3β-Hydroxy-7-drimen-12,11-olide hemihydrate, C
15H
22O
3·0.5H
2O, (I), has two sesquiterpene molecules and one water molecule in the asymmetric unit. The OH groups of both molecules and both H atoms of the water molecule are involved in near-linear intermolecular hydrogen bonds, having O
O distances in the range 2.632 (3)–2.791 (2) Å. 3β-Acetoxy-7-drimen-12,11-olide, C
17H
24O
4, (II), has its ring system in very nearly the same conformation as the two molecules of (I).
Supporting information
CCDC references: 605696; 605697
Compounds (I) and (II) were isolated from the stem bark of Warburgia ugandensis Sprague (Canellaceae) collected in Eldoret, Uasin Gishu District, Kenya. [Please give brief details of preparative procedure, or an appropriate reference] Crystals were grown from a solution in acetone–hexane (Ratio?).
H atoms were placed in calculated positions, guided by difference maps, with C—H bond distances in the range 0.95–1.00 Å and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl H, and thereafter treated as riding. Coordinates for OH H atoms were refined. A torsional parameter was refined for each OH group and each methyl group. The absolute configuration could not be established from the X-ray data, but was assigned based on the configuration of insulicolide A (Rahbaek et al., 1997). Friedel pairs were averaged.
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(I) 3
β-Hydroxy-7-drimen-12,11-olide hemihydrate
top
Crystal data top
C15H22O3·0.5H2O | F(000) = 564 |
Mr = 259.33 | Dx = 1.238 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4619 reflections |
a = 12.875 (3) Å | θ = 2.5–32.0° |
b = 6.153 (2) Å | µ = 0.09 mm−1 |
c = 18.268 (4) Å | T = 120 K |
β = 106.031 (16)° | Prism, colorless |
V = 1390.9 (6) Å3 | 0.42 × 0.35 × 0.20 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer | 3773 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 32.0°, θmin = 3.1° |
ω scans with κ offsets | h = −19→19 |
17077 measured reflections | k = −8→9 |
5214 independent reflections | l = −27→26 |
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)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0505P)2 + 0.0592P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.003 |
5214 reflections | Δρmax = 0.38 e Å−3 |
353 parameters | Δρmin = −0.23 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: 0.007 (2) |
Crystal data top
C15H22O3·0.5H2O | V = 1390.9 (6) Å3 |
Mr = 259.33 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 12.875 (3) Å | µ = 0.09 mm−1 |
b = 6.153 (2) Å | T = 120 K |
c = 18.268 (4) Å | 0.42 × 0.35 × 0.20 mm |
β = 106.031 (16)° | |
Data collection top
Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer | 3773 reflections with I > 2σ(I) |
17077 measured reflections | Rint = 0.040 |
5214 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 1 restraint |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.38 e Å−3 |
5214 reflections | Δρmin = −0.23 e Å−3 |
353 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 | |
O1A | 0.53239 (11) | 0.8344 (3) | 1.01792 (8) | 0.0299 (3) | |
O2A | 0.37960 (12) | 0.8405 (3) | 0.92329 (10) | 0.0392 (4) | |
O3A | 1.01372 (13) | 0.5682 (3) | 0.83070 (10) | 0.0361 (4) | |
H3OA | 1.055 (2) | 0.678 (6) | 0.8468 (16) | 0.054* | |
C1A | 0.86114 (14) | 0.7138 (4) | 0.97246 (10) | 0.0210 (4) | |
H1A1 | 0.8824 | 0.7966 | 1.0208 | 0.025* | |
H1A2 | 0.8478 | 0.5615 | 0.9849 | 0.025* | |
C2A | 0.95405 (15) | 0.7185 (4) | 0.93584 (10) | 0.0240 (4) | |
H2A1 | 0.9713 | 0.8709 | 0.9263 | 0.029* | |
H2A2 | 1.0191 | 0.6522 | 0.9708 | 0.029* | |
C3A | 0.92312 (16) | 0.5942 (4) | 0.86133 (11) | 0.0244 (4) | |
H3A | 0.9013 | 0.4451 | 0.8731 | 0.029* | |
C4A | 0.82503 (16) | 0.6933 (4) | 0.80198 (10) | 0.0234 (4) | |
C5A | 0.73066 (15) | 0.7079 (3) | 0.83992 (9) | 0.0194 (4) | |
H5A | 0.7119 | 0.5532 | 0.8472 | 0.023* | |
C6A | 0.62630 (16) | 0.8045 (4) | 0.78670 (10) | 0.0302 (5) | |
H6A1 | 0.6426 | 0.9493 | 0.7690 | 0.036* | |
H6A2 | 0.6013 | 0.7098 | 0.7414 | 0.036* | |
C7A | 0.53695 (16) | 0.8271 (4) | 0.82450 (11) | 0.0289 (5) | |
H7A | 0.4669 | 0.8688 | 0.7949 | 0.035* | |
C8A | 0.55391 (15) | 0.7902 (3) | 0.89770 (11) | 0.0232 (4) | |
C9A | 0.66147 (14) | 0.7336 (3) | 0.95175 (9) | 0.0187 (4) | |
H9A | 0.6657 | 0.5718 | 0.9570 | 0.022* | |
C10A | 0.75600 (14) | 0.8099 (3) | 0.92124 (9) | 0.0166 (4) | |
C11A | 0.64940 (15) | 0.8286 (4) | 1.02673 (10) | 0.0245 (4) | |
H11A | 0.6864 | 0.7355 | 1.0704 | 0.029* | |
H11B | 0.6805 | 0.9766 | 1.0352 | 0.029* | |
C12A | 0.47787 (17) | 0.8244 (4) | 0.94392 (12) | 0.0288 (5) | |
C13A | 0.7910 (2) | 0.5376 (4) | 0.73353 (12) | 0.0361 (6) | |
H13A | 0.7321 | 0.6032 | 0.6938 | 0.054* | |
H13B | 0.7665 | 0.3998 | 0.7499 | 0.054* | |
H13C | 0.8528 | 0.5108 | 0.7133 | 0.054* | |
C14A | 0.85720 (19) | 0.9103 (4) | 0.77220 (12) | 0.0296 (5) | |
H14A | 0.8874 | 1.0079 | 0.8152 | 0.044* | |
H14B | 0.7932 | 0.9777 | 0.7377 | 0.044* | |
H14C | 0.9114 | 0.8834 | 0.7447 | 0.044* | |
C15A | 0.76189 (16) | 1.0592 (4) | 0.92026 (11) | 0.0231 (4) | |
H15A | 0.7790 | 1.1144 | 0.9726 | 0.035* | |
H15B | 0.6921 | 1.1179 | 0.8908 | 0.035* | |
H15C | 0.8183 | 1.1044 | 0.8968 | 0.035* | |
O1B | 0.46672 (11) | 0.6360 (3) | 0.50293 (8) | 0.0286 (4) | |
O2B | 0.37074 (12) | 0.5687 (4) | 0.38312 (7) | 0.0379 (4) | |
O3B | 0.10653 (15) | 0.2489 (3) | 0.77540 (9) | 0.0374 (4) | |
H3OB | 0.072 (2) | 0.334 (6) | 0.7943 (15) | 0.056* | |
C1B | 0.33611 (17) | 0.4662 (4) | 0.70622 (10) | 0.0244 (4) | |
H1B1 | 0.4152 | 0.4571 | 0.7290 | 0.029* | |
H1B2 | 0.3157 | 0.6218 | 0.7035 | 0.029* | |
C2B | 0.27970 (17) | 0.3486 (4) | 0.75802 (10) | 0.0284 (5) | |
H2B1 | 0.3049 | 0.1960 | 0.7649 | 0.034* | |
H2B2 | 0.2987 | 0.4194 | 0.8087 | 0.034* | |
C3B | 0.15803 (17) | 0.3530 (4) | 0.72424 (11) | 0.0275 (5) | |
H3B | 0.1345 | 0.5085 | 0.7190 | 0.033* | |
C4B | 0.11959 (17) | 0.2460 (4) | 0.64484 (12) | 0.0251 (4) | |
C5B | 0.18268 (15) | 0.3543 (4) | 0.59266 (10) | 0.0210 (4) | |
H5B | 0.1565 | 0.5080 | 0.5867 | 0.025* | |
C6B | 0.15093 (16) | 0.2614 (4) | 0.51106 (11) | 0.0291 (5) | |
H6B1 | 0.1602 | 0.1016 | 0.5138 | 0.035* | |
H6B2 | 0.0735 | 0.2920 | 0.4871 | 0.035* | |
C7B | 0.21586 (16) | 0.3525 (4) | 0.46151 (10) | 0.0282 (5) | |
H7B | 0.1958 | 0.3193 | 0.4087 | 0.034* | |
C8B | 0.30057 (16) | 0.4783 (4) | 0.49016 (10) | 0.0232 (4) | |
C9B | 0.34082 (15) | 0.5409 (3) | 0.57263 (10) | 0.0203 (4) | |
H9B | 0.3067 | 0.6828 | 0.5793 | 0.024* | |
C10B | 0.30801 (15) | 0.3729 (3) | 0.62499 (10) | 0.0190 (4) | |
C11B | 0.46115 (16) | 0.5840 (4) | 0.58015 (10) | 0.0261 (5) | |
H11C | 0.4880 | 0.7071 | 0.6151 | 0.031* | |
H11D | 0.5051 | 0.4537 | 0.5999 | 0.031* | |
C12B | 0.37772 (17) | 0.5612 (4) | 0.45014 (11) | 0.0270 (4) | |
C13B | −0.00170 (16) | 0.2957 (4) | 0.61230 (13) | 0.0352 (5) | |
H13D | −0.0408 | 0.2464 | 0.6483 | 0.053* | |
H13E | −0.0296 | 0.2198 | 0.5637 | 0.053* | |
H13F | −0.0119 | 0.4526 | 0.6043 | 0.053* | |
C14B | 0.13066 (18) | −0.0031 (4) | 0.65216 (13) | 0.0293 (5) | |
H14D | 0.2029 | −0.0402 | 0.6843 | 0.044* | |
H14E | 0.1201 | −0.0673 | 0.6015 | 0.044* | |
H14F | 0.0760 | −0.0601 | 0.6753 | 0.044* | |
C15B | 0.36673 (16) | 0.1566 (3) | 0.62423 (12) | 0.0249 (4) | |
H15D | 0.4443 | 0.1764 | 0.6478 | 0.037* | |
H15E | 0.3549 | 0.1076 | 0.5715 | 0.037* | |
H15F | 0.3385 | 0.0475 | 0.6528 | 0.037* | |
O1W | 0.15716 (15) | 0.8841 (4) | 0.85921 (11) | 0.0503 (5) | |
H1W | 0.229 (3) | 0.859 (7) | 0.8750 (17) | 0.076* | |
H2W | 0.149 (3) | 0.998 (7) | 0.8288 (19) | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0251 (8) | 0.0298 (8) | 0.0410 (8) | 0.0014 (7) | 0.0194 (6) | −0.0033 (8) |
O2A | 0.0196 (7) | 0.0308 (9) | 0.0681 (10) | 0.0000 (8) | 0.0136 (7) | −0.0024 (9) |
O3A | 0.0326 (9) | 0.0296 (9) | 0.0571 (10) | −0.0033 (8) | 0.0306 (8) | −0.0094 (9) |
C1A | 0.0169 (9) | 0.0271 (11) | 0.0188 (8) | 0.0011 (8) | 0.0045 (7) | 0.0019 (8) |
C2A | 0.0177 (9) | 0.0246 (11) | 0.0299 (9) | 0.0030 (9) | 0.0072 (7) | 0.0018 (9) |
C3A | 0.0233 (10) | 0.0206 (10) | 0.0354 (10) | −0.0004 (9) | 0.0181 (8) | −0.0008 (9) |
C4A | 0.0293 (10) | 0.0231 (11) | 0.0200 (8) | −0.0035 (9) | 0.0107 (7) | −0.0026 (8) |
C5A | 0.0202 (9) | 0.0200 (10) | 0.0185 (8) | −0.0038 (8) | 0.0062 (7) | −0.0012 (8) |
C6A | 0.0266 (10) | 0.0399 (14) | 0.0203 (8) | −0.0032 (11) | −0.0002 (7) | 0.0007 (10) |
C7A | 0.0189 (9) | 0.0297 (12) | 0.0327 (10) | −0.0032 (10) | −0.0017 (8) | −0.0001 (10) |
C8A | 0.0154 (8) | 0.0201 (10) | 0.0327 (9) | −0.0002 (8) | 0.0044 (7) | −0.0016 (9) |
C9A | 0.0178 (8) | 0.0183 (9) | 0.0211 (8) | −0.0009 (8) | 0.0076 (7) | −0.0019 (8) |
C10A | 0.0156 (8) | 0.0157 (9) | 0.0182 (8) | 0.0000 (8) | 0.0043 (6) | 0.0005 (8) |
C11A | 0.0224 (9) | 0.0263 (11) | 0.0276 (9) | −0.0004 (9) | 0.0117 (7) | −0.0027 (10) |
C12A | 0.0226 (10) | 0.0184 (10) | 0.0474 (12) | −0.0003 (9) | 0.0130 (9) | −0.0004 (10) |
C13A | 0.0458 (14) | 0.0381 (14) | 0.0294 (10) | −0.0103 (12) | 0.0190 (10) | −0.0108 (11) |
C14A | 0.0375 (12) | 0.0284 (12) | 0.0264 (9) | −0.0023 (10) | 0.0148 (9) | 0.0020 (9) |
C15A | 0.0220 (9) | 0.0185 (10) | 0.0284 (9) | 0.0002 (9) | 0.0064 (8) | −0.0006 (9) |
O1B | 0.0296 (8) | 0.0350 (9) | 0.0232 (6) | −0.0089 (7) | 0.0105 (6) | −0.0003 (7) |
O2B | 0.0359 (8) | 0.0586 (12) | 0.0220 (7) | −0.0074 (9) | 0.0126 (6) | 0.0011 (8) |
O3B | 0.0558 (11) | 0.0265 (9) | 0.0441 (9) | 0.0108 (8) | 0.0374 (8) | 0.0108 (8) |
C1B | 0.0311 (11) | 0.0235 (11) | 0.0190 (8) | −0.0013 (9) | 0.0074 (8) | −0.0028 (8) |
C2B | 0.0376 (11) | 0.0292 (11) | 0.0216 (8) | 0.0015 (10) | 0.0134 (8) | 0.0016 (10) |
C3B | 0.0396 (12) | 0.0200 (10) | 0.0304 (9) | 0.0068 (10) | 0.0224 (9) | 0.0064 (10) |
C4B | 0.0243 (10) | 0.0228 (10) | 0.0321 (10) | 0.0042 (9) | 0.0142 (8) | 0.0055 (9) |
C5B | 0.0224 (9) | 0.0193 (9) | 0.0223 (8) | 0.0011 (8) | 0.0080 (7) | 0.0012 (8) |
C6B | 0.0246 (10) | 0.0354 (13) | 0.0267 (9) | −0.0073 (10) | 0.0063 (8) | −0.0041 (10) |
C7B | 0.0271 (10) | 0.0380 (13) | 0.0199 (8) | −0.0022 (10) | 0.0071 (7) | −0.0052 (10) |
C8B | 0.0259 (10) | 0.0262 (11) | 0.0188 (8) | 0.0003 (9) | 0.0082 (7) | −0.0001 (8) |
C9B | 0.0235 (9) | 0.0191 (10) | 0.0194 (8) | 0.0001 (9) | 0.0076 (7) | −0.0014 (8) |
C10B | 0.0225 (9) | 0.0171 (9) | 0.0177 (8) | 0.0006 (8) | 0.0063 (7) | −0.0016 (8) |
C11B | 0.0296 (10) | 0.0311 (12) | 0.0177 (8) | −0.0065 (10) | 0.0065 (7) | −0.0019 (9) |
C12B | 0.0293 (10) | 0.0299 (12) | 0.0231 (9) | −0.0033 (10) | 0.0096 (8) | −0.0025 (9) |
C13B | 0.0248 (11) | 0.0367 (14) | 0.0479 (12) | 0.0037 (11) | 0.0164 (9) | 0.0105 (12) |
C14B | 0.0295 (11) | 0.0208 (10) | 0.0428 (12) | 0.0005 (9) | 0.0185 (10) | 0.0007 (10) |
C15B | 0.0249 (10) | 0.0206 (10) | 0.0314 (10) | 0.0026 (8) | 0.0112 (8) | 0.0007 (9) |
O1W | 0.0266 (8) | 0.0432 (12) | 0.0734 (13) | −0.0053 (9) | 0.0007 (8) | 0.0288 (10) |
Geometric parameters (Å, º) top
O1A—C12A | 1.342 (3) | O1B—C11B | 1.467 (2) |
O1A—C11A | 1.471 (2) | O2B—C12B | 1.203 (2) |
O2A—C12A | 1.220 (2) | O3B—C3B | 1.437 (2) |
O3A—C3A | 1.435 (2) | O3B—H3OB | 0.82 (3) |
O3A—H3OA | 0.86 (3) | C1B—C2B | 1.525 (3) |
C1A—C2A | 1.524 (3) | C1B—C10B | 1.538 (2) |
C1A—C10A | 1.536 (2) | C1B—H1B1 | 0.9900 |
C1A—H1A1 | 0.9900 | C1B—H1B2 | 0.9900 |
C1A—H1A2 | 0.9900 | C2B—C3B | 1.517 (3) |
C2A—C3A | 1.516 (3) | C2B—H2B1 | 0.9900 |
C2A—H2A1 | 0.9900 | C2B—H2B2 | 0.9900 |
C2A—H2A2 | 0.9900 | C3B—C4B | 1.544 (3) |
C3A—C4A | 1.545 (3) | C3B—H3B | 1.0000 |
C3A—H3A | 1.0000 | C4B—C13B | 1.540 (3) |
C4A—C13A | 1.539 (3) | C4B—C14B | 1.542 (3) |
C4A—C14A | 1.541 (3) | C4B—C5B | 1.562 (3) |
C4A—C5A | 1.559 (3) | C5B—C6B | 1.543 (3) |
C5A—C6A | 1.543 (3) | C5B—C10B | 1.562 (3) |
C5A—C10A | 1.562 (2) | C5B—H5B | 1.0000 |
C5A—H5A | 1.0000 | C6B—C7B | 1.500 (3) |
C6A—C7A | 1.503 (3) | C6B—H6B1 | 0.9900 |
C6A—H6A1 | 0.9900 | C6B—H6B2 | 0.9900 |
C6A—H6A2 | 0.9900 | C7B—C8B | 1.322 (3) |
C7A—C8A | 1.314 (3) | C7B—H7B | 0.9500 |
C7A—H7A | 0.9500 | C8B—C12B | 1.477 (3) |
C8A—C12A | 1.474 (3) | C8B—C9B | 1.502 (3) |
C8A—C9A | 1.503 (3) | C9B—C11B | 1.540 (3) |
C9A—C11A | 1.536 (3) | C9B—C10B | 1.545 (3) |
C9A—C10A | 1.545 (3) | C9B—H9B | 1.0000 |
C9A—H9A | 1.0000 | C10B—C15B | 1.532 (3) |
C10A—C15A | 1.536 (3) | C11B—H11C | 0.9900 |
C11A—H11A | 0.9900 | C11B—H11D | 0.9900 |
C11A—H11B | 0.9900 | C13B—H13D | 0.9800 |
C13A—H13A | 0.9800 | C13B—H13E | 0.9800 |
C13A—H13B | 0.9800 | C13B—H13F | 0.9800 |
C13A—H13C | 0.9800 | C14B—H14D | 0.9800 |
C14A—H14A | 0.9800 | C14B—H14E | 0.9800 |
C14A—H14B | 0.9800 | C14B—H14F | 0.9800 |
C14A—H14C | 0.9800 | C15B—H15D | 0.9800 |
C15A—H15A | 0.9800 | C15B—H15E | 0.9800 |
C15A—H15B | 0.9800 | C15B—H15F | 0.9800 |
C15A—H15C | 0.9800 | O1W—H1W | 0.90 (3) |
O1B—C12B | 1.358 (2) | O1W—H2W | 0.88 (4) |
| | | |
C12A—O1A—C11A | 110.13 (15) | C3B—O3B—H3OB | 113 (2) |
C3A—O3A—H3OA | 106 (2) | C2B—C1B—C10B | 113.31 (18) |
C2A—C1A—C10A | 113.09 (15) | C2B—C1B—H1B1 | 108.9 |
C2A—C1A—H1A1 | 109.0 | C10B—C1B—H1B1 | 108.9 |
C10A—C1A—H1A1 | 109.0 | C2B—C1B—H1B2 | 108.9 |
C2A—C1A—H1A2 | 109.0 | C10B—C1B—H1B2 | 108.9 |
C10A—C1A—H1A2 | 109.0 | H1B1—C1B—H1B2 | 107.7 |
H1A1—C1A—H1A2 | 107.8 | C3B—C2B—C1B | 110.76 (16) |
C3A—C2A—C1A | 109.96 (16) | C3B—C2B—H2B1 | 109.5 |
C3A—C2A—H2A1 | 109.7 | C1B—C2B—H2B1 | 109.5 |
C1A—C2A—H2A1 | 109.7 | C3B—C2B—H2B2 | 109.5 |
C3A—C2A—H2A2 | 109.7 | C1B—C2B—H2B2 | 109.5 |
C1A—C2A—H2A2 | 109.7 | H2B1—C2B—H2B2 | 108.1 |
H2A1—C2A—H2A2 | 108.2 | O3B—C3B—C2B | 109.73 (16) |
O3A—C3A—C2A | 111.47 (17) | O3B—C3B—C4B | 109.58 (18) |
O3A—C3A—C4A | 111.42 (16) | C2B—C3B—C4B | 113.67 (16) |
C2A—C3A—C4A | 113.09 (17) | O3B—C3B—H3B | 107.9 |
O3A—C3A—H3A | 106.8 | C2B—C3B—H3B | 107.9 |
C2A—C3A—H3A | 106.8 | C4B—C3B—H3B | 107.9 |
C4A—C3A—H3A | 106.8 | C13B—C4B—C14B | 106.9 (2) |
C13A—C4A—C14A | 107.22 (16) | C13B—C4B—C3B | 107.79 (17) |
C13A—C4A—C3A | 108.58 (19) | C14B—C4B—C3B | 110.14 (18) |
C14A—C4A—C3A | 110.03 (17) | C13B—C4B—C5B | 108.81 (16) |
C13A—C4A—C5A | 108.38 (17) | C14B—C4B—C5B | 115.19 (19) |
C14A—C4A—C5A | 115.17 (18) | C3B—C4B—C5B | 107.80 (17) |
C3A—C4A—C5A | 107.30 (15) | C6B—C5B—C10B | 111.29 (15) |
C6A—C5A—C4A | 113.08 (15) | C6B—C5B—C4B | 112.83 (17) |
C6A—C5A—C10A | 111.19 (16) | C10B—C5B—C4B | 117.22 (15) |
C4A—C5A—C10A | 117.54 (15) | C6B—C5B—H5B | 104.7 |
C6A—C5A—H5A | 104.5 | C10B—C5B—H5B | 104.7 |
C4A—C5A—H5A | 104.5 | C4B—C5B—H5B | 104.7 |
C10A—C5A—H5A | 104.5 | C7B—C6B—C5B | 113.67 (17) |
C7A—C6A—C5A | 112.94 (16) | C7B—C6B—H6B1 | 108.8 |
C7A—C6A—H6A1 | 109.0 | C5B—C6B—H6B1 | 108.8 |
C5A—C6A—H6A1 | 109.0 | C7B—C6B—H6B2 | 108.8 |
C7A—C6A—H6A2 | 109.0 | C5B—C6B—H6B2 | 108.8 |
C5A—C6A—H6A2 | 109.0 | H6B1—C6B—H6B2 | 107.7 |
H6A1—C6A—H6A2 | 107.8 | C8B—C7B—C6B | 121.09 (17) |
C8A—C7A—C6A | 121.24 (18) | C8B—C7B—H7B | 119.5 |
C8A—C7A—H7A | 119.4 | C6B—C7B—H7B | 119.5 |
C6A—C7A—H7A | 119.4 | C7B—C8B—C12B | 126.89 (18) |
C7A—C8A—C12A | 127.48 (18) | C7B—C8B—C9B | 124.46 (18) |
C7A—C8A—C9A | 124.94 (18) | C12B—C8B—C9B | 108.36 (17) |
C12A—C8A—C9A | 107.10 (16) | C8B—C9B—C11B | 101.17 (15) |
C8A—C9A—C11A | 101.30 (16) | C8B—C9B—C10B | 111.84 (16) |
C8A—C9A—C10A | 111.54 (15) | C11B—C9B—C10B | 120.03 (16) |
C11A—C9A—C10A | 119.31 (16) | C8B—C9B—H9B | 107.7 |
C8A—C9A—H9A | 108.0 | C11B—C9B—H9B | 107.7 |
C11A—C9A—H9A | 108.0 | C10B—C9B—H9B | 107.7 |
C10A—C9A—H9A | 108.0 | C15B—C10B—C1B | 110.35 (16) |
C1A—C10A—C15A | 110.71 (16) | C15B—C10B—C9B | 110.84 (16) |
C1A—C10A—C9A | 108.22 (15) | C1B—C10B—C9B | 108.40 (16) |
C15A—C10A—C9A | 110.75 (16) | C15B—C10B—C5B | 113.19 (16) |
C1A—C10A—C5A | 110.01 (15) | C1B—C10B—C5B | 109.59 (15) |
C15A—C10A—C5A | 112.84 (16) | C9B—C10B—C5B | 104.21 (14) |
C9A—C10A—C5A | 104.03 (14) | O1B—C11B—C9B | 105.47 (14) |
O1A—C11A—C9A | 105.33 (15) | O1B—C11B—H11C | 110.6 |
O1A—C11A—H11A | 110.7 | C9B—C11B—H11C | 110.6 |
C9A—C11A—H11A | 110.7 | O1B—C11B—H11D | 110.6 |
O1A—C11A—H11B | 110.7 | C9B—C11B—H11D | 110.6 |
C9A—C11A—H11B | 110.7 | H11C—C11B—H11D | 108.8 |
H11A—C11A—H11B | 108.8 | O2B—C12B—O1B | 121.4 (2) |
O2A—C12A—O1A | 121.1 (2) | O2B—C12B—C8B | 130.2 (2) |
O2A—C12A—C8A | 129.1 (2) | O1B—C12B—C8B | 108.44 (15) |
O1A—C12A—C8A | 109.78 (16) | C4B—C13B—H13D | 109.5 |
C4A—C13A—H13A | 109.5 | C4B—C13B—H13E | 109.5 |
C4A—C13A—H13B | 109.5 | H13D—C13B—H13E | 109.5 |
H13A—C13A—H13B | 109.5 | C4B—C13B—H13F | 109.5 |
C4A—C13A—H13C | 109.5 | H13D—C13B—H13F | 109.5 |
H13A—C13A—H13C | 109.5 | H13E—C13B—H13F | 109.5 |
H13B—C13A—H13C | 109.5 | C4B—C14B—H14D | 109.5 |
C4A—C14A—H14A | 109.5 | C4B—C14B—H14E | 109.5 |
C4A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | C4B—C14B—H14F | 109.5 |
C4A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | C10B—C15B—H15D | 109.5 |
C10A—C15A—H15A | 109.5 | C10B—C15B—H15E | 109.5 |
C10A—C15A—H15B | 109.5 | H15D—C15B—H15E | 109.5 |
H15A—C15A—H15B | 109.5 | C10B—C15B—H15F | 109.5 |
C10A—C15A—H15C | 109.5 | H15D—C15B—H15F | 109.5 |
H15A—C15A—H15C | 109.5 | H15E—C15B—H15F | 109.5 |
H15B—C15A—H15C | 109.5 | H1W—O1W—H2W | 105 (3) |
C12B—O1B—C11B | 110.67 (16) | | |
| | | |
C10A—C1A—C2A—C3A | −58.2 (2) | C10B—C1B—C2B—C3B | −57.0 (2) |
C1A—C2A—C3A—O3A | −171.62 (17) | C1B—C2B—C3B—O3B | −177.73 (18) |
C1A—C2A—C3A—C4A | 61.9 (2) | C1B—C2B—C3B—C4B | 59.2 (3) |
O3A—C3A—C4A—C13A | 61.4 (2) | O3B—C3B—C4B—C13B | 66.1 (2) |
C2A—C3A—C4A—C13A | −172.13 (17) | C2B—C3B—C4B—C13B | −170.73 (19) |
O3A—C3A—C4A—C14A | −55.7 (2) | O3B—C3B—C4B—C14B | −50.2 (2) |
C2A—C3A—C4A—C14A | 70.8 (2) | C2B—C3B—C4B—C14B | 73.0 (2) |
O3A—C3A—C4A—C5A | 178.32 (17) | O3B—C3B—C4B—C5B | −176.61 (16) |
C2A—C3A—C4A—C5A | −55.2 (2) | C2B—C3B—C4B—C5B | −53.4 (2) |
C13A—C4A—C5A—C6A | −62.8 (2) | C13B—C4B—C5B—C6B | −63.1 (2) |
C14A—C4A—C5A—C6A | 57.2 (2) | C14B—C4B—C5B—C6B | 56.8 (2) |
C3A—C4A—C5A—C6A | −179.89 (18) | C3B—C4B—C5B—C6B | −179.76 (18) |
C13A—C4A—C5A—C10A | 165.48 (18) | C13B—C4B—C5B—C10B | 165.61 (18) |
C14A—C4A—C5A—C10A | −74.5 (2) | C14B—C4B—C5B—C10B | −74.4 (2) |
C3A—C4A—C5A—C10A | 48.4 (2) | C3B—C4B—C5B—C10B | 49.0 (2) |
C4A—C5A—C6A—C7A | −177.59 (19) | C10B—C5B—C6B—C7B | −42.0 (3) |
C10A—C5A—C6A—C7A | −42.8 (3) | C4B—C5B—C6B—C7B | −176.13 (18) |
C5A—C6A—C7A—C8A | 7.3 (3) | C5B—C6B—C7B—C8B | 8.2 (3) |
C6A—C7A—C8A—C12A | 174.0 (2) | C6B—C7B—C8B—C12B | 173.5 (2) |
C6A—C7A—C8A—C9A | 3.0 (4) | C6B—C7B—C8B—C9B | 0.5 (4) |
C7A—C8A—C9A—C11A | 150.6 (2) | C7B—C8B—C9B—C11B | 153.9 (2) |
C12A—C8A—C9A—C11A | −21.9 (2) | C12B—C8B—C9B—C11B | −20.3 (2) |
C7A—C8A—C9A—C10A | 22.6 (3) | C7B—C8B—C9B—C10B | 24.9 (3) |
C12A—C8A—C9A—C10A | −149.91 (17) | C12B—C8B—C9B—C10B | −149.20 (18) |
C2A—C1A—C10A—C15A | −75.9 (2) | C2B—C1B—C10B—C15B | −75.0 (2) |
C2A—C1A—C10A—C9A | 162.57 (17) | C2B—C1B—C10B—C9B | 163.49 (17) |
C2A—C1A—C10A—C5A | 49.5 (2) | C2B—C1B—C10B—C5B | 50.3 (2) |
C8A—C9A—C10A—C1A | −170.75 (16) | C8B—C9B—C10B—C15B | 67.7 (2) |
C11A—C9A—C10A—C1A | 71.7 (2) | C11B—C9B—C10B—C15B | −50.5 (2) |
C8A—C9A—C10A—C15A | 67.7 (2) | C8B—C9B—C10B—C1B | −171.07 (16) |
C11A—C9A—C10A—C15A | −49.9 (2) | C11B—C9B—C10B—C1B | 70.7 (2) |
C8A—C9A—C10A—C5A | −53.8 (2) | C8B—C9B—C10B—C5B | −54.40 (19) |
C11A—C9A—C10A—C5A | −171.37 (17) | C11B—C9B—C10B—C5B | −172.60 (17) |
C6A—C5A—C10A—C1A | −179.03 (16) | C6B—C5B—C10B—C15B | −56.4 (2) |
C4A—C5A—C10A—C1A | −46.5 (2) | C4B—C5B—C10B—C15B | 75.5 (2) |
C6A—C5A—C10A—C15A | −54.8 (2) | C6B—C5B—C10B—C1B | 179.92 (19) |
C4A—C5A—C10A—C15A | 77.7 (2) | C4B—C5B—C10B—C1B | −48.1 (2) |
C6A—C5A—C10A—C9A | 65.3 (2) | C6B—C5B—C10B—C9B | 64.1 (2) |
C4A—C5A—C10A—C9A | −162.20 (17) | C4B—C5B—C10B—C9B | −163.94 (17) |
C12A—O1A—C11A—C9A | −19.5 (2) | C12B—O1B—C11B—C9B | −20.1 (2) |
C8A—C9A—C11A—O1A | 24.7 (2) | C8B—C9B—C11B—O1B | 23.8 (2) |
C10A—C9A—C11A—O1A | 147.45 (17) | C10B—C9B—C11B—O1B | 147.30 (17) |
C11A—O1A—C12A—O2A | −175.4 (2) | C11B—O1B—C12B—O2B | −172.9 (2) |
C11A—O1A—C12A—C8A | 5.3 (2) | C11B—O1B—C12B—C8B | 7.1 (3) |
C7A—C8A—C12A—O2A | 20.0 (4) | C7B—C8B—C12B—O2B | 15.3 (4) |
C9A—C8A—C12A—O2A | −167.8 (2) | C9B—C8B—C12B—O2B | −170.7 (3) |
C7A—C8A—C12A—O1A | −160.9 (2) | C7B—C8B—C12B—O1B | −164.7 (2) |
C9A—C8A—C12A—O1A | 11.4 (2) | C9B—C8B—C12B—O1B | 9.3 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3A—H3OA···O1Wi | 0.86 (3) | 1.79 (3) | 2.632 (3) | 164 (3) |
O3B—H3OB···O3Aii | 0.82 (3) | 1.83 (4) | 2.641 (2) | 168 (3) |
O1W—H1W···O2A | 0.90 (3) | 1.90 (3) | 2.791 (2) | 169 (3) |
O1W—H2W···O3Biii | 0.88 (4) | 1.83 (4) | 2.694 (3) | 166 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y+1, z. |
(II) 3
β-Acetoxy-7-drimen-12,11-olide
top
Crystal data top
C17H24O4 | F(000) = 316 |
Mr = 292.36 | Dx = 1.285 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2218 reflections |
a = 6.802 (3) Å | θ = 2.5–30.0° |
b = 7.918 (4) Å | µ = 0.09 mm−1 |
c = 14.302 (8) Å | T = 120 K |
β = 101.22 (2)° | Prism, colorless |
V = 755.6 (7) Å3 | 0.33 × 0.18 × 0.15 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer | 1456 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 30.0°, θmin = 2.9° |
ω scans with κ offsets | h = −9→9 |
8695 measured reflections | k = −11→11 |
2353 independent reflections | l = −20→20 |
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)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0473P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
2353 reflections | Δρmax = 0.22 e Å−3 |
195 parameters | Δρmin = −0.20 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: 0.012 (3) |
Crystal data top
C17H24O4 | V = 755.6 (7) Å3 |
Mr = 292.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.802 (3) Å | µ = 0.09 mm−1 |
b = 7.918 (4) Å | T = 120 K |
c = 14.302 (8) Å | 0.33 × 0.18 × 0.15 mm |
β = 101.22 (2)° | |
Data collection top
Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer | 1456 reflections with I > 2σ(I) |
8695 measured reflections | Rint = 0.057 |
2353 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.22 e Å−3 |
2353 reflections | Δρmin = −0.20 e Å−3 |
195 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 | 0.8176 (3) | 0.4883 (3) | 0.55905 (12) | 0.0373 (5) | |
O2 | 0.9004 (3) | 0.7238 (3) | 0.64502 (13) | 0.0466 (6) | |
O3 | 0.2946 (2) | 0.7821 (3) | 0.03214 (12) | 0.0303 (5) | |
O4 | −0.0282 (3) | 0.7133 (3) | 0.02549 (13) | 0.0421 (6) | |
C1 | 0.5137 (4) | 0.5137 (4) | 0.24430 (18) | 0.0291 (6) | |
H1A | 0.5911 | 0.4071 | 0.2488 | 0.035* | |
H1B | 0.3883 | 0.4910 | 0.2675 | 0.035* | |
C2 | 0.4608 (4) | 0.5684 (4) | 0.13965 (18) | 0.0281 (6) | |
H2A | 0.5848 | 0.5818 | 0.1138 | 0.034* | |
H2B | 0.3767 | 0.4811 | 0.1017 | 0.034* | |
C3 | 0.3484 (4) | 0.7340 (4) | 0.13273 (17) | 0.0272 (6) | |
H3 | 0.2227 | 0.7178 | 0.1581 | 0.033* | |
C4 | 0.4685 (4) | 0.8808 (4) | 0.18701 (18) | 0.0277 (6) | |
C5 | 0.5321 (4) | 0.8218 (4) | 0.29222 (18) | 0.0273 (6) | |
H5 | 0.4030 | 0.8075 | 0.3150 | 0.033* | |
C6 | 0.6462 (4) | 0.9594 (4) | 0.35766 (18) | 0.0314 (7) | |
H6A | 0.7580 | 1.0015 | 0.3290 | 0.038* | |
H6B | 0.5544 | 1.0553 | 0.3609 | 0.038* | |
C7 | 0.7284 (4) | 0.8995 (4) | 0.45640 (19) | 0.0307 (7) | |
H7 | 0.7873 | 0.9790 | 0.5033 | 0.037* | |
C8 | 0.7213 (4) | 0.7382 (4) | 0.48037 (18) | 0.0298 (7) | |
C9 | 0.6281 (4) | 0.6011 (4) | 0.41395 (19) | 0.0307 (7) | |
H9 | 0.4839 | 0.5919 | 0.4190 | 0.037* | |
C10 | 0.6365 (4) | 0.6465 (4) | 0.30899 (18) | 0.0265 (6) | |
C11 | 0.7360 (4) | 0.4441 (4) | 0.45954 (19) | 0.0327 (7) | |
H11A | 0.6413 | 0.3483 | 0.4562 | 0.039* | |
H11B | 0.8452 | 0.4117 | 0.4263 | 0.039* | |
C12 | 0.8213 (4) | 0.6600 (4) | 0.5705 (2) | 0.0337 (7) | |
C13 | 0.3243 (4) | 1.0323 (4) | 0.1838 (2) | 0.0392 (8) | |
H13A | 0.2183 | 1.0040 | 0.2187 | 0.059* | |
H13B | 0.2643 | 1.0581 | 0.1173 | 0.059* | |
H13C | 0.3988 | 1.1309 | 0.2132 | 0.059* | |
C14 | 0.6407 (4) | 0.9339 (4) | 0.1383 (2) | 0.0362 (7) | |
H14A | 0.7388 | 0.9999 | 0.1830 | 0.054* | |
H14B | 0.5877 | 1.0027 | 0.0821 | 0.054* | |
H14C | 0.7057 | 0.8330 | 0.1187 | 0.054* | |
C15 | 0.8545 (3) | 0.6492 (4) | 0.29435 (18) | 0.0310 (7) | |
H15A | 0.9130 | 0.5362 | 0.3063 | 0.047* | |
H15B | 0.9322 | 0.7300 | 0.3387 | 0.047* | |
H15C | 0.8573 | 0.6829 | 0.2287 | 0.047* | |
C16 | 0.1016 (4) | 0.7681 (4) | −0.01206 (18) | 0.0278 (6) | |
C17 | 0.0738 (4) | 0.8303 (4) | −0.11191 (18) | 0.0316 (7) | |
H17A | −0.0402 | 0.7720 | −0.1512 | 0.047* | |
H17B | 0.1953 | 0.8077 | −0.1371 | 0.047* | |
H17C | 0.0480 | 0.9521 | −0.1132 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0408 (11) | 0.0408 (15) | 0.0292 (11) | 0.0011 (10) | 0.0044 (8) | 0.0066 (10) |
O2 | 0.0573 (12) | 0.0554 (15) | 0.0253 (10) | −0.0093 (13) | 0.0034 (9) | 0.0001 (11) |
O3 | 0.0265 (9) | 0.0368 (13) | 0.0257 (9) | −0.0003 (9) | 0.0004 (7) | −0.0002 (8) |
O4 | 0.0322 (10) | 0.0568 (15) | 0.0349 (12) | −0.0113 (11) | 0.0003 (8) | 0.0074 (11) |
C1 | 0.0292 (13) | 0.0250 (16) | 0.0326 (15) | −0.0013 (12) | 0.0048 (12) | −0.0010 (13) |
C2 | 0.0299 (13) | 0.0237 (17) | 0.0280 (14) | −0.0027 (13) | −0.0007 (11) | −0.0022 (13) |
C3 | 0.0267 (12) | 0.0302 (17) | 0.0241 (14) | −0.0004 (13) | 0.0033 (10) | −0.0004 (13) |
C4 | 0.0268 (12) | 0.0263 (16) | 0.0285 (15) | 0.0013 (12) | 0.0016 (11) | −0.0007 (13) |
C5 | 0.0261 (12) | 0.0241 (16) | 0.0304 (15) | 0.0042 (12) | 0.0024 (11) | −0.0016 (13) |
C6 | 0.0319 (13) | 0.0263 (17) | 0.0344 (15) | 0.0033 (13) | 0.0024 (12) | −0.0024 (13) |
C7 | 0.0280 (14) | 0.0361 (19) | 0.0267 (14) | 0.0001 (13) | 0.0018 (11) | −0.0081 (14) |
C8 | 0.0258 (13) | 0.0349 (19) | 0.0282 (15) | 0.0021 (13) | 0.0045 (11) | −0.0008 (14) |
C9 | 0.0291 (12) | 0.0287 (17) | 0.0335 (15) | 0.0016 (13) | 0.0045 (11) | 0.0007 (13) |
C10 | 0.0282 (12) | 0.0260 (16) | 0.0239 (13) | 0.0017 (12) | 0.0015 (10) | 0.0026 (12) |
C11 | 0.0309 (14) | 0.0364 (19) | 0.0293 (15) | 0.0038 (14) | 0.0021 (12) | 0.0019 (13) |
C12 | 0.0314 (14) | 0.043 (2) | 0.0285 (15) | −0.0039 (14) | 0.0095 (12) | −0.0001 (14) |
C13 | 0.0440 (15) | 0.0298 (18) | 0.0390 (17) | 0.0096 (14) | −0.0038 (13) | −0.0043 (14) |
C14 | 0.0384 (14) | 0.0350 (19) | 0.0325 (14) | −0.0072 (13) | 0.0000 (12) | 0.0020 (13) |
C15 | 0.0294 (12) | 0.0306 (17) | 0.0325 (14) | 0.0012 (13) | 0.0045 (11) | −0.0027 (14) |
C16 | 0.0271 (13) | 0.0242 (16) | 0.0299 (14) | 0.0004 (12) | 0.0003 (11) | −0.0063 (12) |
C17 | 0.0316 (13) | 0.0296 (17) | 0.0300 (15) | −0.0028 (13) | −0.0034 (11) | 0.0010 (13) |
Geometric parameters (Å, º) top
O1—C12 | 1.369 (4) | C7—C8 | 1.326 (4) |
O1—C11 | 1.466 (3) | C7—H7 | 0.9500 |
O2—C12 | 1.207 (3) | C8—C12 | 1.472 (4) |
O3—C16 | 1.346 (3) | C8—C9 | 1.499 (4) |
O3—C3 | 1.464 (3) | C9—C11 | 1.525 (4) |
O4—C16 | 1.201 (3) | C9—C10 | 1.555 (4) |
C1—C2 | 1.532 (3) | C9—H9 | 1.0000 |
C1—C10 | 1.536 (4) | C10—C15 | 1.537 (3) |
C1—H1A | 0.9900 | C11—H11A | 0.9900 |
C1—H1B | 0.9900 | C11—H11B | 0.9900 |
C2—C3 | 1.511 (4) | C13—H13A | 0.9800 |
C2—H2A | 0.9900 | C13—H13B | 0.9800 |
C2—H2B | 0.9900 | C13—H13C | 0.9800 |
C3—C4 | 1.540 (4) | C14—H14A | 0.9800 |
C3—H3 | 1.0000 | C14—H14B | 0.9800 |
C4—C13 | 1.544 (4) | C14—H14C | 0.9800 |
C4—C14 | 1.534 (4) | C15—H15A | 0.9800 |
C4—C5 | 1.555 (4) | C15—H15B | 0.9800 |
C5—C6 | 1.544 (4) | C15—H15C | 0.9800 |
C5—C10 | 1.556 (4) | C16—C17 | 1.488 (4) |
C5—H5 | 1.0000 | C17—H17A | 0.9800 |
C6—C7 | 1.492 (4) | C17—H17B | 0.9800 |
C6—H6A | 0.9900 | C17—H17C | 0.9800 |
C6—H6B | 0.9900 | | |
| | | |
C12—O1—C11 | 110.4 (2) | C11—C9—C10 | 119.8 (2) |
C16—O3—C3 | 118.3 (2) | C8—C9—H9 | 107.9 |
C2—C1—C10 | 113.0 (2) | C11—C9—H9 | 107.9 |
C2—C1—H1A | 109.0 | C10—C9—H9 | 107.9 |
C10—C1—H1A | 109.0 | C1—C10—C15 | 110.7 (2) |
C2—C1—H1B | 109.0 | C1—C10—C9 | 107.8 (2) |
C10—C1—H1B | 109.0 | C15—C10—C9 | 110.6 (2) |
H1A—C1—H1B | 107.8 | C1—C10—C5 | 109.84 (19) |
C3—C2—C1 | 109.2 (2) | C15—C10—C5 | 113.0 (2) |
C3—C2—H2A | 109.8 | C9—C10—C5 | 104.7 (2) |
C1—C2—H2A | 109.8 | O1—C11—C9 | 106.3 (2) |
C3—C2—H2B | 109.8 | O1—C11—H11A | 110.5 |
C1—C2—H2B | 109.8 | C9—C11—H11A | 110.5 |
H2A—C2—H2B | 108.3 | O1—C11—H11B | 110.5 |
O3—C3—C2 | 108.4 (2) | C9—C11—H11B | 110.5 |
O3—C3—C4 | 107.8 (2) | H11A—C11—H11B | 108.7 |
C2—C3—C4 | 114.20 (19) | O2—C12—O1 | 121.1 (3) |
O3—C3—H3 | 108.8 | O2—C12—C8 | 130.3 (3) |
C2—C3—H3 | 108.8 | O1—C12—C8 | 108.6 (2) |
C4—C3—H3 | 108.8 | C4—C13—H13A | 109.5 |
C14—C4—C3 | 110.8 (2) | C4—C13—H13B | 109.5 |
C13—C4—C14 | 108.1 (2) | H13A—C13—H13B | 109.5 |
C3—C4—C13 | 107.4 (2) | C4—C13—H13C | 109.5 |
C14—C4—C5 | 115.4 (2) | H13A—C13—H13C | 109.5 |
C3—C4—C5 | 106.3 (2) | H13B—C13—H13C | 109.5 |
C13—C4—C5 | 108.6 (2) | C4—C14—H14A | 109.5 |
C6—C5—C4 | 112.8 (2) | C4—C14—H14B | 109.5 |
C6—C5—C10 | 112.05 (19) | H14A—C14—H14B | 109.5 |
C4—C5—C10 | 116.8 (2) | C4—C14—H14C | 109.5 |
C6—C5—H5 | 104.6 | H14A—C14—H14C | 109.5 |
C4—C5—H5 | 104.6 | H14B—C14—H14C | 109.5 |
C10—C5—H5 | 104.6 | C10—C15—H15A | 109.5 |
C7—C6—C5 | 113.6 (3) | C10—C15—H15B | 109.5 |
C7—C6—H6A | 108.8 | H15A—C15—H15B | 109.5 |
C5—C6—H6A | 108.8 | C10—C15—H15C | 109.5 |
C7—C6—H6B | 108.8 | H15A—C15—H15C | 109.5 |
C5—C6—H6B | 108.8 | H15B—C15—H15C | 109.5 |
H6A—C6—H6B | 107.7 | O4—C16—O3 | 123.7 (2) |
C8—C7—C6 | 121.7 (3) | O4—C16—C17 | 125.6 (2) |
C8—C7—H7 | 119.1 | O3—C16—C17 | 110.7 (2) |
C6—C7—H7 | 119.1 | C16—C17—H17A | 109.5 |
C7—C8—C12 | 126.7 (3) | C16—C17—H17B | 109.5 |
C7—C8—C9 | 124.4 (3) | H17A—C17—H17B | 109.5 |
C12—C8—C9 | 108.5 (3) | C16—C17—H17C | 109.5 |
C8—C9—C11 | 102.2 (2) | H17A—C17—H17C | 109.5 |
C8—C9—C10 | 110.7 (2) | H17B—C17—H17C | 109.5 |
| | | |
C10—C1—C2—C3 | −56.9 (3) | C2—C1—C10—C15 | −74.8 (3) |
C16—O3—C3—C2 | 107.0 (2) | C2—C1—C10—C9 | 164.1 (2) |
C16—O3—C3—C4 | −128.9 (2) | C2—C1—C10—C5 | 50.6 (3) |
C1—C2—C3—O3 | −178.54 (19) | C8—C9—C10—C1 | −172.3 (2) |
C1—C2—C3—C4 | 61.2 (3) | C11—C9—C10—C1 | 69.3 (3) |
O3—C3—C4—C13 | 66.7 (3) | C8—C9—C10—C15 | 66.6 (3) |
C2—C3—C4—C13 | −172.7 (2) | C11—C9—C10—C15 | −51.8 (3) |
O3—C3—C4—C14 | −51.1 (3) | C8—C9—C10—C5 | −55.4 (3) |
C2—C3—C4—C14 | 69.5 (3) | C11—C9—C10—C5 | −173.8 (2) |
O3—C3—C4—C5 | −177.18 (19) | C6—C5—C10—C1 | 178.4 (2) |
C2—C3—C4—C5 | −56.6 (3) | C4—C5—C10—C1 | −49.4 (3) |
C14—C4—C5—C6 | 59.5 (3) | C6—C5—C10—C15 | −57.5 (3) |
C3—C4—C5—C6 | −177.2 (2) | C4—C5—C10—C15 | 74.7 (3) |
C13—C4—C5—C6 | −61.9 (3) | C6—C5—C10—C9 | 62.9 (3) |
C14—C4—C5—C10 | −72.3 (3) | C4—C5—C10—C9 | −164.9 (2) |
C3—C4—C5—C10 | 50.9 (3) | C12—O1—C11—C9 | −17.0 (3) |
C13—C4—C5—C10 | 166.2 (2) | C8—C9—C11—O1 | 20.2 (3) |
C4—C5—C6—C7 | −173.6 (2) | C10—C9—C11—O1 | 142.9 (2) |
C10—C5—C6—C7 | −39.4 (3) | C11—O1—C12—O2 | −173.0 (2) |
C5—C6—C7—C8 | 7.1 (4) | C11—O1—C12—C8 | 6.0 (3) |
C6—C7—C8—C12 | 170.7 (2) | C7—C8—C12—O2 | 13.2 (5) |
C6—C7—C8—C9 | −1.6 (4) | C9—C8—C12—O2 | −173.5 (3) |
C7—C8—C9—C11 | 156.4 (3) | C7—C8—C12—O1 | −165.6 (3) |
C12—C8—C9—C11 | −17.1 (3) | C9—C8—C12—O1 | 7.6 (3) |
C7—C8—C9—C10 | 27.8 (4) | C3—O3—C16—O4 | −2.5 (4) |
C12—C8—C9—C10 | −145.7 (2) | C3—O3—C16—C17 | 177.2 (2) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H22O3·0.5H2O | C17H24O4 |
Mr | 259.33 | 292.36 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 12.875 (3), 6.153 (2), 18.268 (4) | 6.802 (3), 7.918 (4), 14.302 (8) |
β (°) | 106.031 (16) | 101.22 (2) |
V (Å3) | 1390.9 (6) | 755.6 (7) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.42 × 0.35 × 0.20 | 0.33 × 0.18 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer | Nonius KappaCCD area-detector (with Oxford Cryostream) diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17077, 5214, 3773 | 8695, 2353, 1456 |
Rint | 0.040 | 0.057 |
(sin θ/λ)max (Å−1) | 0.746 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.112, 1.04 | 0.051, 0.108, 0.98 |
No. of reflections | 5214 | 2353 |
No. of parameters | 353 | 195 |
No. of restraints | 1 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.23 | 0.22, −0.20 |
Selected geometric parameters (Å, º) for (I) topO1A—C12A | 1.342 (3) | O2B—C12B | 1.203 (2) |
O2A—C12A | 1.220 (2) | O3B—C3B | 1.437 (2) |
C7A—C8A | 1.314 (3) | C7B—C8B | 1.322 (3) |
| | | |
C10A—C1A—C2A—C3A | −58.2 (2) | C10B—C1B—C2B—C3B | −57.0 (2) |
C1A—C2A—C3A—C4A | 61.9 (2) | C1B—C2B—C3B—C4B | 59.2 (3) |
C2A—C3A—C4A—C5A | −55.2 (2) | C2B—C3B—C4B—C5B | −53.4 (2) |
C3A—C4A—C5A—C10A | 48.4 (2) | C3B—C4B—C5B—C10B | 49.0 (2) |
C10A—C5A—C6A—C7A | −42.8 (3) | C10B—C5B—C6B—C7B | −42.0 (3) |
C5A—C6A—C7A—C8A | 7.3 (3) | C5B—C6B—C7B—C8B | 8.2 (3) |
C6A—C7A—C8A—C9A | 3.0 (4) | C6B—C7B—C8B—C9B | 0.5 (4) |
C12A—C8A—C9A—C11A | −21.9 (2) | C12B—C8B—C9B—C11B | −20.3 (2) |
C7A—C8A—C9A—C10A | 22.6 (3) | C7B—C8B—C9B—C10B | 24.9 (3) |
C2A—C1A—C10A—C5A | 49.5 (2) | C2B—C1B—C10B—C5B | 50.3 (2) |
C8A—C9A—C10A—C5A | −53.8 (2) | C8B—C9B—C10B—C5B | −54.40 (19) |
C4A—C5A—C10A—C1A | −46.5 (2) | C4B—C5B—C10B—C1B | −48.1 (2) |
C6A—C5A—C10A—C9A | 65.3 (2) | C6B—C5B—C10B—C9B | 64.1 (2) |
C12A—O1A—C11A—C9A | −19.5 (2) | C12B—O1B—C11B—C9B | −20.1 (2) |
C8A—C9A—C11A—O1A | 24.7 (2) | C8B—C9B—C11B—O1B | 23.8 (2) |
C11A—O1A—C12A—C8A | 5.3 (2) | C11B—O1B—C12B—C8B | 7.1 (3) |
C9A—C8A—C12A—O1A | 11.4 (2) | C9B—C8B—C12B—O1B | 9.3 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3A—H3OA···O1Wi | 0.86 (3) | 1.79 (3) | 2.632 (3) | 164 (3) |
O3B—H3OB···O3Aii | 0.82 (3) | 1.83 (4) | 2.641 (2) | 168 (3) |
O1W—H1W···O2A | 0.90 (3) | 1.90 (3) | 2.791 (2) | 169 (3) |
O1W—H2W···O3Biii | 0.88 (4) | 1.83 (4) | 2.694 (3) | 166 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y+1, z. |
Selected geometric parameters (Å, º) for (II) topO2—C12 | 1.207 (3) | C7—C8 | 1.326 (4) |
O4—C16 | 1.201 (3) | | |
| | | |
C10—C1—C2—C3 | −56.9 (3) | C2—C1—C10—C5 | 50.6 (3) |
C1—C2—C3—C4 | 61.2 (3) | C8—C9—C10—C5 | −55.4 (3) |
C2—C3—C4—C5 | −56.6 (3) | C4—C5—C10—C1 | −49.4 (3) |
C3—C4—C5—C10 | 50.9 (3) | C6—C5—C10—C9 | 62.9 (3) |
C10—C5—C6—C7 | −39.4 (3) | C12—O1—C11—C9 | −17.0 (3) |
C5—C6—C7—C8 | 7.1 (4) | C8—C9—C11—O1 | 20.2 (3) |
C6—C7—C8—C9 | −1.6 (4) | C11—O1—C12—C8 | 6.0 (3) |
C12—C8—C9—C11 | −17.1 (3) | C9—C8—C12—O1 | 7.6 (3) |
C7—C8—C9—C10 | 27.8 (4) | | |
Plants of the genus Warburgia are of interest because of their use by herbalists in Kenya for the treatment of a number of parasitic diseases (Kokwaro, 1976). Isolation of drimanolide-class sesquiterpenes (I) and (II) from the stem bark of Warburgia ugandensis Sprague (Canellaceae) has been described by Kioy et al. (1990). The molecular structures of 3β-hydroxy-7-drimen-12,11-olide hemihydrate, (I), and 3β-acetoxy-7-drimen-12,11-olide, (II), were determined in order to ascertain unambiguously the relative stereochemistry of the 3-OH and 3-OAc groups, respectively, as well as to confirm the relative configurations of the other asymmetric centers.
One of the two independent molecules of (I) is shown in Fig. 1. The OH group at C3 is seen to be β-oriented, and the configurations at the other chiral centers are confirmed to be those reported by Kioy et al. (1990). The conformations of the two independent molecules are nearly identical, with maximum deviation in an endocyclic torsion angle of 2.5 (6)°, about the double bond C7═C8. The OH-carrying A ring has a chair conformation, the central B ring a half-chair conformation, and the lactone ring a C2 half-chair conformation, with the axis passing through C12 and bisecting C9—C11. The most notable difference in the conformations of the two molecules involves the OH group, in which the O—H bond is roughly parallel to C10—C15 in the A molecule and roughly antiparallel in the B molecule, in accordance with the hydrogen-bonding scheme. The OH group of the A molecule donates a hydrogen bond to the water molecule, while the OH of the B molecule instead donates to the OH group of the A molecule. The lactone carbonyl atom O2 of the A molecule accepts a hydrogen bond (from water), but that of the B molecule is not involved in hydrogen bonding. The acceptor for the second hydrogen bond donated by water is the OH group of the B molecule.
Compound (II) is shown in Fig. 2, and the configurations at all the chiral centers are seen to be the same as those of (I). The conformation of the ring system also agrees well with that of (I): the largest individual difference between an endocyclic torsion angle in (II) and the corresponding average value in (I) is 4.1 (5)°, for C7—C8—C9—C10. The conformations of the ring system in both title compounds agree fairly well with those of two molecules also having the drimanolide skeleton, insulicolide A (Rahbaek et al., 1997) and iresin dibromobenzoate (Rossman & Lipscomb, 1958). The cell dimensions of (II) at room temperature (299 K), measured on a Nonius CAD-4 diffractometer using Cu Kα radiation, are a = 6.8885 (6), b = 7.9753 (8) and c = 14.411 (2) Å, and β = 101.613 (7)°.