Bicyclo­[2.2.2]oct-7-ene-2,3,5,6-tetra­carboxylic dianhydride

Hu, T.

doi:10.1107/S1600536808012452

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1021

doi:10.1107/S1600536808012452

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Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride

Tuoping Hu ^a ^*

^aDepartment of Chemistry, North University of China, Taiyuan, Shanxi 030051, People's Republic of China
^*Correspondence e-mail: hutuopingsx@yahoo.com.cn

(Received 5 April 2008; accepted 29 April 2008; online 10 May 2008)

In the title compound, C₁₂H₈O₆, molecules are linked by weak C—H⋯O interactions involving all the potential donors, generating a three-dimensional network.

Experimental

Crystal data

C₁₂H₈O₆
M_r = 248.18
Monoclinic, P 2₁ /n
a = 7.627 (2) Å
b = 13.877 (3) Å
c = 9.823 (2) Å
β = 100.68 (2)°
V = 1021.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 (2) K
0.28 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.921, T_max = 0.987
11412 measured reflections
2119 independent reflections
1460 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.099
S = 1.01
2118 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.98	2.50	3.313 (3)	140
C8—H8⋯O3ⁱⁱ	0.98	2.58	3.175 (2)	119
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012452/sg2233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012452/sg2233Isup2.hkl

checkCIF report

Comment top

The molecule of the title complex, (I) (Fig. 1), is neutral. Molecules are linked by C—H···O weak interactions involving all the potential donors, generating a three-dimensional network, as shown in Fig. 2. No conventional hydrogen bonding was found in the structure.

Related literature top

Please supply any relevant related literature.

Experimental top

The title compound was obtained unintentionally as the product of an attempted synthesis of a polymeric network complex of znic with the bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid. The title compound (0.4 mmol) and Zn(NO₃)₂. 6H₂O (0.2 mmol) were dissolved in 15 ml distilled water, to which 2 drops of H₃PO4 (w.t. 18%) was added. The solution was put into the oven at 50 centigrade degree for 1 day. Colourless prism crystals were collected by filtration.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure showing 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram viewed down the a axis.

Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride top

Crystal data top

C₁₂H₈O₆	F(000) = 512
M_r = 248.18	D_x = 1.613 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2677 reflections
a = 7.627 (2) Å	θ = 2.9–24.1°
b = 13.877 (3) Å	µ = 0.13 mm⁻¹
c = 9.823 (2) Å	T = 296 K
β = 100.68 (2)°	Prism, colourless
V = 1021.7 (4) Å³	0.28 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2119 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.921, T_max = 0.987	k = −17→15
11412 measured reflections	l = −11→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0334P)² + 0.3914P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2118 reflections	Δρ_max = 0.21 e Å⁻³
164 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.005 (1)

