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

Abstract

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,

• a = 7.627 (2) Å

• b = 13.877 (3) Å

• c = 9.823 (2) Å

• β = 100.68 (2)°

• V = 1021.7 (4) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined using a riding model with C—H = 0.980 Å and 0.930 Å, respectively, with U_iso(H) = 1.2 times U_eq(C). Reflection -111 was omitted because it was eclipsed by the beam stop.

Figures

Fig. 1.

Molecular structure showing 50% probability displacement ellipsoids.

Fig. 2.

Packing diagram viewed down the a axis.

Crystal data

C12H8O6	F000 = 512
Mr = 248.18	Dx = 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 = 2.9–24.1º
b = 13.877 (3) Å	µ = 0.13 mm−1
c = 9.823 (2) Å	T = 296 (2) K
β = 100.68 (2)º	Prism, colourless
V = 1021.7 (4) Å3	0.28 × 0.16 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2119 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.051
T = 296(2) K	θmax = 26.5º
φ and ω scans	θmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.921, Tmax = 0.987	k = −17→15
11412 measured reflections	l = −11→12

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0334P)2 + 0.3914P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.21 e Å−3
2118 reflections	Δρmin = −0.16 e Å−3
164 parameters	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)
Secondary atom site location: difference Fourier map

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.