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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o841.
Published online 2008 April 16. doi:  10.1107/S1600536808009677
PMCID: PMC2961091

8-Methyl-5-methyl­ene-2-oxotricyclo[5.3.1.13,9]dodecan-endo-8-ol

Abstract

The title compound, C14H20O2, crystallizes with homochiral chains of mol­ecules hydrogen bonded together along the b axis. Adjacent chains in the ab plane contain mol­ecules of the same chirality, leading to a chiral segregation of the mol­ecules into layers.

Related literature

For related literature, see: Yue et al. (2002 [triangle], 2006 [triangle], 2007 [triangle], 1997 [triangle], 2000 [triangle]).

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Object name is e-64-0o841-scheme1.jpg

Experimental

Crystal data

  • C14H20O2
  • M r = 220.3
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o841-efi1.jpg
  • a = 7.554 (3) Å
  • b = 13.196 (3) Å
  • c = 12.597 (5) Å
  • β = 108.16 (2)°
  • V = 1193.2 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 294 K
  • 0.25 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 2247 measured reflections
  • 2079 independent reflections
  • 1296 reflections with I > 2σ(I)
  • R int = 0.016
  • 1 standard reflection frequency: 30 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.052
  • S = 1.27
  • 2079 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: RAELS (Rae, 2000 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]) and CrystalMaker (Palmer, 2005 [triangle]); software used to prepare material for publication: local programs.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009677/hg2391sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009677/hg2391Isup2.hkl

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

Acknowledgments

This research was supported by the Australian Research Council and the Shanghai Pujiang Program (WY).

supplementary crystallographic information

Comment

The preparation of this compound is part of a project involving alicyclic diols (Yue et al. 2002, 2006, 2007). The title compound (Fig. 1) crystallizes in space group P21/c with homochiral chains of molecules along b which are held together by O—H···O═C hydrogen bonding. Adjacent chains along a are of the same chirality, leading to chirally pure layers within the crystal which are shaded light and dark in Fig. 2. It is unusual to observe chirally pure layers within a centrosymmetric lattice. In this case the layer is generated by a combination of the 21 screw axis along b and translation along the short a axis, neither of which generates a change in chirality.

Experimental

5-Methylidenetricyclo[5.3.1.13,9]dodecane-2,8-dione (Yue et al., 1997, 2000) was reacted with ca 1 equivalent of methyllithium in tetrahydrofuran solution. After standard work up of the reaction, the crude solid product was recrystallized to afford the title compound of m.p. 105–107°C. 13C NMR (75.5 MHz, CDCl3) δ: 28.1 (CH2), 30.9 (CH2), 31.9 (CH3), 34.7 (CH2), 38.6 (CH2), 38.8 (CH), 40.6 (CH), 42.7 (CH), 43.3 (CH), 45.3 (CH2), 74.8 (C), 119.3 (CH2), 148.2 (C), 219.9 (C). 1H NMR (300 MHz, CDCl3) δ: 1.44 (s, 3H), 1.83–1.98 (m, 4H), 2.01–2.21 (m, 4H), 2.29–2.47 (m, 4H), 2.66–2.76 (m, 2H), 2.99 (dd, J = 14.3, 7.1 Hz, 1H), 4.94 (d, J = 15.1 Hz, 2H). X-ray quality crystals were obtained from diethyl ether solution.

Refinement

Hydrogen atoms attached to C were included at calculated positions (C—H = 1.0 Å). The hydroxy hydrogen atom was located on a difference map, and was then fixed at a position along the O···O vector with O—H = 1.0 Å. All hydrogen atoms were refined with isotropic thermal parameters equivalent to those of the atom to which they were bonded.

Figures

Fig. 1.
Molecular structure of the compound, with ellipsoids drawn at 30% probability level.
Fig. 2.
Unit cell diagram showing the O—H···O═C hydrogen bonded chain along b. Adjacent layers along c are chirally pure with alternating chirality. This is indicated by light and dark shading of C atoms.

