The stereochemistry of the title compound, C15H26O2, has been established. Intermolecular hydrogen bonds are observed between the hydroxyl groups.
Supporting information
CCDC reference: 175348
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.046
- wR factor = 0.117
- Data-to-parameter ratio = 10.4
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
Alert Level B:
DENSM_01 Alert B _exptl_crystal_density_method is given but no value of
_exptl_crystal_density_meas is reported.
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.
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 25.60
From the CIF: _reflns_number_total 1554
Count of symmetry unique reflns 1582
Completeness (_total/calc) 98.23%
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.
1 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
2 Alert Level C = Please check
Dans un réacteur contenant 2 g (9,8 mmol) de 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 1,54 g (9,8 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 le m\' elange héxane/acétate d'éthyle (95/5). Rendement
65%; point de fusion 359 K. Les cristaux ont été préparés 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
C15H26O2 | Dx = 1.110 Mg m−3 |
Mr = 238.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8437 reflections |
a = 5.9498 (2) Å | θ = 1.0–25.6° |
b = 9.7014 (4) Å | µ = 0.07 mm−1 |
c = 24.7207 (9) Å | T = 298 K |
V = 1426.9 (1) Å3 | Cube, incolore |
Z = 4 | 0.45 × 0.40 × 0.40 mm |
F(000) = 552 | |
Data collection top
KappaCCD diffractometer | Rint = 0.038 |
Radiation source: tube scéllé, foyer fin | θmax = 25.6° |
ϕ scan | h = −7→7 |
8437 measured reflections | k = −11→11 |
1554 independent reflections | l = 0→30 |
1482 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters not refined |
S = 1.14 | w = 1/[σ2(Fo2) + (0.051P)2 + 0.2724P] where P = (Fo2 + 2Fc2)/3 |
1608 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.11 e Å−3 |
Crystal data top
C15H26O2 | V = 1426.9 (1) Å3 |
Mr = 238.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.9498 (2) Å | µ = 0.07 mm−1 |
b = 9.7014 (4) Å | T = 298 K |
c = 24.7207 (9) Å | 0.45 × 0.40 × 0.40 mm |
Data collection top
KappaCCD diffractometer | 1482 reflections with I > 2σ(I) |
8437 measured reflections | Rint = 0.038 |
1554 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters not refined |
S = 1.14 | Δρmax = 0.14 e Å−3 |
1608 reflections | Δρmin = −0.11 e Å−3 |
154 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 | |
O12 | 0.5586 (3) | −0.10413 (15) | 0.28912 (6) | 0.0461 (4) | |
H12 | 0.6472 | −0.0207 | 0.2786 | 0.066* | |
O13 | 0.5055 (3) | 0.16673 (16) | 0.28099 (7) | 0.0525 (4) | |
H13 | 0.4979 | 0.2311 | 0.2580 | 0.073* | |
C1 | 0.4924 (3) | −0.00635 (18) | 0.37631 (8) | 0.0332 (4) | |
H1 | 0.6281 | 0.0451 | 0.3703 | 0.054* | |
C2 | 0.5594 (5) | −0.1410 (2) | 0.40233 (8) | 0.0469 (5) | |
H2 | 0.6814 | −0.1335 | 0.4276 | 0.068* | |
C3 | 0.4658 (6) | −0.2617 (2) | 0.39342 (10) | 0.0594 (7) | |
C4 | 0.2798 (6) | −0.2808 (2) | 0.35362 (11) | 0.0645 (8) | |
H4A | 0.3329 | −0.3380 | 0.3246 | 0.087* | |
H4B | 0.1541 | −0.3245 | 0.3709 | 0.087* | |
C5 | 0.1989 (5) | −0.1476 (2) | 0.32664 (10) | 0.0509 (6) | |
H5A | 0.1385 | −0.1668 | 0.2914 | 0.071* | |
H5B | 0.0835 | −0.1090 | 0.3492 | 0.071* | |
C6 | 0.3822 (4) | −0.03923 (19) | 0.32077 (8) | 0.0355 (4) | |
C7 | 0.3038 (4) | 0.0877 (2) | 0.28691 (9) | 0.0454 (5) | |
C8 | 0.1153 (5) | 0.1727 (3) | 0.31328 (13) | 0.0641 (7) | |
H8A | 0.0142 | 0.1052 | 0.3279 | 0.084* | |
H8B | 0.0447 | 0.2188 | 0.2834 | 0.084* | |
C9 | 0.1751 (6) | 0.2748 (3) | 0.35747 (15) | 0.0766 (9) | |
H9A | 0.0387 | 0.2895 | 0.3774 | 0.099* | |
H9B | 0.2142 | 0.3576 | 0.3384 | 0.099* | |
C10 | 0.3606 (5) | 0.2387 (2) | 0.39720 (12) | 0.0602 (7) | |
H10A | 0.5032 | 0.2531 | 0.3799 | 0.081* | |
H10B | 0.3508 | 0.2957 | 0.4289 | 0.081* | |
C11 | 0.3760 (4) | 0.0911 (2) | 0.41849 (9) | 0.0417 (5) | |
C14 | 0.2225 (6) | 0.0436 (3) | 0.23089 (11) | 0.0676 (8) | |
H14A | 0.3378 | −0.0105 | 0.2139 | 0.088* | |
H14B | 0.1917 | 0.1235 | 0.2092 | 0.088* | |
H14C | 0.0884 | −0.0106 | 0.2344 | 0.088* | |
C15 | 0.1481 (5) | 0.0386 (3) | 0.43849 (11) | 0.0602 (7) | |
H15A | 0.0461 | 0.0307 | 0.4086 | 0.080* | |
H15B | 0.0885 | 0.1026 | 0.4644 | 0.080* | |
H15C | 0.1667 | −0.0499 | 0.4552 | 0.080* | |
C16 | 0.5272 (5) | 0.0970 (3) | 0.46917 (11) | 0.0644 (8) | |
H16A | 0.5423 | 0.0073 | 0.4852 | 0.086* | |
H16B | 0.4615 | 0.1591 | 0.4949 | 0.086* | |
H16C | 0.6727 | 0.1305 | 0.4587 | 0.086* | |
C17 | 0.5425 (11) | −0.3909 (3) | 0.42168 (15) | 0.1039 (16) | |
H17A | 0.6603 | −0.3690 | 0.4468 | 0.124* | |
H17B | 0.5975 | −0.4552 | 0.3953 | 0.124* | |
H17C | 0.4183 | −0.4311 | 0.4408 | 0.124* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O12 | 0.0582 (10) | 0.0420 (8) | 0.0382 (7) | 0.0000 (7) | 0.0051 (8) | −0.0060 (6) |
O13 | 0.0584 (10) | 0.0455 (8) | 0.0537 (9) | −0.0111 (8) | −0.0030 (9) | 0.0179 (7) |
C1 | 0.0310 (9) | 0.0339 (9) | 0.0347 (9) | −0.0039 (8) | −0.0015 (9) | −0.0037 (7) |
C2 | 0.0585 (14) | 0.0459 (11) | 0.0363 (10) | 0.0041 (11) | −0.0055 (11) | 0.0019 (9) |
C3 | 0.095 (2) | 0.0395 (11) | 0.0441 (11) | −0.0017 (14) | −0.0008 (15) | 0.0075 (9) |
C4 | 0.096 (2) | 0.0426 (12) | 0.0550 (14) | −0.0285 (15) | 0.0003 (16) | 0.0035 (11) |
C5 | 0.0594 (14) | 0.0496 (12) | 0.0437 (12) | −0.0232 (12) | −0.0077 (12) | −0.0010 (10) |
C6 | 0.0399 (10) | 0.0341 (9) | 0.0323 (9) | −0.0047 (9) | −0.0010 (9) | −0.0007 (8) |
C7 | 0.0466 (12) | 0.0447 (11) | 0.0447 (12) | −0.0039 (10) | −0.0085 (11) | 0.0094 (9) |
C8 | 0.0565 (15) | 0.0635 (15) | 0.0723 (17) | 0.0178 (14) | −0.0114 (15) | 0.0129 (14) |
C9 | 0.087 (2) | 0.0530 (15) | 0.090 (2) | 0.0286 (16) | 0.004 (2) | −0.0001 (15) |
C10 | 0.0720 (17) | 0.0399 (11) | 0.0686 (16) | 0.0044 (12) | 0.0047 (16) | −0.0142 (11) |
C11 | 0.0400 (11) | 0.0457 (11) | 0.0393 (10) | −0.0022 (10) | 0.0019 (10) | −0.0109 (9) |
C14 | 0.080 (2) | 0.0742 (17) | 0.0486 (14) | −0.0095 (17) | −0.0212 (15) | 0.0153 (12) |
C15 | 0.0490 (14) | 0.0815 (18) | 0.0501 (13) | −0.0048 (14) | 0.0119 (13) | −0.0098 (13) |
C16 | 0.0612 (16) | 0.0815 (18) | 0.0506 (13) | 0.0026 (16) | −0.0073 (13) | −0.0270 (13) |
C17 | 0.181 (5) | 0.0498 (15) | 0.081 (2) | 0.003 (2) | −0.015 (3) | 0.0261 (15) |
Geometric parameters (Å, º) top
O12—C6 | 1.453 (3) | C5—C6 | 1.521 (3) |
O13—C7 | 1.431 (3) | C6—C7 | 1.561 (3) |
C1—C2 | 1.510 (3) | C7—C14 | 1.528 (4) |
C1—C6 | 1.554 (3) | C7—C8 | 1.537 (4) |
C1—C11 | 1.569 (3) | C8—C9 | 1.517 (5) |
C2—C3 | 1.315 (3) | C9—C10 | 1.518 (4) |
C3—C4 | 1.492 (4) | C10—C11 | 1.529 (3) |
C3—C17 | 1.506 (4) | C11—C15 | 1.530 (3) |
C4—C5 | 1.532 (4) | C11—C16 | 1.544 (3) |
| | | |
C2—C1—C6 | 108.07 (15) | O13—C7—C14 | 108.8 (2) |
C2—C1—C11 | 110.77 (17) | O13—C7—C8 | 111.6 (2) |
C6—C1—C11 | 121.65 (17) | C14—C7—C8 | 107.7 (2) |
C3—C2—C1 | 125.9 (2) | O13—C7—C6 | 103.12 (18) |
C2—C3—C4 | 122.4 (2) | C14—C7—C6 | 111.1 (2) |
C2—C3—C17 | 122.3 (3) | C8—C7—C6 | 114.4 (2) |
C4—C3—C17 | 115.3 (3) | C9—C8—C7 | 119.0 (3) |
C3—C4—C5 | 114.5 (2) | C8—C9—C10 | 119.1 (2) |
C6—C5—C4 | 113.5 (2) | C9—C10—C11 | 118.8 (2) |
O12—C6—C5 | 105.64 (16) | C10—C11—C15 | 111.7 (2) |
O12—C6—C1 | 105.06 (17) | C10—C11—C16 | 106.2 (2) |
C5—C6—C1 | 111.09 (16) | C15—C11—C16 | 105.5 (2) |
O12—C6—C7 | 105.60 (17) | C10—C11—C1 | 111.22 (19) |
C5—C6—C7 | 112.49 (19) | C15—C11—C1 | 113.94 (19) |
C1—C6—C7 | 115.96 (16) | C16—C11—C1 | 107.75 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O12i | 0.85 (1) | 2.01 (1) | 2.844 (2) | 171 (1) |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C15H26O2 |
Mr | 238.37 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 5.9498 (2), 9.7014 (4), 24.7207 (9) |
V (Å3) | 1426.9 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.45 × 0.40 × 0.40 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8437, 1554, 1482 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.608 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.117, 1.14 |
No. of reflections | 1608 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.14, −0.11 |
Selected geometric parameters (Å, º) topO12—C6 | 1.453 (3) | C3—C4 | 1.492 (4) |
O13—C7 | 1.431 (3) | C3—C17 | 1.506 (4) |
C1—C6 | 1.554 (3) | C6—C7 | 1.561 (3) |
C1—C11 | 1.569 (3) | C9—C10 | 1.518 (4) |
C2—C3 | 1.315 (3) | C11—C16 | 1.544 (3) |
| | | |
C2—C1—C6 | 108.07 (15) | C4—C3—C17 | 115.3 (3) |
C2—C1—C11 | 110.77 (17) | C1—C6—C7 | 115.96 (16) |
C6—C1—C11 | 121.65 (17) | C9—C8—C7 | 119.0 (3) |
C3—C2—C1 | 125.9 (2) | C8—C9—C10 | 119.1 (2) |
C2—C3—C4 | 122.4 (2) | C9—C10—C11 | 118.8 (2) |
C2—C3—C17 | 122.3 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O12i | 0.846 (2) | 2.006 (2) | 2.844 (2) | 171.0 (1) |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
L'étude de la composition chimique de l'huile essentielle de Cèdre de l'Atlas (Joseph & Dev, 1968; Nambudiry & Rao, 1974; Teisseire & Plattier, 1974) a toujours montré que, lors de l'extraction, le β-himachalène est le sesquiterpène majoritaire de la fraction des hydrocarbures. Ce composé a fait l'objet d'une hémisynthèse importante (Chiaroni et al., 1996; Lassaba et al., 1997) dans le but de préparer des produits aux propriétés olfactives utilisables dans la parfumerie et la cosmétique. Les résultats que nous rapportons dans ce travail concerne l'étude structurale des produits obtenus par oxydation du β-himachalène avec le permanganate de potassium. Ainsi, l'action d'un équivalent de 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 65% à l'himachal-2-ène-6,7-diol dont la structure a été déterminée par des études RMN 1H, 13C et par spectrométrie de masse.
Sur la base de la connaissance de la structure absolue du fragment himachalène (Joseph & Dev, 1968; Chiaroni et al., 1991), la configuration des atomes de carbone en position 1, 6 e t 7 a été déterminée par une étude par diffraction des RX d'un monocristal de ce produit ce qui nous a permis d'identifier le (1R,6S,7R)-himachal-2-ène-6,7-diol, (I) (Fig. 1). La double liaison C2C3 confère au cycle à 6 chaînons une conformation enveloppe: l'atome C6 est situé à 0.640 (2) Å du plan moyen formé par les atomes C1–C5 (écart type: 0.0117 Å). Le fragment C1—C6—C8—C9—C10 du cycle à 7 chaînons est plan (écart type: 0.0747 Å), avec C7 situé à 0.725 (2) Å e t C11 à -0.739 (2) Å. On note des variations des distances C—C importantes, de 1.492 (4) à 1.569 (3) Å (Tableau 1). Les atomes d'oxygène des deux diols sont situés à 2.654 (2) Å, mais l'angle O12—H12···O13 [120.29 (16)°] n'est pas favorable à une interaction de type hydrogène. Par contre, il existe une liaison hydrogène inter-moléculaire reliant les deux hydroxyles O13 et O12 (Tableau 2).