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

Gidaly, M.P.; Harris, A.D.; Amado-Sierra, M. del R.I.; Jones, D.S.; Etzkorn, M.

doi:10.1107/S1600536809005844

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o729

doi:10.1107/S1600536809005844

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

Matthew P. Gidaly,^a Andria D. Harris,^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 Blvd, Charlotte, NC 28223, USA
^*Correspondence e-mail: djones@uncc.edu, metzkorn@uncc.edu

(Received 31 December 2008; accepted 18 February 2009; online 11 March 2009)

The title compound, C₁₀H₈O₂, is a precursor to an unusual bis-homoaromatic dication and to heterodiamantanes and other oxa-cage compounds. Two independent molecules, each of which is situated on a center of symmetry, comprise the unit cell. Both molecules are in nearly identical chair conformations.

Related literature

For related structures, see: Eaton et al. (2002 ); Harris et al. (2008 ); Masters et al. (1994 ). For the synthesis and related details, see: Hafner & Goliasch (1961 ); Weiss et al. (1960 ); Dilthey & Quint (1930 ); Garbisch & Sprecher (1966 ); Saito & Ito (2008 ); Baggiolini et al. (1967 ); Klinsmann et al. (1972 ); Amman et al. (1980 ); Amman & Ganter (1977 , 1981 ); Prakash et al. (1987 ); Harris et al. (2008).

Experimental

Crystal data

C₁₀H₈O₂
M_r = 160.16
Triclinic, $[P \overline 1]$
a = 6.4458 (7) Å
b = 6.6120 (6) Å
c = 8.9758 (6) Å
α = 81.671 (8)°
β = 79.176 (10)°
γ = 84.745 (8)°
V = 370.96 (6) Å³
Z = 2
Cu Kα radiation
μ = 0.82 mm⁻¹
T = 295 K
0.3 × 0.2 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2624 measured reflections
1329 independent reflections
1179 reflections with I > 2σ(I)
R_int = 0.045
3 standard reflections every 82 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.092
S = 1.12
1329 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.2 e Å⁻³
Δρ_min = −0.15 e Å⁻³

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/S1600536809005844/fl2229sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005844/fl2229Isup2.hkl

checkCIF report

Comment top

The polycyclic title compound, dione 4, is formally a dimer of the elusive cyclopentadienone 1. The latter compound has only a fleeting existence and could be trapped in the form of its Diels-Alder adduct 3 (Hafner & Goliasch, 1961) or stabilized as an iron pentacarbonyl complex (Weiss et al., 1960), although derivatives with bulky substituents have been prepared as stable monomers (Dilthey & Quint, 1930; Garbisch & Sprecher, 1966; Saito & Ito, 2008). The title compound 4 is accessible through photoisomerization of Diels-Alder adduct 3, a transformation that has been thoroughly studied (Baggiolini et al., 1967; Klinsmann et al., 1972) since dione 4 – via diol 5 (Amman et al., 1980; Amman & Ganter, 1977; Amman & Ganter, 1981) - is a valuable precursor to an unusual bishomoaromatic dication (Prakash et al., 1987) and to heterodiamantanes and other oxa-cage compounds (Amman et al., 1980; Amman & Ganter, 1977; Amman & Ganter, 1981). We have recently reported the structure of diol derivative 5 (Harris et al., 2008) and herein report the structure of the parent dione 4.

Two independent molecules, each of which is situated on a center of symmetry, comprise the unit cell. Both molecules are in nearly identical "chair" conformations, with a maximum deviation between corresponding bond lengths of 0.01 Å. The molecular packing exhibits several short intermolecular contacts, with the shortest being 0.15 Å less than the sum of the van der Waals radii.

Two related structures have been reported. The first (Eaton et al., 2002) has a chlorine atom in place of each hydrogen atom of the title compound, while the second (Masters et al., 1994) lacks the double bonds of the title compound and has methyl groups on each of the four bridgehead carbon atoms.

Related literature top

For related structures, see: Eaton et al. (2002); Harris et al. (2008); Masters et al. (1994). For the synthesis and related details, see: Hafner & Goliasch (1961); Weiss et al. (1960); Dilthey & Quint (1930); Garbisch & Sprecher (1966); Saito & Ito (2008); Baggiolini et al. (1967); Klinsmann et al. (1972); Amman et al. (1980); Amman & Ganter (1977, 1981); Prakash et al. (1987); Harris et al. (2008).

Experimental top

The synthesis of the title compound, 4, is described in our previous structure report (Harris et al., 2008). Crystals for data collection were obtained from a chloroform solution.

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, -y + 1, -z + 2; (ii) -x + 1, -y + 2, -z + 1]
	Fig. 2. The formation of the title compound.

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

Crystal data top

C₁₀H₈O₂	Z = 2
M_r = 160.16	F(000) = 168
Triclinic, P1	D_x = 1.434 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 6.4458 (7) Å	Cell parameters from 24 reflections
b = 6.6120 (6) Å	θ = 10.1–44.8°
c = 8.9758 (6) Å	µ = 0.82 mm⁻¹
α = 81.671 (8)°	T = 295 K
β = 79.176 (10)°	Prism, yellow
γ = 84.745 (8)°	0.3 × 0.2 × 0.2 mm
V = 370.96 (6) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	θ_max = 67.4°, θ_min = 5.1°
Non–profiled ω/2θ scans	h = −7→7
2624 measured reflections	k = −7→7
1329 independent reflections	l = −10→10
1179 reflections with I > 2σ(I)	3 standard reflections every 82 reflections
R_int = 0.045	intensity decay: 1%

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0242P)² + 0.0776P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.037	(Δ/σ)_max < 0.001
wR(F²) = 0.092	Δρ_max = 0.2 e Å⁻³
S = 1.12	Δρ_min = −0.15 e Å⁻³
1329 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
110 parameters	Extinction coefficient: 0.115 (5)
0 restraints

Crystal data top

C₁₀H₈O₂	γ = 84.745 (8)°
M_r = 160.16	V = 370.96 (6) Å³
Triclinic, P1	Z = 2
a = 6.4458 (7) Å	Cu Kα radiation
b = 6.6120 (6) Å	µ = 0.82 mm⁻¹
c = 8.9758 (6) Å	T = 295 K
α = 81.671 (8)°	0.3 × 0.2 × 0.2 mm
β = 79.176 (10)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.045
2624 measured reflections	3 standard reflections every 82 reflections
1329 independent reflections	intensity decay: 1%
1179 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.12	Δρ_max = 0.2 e Å⁻³
1329 reflections	Δρ_min = −0.15 e Å⁻³
110 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	0.30420 (16)	0.67650 (15)	0.48107 (14)	0.0495 (3)
O2	−0.21014 (18)	0.85668 (16)	0.94715 (16)	0.0593 (4)
C5	0.5818 (2)	0.8181 (2)	0.58171 (17)	0.0369 (4)
H5	0.5912	0.6967	0.6575	0.044*
C10	−0.2032 (2)	0.5136 (2)	1.09484 (17)	0.0392 (4)
H10	−0.3204	0.556	1.173	0.047*
C8	0.1509 (2)	0.6126 (2)	1.13965 (18)	0.0438 (4)
H8	0.1613	0.6898	1.2164	0.053*
C7	0.0067 (2)	0.4394 (2)	1.15786 (17)	0.0409 (4)
H7	−0.0169	0.3633	1.2611	0.049*
C3	0.2728 (2)	1.0665 (2)	0.67086 (18)	0.0423 (4)
H3	0.1766	1.0349	0.7606	0.051*
C2	0.5100 (2)	1.0222 (2)	0.65388 (17)	0.0381 (4)
H2	0.566	1.0299	0.747	0.046*
C9	−0.2602 (2)	0.3614 (2)	1.00162 (19)	0.0427 (4)
H9	−0.3583	0.2631	1.0381	0.051*
C1	0.4297 (2)	0.8034 (2)	0.47378 (17)	0.0362 (4)
C6	−0.1443 (2)	0.6803 (2)	0.96120 (18)	0.0395 (4)
C4	0.7783 (2)	0.8433 (2)	0.46039 (19)	0.0420 (4)
H4	0.9153	0.8016	0.4756	0.05*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0444 (6)	0.0450 (6)	0.0619 (8)	−0.0112 (5)	−0.0102 (5)	−0.0107 (5)
O2	0.0608 (7)	0.0390 (6)	0.0810 (9)	0.0080 (5)	−0.0283 (6)	−0.0043 (6)
C5	0.0368 (7)	0.0364 (7)	0.0373 (8)	0.0005 (5)	−0.0110 (6)	−0.0003 (6)
C10	0.0323 (6)	0.0466 (8)	0.0378 (8)	−0.0031 (6)	−0.0034 (5)	−0.0066 (6)
C8	0.0398 (7)	0.0495 (8)	0.0480 (9)	0.0004 (6)	−0.0172 (7)	−0.0161 (7)
C7	0.0418 (7)	0.0494 (8)	0.0317 (7)	−0.0050 (6)	−0.0099 (6)	0.0005 (6)
C3	0.0413 (7)	0.0427 (8)	0.0405 (8)	−0.0024 (6)	0.0024 (6)	−0.0102 (6)
C2	0.0421 (7)	0.0429 (8)	0.0312 (7)	−0.0024 (6)	−0.0106 (6)	−0.0060 (6)
C9	0.0335 (7)	0.0417 (8)	0.0554 (10)	−0.0060 (6)	−0.0128 (6)	−0.0057 (7)
C1	0.0331 (6)	0.0369 (7)	0.0395 (8)	0.0010 (5)	−0.0063 (6)	−0.0102 (6)
C6	0.0351 (7)	0.0397 (8)	0.0468 (9)	−0.0015 (6)	−0.0169 (6)	−0.0041 (6)
C4	0.0317 (7)	0.0420 (8)	0.0523 (9)	0.0026 (6)	−0.0083 (6)	−0.0086 (7)

Geometric parameters (Å, º) top

O1—C1	1.2049 (16)	C8—H8	0.93
O2—C6	1.2012 (17)	C7—C6ⁱ	1.522 (2)
C5—C4	1.5116 (19)	C7—H7	0.98
C5—C1	1.5202 (19)	C3—C4ⁱⁱ	1.326 (2)
C5—C2	1.575 (2)	C3—C2	1.5129 (19)
C5—H5	0.98	C3—H3	0.93
C10—C9	1.509 (2)	C2—H2	0.98
C10—C6	1.5232 (19)	C9—H9	0.93
C10—C7	1.5741 (19)	C1—C2ⁱⁱ	1.5248 (18)
C10—H10	0.98	C6—C7ⁱ	1.522 (2)
C8—C9ⁱ	1.326 (2)	C4—H4	0.93
C8—C7	1.512 (2)

C4—C5—C1	96.67 (11)	C4ⁱⁱ—C3—C2	110.37 (12)
C4—C5—C2	111.33 (11)	C4ⁱⁱ—C3—H3	124.8
C1—C5—C2	105.88 (10)	C2—C3—H3	124.8
C4—C5—H5	113.8	C3—C2—C1ⁱⁱ	96.61 (10)
C1—C5—H5	113.8	C3—C2—C5	111.11 (11)
C2—C5—H5	113.8	C1ⁱⁱ—C2—C5	106.04 (11)
C9—C10—C6	96.32 (12)	C3—C2—H2	113.9
C9—C10—C7	111.22 (12)	C1ⁱⁱ—C2—H2	113.9
C6—C10—C7	106.35 (11)	C5—C2—H2	113.9
C9—C10—H10	113.8	C8ⁱ—C9—C10	110.46 (13)
C6—C10—H10	113.8	C8ⁱ—C9—H9	124.8
C7—C10—H10	113.8	C10—C9—H9	124.8
C9ⁱ—C8—C7	110.14 (14)	O1—C1—C5	128.74 (13)
C9ⁱ—C8—H8	124.9	O1—C1—C2ⁱⁱ	128.48 (14)
C7—C8—H8	124.9	C5—C1—C2ⁱⁱ	102.57 (11)
C8—C7—C6ⁱ	96.36 (11)	O2—C6—C7ⁱ	128.63 (14)
C8—C7—C10	111.33 (11)	O2—C6—C10	128.41 (15)
C6ⁱ—C7—C10	106.49 (12)	C7ⁱ—C6—C10	102.44 (11)
C8—C7—H7	113.7	C3ⁱⁱ—C4—C5	110.25 (12)
C6ⁱ—C7—H7	113.7	C3ⁱⁱ—C4—H4	124.9
C10—C7—H7	113.7	C5—C4—H4	124.9

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈O₂
M_r	160.16
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.4458 (7), 6.6120 (6), 8.9758 (6)
α, β, γ (°)	81.671 (8), 79.176 (10), 84.745 (8)
V (Å³)	370.96 (6)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2624, 1329, 1179
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.092, 1.12
No. of reflections	1329
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.2, −0.15

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).

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.

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