Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008908/qa0328sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008908/qa0328Isup2.hkl |
CCDC reference: 150386
The title compound was synthesized according to the method of Hünig et al. (1979) in two steps. A solution of freshly sublimed maleic anhydride (19.6 g, 200 mmol) in dried benzene (50 ml) was heated to approximately 350 K. Butadiene was then passed into the solution for 30 min with continuous stirring. The reaction product, 4-cyclohexene-1,2-dicarboxylic acid anhydride, was washed with petroleum ether and recrystallized from diethyl ether. The second step comprised the hydrolysis of the anhydride. 4-Cyclohexene-1,2-dicarboxylic acid anhydride (1 g) was dissolved in water (10 ml) and refluxed under a take-off condenser for 2 h. When the solution was cooled down to room temperature the product precipitated. Recrystallization from ethyl acetate yielded crystals suitable for an X-ray structure analysis.
All H atoms were located by difference Fourier synthesis and refined with U(H) = 1.2Ueq(C) or U(H) = 1.2Ueq(O) using a riding model with Csp2—H = 0.95, C—H(secondary) = 0.99, C—H(tertiary) = 1.00 and O—H = 0.84 Å. The OH groups were allowed to rotate about the C—O axis.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1991).
C8H10O4 | Z = 2 |
Mr = 170.16 | F(000) = 180 |
Triclinic, P1 | Dx = 1.400 Mg m−3 |
a = 6.308 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.892 (4) Å | Cell parameters from 2610 reflections |
c = 10.875 (7) Å | θ = 0–25° |
α = 74.57 (1)° | µ = 0.11 mm−1 |
β = 73.78 (1)° | T = 173 K |
γ = 64.41 (1)° | Block, colourless |
V = 403.6 (4) Å3 | 0.25 × 0.15 × 0.15 mm |
Siemens CCD three-circle diffractometer | 1645 independent reflections |
Radiation source: fine-focus sealed tube | 1151 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.972, Tmax = 0.983 | k = −8→8 |
4809 measured reflections | l = −13→13 |
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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.335P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1645 reflections | Δρmax = 0.29 e Å−3 |
112 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.068 (11) |
C8H10O4 | γ = 64.41 (1)° |
Mr = 170.16 | V = 403.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.308 (4) Å | Mo Kα radiation |
b = 6.892 (4) Å | µ = 0.11 mm−1 |
c = 10.875 (7) Å | T = 173 K |
α = 74.57 (1)° | 0.25 × 0.15 × 0.15 mm |
β = 73.78 (1)° |
Siemens CCD three-circle diffractometer | 1645 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | 1151 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.983 | Rint = 0.043 |
4809 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.29 e Å−3 |
1645 reflections | Δρmin = −0.23 e Å−3 |
112 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space, by a combination of seven sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.5 cm. Coverage of the unique set is 100% complete to at least 25.0° in θ. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
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. All H atoms were located by difference Fourier synthesis and refined with fixed individual displacement parameters [U(H) = 1.2Ueq(C) or U(H) = 1.2Ueq(O)] using a riding model with Csp2—H = 0.95, C—H(secondary) = 0.99 or C—H(tertiary) = 1.00 Å. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2870 (4) | 0.9379 (4) | 0.1571 (2) | 0.0207 (5) | |
H1 | 0.2886 | 1.0619 | 0.0844 | 0.025* | |
C11 | 0.3757 (5) | 0.7395 (4) | 0.0938 (2) | 0.0211 (5) | |
O11 | 0.5894 (3) | 0.6295 (3) | 0.06430 (17) | 0.0291 (5) | |
O12 | 0.2065 (3) | 0.7016 (3) | 0.06806 (18) | 0.0314 (5) | |
H12 | 0.2686 | 0.5893 | 0.0334 | 0.038* | |
C2 | 0.4616 (4) | 0.9163 (4) | 0.2388 (2) | 0.0186 (5) | |
H2 | 0.6241 | 0.8810 | 0.1824 | 0.022* | |
C21 | 0.4762 (4) | 0.7318 (4) | 0.3530 (2) | 0.0202 (5) | |
O21 | 0.3789 (3) | 0.6042 (3) | 0.36908 (16) | 0.0257 (5) | |
O22 | 0.6098 (3) | 0.7174 (3) | 0.43200 (16) | 0.0273 (5) | |
H22 | 0.6136 | 0.6115 | 0.4926 | 0.033* | |
C3 | 0.3894 (4) | 1.1354 (4) | 0.2828 (2) | 0.0244 (6) | |
H3B | 0.4747 | 1.1103 | 0.3529 | 0.029* | |
H3A | 0.4393 | 1.2365 | 0.2089 | 0.029* | |
C4 | 0.1265 (5) | 1.2383 (5) | 0.3306 (3) | 0.0342 (7) | |
H4 | 0.0693 | 1.3529 | 0.3791 | 0.041* | |
C5 | −0.0315 (5) | 1.1790 (5) | 0.3091 (3) | 0.0353 (7) | |
H5 | −0.1950 | 1.2524 | 0.3451 | 0.042* | |
C6 | 0.0271 (4) | 1.0045 (4) | 0.2322 (2) | 0.0249 (6) | |
H6A | −0.0833 | 1.0592 | 0.1704 | 0.030* | |
H6B | 0.0049 | 0.8754 | 0.2918 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0258 (14) | 0.0184 (12) | 0.0182 (12) | −0.0082 (11) | −0.0056 (10) | −0.0024 (9) |
C11 | 0.0271 (14) | 0.0231 (13) | 0.0149 (11) | −0.0111 (11) | −0.0061 (10) | −0.0013 (9) |
O11 | 0.0294 (11) | 0.0316 (11) | 0.0300 (10) | −0.0101 (9) | −0.0036 (8) | −0.0158 (8) |
O12 | 0.0339 (11) | 0.0309 (11) | 0.0377 (11) | −0.0109 (9) | −0.0119 (9) | −0.0161 (8) |
C2 | 0.0193 (12) | 0.0207 (12) | 0.0170 (11) | −0.0065 (10) | −0.0035 (9) | −0.0067 (9) |
C21 | 0.0173 (12) | 0.0205 (12) | 0.0195 (12) | −0.0015 (10) | −0.0037 (9) | −0.0081 (9) |
O21 | 0.0318 (11) | 0.0249 (10) | 0.0250 (9) | −0.0136 (8) | −0.0103 (8) | −0.0019 (7) |
O22 | 0.0354 (11) | 0.0296 (10) | 0.0227 (9) | −0.0158 (9) | −0.0140 (8) | 0.0008 (7) |
C3 | 0.0276 (14) | 0.0215 (13) | 0.0272 (13) | −0.0095 (11) | −0.0073 (11) | −0.0068 (10) |
C4 | 0.0300 (16) | 0.0297 (15) | 0.0430 (16) | −0.0038 (13) | −0.0062 (13) | −0.0205 (13) |
C5 | 0.0233 (15) | 0.0376 (16) | 0.0441 (17) | −0.0046 (13) | −0.0019 (12) | −0.0226 (13) |
C6 | 0.0217 (14) | 0.0246 (13) | 0.0287 (13) | −0.0067 (11) | −0.0059 (11) | −0.0077 (10) |
C1—C11 | 1.510 (3) | C2—C3 | 1.544 (3) |
C1—C2 | 1.536 (3) | C21—O21 | 1.226 (3) |
C1—C6 | 1.538 (3) | C21—O22 | 1.321 (3) |
C11—O11 | 1.225 (3) | C3—C4 | 1.491 (4) |
C11—O12 | 1.316 (3) | C4—C5 | 1.322 (4) |
C2—C21 | 1.513 (3) | C5—C6 | 1.503 (4) |
C11—C1—C2 | 111.4 (2) | C1—C2—C3 | 110.21 (19) |
C11—C1—C6 | 114.59 (19) | O21—C21—O22 | 123.1 (2) |
C2—C1—C6 | 112.48 (19) | O21—C21—C2 | 123.5 (2) |
O11—C11—O12 | 123.3 (2) | O22—C21—C2 | 113.4 (2) |
O11—C11—C1 | 122.0 (2) | C4—C3—C2 | 112.0 (2) |
O12—C11—C1 | 114.7 (2) | C5—C4—C3 | 123.7 (3) |
C21—C2—C1 | 111.11 (19) | C4—C5—C6 | 125.2 (3) |
C21—C2—C3 | 111.80 (19) | C5—C6—C1 | 110.6 (2) |
C2—C1—C11—O11 | −29.1 (3) | C1—C2—C21—O22 | −175.01 (19) |
C6—C1—C11—O11 | −158.3 (2) | C3—C2—C21—O22 | −51.4 (3) |
C2—C1—C11—O12 | 153.8 (2) | C21—C2—C3—C4 | −79.9 (3) |
C6—C1—C11—O12 | 24.7 (3) | C1—C2—C3—C4 | 44.2 (3) |
C11—C1—C2—C21 | −65.2 (3) | C2—C3—C4—C5 | −15.3 (4) |
C6—C1—C2—C21 | 65.1 (3) | C3—C4—C5—C6 | −1.3 (5) |
C11—C1—C2—C3 | 170.32 (19) | C4—C5—C6—C1 | −12.2 (4) |
C6—C1—C2—C3 | −59.4 (3) | C11—C1—C6—C5 | 170.8 (2) |
C1—C2—C21—O21 | 6.8 (3) | C2—C1—C6—C5 | 42.2 (3) |
C3—C2—C21—O21 | 130.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.84 | 1.83 | 2.667 (3) | 172 |
O22—H22···O21ii | 0.84 | 1.81 | 2.645 (3) | 176 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H10O4 |
Mr | 170.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.308 (4), 6.892 (4), 10.875 (7) |
α, β, γ (°) | 74.57 (1), 73.78 (1), 64.41 (1) |
V (Å3) | 403.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.25 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Empirical (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.972, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4809, 1645, 1151 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.127, 1.08 |
No. of reflections | 1645 |
No. of parameters | 112 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.23 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1991).
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.84 | 1.83 | 2.667 (3) | 172 |
O22—H22···O21ii | 0.84 | 1.81 | 2.645 (3) | 176 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
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The crystal structure of the title compound, (I), was determined in order to establish unambiguously the nature of a reaction product. The molecular geometry and the crystal structure of the title compound agree well with the structure determined at room temperature (Küppers & Kim, 1993). A least-squares fit of all non-H atoms shows an r.m.s. deviation of 0.014 Å. The cyclohexene ring exhibits a half-chair conformation, with atoms C3, C4, C5 and C6 in a common plane (σ = 0.003 Å) and C1 0.326 (5) Å above and C2 0.400 (5) Å below that plane. The cell axes are a little shorter at 173 K, and the anisotropic displacement parameters are, as expected, smaller. However, there are no significant differences between the structures at different temperatures. The crystal packing is stabilized by two hydrogen bonds (Table 1).