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

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

doi:10.1107/S1600536808035423

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2270

doi:10.1107/S1600536808035423

Open

access

anti-Tricyclo[4.2.1.1^2,5]deca-3,7-diene-9-endo,10-endo-diol

Andria D. Harris,^a Amy D. Baucom,^a Maria del Rosario I. Amado Sierra,^a Daniel S. Jones ^a ^* and Markus Etzkorn ^a ^*

^aDepartment of Chemistry, The University of North Carolina at Charlotte, 9201 University City Boulevard, Charlotte, NC 28223, USA
^*Correspondence e-mail: djones@uncc.edu, metzkorn@uncc.edu

(Received 30 September 2008; accepted 29 October 2008; online 8 November 2008)

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 ). 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

Crystal data

C₁₀H₁₂O₂
M_r = 164.2
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 1.08
1419 reflections
112 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HO1⋯O2ⁱ	0.82	1.95	2.7452 (15)	163
O2—HO2⋯O1	0.82	1.99	2.8005 (14)	170
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; 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 ).

Supporting information

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

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

checkCIF report

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 LiAlH₄in THF yielded diol 4 (Amman et al., 1980; Prakash et al., 1987). We were able to grow single crystals of diol 4 from CHCl₃and thus provide structural details of the otherwise fully characterized compound (Amman et al., 1980).

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

	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.

anti-Tricyclo[4.2.1.1^2,5]deca-3,7-diene-9-endo,10-endo- diol top

Crystal data top

C₁₀H₁₂O₂	F(000) = 352
M_r = 164.2	D_x = 1.385 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 22 reflections
a = 10.3730 (14) Å	θ = 36.5–41.8°
b = 9.8494 (14) Å	µ = 0.77 mm⁻¹
c = 7.7128 (11) Å	T = 295 K
β = 91.850 (11)°	Irregular, brown
V = 787.59 (19) Å³	0.5 × 0.5 × 0.5 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	θ_max = 67.5°, θ_min = 4.3°
Nonprofiled ω/2θ scans	h = −12→12
5405 measured reflections	k = −11→11
1419 independent reflections	l = −9→9
1386 reflections with I > 2σ(I)	3 standard reflections every 60 min
R_int = 0.038	intensity decay: none

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0449P)² + 0.2879P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.039	(Δ/σ)_max < 0.001
wR(F²) = 0.100	Δρ_max = 0.25 e Å⁻³
S = 1.08	Δρ_min = −0.19 e Å⁻³
1419 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
112 parameters	Extinction coefficient: 0.025 (2)
0 restraints

