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The structure of the title compound, C8H10O4, previously determined by Küppers & Kim [Acta Cryst. (1993), C49, 1218-1220] has been redetermined at 173 K. The cyclo­hexene ring exhibits a half-chair conformation. The molecular geometry and the crystal packing, which is stabilized by two hydrogen bonds, agree well with the room-temperature structure determination.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008908/qa0328sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008908/qa0328Isup2.hkl
Contains datablock I

CCDC reference: 150386

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

cis-4-cyclohexene-1,2-dicarboxylic acid top
Crystal data top
C8H10O4Z = 2
Mr = 170.16F(000) = 180
Triclinic, P1Dx = 1.400 Mg m3
a = 6.308 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.892 (4) ÅCell parameters from 2610 reflections
c = 10.875 (7) Åθ = 0–25°
α = 74.57 (1)°µ = 0.11 mm1
β = 73.78 (1)°T = 173 K
γ = 64.41 (1)°Block, colourless
V = 403.6 (4) Å30.25 × 0.15 × 0.15 mm
Data collection top
Siemens CCD three-circle
diffractometer
1645 independent reflections
Radiation source: fine-focus sealed tube1151 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 26.4°, θmin = 2.0°
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.972, Tmax = 0.983k = 88
4809 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-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 reflectionsΔρmax = 0.29 e Å3
112 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.068 (11)
Crystal data top
C8H10O4γ = 64.41 (1)°
Mr = 170.16V = 403.6 (4) Å3
Triclinic, P1Z = 2
a = 6.308 (4) ÅMo Kα radiation
b = 6.892 (4) ŵ = 0.11 mm1
c = 10.875 (7) ÅT = 173 K
α = 74.57 (1)°0.25 × 0.15 × 0.15 mm
β = 73.78 (1)°
Data collection top
Siemens CCD three-circle
diffractometer
1645 independent reflections
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
1151 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.983Rint = 0.043
4809 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.08Δρmax = 0.29 e Å3
1645 reflectionsΔρmin = 0.23 e Å3
112 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2870 (4)0.9379 (4)0.1571 (2)0.0207 (5)
H10.28861.06190.08440.025*
C110.3757 (5)0.7395 (4)0.0938 (2)0.0211 (5)
O110.5894 (3)0.6295 (3)0.06430 (17)0.0291 (5)
O120.2065 (3)0.7016 (3)0.06806 (18)0.0314 (5)
H120.26860.58930.03340.038*
C20.4616 (4)0.9163 (4)0.2388 (2)0.0186 (5)
H20.62410.88100.18240.022*
C210.4762 (4)0.7318 (4)0.3530 (2)0.0202 (5)
O210.3789 (3)0.6042 (3)0.36908 (16)0.0257 (5)
O220.6098 (3)0.7174 (3)0.43200 (16)0.0273 (5)
H220.61360.61150.49260.033*
C30.3894 (4)1.1354 (4)0.2828 (2)0.0244 (6)
H3B0.47471.11030.35290.029*
H3A0.43931.23650.20890.029*
C40.1265 (5)1.2383 (5)0.3306 (3)0.0342 (7)
H40.06931.35290.37910.041*
C50.0315 (5)1.1790 (5)0.3091 (3)0.0353 (7)
H50.19501.25240.34510.042*
C60.0271 (4)1.0045 (4)0.2322 (2)0.0249 (6)
H6A0.08331.05920.17040.030*
H6B0.00490.87540.29180.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0258 (14)0.0184 (12)0.0182 (12)0.0082 (11)0.0056 (10)0.0024 (9)
C110.0271 (14)0.0231 (13)0.0149 (11)0.0111 (11)0.0061 (10)0.0013 (9)
O110.0294 (11)0.0316 (11)0.0300 (10)0.0101 (9)0.0036 (8)0.0158 (8)
O120.0339 (11)0.0309 (11)0.0377 (11)0.0109 (9)0.0119 (9)0.0161 (8)
C20.0193 (12)0.0207 (12)0.0170 (11)0.0065 (10)0.0035 (9)0.0067 (9)
C210.0173 (12)0.0205 (12)0.0195 (12)0.0015 (10)0.0037 (9)0.0081 (9)
O210.0318 (11)0.0249 (10)0.0250 (9)0.0136 (8)0.0103 (8)0.0019 (7)
O220.0354 (11)0.0296 (10)0.0227 (9)0.0158 (9)0.0140 (8)0.0008 (7)
C30.0276 (14)0.0215 (13)0.0272 (13)0.0095 (11)0.0073 (11)0.0068 (10)
C40.0300 (16)0.0297 (15)0.0430 (16)0.0038 (13)0.0062 (13)0.0205 (13)
C50.0233 (15)0.0376 (16)0.0441 (17)0.0046 (13)0.0019 (12)0.0226 (13)
C60.0217 (14)0.0246 (13)0.0287 (13)0.0067 (11)0.0059 (11)0.0077 (10)
Geometric parameters (Å, º) top
C1—C111.510 (3)C2—C31.544 (3)
C1—C21.536 (3)C21—O211.226 (3)
C1—C61.538 (3)C21—O221.321 (3)
C11—O111.225 (3)C3—C41.491 (4)
C11—O121.316 (3)C4—C51.322 (4)
C2—C211.513 (3)C5—C61.503 (4)
C11—C1—C2111.4 (2)C1—C2—C3110.21 (19)
C11—C1—C6114.59 (19)O21—C21—O22123.1 (2)
C2—C1—C6112.48 (19)O21—C21—C2123.5 (2)
O11—C11—O12123.3 (2)O22—C21—C2113.4 (2)
O11—C11—C1122.0 (2)C4—C3—C2112.0 (2)
O12—C11—C1114.7 (2)C5—C4—C3123.7 (3)
C21—C2—C1111.11 (19)C4—C5—C6125.2 (3)
C21—C2—C3111.80 (19)C5—C6—C1110.6 (2)
C2—C1—C11—O1129.1 (3)C1—C2—C21—O22175.01 (19)
C6—C1—C11—O11158.3 (2)C3—C2—C21—O2251.4 (3)
C2—C1—C11—O12153.8 (2)C21—C2—C3—C479.9 (3)
C6—C1—C11—O1224.7 (3)C1—C2—C3—C444.2 (3)
C11—C1—C2—C2165.2 (3)C2—C3—C4—C515.3 (4)
C6—C1—C2—C2165.1 (3)C3—C4—C5—C61.3 (5)
C11—C1—C2—C3170.32 (19)C4—C5—C6—C112.2 (4)
C6—C1—C2—C359.4 (3)C11—C1—C6—C5170.8 (2)
C1—C2—C21—O216.8 (3)C2—C1—C6—C542.2 (3)
C3—C2—C21—O21130.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11i0.841.832.667 (3)172
O22—H22···O21ii0.841.812.645 (3)176
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC8H10O4
Mr170.16
Crystal system, space groupTriclinic, 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)
V3)403.6 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.25 × 0.15 × 0.15
Data collection
DiffractometerSiemens CCD three-circle
diffractometer
Absorption correctionEmpirical
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.972, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
4809, 1645, 1151
Rint0.043
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.127, 1.08
No. of reflections1645
No. of parameters112
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.23

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1991).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11i0.841.832.667 (3)172
O22—H22···O21ii0.841.812.645 (3)176
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.
 

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