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

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

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.100
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT432_ALERT_2_C Short Inter X...Y Contact  O4     ..  C10     ..       3.01 Ang.

Alert level G
PLAT793_ALERT_4_G Check the Absolute Configuration of C2     .....          R
PLAT793_ALERT_4_G Check the Absolute Configuration of C4     .....          S
PLAT793_ALERT_4_G Check the Absolute Configuration of C7     .....          R
PLAT793_ALERT_4_G Check the Absolute Configuration of C9     .....          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

Related literature

Please supply any relevant related literature.

S2. 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.

S3. 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.

Computing details

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

	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

Crystal data

C12H8O6	F(000) = 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 = 2.9–24.1°
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) Å^3	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)
Graphite monochromator	Rint = 0.051
ϕ and ω scans	θmax = 26.5°, θmin = 2.6°
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 F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0334P)^2 + 0.3914P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2118 reflections	Δρmax = 0.21 e Å^−3
164 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.005 (1)

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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	0.98	2.50	3.313 (3)	140
C8—H8···O3^ii	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.