Crystal data top

C₁₀H₁₂O₂	V = 787.59 (19) Å³
M_r = 164.2	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.3730 (14) Å	µ = 0.77 mm⁻¹
b = 9.8494 (14) Å	T = 295 K
c = 7.7128 (11) Å	0.5 × 0.5 × 0.5 mm
β = 91.850 (11)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.038
5405 measured reflections	3 standard reflections every 60 min
1419 independent reflections	intensity decay: none
1386 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.08	Δρ_max = 0.25 e Å⁻³
1419 reflections	Δρ_min = −0.19 e Å⁻³
112 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.79276 (9)	0.37798 (11)	−0.08942 (13)	0.0372 (3)
HO1	0.7463	0.3684	−0.1766	0.056*
O2	0.68564 (9)	0.15711 (10)	0.08353 (13)	0.0375 (3)
HO2	0.7252	0.2197	0.0396	0.056*
C10	0.44926 (13)	0.09207 (14)	0.11758 (19)	0.0306 (3)
H10	0.4357	0.1453	0.2228	0.037*
C2	0.96268 (12)	0.55937 (14)	−0.15964 (18)	0.0301 (3)
H2	0.9118	0.607	−0.2501	0.036*
C7	0.53244 (12)	0.06358 (14)	−0.15675 (17)	0.0296 (3)
H7	0.5816	0.0942	−0.2559	0.036*
C5	1.03469 (12)	0.36341 (14)	−0.01805 (19)	0.0309 (3)
H5	1.0383	0.2646	−0.0035	0.037*
C1	0.92078 (12)	0.40891 (14)	−0.13877 (18)	0.0307 (3)
H1	0.9328	0.3648	−0.251	0.037*
C6	0.55870 (13)	0.15044 (13)	0.00772 (18)	0.0295 (3)
H6	0.5339	0.2437	−0.0224	0.035*
C3	1.09864 (13)	0.52746 (16)	−0.21451 (18)	0.0352 (4)
H3	1.1454	0.5778	−0.2928	0.042*
C8	0.39004 (13)	0.09802 (14)	−0.1751 (2)	0.0342 (4)
H8	0.3435	0.1069	−0.2796	0.041*
C9	0.34268 (13)	0.11333 (14)	−0.0195 (2)	0.0352 (4)
H9	0.2573	0.1339	0.0027	0.042*
C4	1.13997 (13)	0.41653 (15)	−0.1333 (2)	0.0363 (4)
H4	1.2207	0.3772	−0.1448	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0281 (5)	0.0435 (6)	0.0395 (6)	−0.0110 (4)	−0.0058 (4)	0.0054 (5)
O2	0.0326 (6)	0.0343 (6)	0.0447 (6)	−0.0107 (4)	−0.0120 (4)	0.0087 (4)
C10	0.0302 (7)	0.0286 (7)	0.0332 (7)	0.0013 (5)	0.0017 (5)	−0.0035 (5)
C2	0.0264 (7)	0.0336 (7)	0.0301 (7)	−0.0008 (5)	−0.0023 (5)	0.0079 (6)
C7	0.0291 (7)	0.0315 (7)	0.0281 (7)	−0.0037 (5)	−0.0017 (5)	0.0057 (5)
C5	0.0278 (7)	0.0246 (6)	0.0403 (8)	0.0030 (5)	0.0023 (6)	0.0017 (6)
C1	0.0276 (7)	0.0332 (7)	0.0312 (7)	−0.0041 (5)	0.0004 (5)	−0.0012 (6)
C6	0.0285 (7)	0.0241 (6)	0.0353 (8)	−0.0024 (5)	−0.0060 (5)	0.0037 (5)
C3	0.0311 (7)	0.0438 (8)	0.0310 (7)	−0.0054 (6)	0.0067 (6)	0.0003 (6)
C8	0.0313 (7)	0.0279 (7)	0.0424 (8)	−0.0039 (6)	−0.0124 (6)	0.0100 (6)
C9	0.0253 (7)	0.0271 (7)	0.0530 (9)	0.0041 (5)	−0.0012 (6)	0.0042 (6)
C4	0.0278 (7)	0.0405 (8)	0.0411 (8)	0.0040 (6)	0.0075 (6)	−0.0050 (6)

Geometric parameters (Å, º) top

O1—C1	1.4261 (16)	C7—H7	0.98
O1—HO1	0.82	C5—C4	1.5227 (18)
O2—C6	1.4248 (16)	C5—C1	1.5469 (19)
O2—HO2	0.82	C5—C2ⁱⁱ	1.567 (2)
C10—C9	1.520 (2)	C5—H5	0.98
C10—C6	1.5490 (18)	C1—H1	0.98
C10—C7ⁱ	1.5728 (18)	C6—H6	0.98
C10—H10	0.98	C3—C4	1.324 (2)
C2—C3	1.5183 (18)	C3—H3	0.93
C2—C1	1.5542 (19)	C8—C9	1.320 (2)
C2—C5ⁱⁱ	1.567 (2)	C8—H8	0.93
C2—H2	0.98	C9—H9	0.93
C7—C8	1.5178 (18)	C4—H4	0.93
C7—C6	1.5469 (19)

C1—O1—HO1	109.5	C2ⁱⁱ—C5—H5	112.5
C6—O2—HO2	109.5	O1—C1—C5	118.51 (12)
C9—C10—C6	95.61 (11)	O1—C1—C2	119.82 (11)
C9—C10—C7ⁱ	110.40 (11)	C5—C1—C2	97.34 (10)
C6—C10—C7ⁱ	112.38 (11)	O1—C1—H1	106.7
C9—C10—H10	112.4	C5—C1—H1	106.7
C6—C10—H10	112.4	C2—C1—H1	106.7
C7ⁱ—C10—H10	112.4	O2—C6—C7	119.86 (11)
C3—C2—C1	95.56 (11)	O2—C6—C10	118.46 (11)
C3—C2—C5ⁱⁱ	110.74 (11)	C7—C6—C10	97.50 (10)
C1—C2—C5ⁱⁱ	111.67 (11)	O2—C6—H6	106.6
C3—C2—H2	112.6	C7—C6—H6	106.6
C1—C2—H2	112.6	C10—C6—H6	106.6
C5ⁱⁱ—C2—H2	112.6	C4—C3—C2	109.17 (12)
C8—C7—C6	95.63 (11)	C4—C3—H3	125.4
C8—C7—C10ⁱ	110.29 (11)	C2—C3—H3	125.4
C6—C7—C10ⁱ	111.38 (11)	C9—C8—C7	109.28 (12)
C8—C7—H7	112.8	C9—C8—H8	125.4
C6—C7—H7	112.8	C7—C8—H8	125.4
C10ⁱ—C7—H7	112.8	C8—C9—C10	109.46 (12)
C4—C5—C1	95.60 (11)	C8—C9—H9	125.3
C4—C5—C2ⁱⁱ	110.56 (11)	C10—C9—H9	125.3
C1—C5—C2ⁱⁱ	112.16 (11)	C3—C4—C5	109.41 (12)
C4—C5—H5	112.5	C3—C4—H4	125.3
C1—C5—H5	112.5	C5—C4—H4	125.3

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···O2ⁱⁱⁱ	0.82	1.95	2.7452 (15)	163
O2—HO2···O1	0.82	1.99	2.8005 (14)	170

Symmetry code: (iii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂O₂
M_r	164.2
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.3730 (14), 9.8494 (14), 7.7128 (11)
β (°)	91.850 (11)
V (Å³)	787.59 (19)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.5 × 0.5 × 0.5

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5405, 1419, 1386
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 1.08
No. of reflections	1419
No. of parameters	112
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.19

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···O2ⁱ	0.82	1.95	2.7452 (15)	163
O2—HO2···O1	0.82	1.99	2.8005 (14)	170

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

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

Amman, W. & Ganter, C. (1977). Helv. Chim. Acta, 60, 1924–1925. CrossRef Web of Science Google Scholar
Amman, W. & Ganter, C. (1981). Helv. Chim. Acta, 65, 966–1022. Google Scholar
Amman, W., Jäggi, F. J. & Ganter, C. (1980). Helv. Chim. Acta, 63, 2019–2041. CrossRef Web of Science Google Scholar
Baggiolini, E., Herzog, E. G., Iwaski, S., Schorta, R. & Schaffner, K. (1967). Helv. Chim. Acta, 50, 297–306. CrossRef CAS Web of Science Google Scholar
Eaton, P. E., Tang, D. & Gilardi, R. (2002). Tetrahedron Lett. 43, 3–5. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Herzog, E. G. (1958). PhD thesis, ETH Zürich, Switzerland. Google Scholar
Klinsmann, U., Gauthier, J., Schaffner, K., Pasternak, M. & Fuchs, B. (1972). Helv. Chim. Acta, 55, 2643–2659. CrossRef CAS Web of Science Google Scholar
Prakash, G. K. S., Farnia, M., Keyanian, S., Olah, G. A., Kuhn, H. J. & Schaffner, K. (1987). J. Am. Chem. Soc. 109, 911–912. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar