organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Penta­cyclo­[9.3.1.12,6.14,8.19,13]octa­deca-1(2),8(9)-diene

aChemistry Department, University of Cyprus, Nicosia 1678, Cyprus
*Correspondence e-mail: ioannou.savvas@ucy.ac.cy

(Received 9 May 2012; accepted 13 June 2012; online 20 June 2012)

The title compound, C18H24, was the main product of thermolysis of noradamantene dimer (hepta­cyclo­[9.3.1.12,6.14,8.19,13.01,9.02,8]octa­deca­ne). The crystal structure was determined to prove that the thermolysis product of noradamantene dimer is favored by stretch release due to ring opening of the four-membered ring. The bond length of the quaternary C atoms of the starting material was calculated as 1.6 Å, enlarged in comparison to other single bonds. After the rearrangement, the stretch release of the above carbons leads to an increase of the distance between them (2.824 Å) with respect to the crystallographic data.

Related literature

For reviews on noradamantene and analogous pyramidalized alkenes, see: Borden (1989[Borden, W. T. (1989). Chem. Rev. 89, 1095-1109.], 1996[Borden, W. T. (1996). Synlett, pp. 711-719.]); Vázquez & Camps (2005)[Vázquez, S. & Camps, P. (2005). Tetrahedron, 61, 5147-5208.]. For the syntheses of noradamantene dimer, see: Renzoni et al. (1986)[Renzoni, G. E., Yin, T. & Borden, W. T. (1986). J. Am. Chem. Soc. 108, 7121-7122.] and for related analogs, see: Camps et al. (1996a[Camps, P., Font-Bardia, M., Perez, F., Sola, L., Solans, X. & Vazquez, S. (1996a). Tetrahedron Lett. 37, 8601-8604.],b[Camps, P., Luque, F. J., Orozco, M., Perez, F. & Vazquez, S. (1996b). Tetrahedron Lett. 37, 8605-8608.]). For the synthesis of the precursor diiodide (3,7-diiodo-tricyclo-[3.3.1.03,7]nona­ne), an important inter­mediate in the synthetic route towards the generation of noradamantene, see: Ioannou & Nicolaides (2009[Ioannou, S. & Nicolaides, A. V. (2009). Tetrahedron Lett. 50, 6938-6940.]). For the synthesis of [2]diadamantane, see: McKervey (1980[McKervey, M. A. (1980). Tetrahedron, 36, 971-992.]); Graham et al. (1973[Graham, W. D., Schleyer, P., v, R., Hagaman, E. W. & Wenkert, E. (1973). J. Am. Chem. Soc. 95, 5785-5786.]).

[Scheme 1]

Experimental

Crystal data
  • C18H24

  • Mr = 240.37

  • Orthorhombic, C c m b

  • a = 8.5855 (6) Å

  • b = 15.6618 (10) Å

  • c = 9.3156 (6) Å

  • V = 1252.62 (14) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 100 K

  • 0.15 × 0.07 × 0.04 mm

Data collection
  • Oxford Diffraction SuperNova Dual (Cu) Atlas diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]) Tmin = 0.530, Tmax = 1.000

  • 2341 measured reflections

  • 640 independent reflections

  • 514 reflections with I > 2σ(I)

  • Rint = 0.033

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.117

  • S = 1.06

  • 640 reflections

  • 62 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.44 e Å−3

  • Δρmin = −0.16 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and publCIF (Westrip (2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Pyramidalized alkenes is a special category of olefins which have their four substituents of the double bond not lying on the same plane (Borden 1989, 1996, Vázquez & Camps, 2005). This fact makes the higher pyramidalized alkenes (like noradamantene) very reactive and impossible to isolate at ambient conditions. Due to their high reactivity, once they form, they react instantly with any nucleophile. In the absence of any reactive compound during their formation, the most common product is their [2 + 2] dimer. Noradamantene (n=1) is the second member of a homologous series of this category (figure 3) and it can serve as a building block for the formation of larger polycyclic hydrocarbons like the title compound. The most pyramidallized alkene (n=0) of the same homologous series is rearranged spontaneously to the corresponding diene once the dimer is formed (Camps et al. 1996a,b) (figure 3). This is attributed to its grater stretch due to the smaller carbon side chain. The title compound is the main product of thermolysis of noradamantene dimer and its formation depends on the reaction conditions. At different reaction conditions (higher temperatures, reaction time) [2]diadamantane (McKervey 1980, Graham et al. 1973) and another asymmetric diene were identified among the products.

Related literature top

For reviews on noradamantene and analogous pyramidalized alkenes, see: Borden (1989, 1996); Vázquez & Camps (2005). For the syntheses of noradamantene dimer, see: Renzoni et al. (1986) and for related analogs, see: Camps et al. (1996a,b). For the synthesis of the precursor diiodide (3,7-diiodo-tricyclo-[3.3.1.03,7]nonane), an important intermediate in the synthetic route towards the generation of noradamantene, see: Ioannou & Nicolaides (2009). For the synthesis of [2]diadamantane, see: McKervey (1980); Graham et al. (1973).

Experimental top

Synthesis of pentacyclo [9.3.1.12,6.14,8.19,13] octadeca-di-1(2),8(9)-ene. Heptacyclo [9.3.1.12,6.14,8.19,13.01,9.02,8] octadecane(10 mg,0.042 mmol) was placed in a cylindrical glass container with small diameter (~5 mm suitable for glass workshops) sealed at the bottom edge, while the other edge was connected at the vacuum line. The glass cylinder was washed three times with argon and placed under vacuum for 5 minutes after which the opened edge was sealed as well with the use of a flamethrower, encapsulating the reactant under vacuum. The capsule was placed in a controlled temperature oven at 350 oC for 5 minutes. Crystals of the product and the reactant were formed when the capsule cooled down to room temperature. The starting material was removed by breaking carefully the glass of the one edge and washing the solid with hexane 3x1 ml. The residue was mostly product which was recrystallized by sealing the capsule again under vacuum and reheating it at 350°C for another 5 minutes. Colorless crystals of pure product were formed when the capsule cooled down to room temperature.

Refinement top

The H atoms are positioned with idealized geometry and refined using a riding model with Uiso(H) = 1.2 of Ueq (C).

Structure description top

Pyramidalized alkenes is a special category of olefins which have their four substituents of the double bond not lying on the same plane (Borden 1989, 1996, Vázquez & Camps, 2005). This fact makes the higher pyramidalized alkenes (like noradamantene) very reactive and impossible to isolate at ambient conditions. Due to their high reactivity, once they form, they react instantly with any nucleophile. In the absence of any reactive compound during their formation, the most common product is their [2 + 2] dimer. Noradamantene (n=1) is the second member of a homologous series of this category (figure 3) and it can serve as a building block for the formation of larger polycyclic hydrocarbons like the title compound. The most pyramidallized alkene (n=0) of the same homologous series is rearranged spontaneously to the corresponding diene once the dimer is formed (Camps et al. 1996a,b) (figure 3). This is attributed to its grater stretch due to the smaller carbon side chain. The title compound is the main product of thermolysis of noradamantene dimer and its formation depends on the reaction conditions. At different reaction conditions (higher temperatures, reaction time) [2]diadamantane (McKervey 1980, Graham et al. 1973) and another asymmetric diene were identified among the products.

For reviews on noradamantene and analogous pyramidalized alkenes, see: Borden (1989, 1996); Vázquez & Camps (2005). For the syntheses of noradamantene dimer, see: Renzoni et al. (1986) and for related analogs, see: Camps et al. (1996a,b). For the synthesis of the precursor diiodide (3,7-diiodo-tricyclo-[3.3.1.03,7]nonane), an important intermediate in the synthetic route towards the generation of noradamantene, see: Ioannou & Nicolaides (2009). For the synthesis of [2]diadamantane, see: McKervey (1980); Graham et al. (1973).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip (2010).

Figures top
[Figure 1] Fig. 1. Structure of the title compound pentacyclo [9.3.1.12,6.14,8.19,13] octadeca-di-1(2),8(9)-ene with the atom-labelling. Displacement elipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing of the title compound, viewed along [1 0 0].
[Figure 3] Fig. 3. Dimer rearrangement of the two first members of a homologous series of pyramidalized alkenes.
[Figure 4] Fig. 4. The formation of the title compound.
Pentacyclo[9.3.1.12,6.14,8.19,13]octadeca-1(2),8(9)-diene top
Crystal data top
C18H24F(000) = 528
Mr = 240.37Dx = 1.275 Mg m3
Orthorhombic, CcmbMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2bcCell parameters from 1022 reflections
a = 8.5855 (6) Åθ = 3.4–28.9°
b = 15.6618 (10) ŵ = 0.07 mm1
c = 9.3156 (6) ÅT = 100 K
V = 1252.62 (14) Å3Polyhedral, colorless
Z = 40.15 × 0.07 × 0.04 mm
Data collection top
Oxford Diffraction SuperNova Dual (Cu) Atlas
diffractometer
640 independent reflections
Radiation source: SuperNova (Mo) X-ray Source514 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.033
Detector resolution: 10.4223 pixels mm-1θmax = 26.0°, θmin = 3.5°
ω scansh = 109
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 1918
Tmin = 0.530, Tmax = 1.000l = 118
2341 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0549P)2 + 0.8624P]
where P = (Fo2 + 2Fc2)/3
640 reflections(Δ/σ)max < 0.001
62 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C18H24V = 1252.62 (14) Å3
Mr = 240.37Z = 4
Orthorhombic, CcmbMo Kα radiation
a = 8.5855 (6) ŵ = 0.07 mm1
b = 15.6618 (10) ÅT = 100 K
c = 9.3156 (6) Å0.15 × 0.07 × 0.04 mm
Data collection top
Oxford Diffraction SuperNova Dual (Cu) Atlas
diffractometer
640 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
514 reflections with I > 2σ(I)
Tmin = 0.530, Tmax = 1.000Rint = 0.033
2341 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.44 e Å3
640 reflectionsΔρmin = 0.16 e Å3
62 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.

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 > σ(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*/UeqOcc. (<1)
C10.11524 (14)0.04287 (9)0.10813 (13)0.0158 (4)
C20.00121 (16)0.09715 (9)0.19231 (15)0.0180 (4)
C30.20910 (17)0.09726 (9)0.00491 (15)0.0178 (4)
C40.10310 (16)0.15159 (9)0.09316 (15)0.0177 (4)
C50.00000.20830 (13)0.00000.0190 (5)
H5A0.06410.24460.06030.023*0.50
H5B0.06410.24460.06030.023*0.50
H2A0.0646 (17)0.0622 (11)0.2559 (18)0.024 (4)*
H2B0.0618 (18)0.1376 (11)0.256 (2)0.032 (4)*
H3A0.2779 (19)0.1360 (11)0.0608 (17)0.028 (4)*
H3B0.2842 (18)0.0618 (11)0.0514 (15)0.023 (4)*
H40.1732 (16)0.1880 (9)0.1554 (15)0.012 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0144 (7)0.0184 (7)0.0147 (7)0.0009 (5)0.0028 (5)0.0008 (6)
C20.0205 (8)0.0174 (8)0.0161 (7)0.0012 (6)0.0007 (6)0.0008 (6)
C30.0162 (7)0.0180 (8)0.0192 (8)0.0013 (6)0.0001 (6)0.0012 (6)
C40.0192 (7)0.0140 (7)0.0201 (7)0.0025 (5)0.0002 (6)0.0043 (6)
C50.0223 (10)0.0120 (10)0.0228 (10)0.0000.0051 (8)0.000
Geometric parameters (Å, º) top
C1—C1i1.343 (3)C3—H3B1.000 (16)
C1—C21.5153 (18)C4—C51.5250 (17)
C1—C31.5164 (18)C4—C3ii1.5450 (19)
C2—C41.5434 (18)C4—H41.012 (14)
C2—H2A0.984 (17)C5—C4ii1.5250 (17)
C2—H2B1.009 (18)C5—H5A0.9700
C3—C4ii1.5450 (19)C5—H5B0.9700
C3—H3A0.994 (17)
C1i—C1—C2124.13 (7)H3A—C3—H3B103.3 (13)
C1i—C1—C3124.17 (7)C5—C4—C2109.00 (11)
C2—C1—C3110.88 (11)C5—C4—C3ii109.04 (11)
C1—C2—C4112.03 (11)C2—C4—C3ii113.04 (11)
C1—C2—H2A111.7 (10)C5—C4—H4110.1 (8)
C4—C2—H2A109.5 (9)C2—C4—H4108.3 (8)
C1—C2—H2B108.7 (9)C3ii—C4—H4107.4 (8)
C4—C2—H2B107.6 (10)C4—C5—C4ii108.75 (15)
H2A—C2—H2B107.0 (15)C4—C5—H5A109.9
C1—C3—C4ii111.80 (11)C4ii—C5—H5A109.9
C1—C3—H3A109.1 (9)C4—C5—H5B109.9
C4ii—C3—H3A108.9 (9)C4ii—C5—H5B109.9
C1—C3—H3B111.3 (9)H5A—C5—H5B108.3
C4ii—C3—H3B112.1 (9)
Symmetry codes: (i) x, y, z; (ii) x, y, z.

Experimental details

Crystal data
Chemical formulaC18H24
Mr240.37
Crystal system, space groupOrthorhombic, Ccmb
Temperature (K)100
a, b, c (Å)8.5855 (6), 15.6618 (10), 9.3156 (6)
V3)1252.62 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.15 × 0.07 × 0.04
Data collection
DiffractometerOxford Diffraction SuperNova Dual (Cu) Atlas
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.530, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2341, 640, 514
Rint0.033
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.117, 1.06
No. of reflections640
No. of parameters62
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.44, 0.16

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and publCIF (Westrip (2010).

 

Acknowledgements

We are grateful to the Research Promotion Foundation (IΠE) of Cyprus and the European Structural Funds for grant ANABAΘ/ΠAΓIO/0308/12 which allowed the purchase of the XRD instrument, NEKYΠ/0308/02 enabling the purchase of a 500 MHz NMR spectrometer, of the RSC journal archive and for access to Reaxys and financial support to SI (ΠENEK/ENIΣX/0308/01). Partial financial support (SI) was also provided by the SRP "Inter­esting Divalent Carbon Compounds" granted by UCY. The A. G. Leventis Foundation is gratefully acknowledged for a generous donation to the University of Cyprus enabling the purchase of the 300 MHz NMR spectrometer. Dr Athanassios Nicolaides and Dr Anastasios Tasiopoulosor are thanked for their illuminating comments.

References

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First citationBorden, W. T. (1996). Synlett, pp. 711–719.  CrossRef Google Scholar
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