are different in the two structures. The packing in nimonol is due to O—H
O hydrogen bonds while in 6-oxonimonol it is due to C—H
O hydrogen bonds.
Supporting information
CCDC references: 140957; 140958
Crystals of nimonol (I) and 6-oxonimonol (II) were prepared from the methanol by slow evaporation.
The H atoms were placed at calculated positions and refined as riding using SHELXL97 (Sheldrick, 1997).
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: SDP (Frenz, 1984); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Crystal data top
C28H36O5 | F(000) = 488 |
Mr = 452.57 | Dx = 1.195 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54180 Å |
a = 10.087 (3) Å | Cell parameters from 20 reflections |
b = 11.044 (3) Å | θ = 14–35° |
c = 12.342 (3) Å | µ = 0.65 mm−1 |
β = 113.86 (2)° | T = 293 K |
V = 1257.3 (6) Å3 | Needle, colourless |
Z = 2 | 0.30 × 0.20 × 0.10 mm |
Data collection top
Enraf Nonius CAD-4 diffractometer | Rint = 0.038 |
Radiation source: fine-focus sealed tube | θmax = 72.0°, θmin = 3.9° |
Graphite monochromator | h = 0→12 |
ω/2θ scans | k = 0→13 |
3002 measured reflections | l = −15→13 |
2612 independent reflections | 3 standard reflections every 100 reflections |
2443 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.194 | Calculated w = 1/[σ2(Fo2) + (0.1295P)2 + 0.1402P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
2612 reflections | Δρmax = 0.21 e Å−3 |
298 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0022 (14) |
Crystal data top
C28H36O5 | V = 1257.3 (6) Å3 |
Mr = 452.57 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 10.087 (3) Å | µ = 0.65 mm−1 |
b = 11.044 (3) Å | T = 293 K |
c = 12.342 (3) Å | 0.30 × 0.20 × 0.10 mm |
β = 113.86 (2)° | |
Data collection top
Enraf Nonius CAD-4 diffractometer | Rint = 0.038 |
3002 measured reflections | 3 standard reflections every 100 reflections |
2612 independent reflections | intensity decay: 3% |
2443 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 1 restraint |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.21 e Å−3 |
2612 reflections | Δρmin = −0.22 e Å−3 |
298 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. The two structures were solved by direct method by SHELXS86 (Sheldrick, 1986) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.0721 (6) | 0.6257 (5) | 0.3588 (4) | 0.1109 (15) | |
O2 | 0.2463 (3) | 0.2317 (3) | 0.5431 (2) | 0.0752 (8) | |
H2 | 0.1971 | 0.1960 | 0.5721 | 0.113* | |
O3 | 0.4098 (2) | 0.2294 (2) | 0.4128 (2) | 0.0555 (6) | |
O4 | 0.5396 (4) | 0.0891 (4) | 0.5454 (3) | 0.0873 (10) | |
O5 | 0.6962 (5) | 0.0809 (5) | −0.0689 (5) | 0.1110 (14) | |
C1 | 0.0816 (4) | 0.4812 (4) | 0.1878 (3) | 0.0628 (9) | |
H1 | 0.1060 | 0.4967 | 0.1241 | 0.075* | |
C2 | 0.0516 (4) | 0.5736 (4) | 0.2439 (4) | 0.0691 (9) | |
H2A | 0.0595 | 0.6526 | 0.2210 | 0.083* | |
C3 | 0.0069 (5) | 0.5519 (4) | 0.3404 (4) | 0.0705 (10) | |
C4 | 0.0595 (4) | 0.4390 (4) | 0.4172 (3) | 0.0618 (9) | |
C5 | 0.1441 (3) | 0.3549 (3) | 0.3642 (3) | 0.0528 (7) | |
H5 | 0.2394 | 0.3929 | 0.3869 | 0.063* | |
C6 | 0.1754 (4) | 0.2270 (4) | 0.4169 (3) | 0.0596 (8) | |
H6 | 0.0843 | 0.1820 | 0.3936 | 0.072* | |
C7 | 0.2776 (4) | 0.1595 (3) | 0.3736 (3) | 0.0560 (7) | |
H7 | 0.2983 | 0.0787 | 0.4093 | 0.067* | |
C8 | 0.2191 (4) | 0.1487 (3) | 0.2382 (3) | 0.0570 (8) | |
C9 | 0.1792 (4) | 0.2769 (3) | 0.1843 (3) | 0.0544 (7) | |
H9 | 0.2709 | 0.3216 | 0.2138 | 0.065* | |
C10 | 0.0767 (4) | 0.3522 (4) | 0.2257 (3) | 0.0555 (8) | |
C26 | 0.5303 (4) | 0.1860 (4) | 0.4999 (4) | 0.0651 (9) | |
C11 | 0.1306 (5) | 0.2720 (5) | 0.0487 (3) | 0.0711 (10) | |
H11A | 0.0397 | 0.2282 | 0.0145 | 0.085* | |
H11B | 0.1128 | 0.3540 | 0.0179 | 0.085* | |
C12 | 0.2376 (6) | 0.2133 (7) | 0.0093 (4) | 0.100 (2) | |
H12A | 0.2709 | 0.2740 | −0.0307 | 0.120* | |
H12B | 0.1868 | 0.1518 | −0.0488 | 0.120* | |
C13 | 0.3704 (4) | 0.1546 (3) | 0.1043 (3) | 0.0534 (7) | |
C14 | 0.3346 (5) | 0.0969 (4) | 0.2010 (3) | 0.0631 (9) | |
C15 | 0.4117 (9) | −0.0024 (5) | 0.2391 (6) | 0.117 (3) | |
H15 | 0.4104 | −0.0493 | 0.3013 | 0.140* | |
C16 | 0.5019 (9) | −0.0316 (6) | 0.1715 (6) | 0.114 (3) | |
H16A | 0.5003 | −0.1176 | 0.1549 | 0.136* | |
H16B | 0.6015 | −0.0054 | 0.2138 | 0.136* | |
C17 | 0.4252 (5) | 0.0416 (4) | 0.0582 (4) | 0.0657 (9) | |
H17 | 0.3394 | −0.0046 | 0.0079 | 0.079* | |
C18 | 0.4913 (6) | 0.2469 (5) | 0.1548 (6) | 0.0909 (16) | |
H18A | 0.5114 | 0.2816 | 0.0917 | 0.136* | |
H18B | 0.5769 | 0.2080 | 0.2103 | 0.136* | |
H18C | 0.4620 | 0.3097 | 0.1943 | 0.136* | |
C19 | −0.0840 (4) | 0.3112 (5) | 0.1690 (4) | 0.0774 (12) | |
H19A | −0.0912 | 0.2290 | 0.1914 | 0.116* | |
H19B | −0.1192 | 0.3165 | 0.0843 | 0.116* | |
H19C | −0.1409 | 0.3627 | 0.1961 | 0.116* | |
C20 | 0.5115 (5) | 0.0650 (4) | −0.0130 (4) | 0.0660 (9) | |
C21 | 0.6550 (6) | 0.0580 (6) | 0.0205 (5) | 0.0885 (14) | |
H21 | 0.7197 | 0.0394 | 0.0972 | 0.106* | |
C22 | 0.4568 (7) | 0.0955 (6) | −0.1370 (5) | 0.0915 (15) | |
H22 | 0.3605 | 0.1071 | −0.1887 | 0.110* | |
C23 | 0.5748 (11) | 0.1039 (7) | −0.1626 (7) | 0.117 (2) | |
H23 | 0.5712 | 0.1234 | −0.2370 | 0.140* | |
C27 | 0.6485 (5) | 0.2760 (6) | 0.5279 (5) | 0.0858 (13) | |
H27A | 0.6127 | 0.3463 | 0.4789 | 0.129* | |
H27B | 0.7269 | 0.2412 | 0.5132 | 0.129* | |
H27C | 0.6825 | 0.2989 | 0.6098 | 0.129* | |
C28 | 0.1637 (5) | 0.4903 (5) | 0.5381 (4) | 0.0771 (11) | |
H28A | 0.2028 | 0.4249 | 0.5932 | 0.116* | |
H28B | 0.1119 | 0.5448 | 0.5676 | 0.116* | |
H28C | 0.2414 | 0.5329 | 0.5287 | 0.116* | |
C29 | −0.0671 (5) | 0.3782 (6) | 0.4347 (5) | 0.0847 (13) | |
H29A | −0.0327 | 0.3074 | 0.4832 | 0.127* | |
H29B | −0.1401 | 0.3553 | 0.3591 | 0.127* | |
H29C | −0.1077 | 0.4337 | 0.4728 | 0.127* | |
C30 | 0.0917 (6) | 0.0560 (5) | 0.1977 (5) | 0.0808 (12) | |
H30A | 0.0164 | 0.0852 | 0.2197 | 0.121* | |
H30B | 0.1261 | −0.0206 | 0.2351 | 0.121* | |
H30C | 0.0540 | 0.0466 | 0.1132 | 0.121* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.137 (3) | 0.106 (3) | 0.109 (3) | 0.051 (3) | 0.069 (3) | 0.004 (2) |
O2 | 0.0798 (17) | 0.092 (2) | 0.0579 (13) | −0.0025 (16) | 0.0320 (12) | 0.0106 (15) |
O3 | 0.0491 (12) | 0.0567 (12) | 0.0556 (12) | −0.0007 (10) | 0.0159 (9) | 0.0058 (10) |
O4 | 0.078 (2) | 0.091 (2) | 0.0832 (19) | 0.0158 (17) | 0.0226 (15) | 0.0309 (18) |
O5 | 0.119 (3) | 0.120 (4) | 0.123 (3) | 0.002 (3) | 0.078 (3) | −0.011 (3) |
C1 | 0.0562 (18) | 0.068 (2) | 0.0613 (18) | 0.0127 (16) | 0.0202 (15) | 0.0061 (17) |
C2 | 0.070 (2) | 0.062 (2) | 0.076 (2) | 0.0118 (18) | 0.0304 (18) | 0.0053 (18) |
C3 | 0.066 (2) | 0.073 (2) | 0.070 (2) | 0.0128 (19) | 0.0246 (17) | −0.0075 (19) |
C4 | 0.0514 (17) | 0.072 (2) | 0.0655 (18) | −0.0027 (16) | 0.0271 (15) | −0.0065 (18) |
C5 | 0.0418 (14) | 0.0620 (18) | 0.0538 (16) | −0.0048 (13) | 0.0186 (12) | 0.0003 (14) |
C6 | 0.0567 (17) | 0.063 (2) | 0.0591 (17) | −0.0066 (16) | 0.0235 (14) | 0.0056 (15) |
C7 | 0.0542 (17) | 0.0517 (17) | 0.0619 (17) | −0.0055 (14) | 0.0231 (14) | 0.0099 (15) |
C8 | 0.0596 (18) | 0.0486 (16) | 0.0600 (17) | −0.0033 (15) | 0.0214 (14) | −0.0008 (14) |
C9 | 0.0510 (16) | 0.0532 (16) | 0.0541 (16) | 0.0046 (14) | 0.0164 (13) | 0.0016 (14) |
C10 | 0.0462 (16) | 0.0607 (19) | 0.0558 (16) | 0.0008 (14) | 0.0167 (13) | 0.0001 (15) |
C26 | 0.055 (2) | 0.077 (2) | 0.0604 (17) | 0.0108 (17) | 0.0208 (15) | 0.0025 (18) |
C11 | 0.069 (2) | 0.080 (3) | 0.0535 (17) | 0.020 (2) | 0.0135 (15) | 0.0003 (18) |
C12 | 0.089 (3) | 0.150 (6) | 0.0541 (19) | 0.054 (4) | 0.023 (2) | 0.020 (3) |
C13 | 0.0584 (18) | 0.0469 (15) | 0.0500 (15) | 0.0029 (14) | 0.0168 (13) | −0.0008 (13) |
C14 | 0.080 (2) | 0.0485 (17) | 0.0640 (19) | 0.0044 (16) | 0.0326 (17) | 0.0007 (15) |
C15 | 0.189 (7) | 0.078 (3) | 0.133 (5) | 0.062 (4) | 0.116 (5) | 0.049 (3) |
C16 | 0.178 (7) | 0.079 (3) | 0.122 (4) | 0.066 (4) | 0.101 (5) | 0.042 (3) |
C17 | 0.079 (2) | 0.0498 (17) | 0.071 (2) | −0.0031 (17) | 0.0325 (19) | −0.0090 (16) |
C18 | 0.092 (3) | 0.073 (3) | 0.129 (4) | −0.025 (2) | 0.067 (3) | −0.047 (3) |
C19 | 0.0480 (19) | 0.092 (3) | 0.082 (2) | 0.0003 (19) | 0.0152 (17) | −0.016 (2) |
C20 | 0.082 (2) | 0.0535 (19) | 0.0665 (19) | 0.0034 (17) | 0.0336 (17) | −0.0104 (16) |
C21 | 0.086 (3) | 0.099 (4) | 0.089 (3) | 0.003 (3) | 0.043 (2) | −0.016 (3) |
C22 | 0.113 (4) | 0.089 (3) | 0.074 (2) | 0.018 (3) | 0.039 (3) | 0.004 (2) |
C23 | 0.182 (8) | 0.091 (4) | 0.120 (5) | 0.013 (5) | 0.105 (6) | 0.005 (4) |
C27 | 0.054 (2) | 0.091 (3) | 0.094 (3) | 0.000 (2) | 0.011 (2) | −0.016 (3) |
C28 | 0.076 (3) | 0.086 (3) | 0.068 (2) | −0.004 (2) | 0.029 (2) | −0.017 (2) |
C29 | 0.067 (2) | 0.102 (4) | 0.102 (3) | −0.005 (2) | 0.052 (2) | −0.007 (3) |
C30 | 0.084 (3) | 0.063 (2) | 0.088 (3) | −0.018 (2) | 0.026 (2) | −0.016 (2) |
Geometric parameters (Å, º) top
O1—C3 | 1.223 (5) | C12—H12B | 0.9700 |
O2—C6 | 1.428 (4) | C13—C14 | 1.520 (5) |
O2—H2 | 0.8200 | C13—C18 | 1.516 (6) |
O3—C26 | 1.344 (5) | C13—C17 | 1.562 (5) |
O3—C7 | 1.445 (4) | C14—C15 | 1.316 (6) |
O4—C26 | 1.195 (6) | C15—C16 | 1.497 (7) |
O5—C23 | 1.325 (10) | C15—H15 | 0.9300 |
O5—C21 | 1.350 (6) | C16—C17 | 1.527 (7) |
C1—C2 | 1.334 (6) | C16—H16A | 0.9700 |
C1—C10 | 1.506 (6) | C16—H16B | 0.9700 |
C1—H1 | 0.9300 | C17—C20 | 1.487 (6) |
C2—C3 | 1.455 (6) | C17—H17 | 0.9800 |
C2—H2A | 0.9300 | C18—H18A | 0.9600 |
C3—C4 | 1.526 (6) | C18—H18B | 0.9600 |
C4—C29 | 1.533 (5) | C18—H18C | 0.9600 |
C4—C28 | 1.543 (6) | C19—H19A | 0.9600 |
C4—C5 | 1.572 (5) | C19—H19B | 0.9600 |
C5—C6 | 1.534 (5) | C19—H19C | 0.9600 |
C5—C10 | 1.563 (5) | C20—C21 | 1.338 (7) |
C5—H5 | 0.9800 | C20—C22 | 1.442 (6) |
C6—C7 | 1.533 (5) | C21—H21 | 0.9300 |
C6—H6 | 0.9800 | C22—C23 | 1.353 (10) |
C7—C8 | 1.534 (5) | C22—H22 | 0.9300 |
C7—H7 | 0.9800 | C23—H23 | 0.9300 |
C8—C14 | 1.526 (5) | C27—H27A | 0.9600 |
C8—C9 | 1.547 (5) | C27—H27B | 0.9600 |
C8—C30 | 1.558 (5) | C27—H27C | 0.9600 |
C9—C11 | 1.542 (5) | C28—H28A | 0.9600 |
C9—C10 | 1.565 (5) | C28—H28B | 0.9600 |
C9—H9 | 0.9800 | C28—H28C | 0.9600 |
C10—C19 | 1.551 (5) | C29—H29A | 0.9600 |
C26—C27 | 1.482 (7) | C29—H29B | 0.9600 |
C11—C12 | 1.499 (6) | C29—H29C | 0.9600 |
C11—H11A | 0.9700 | C30—H30A | 0.9600 |
C11—H11B | 0.9700 | C30—H30B | 0.9600 |
C12—C13 | 1.523 (5) | C30—H30C | 0.9600 |
C12—H12A | 0.9700 | | |
| | | |
C6—O2—H2 | 109.5 | C18—C13—C12 | 109.9 (5) |
C26—O3—C7 | 119.4 (3) | C14—C13—C17 | 100.5 (3) |
C23—O5—C21 | 105.5 (5) | C18—C13—C17 | 110.0 (3) |
C2—C1—C10 | 121.3 (4) | C12—C13—C17 | 113.0 (3) |
C2—C1—H1 | 119.3 | C15—C14—C13 | 109.7 (4) |
C10—C1—H1 | 119.3 | C15—C14—C8 | 128.1 (4) |
C1—C2—C3 | 120.6 (4) | C13—C14—C8 | 122.1 (3) |
C1—C2—H2A | 119.7 | C14—C15—C16 | 112.6 (4) |
C3—C2—H2A | 119.7 | C14—C15—H15 | 123.7 |
O1—C3—C2 | 118.9 (4) | C16—C15—H15 | 123.7 |
O1—C3—C4 | 121.2 (4) | C15—C16—C17 | 101.5 (4) |
C2—C3—C4 | 119.9 (3) | C15—C16—H16A | 111.5 |
C3—C4—C29 | 110.2 (4) | C17—C16—H16A | 111.5 |
C3—C4—C28 | 103.4 (4) | C15—C16—H16B | 111.5 |
C29—C4—C28 | 107.8 (4) | C17—C16—H16B | 111.5 |
C3—C4—C5 | 109.6 (3) | H16A—C16—H16B | 109.3 |
C29—C4—C5 | 115.0 (4) | C20—C17—C16 | 115.6 (4) |
C28—C4—C5 | 110.3 (3) | C20—C17—C13 | 117.0 (3) |
C6—C5—C10 | 111.8 (3) | C16—C17—C13 | 102.2 (3) |
C6—C5—C4 | 114.9 (3) | C20—C17—H17 | 107.1 |
C10—C5—C4 | 113.4 (3) | C16—C17—H17 | 107.1 |
C6—C5—H5 | 105.2 | C13—C17—H17 | 107.1 |
C10—C5—H5 | 105.2 | C13—C18—H18A | 109.5 |
C4—C5—H5 | 105.2 | C13—C18—H18B | 109.5 |
O2—C6—C5 | 110.9 (3) | H18A—C18—H18B | 109.5 |
O2—C6—C7 | 106.7 (3) | C13—C18—H18C | 109.5 |
C5—C6—C7 | 110.6 (3) | H18A—C18—H18C | 109.5 |
O2—C6—H6 | 109.5 | H18B—C18—H18C | 109.5 |
C5—C6—H6 | 109.5 | C10—C19—H19A | 109.5 |
C7—C6—H6 | 109.5 | C10—C19—H19B | 109.5 |
O3—C7—C8 | 107.6 (3) | H19A—C19—H19B | 109.5 |
O3—C7—C6 | 106.5 (3) | C10—C19—H19C | 109.5 |
C8—C7—C6 | 113.6 (3) | H19A—C19—H19C | 109.5 |
O3—C7—H7 | 109.7 | H19B—C19—H19C | 109.5 |
C8—C7—H7 | 109.7 | C21—C20—C22 | 104.0 (4) |
C6—C7—H7 | 109.7 | C21—C20—C17 | 128.8 (4) |
C14—C8—C7 | 110.6 (3) | C22—C20—C17 | 127.1 (4) |
C14—C8—C9 | 108.1 (3) | C20—C21—O5 | 112.9 (5) |
C7—C8—C9 | 108.4 (3) | C20—C21—H21 | 123.5 |
C14—C8—C30 | 106.8 (3) | O5—C21—H21 | 123.5 |
C7—C8—C30 | 107.8 (3) | C23—C22—C20 | 105.6 (6) |
C9—C8—C30 | 115.2 (3) | C23—C22—H22 | 127.2 |
C11—C9—C8 | 110.4 (3) | C20—C22—H22 | 127.2 |
C11—C9—C10 | 114.3 (3) | O5—C23—C22 | 111.9 (5) |
C8—C9—C10 | 115.9 (3) | O5—C23—H23 | 124.0 |
C11—C9—H9 | 105.0 | C22—C23—H23 | 124.0 |
C8—C9—H9 | 105.0 | C26—C27—H27A | 109.5 |
C10—C9—H9 | 105.0 | C26—C27—H27B | 109.5 |
C1—C10—C19 | 107.2 (3) | H27A—C27—H27B | 109.5 |
C1—C10—C5 | 105.5 (3) | C26—C27—H27C | 109.5 |
C19—C10—C5 | 114.3 (3) | H27A—C27—H27C | 109.5 |
C1—C10—C9 | 107.0 (3) | H27B—C27—H27C | 109.5 |
C19—C10—C9 | 113.9 (3) | C4—C28—H28A | 109.5 |
C5—C10—C9 | 108.4 (3) | C4—C28—H28B | 109.5 |
O4—C26—O3 | 124.7 (4) | H28A—C28—H28B | 109.5 |
O4—C26—C27 | 126.1 (4) | C4—C28—H28C | 109.5 |
O3—C26—C27 | 109.2 (4) | H28A—C28—H28C | 109.5 |
C12—C11—C9 | 114.4 (3) | H28B—C28—H28C | 109.5 |
C12—C11—H11A | 108.7 | C4—C29—H29A | 109.5 |
C9—C11—H11A | 108.7 | C4—C29—H29B | 109.5 |
C12—C11—H11B | 108.7 | H29A—C29—H29B | 109.5 |
C9—C11—H11B | 108.7 | C4—C29—H29C | 109.5 |
H11A—C11—H11B | 107.6 | H29A—C29—H29C | 109.5 |
C11—C12—C13 | 117.3 (3) | H29B—C29—H29C | 109.5 |
C11—C12—H12A | 108.0 | C8—C30—H30A | 109.5 |
C13—C12—H12A | 108.0 | C8—C30—H30B | 109.5 |
C11—C12—H12B | 108.0 | H30A—C30—H30B | 109.5 |
C13—C12—H12B | 108.0 | C8—C30—H30C | 109.5 |
H12A—C12—H12B | 107.2 | H30A—C30—H30C | 109.5 |
C14—C13—C18 | 111.5 (4) | H30B—C30—H30C | 109.5 |
C14—C13—C12 | 111.6 (4) | | |
| | | |
C10—C1—C2—C3 | −2.8 (6) | C8—C9—C10—C1 | 166.4 (3) |
C1—C2—C3—O1 | −151.2 (5) | C11—C9—C10—C19 | 54.7 (5) |
C1—C2—C3—C4 | 29.2 (6) | C8—C9—C10—C19 | −75.4 (4) |
O1—C3—C4—C29 | 46.3 (6) | C11—C9—C10—C5 | −176.9 (3) |
C2—C3—C4—C29 | −134.2 (4) | C8—C9—C10—C5 | 53.0 (4) |
O1—C3—C4—C28 | −68.7 (5) | C7—O3—C26—O4 | 3.7 (6) |
C2—C3—C4—C28 | 110.9 (4) | C7—O3—C26—C27 | −177.3 (3) |
O1—C3—C4—C5 | 173.8 (4) | C8—C9—C11—C12 | −54.5 (6) |
C2—C3—C4—C5 | −6.7 (5) | C10—C9—C11—C12 | 172.8 (5) |
C3—C4—C5—C6 | −167.8 (3) | C9—C11—C12—C13 | 6.4 (8) |
C29—C4—C5—C6 | −43.1 (4) | C11—C12—C13—C14 | 35.4 (7) |
C28—C4—C5—C6 | 79.0 (4) | C11—C12—C13—C18 | −88.9 (7) |
C3—C4—C5—C10 | −37.6 (4) | C11—C12—C13—C17 | 147.8 (5) |
C29—C4—C5—C10 | 87.2 (4) | C18—C13—C14—C15 | −91.9 (6) |
C28—C4—C5—C10 | −150.7 (3) | C12—C13—C14—C15 | 144.7 (6) |
C10—C5—C6—O2 | 175.8 (3) | C17—C13—C14—C15 | 24.7 (6) |
C4—C5—C6—O2 | −53.1 (4) | C18—C13—C14—C8 | 91.0 (5) |
C10—C5—C6—C7 | 57.7 (4) | C12—C13—C14—C8 | −32.3 (6) |
C4—C5—C6—C7 | −171.3 (3) | C17—C13—C14—C8 | −152.4 (3) |
C26—O3—C7—C8 | −128.7 (3) | C7—C8—C14—C15 | 52.0 (7) |
C26—O3—C7—C6 | 109.1 (3) | C9—C8—C14—C15 | 170.6 (6) |
O2—C6—C7—O3 | −60.4 (4) | C30—C8—C14—C15 | −65.0 (7) |
C5—C6—C7—O3 | 60.2 (3) | C7—C8—C14—C13 | −131.5 (4) |
O2—C6—C7—C8 | −178.7 (3) | C9—C8—C14—C13 | −13.0 (5) |
C5—C6—C7—C8 | −58.1 (4) | C30—C8—C14—C13 | 111.5 (4) |
O3—C7—C8—C14 | 54.3 (4) | C13—C14—C15—C16 | −3.6 (8) |
C6—C7—C8—C14 | 172.0 (3) | C8—C14—C15—C16 | 173.2 (5) |
O3—C7—C8—C9 | −64.0 (4) | C14—C15—C16—C17 | −19.6 (9) |
C6—C7—C8—C9 | 53.6 (4) | C15—C16—C17—C20 | 161.4 (5) |
O3—C7—C8—C30 | 170.7 (3) | C15—C16—C17—C13 | 33.2 (6) |
C6—C7—C8—C30 | −71.6 (4) | C14—C13—C17—C20 | −162.4 (4) |
C14—C8—C9—C11 | 55.8 (4) | C18—C13—C17—C20 | −44.7 (5) |
C7—C8—C9—C11 | 175.7 (3) | C12—C13—C17—C20 | 78.5 (5) |
C30—C8—C9—C11 | −63.5 (4) | C14—C13—C17—C16 | −35.0 (5) |
C14—C8—C9—C10 | −172.3 (3) | C18—C13—C17—C16 | 82.6 (5) |
C7—C8—C9—C10 | −52.4 (4) | C12—C13—C17—C16 | −154.1 (5) |
C30—C8—C9—C10 | 68.4 (4) | C16—C17—C20—C21 | −18.2 (7) |
C2—C1—C10—C19 | 82.2 (5) | C13—C17—C20—C21 | 102.3 (6) |
C2—C1—C10—C5 | −40.0 (5) | C16—C17—C20—C22 | 158.7 (5) |
C2—C1—C10—C9 | −155.3 (4) | C13—C17—C20—C22 | −80.8 (6) |
C6—C5—C10—C1 | −168.4 (3) | C22—C20—C21—O5 | 0.1 (7) |
C4—C5—C10—C1 | 59.8 (4) | C17—C20—C21—O5 | 177.5 (5) |
C6—C5—C10—C19 | 74.1 (4) | C23—O5—C21—C20 | 0.3 (7) |
C4—C5—C10—C19 | −57.7 (4) | C21—C20—C22—C23 | −0.4 (7) |
C6—C5—C10—C9 | −54.1 (4) | C17—C20—C22—C23 | −177.9 (5) |
C4—C5—C10—C9 | 174.1 (3) | C21—O5—C23—C22 | −0.6 (8) |
C11—C9—C10—C1 | −63.6 (4) | C20—C22—C23—O5 | 0.6 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | H···A | D···A | D—H···A |
O2—H2···O1i | 1.95 (1) | 2.768 (6) | 175 (4) |
C1—H1···O5ii | 2.56 (6) | 3.325 (7) | 130 (4) |
C23—H23···O4iii | 2.48 (8) | 3.472 (9) | 153 (5) |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) −x+1, y+1/2, −z; (iii) x, y, z−1. |
Crystal data top
C28H34O5 | Dx = 1.243 Mg m−3 |
Mr = 450.55 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 10.805 (1) Å | θ = 12–36° |
b = 12.710 (2) Å | µ = 0.67 mm−1 |
c = 17.538 (2) Å | T = 293 K |
V = 2408.5 (5) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.25 × 0.15 mm |
F(000) = 968 | |
Data collection top
Enraf Nonius CAD-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 67.9°, θmin = 4.3° |
Graphite monochromator | h = 0→12 |
ω/2θ scans | k = 0→15 |
2481 measured reflections | l = 0→21 |
2481 independent reflections | 3 standard reflections every 100 reflections |
2222 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.129 | Calculated w = 1/[σ2(Fo2) + (0.1007P)2 + 1.2632P] where P = (Fo2 + 2Fc2)/3 |
S = 0.80 | (Δ/σ)max = 0.001 |
2481 reflections | Δρmax = 0.22 e Å−3 |
298 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0053 (5) |
Crystal data top
C28H34O5 | V = 2408.5 (5) Å3 |
Mr = 450.55 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 10.805 (1) Å | µ = 0.67 mm−1 |
b = 12.710 (2) Å | T = 293 K |
c = 17.538 (2) Å | 0.30 × 0.25 × 0.15 mm |
Data collection top
Enraf Nonius CAD-4 diffractometer | Rint = 0.000 |
2481 measured reflections | 3 standard reflections every 100 reflections |
2481 independent reflections | intensity decay: 3% |
2222 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.80 | Δρmax = 0.22 e Å−3 |
2481 reflections | Δρmin = −0.23 e Å−3 |
298 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 | −0.0612 (2) | 0.2036 (2) | 0.23388 (16) | 0.0726 (7) | |
O2 | 0.4187 (2) | 0.17737 (18) | 0.15882 (16) | 0.0673 (7) | |
O3 | 0.34749 (19) | 0.36430 (15) | 0.02342 (10) | 0.0436 (5) | |
O4 | 0.3623 (6) | 0.2081 (2) | −0.02861 (19) | 0.141 (2) | |
O5 | 0.5029 (3) | 0.9223 (2) | −0.08528 (19) | 0.0876 (9) | |
C1 | 0.1231 (3) | 0.4331 (2) | 0.22804 (18) | 0.0505 (7) | |
H1 | 0.1109 | 0.5049 | 0.2351 | 0.061* | |
C2 | 0.0259 (3) | 0.3710 (3) | 0.2306 (2) | 0.0600 (9) | |
H2 | −0.0511 | 0.4017 | 0.2388 | 0.072* | |
C3 | 0.0311 (3) | 0.2561 (3) | 0.22131 (19) | 0.0534 (7) | |
C4 | 0.1529 (3) | 0.2049 (2) | 0.19915 (18) | 0.0497 (7) | |
C5 | 0.2388 (3) | 0.2909 (2) | 0.16667 (16) | 0.0405 (6) | |
H5 | 0.1963 | 0.3141 | 0.1202 | 0.049* | |
C6 | 0.3647 (3) | 0.2557 (2) | 0.13848 (17) | 0.0441 (7) | |
C7 | 0.4270 (3) | 0.3347 (2) | 0.08616 (16) | 0.0410 (6) | |
H7 | 0.5051 | 0.3061 | 0.0668 | 0.049* | |
C8 | 0.4510 (2) | 0.4368 (2) | 0.13144 (15) | 0.0378 (6) | |
C9 | 0.3255 (2) | 0.47593 (19) | 0.16407 (14) | 0.0360 (6) | |
H9 | 0.2728 | 0.4871 | 0.1193 | 0.043* | |
C10 | 0.2534 (3) | 0.3945 (2) | 0.21429 (16) | 0.0410 (6) | |
C11 | 0.3420 (3) | 0.5855 (2) | 0.19918 (16) | 0.0469 (7) | |
H11A | 0.2655 | 0.6063 | 0.2238 | 0.056* | |
H11B | 0.4059 | 0.5824 | 0.2379 | 0.056* | |
C12 | 0.3767 (4) | 0.6673 (2) | 0.1409 (2) | 0.0620 (9) | |
H12A | 0.4313 | 0.7179 | 0.1651 | 0.074* | |
H12B | 0.3022 | 0.7046 | 0.1261 | 0.074* | |
C13 | 0.4401 (2) | 0.6274 (2) | 0.06832 (15) | 0.0376 (6) | |
C14 | 0.5031 (2) | 0.5217 (2) | 0.07965 (15) | 0.0377 (6) | |
C15 | 0.6087 (3) | 0.5176 (3) | 0.0411 (2) | 0.0525 (8) | |
H15 | 0.6604 | 0.4591 | 0.0399 | 0.063* | |
C16 | 0.6348 (3) | 0.6182 (3) | −0.0002 (2) | 0.0592 (9) | |
H16A | 0.6117 | 0.6135 | −0.0535 | 0.071* | |
H16B | 0.7215 | 0.6375 | 0.0036 | 0.071* | |
C17 | 0.5529 (3) | 0.6954 (2) | 0.04252 (17) | 0.0425 (6) | |
H17 | 0.5978 | 0.7139 | 0.0892 | 0.051* | |
C18 | 0.3466 (3) | 0.6196 (2) | 0.0019 (2) | 0.0532 (8) | |
H18A | 0.3068 | 0.6865 | −0.0052 | 0.080* | |
H18B | 0.2855 | 0.5672 | 0.0135 | 0.080* | |
H18C | 0.3894 | 0.6004 | −0.0440 | 0.080* | |
C19 | 0.3130 (4) | 0.3800 (3) | 0.29406 (16) | 0.0574 (8) | |
H19A | 0.3964 | 0.3553 | 0.2883 | 0.086* | |
H19B | 0.2660 | 0.3297 | 0.3228 | 0.086* | |
H19C | 0.3134 | 0.4462 | 0.3204 | 0.086* | |
C20 | 0.5235 (3) | 0.7975 (2) | 0.00354 (18) | 0.0480 (7) | |
C21 | 0.5328 (4) | 0.8195 (3) | −0.0705 (2) | 0.0677 (10) | |
H21 | 0.5565 | 0.7712 | −0.1076 | 0.081* | |
C22 | 0.4864 (3) | 0.8930 (2) | 0.0391 (2) | 0.0617 (9) | |
H22 | 0.4722 | 0.9036 | 0.0908 | 0.074* | |
C23 | 0.4758 (4) | 0.9653 (3) | −0.0172 (3) | 0.0798 (13) | |
H23 | 0.4529 | 1.0351 | −0.0099 | 0.096* | |
C26 | 0.3239 (4) | 0.2940 (2) | −0.03131 (18) | 0.0594 (9) | |
C27 | 0.2445 (4) | 0.3391 (3) | −0.09219 (19) | 0.0701 (10) | |
H27A | 0.2256 | 0.4111 | −0.0802 | 0.105* | |
H27B | 0.1690 | 0.2995 | −0.0956 | 0.105* | |
H27C | 0.2874 | 0.3360 | −0.1401 | 0.105* | |
C28 | 0.2003 (4) | 0.1468 (3) | 0.2706 (2) | 0.0740 (11) | |
H28A | 0.2777 | 0.1131 | 0.2592 | 0.111* | |
H28B | 0.1409 | 0.0947 | 0.2858 | 0.111* | |
H28C | 0.2119 | 0.1963 | 0.3113 | 0.111* | |
C29 | 0.1278 (4) | 0.1233 (3) | 0.1361 (2) | 0.0761 (11) | |
H29A | 0.2042 | 0.0904 | 0.1215 | 0.114* | |
H29B | 0.0921 | 0.1578 | 0.0927 | 0.114* | |
H29C | 0.0716 | 0.0709 | 0.1548 | 0.114* | |
C30 | 0.5509 (3) | 0.4112 (3) | 0.19176 (19) | 0.0539 (8) | |
H30A | 0.5207 | 0.3575 | 0.2255 | 0.081* | |
H30B | 0.5696 | 0.4734 | 0.2206 | 0.081* | |
H30C | 0.6245 | 0.3868 | 0.1667 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0585 (14) | 0.0664 (15) | 0.0930 (18) | −0.0181 (13) | 0.0096 (14) | 0.0088 (15) |
O2 | 0.0669 (15) | 0.0444 (12) | 0.0906 (17) | 0.0179 (11) | 0.0097 (14) | 0.0199 (12) |
O3 | 0.0501 (11) | 0.0381 (9) | 0.0428 (10) | 0.0024 (9) | −0.0030 (9) | −0.0088 (8) |
O4 | 0.282 (6) | 0.0472 (15) | 0.093 (2) | 0.044 (3) | −0.067 (3) | −0.0243 (15) |
O5 | 0.099 (2) | 0.0670 (16) | 0.096 (2) | −0.0132 (17) | −0.0195 (19) | 0.0406 (17) |
C1 | 0.0545 (17) | 0.0393 (14) | 0.0577 (17) | 0.0061 (13) | 0.0163 (15) | 0.0046 (14) |
C2 | 0.0516 (18) | 0.0536 (17) | 0.075 (2) | 0.0080 (15) | 0.0157 (17) | 0.0122 (17) |
C3 | 0.0527 (17) | 0.0537 (17) | 0.0538 (17) | −0.0072 (15) | 0.0032 (15) | 0.0093 (15) |
C4 | 0.0531 (17) | 0.0390 (14) | 0.0571 (17) | −0.0034 (14) | 0.0013 (15) | 0.0066 (13) |
C5 | 0.0445 (14) | 0.0333 (13) | 0.0438 (14) | 0.0001 (12) | 0.0000 (12) | 0.0036 (11) |
C6 | 0.0485 (16) | 0.0303 (13) | 0.0536 (16) | 0.0058 (12) | −0.0011 (14) | 0.0001 (12) |
C7 | 0.0395 (14) | 0.0326 (13) | 0.0509 (15) | 0.0061 (11) | 0.0015 (12) | −0.0036 (12) |
C8 | 0.0381 (13) | 0.0316 (12) | 0.0438 (14) | 0.0025 (11) | −0.0030 (12) | −0.0001 (11) |
C9 | 0.0405 (14) | 0.0325 (12) | 0.0350 (12) | 0.0029 (11) | −0.0012 (11) | −0.0009 (10) |
C10 | 0.0496 (16) | 0.0328 (13) | 0.0406 (13) | 0.0003 (12) | 0.0027 (12) | 0.0010 (11) |
C11 | 0.0588 (18) | 0.0379 (13) | 0.0441 (14) | −0.0038 (14) | 0.0058 (14) | −0.0091 (12) |
C12 | 0.083 (2) | 0.0341 (14) | 0.069 (2) | −0.0005 (16) | 0.027 (2) | −0.0068 (14) |
C13 | 0.0369 (13) | 0.0308 (12) | 0.0452 (14) | 0.0003 (11) | 0.0026 (12) | 0.0001 (12) |
C14 | 0.0367 (13) | 0.0329 (12) | 0.0437 (13) | 0.0001 (11) | −0.0029 (12) | −0.0024 (11) |
C15 | 0.0430 (15) | 0.0436 (15) | 0.071 (2) | 0.0085 (13) | 0.0088 (15) | 0.0029 (15) |
C16 | 0.0450 (16) | 0.0522 (18) | 0.081 (2) | −0.0008 (15) | 0.0184 (16) | 0.0078 (17) |
C17 | 0.0389 (13) | 0.0382 (14) | 0.0504 (15) | −0.0056 (12) | −0.0050 (12) | 0.0011 (12) |
C18 | 0.0424 (15) | 0.0462 (16) | 0.071 (2) | −0.0066 (14) | −0.0140 (15) | 0.0144 (16) |
C19 | 0.077 (2) | 0.0567 (18) | 0.0388 (14) | −0.0006 (18) | −0.0024 (15) | 0.0060 (14) |
C20 | 0.0415 (14) | 0.0410 (14) | 0.0614 (17) | −0.0085 (13) | −0.0050 (14) | 0.0084 (14) |
C21 | 0.075 (2) | 0.061 (2) | 0.067 (2) | −0.0126 (19) | −0.0063 (19) | 0.0193 (18) |
C22 | 0.061 (2) | 0.0445 (16) | 0.080 (2) | −0.0004 (16) | −0.0152 (19) | 0.0059 (16) |
C23 | 0.069 (2) | 0.0470 (18) | 0.123 (4) | −0.0054 (18) | −0.025 (3) | 0.026 (2) |
C26 | 0.093 (3) | 0.0364 (15) | 0.0493 (17) | −0.0075 (17) | −0.0017 (18) | −0.0077 (13) |
C27 | 0.087 (3) | 0.071 (2) | 0.0524 (18) | −0.021 (2) | −0.0131 (19) | −0.0044 (17) |
C28 | 0.076 (2) | 0.059 (2) | 0.087 (3) | −0.0012 (19) | 0.004 (2) | 0.036 (2) |
C29 | 0.088 (3) | 0.0493 (19) | 0.091 (3) | −0.022 (2) | 0.017 (2) | −0.0111 (19) |
C30 | 0.0507 (17) | 0.0526 (17) | 0.0586 (18) | 0.0042 (15) | −0.0113 (15) | 0.0078 (16) |
Geometric parameters (Å, º) top
O1—C3 | 1.220 (4) | C13—C18 | 1.545 (4) |
O2—C6 | 1.208 (3) | C13—C17 | 1.561 (4) |
O3—C26 | 1.336 (3) | C14—C15 | 1.328 (4) |
O3—C7 | 1.446 (3) | C15—C16 | 1.496 (4) |
O4—C26 | 1.170 (4) | C15—H15 | 0.9300 |
O5—C23 | 1.345 (6) | C16—C17 | 1.520 (4) |
O5—C21 | 1.371 (5) | C16—H16A | 0.9700 |
C1—C2 | 1.314 (5) | C16—H16B | 0.9700 |
C1—C10 | 1.511 (4) | C17—C20 | 1.500 (4) |
C1—H1 | 0.9300 | C17—H17 | 0.9800 |
C2—C3 | 1.470 (5) | C18—H18A | 0.9600 |
C2—H2 | 0.9300 | C18—H18B | 0.9600 |
C3—C4 | 1.520 (5) | C18—H18C | 0.9600 |
C4—C29 | 1.540 (5) | C19—H19A | 0.9600 |
C4—C5 | 1.543 (4) | C19—H19B | 0.9600 |
C4—C28 | 1.542 (5) | C19—H19C | 0.9600 |
C5—C6 | 1.515 (4) | C20—C21 | 1.333 (5) |
C5—C10 | 1.567 (4) | C20—C22 | 1.422 (5) |
C5—H5 | 0.9800 | C21—H21 | 0.9300 |
C6—C7 | 1.518 (4) | C22—C23 | 1.355 (5) |
C7—C8 | 1.542 (4) | C22—H22 | 0.9300 |
C7—H7 | 0.9800 | C23—H23 | 0.9300 |
C8—C14 | 1.519 (4) | C26—C27 | 1.485 (5) |
C8—C30 | 1.546 (4) | C27—H27A | 0.9600 |
C8—C9 | 1.554 (4) | C27—H27B | 0.9600 |
C9—C11 | 1.533 (3) | C27—H27C | 0.9600 |
C9—C10 | 1.567 (4) | C28—H28A | 0.9600 |
C9—H9 | 0.9800 | C28—H28B | 0.9600 |
C10—C19 | 1.551 (4) | C28—H28C | 0.9600 |
C11—C12 | 1.506 (4) | C29—H29A | 0.9600 |
C11—H11A | 0.9700 | C29—H29B | 0.9600 |
C11—H11B | 0.9700 | C29—H29C | 0.9600 |
C12—C13 | 1.531 (4) | C30—H30A | 0.9600 |
C12—H12A | 0.9700 | C30—H30B | 0.9600 |
C12—H12B | 0.9700 | C30—H30C | 0.9600 |
C13—C14 | 1.519 (4) | | |
| | | |
C26—O3—C7 | 119.1 (2) | C15—C14—C13 | 110.7 (2) |
C23—O5—C21 | 105.8 (3) | C8—C14—C13 | 122.7 (2) |
C2—C1—C10 | 123.7 (3) | C14—C15—C16 | 112.0 (3) |
C2—C1—H1 | 118.2 | C14—C15—H15 | 124.0 |
C10—C1—H1 | 118.2 | C16—C15—H15 | 124.0 |
C1—C2—C3 | 124.2 (3) | C15—C16—C17 | 101.7 (2) |
C1—C2—H2 | 117.9 | C15—C16—H16A | 111.4 |
C3—C2—H2 | 117.9 | C17—C16—H16A | 111.4 |
O1—C3—C2 | 119.5 (3) | C15—C16—H16B | 111.4 |
O1—C3—C4 | 121.3 (3) | C17—C16—H16B | 111.4 |
C2—C3—C4 | 119.1 (3) | H16A—C16—H16B | 109.3 |
C3—C4—C29 | 108.6 (3) | C20—C17—C16 | 117.2 (3) |
C3—C4—C5 | 108.1 (2) | C20—C17—C13 | 116.5 (2) |
C29—C4—C5 | 108.5 (3) | C16—C17—C13 | 103.9 (2) |
C3—C4—C28 | 106.6 (3) | C20—C17—H17 | 106.1 |
C29—C4—C28 | 108.6 (3) | C16—C17—H17 | 106.1 |
C5—C4—C28 | 116.1 (3) | C13—C17—H17 | 106.1 |
C6—C5—C4 | 116.8 (2) | C13—C18—H18A | 109.5 |
C6—C5—C10 | 109.3 (2) | C13—C18—H18B | 109.5 |
C4—C5—C10 | 117.3 (2) | H18A—C18—H18B | 109.5 |
C6—C5—H5 | 103.8 | C13—C18—H18C | 109.5 |
C4—C5—H5 | 103.8 | H18A—C18—H18C | 109.5 |
C10—C5—H5 | 103.8 | H18B—C18—H18C | 109.5 |
O2—C6—C5 | 125.5 (3) | C10—C19—H19A | 109.5 |
O2—C6—C7 | 120.7 (3) | C10—C19—H19B | 109.5 |
C5—C6—C7 | 113.6 (2) | H19A—C19—H19B | 109.5 |
O3—C7—C6 | 111.6 (2) | C10—C19—H19C | 109.5 |
O3—C7—C8 | 105.9 (2) | H19A—C19—H19C | 109.5 |
C6—C7—C8 | 108.6 (2) | H19B—C19—H19C | 109.5 |
O3—C7—H7 | 110.2 | C21—C20—C22 | 105.6 (3) |
C6—C7—H7 | 110.2 | C21—C20—C17 | 127.6 (3) |
C8—C7—H7 | 110.2 | C22—C20—C17 | 126.7 (3) |
C14—C8—C7 | 110.6 (2) | C20—C21—O5 | 111.5 (4) |
C14—C8—C30 | 107.5 (2) | C20—C21—H21 | 124.3 |
C7—C8—C30 | 107.0 (2) | O5—C21—H21 | 124.3 |
C14—C8—C9 | 108.4 (2) | C23—C22—C20 | 106.5 (4) |
C7—C8—C9 | 108.2 (2) | C23—C22—H22 | 126.8 |
C30—C8—C9 | 115.1 (2) | C20—C22—H22 | 126.8 |
C11—C9—C8 | 109.7 (2) | O5—C23—C22 | 110.6 (4) |
C11—C9—C10 | 115.6 (2) | O5—C23—H23 | 124.7 |
C8—C9—C10 | 115.4 (2) | C22—C23—H23 | 124.7 |
C11—C9—H9 | 104.9 | O4—C26—O3 | 121.9 (4) |
C8—C9—H9 | 104.9 | O4—C26—C27 | 126.5 (3) |
C10—C9—H9 | 104.9 | O3—C26—C27 | 111.6 (3) |
C1—C10—C19 | 106.3 (2) | C26—C27—H27A | 109.5 |
C1—C10—C9 | 109.8 (2) | C26—C27—H27B | 109.5 |
C19—C10—C9 | 112.3 (2) | H27A—C27—H27B | 109.5 |
C1—C10—C5 | 105.3 (2) | C26—C27—H27C | 109.5 |
C19—C10—C5 | 115.1 (2) | H27A—C27—H27C | 109.5 |
C9—C10—C5 | 107.8 (2) | H27B—C27—H27C | 109.5 |
C12—C11—C9 | 112.5 (2) | C4—C28—H28A | 109.5 |
C12—C11—H11A | 109.1 | C4—C28—H28B | 109.5 |
C9—C11—H11A | 109.1 | H28A—C28—H28B | 109.5 |
C12—C11—H11B | 109.1 | C4—C28—H28C | 109.5 |
C9—C11—H11B | 109.1 | H28A—C28—H28C | 109.5 |
H11A—C11—H11B | 107.8 | H28B—C28—H28C | 109.5 |
C11—C12—C13 | 116.5 (2) | C4—C29—H29A | 109.5 |
C11—C12—H12A | 108.2 | C4—C29—H29B | 109.5 |
C13—C12—H12A | 108.2 | H29A—C29—H29B | 109.5 |
C11—C12—H12B | 108.2 | C4—C29—H29C | 109.5 |
C13—C12—H12B | 108.2 | H29A—C29—H29C | 109.5 |
H12A—C12—H12B | 107.3 | H29B—C29—H29C | 109.5 |
C14—C13—C12 | 112.6 (2) | C8—C30—H30A | 109.5 |
C14—C13—C18 | 109.6 (2) | C8—C30—H30B | 109.5 |
C12—C13—C18 | 110.8 (3) | H30A—C30—H30B | 109.5 |
C14—C13—C17 | 100.3 (2) | C8—C30—H30C | 109.5 |
C12—C13—C17 | 114.0 (2) | H30A—C30—H30C | 109.5 |
C18—C13—C17 | 109.1 (2) | H30B—C30—H30C | 109.5 |
C15—C14—C8 | 126.5 (3) | | |
| | | |
C10—C1—C2—C3 | 0.7 (6) | C4—C5—C10—C1 | −53.5 (3) |
C1—C2—C3—O1 | 171.0 (4) | C6—C5—C10—C19 | −72.7 (3) |
C1—C2—C3—C4 | −6.7 (6) | C4—C5—C10—C19 | 63.3 (3) |
O1—C3—C4—C29 | 47.3 (4) | C6—C5—C10—C9 | 53.4 (3) |
C2—C3—C4—C29 | −135.1 (3) | C4—C5—C10—C9 | −170.6 (2) |
O1—C3—C4—C5 | 164.9 (3) | C8—C9—C11—C12 | 64.4 (3) |
C2—C3—C4—C5 | −17.4 (4) | C10—C9—C11—C12 | −163.0 (3) |
O1—C3—C4—C28 | −69.6 (4) | C9—C11—C12—C13 | −24.2 (5) |
C2—C3—C4—C28 | 108.0 (4) | C11—C12—C13—C14 | −23.1 (4) |
C3—C4—C5—C6 | −178.1 (2) | C11—C12—C13—C18 | 100.1 (4) |
C29—C4—C5—C6 | −60.4 (3) | C11—C12—C13—C17 | −136.4 (3) |
C28—C4—C5—C6 | 62.3 (4) | C7—C8—C14—C15 | −61.4 (4) |
C3—C4—C5—C10 | 49.2 (3) | C30—C8—C14—C15 | 55.1 (4) |
C29—C4—C5—C10 | 166.9 (3) | C9—C8—C14—C15 | −179.9 (3) |
C28—C4—C5—C10 | −70.5 (4) | C7—C8—C14—C13 | 121.4 (3) |
C4—C5—C6—O2 | −23.8 (4) | C30—C8—C14—C13 | −122.1 (3) |
C10—C5—C6—O2 | 112.5 (3) | C9—C8—C14—C13 | 3.0 (3) |
C4—C5—C6—C7 | 162.1 (2) | C12—C13—C14—C15 | −142.4 (3) |
C10—C5—C6—C7 | −61.6 (3) | C18—C13—C14—C15 | 93.7 (3) |
C26—O3—C7—C6 | −70.4 (3) | C17—C13—C14—C15 | −20.9 (3) |
C26—O3—C7—C8 | 171.5 (3) | C12—C13—C14—C8 | 35.1 (4) |
O2—C6—C7—O3 | 132.3 (3) | C18—C13—C14—C8 | −88.7 (3) |
C5—C6—C7—O3 | −53.3 (3) | C17—C13—C14—C8 | 156.6 (2) |
O2—C6—C7—C8 | −111.4 (3) | C8—C14—C15—C16 | −176.3 (3) |
C5—C6—C7—C8 | 63.1 (3) | C13—C14—C15—C16 | 1.1 (4) |
O3—C7—C8—C14 | −55.0 (3) | C14—C15—C16—C17 | 19.8 (4) |
C6—C7—C8—C14 | −175.1 (2) | C15—C16—C17—C20 | −161.6 (3) |
O3—C7—C8—C30 | −171.8 (2) | C15—C16—C17—C13 | −31.6 (3) |
C6—C7—C8—C30 | 68.2 (3) | C14—C13—C17—C20 | 162.4 (3) |
O3—C7—C8—C9 | 63.6 (3) | C12—C13—C17—C20 | −77.0 (3) |
C6—C7—C8—C9 | −56.5 (3) | C18—C13—C17—C20 | 47.4 (3) |
C14—C8—C9—C11 | −51.6 (3) | C14—C13—C17—C16 | 31.9 (3) |
C7—C8—C9—C11 | −171.6 (2) | C12—C13—C17—C16 | 152.5 (3) |
C30—C8—C9—C11 | 68.8 (3) | C18—C13—C17—C16 | −83.1 (3) |
C14—C8—C9—C10 | 175.7 (2) | C16—C17—C20—C21 | 18.7 (5) |
C7—C8—C9—C10 | 55.7 (3) | C13—C17—C20—C21 | −105.2 (4) |
C30—C8—C9—C10 | −64.0 (3) | C16—C17—C20—C22 | −157.4 (3) |
C2—C1—C10—C19 | −95.3 (4) | C13—C17—C20—C22 | 78.7 (4) |
C2—C1—C10—C9 | 143.0 (3) | C22—C20—C21—O5 | −0.6 (4) |
C2—C1—C10—C5 | 27.2 (4) | C17—C20—C21—O5 | −177.5 (3) |
C11—C9—C10—C1 | 62.1 (3) | C23—O5—C21—C20 | 0.8 (5) |
C8—C9—C10—C1 | −168.0 (2) | C21—C20—C22—C23 | 0.2 (4) |
C11—C9—C10—C19 | −55.9 (3) | C17—C20—C22—C23 | 177.1 (3) |
C8—C9—C10—C19 | 74.0 (3) | C21—O5—C23—C22 | −0.6 (5) |
C11—C9—C10—C5 | 176.3 (2) | C20—C22—C23—O5 | 0.2 (4) |
C8—C9—C10—C5 | −53.8 (3) | C7—O3—C26—O4 | 2.7 (6) |
C6—C5—C10—C1 | 170.5 (2) | C7—O3—C26—C27 | −178.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27C···O1i | 0.96 (1) | 2.37 (1) | 3.298 (5) | 161 (1) |
C23—H23···O4ii | 0.93 (1) | 2.43 (1) | 3.226 (5) | 162 (1) |
C11—H11A···O1iii | 0.97 (1) | 2.64 (1) | 3.583 (4) | 165 (1) |
C1—H1···O1iii | 0.93 (1) | 2.64 (1) | 3.565 (4) | 174 (1) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C28H36O5 | C28H34O5 |
Mr | 452.57 | 450.55 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.087 (3), 11.044 (3), 12.342 (3) | 10.805 (1), 12.710 (2), 17.538 (2) |
α, β, γ (°) | 90.00 (2), 113.86 (2), 90.00 (2) | 90.00 (1), 90.00 (1), 90.00 (1) |
V (Å3) | 1257.3 (6) | 2408.5 (5) |
Z | 2 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.65 | 0.67 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 | 0.30 × 0.25 × 0.15 |
|
Data collection |
Diffractometer | Enraf Nonius CAD-4 diffractometer | Enraf Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3002, 2612, 2443 | 2481, 2481, 2222 |
Rint | 0.038 | 0.000 |
(sin θ/λ)max (Å−1) | 0.617 | 0.601 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.194, 1.15 | 0.043, 0.129, 0.80 |
No. of reflections | 2612 | 2481 |
No. of parameters | 298 | 298 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 | 0.22, −0.23 |
Selected geometric parameters (Å, º) for (I) topO1—C3 | 1.223 (5) | O4—C26 | 1.195 (6) |
O2—C6 | 1.428 (4) | O5—C23 | 1.325 (10) |
O3—C26 | 1.344 (5) | O5—C21 | 1.350 (6) |
O3—C7 | 1.445 (4) | | |
| | | |
C26—O3—C7 | 119.4 (3) | O3—C7—C6 | 106.5 (3) |
C23—O5—C21 | 105.5 (5) | C8—C7—C6 | 113.6 (3) |
O1—C3—C2 | 118.9 (4) | O4—C26—O3 | 124.7 (4) |
O1—C3—C4 | 121.2 (4) | O4—C26—C27 | 126.1 (4) |
O2—C6—C5 | 110.9 (3) | O3—C26—C27 | 109.2 (4) |
O2—C6—C7 | 106.7 (3) | C20—C21—O5 | 112.9 (5) |
O3—C7—C8 | 107.6 (3) | O5—C23—C22 | 111.9 (5) |
| | | |
O1—C3—C4—C29 | 46.3 (6) | C26—O3—C7—C6 | 109.1 (3) |
O1—C3—C4—C28 | −68.7 (5) | O2—C6—C7—O3 | −60.4 (4) |
C4—C5—C6—O2 | −53.1 (4) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | H···A | D···A | D—H···A |
O2—H2···O1i | 1.950 (6) | 2.768 (6) | 175 (4) |
C1—H1···O5ii | 2.56 (6) | 3.325 (7) | 130 (4) |
C23—H23···O4iii | 2.48 (8) | 3.472 (9) | 153 (5) |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) −x+1, y+1/2, −z; (iii) x, y, z−1. |
Selected geometric parameters (Å, º) for (II) topO1—C3 | 1.220 (4) | O4—C26 | 1.170 (4) |
O2—C6 | 1.208 (3) | O5—C23 | 1.345 (6) |
O3—C26 | 1.336 (3) | O5—C21 | 1.371 (5) |
O3—C7 | 1.446 (3) | | |
| | | |
C26—O3—C7 | 119.1 (2) | C20—C21—O5 | 111.5 (4) |
C23—O5—C21 | 105.8 (3) | O5—C21—H21 | 124.3 |
O1—C3—C2 | 119.5 (3) | O4—C26—O3 | 121.9 (4) |
O1—C3—C4 | 121.3 (3) | O4—C26—C27 | 126.5 (3) |
O3—C7—C6 | 111.6 (2) | O3—C26—C27 | 111.6 (3) |
O3—C7—C8 | 105.9 (2) | | |
| | | |
O1—C3—C4—C29 | 47.3 (4) | C26—O3—C7—C6 | −70.4 (3) |
O1—C3—C4—C28 | −69.6 (4) | O2—C6—C7—O3 | 132.3 (3) |
C4—C5—C6—O2 | −23.8 (4) | | |
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Neem leaves and neem oil have been used as ecofriendly insecticides in India for a long time and the constituents of neem like azadirachtins and a few other bioactive constituents have been studied for their biological activity (Govindachari, Narashiman et al., 1996). Recently the X-ray structures of a few azadirachtins and a few other compounds have been reported (Bilton et al., 1987; Kabaleeswaran et al., 1994; Govindachari, Geetha Gopalakrishnan et al., 1996). Nimonol, one of the limonoids, isolated from the leaves of neem (Suresh et al., 1997) exhibits antifeedant and ecdysis activity similar but to a lesser extent than the azadirachtins. The stereochemistry was clearly established by NMR techniques (Suresh et al., 1997). 6-Oxonimonol is a derivative of nimonol and was prepared to study the change of activity with the native compound. This paper reports the crystal structures of both nimonol, (I), and 6-oxonimonol, (II). However the absolute structure was not established by X-ray techniques.
The conformations of the B, C and D rings are chair, sofa and envelope, respectively, in both structures (Duax et al., 1975). However the ring A exists as a half-chair in nimonol and as a sofa in 6-oxonimonol. Consequently the torsion angles C1—C2—C3—O1, C2—C3—C4—C28 and C2—C3—C4—C29 are different in two structures. The furan ring E is pseudoaxially subsituted in both the structures with respect to the ring D. The orientation of the acetoxy group at C7, defined by the torsion angle C6—C7—O3—C26 is 109.1 (3)° (anticlinal) in nimonol and 70.4 (3)° (synclinal) in 6-oxonimonol. However, the orientations of the methyl carbons are close to one another. The ring pairs A/B and B/C are trans fused and C/D is quasi-trans fused in the two structures.
The geometric data pertinent to defining the hydrogen bonding scheme in nimonol,(I) are given in Table 2. However in 6-oxonimonol the molecular packing is due to C—H···O hydrogen bonds.