organic compounds
N-[(3aR*,3bS*)-1,3b,7,7-Tetramethyl-3a,3b,4,5,6,7,7a,7b-octahydro-3H-cyclopenta[3,4]cyclobuta[1,2]benzen-3a-yl]acetamide
aLaboratoire de Chimie des Substances Naturelles, "Unité Associé au CNRST (URAC16)", Faculté des Sciences Semlalia, BP 2390, Bd My Abdellah, Université Cadi Ayyad, 40000 Marrakech, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: aitelhad2017@gmail.com
The title compound, C17H27NO, is built up from a four-membered ring to which a six- and a five-membered ring are fused. The cyclohexane ring has a chair conformation, while the cyclopentene ring has an with the C atom substituted by the acetamide group as the flap. The dihedral angles between the mean plane of the central cyclobutane ring and the mean planes of the cyclopentene and cyclohexane rings are 62.52 (2) and 61.06 (11)°, respectively. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction.
Keywords: crystal structure; β-himachalene; three fused rings; hydrogen bonding.
CCDC reference: 1533486
Structure description
Our work lies within the framework of the valorization of the most abundant essential oils in Morocco, such as that of Atlas cedar (Cedrus atlantica). This oil is made up mainly (75%) of bicyclic sesquiterpene hydrocarbons, among which is found the compound, β-himachalene (2,6,6,9-tetramethylbicyclo [5.4.01,7]undeca-1,8-diene; El Haib et al., 2011). The reactivity of this sesquiterpene and its derivatives has been studied extensively by our team (Zaki et al., 2014; Benharref et al., 2015, 2016) in order to prepare new products having olfactive properties suitable for the perfume or cosmetics industries. These compounds have been tested, using the food-poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004). Herein, we present the of the title compound, synthesized by the reaction of 6α,7α-epoxyhimachalene with BF3OEt in acetonitrile under argon.
The title compound, is built up from three fused rings (Fig. 1). The central four-membered cyclobutane ring has a folded conformation, with the C6/C7/C11 plane inclined to the C6/C1/C11 plane by 24.99 (17)°. The cyclohexane ring, C1–C6, has a chair conformation, while the cyclopentene ring, C7–C11, has an with atom C11 as the flap. The dihedral angles between the mean plane of the central cyclobutane ring and mean planes of the cyclopentene and cyclohexane rings are 62.52 (2) and 61.06 (11)°, respectively. The latter two ring mean planes are inclined to one another by 24.29 (10)°.
In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains running along the b-axis direction (Fig. 2 and Table 1).
The compound crystallized in the P212121; however, it was only possible crystallographically to determine the of the asymmetric centers, C11 and C1 (viz. 3aR*,3bS*) [Flack parameter = 0.2 (3)].
Synthesis and crystallization
1 g (4.5 mmol) of 6α,7α-epoxyhimachalene (El Jamili et al., 2002) was dissolved in 10 ml of CH3CN and stirred at 273 K under argon. BF3OEt (1% mmol) was added to the solution, and the reaction mixture was stirred and monitored by TLC. After completion of the reaction, the solvent was removed and the residue obtained was chromatographed on silica eluting with hexane–ethylacetate (90:10), which allowed the isolation of the title compound (yield 783 mg, 68%). It was recrystallized from ethyl acetate with colourless prismatic crystals being obtained on slow evaporation of the solvent.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1533486
https://doi.org/10.1107/S2414314617002759/su4132sup1.cif
contains datablocks I, block. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2414314617002759/su4132Isup3.cml
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002759/su4132Isup2.hkl
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).C17H27NO | Dx = 1.104 Mg m−3 |
Mr = 261.39 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 3245 reflections |
a = 9.7147 (3) Å | θ = 2.4–26.4° |
b = 10.0052 (3) Å | µ = 0.07 mm−1 |
c = 16.3078 (5) Å | T = 296 K |
V = 1585.08 (8) Å3 | Prismatic, colourless |
Z = 4 | 0.24 × 0.2 × 0.15 mm |
F(000) = 576 |
Bruker X8 APEX diffractometer | 3045 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
φ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −12→12 |
Tmin = 0.679, Tmax = 0.746 | k = −12→12 |
21647 measured reflections | l = −20→20 |
3245 independent reflections |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0661P)2 + 0.1181P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3245 reflections | Δρmax = 0.16 e Å−3 |
177 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 2562 quotients [(I+)-(I-)]/[(I+)+(I-)] Parsons et al., 2013). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (3) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O | 0.46368 (18) | 0.20049 (12) | 0.74419 (10) | 0.0619 (4) | |
N | 0.55804 (17) | 0.40475 (13) | 0.73000 (9) | 0.0411 (3) | |
H1 | 0.5638 | 0.4844 | 0.7495 | 0.049* | |
C11 | 0.64696 (18) | 0.36750 (15) | 0.66154 (9) | 0.0360 (4) | |
C12 | 0.4681 (2) | 0.31984 (17) | 0.76358 (11) | 0.0453 (4) | |
C6 | 0.69562 (17) | 0.43016 (16) | 0.53776 (10) | 0.0364 (3) | |
H6 | 0.7676 | 0.3666 | 0.5219 | 0.044* | |
C7 | 0.73241 (18) | 0.48392 (16) | 0.62519 (10) | 0.0375 (4) | |
H7 | 0.6959 | 0.5731 | 0.6373 | 0.045* | |
C8 | 0.8777 (2) | 0.4611 (2) | 0.65449 (11) | 0.0465 (4) | |
C1 | 0.57532 (19) | 0.34851 (16) | 0.57585 (10) | 0.0377 (4) | |
C10 | 0.7562 (2) | 0.26419 (17) | 0.68906 (11) | 0.0450 (4) | |
H10A | 0.7362 | 0.2307 | 0.7436 | 0.054* | |
H10B | 0.7604 | 0.1895 | 0.6512 | 0.054* | |
C9 | 0.8879 (2) | 0.3419 (2) | 0.68825 (11) | 0.0503 (5) | |
H9 | 0.9698 | 0.3088 | 0.7097 | 0.060* | |
C2 | 0.4392 (2) | 0.4263 (2) | 0.57236 (13) | 0.0501 (4) | |
H2A | 0.3639 | 0.3657 | 0.5843 | 0.060* | |
H2B | 0.4400 | 0.4948 | 0.6145 | 0.060* | |
C5 | 0.6687 (2) | 0.52181 (19) | 0.46369 (11) | 0.0487 (4) | |
C14 | 0.5561 (2) | 0.20669 (17) | 0.54345 (12) | 0.0501 (5) | |
H14A | 0.5090 | 0.2097 | 0.4917 | 0.075* | |
H14B | 0.5026 | 0.1558 | 0.5819 | 0.075* | |
H14C | 0.6444 | 0.1653 | 0.5364 | 0.075* | |
C4 | 0.5275 (2) | 0.5893 (2) | 0.47089 (15) | 0.0623 (6) | |
H4A | 0.5312 | 0.6562 | 0.5139 | 0.075* | |
H4B | 0.5068 | 0.6347 | 0.4198 | 0.075* | |
C13 | 0.3712 (3) | 0.3780 (2) | 0.82582 (14) | 0.0648 (6) | |
H13A | 0.3881 | 0.3379 | 0.8783 | 0.097* | |
H13B | 0.2779 | 0.3606 | 0.8095 | 0.097* | |
H13C | 0.3855 | 0.4728 | 0.8294 | 0.097* | |
C3 | 0.4136 (2) | 0.4919 (2) | 0.48979 (15) | 0.0626 (6) | |
H3A | 0.4095 | 0.4240 | 0.4474 | 0.075* | |
H3B | 0.3260 | 0.5384 | 0.4908 | 0.075* | |
C17 | 0.9909 (3) | 0.5609 (3) | 0.64255 (19) | 0.0764 (7) | |
H17A | 1.0111 | 0.5689 | 0.5852 | 0.115* | |
H17B | 1.0717 | 0.5316 | 0.6713 | 0.115* | |
H17C | 0.9623 | 0.6461 | 0.6636 | 0.115* | |
C15 | 0.6744 (3) | 0.4361 (3) | 0.38512 (12) | 0.0686 (6) | |
H15A | 0.7655 | 0.4006 | 0.3785 | 0.103* | |
H15B | 0.6516 | 0.4905 | 0.3386 | 0.103* | |
H15C | 0.6097 | 0.3639 | 0.3894 | 0.103* | |
C16 | 0.7806 (3) | 0.6283 (2) | 0.45821 (16) | 0.0692 (6) | |
H16A | 0.7769 | 0.6843 | 0.5060 | 0.104* | |
H16B | 0.7663 | 0.6817 | 0.4101 | 0.104* | |
H16C | 0.8691 | 0.5859 | 0.4551 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O | 0.0905 (12) | 0.0292 (6) | 0.0660 (9) | −0.0092 (7) | 0.0235 (9) | −0.0004 (6) |
N | 0.0606 (9) | 0.0254 (6) | 0.0374 (7) | −0.0015 (6) | 0.0102 (6) | −0.0026 (5) |
C11 | 0.0496 (9) | 0.0261 (7) | 0.0323 (7) | −0.0008 (6) | 0.0033 (6) | −0.0010 (6) |
C12 | 0.0628 (11) | 0.0324 (8) | 0.0408 (9) | −0.0014 (8) | 0.0090 (8) | 0.0021 (7) |
C6 | 0.0440 (8) | 0.0331 (7) | 0.0323 (8) | −0.0005 (7) | −0.0010 (7) | 0.0007 (6) |
C7 | 0.0502 (9) | 0.0288 (7) | 0.0335 (8) | −0.0027 (7) | 0.0021 (7) | −0.0017 (6) |
C8 | 0.0522 (10) | 0.0522 (11) | 0.0351 (8) | −0.0082 (8) | −0.0043 (7) | −0.0077 (8) |
C1 | 0.0464 (9) | 0.0297 (7) | 0.0371 (8) | −0.0011 (7) | −0.0017 (7) | 0.0005 (6) |
C10 | 0.0634 (11) | 0.0356 (8) | 0.0361 (8) | 0.0070 (8) | −0.0018 (8) | −0.0003 (7) |
C9 | 0.0544 (10) | 0.0588 (11) | 0.0377 (8) | 0.0081 (9) | −0.0093 (8) | −0.0036 (8) |
C2 | 0.0456 (10) | 0.0472 (10) | 0.0574 (11) | 0.0023 (8) | −0.0004 (8) | 0.0046 (8) |
C5 | 0.0621 (11) | 0.0465 (9) | 0.0374 (8) | −0.0038 (9) | −0.0030 (8) | 0.0109 (8) |
C14 | 0.0672 (12) | 0.0362 (8) | 0.0469 (9) | −0.0088 (8) | −0.0039 (9) | −0.0075 (8) |
C4 | 0.0727 (14) | 0.0504 (11) | 0.0639 (13) | 0.0082 (10) | −0.0129 (11) | 0.0199 (10) |
C13 | 0.0816 (15) | 0.0485 (11) | 0.0644 (13) | −0.0031 (11) | 0.0302 (12) | −0.0019 (10) |
C3 | 0.0568 (12) | 0.0622 (12) | 0.0688 (13) | 0.0078 (10) | −0.0165 (10) | 0.0066 (11) |
C17 | 0.0675 (14) | 0.0815 (17) | 0.0801 (16) | −0.0270 (13) | −0.0117 (13) | −0.0002 (14) |
C15 | 0.0926 (17) | 0.0794 (15) | 0.0337 (9) | 0.0005 (14) | −0.0072 (11) | 0.0078 (10) |
C16 | 0.0830 (16) | 0.0633 (13) | 0.0614 (13) | −0.0165 (12) | 0.0042 (12) | 0.0232 (12) |
O—C12 | 1.236 (2) | C2—H2B | 0.9700 |
N—C12 | 1.336 (2) | C5—C16 | 1.525 (3) |
N—C11 | 1.460 (2) | C5—C4 | 1.533 (3) |
N—H1 | 0.8600 | C5—C15 | 1.543 (3) |
C11—C10 | 1.548 (2) | C14—H14A | 0.9600 |
C11—C7 | 1.548 (2) | C14—H14B | 0.9600 |
C11—C1 | 1.573 (2) | C14—H14C | 0.9600 |
C12—C13 | 1.502 (3) | C4—C3 | 1.507 (3) |
C6—C5 | 1.539 (2) | C4—H4A | 0.9700 |
C6—C1 | 1.555 (2) | C4—H4B | 0.9700 |
C6—C7 | 1.565 (2) | C13—H13A | 0.9600 |
C6—H6 | 0.9800 | C13—H13B | 0.9600 |
C7—C8 | 1.507 (3) | C13—H13C | 0.9600 |
C7—H7 | 0.9800 | C3—H3A | 0.9700 |
C8—C9 | 1.317 (3) | C3—H3B | 0.9700 |
C8—C17 | 1.498 (3) | C17—H17A | 0.9600 |
C1—C14 | 1.526 (2) | C17—H17B | 0.9600 |
C1—C2 | 1.536 (3) | C17—H17C | 0.9600 |
C10—C9 | 1.497 (3) | C15—H15A | 0.9600 |
C10—H10A | 0.9700 | C15—H15B | 0.9600 |
C10—H10B | 0.9700 | C15—H15C | 0.9600 |
C9—H9 | 0.9300 | C16—H16A | 0.9600 |
C2—C3 | 1.518 (3) | C16—H16B | 0.9600 |
C2—H2A | 0.9700 | C16—H16C | 0.9600 |
C12—N—C11 | 122.55 (13) | C16—C5—C4 | 109.55 (17) |
C12—N—H1 | 118.7 | C16—C5—C6 | 109.93 (16) |
C11—N—H1 | 118.7 | C4—C5—C6 | 110.77 (16) |
N—C11—C10 | 110.76 (13) | C16—C5—C15 | 108.28 (19) |
N—C11—C7 | 114.70 (13) | C4—C5—C15 | 109.93 (19) |
C10—C11—C7 | 104.23 (14) | C6—C5—C15 | 108.33 (16) |
N—C11—C1 | 116.65 (14) | C1—C14—H14A | 109.5 |
C10—C11—C1 | 118.71 (13) | C1—C14—H14B | 109.5 |
C7—C11—C1 | 89.31 (12) | H14A—C14—H14B | 109.5 |
O—C12—N | 122.17 (17) | C1—C14—H14C | 109.5 |
O—C12—C13 | 121.68 (18) | H14A—C14—H14C | 109.5 |
N—C12—C13 | 116.15 (15) | H14B—C14—H14C | 109.5 |
C5—C6—C1 | 119.91 (15) | C3—C4—C5 | 112.80 (16) |
C5—C6—C7 | 123.30 (14) | C3—C4—H4A | 109.0 |
C1—C6—C7 | 89.32 (12) | C5—C4—H4A | 109.0 |
C5—C6—H6 | 107.5 | C3—C4—H4B | 109.0 |
C1—C6—H6 | 107.5 | C5—C4—H4B | 109.0 |
C7—C6—H6 | 107.5 | H4A—C4—H4B | 107.8 |
C8—C7—C11 | 105.46 (14) | C12—C13—H13A | 109.5 |
C8—C7—C6 | 116.76 (14) | C12—C13—H13B | 109.5 |
C11—C7—C6 | 88.15 (12) | H13A—C13—H13B | 109.5 |
C8—C7—H7 | 114.4 | C12—C13—H13C | 109.5 |
C11—C7—H7 | 114.4 | H13A—C13—H13C | 109.5 |
C6—C7—H7 | 114.4 | H13B—C13—H13C | 109.5 |
C9—C8—C17 | 127.1 (2) | C4—C3—C2 | 109.92 (18) |
C9—C8—C7 | 109.89 (17) | C4—C3—H3A | 109.7 |
C17—C8—C7 | 123.02 (18) | C2—C3—H3A | 109.7 |
C14—C1—C2 | 110.68 (15) | C4—C3—H3B | 109.7 |
C14—C1—C6 | 116.25 (15) | C2—C3—H3B | 109.7 |
C2—C1—C6 | 111.46 (13) | H3A—C3—H3B | 108.2 |
C14—C1—C11 | 118.32 (14) | C8—C17—H17A | 109.5 |
C2—C1—C11 | 110.66 (14) | C8—C17—H17B | 109.5 |
C6—C1—C11 | 87.65 (12) | H17A—C17—H17B | 109.5 |
C9—C10—C11 | 103.70 (14) | C8—C17—H17C | 109.5 |
C9—C10—H10A | 111.0 | H17A—C17—H17C | 109.5 |
C11—C10—H10A | 111.0 | H17B—C17—H17C | 109.5 |
C9—C10—H10B | 111.0 | C5—C15—H15A | 109.5 |
C11—C10—H10B | 111.0 | C5—C15—H15B | 109.5 |
H10A—C10—H10B | 109.0 | H15A—C15—H15B | 109.5 |
C8—C9—C10 | 114.17 (17) | C5—C15—H15C | 109.5 |
C8—C9—H9 | 122.9 | H15A—C15—H15C | 109.5 |
C10—C9—H9 | 122.9 | H15B—C15—H15C | 109.5 |
C3—C2—C1 | 113.15 (17) | C5—C16—H16A | 109.5 |
C3—C2—H2A | 108.9 | C5—C16—H16B | 109.5 |
C1—C2—H2A | 108.9 | H16A—C16—H16B | 109.5 |
C3—C2—H2B | 108.9 | C5—C16—H16C | 109.5 |
C1—C2—H2B | 108.9 | H16A—C16—H16C | 109.5 |
H2A—C2—H2B | 107.8 | H16B—C16—H16C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1···Oi | 0.86 | 2.18 | 2.9962 (18) | 158 |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
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