Crystal data top

C₁₂H₈O₆	V = 1021.7 (4) Å³
M_r = 248.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.627 (2) Å	µ = 0.13 mm⁻¹
b = 13.877 (3) Å	T = 296 K
c = 9.823 (2) Å	0.28 × 0.16 × 0.10 mm
β = 100.68 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2119 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1460 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.987	R_int = 0.051
11412 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.01	Δρ_max = 0.21 e Å⁻³
2118 reflections	Δρ_min = −0.16 e Å⁻³
164 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	0.7820 (3)	0.83700 (16)	0.6304 (2)	0.0449 (5)
C2	0.5829 (2)	0.84372 (13)	0.61717 (19)	0.0355 (4)
H2	0.5239	0.8381	0.5200	0.043*
C3	0.5305 (2)	0.93909 (13)	0.68048 (19)	0.0350 (4)
H3	0.5646	0.9952	0.6307	0.042*
C4	0.3256 (2)	0.93415 (13)	0.67248 (18)	0.0344 (4)
H4	0.2633	0.9301	0.5760	0.041*
C5	0.2627 (3)	1.01999 (15)	0.7435 (2)	0.0416 (5)
C6	0.1858 (3)	0.89126 (15)	0.8635 (2)	0.0434 (5)
C7	0.2788 (2)	0.84782 (13)	0.75613 (18)	0.0352 (4)
H7	0.1984	0.8039	0.6962	0.042*
C8	0.4506 (2)	0.79445 (13)	0.82409 (18)	0.0354 (4)
H8	0.4251	0.7413	0.8831	0.042*
C9	0.5347 (2)	0.75817 (13)	0.70190 (19)	0.0358 (4)
H9	0.4526	0.7145	0.6429	0.043*
C10	0.7097 (3)	0.70890 (16)	0.7535 (2)	0.0462 (5)
C11	0.5767 (2)	0.86683 (14)	0.90425 (19)	0.0392 (5)
H11	0.6221	0.8602	0.9984	0.047*
C12	0.6180 (2)	0.94061 (14)	0.83043 (19)	0.0394 (5)
H12	0.6951	0.9895	0.8686	0.047*
O1	0.88296 (19)	0.89053 (13)	0.58906 (17)	0.0638 (5)
O2	0.7409 (2)	0.64134 (12)	0.82843 (18)	0.0681 (5)
O3	0.2829 (2)	1.10382 (11)	0.72476 (16)	0.0596 (4)
O4	0.1289 (2)	0.85316 (12)	0.95463 (16)	0.0629 (5)
O5	0.84589 (17)	0.75576 (11)	0.70513 (15)	0.0537 (4)
O6	0.17498 (18)	0.99043 (10)	0.84767 (14)	0.0485 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0359 (11)	0.0528 (13)	0.0462 (12)	0.0033 (10)	0.0079 (9)	−0.0067 (10)
C2	0.0311 (9)	0.0378 (11)	0.0373 (10)	0.0016 (8)	0.0054 (7)	−0.0023 (8)
C3	0.0334 (9)	0.0298 (10)	0.0422 (10)	−0.0030 (8)	0.0076 (8)	0.0016 (8)
C4	0.0337 (9)	0.0331 (10)	0.0351 (9)	0.0039 (8)	0.0031 (7)	−0.0014 (8)
C5	0.0405 (11)	0.0389 (12)	0.0429 (11)	0.0098 (9)	0.0018 (9)	−0.0003 (9)
C6	0.0355 (10)	0.0470 (13)	0.0482 (12)	0.0008 (9)	0.0089 (9)	−0.0024 (10)
C7	0.0313 (9)	0.0327 (11)	0.0411 (10)	−0.0025 (8)	0.0052 (8)	−0.0035 (8)
C8	0.0375 (10)	0.0297 (10)	0.0390 (10)	0.0002 (8)	0.0070 (8)	0.0033 (8)
C9	0.0328 (9)	0.0309 (10)	0.0423 (10)	0.0017 (8)	0.0033 (8)	−0.0024 (8)
C10	0.0455 (12)	0.0419 (13)	0.0490 (12)	0.0112 (10)	0.0031 (9)	−0.0021 (10)
C11	0.0386 (10)	0.0415 (11)	0.0353 (10)	0.0047 (9)	0.0013 (8)	−0.0021 (9)
C12	0.0349 (10)	0.0369 (11)	0.0448 (11)	−0.0035 (8)	0.0034 (8)	−0.0078 (9)
O1	0.0392 (8)	0.0791 (12)	0.0768 (11)	−0.0069 (8)	0.0205 (8)	0.0052 (9)
O2	0.0689 (11)	0.0550 (10)	0.0784 (11)	0.0261 (8)	0.0083 (9)	0.0170 (9)
O3	0.0726 (11)	0.0345 (9)	0.0716 (11)	0.0137 (7)	0.0131 (8)	0.0022 (8)
O4	0.0655 (10)	0.0696 (11)	0.0616 (10)	−0.0019 (8)	0.0328 (8)	0.0038 (8)
O5	0.0326 (7)	0.0582 (10)	0.0685 (10)	0.0107 (7)	0.0044 (7)	0.0018 (8)
O6	0.0500 (8)	0.0464 (9)	0.0516 (8)	0.0096 (6)	0.0161 (7)	−0.0056 (7)

Geometric parameters (Å, º) top

C1—O1	1.194 (2)	C6—O6	1.386 (2)
C1—O5	1.384 (2)	C6—C7	1.502 (3)
C1—C2	1.503 (3)	C7—C8	1.545 (2)
C2—C9	1.533 (3)	C7—H7	0.9800
C2—C3	1.546 (3)	C8—C11	1.508 (3)
C2—H2	0.9800	C8—C9	1.546 (3)
C3—C12	1.500 (3)	C8—H8	0.9800
C3—C4	1.551 (2)	C9—C10	1.502 (3)
C3—H3	0.9800	C9—H9	0.9800
C4—C5	1.504 (3)	C10—O2	1.188 (2)
C4—C7	1.532 (3)	C10—O5	1.382 (3)
C4—H4	0.9800	C11—C12	1.326 (3)
C5—O3	1.192 (2)	C11—H11	0.9300
C5—O6	1.384 (2)	C12—H12	0.9300
C6—O4	1.189 (2)

