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Acta Cryst. (2008). E64, o2270    [ doi:10.1107/S1600536808035423 ]

anti-Tricyclo[4.2.1.12,5]deca-3,7-diene-9-endo,10-endo-diol

A. D. Harris, A. D. Baucom, M. del R. I. A. Sierra, D. S. Jones and M. Etzkorn

Abstract top

The title compound, C10H12O2, was synthesized as a candidate for further functionalization. The asymmetric unit comprises two independent molecules, both of which are situated on a center of symmetry. Both molecules are involved in a network of hydrogen bonding, with each alcohol group participating in one hydrogen bond as a donor and in a second hydrogen bond as an acceptor.

Comment top

The polycyclic title compound 4 has gained importance as a precursor to a bishomoaromatic dication (Prakash et al., 1987) and was furthermore investigated in a synthetic approach to heterodiamantanes (Amman et al., 1980; Amman & Ganter, 1977; Amman & Ganter, 1981). We were interested in the functionalization of dienedione 3, which is a rather challenging task if one considers the issue of chemoselectivity, regioselectivity and stereoselectivity in a relatively small polycyclic skeleton with two olefinic bonds and two carbonyl groups in close proximity. Furthermore, a thermally induced isomerization of compound 3 to the endo-cyclopentadienone dimer 2 (Baggiolini et al., 1967; Klinsmann et al., 1972) prohibited several functionalization reactions that required forcing conditions. We therefore focused on the thermally stable dienediol 4.

Two pairs of independent molecules (Figure 1) comprise the four molecules in the unit cell, each of which is situated on a center of symmetry. All of the molecules are involved in a network of hydrogen bonding (Figure 2), with each alcohol group participating in one hydrogen bond as a donor and in a second hydrogen bond as an acceptor.

Related literature top

For a related structure, see: Eaton et al. (2002). For synthesis details, see: Baggiolini et al. (1967); Klinsmann et al. (1972); Prakash et al. (1987); Herzog (1958). For synthesis details and compound characterization, see: Amman et al. (1980). For synthetic routes utilizing the title compound as a starting material, see: Amman & Ganter (1977, 1981).

Experimental top

Preparation of dienedione 2 (Herzog, 1958): A solution of sodium ethoxide in ethanol was prepared by adding sodium (44.4 g, 1.94 mol) in small pieces to ethanol (2 l). A mixture of freshly distilled cyclopentadiene monomer (74 g, 1.12 mol) and isoamylnitrite (131 g, 1.12 mol) was then added dropwise at 15–20 °C. The dark brown reaction mixture was stirred for 30 minutes, poured on ice (0.5 kg) and extracted with ether (3 × 300 ml). These organic extracts were discarded, and the aqueous phase was acidified to pH 3 with 2.5 M sulfuric acid (ca 600 ml). After saturating with sodium chloride (ca 250 g) the aqueous phase was extracted with ether (5 × 600 ml). The combined organic phase was concentrated to a third of its volume, washed with water (100 ml) and dried (MgSO4). After removal of the solvent the viscous brown oil obtained (62 g) was refluxed in 1M sulfuric acid (1500 ml) for several hours and stirred at room temperature overnight. The reaction mixture was saturated with sodium chloride (ca 0.5 kg) and extracted with ether (5 × 400 ml). The combined organic phase was concentrated, washed with water, and dried (MgSO4). After removal of the solvent a pale-brown crude product was obtained. Sublimation furnished the clean product (27 g, 30% with respect to cyclopentadiene) as a colorless solid.

After the photoisomerization of dienedione 2 to dienedione 3 (Baggiolini et al., 1967; Klinsmann et al., 1972) a reduction with LiAlH4 in THF yielded diol 4 (Amman et al., 1980; Prakash et al., 1987). We were able to grow single crystals of diol 4 from CHCl3 and thus provide structural details of the otherwise fully characterized compound (Amman et al., 1980).

Refinement top

H atoms were constrained using a riding model. The olefinic C—H bond lengths were fixed at 0.93 Å and the methine C—H bond lengths at 0.98 Å, with Uiso(H) = 1.2 Ueq. (C). The O—H bond lengths were fixed at 0.82 Å, with Uiso(H) = 1.5 Ueq. (C), and the torsion angles about the C—O bonds were refined.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of the two independent molecules of the title compound, 4, with 50% probability displacement ellipsoids. [Symmetry codes: (i) -x + 1, -y, -z; (ii) -x + 2, -y + 1, -z]
[Figure 2] Fig. 2. Packing diagram showing two of the hydrogen bonds in the hydrogen bonding network of the structure.
[Figure 3] Fig. 3. The formation of the title compound.
anti-Tricyclo[4.2.1.12,5]deca-3,7-diene-9-endo,10-endo- diol top
Crystal data top
C10H12O2F(000) = 352
Mr = 164.2Dx = 1.385 Mg m−3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 22 reflections
a = 10.3730 (14) Åθ = 36.5–41.8°
b = 9.8494 (14) ŵ = 0.77 mm−1
c = 7.7128 (11) ÅT = 295 K
β = 91.850 (11)°Irregular, brown
V = 787.59 (19) Å30.5 × 0.5 × 0.5 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		θmax = 67.5°, θmin = 4.3°
Nonprofiled ω/2θ scansh = −12→12
5405 measured reflectionsk = −11→11
1419 independent reflectionsl = −9→9
1386 reflections with I > 2σ(I)3 standard reflections every 60 min
Rint = 0.038 intensity decay: none
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0449P)2 + 0.2879P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.039(Δ/σ)max < 0.001
wR(F2) = 0.100Δρmax = 0.25 e Å−3
S = 1.08Δρmin = −0.18 e Å−3
1419 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
112 parametersExtinction coefficient: 0.025 (2)
0 restraints
Crystal data top
C10H12O2V = 787.59 (19) Å3
Mr = 164.2Z = 4
Monoclinic, P21/cCu Kα radiation
a = 10.3730 (14) ŵ = 0.77 mm−1
b = 9.8494 (14) ÅT = 295 K
c = 7.7128 (11) Å0.5 × 0.5 × 0.5 mm
β = 91.850 (11)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.038
5405 measured reflectionsθmax = 67.5°
1419 independent reflections3 standard reflections every 60 min
1386 reflections with I > 2σ(I) intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.100Δρmax = 0.25 e Å−3
S = 1.08Δρmin = −0.18 e Å−3
1419 reflectionsAbsolute structure: ?
112 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.79276 (9)0.37798 (11)−0.08942 (13)0.0372 (3)
HO10.74630.3684−0.17660.056*
O20.68564 (9)0.15711 (10)0.08353 (13)0.0375 (3)
HO20.72520.21970.03960.056*
C100.44926 (13)0.09207 (14)0.11758 (19)0.0306 (3)
H100.43570.14530.22280.037*
C20.96268 (12)0.55937 (14)−0.15964 (18)0.0301 (3)
H20.91180.607−0.25010.036*
C70.53244 (12)0.06358 (14)−0.15675 (17)0.0296 (3)
H70.58160.0942−0.25590.036*
C51.03469 (12)0.36341 (14)−0.01805 (19)0.0309 (3)
H51.03830.2646−0.00350.037*
C10.92078 (12)0.40891 (14)−0.13877 (18)0.0307 (3)
H10.93280.3648−0.2510.037*
C60.55870 (13)0.15044 (13)0.00772 (18)0.0295 (3)
H60.53390.2437−0.02240.035*
C31.09864 (13)0.52746 (16)−0.21451 (18)0.0352 (4)
H31.14540.5778−0.29280.042*
C80.39004 (13)0.09802 (14)−0.1751 (2)0.0342 (4)
H80.34350.1069−0.27960.041*
C90.34268 (13)0.11333 (14)−0.0195 (2)0.0352 (4)
H90.25730.13390.00270.042*
C41.13997 (13)0.41653 (15)−0.1333 (2)0.0363 (4)
H41.22070.3772−0.14480.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0281 (5)0.0435 (6)0.0395 (6)−0.0110 (4)−0.0058 (4)0.0054 (5)
O20.0326 (6)0.0343 (6)0.0447 (6)−0.0107 (4)−0.0120 (4)0.0087 (4)
C100.0302 (7)0.0286 (7)0.0332 (7)0.0013 (5)0.0017 (5)−0.0035 (5)
C20.0264 (7)0.0336 (7)0.0301 (7)−0.0008 (5)−0.0023 (5)0.0079 (6)
C70.0291 (7)0.0315 (7)0.0281 (7)−0.0037 (5)−0.0017 (5)0.0057 (5)
C50.0278 (7)0.0246 (6)0.0403 (8)0.0030 (5)0.0023 (6)0.0017 (6)
C10.0276 (7)0.0332 (7)0.0312 (7)−0.0041 (5)0.0004 (5)−0.0012 (6)
C60.0285 (7)0.0241 (6)0.0353 (8)−0.0024 (5)−0.0060 (5)0.0037 (5)
C30.0311 (7)0.0438 (8)0.0310 (7)−0.0054 (6)0.0067 (6)0.0003 (6)
C80.0313 (7)0.0279 (7)0.0424 (8)−0.0039 (6)−0.0124 (6)0.0100 (6)
C90.0253 (7)0.0271 (7)0.0530 (9)0.0041 (5)−0.0012 (6)0.0042 (6)
C40.0278 (7)0.0405 (8)0.0411 (8)0.0040 (6)0.0075 (6)−0.0050 (6)
Geometric parameters (Å, °) top
O1—C11.4261 (16)C7—H70.98
O1—HO10.82C5—C41.5227 (18)
O2—C61.4248 (16)C5—C11.5469 (19)
O2—HO20.82C5—C2ii1.567 (2)
C10—C91.520 (2)C5—H50.98
C10—C61.5490 (18)C1—H10.98
C10—C7i1.5728 (18)C6—H60.98
C10—H100.98C3—C41.324 (2)
C2—C31.5183 (18)C3—H30.93
C2—C11.5542 (19)C8—C91.320 (2)
C2—C5ii1.567 (2)C8—H80.93
C2—H20.98C9—H90.93
C7—C81.5178 (18)C4—H40.93
C7—C61.5469 (19)
C1—O1—HO1109.5C2ii—C5—H5112.5
C6—O2—HO2109.5O1—C1—C5118.51 (12)
C9—C10—C695.61 (11)O1—C1—C2119.82 (11)
C9—C10—C7i110.40 (11)C5—C1—C297.34 (10)
C6—C10—C7i112.38 (11)O1—C1—H1106.7
C9—C10—H10112.4C5—C1—H1106.7
C6—C10—H10112.4C2—C1—H1106.7
C7i—C10—H10112.4O2—C6—C7119.86 (11)
C3—C2—C195.56 (11)O2—C6—C10118.46 (11)
C3—C2—C5ii110.74 (11)C7—C6—C1097.50 (10)
C1—C2—C5ii111.67 (11)O2—C6—H6106.6
C3—C2—H2112.6C7—C6—H6106.6
C1—C2—H2112.6C10—C6—H6106.6
C5ii—C2—H2112.6C4—C3—C2109.17 (12)
C8—C7—C695.63 (11)C4—C3—H3125.4
C8—C7—C10i110.29 (11)C2—C3—H3125.4
C6—C7—C10i111.38 (11)C9—C8—C7109.28 (12)
C8—C7—H7112.8C9—C8—H8125.4
C6—C7—H7112.8C7—C8—H8125.4
C10i—C7—H7112.8C8—C9—C10109.46 (12)
C4—C5—C195.60 (11)C8—C9—H9125.3
C4—C5—C2ii110.56 (11)C10—C9—H9125.3
C1—C5—C2ii112.16 (11)C3—C4—C5109.41 (12)
C4—C5—H5112.5C3—C4—H4125.3
C1—C5—H5112.5C5—C4—H4125.3
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O2iii0.821.952.7452 (15)163
O2—HO2···O10.821.992.8005 (14)170
Symmetry codes: (iii) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O2i0.821.952.7452 (15)163
O2—HO2···O10.821.992.8005 (14)170
Symmetry codes: (i) x, −y+1/2, z−1/2.
Acknowledgements top

Acknowledgement is made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research. This work was supported in part by funds provided by The University of North Carolina at Charlotte.

references
References top

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