Crystal data

C14H20O2F000 = 480.0
Mr = 220.3Dx = 1.23 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
a = 7.554 (3) ÅCell parameters from 11 reflections
b = 13.196 (3) Åθ = 10–11º
c = 12.597 (5) ŵ = 0.08 mm1
β = 108.16 (2)ºT = 294 K
V = 1193.2 (7) Å3Block, colourless
Z = 40.25 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometerθmax = 25º
ω/2θ scansh = 0→8
Absorption correction: nonek = 0→15
2247 measured reflectionsl = −15→15
2079 independent reflections1 standard reflections
1296 reflections with I > 2σ(I) every 30 min
Rint = 0.016 intensity decay: none

Refinement

Refinement on FH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.049  w = 1/[σ2(F) + 0.0004F2]
wR(F2) = 0.052(Δ/σ)max = 0.003
S = 1.27Δρmax = 0.28 e Å3
2079 reflectionsΔρmin = −0.28 e Å3
145 parametersExtinction correction: none

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

xyzUiso*/Ueq
O10.5397 (2)0.2837 (1)0.1016 (1)0.0557 (5)
O20.6667 (2)−0.0303 (1)0.4412 (1)0.0595 (5)
C10.4341 (3)0.2236 (2)0.2535 (2)0.0417 (6)
C20.4327 (3)0.2060 (2)0.1324 (2)0.0416 (6)
C30.5169 (3)0.1035 (2)0.1158 (2)0.0429 (6)
C40.4404 (3)0.0172 (2)0.1708 (2)0.0447 (6)
C50.4266 (3)0.0387 (2)0.2886 (2)0.0438 (6)
C60.6110 (3)0.0420 (2)0.3790 (2)0.0426 (6)
C70.7296 (3)0.1362 (2)0.3922 (2)0.0430 (6)
C80.6271 (3)0.2343 (2)0.3406 (2)0.0452 (6)
C90.3273 (3)0.1393 (2)0.2908 (2)0.0477 (6)
C100.7322 (3)0.1007 (2)0.1397 (2)0.0522 (6)
C110.8518 (3)0.0511 (2)0.2448 (2)0.0498 (6)
C120.8989 (3)0.1092 (2)0.3527 (2)0.0535 (6)
C130.9221 (4)−0.0409 (2)0.2436 (2)0.0705 (8)
C140.2323 (4)0.2130 (2)0.0531 (2)0.0609 (7)
H1O10.46770.34860.08660.056
HC10.36550.28830.25420.042
HC30.46430.09000.03380.043
H1C40.5236−0.04290.17660.045
H2C40.31240.00050.12080.045
HC50.3507−0.01650.30740.044
HC70.78110.14890.47440.043
H1C80.70850.27100.30410.045
H2C80.61190.27640.40330.045
H1C90.19690.13580.23870.048
H2C90.32470.15340.36820.048
H1C100.77510.17260.14140.052
H2C100.75580.06450.07570.052
H1C120.96120.17380.34280.054
H2C120.98720.06730.41220.054
H1C130.8958−0.07870.17150.071
H2C131.0014−0.07240.31470.071
H1C140.15440.15940.07280.061
H2C140.17980.28120.06040.061
H3C140.23210.2029−0.02560.061

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.080 (1)0.0411 (9)0.0500 (9)−0.0072 (8)0.0264 (9)0.0068 (7)
O20.071 (1)0.050 (1)0.051 (1)0.0052 (9)0.0098 (9)0.0139 (8)
C10.047 (1)0.037 (1)0.041 (1)0.005 (1)0.014 (1)0.000 (1)
C20.052 (2)0.034 (1)0.038 (1)−0.003 (1)0.013 (1)0.001 (1)
C30.054 (1)0.040 (1)0.033 (1)−0.004 (1)0.010 (1)−0.006 (1)
C40.049 (2)0.038 (1)0.041 (1)−0.005 (1)0.005 (1)−0.003 (1)
C50.044 (1)0.042 (1)0.045 (1)−0.005 (1)0.014 (1)0.007 (1)
C60.052 (2)0.044 (1)0.034 (1)0.002 (1)0.018 (1)0.002 (1)
C70.048 (1)0.046 (1)0.031 (1)−0.002 (1)0.008 (1)−0.005 (1)
C80.059 (2)0.038 (1)0.038 (1)−0.003 (1)0.014 (1)−0.006 (1)
C90.048 (1)0.052 (1)0.045 (1)0.001 (1)0.018 (1)0.004 (1)
C100.062 (2)0.055 (2)0.045 (1)−0.002 (1)0.024 (1)−0.007 (1)
C110.041 (1)0.051 (1)0.059 (2)−0.003 (1)0.019 (1)−0.006 (1)
C120.045 (1)0.059 (2)0.052 (1)−0.002 (1)0.008 (1)−0.008 (1)
C130.059 (2)0.060 (2)0.090 (2)0.005 (1)0.019 (2)−0.008 (2)
C140.064 (2)0.058 (2)0.050 (1)0.004 (1)0.002 (1)0.008 (1)

Geometric parameters (Å, °)