O1—C1—O5	120.12 (18)	C6—C7—C8	111.21 (15)
O1—C1—C2	129.6 (2)	C4—C7—C8	110.07 (15)
O5—C1—C2	110.29 (18)	C6—C7—H7	110.3
C1—C2—C9	104.20 (15)	C4—C7—H7	110.3
C1—C2—C3	110.54 (15)	C8—C7—H7	110.3
C9—C2—C3	109.79 (15)	C11—C8—C7	108.31 (15)
C1—C2—H2	110.7	C11—C8—C9	107.83 (15)
C9—C2—H2	110.7	C7—C8—C9	105.15 (14)
C3—C2—H2	110.7	C11—C8—H8	111.7
C12—C3—C2	107.81 (15)	C7—C8—H8	111.7
C12—C3—C4	108.10 (15)	C9—C8—H8	111.7
C2—C3—C4	105.96 (14)	C10—C9—C2	104.37 (15)
C12—C3—H3	111.6	C10—C9—C8	110.90 (15)
C2—C3—H3	111.6	C2—C9—C8	110.18 (14)
C4—C3—H3	111.6	C10—C9—H9	110.4
C5—C4—C7	104.15 (16)	C2—C9—H9	110.4
C5—C4—C3	110.29 (15)	C8—C9—H9	110.4
C7—C4—C3	109.89 (14)	O2—C10—O5	120.48 (18)
C5—C4—H4	110.8	O2—C10—C9	129.2 (2)
C7—C4—H4	110.8	O5—C10—C9	110.31 (17)
C3—C4—H4	110.8	C12—C11—C8	114.96 (16)
O3—C5—O6	119.82 (19)	C12—C11—H11	122.5
O3—C5—C4	129.8 (2)	C8—C11—H11	122.5
O6—C5—C4	110.36 (17)	C11—C12—C3	114.75 (17)
O4—C6—O6	120.26 (19)	C11—C12—H12	122.6
O4—C6—C7	129.5 (2)	C3—C12—H12	122.6
O6—C6—C7	110.22 (17)	C10—O5—C1	110.67 (15)
C6—C7—C4	104.49 (15)	C5—O6—C6	110.52 (16)

O1—C1—C2—C9	−175.3 (2)	C4—C7—C8—C9	−62.20 (17)
O5—C1—C2—C9	3.2 (2)	C1—C2—C9—C10	−1.16 (19)
O1—C1—C2—C3	−57.4 (3)	C3—C2—C9—C10	−119.57 (16)
O5—C1—C2—C3	121.13 (17)	C1—C2—C9—C8	117.95 (15)
C1—C2—C3—C12	−59.7 (2)	C3—C2—C9—C8	−0.46 (19)
C9—C2—C3—C12	54.68 (18)	C11—C8—C9—C10	61.6 (2)
C1—C2—C3—C4	−175.28 (15)	C7—C8—C9—C10	176.98 (15)
C9—C2—C3—C4	−60.87 (18)	C11—C8—C9—C2	−53.47 (18)
C12—C3—C4—C5	59.5 (2)	C7—C8—C9—C2	61.93 (17)
C2—C3—C4—C5	174.86 (15)	C2—C9—C10—O2	176.5 (2)
C12—C3—C4—C7	−54.75 (19)	C8—C9—C10—O2	57.9 (3)
C2—C3—C4—C7	60.60 (18)	C2—C9—C10—O5	−1.2 (2)
C7—C4—C5—O3	172.72 (19)	C8—C9—C10—O5	−119.86 (17)
C3—C4—C5—O3	54.9 (3)	C7—C8—C11—C12	−56.8 (2)
C7—C4—C5—O6	−4.85 (19)	C9—C8—C11—C12	56.5 (2)
C3—C4—C5—O6	−122.71 (16)	C8—C11—C12—C3	0.4 (2)
O4—C6—C7—C4	−177.8 (2)	C2—C3—C12—C11	−57.5 (2)
O6—C6—C7—C4	0.55 (19)	C4—C3—C12—C11	56.6 (2)
O4—C6—C7—C8	−59.1 (3)	O2—C10—O5—C1	−174.58 (19)
O6—C6—C7—C8	119.27 (16)	C9—C10—O5—C1	3.4 (2)
C5—C4—C7—C6	2.49 (18)	O1—C1—O5—C10	174.51 (19)
C3—C4—C7—C6	120.62 (15)	C2—C1—O5—C10	−4.2 (2)
C5—C4—C7—C8	−117.01 (16)	O3—C5—O6—C6	−172.38 (18)
C3—C4—C7—C8	1.1 (2)	C4—C5—O6—C6	5.5 (2)
C6—C7—C8—C11	−62.4 (2)	O4—C6—O6—C5	174.79 (18)
C4—C7—C8—C11	52.87 (19)	C7—C6—O6—C5	−3.7 (2)
C6—C7—C8—C9	−177.52 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.98	2.50	3.313 (3)	140
C8—H8···O3ⁱⁱ	0.98	2.58	3.175 (2)	119

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₈O₆
M_r	248.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.627 (2), 13.877 (3), 9.823 (2)
β (°)	100.68 (2)
V (Å³)	1021.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.28 × 0.16 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.921, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	11412, 2119, 1460
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.099, 1.01
No. of reflections	2118
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.16

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.98	2.50	3.313 (3)	140
C8—H8···O3ⁱⁱ	0.98	2.58	3.175 (2)	119

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

The author acknowledges funding support from the Natural Science Foundation of Shanxi Province (2007011033), the Program of Technological Industrialization in Universities of Shanxi Province (20070308) and the Start-up Fund of the North University of China.

References

Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar