PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1648.
Published online 2010 June 16. doi:  10.1107/S1600536810021951
PMCID: PMC3006803

Dispiro­[cyclo­propane-1,5′-endo-tricyclo­[5.2.1.02,6]deca-3,8-diene-10′,1′′-cyclo­propane]

Abstract

The title compound, C14H16, is built up from three five-membered rings. Two of the five-membered rings display an envelope conformation and the third one is almost planar (r.m.s. deviation = 0.014 Å).

Related literature

For the synthesis, see: Khusnutdinov et al. (1988 [triangle]); Wilcox et al. (1961 [triangle]). For related structures, see: Caira et al. (1995 [triangle]); Haumann et al. (1997 [triangle]); Brookings et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1648-scheme1.jpg

Experimental

Crystal data

  • C14H16
  • M r = 184.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1648-efi1.jpg
  • a = 6.4079 (5) Å
  • b = 8.6355 (8) Å
  • c = 10.7216 (10) Å
  • α = 68.488 (9)°
  • β = 81.625 (7)°
  • γ = 73.351 (8)°
  • V = 528.27 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 293 K
  • 0.23 × 0.22 × 0.21 mm

Data collection

  • Oxford Diffraction Xcalibur S diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 [triangle]) T min = 0.775, T max = 1
  • 3444 measured reflections
  • 2269 independent reflections
  • 1348 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.168
  • S = 0.99
  • 2269 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021951/gk2280sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021951/gk2280Isup2.hkl

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

Acknowledgments

The work was undertaken with financial support from the Polish State Committee of Scientific Research, grant No. NN204271535.

supplementary crystallographic information

Comment

The title compound (I) is a product of cyclodimerization of spiro[2.4]hepta-4,6-diene. After few weeks of storing of the starting diene at room temperature big crystals of (I) were isolated with relatively high yield. In contrast to previously reported method of synthesis of (I) (Khusnutdinov et al. 1988), we did not use the additional heating and the catalyst.

The X-ray crystallographic analysis confirms this proposed molecular structure (Fig. 1). The C14H16 is built up from three five-membered rings and two three-membered rings. The one of the five-membered rings (C2—C3—C4—C5—C6) is almost planar. The mean deviation of the five atoms C2, C3, C4, C5, C6 from their least-squares plane is 0.0136 Å. Additionally, the C5 atom is a junction between the five-membered ring and a cyclopropane ring. The dihedral angle between the central ring planes is 89.89 (2)°.

The second and third five-membered rings (C1—C2—C6—C7—C10 and C7—C8—C9—C1—C10) have an envelope conformation.The C10 atom is a junction with the second cyclopropane ring.

The typical C2=C3 and C6=C7 double bonds lengths 1.312 (3) Å, 1.309 (3) Å respectively suggest that the C2, C3, C6, C7 atoms are sp2 hybridized. The bond lengths and angles are within normal ranges (Brookings et al. 2001; Caira et al. 1995; Haumann et al. 1997).

Experimental

Spiro[2.4]hepta-4,6-diene was obtained according to the literature procedure (Wilcox et al., 1961). First fraction from the final distillation of spiro[2.4]hepta-4,6-diene (2.05 g) was stored at room temperature for few weeks. After this time large, colorless crystals of the title compound deposited with 54% (1.10 g) yield.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.93–0.98 Å, Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 25% probability level.

Crystal data

C14H16Z = 2
Mr = 184.27F(000) = 200
Triclinic, P1Dx = 1.158 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.4079 (5) ÅCell parameters from 1384 reflections
b = 8.6355 (8) Åθ = 2.6–28.5°
c = 10.7216 (10) ŵ = 0.07 mm1
α = 68.488 (9)°T = 293 K
β = 81.625 (7)°Block, colourless
γ = 73.351 (8)°0.23 × 0.22 × 0.21 mm
V = 528.27 (8) Å3

Data collection

Oxford Diffraction Xcalibur S diffractometer2269 independent reflections
graphite1348 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1Rint = 0.024
ω scansθmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)h = −8→8
Tmin = 0.775, Tmax = 1k = −10→10
3444 measured reflectionsl = −8→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H-atom parameters constrained
S = 0.99w = 1/[σ2(Fo2) + (0.095P)2] where P = (Fo2 + 2Fc2)/3
2269 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.15 e Å3

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.
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)

xyzUiso*/Ueq
C10.7397 (3)0.6967 (3)0.2398 (2)0.0523 (6)
H1A0.77890.78460.26230.063*
C20.7772 (3)0.5136 (3)0.35036 (19)0.0469 (5)
H2A0.72910.5220.43920.056*
C30.9992 (3)0.3926 (3)0.3543 (2)0.0577 (6)
H3A1.12340.41040.37630.069*
C40.9994 (3)0.2591 (3)0.3232 (2)0.0539 (6)
H4A1.12410.17310.31910.065*
C50.7809 (3)0.2602 (2)0.29543 (19)0.0441 (5)
C60.6293 (3)0.4281 (2)0.30671 (18)0.0398 (5)
H6A0.51220.40350.37490.048*
C70.5333 (3)0.5718 (2)0.17594 (18)0.0451 (5)
H7A0.40420.55980.1450.054*
C80.7187 (4)0.5983 (3)0.0741 (2)0.0559 (6)
H8A0.74370.5677−0.00240.067*
C90.8395 (3)0.6717 (3)0.1112 (2)0.0594 (6)
H9A0.96460.70270.06580.071*
C100.5010 (3)0.7287 (2)0.21729 (19)0.0455 (5)
C110.3131 (4)0.7909 (3)0.3016 (2)0.0631 (6)
H11A0.34340.82750.3710.076*
H11B0.19330.73630.32350.076*
C120.3480 (4)0.8997 (3)0.1568 (2)0.0646 (6)
H12A0.24890.91020.09210.078*
H12B0.3991.00140.13960.078*
C130.7460 (4)0.1787 (3)0.2006 (2)0.0620 (6)
H13A0.61990.23520.14560.074*
H13B0.8740.12320.15770.074*
C140.7068 (4)0.0959 (3)0.3469 (2)0.0644 (6)
H14B0.8112−0.00990.3930.077*
H14C0.55690.10220.38090.077*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0501 (12)0.0406 (12)0.0711 (14)−0.0082 (9)−0.0029 (10)−0.0272 (11)
C20.0463 (11)0.0487 (13)0.0494 (11)−0.0028 (9)−0.0071 (9)−0.0260 (10)
C30.0425 (12)0.0604 (15)0.0706 (14)−0.0029 (10)−0.0187 (10)−0.0245 (12)
C40.0396 (11)0.0502 (14)0.0637 (13)0.0054 (10)−0.0080 (9)−0.0207 (11)
C50.0454 (11)0.0349 (11)0.0479 (11)−0.0001 (9)−0.0058 (9)−0.0156 (9)
C60.0368 (10)0.0360 (11)0.0435 (10)−0.0049 (8)0.0011 (8)−0.0143 (8)
C70.0419 (10)0.0398 (12)0.0527 (12)0.0024 (9)−0.0124 (9)−0.0205 (9)
C80.0647 (14)0.0459 (13)0.0417 (11)0.0098 (11)−0.0027 (10)−0.0156 (10)
C90.0503 (13)0.0419 (13)0.0681 (14)−0.0068 (10)0.0119 (11)−0.0077 (11)
C100.0434 (11)0.0351 (12)0.0542 (12)0.0013 (9)−0.0025 (9)−0.0193 (9)
C110.0592 (14)0.0509 (15)0.0694 (15)0.0054 (11)0.0040 (11)−0.0267 (12)
C120.0638 (14)0.0429 (14)0.0744 (16)0.0062 (11)−0.0035 (12)−0.0204 (12)
C130.0758 (15)0.0457 (14)0.0672 (15)−0.0036 (12)−0.0123 (12)−0.0279 (12)
C140.0731 (15)0.0398 (13)0.0736 (16)−0.0078 (11)−0.0065 (12)−0.0158 (11)

Geometric parameters (Å, °)

C1—C91.496 (3)C7—C101.525 (2)
C1—C101.513 (3)C7—H7A0.98
C1—C21.566 (3)C8—C91.309 (3)
C1—H1A0.98C8—H8A0.93
C2—C31.500 (3)C9—H9A0.93
C2—C61.564 (2)C10—C121.489 (3)
C2—H2A0.98C10—C111.491 (3)
C3—C41.312 (3)C11—C121.514 (3)
C3—H3A0.93C11—H11A0.97
C4—C51.470 (3)C11—H11B0.97
C4—H4A0.93C12—H12A0.97
C5—C131.503 (3)C12—H12B0.97
C5—C141.509 (3)C13—C141.483 (3)
C5—C61.532 (3)C13—H13A0.97
C6—C71.556 (3)C13—H13B0.97
C6—H6A0.98C14—H14B0.97
C7—C81.500 (3)C14—H14C0.97
C9—C1—C10100.07 (16)C9—C8—C7108.46 (17)
C9—C1—C2106.78 (17)C9—C8—H8A125.8
C10—C1—C299.49 (14)C7—C8—H8A125.8
C9—C1—H1A116C8—C9—C1107.59 (16)
C10—C1—H1A116C8—C9—H9A126.2
C2—C1—H1A116C1—C9—H9A126.2
C3—C2—C6103.53 (15)C12—C10—C1161.07 (14)
C3—C2—C1117.77 (17)C12—C10—C1125.94 (18)
C6—C2—C1102.59 (14)C11—C10—C1126.01 (17)
C3—C2—H2A110.8C12—C10—C7125.59 (17)
C6—C2—H2A110.8C11—C10—C7125.14 (17)
C1—C2—H2A110.8C1—C10—C794.78 (15)
C4—C3—C2112.80 (18)C10—C11—C1259.39 (13)
C4—C3—H3A123.6C10—C11—H11A117.8
C2—C3—H3A123.6C12—C11—H11A117.8
C3—C4—C5112.61 (19)C10—C11—H11B117.8
C3—C4—H4A123.7C12—C11—H11B117.8
C5—C4—H4A123.7H11A—C11—H11B115
C4—C5—C13122.29 (18)C10—C12—C1159.55 (14)
C4—C5—C14120.29 (18)C10—C12—H12A117.8
C13—C5—C1458.99 (13)C11—C12—H12A117.8
C4—C5—C6105.79 (15)C10—C12—H12B117.8
C13—C5—C6123.02 (17)C11—C12—H12B117.8
C14—C5—C6120.92 (17)H12A—C12—H12B115
C5—C6—C7118.11 (15)C14—C13—C560.73 (13)
C5—C6—C2105.17 (14)C14—C13—H13A117.7
C7—C6—C2102.28 (14)C5—C13—H13A117.7
C5—C6—H6A110.2C14—C13—H13B117.7
C7—C6—H6A110.2C5—C13—H13B117.7
C2—C6—H6A110.2H13A—C13—H13B114.8
C8—C7—C1099.26 (15)C13—C14—C560.28 (13)
C8—C7—C6107.61 (16)C13—C14—H14B117.7
C10—C7—C699.27 (14)C5—C14—H14B117.7
C8—C7—H7A116.1C13—C14—H14C117.7
C10—C7—H7A116.1C5—C14—H14C117.7
C6—C7—H7A116.1H14B—C14—H14C114.9
C9—C1—C2—C345.1 (2)C6—C7—C8—C9−70.4 (2)
C10—C1—C2—C3148.69 (16)C7—C8—C9—C10.2 (2)
C9—C1—C2—C6−67.80 (18)C10—C1—C9—C8−33.2 (2)
C10—C1—C2—C635.83 (17)C2—C1—C9—C870.0 (2)
C6—C2—C3—C4−0.8 (2)C9—C1—C10—C12−91.6 (2)
C1—C2—C3—C4−113.1 (2)C2—C1—C10—C12159.29 (19)
C2—C3—C4—C5−1.3 (3)C9—C1—C10—C11−169.39 (19)
C3—C4—C5—C13150.9 (2)C2—C1—C10—C1181.5 (2)
C3—C4—C5—C14−138.8 (2)C9—C1—C10—C749.82 (17)
C3—C4—C5—C62.8 (2)C2—C1—C10—C7−59.27 (16)
C4—C5—C6—C7110.17 (18)C8—C7—C10—C1292.4 (2)
C13—C5—C6—C7−37.6 (3)C6—C7—C10—C12−157.93 (19)
C14—C5—C6—C7−108.5 (2)C8—C7—C10—C11169.4 (2)
C4—C5—C6—C2−3.09 (19)C6—C7—C10—C11−80.9 (2)
C13—C5—C6—C2−150.86 (18)C8—C7—C10—C1−49.28 (17)
C14—C5—C6—C2138.22 (18)C6—C7—C10—C160.43 (16)
C3—C2—C6—C52.37 (18)C1—C10—C11—C12115.3 (2)
C1—C2—C6—C5125.38 (16)C7—C10—C11—C12−115.1 (2)
C3—C2—C6—C7−121.60 (17)C1—C10—C12—C11−115.4 (2)
C1—C2—C6—C71.41 (17)C7—C10—C12—C11114.4 (2)
C5—C6—C7—C8−49.8 (2)C4—C5—C13—C14108.4 (2)
C2—C6—C7—C865.04 (17)C6—C5—C13—C14−108.9 (2)
C5—C6—C7—C10−152.68 (15)C4—C5—C14—C13−111.8 (2)
C2—C6—C7—C10−37.84 (17)C6—C5—C14—C13112.4 (2)
C10—C7—C8—C932.5 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2280).

References

  • Brookings, D. C., Harrison, S. A., Whitby, R. J., Crombie, B. & Jones, R. V. H. (2001). Organometallics, 20, 4574–4583.
  • Caira, M. R., Bedekar, A. V. & Singh, V. (1995). J. Chem. Crystallogr.25, 583–587.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Haumann, T., Boese, R., Kozhushkov, S. I., Rauch, K. & de Meijere, A. (1997). Liebigs Ann Chem 10, 2047–2053.
  • Khusnutdinov, R. I., Dokichev, V. A., Galeev, D. K., Asylguzhina, N. F., Sultanov, S. Z. & Dzhemilev, U. M. (1988). Russ. Chem. Bull.37, 1932–1935.
  • Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wilcox, C. F. & Craig, R. R. (1961). J. Am. Chem. Soc.83, 3866–3871.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography