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Acta Cryst. (2007). E63, o3977    [ doi:10.1107/S1600536807042596 ]

exo-8,exo-11-Divinylpentacyclo[5.4.0.02,6.03,10.05,6]undecane-endo-8,endo-11-diol

G. A. Boyle, T. Govender, R. Karpoormath and H. G. Kruger

Abstract top

The title molecule, C15H18O2, exhibits C-C bond lengths that deviate from the normal value of 1.54 Å. A number of long [e.g. 1.5712 (16) Å] and short [e.g. 1.5237 (17) Å] C-C bonds are observed. The molecules are arranged in two-dimensional hydrogen-bonded (O-H...O) sheets with only hydrophobic van der Waals interactions between neighbouring sheets.

Comment top

The title compound (I) consists of a large apolar (lipophilic) hydrocarbon skeleton with polar dihydroxy units (Fig. 1). This unique compound is used as a starting molecule and derivatives thereof are coupled with desired peptides as potential HIV-1 protease inhibitors. A number of publications have focused on the molecular geometries of pentacycloundecane (PCU) cage derivatives (Flippen-Anderson et al., 1991; Linden et al., 2005; Kruger et al., 2005; Kruger et al., 2006). It has been reported that these compounds exhibit bond lengths deviating from the normal value of 1.54 Å. The shortening and elongation of specific C—C bonds in the cage molecule is also observed in (i) with the C—C bonds between C3—C4 & C4—C5 being the shortest (1.5237 (17) Å & 1.5256 (17) Å respectively) and the bonds between C1—C7 & C1—C2 being the longest (1.5712 (16) Å & 1.5626 (16) Å respectively). Interestingly the bonds between the cage and the alkene side chains (C11—C12 and C8—C14) are surprisingly shorter than expected value of C—C bonds (1.54 Å) with values of 1.5173 (16) Å and 1.5212 (15) Å respectively. The ethylene chains are in an energetically favorable conformation, with atoms C8, C11, C12, C13, C14 coplanar. Atoms C13 and C15 appear to be in a trans conformation with respect to each other. This allows the two hydroxyl groups to be in a favorable conformation for intra- and intermolecular hydrogen bonding.

In (I), the molecules pack in hydrogen-bonded bilayers. Both hydroxyl groups on the molecule participate in both intramolecular and intermolecular hydrogen bonding, each acting as a hydrogen bond donor and acceptor. Atom O2 interacts with atom O1 via H2A and atom O1 interacts with O2 of another cage molecule via H1A. Thus forming a hydrogen-bonded linear chain (Fig. 2). Because both the hydroxy groups of a molecule are involved in hydrogen bonding, molecules are connected in a linear fashion forming a sheet with alternating hydrogen bonding between the molecules. The linear sheets do not show any hydrogen bonding between the lipophilic parts of the bilayers but do show short contacts.

Related literature top

For similar structures, see: Flippen-Anderson et al. (1991); Linden et al. (2005); Kruger et al. (2005, 2006).

Experimental top

A solution of Pentacyclo[5.4.0.02,6.03,10.05,6]undecane-8,11-dione (20.0 g, 0.115 mol) in dry THF (200 ml) was added dropwise over 2 h to a stirred suspension of vinylmagnesium bromide under nitrogen at 0°C. After the addition had been completed, the external ice-water bath was removed, and the reaction mixture was allowed to warm gradually to room temperature while stirring under nitrogen for 24 h. The reaction was quenched via addition of saturated aqueous NH4Cl (until pH is 6~7), the layers were separated, and the aqueous layer was extracted with EtOAc (2 x 500 ml). The combined organic extracts were dried (Na2SO4) and filtered, and the filtrate was concentrated in vacuo. The residue was recrystallized from hexane, thereby affording pure (I) (27.0 g, 91%) as a colorless microcrystalline solid: m.p. 82–83 °C.

Refinement top

All hydrogen atoms were first located in the difference map then positioned geometrically and allowed to ride on their respective parent atoms.

Computing details top

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL (Bruker, 1999); molecular graphics: Mercury (Macrae et al., 2006) and WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atomic numbering scheme and ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. Depiction of the intramolecular and intermolecular hydrogen bonding.
exo-8-exo-11-Divinylpentacyclo[5.4.0.02,6.03,10.05,6]\ undecane-endo-8,endo-11-diol top
Crystal data top
C15H18O2F000 = 496
Mr = 230.29Dx = 1.289 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1016 reflections
a = 6.9355 (5) Åθ = 3.6–28.3º
b = 21.3303 (13) ŵ = 0.08 mm−1
c = 8.1859 (5) ÅT = 173 (2) K
β = 101.435 (3)ºIrregular, colourless
V = 1186.95 (13) Å30.48 × 0.40 × 0.34 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2525 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Monochromator: graphiteθmax = 28.0º
T = 173(2) Kθmin = 1.9º
φ and ω scansh = −9→9
Absorption correction: nonek = −28→28
15589 measured reflectionsl = −10→10
2869 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0599P)2 + 0.3441P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2869 reflectionsΔρmax = 0.35 e Å−3
156 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C15H18O2V = 1186.95 (13) Å3
Mr = 230.29Z = 4
Monoclinic, P21/cMo Kα
a = 6.9355 (5) ŵ = 0.08 mm−1
b = 21.3303 (13) ÅT = 173 (2) K
c = 8.1859 (5) Å0.48 × 0.40 × 0.34 mm
β = 101.435 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2869 independent reflections
Absorption correction: none2525 reflections with I > 2σ(I)
15589 measured reflectionsRint = 0.031
Refinement top
R[F2 > 2σ(F2)] = 0.041156 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 1.08Δρmax = 0.35 e Å−3
2869 reflectionsΔρmin = −0.20 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
C10.93905 (16)0.33993 (5)0.24919 (14)0.0231 (2)
H11.05230.31010.27240.028*
C20.99718 (17)0.41041 (6)0.23947 (15)0.0269 (3)
H21.14000.42030.24950.032*
C30.85062 (18)0.44024 (5)0.09116 (15)0.0273 (3)
H30.90470.4482−0.01150.033*
C40.7748 (2)0.49790 (6)0.16851 (17)0.0323 (3)
H4A0.66230.51800.09340.039*
H4B0.87940.52920.20720.039*
C50.71320 (18)0.46260 (5)0.31196 (15)0.0275 (3)
H50.65370.48890.39030.033*
C60.90169 (17)0.42568 (5)0.39229 (15)0.0264 (3)
H60.98820.44450.49250.032*
C70.84341 (16)0.35538 (5)0.40315 (14)0.0225 (2)
H70.90500.33370.50900.027*
C80.61711 (16)0.35801 (5)0.36817 (13)0.0208 (2)
C90.58290 (16)0.40754 (5)0.22715 (14)0.0230 (2)
H90.44130.41960.19300.028*
C100.68068 (17)0.39180 (5)0.07136 (14)0.0234 (2)
H100.58580.3964−0.03720.028*
C110.79558 (16)0.32932 (5)0.08322 (14)0.0220 (2)
C120.8997 (2)0.32246 (6)−0.06228 (16)0.0306 (3)
H120.81820.3212−0.17020.037*
C131.0912 (2)0.31811 (7)−0.0554 (2)0.0420 (3)
H13A1.17960.31920.04930.050*
H13B1.14050.3139−0.15520.050*
C140.54886 (18)0.38205 (6)0.52223 (15)0.0281 (3)
H140.62160.41530.58230.034*
C150.3968 (2)0.36033 (7)0.57897 (16)0.0339 (3)
H15A0.32030.32700.52250.041*
H15B0.36380.37800.67640.041*
O10.51761 (12)0.30019 (4)0.31854 (10)0.02288 (19)
H1A0.55840.27240.38980.034*
O20.67635 (13)0.27405 (4)0.07257 (10)0.0267 (2)
H2A0.60920.27500.14740.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0207 (5)0.0224 (5)0.0256 (5)0.0012 (4)0.0035 (4)−0.0025 (4)
C20.0228 (5)0.0253 (6)0.0332 (6)−0.0043 (4)0.0069 (4)−0.0040 (5)
C30.0337 (6)0.0214 (5)0.0291 (6)−0.0037 (4)0.0114 (5)0.0022 (4)
C40.0400 (7)0.0204 (5)0.0381 (7)−0.0016 (5)0.0115 (5)0.0027 (5)
C50.0333 (6)0.0190 (5)0.0319 (6)0.0008 (4)0.0104 (5)−0.0009 (4)
C60.0278 (6)0.0240 (5)0.0268 (5)−0.0054 (4)0.0040 (4)−0.0055 (4)
C70.0226 (5)0.0226 (5)0.0210 (5)0.0003 (4)0.0011 (4)−0.0019 (4)
C80.0226 (5)0.0190 (5)0.0207 (5)−0.0006 (4)0.0040 (4)−0.0001 (4)
C90.0222 (5)0.0215 (5)0.0254 (5)0.0033 (4)0.0053 (4)0.0042 (4)
C100.0258 (5)0.0229 (5)0.0215 (5)−0.0003 (4)0.0046 (4)0.0039 (4)
C110.0248 (5)0.0200 (5)0.0216 (5)−0.0030 (4)0.0054 (4)−0.0012 (4)
C120.0399 (7)0.0279 (6)0.0267 (6)−0.0051 (5)0.0135 (5)−0.0039 (5)
C130.0442 (8)0.0430 (8)0.0456 (8)−0.0066 (6)0.0256 (6)−0.0098 (6)
C140.0329 (6)0.0271 (6)0.0249 (6)0.0026 (5)0.0075 (5)−0.0014 (4)
C150.0337 (6)0.0423 (7)0.0275 (6)0.0035 (5)0.0102 (5)−0.0013 (5)
O10.0263 (4)0.0213 (4)0.0204 (4)−0.0038 (3)0.0034 (3)0.0019 (3)
O20.0356 (5)0.0229 (4)0.0232 (4)−0.0089 (3)0.0096 (3)−0.0052 (3)
Geometric parameters (Å, °) top
C1—C111.5333 (15)C8—O11.4322 (13)
C1—C21.5626 (16)C8—C141.5212 (15)
C1—C71.5712 (16)C8—C91.5481 (15)
C1—H11.0000C9—C101.5944 (15)
C2—C31.5565 (17)C9—H91.0000
C2—C61.5614 (17)C10—C111.5459 (15)
C2—H21.0000C10—H101.0000
C3—C41.5237 (17)C11—O21.4328 (13)
C3—C101.5516 (16)C11—C121.5173 (16)
C3—H31.0000C12—C131.322 (2)
C4—C51.5256 (17)C12—H120.9500
C4—H4A0.9900C13—H13A0.9500
C4—H4B0.9900C13—H13B0.9500
C5—C61.5558 (17)C14—C151.3177 (18)
C5—C91.5585 (16)C14—H140.9500
C5—H51.0000C15—H15A0.9500
C6—C71.5601 (16)C15—H15B0.9500
C6—H61.0000O1—H1A0.8400
C7—C81.5396 (15)O2—H2A0.8400
C7—H71.0000
C11—C1—C2103.03 (9)C6—C7—H7115.0
C11—C1—C7116.02 (9)C1—C7—H7115.0
C2—C1—C789.61 (8)O1—C8—C14108.29 (9)
C11—C1—H1114.9O1—C8—C7115.95 (9)
C2—C1—H1114.9C14—C8—C7109.35 (9)
C7—C1—H1114.9O1—C8—C9112.47 (9)
C3—C2—C6102.97 (9)C14—C8—C9111.18 (9)
C3—C2—C1107.33 (9)C7—C8—C999.41 (9)
C6—C2—C190.30 (9)C8—C9—C5101.10 (9)
C3—C2—H2117.4C8—C9—C10115.21 (9)
C6—C2—H2117.4C5—C9—C10102.36 (9)
C1—C2—H2117.4C8—C9—H9112.4
C4—C3—C10105.27 (10)C5—C9—H9112.4
C4—C3—C2103.39 (10)C10—C9—H9112.4
C10—C3—C2100.03 (9)C11—C10—C3101.31 (9)
C4—C3—H3115.4C11—C10—C9115.28 (9)
C10—C3—H3115.4C3—C10—C9102.17 (9)
C2—C3—H3115.4C11—C10—H10112.4
C3—C4—C595.39 (9)C3—C10—H10112.4
C3—C4—H4A112.7C9—C10—H10112.4
C5—C4—H4A112.7O2—C11—C12103.39 (9)
C3—C4—H4B112.7O2—C11—C1116.15 (9)
C5—C4—H4B112.7C12—C11—C1112.55 (10)
H4A—C4—H4B110.2O2—C11—C10114.93 (9)
C4—C5—C6103.59 (10)C12—C11—C10110.69 (9)
C4—C5—C9104.78 (10)C1—C11—C1099.46 (9)
C6—C5—C999.86 (9)C13—C12—C11127.17 (12)
C4—C5—H5115.5C13—C12—H12116.4
C6—C5—H5115.5C11—C12—H12116.4
C9—C5—H5115.5C12—C13—H13A120.0
C5—C6—C7107.76 (9)C12—C13—H13B120.0
C5—C6—C2102.78 (9)H13A—C13—H13B120.0
C7—C6—C290.06 (8)C15—C14—C8125.17 (12)
C5—C6—H6117.4C15—C14—H14117.4
C7—C6—H6117.4C8—C14—H14117.4
C2—C6—H6117.4C14—C15—H15A120.0
C8—C7—C6102.74 (9)C14—C15—H15B120.0
C8—C7—C1115.81 (9)H15A—C15—H15B120.0
C6—C7—C190.03 (8)C8—O1—H1A109.5
C8—C7—H7115.0C11—O2—H2A109.5
C11—C1—C2—C312.86 (11)C14—C8—C9—C560.93 (11)
C7—C1—C2—C3−103.80 (9)C7—C8—C9—C5−54.18 (10)
C11—C1—C2—C6116.56 (9)O1—C8—C9—C10−67.96 (12)
C7—C1—C2—C6−0.10 (8)C14—C8—C9—C10170.41 (9)
C6—C2—C3—C433.62 (11)C7—C8—C9—C1055.30 (11)
C1—C2—C3—C4128.07 (10)C4—C5—C9—C8151.87 (9)
C6—C2—C3—C10−74.86 (10)C6—C5—C9—C844.86 (10)
C1—C2—C3—C1019.58 (11)C4—C5—C9—C1032.70 (11)
C10—C3—C4—C551.65 (11)C6—C5—C9—C10−74.31 (10)
C2—C3—C4—C5−52.87 (11)C4—C3—C10—C11−151.85 (9)
C3—C4—C5—C652.79 (11)C2—C3—C10—C11−44.86 (10)
C3—C4—C5—C9−51.46 (11)C4—C3—C10—C9−32.59 (11)
C4—C5—C6—C7−127.37 (10)C2—C3—C10—C974.39 (10)
C9—C5—C6—C7−19.40 (11)C8—C9—C10—C110.03 (13)
C4—C5—C6—C2−33.14 (11)C5—C9—C10—C11108.76 (10)
C9—C5—C6—C274.83 (10)C8—C9—C10—C3−108.86 (10)
C3—C2—C6—C5−0.27 (11)C5—C9—C10—C3−0.14 (10)
C1—C2—C6—C5−108.14 (9)C2—C1—C11—O2−164.04 (9)
C3—C2—C6—C7107.97 (9)C7—C1—C11—O2−68.00 (13)
C1—C2—C6—C70.10 (8)C2—C1—C11—C1277.06 (11)
C5—C6—C7—C8−13.17 (11)C7—C1—C11—C12173.10 (9)
C2—C6—C7—C8−116.62 (9)C2—C1—C11—C10−40.14 (10)
C5—C6—C7—C1103.35 (9)C7—C1—C11—C1055.90 (11)
C2—C6—C7—C1−0.10 (8)C3—C10—C11—O2178.71 (9)
C11—C1—C7—C8−0.04 (14)C9—C10—C11—O269.30 (12)
C2—C1—C7—C8104.29 (10)C3—C10—C11—C12−64.64 (11)
C11—C1—C7—C6−104.24 (10)C9—C10—C11—C12−174.05 (9)
C2—C1—C7—C60.10 (8)C3—C10—C11—C153.96 (10)
C6—C7—C8—O1161.29 (9)C9—C10—C11—C1−55.45 (11)
C1—C7—C8—O164.97 (12)O2—C11—C12—C13−118.34 (14)
C6—C7—C8—C14−75.97 (11)C1—C11—C12—C137.78 (18)
C1—C7—C8—C14−172.29 (9)C10—C11—C12—C13118.09 (15)
C6—C7—C8—C940.53 (10)O1—C8—C14—C15−12.52 (16)
C1—C7—C8—C9−55.78 (11)C7—C8—C14—C15−139.71 (13)
O1—C8—C9—C5−177.44 (9)C9—C8—C14—C15111.52 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O10.841.732.5409 (12)160
O1—H1A···O2i0.841.852.6713 (11)167
Symmetry codes: (i) x, −y+1/2, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O10.841.732.5409 (12)160
O1—H1A···O2i0.841.852.6713 (11)167
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

We thank Dr Manuel Fernandes of the Jan Boeyens Structural Chemistry Laboratory at the University of the Witwatersrand for his assistance in the aquisition of the crystallographic data. This work was supported by grants from the National Research Foundation (South Africa), GUN 2046819 and the University of KwaZulu-Natal.

references
References top

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