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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2270.
Published online 2008 November 8. doi:  10.1107/S1600536808035423
PMCID: PMC2959889

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

Abstract

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.

Related literature

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

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Object name is e-64-o2270-scheme1.jpg

Experimental

Crystal data

  • C10H12O2
  • M r = 164.2
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2270-efi1.jpg
  • a = 10.3730 (14) Å
  • b = 9.8494 (14) Å
  • c = 7.7128 (11) Å
  • β = 91.850 (11)°
  • V = 787.59 (19) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.77 mm−1
  • T = 295 (2) K
  • 0.5 × 0.5 × 0.5 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 5405 measured reflections
  • 1419 independent reflections
  • 1386 reflections with I > 2σ(I)
  • R int = 0.038
  • 3 standard reflections frequency: 60 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.100
  • S = 1.08
  • 1419 reflections
  • 112 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.19 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035423/fj2159sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035423/fj2159Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

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]
Fig. 2.
Packing diagram showing two of the hydrogen bonds in the hydrogen bonding network of the structure.
Fig. 3.
The formation of the title compound.

Crystal data

C10H12O2F000 = 352
Mr = 164.2Dx = 1.385 Mg m3
Monoclinic, P21/cCu Kα radiation λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 22 reflections
a = 10.3730 (14) Åθ = 36.5–41.8º
b = 9.8494 (14) ŵ = 0.77 mm1
c = 7.7128 (11) ÅT = 295 (2) K
β = 91.850 (11)ºIrregular, brown
V = 787.59 (19) Å30.5 × 0.5 × 0.5 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerθmin = 4.3º
Nonprofiled ω/2θ scansh = −12→12
Absorption correction: nonek = −11→11
5405 measured reflectionsl = −9→9
1419 independent reflections3 standard reflections
1386 reflections with I > 2σ(I) every 60 min
Rint = 0.038 intensity decay: none
θmax = 67.5º

Refinement

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 Å3
S = 1.08Δρmin = −0.18 e Å3
1419 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
112 parametersExtinction coefficient: 0.025 (2)

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2159).

References

  • Amman, W. & Ganter, C. (1977). Helv. Chim. Acta, 60, 1924–1925.
  • Amman, W. & Ganter, C. (1981). Helv. Chim. Acta, 65, 966–1022.
  • Amman, W., Jäggi, F. J. & Ganter, C. (1980). Helv. Chim. Acta, 63, 2019–2041.
  • Baggiolini, E., Herzog, E. G., Iwaski, S., Schorta, R. & Schaffner, K. (1967). Helv. Chim. Acta, 50, 297–306.
  • Eaton, P. E., Tang, D. & Gilardi, R. (2002). Tetrahedron Lett.43, 3–5.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
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  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Herzog, E. G. (1958). PhD thesis, ETH Zürich, Switzerland.
  • Klinsmann, U., Gauthier, J., Schaffner, K., Pasternak, M. & Fuchs, B. (1972). Helv. Chim. Acta, 55, 2643–2659.
  • Prakash, G. K. S., Farnia, M., Keyanian, S., Olah, G. A., Kuhn, H. J. & Schaffner, K. (1987). J. Am. Chem. Soc.109, 911–912.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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