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

Grubba, R.; Ponikiewski, Ł.; Pikies, J.

doi:10.1107/S1600536810021951

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1648

doi:10.1107/S1600536810021951

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Dispiro[cyclopropane-1,5′-endo-tricyclo[5.2.1.0^2,6]deca-3,8-diene-10′,1′′-cyclopropane]

Rafał Grubba,^a Łukasz Ponikiewski ^a ^* and Jerzy Pikies ^a

^aChemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk PL 80233, Poland
^*Correspondence e-mail: lukasz.ponikiewski@pg.gda.pl

(Received 1 June 2010; accepted 8 June 2010; online 16 June 2010)

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 ); Wilcox et al. (1961 ). For related structures, see: Caira et al. (1995 ); Haumann et al. (1997 ); Brookings et al. (2001 ).

Experimental

Crystal data

C₁₄H₁₆
M_r = 184.27
Triclinic, $[P \overline 1]$
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 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.060
wR(F²) = 0.168
S = 0.99
2269 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 I, global. DOI: 10.1107/S1600536810021951/gk2280sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 25% probability level.

Dispiro[cyclopropane-1,5'-endo-tricyclo[5.2.1.0^2,6]deca-3,8-diene- 10',1''-cyclopropane] top

Crystal data top

C₁₄H₁₆	Z = 2
M_r = 184.27	F(000) = 200
Triclinic, P1	D_x = 1.158 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4079 (5) Å	Cell parameters from 1384 reflections
b = 8.6355 (8) Å	θ = 2.6–28.5°
c = 10.7216 (10) Å	µ = 0.07 mm⁻¹
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 top

Oxford Diffraction Xcalibur S diffractometer	2269 independent reflections
Graphite monochromator	1348 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −8→8
T_min = 0.775, T_max = 1	k = −10→10
3444 measured reflections	l = −8→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.095P)²] where P = (F_o² + 2F_c²)/3
2269 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₄H₁₆	γ = 73.351 (8)°
M_r = 184.27	V = 528.27 (8) Å³
Triclinic, P1	Z = 2
a = 6.4079 (5) Å	Mo Kα radiation
b = 8.6355 (8) Å	µ = 0.07 mm⁻¹
c = 10.7216 (10) Å	T = 293 K
α = 68.488 (9)°	0.23 × 0.22 × 0.21 mm
β = 81.625 (7)°

Data collection top

Oxford Diffraction Xcalibur S diffractometer	2269 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1348 reflections with I > 2σ(I)
T_min = 0.775, T_max = 1	R_int = 0.024
3444 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 0.99	Δρ_max = 0.22 e Å⁻³
2269 reflections	Δρ_min = −0.15 e Å⁻³
127 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

	x	y	z	U_iso*/U_eq
C1	0.7397 (3)	0.6967 (3)	0.2398 (2)	0.0523 (6)
H1A	0.7789	0.7846	0.2623	0.063*
C2	0.7772 (3)	0.5136 (3)	0.35036 (19)	0.0469 (5)
H2A	0.7291	0.522	0.4392	0.056*
C3	0.9992 (3)	0.3926 (3)	0.3543 (2)	0.0577 (6)
H3A	1.1234	0.4104	0.3763	0.069*
C4	0.9994 (3)	0.2591 (3)	0.3232 (2)	0.0539 (6)
H4A	1.1241	0.1731	0.3191	0.065*
C5	0.7809 (3)	0.2602 (2)	0.29543 (19)	0.0441 (5)
C6	0.6293 (3)	0.4281 (2)	0.30671 (18)	0.0398 (5)
H6A	0.5122	0.4035	0.3749	0.048*
C7	0.5333 (3)	0.5718 (2)	0.17594 (18)	0.0451 (5)
H7A	0.4042	0.5598	0.145	0.054*
C8	0.7187 (4)	0.5983 (3)	0.0741 (2)	0.0559 (6)
H8A	0.7437	0.5677	−0.0024	0.067*
C9	0.8395 (3)	0.6717 (3)	0.1112 (2)	0.0594 (6)
H9A	0.9646	0.7027	0.0658	0.071*
C10	0.5010 (3)	0.7287 (2)	0.21729 (19)	0.0455 (5)
C11	0.3131 (4)	0.7909 (3)	0.3016 (2)	0.0631 (6)
H11A	0.3434	0.8275	0.371	0.076*
H11B	0.1933	0.7363	0.3235	0.076*
C12	0.3480 (4)	0.8997 (3)	0.1568 (2)	0.0646 (6)
H12A	0.2489	0.9102	0.0921	0.078*
H12B	0.399	1.0014	0.1396	0.078*
C13	0.7460 (4)	0.1787 (3)	0.2006 (2)	0.0620 (6)
H13A	0.6199	0.2352	0.1456	0.074*
H13B	0.874	0.1232	0.1577	0.074*
C14	0.7068 (4)	0.0959 (3)	0.3469 (2)	0.0644 (6)
H14B	0.8112	−0.0099	0.393	0.077*
H14C	0.5569	0.1022	0.3809	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0501 (12)	0.0406 (12)	0.0711 (14)	−0.0082 (9)	−0.0029 (10)	−0.0272 (11)
C2	0.0463 (11)	0.0487 (13)	0.0494 (11)	−0.0028 (9)	−0.0071 (9)	−0.0260 (10)
C3	0.0425 (12)	0.0604 (15)	0.0706 (14)	−0.0029 (10)	−0.0187 (10)	−0.0245 (12)
C4	0.0396 (11)	0.0502 (14)	0.0637 (13)	0.0054 (10)	−0.0080 (9)	−0.0207 (11)
C5	0.0454 (11)	0.0349 (11)	0.0479 (11)	−0.0001 (9)	−0.0058 (9)	−0.0156 (9)
C6	0.0368 (10)	0.0360 (11)	0.0435 (10)	−0.0049 (8)	0.0011 (8)	−0.0143 (8)
C7	0.0419 (10)	0.0398 (12)	0.0527 (12)	0.0024 (9)	−0.0124 (9)	−0.0205 (9)
C8	0.0647 (14)	0.0459 (13)	0.0417 (11)	0.0098 (11)	−0.0027 (10)	−0.0156 (10)
C9	0.0503 (13)	0.0419 (13)	0.0681 (14)	−0.0068 (10)	0.0119 (11)	−0.0077 (11)
C10	0.0434 (11)	0.0351 (12)	0.0542 (12)	0.0013 (9)	−0.0025 (9)	−0.0193 (9)
C11	0.0592 (14)	0.0509 (15)	0.0694 (15)	0.0054 (11)	0.0040 (11)	−0.0267 (12)
C12	0.0638 (14)	0.0429 (14)	0.0744 (16)	0.0062 (11)	−0.0035 (12)	−0.0204 (12)
C13	0.0758 (15)	0.0457 (14)	0.0672 (15)	−0.0036 (12)	−0.0123 (12)	−0.0279 (12)
C14	0.0731 (15)	0.0398 (13)	0.0736 (16)	−0.0078 (11)	−0.0065 (12)	−0.0158 (11)

Geometric parameters (Å, º) top

C1—C9	1.496 (3)	C7—C10	1.525 (2)
C1—C10	1.513 (3)	C7—H7A	0.98
C1—C2	1.566 (3)	C8—C9	1.309 (3)
C1—H1A	0.98	C8—H8A	0.93
C2—C3	1.500 (3)	C9—H9A	0.93
C2—C6	1.564 (2)	C10—C12	1.489 (3)
C2—H2A	0.98	C10—C11	1.491 (3)
C3—C4	1.312 (3)	C11—C12	1.514 (3)
C3—H3A	0.93	C11—H11A	0.97
C4—C5	1.470 (3)	C11—H11B	0.97
C4—H4A	0.93	C12—H12A	0.97
C5—C13	1.503 (3)	C12—H12B	0.97
C5—C14	1.509 (3)	C13—C14	1.483 (3)
C5—C6	1.532 (3)	C13—H13A	0.97
C6—C7	1.556 (3)	C13—H13B	0.97
C6—H6A	0.98	C14—H14B	0.97
C7—C8	1.500 (3)	C14—H14C	0.97

C9—C1—C10	100.07 (16)	C9—C8—C7	108.46 (17)
C9—C1—C2	106.78 (17)	C9—C8—H8A	125.8
C10—C1—C2	99.49 (14)	C7—C8—H8A	125.8
C9—C1—H1A	116	C8—C9—C1	107.59 (16)
C10—C1—H1A	116	C8—C9—H9A	126.2
C2—C1—H1A	116	C1—C9—H9A	126.2
C3—C2—C6	103.53 (15)	C12—C10—C11	61.07 (14)
C3—C2—C1	117.77 (17)	C12—C10—C1	125.94 (18)
C6—C2—C1	102.59 (14)	C11—C10—C1	126.01 (17)
C3—C2—H2A	110.8	C12—C10—C7	125.59 (17)
C6—C2—H2A	110.8	C11—C10—C7	125.14 (17)
C1—C2—H2A	110.8	C1—C10—C7	94.78 (15)
C4—C3—C2	112.80 (18)	C10—C11—C12	59.39 (13)
C4—C3—H3A	123.6	C10—C11—H11A	117.8
C2—C3—H3A	123.6	C12—C11—H11A	117.8
C3—C4—C5	112.61 (19)	C10—C11—H11B	117.8
C3—C4—H4A	123.7	C12—C11—H11B	117.8
C5—C4—H4A	123.7	H11A—C11—H11B	115
C4—C5—C13	122.29 (18)	C10—C12—C11	59.55 (14)
C4—C5—C14	120.29 (18)	C10—C12—H12A	117.8
C13—C5—C14	58.99 (13)	C11—C12—H12A	117.8
C4—C5—C6	105.79 (15)	C10—C12—H12B	117.8
C13—C5—C6	123.02 (17)	C11—C12—H12B	117.8
C14—C5—C6	120.92 (17)	H12A—C12—H12B	115
C5—C6—C7	118.11 (15)	C14—C13—C5	60.73 (13)
C5—C6—C2	105.17 (14)	C14—C13—H13A	117.7
C7—C6—C2	102.28 (14)	C5—C13—H13A	117.7
C5—C6—H6A	110.2	C14—C13—H13B	117.7
C7—C6—H6A	110.2	C5—C13—H13B	117.7
C2—C6—H6A	110.2	H13A—C13—H13B	114.8
C8—C7—C10	99.26 (15)	C13—C14—C5	60.28 (13)
C8—C7—C6	107.61 (16)	C13—C14—H14B	117.7
C10—C7—C6	99.27 (14)	C5—C14—H14B	117.7
C8—C7—H7A	116.1	C13—C14—H14C	117.7
C10—C7—H7A	116.1	C5—C14—H14C	117.7
C6—C7—H7A	116.1	H14B—C14—H14C	114.9

C9—C1—C2—C3	45.1 (2)	C6—C7—C8—C9	−70.4 (2)
C10—C1—C2—C3	148.69 (16)	C7—C8—C9—C1	0.2 (2)
C9—C1—C2—C6	−67.80 (18)	C10—C1—C9—C8	−33.2 (2)
C10—C1—C2—C6	35.83 (17)	C2—C1—C9—C8	70.0 (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—C12	159.29 (19)
C2—C3—C4—C5	−1.3 (3)	C9—C1—C10—C11	−169.39 (19)
C3—C4—C5—C13	150.9 (2)	C2—C1—C10—C11	81.5 (2)
C3—C4—C5—C14	−138.8 (2)	C9—C1—C10—C7	49.82 (17)
C3—C4—C5—C6	2.8 (2)	C2—C1—C10—C7	−59.27 (16)
C4—C5—C6—C7	110.17 (18)	C8—C7—C10—C12	92.4 (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—C11	169.4 (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—C2	138.22 (18)	C6—C7—C10—C1	60.43 (16)
C3—C2—C6—C5	2.37 (18)	C1—C10—C11—C12	115.3 (2)
C1—C2—C6—C5	125.38 (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—C7	1.41 (17)	C7—C10—C12—C11	114.4 (2)
C5—C6—C7—C8	−49.8 (2)	C4—C5—C13—C14	108.4 (2)
C2—C6—C7—C8	65.04 (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—C13	112.4 (2)
C10—C7—C8—C9	32.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆
M_r	184.27
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.4079 (5), 8.6355 (8), 10.7216 (10)
α, β, γ (°)	68.488 (9), 81.625 (7), 73.351 (8)
V (Å³)	528.27 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.23 × 0.22 × 0.21

Data collection
Diffractometer	Oxford Diffraction Xcalibur S diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.775, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	3444, 2269, 1348
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.168, 0.99
No. of reflections	2269
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.15

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

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

References

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