O1—C21.432 (2)C7—C81.544 (3)
O1—H1O11.000C7—C121.551 (3)
O2—C61.223 (2)C7—HC71.000
C1—C21.540 (3)C8—H1C81.000
C1—C81.534 (3)C8—H2C81.000
C1—C91.531 (3)C9—H1C91.000
C1—HC11.000C9—H2C91.000
C2—C31.536 (3)C10—C111.501 (3)
C2—C141.535 (3)C10—H1C101.000
C3—C41.536 (3)C10—H2C101.000
C3—C101.560 (3)C11—C121.503 (3)
C3—HC31.000C11—C131.327 (3)
C4—C51.546 (3)C12—H1C121.000
C4—H1C41.000C12—H2C121.000
C4—H2C41.000C13—H1C131.000
C5—C61.500 (3)C13—H2C131.000
C5—C91.529 (3)C14—H1C141.000
C5—HC51.000C14—H2C141.000
C6—C71.511 (3)C14—H3C141.000
C2—O1—H1O1110.1C8—C7—HC7106.1
C2—C1—C8115.7 (2)C12—C7—HC7106.1
C2—C1—C9110.7 (2)C1—C8—C7117.6 (2)
C2—C1—HC1107.1C1—C8—H1C8107.4
C8—C1—C9108.7 (2)C1—C8—H2C8107.4
C8—C1—HC1107.1C7—C8—H1C8107.4
C9—C1—HC1107.1C7—C8—H2C8107.4
O1—C2—C1109.3 (2)H1C8—C8—H2C8109.5
O1—C2—C3107.5 (2)C1—C9—C5108.5 (2)
O1—C2—C14107.8 (2)C1—C9—H1C9109.7
C1—C2—C3113.1 (2)C1—C9—H2C9109.7
C1—C2—C14109.6 (2)C5—C9—H1C9109.7
C3—C2—C14109.3 (2)C5—C9—H2C9109.7
C2—C3—C4111.2 (2)H1C9—C9—H2C9109.5
C2—C3—C10116.5 (2)C3—C10—C11119.0 (2)
C2—C3—HC3104.4C3—C10—H1C10107.0
C4—C3—C10114.3 (2)C3—C10—H2C10107.0
C4—C3—HC3104.4C11—C10—H1C10107.0
C10—C3—HC3104.4C11—C10—H2C10107.0
C3—C4—C5116.3 (2)H1C10—C10—H2C10109.5
C3—C4—H1C4107.7C10—C11—C12118.8 (2)
C3—C4—H2C4107.7C10—C11—C13121.5 (2)
C5—C4—H1C4107.7C12—C11—C13119.6 (2)
C5—C4—H2C4107.7C7—C12—C11114.9 (2)
H1C4—C4—H2C4109.5C7—C12—H1C12108.1
C4—C5—C6114.2 (2)C7—C12—H2C12108.1
C4—C5—C9110.9 (2)C11—C12—H1C12108.1
C4—C5—HC5107.9C11—C12—H2C12108.1
C6—C5—C9107.8 (2)H1C12—C12—H2C12109.5
C6—C5—HC5107.9C11—C13—H1C13120.0
C9—C5—HC5107.9C11—C13—H2C13120.0
O2—C6—C5121.1 (2)H1C13—C13—H2C13120.0
O2—C6—C7119.9 (2)C2—C14—H1C14109.5
C5—C6—C7119.1 (2)C2—C14—H2C14109.5
C6—C7—C8116.2 (2)C2—C14—H3C14109.5
C6—C7—C12107.2 (2)H1C14—C14—H2C14109.5
C6—C7—HC7106.1H1C14—C14—H3C14109.5
C8—C7—C12114.4 (2)H2C14—C14—H3C14109.5
H1O1—O1—C2—C1−75.5HC3—C3—C10—H2C10−18.6
H1O1—O1—C2—C3161.4C3—C4—C5—C6−72.0 (2)
H1O1—O1—C2—C1443.6C3—C4—C5—C950.0 (2)
C8—C1—C2—O1−53.4 (2)C3—C4—C5—HC5168.0
C8—C1—C2—C366.3 (2)H1C4—C4—C5—C649.0
C8—C1—C2—C14−171.4 (2)H1C4—C4—C5—C9171.0
C9—C1—C2—O1−177.7 (2)H1C4—C4—C5—HC5−71.0
C9—C1—C2—C3−58.0 (2)H2C4—C4—C5—C6167.0
C9—C1—C2—C1464.3 (2)H2C4—C4—C5—C9−71.0
HC1—C1—C2—O165.9H2C4—C4—C5—HC547.0
HC1—C1—C2—C3−174.4C4—C5—C6—O2−100.9 (2)
HC1—C1—C2—C14−52.1C4—C5—C6—C778.6 (2)
C2—C1—C8—C7−85.4 (2)C9—C5—C6—O2135.4 (2)
C2—C1—C8—H1C835.7C9—C5—C6—C7−45.1 (2)
C2—C1—C8—H2C8153.4HC5—C5—C6—O219.1
C9—C1—C8—C739.9 (2)HC5—C5—C6—C7−161.4
C9—C1—C8—H1C8161.0C4—C5—C9—C1−57.7 (2)
C9—C1—C8—H2C8−81.3C4—C5—C9—H1C962.2
HC1—C1—C8—C7155.3C4—C5—C9—H2C9−177.5
HC1—C1—C8—H1C8−83.6C6—C5—C9—C168.0 (2)
HC1—C1—C8—H2C834.1C6—C5—C9—H1C9−172.2
C2—C1—C9—C562.6 (2)C6—C5—C9—H2C9−51.9
C2—C1—C9—H1C9−57.2HC5—C5—C9—C1−175.7
C2—C1—C9—H2C9−177.5HC5—C5—C9—H1C9−55.8
C8—C1—C9—C5−65.6 (2)HC5—C5—C9—H2C964.5
C8—C1—C9—H1C9174.6O2—C6—C7—C8−160.0 (2)
C8—C1—C9—H2C954.3O2—C6—C7—C1270.7 (2)
HC1—C1—C9—C5179.0O2—C6—C7—HC7−42.4
HC1—C1—C9—H1C959.2C5—C6—C7—C820.5 (3)
HC1—C1—C9—H2C9−61.1C5—C6—C7—C12−108.8 (2)
O1—C2—C3—C4167.3 (2)C5—C6—C7—HC7138.1
O1—C2—C3—C1034.0 (2)C6—C7—C8—C1−17.6 (3)
O1—C2—C3—HC3−80.6C6—C7—C8—H1C8−138.8
C1—C2—C3—C446.6 (2)C6—C7—C8—H2C8103.6
C1—C2—C3—C10−86.8 (2)C12—C7—C8—C1108.2 (2)
C1—C2—C3—HC3158.7C12—C7—C8—H1C8−13.0
C14—C2—C3—C4−75.8 (2)C12—C7—C8—H2C8−130.7
C14—C2—C3—C10150.8 (2)HC7—C7—C8—C1−135.2
C14—C2—C3—HC336.2HC7—C7—C8—H1C8103.6
O1—C2—C14—H1C14180.0HC7—C7—C8—H2C8−14.0
O1—C2—C14—H2C14−60.0C6—C7—C12—C1145.4 (2)
O1—C2—C14—H3C1460.0C6—C7—C12—H1C12166.2
C1—C2—C14—H1C14−61.1C6—C7—C12—H2C12−75.4
C1—C2—C14—H2C1458.9C8—C7—C12—C11−84.9 (2)
C1—C2—C14—H3C14178.9C8—C7—C12—H1C1235.9
C3—C2—C14—H1C1463.4C8—C7—C12—H2C12154.3
C3—C2—C14—H2C14−176.6HC7—C7—C12—C11158.4
C3—C2—C14—H3C14−56.6HC7—C7—C12—H1C12−80.8
C2—C3—C4—C5−43.4 (2)HC7—C7—C12—H2C1237.6
C2—C3—C4—H1C4−164.4C3—C10—C11—C12−80.0 (3)
C2—C3—C4—H2C477.6C3—C10—C11—C13102.6 (3)
C10—C3—C4—C591.0 (2)H1C10—C10—C11—C1241.4
C10—C3—C4—H1C4−30.0H1C10—C10—C11—C13−136.0
C10—C3—C4—H2C4−148.0H2C10—C10—C11—C12158.7
HC3—C3—C4—C5−155.5H2C10—C10—C11—C13−18.7
HC3—C3—C4—H1C483.5C10—C11—C12—C763.8 (3)
HC3—C3—C4—H2C4−34.5C10—C11—C12—H1C12−57.0
C2—C3—C10—C11105.5 (2)C10—C11—C12—H2C12−175.4
C2—C3—C10—H1C10−15.8C13—C11—C12—C7−118.7 (2)
C2—C3—C10—H2C10−133.1C13—C11—C12—H1C12120.5
C4—C3—C10—C11−26.4 (3)C13—C11—C12—H2C122.1
C4—C3—C10—H1C10−147.8C10—C11—C13—H1C130.0
C4—C3—C10—H2C1094.9C10—C11—C13—H2C13−180.0
HC3—C3—C10—C11−139.9C12—C11—C13—H1C13−177.4
HC3—C3—C10—H1C1098.7C12—C11—C13—H2C132.6

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O1···O2i1.001.872.867 (4)180

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2391).

References

  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Johnson, C. K. (1976). ORTEPII Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
  • Palmer, D. (2005). CrystalMaker CrystalMaker Software Ltd, Yarnton, Oxfordshire, England. http://www.CrystalMakerco.uk.
  • Rae, A. D. (2000). RAELS. Australian National University, Canberra, Australia.
  • Yue, W., Bishop, R., Craig, D. C. & Scudder, M. L. (2000). Tetrahedron, 56, 6667–6673.
  • Yue, W., Bishop, R., Craig, D. C. & Scudder, M. L. (2002). CrystEngComm, 4, 591–595.
  • Yue, W., Bishop, R., Craig, D. C. & Scudder, M. L. (2007). Acta Cryst. E63, o4689.
  • Yue, W., Bishop, R., Scudder, M. L. & Craig, D. C. (1997). J. Chem. Soc. Perkin Trans. 1, pp. 2937–2946.
  • Yue, W., Nakano, K., Bishop, R., Craig, D. C., Harris, K. D. M. & Scudder, M. L. (2006). CrystEngComm, 8, 250–256.

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