Buy article online - an online subscription or single-article purchase is required to access this article.
The stereochemistry of the title compound, C15H26O3, has been established. The compound crystallizes with three molecules in the asymmetric unit and significant variations in the bond distances and angles are reported. Intermolecular hydrogen bonds are observed between the hydroxyl groups.
Supporting information
CCDC reference: 175354
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.090
- Data-to-parameter ratio = 8.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
EXPT_002 Alert A _exptl_crystal_density_meas is missing, although a method
has been given. Density measured experimentally (Mg m-3).
The following tests will not be performed.
DENSX_01
CELLV_02 Alert A The supplied cell volume s.u. differs from that
calculated from the cell parameter s.u.'s by > 8
Calculated cell volume su = 26.91
Cell volume su given = 3.00
Alert Level B:
DENSM_01 Alert B _exptl_crystal_density_method is given but no value of
_exptl_crystal_density_meas is reported.
PLAT_707 Alert B D...A Calc 3.007(4), Rep 3.018(3), Dev. 2.75 Sigma
O56 -O56 1.555 2.674
Alert Level C:
CRYSC_01 Alert C The word below has not been recognised as a standard
identifier.
incolore
CRYSC_01 Alert C No recognised colour has been given for crystal colour.
PLAT_726 Alert C H...A Calc 2.05171, Rep 2.062(2), Dev. 0.01 Ang.
H56 -O56 1.555 2.674
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.34
From the CIF: _reflns_number_total 3985
Count of symmetry unique reflns 4186
Completeness (_total/calc) 95.20%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
2 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
3 Alert Level C = Please check
Dans un réacteur contenant 2 g (9,8 mmol) du β-himachalène solubilisé
dans une solution de 30 ml d'un mélange acétone–eau (9/1) e t
maintenu sous agitation à une température de 263 K, on ajoute
progressivement trois équivalents (29,4 mmol) de permanganate de potassium
finement broyé. Après 16 h, la solution est filtrée sur célite puis
extraite avec de l'éther. Après avoir évaporé une bonne partie de
l'acétone, les phases éthérées sont lavées avec une solution
aqueuse d'hydrogénocarbonate de sodium à 15% puis à l'eau, séchées
sur sulfate de magnésium et concentrées sous pression réduite. Le
résidu obtenu est chromatographié sur colonne de gel de silice avec comme
éluant un mélange héxane/acétate d'éthyle (95/5). Rendement
30%; point de fusion 362 K. Les cristaux ont été obtenus par
évaporation, à température ambiante, de solutions saturées dans
l'héxane.
L'absence d'atomes présentant une diffusion anomale significative ne
permet pas de déterminer la configuration absolue de ces molécules. Les
réflexions ont donc été moyennées en appliquant la loi de Friedel
avant affinement.
Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus (Mackay et al., 1999).
Crystal data top
C15H26O3 | Dx = 1.233 Mg m−3 |
Mr = 254.37 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P32 | Cell parameters from 9812 reflections |
a = 21.266 (9) Å | θ = 2.9–26.3° |
c = 7.873 (5) Å | µ = 0.08 mm−1 |
V = 3083.5 (3) Å3 | T = 298 K |
Z = 9 | Prisme, incolore |
F(000) = 1260 | 0.45 × 0.25 × 0.20 mm |
Data collection top
KappaCCD diffractometer | Rint = 0.052 |
Radiation source: fine-focus sealed tube | θmax = 26.3° |
ϕ scan | h = 0→26 |
9812 measured reflections | k = −26→0 |
3985 independent reflections | l = −9→9 |
3740 reflections with I > 2σ(I) | |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0342P)2 + 1.0542P] where P = (Fo2 + 2Fc2)/3 |
3985 reflections | (Δ/σ)max = 0.001 |
485 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C15H26O3 | Z = 9 |
Mr = 254.37 | Mo Kα radiation |
Trigonal, P32 | µ = 0.08 mm−1 |
a = 21.266 (9) Å | T = 298 K |
c = 7.873 (5) Å | 0.45 × 0.25 × 0.20 mm |
V = 3083.5 (3) Å3 | |
Data collection top
KappaCCD diffractometer | 3740 reflections with I > 2σ(I) |
9812 measured reflections | Rint = 0.052 |
3985 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.19 e Å−3 |
3985 reflections | Δρmin = −0.23 e Å−3 |
485 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 | |
O13 | −0.22933 (11) | 0.49319 (11) | 0.8310 (2) | 0.0364 (4) | |
H13 | −0.2263 | 0.4543 | 0.7862 | 0.085 (15)* | |
O16 | −0.33063 (11) | 0.37593 (10) | 0.3954 (3) | 0.0372 (4) | |
H16 | −0.3368 | 0.3485 | 0.2938 | 0.15 (3)* | |
O18 | −0.18260 (10) | 0.47803 (10) | 0.5090 (3) | 0.0285 (4) | |
O33 | 0.17476 (11) | 0.56695 (11) | 0.0680 (3) | 0.0351 (4) | |
H33 | 0.2109 | 0.5617 | 0.1185 | 0.091 (16)* | |
O36 | 0.29161 (10) | 0.66273 (10) | 0.5070 (3) | 0.0339 (4) | |
H36 | 0.3224 | 0.6794 | 0.6097 | 0.065 (12)* | |
O38 | 0.18580 (9) | 0.51703 (10) | 0.3860 (3) | 0.0276 (4) | |
O53 | 0.03739 (11) | 0.88327 (11) | 1.1630 (3) | 0.0357 (4) | |
H53 | 0.0049 | 0.8858 | 1.0994 | 0.073 (14)* | |
O56 | 0.03498 (10) | 0.99160 (10) | 0.7245 (3) | 0.0347 (4) | |
H56 | 0.0243 | 1.0085 | 0.6217 | 0.093 (16)* | |
O58 | −0.02502 (9) | 0.84137 (10) | 0.8403 (2) | 0.0271 (4) | |
C1 | −0.27773 (13) | 0.50178 (13) | 0.4851 (4) | 0.0260 (5) | |
H1 | −0.3060 | 0.4704 | 0.5796 | 0.031* | |
C2 | −0.28211 (14) | 0.44970 (13) | 0.3421 (4) | 0.0292 (5) | |
H2 | −0.2981 | 0.4605 | 0.2348 | 0.035* | |
C3 | −0.20305 (15) | 0.46710 (14) | 0.3312 (4) | 0.0305 (5) | |
C4 | −0.15629 (16) | 0.54448 (16) | 0.2568 (4) | 0.0384 (6) | |
H4A | −0.1099 | 0.5522 | 0.2163 | 0.046* | |
H4B | −0.1813 | 0.5530 | 0.1644 | 0.046* | |
C5 | −0.14649 (15) | 0.59334 (15) | 0.4092 (4) | 0.0356 (6) | |
H5A | −0.1619 | 0.6281 | 0.3827 | 0.043* | |
H5B | −0.0965 | 0.6191 | 0.4476 | 0.043* | |
C6 | −0.19671 (13) | 0.53741 (13) | 0.5416 (4) | 0.0259 (5) | |
C7 | −0.18146 (14) | 0.55600 (14) | 0.7303 (4) | 0.0307 (6) | |
C8 | −0.19654 (17) | 0.61593 (16) | 0.7865 (4) | 0.0419 (7) | |
H8A | −0.1615 | 0.6607 | 0.7314 | 0.050* | |
H8B | −0.1880 | 0.6229 | 0.9078 | 0.050* | |
C9 | −0.27278 (19) | 0.60367 (19) | 0.7502 (5) | 0.0474 (8) | |
H9A | −0.3084 | 0.5544 | 0.7822 | 0.057* | |
H9B | −0.2809 | 0.6364 | 0.8207 | 0.057* | |
C10 | −0.28487 (19) | 0.61567 (17) | 0.5647 (5) | 0.0446 (7) | |
H10A | −0.2393 | 0.6541 | 0.5196 | 0.053* | |
H10B | −0.3193 | 0.6330 | 0.5615 | 0.053* | |
C11 | −0.31283 (15) | 0.54959 (14) | 0.4446 (4) | 0.0337 (6) | |
C12 | −0.10279 (16) | 0.57805 (17) | 0.7754 (4) | 0.0422 (7) | |
H12A | −0.0976 | 0.5788 | 0.8966 | 0.063* | |
H12B | −0.0705 | 0.6255 | 0.7303 | 0.063* | |
H12C | −0.0911 | 0.5436 | 0.7274 | 0.063* | |
C14 | −0.39532 (17) | 0.50003 (19) | 0.4697 (5) | 0.0486 (8) | |
H14A | −0.4050 | 0.4835 | 0.5853 | 0.073* | |
H14B | −0.4128 | 0.4590 | 0.3951 | 0.073* | |
H14C | −0.4196 | 0.5267 | 0.4443 | 0.073* | |
C15 | −0.3022 (2) | 0.57790 (19) | 0.2623 (5) | 0.0497 (8) | |
H15A | −0.3245 | 0.6073 | 0.2491 | 0.074* | |
H15B | −0.3241 | 0.5376 | 0.1850 | 0.074* | |
H15C | −0.2512 | 0.6066 | 0.2383 | 0.074* | |
C17 | −0.19022 (19) | 0.41009 (18) | 0.2516 (5) | 0.0464 (8) | |
H17A | −0.1398 | 0.4244 | 0.2615 | 0.070* | |
H17B | −0.2035 | 0.4049 | 0.1338 | 0.070* | |
H17C | −0.2191 | 0.3646 | 0.3088 | 0.070* | |
C21 | 0.16653 (12) | 0.61507 (13) | 0.4147 (3) | 0.0243 (5) | |
H21 | 0.1987 | 0.6434 | 0.3213 | 0.029* | |
C22 | 0.21724 (13) | 0.61640 (14) | 0.5574 (4) | 0.0269 (5) | |
H22 | 0.2070 | 0.6325 | 0.6652 | 0.032* | |
C23 | 0.19646 (14) | 0.53615 (14) | 0.5662 (4) | 0.0292 (5) | |
C24 | 0.11922 (16) | 0.49183 (16) | 0.6378 (4) | 0.0368 (6) | |
H24A | 0.1115 | 0.5173 | 0.7304 | 0.044* | |
H24B | 0.1096 | 0.4447 | 0.6777 | 0.044* | |
C25 | 0.07117 (15) | 0.48425 (15) | 0.4840 (4) | 0.0353 (6) | |
H25A | 0.0444 | 0.4345 | 0.4437 | 0.042* | |
H25B | 0.0374 | 0.5010 | 0.5103 | 0.042* | |
C26 | 0.12892 (13) | 0.53428 (13) | 0.3553 (3) | 0.0254 (5) | |
C27 | 0.11028 (14) | 0.52060 (14) | 0.1657 (4) | 0.0304 (6) | |
C28 | 0.05379 (15) | 0.54081 (17) | 0.1099 (4) | 0.0397 (7) | |
H28A | 0.0472 | 0.5334 | −0.0119 | 0.048* | |
H28B | 0.0080 | 0.5070 | 0.1630 | 0.048* | |
C29 | 0.06943 (17) | 0.61765 (18) | 0.1484 (4) | 0.0419 (7) | |
H29A | 0.0384 | 0.6281 | 0.0777 | 0.050* | |
H29B | 0.1194 | 0.6517 | 0.1182 | 0.050* | |
C30 | 0.05744 (16) | 0.62971 (18) | 0.3344 (4) | 0.0412 (7) | |
H30A | 0.0167 | 0.5851 | 0.3769 | 0.049* | |
H30B | 0.0433 | 0.6666 | 0.3379 | 0.049* | |
C31 | 0.12165 (14) | 0.65268 (15) | 0.4578 (4) | 0.0338 (6) | |
C32 | 0.08458 (17) | 0.44170 (16) | 0.1176 (4) | 0.0430 (7) | |
H32A | 0.0789 | 0.4362 | −0.0034 | 0.064* | |
H32B | 0.0389 | 0.4104 | 0.1716 | 0.064* | |
H32C | 0.1198 | 0.4290 | 0.1545 | 0.064* | |
C34 | 0.17431 (18) | 0.73452 (16) | 0.4401 (5) | 0.0452 (7) | |
H34A | 0.1910 | 0.7455 | 0.3248 | 0.068* | |
H34B | 0.2151 | 0.7487 | 0.5142 | 0.068* | |
H34C | 0.1499 | 0.7606 | 0.4703 | 0.068* | |
C35 | 0.09058 (18) | 0.6398 (2) | 0.6389 (4) | 0.0465 (7) | |
H35A | 0.1297 | 0.6582 | 0.7196 | 0.070* | |
H35B | 0.0592 | 0.5887 | 0.6571 | 0.070* | |
H35C | 0.0635 | 0.6645 | 0.6532 | 0.070* | |
C37 | 0.25143 (17) | 0.52008 (18) | 0.6451 (4) | 0.0436 (7)* | |
H37A | 0.2341 | 0.4689 | 0.6386 | 0.065* | |
H37B | 0.2586 | 0.5350 | 0.7620 | 0.065* | |
H37C | 0.2966 | 0.5461 | 0.5851 | 0.065* | |
C41 | 0.09751 (13) | 0.92800 (13) | 0.8167 (3) | 0.0247 (5) | |
H41 | 0.0979 | 0.9585 | 0.9105 | 0.030* | |
C42 | 0.05326 (14) | 0.93750 (14) | 0.6736 (4) | 0.0275 (5) | |
H42 | 0.0802 | 0.9508 | 0.5662 | 0.033* | |
C43 | −0.01377 (14) | 0.86128 (14) | 0.6633 (3) | 0.0296 (5) | |
C44 | 0.00960 (17) | 0.80838 (16) | 0.5911 (4) | 0.0381 (6) | |
H44A | −0.0321 | 0.7637 | 0.5520 | 0.046* | |
H44B | 0.0436 | 0.8303 | 0.4979 | 0.046* | |
C45 | 0.04582 (16) | 0.79455 (15) | 0.7443 (4) | 0.0343 (6) | |
H45A | 0.0949 | 0.8056 | 0.7180 | 0.041* | |
H45B | 0.0178 | 0.7448 | 0.7839 | 0.041* | |
C46 | 0.04536 (13) | 0.84831 (13) | 0.8742 (4) | 0.0255 (5) | |
C47 | 0.04673 (15) | 0.83166 (15) | 1.0630 (4) | 0.0315 (6) | |
C48 | 0.11947 (17) | 0.84032 (18) | 1.1192 (4) | 0.0427 (7) | |
H48A | 0.1170 | 0.8315 | 1.2406 | 0.051* | |
H48B | 0.1251 | 0.8026 | 1.0643 | 0.051* | |
C49 | 0.18710 (17) | 0.91239 (19) | 1.0841 (5) | 0.0468 (8) | |
H49A | 0.2260 | 0.9163 | 1.1556 | 0.056* | |
H49B | 0.1779 | 0.9511 | 1.1161 | 0.056* | |
C50 | 0.21254 (17) | 0.92371 (18) | 0.8994 (5) | 0.0442 (7) | |
H50A | 0.2028 | 0.8772 | 0.8545 | 0.053* | |
H50B | 0.2648 | 0.9556 | 0.8986 | 0.053* | |
C51 | 0.17899 (15) | 0.95560 (15) | 0.7759 (4) | 0.0341 (6) | |
C52 | −0.01518 (18) | 0.75499 (17) | 1.1076 (4) | 0.0434 (7) | |
H52A | −0.0195 | 0.7496 | 1.2288 | 0.065* | |
H52B | −0.0047 | 0.7195 | 1.0609 | 0.065* | |
H52C | −0.0599 | 0.7480 | 1.0610 | 0.065* | |
C54 | 0.21837 (17) | 1.03857 (17) | 0.7953 (5) | 0.0474 (8) | |
H54A | 0.2675 | 1.0590 | 0.7562 | 0.071* | |
H54B | 0.2184 | 1.0508 | 0.9127 | 0.071* | |
H54C | 0.1938 | 1.0577 | 0.7292 | 0.071* | |
C55 | 0.19445 (18) | 0.9406 (2) | 0.5934 (5) | 0.0475 (8) | |
H55A | 0.1763 | 0.9618 | 0.5137 | 0.071* | |
H55B | 0.1708 | 0.8891 | 0.5749 | 0.071* | |
H55C | 0.2459 | 0.9614 | 0.5780 | 0.071* | |
C57 | −0.08066 (18) | 0.85552 (19) | 0.5828 (4) | 0.0466 (7) | |
H57A | −0.1202 | 0.8065 | 0.5925 | 0.070* | |
H57B | −0.0713 | 0.8686 | 0.4650 | 0.070* | |
H57C | −0.0931 | 0.8878 | 0.6395 | 0.070* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O13 | 0.0380 (11) | 0.0358 (11) | 0.0274 (11) | 0.0126 (9) | 0.0052 (8) | 0.0017 (8) |
O16 | 0.0362 (10) | 0.0238 (9) | 0.0433 (12) | 0.0088 (8) | −0.0032 (8) | −0.0028 (8) |
O18 | 0.0309 (9) | 0.0301 (9) | 0.0269 (10) | 0.0171 (8) | −0.0004 (7) | −0.0029 (7) |
O33 | 0.0349 (10) | 0.0394 (11) | 0.0254 (10) | 0.0144 (9) | 0.0031 (7) | 0.0046 (8) |
O36 | 0.0227 (9) | 0.0343 (10) | 0.0393 (11) | 0.0101 (8) | −0.0032 (8) | −0.0045 (8) |
O38 | 0.0308 (9) | 0.0299 (9) | 0.0252 (9) | 0.0174 (8) | −0.0001 (7) | −0.0003 (7) |
O53 | 0.0469 (11) | 0.0407 (11) | 0.0263 (10) | 0.0271 (9) | −0.0032 (8) | −0.0036 (8) |
O56 | 0.0405 (11) | 0.0332 (10) | 0.0398 (12) | 0.0254 (9) | 0.0017 (8) | 0.0055 (8) |
O58 | 0.0262 (9) | 0.0300 (9) | 0.0260 (10) | 0.0148 (7) | −0.0004 (7) | 0.0011 (7) |
C1 | 0.0261 (12) | 0.0231 (12) | 0.0280 (14) | 0.0117 (10) | 0.0019 (9) | 0.0016 (9) |
C2 | 0.0343 (14) | 0.0223 (12) | 0.0284 (14) | 0.0121 (11) | −0.0041 (10) | −0.0009 (9) |
C3 | 0.0368 (14) | 0.0331 (14) | 0.0232 (13) | 0.0186 (12) | 0.0005 (10) | −0.0047 (10) |
C4 | 0.0372 (15) | 0.0398 (15) | 0.0310 (16) | 0.0139 (13) | 0.0102 (11) | 0.0051 (12) |
C5 | 0.0311 (14) | 0.0285 (13) | 0.0378 (16) | 0.0077 (11) | 0.0082 (11) | 0.0033 (11) |
C6 | 0.0254 (12) | 0.0225 (11) | 0.0273 (14) | 0.0101 (10) | 0.0031 (9) | −0.0004 (9) |
C7 | 0.0297 (13) | 0.0263 (13) | 0.0285 (15) | 0.0082 (11) | 0.0015 (10) | −0.0034 (10) |
C8 | 0.0446 (17) | 0.0356 (15) | 0.0407 (18) | 0.0165 (13) | −0.0017 (13) | −0.0139 (12) |
C9 | 0.0515 (19) | 0.0464 (18) | 0.051 (2) | 0.0293 (16) | 0.0031 (14) | −0.0140 (14) |
C10 | 0.0496 (18) | 0.0372 (16) | 0.057 (2) | 0.0294 (14) | 0.0028 (14) | −0.0031 (13) |
C11 | 0.0338 (14) | 0.0313 (14) | 0.0409 (16) | 0.0199 (12) | 0.0021 (11) | 0.0047 (11) |
C12 | 0.0308 (15) | 0.0434 (17) | 0.0417 (18) | 0.0106 (13) | −0.0053 (12) | −0.0079 (13) |
C14 | 0.0344 (16) | 0.0515 (19) | 0.065 (2) | 0.0253 (15) | 0.0008 (14) | 0.0076 (16) |
C15 | 0.063 (2) | 0.0484 (18) | 0.047 (2) | 0.0349 (17) | −0.0002 (15) | 0.0141 (14) |
C17 | 0.0551 (19) | 0.0497 (18) | 0.0444 (19) | 0.0337 (16) | 0.0031 (14) | −0.0112 (14) |
C21 | 0.0215 (11) | 0.0272 (12) | 0.0234 (13) | 0.0116 (10) | 0.0014 (9) | 0.0006 (9) |
C22 | 0.0237 (12) | 0.0308 (13) | 0.0256 (13) | 0.0133 (10) | 0.0003 (9) | −0.0014 (9) |
C23 | 0.0342 (14) | 0.0343 (14) | 0.0204 (13) | 0.0182 (12) | −0.0020 (10) | −0.0001 (10) |
C24 | 0.0399 (15) | 0.0364 (14) | 0.0285 (15) | 0.0150 (12) | 0.0059 (11) | 0.0089 (11) |
C25 | 0.0301 (14) | 0.0330 (14) | 0.0341 (15) | 0.0092 (11) | 0.0059 (11) | 0.0053 (11) |
C26 | 0.0203 (11) | 0.0263 (12) | 0.0271 (13) | 0.0098 (10) | 0.0006 (9) | 0.0025 (9) |
C27 | 0.0275 (13) | 0.0284 (13) | 0.0264 (14) | 0.0073 (11) | −0.0018 (10) | 0.0011 (10) |
C28 | 0.0304 (14) | 0.0461 (16) | 0.0375 (17) | 0.0154 (13) | −0.0090 (11) | 0.0001 (12) |
C29 | 0.0365 (15) | 0.0486 (18) | 0.0470 (19) | 0.0261 (14) | −0.0102 (13) | 0.0049 (13) |
C30 | 0.0304 (14) | 0.0485 (17) | 0.0537 (19) | 0.0265 (13) | −0.0020 (13) | 0.0002 (14) |
C31 | 0.0289 (13) | 0.0370 (14) | 0.0404 (16) | 0.0201 (12) | 0.0009 (11) | −0.0022 (11) |
C32 | 0.0454 (17) | 0.0344 (15) | 0.0379 (17) | 0.0116 (13) | −0.0063 (13) | −0.0070 (12) |
C34 | 0.0472 (18) | 0.0336 (15) | 0.060 (2) | 0.0245 (14) | −0.0016 (14) | −0.0054 (13) |
C35 | 0.0451 (17) | 0.061 (2) | 0.0450 (19) | 0.0355 (16) | 0.0085 (14) | −0.0049 (15) |
C41 | 0.0259 (12) | 0.0234 (12) | 0.0278 (14) | 0.0145 (10) | 0.0016 (9) | −0.0002 (9) |
C42 | 0.0310 (13) | 0.0302 (13) | 0.0252 (14) | 0.0181 (11) | 0.0044 (10) | 0.0033 (10) |
C43 | 0.0337 (14) | 0.0329 (14) | 0.0225 (14) | 0.0169 (11) | −0.0018 (10) | −0.0001 (10) |
C44 | 0.0478 (17) | 0.0362 (15) | 0.0286 (15) | 0.0198 (13) | −0.0016 (12) | −0.0079 (11) |
C45 | 0.0430 (16) | 0.0272 (13) | 0.0359 (16) | 0.0200 (12) | 0.0025 (12) | −0.0039 (11) |
C46 | 0.0274 (12) | 0.0254 (12) | 0.0277 (14) | 0.0163 (10) | −0.0014 (9) | −0.0008 (9) |
C47 | 0.0409 (15) | 0.0332 (14) | 0.0271 (15) | 0.0235 (12) | −0.0016 (11) | 0.0004 (10) |
C48 | 0.0518 (18) | 0.0512 (18) | 0.0376 (18) | 0.0351 (15) | −0.0068 (13) | 0.0059 (13) |
C49 | 0.0374 (16) | 0.0556 (19) | 0.054 (2) | 0.0285 (15) | −0.0159 (14) | −0.0022 (15) |
C50 | 0.0337 (15) | 0.0484 (18) | 0.059 (2) | 0.0271 (14) | −0.0025 (13) | 0.0012 (14) |
C51 | 0.0269 (13) | 0.0354 (14) | 0.0419 (16) | 0.0171 (11) | 0.0029 (11) | −0.0005 (11) |
C52 | 0.0554 (19) | 0.0383 (16) | 0.0386 (17) | 0.0249 (15) | 0.0042 (13) | 0.0097 (12) |
C54 | 0.0322 (15) | 0.0359 (16) | 0.069 (2) | 0.0134 (13) | 0.0044 (14) | 0.0035 (15) |
C55 | 0.0419 (17) | 0.057 (2) | 0.050 (2) | 0.0301 (16) | 0.0168 (14) | 0.0032 (15) |
C57 | 0.0416 (17) | 0.056 (2) | 0.0405 (18) | 0.0230 (15) | −0.0140 (13) | −0.0007 (14) |
Geometric parameters (Å, º) top
O13—C7 | 1.446 (3) | C21—C26 | 1.561 (3) |
O16—C2 | 1.443 (3) | C22—C23 | 1.536 (4) |
O18—C3 | 1.450 (3) | C23—C37 | 1.506 (4) |
O18—C6 | 1.459 (3) | C23—C24 | 1.535 (4) |
O33—C27 | 1.446 (3) | C24—C25 | 1.540 (4) |
O36—C22 | 1.439 (3) | C25—C26 | 1.537 (3) |
O38—C26 | 1.449 (3) | C26—C27 | 1.534 (4) |
O38—C23 | 1.462 (3) | C27—C28 | 1.529 (4) |
O53—C47 | 1.443 (3) | C27—C32 | 1.530 (4) |
O56—C42 | 1.443 (3) | C28—C29 | 1.526 (4) |
O58—C43 | 1.441 (3) | C29—C30 | 1.529 (5) |
O58—C46 | 1.453 (3) | C30—C31 | 1.543 (4) |
C1—C2 | 1.549 (4) | C31—C34 | 1.534 (4) |
C1—C6 | 1.560 (3) | C31—C35 | 1.538 (4) |
C1—C11 | 1.566 (3) | C41—C42 | 1.545 (3) |
C2—C3 | 1.533 (4) | C41—C46 | 1.558 (3) |
C3—C17 | 1.506 (4) | C41—C51 | 1.560 (3) |
C3—C4 | 1.550 (4) | C42—C43 | 1.535 (4) |
C4—C5 | 1.532 (4) | C43—C57 | 1.506 (4) |
C5—C6 | 1.540 (3) | C43—C44 | 1.548 (4) |
C6—C7 | 1.529 (4) | C44—C45 | 1.537 (4) |
C7—C8 | 1.527 (4) | C45—C46 | 1.538 (3) |
C7—C12 | 1.536 (4) | C46—C47 | 1.532 (4) |
C8—C9 | 1.535 (5) | C47—C48 | 1.529 (4) |
C9—C10 | 1.527 (5) | C47—C52 | 1.539 (4) |
C10—C11 | 1.545 (4) | C48—C49 | 1.513 (5) |
C11—C15 | 1.529 (4) | C49—C50 | 1.528 (5) |
C11—C14 | 1.542 (4) | C50—C51 | 1.548 (4) |
C21—C22 | 1.548 (3) | C51—C54 | 1.536 (4) |
C21—C31 | 1.559 (3) | C51—C55 | 1.543 (4) |
| | | |
C3—O18—C6 | 97.68 (17) | C27—C26—C25 | 118.0 (2) |
C26—O38—C23 | 97.16 (17) | O38—C26—C21 | 101.27 (18) |
C43—O58—C46 | 97.86 (18) | C27—C26—C21 | 116.2 (2) |
C2—C1—C6 | 102.21 (19) | C25—C26—C21 | 110.9 (2) |
C2—C1—C11 | 116.0 (2) | O33—C27—C28 | 105.4 (2) |
C6—C1—C11 | 120.8 (2) | O33—C27—C32 | 108.2 (2) |
O16—C2—C3 | 112.4 (2) | C28—C27—C32 | 109.7 (2) |
O16—C2—C1 | 108.7 (2) | O33—C27—C26 | 108.74 (19) |
C3—C2—C1 | 101.6 (2) | C28—C27—C26 | 113.0 (2) |
O18—C3—C17 | 111.7 (2) | C32—C27—C26 | 111.4 (2) |
O18—C3—C2 | 100.9 (2) | C29—C28—C27 | 117.5 (2) |
C17—C3—C2 | 116.6 (2) | C28—C29—C30 | 113.9 (3) |
O18—C3—C4 | 102.3 (2) | C29—C30—C31 | 117.4 (2) |
C17—C3—C4 | 114.8 (2) | C34—C31—C35 | 106.9 (3) |
C2—C3—C4 | 108.8 (2) | C34—C31—C30 | 109.3 (2) |
C5—C4—C3 | 102.8 (2) | C35—C31—C30 | 107.1 (2) |
C4—C5—C6 | 101.5 (2) | C34—C31—C21 | 106.0 (2) |
O18—C6—C7 | 106.61 (19) | C35—C31—C21 | 115.4 (2) |
O18—C6—C5 | 100.70 (19) | C30—C31—C21 | 111.9 (2) |
C7—C6—C5 | 118.8 (2) | C42—C41—C46 | 101.84 (19) |
O18—C6—C1 | 100.63 (18) | C42—C41—C51 | 115.8 (2) |
C7—C6—C1 | 116.2 (2) | C46—C41—C51 | 121.5 (2) |
C5—C6—C1 | 110.7 (2) | O56—C42—C43 | 112.2 (2) |
O13—C7—C8 | 105.5 (2) | O56—C42—C41 | 109.0 (2) |
O13—C7—C6 | 109.49 (19) | C43—C42—C41 | 101.83 (19) |
C8—C7—C6 | 113.0 (2) | O58—C43—C57 | 111.8 (2) |
O13—C7—C12 | 108.1 (2) | O58—C43—C42 | 100.94 (19) |
C8—C7—C12 | 109.2 (2) | C57—C43—C42 | 116.7 (2) |
C6—C7—C12 | 111.2 (2) | O58—C43—C44 | 102.0 (2) |
C7—C8—C9 | 116.7 (2) | C57—C43—C44 | 114.8 (2) |
C10—C9—C8 | 113.7 (3) | C42—C43—C44 | 108.7 (2) |
C9—C10—C11 | 117.0 (3) | C45—C44—C43 | 103.0 (2) |
C15—C11—C14 | 106.5 (3) | C44—C45—C46 | 100.9 (2) |
C15—C11—C10 | 107.6 (2) | O58—C46—C47 | 107.0 (2) |
C14—C11—C10 | 109.4 (3) | O58—C46—C45 | 101.02 (19) |
C15—C11—C1 | 115.0 (2) | C47—C46—C45 | 117.8 (2) |
C14—C11—C1 | 106.2 (2) | O58—C46—C41 | 101.19 (18) |
C10—C11—C1 | 112.0 (2) | C47—C46—C41 | 116.6 (2) |
C22—C21—C31 | 115.6 (2) | C45—C46—C41 | 110.5 (2) |
C22—C21—C26 | 101.93 (19) | O53—C47—C48 | 105.4 (2) |
C31—C21—C26 | 121.5 (2) | O53—C47—C46 | 109.1 (2) |
O36—C22—C23 | 112.3 (2) | C48—C47—C46 | 112.8 (2) |
O36—C22—C21 | 109.2 (2) | O53—C47—C52 | 108.1 (2) |
C23—C22—C21 | 101.62 (19) | C48—C47—C52 | 109.9 (2) |
O38—C23—C37 | 111.6 (2) | C46—C47—C52 | 111.2 (2) |
O38—C23—C24 | 102.5 (2) | C49—C48—C47 | 117.5 (2) |
C37—C23—C24 | 115.0 (2) | C48—C49—C50 | 114.6 (3) |
O38—C23—C22 | 100.62 (19) | C49—C50—C51 | 117.5 (2) |
C37—C23—C22 | 116.5 (2) | C54—C51—C55 | 106.3 (3) |
C24—C23—C22 | 108.9 (2) | C54—C51—C50 | 109.5 (3) |
C23—C24—C25 | 103.0 (2) | C55—C51—C50 | 107.5 (2) |
C26—C25—C24 | 100.8 (2) | C54—C51—C41 | 106.1 (2) |
O38—C26—C27 | 106.48 (19) | C55—C51—C41 | 115.2 (2) |
O38—C26—C25 | 101.17 (19) | C50—C51—C41 | 112.0 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O16i | 0.93 (1) | 2.33 (1) | 3.122 (3) | 143 (1) |
O16—H16···O16ii | 0.96 (1) | 2.10 (1) | 3.032 (3) | 163 (1) |
O33—H33···O36iii | 0.92 (1) | 2.37 (1) | 3.134 (4) | 140 (1) |
O36—H36···O36iv | 0.99 (1) | 2.03 (1) | 3.008 (3) | 171 (1) |
O53—H53···O56v | 0.88 (1) | 2.39 (1) | 3.106 (3) | 139 (1) |
O56—H56···O56vi | 0.96 (1) | 2.06 (1) | 3.018 (3) | 175 (1) |
Symmetry codes: (i) −x+y−1, −x, z+1/3; (ii) −y, x−y+1, z−1/3; (iii) −y+1, x−y+1, z−1/3; (iv) −x+y, −x+1, z+1/3; (v) −x+y−1, −x+1, z+1/3; (vi) −y+1, x−y+2, z−1/3. |
Experimental details
Crystal data |
Chemical formula | C15H26O3 |
Mr | 254.37 |
Crystal system, space group | Trigonal, P32 |
Temperature (K) | 298 |
a, c (Å) | 21.266 (9), 7.873 (5) |
V (Å3) | 3083.5 (3) |
Z | 9 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.45 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9812, 3985, 3740 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.624 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.090, 1.09 |
No. of reflections | 3985 |
No. of parameters | 485 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.23 |
Selected geometric parameters (Å, º) topC1—C6 | 1.560 (3) | C23—C37 | 1.506 (4) |
C1—C11 | 1.566 (3) | C41—C46 | 1.558 (3) |
C3—C17 | 1.506 (4) | C41—C51 | 1.560 (3) |
C21—C31 | 1.559 (3) | C43—C57 | 1.506 (4) |
C21—C26 | 1.561 (3) | | |
| | | |
C6—C1—C11 | 120.8 (2) | C46—C41—C51 | 121.5 (2) |
C31—C21—C26 | 121.5 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O16i | 0.931 (2) | 2.325 (2) | 3.122 (3) | 143.4 (1) |
O16—H16···O16ii | 0.959 (2) | 2.102 (2) | 3.032 (3) | 163.4 (1) |
O33—H33···O36iii | 0.920 (1) | 2.370 (2) | 3.134 (4) | 140.4 (1) |
O36—H36···O36iv | 0.988 (1) | 2.027 (2) | 3.008 (3) | 171.2 (1) |
O53—H53···O56v | 0.876 (1) | 2.393 (2) | 3.106 (3) | 138.6 (1) |
O56—H56···O56vi | 0.958 (1) | 2.062 (2) | 3.018 (3) | 175.2 (1) |
Symmetry codes: (i) −x+y−1, −x, z+1/3; (ii) −y, x−y+1, z−1/3; (iii) −y+1, x−y+1, z−1/3; (iv) −x+y, −x+1, z+1/3; (v) −x+y−1, −x+1, z+1/3; (vi) −y+1, x−y+2, z−1/3. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Ce travail fait suite à celui publié dans ce même volume (El Jamili et al., 2001) et concerne l'étude structurale des produits obtenus par oxydation du β-himachalène avec le permanganate de potassium. Ainsi, l'action d'un excès de permanganate de potassium KMnO4, finement broyé, sur le β-himachalène dans un mélange d'acétone–eau (9/1) à une température de 263 K conduit régiosélectivement avec un rendement de 30% au composé étudié. Malgré des études RMN à haute résolution mono et bidimensionnelle, nous n'avons pas pu déduire sa structure. Toutefois, une étude aux rayons X d'un monocristal de ce composé nous a permis, sur la base de la connaissance de la structure absolue du fragment himachalène (Joseph & Dev, 1968; Chiaroni et al., 1991), de lui attribuer la structure (1S,2S,3R,6S,7R)-3,6-époxyhimachalane-2,7-diol, (I) (Fig. 1).
Sa formation provient certainement du réarrangement de l'himachal-2,3,6,7 - tétraol. La maille hexagonale contient trois molécules indépendantes qui sont parfaitement superposables, aux erreurs expérimentales près (Fig. 2). Cependant, les distances et angles de liaison entre atomes de carbone montrent des variations importantes et significatives par rapport aux erreurs expérimentales (Table 1). Ainsi, la distance C—C varie entre 1.506 (4) e t 1.566 (3) Å, et l'angle C—C—C varie entre 100.8 (2) e t 121.5 (2)°. Il est intéressant de remarquer que les distances les plus courtes se retrouvent sur les trois molécules. Ainsi, la distance C3—C17 (ou C23—C37, ou C43—C57) est égale à 1.506 (4) Å dans les trois molécules indépendantes. De même, les deux distances C—C les plus longues C1—C6 et C1—C11 varient entre 1.558 (3) e t 1.561 (3) Å e t 1.559 (3) e t 1.566 (3) Å, respectivement, sur les trois molécules. On notera que ces deux distances les plus longues correspondent à l'angle C—C—C le plus ouvert: de 120.8 (2) à 121.5 (2)°. Le fragment C1—C7—C8—C10—C11, ou son équivalent dans les deux autres molécules, est plan et les atomes C6 et C9 sont situés de part et d'autre de ce plan: entre -0.742 (3) e t -0.749 (3) Å pour C6 et 0.796 (4) e t 0.809 (3) Å pour C9. Le pont oxo C3—O18—C6 divize le cycle à six chaînons en deux fragments plans: C6—C1—C2—C3 et C3—C4—C5—C6. Les angles dièdres entre ces trois plans sont remarquablement constants dans les trois molécules: (i) angle C3—O18—C6 et C3—C4—C5—C6: 124.1 (3)° [124.0 (3), 123.9 (3)°]; (ii) angle C3—O18—C6 et C6—C1—C2—C3: 57.7 (3)° [57.6 (2), 57.2 (3)°]; (iii) angle C3—C4—C5—C6 et C6—C1—C2—C3: 66.5 (2)° [66.5 (2), 66.8 (3)°]. Par ailleurs, l'atome O18 (ou 038, ou O58) est en interaction avec les deux fonctions OH: l'atome O18 est à 2.931 (3) Å de O16 [2.932 (3) e t 2.931 (3) Å pour les deux autre molécules] et à 2.800 (3) Å de O13 [2.775 (3) e t 2.798 (3) Å pour les deux autres molécules] mais l'angle O13—H13···O18 n'est pas favorable à une liaison hydrogène: 111.1 (4)° [114.7 (3) e t 124.7 (3)°]. Par contre, chaque molécule de ce composé établit deux liaisons hydrogène intermoléculaires: O13—H13····O16 et O16—H16····O16 (et leurs correspondants dans les deux autres molécules) dont les distances et les angles sont indiqués dans le Tableau 2.