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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o992.
Published online 2008 May 3. doi:  10.1107/S1600536808012592
PMCID: PMC2961601

Low-temperature redetermination of trans-cyclo­hexane-1,2-dicarboxylic acid

Abstract

The mol­ecule of the title compound, C8H12O4, lies on a twofold rotation axis that passes through the mid-points of two opposite C—C bonds of the ring. Carboxyl groups of adjacent mol­ecules are linked by pairs of hydrogen bonds around a centre of inversion; this inter­action gives rise to a chain that runs along [101].

Related literature

Studies on the metal derivatives of trans-1,2-cyclo­hexa­ne­dicarboxylic acid refer to the room-temperature structure of Benedetti et al. (1969 [triangle]). The absence of a preferred orientation (either axial or equatorial) of the carboxyl groups in cyclo­hexa­nedicarboxylic acids is discussed in the case of 1,3-cyclo­hexanedicarboxylic acid by van Koningsveld (1984 [triangle]). For the crystal structure of 1,4-cyclo­hexa­nedicarboxylic acid, see: Luger et al. (1972 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o992-scheme1.jpg

Experimental

Crystal data

  • C8H12O4
  • M r = 172.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o992-efi2.jpg
  • a = 5.585 (1) Å
  • b = 13.840 (3) Å
  • c = 10.035 (2) Å
  • β = 96.114 (3)°
  • V = 771.3 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 100 (2) K
  • 0.38 × 0.06 × 0.04 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 2320 measured reflections
  • 883 independent reflections
  • 715 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.115
  • S = 1.07
  • 883 reflections
  • 59 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012592/cv2404sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012592/cv2404Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Crystallographic studies of the metal derivatives of trans-1,2-cyclohexanedicarboxylic acid occasionally refer to the room-temperature crystal structure of the dicarboxylic acid, which was reported in 1969. The report (Benedetti et al., 1969) contains typographical errors that have since been corrected in the Cambridge Structural Database (Version 5.29, Nov. 2007). The reported monoclinic cell dimensions can be transformed to 5.65 (1), b 13.34 (3), c 10.22 (3) Å; β 97.2 (2)°.

Whereas the low-temperature unit cell has a slightly larger volume compared with the room-temperature cell, the low-temperature cell has a much longer b-axis [13.840 (3) Å]. The bond distances and angles of room-temperature structure are normal; those of the present study are not significantly different despite the longer axis. Possibly, the expansion of this axis is a genuine observation. Moreover, the present study is able to establish the hydrogen bonding scheme of the compound (Scheme I, Fig. 1). Adjacent molecules are linked by a linear O–H···O hydrogen bond [2.662 (2) Å] into a chain (Fig. 2).

The crystal structures of 1,3- and 1,4-cyclohexanedicarboxylic acids have already been reported (van Koningsveld, 1984; Luger et al., 1972).

Experimental

The commercially available acid was recrystallized from ethanol.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.99 to 1.00 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 U(C). The acid H-atom was located in a difference Fourier map, and was isotropically refined with a distance restraint of O–H 0.85 (1) Å.

Figures

Fig. 1.
The molecular structure of the title compound with atomic numbering and 70% probability displacement ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radiius. The unlabeled atoms are related to the labeled ones by 1 - x, y, 1/2 - z.
Fig. 2.
A portion of the crystal packing showing the hydrogen-bonded (dashed lines) chain.

Crystal data

C8H12O4F000 = 368
Mr = 172.18Dx = 1.483 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 739 reflections
a = 5.585 (1) Åθ = 3.6–28.2º
b = 13.840 (3) ŵ = 0.12 mm1
c = 10.035 (2) ÅT = 100 (2) K
β = 96.114 (3)ºStrip, colourless
V = 771.3 (3) Å30.38 × 0.06 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 2.9º
ω scansh = −7→7
Absorption correction: Nonek = −17→17
2320 measured reflectionsl = −13→8
883 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0635P)2 + 0.2009P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
883 reflectionsΔρmax = 0.31 e Å3
59 parametersΔρmin = −0.28 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.0840 (2)0.1596 (1)0.0902 (1)0.0173 (3)
O20.4725 (2)0.1968 (1)0.0869 (1)0.0166 (3)
C10.3157 (3)0.1471 (1)0.1279 (2)0.0122 (3)
C20.3668 (2)0.0626 (1)0.2220 (2)0.0122 (4)
C30.2893 (3)−0.0314 (1)0.1475 (2)0.0139 (4)
C40.3647 (3)−0.1208 (1)0.2303 (2)0.0159 (4)
H1o0.068 (4)0.206 (1)0.035 (2)0.036 (6)*
H20.26760.07040.29860.015*
H3a0.1121−0.03150.12610.017*
H3b0.3626−0.03390.06200.017*
H4a0.2799−0.12180.31200.019*
H4b0.3184−0.17960.17760.019*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0124 (6)0.0179 (6)0.0205 (7)0.0008 (4)−0.0027 (5)0.0074 (5)
O20.0149 (6)0.0153 (6)0.0186 (6)−0.0017 (4)−0.0028 (4)0.0048 (4)
C10.0140 (7)0.0112 (7)0.0107 (8)0.0012 (5)−0.0025 (6)−0.0034 (6)
C20.0115 (7)0.0118 (7)0.0126 (8)0.0003 (5)−0.0025 (6)−0.0004 (6)
C30.0138 (7)0.0141 (7)0.0134 (8)−0.0013 (5)−0.0012 (6)−0.0014 (6)
C40.0170 (8)0.0109 (7)0.0190 (9)−0.0011 (5)−0.0012 (6)0.0003 (6)

Geometric parameters (Å, °)

O1—C11.321 (2)O1—H1o0.85 (1)
O2—C11.220 (2)C2—H21.0000
C1—C21.511 (2)C3—H3a0.9900
C2—C2i1.533 (3)C3—H3b0.9900
C2—C31.5397 (19)C4—H4a0.9900
C3—C41.523 (2)C4—H4b0.9900
C4—C4i1.521 (3)
O2—C1—O1123.1 (1)C3—C2—H2108.3
O2—C1—C2123.6 (1)C4—C3—H3a109.2
O1—C1—C2113.3 (1)C2—C3—H3a109.2
C1—C2—C2i109.9 (1)C4—C3—H3b109.2
C1—C2—C3109.0 (1)C2—C3—H3b109.2
C2i—C2—C3112.9 (1)H3a—C3—H3b107.9
C4—C3—C2112.0 (1)C4i—C4—H4a109.5
C4i—C4—C3110.5 (1)C3—C4—H4a109.5
C1—O1—H1o109 (1)C4i—C4—H4b109.5
C1—C2—H2108.3C3—C4—H4b109.5
C2i—C2—H2108.3H4a—C4—H4b108.1
O2—C1—C2—C2i11.2 (2)C1—C2—C3—C4172.7 (1)
O1—C1—C2—C2i−171.2 (1)C2i—C2—C3—C450.2 (2)
O2—C1—C2—C3−113.0 (2)C2—C3—C4—C4i−56.6 (2)
O1—C1—C2—C364.6 (2)

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···O2ii0.85 (1)1.81 (1)2.662 (2)178 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2404).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Benedetti, E., Corradini, P., Perrone, C. & Post, B. (1969). J. Am. Chem. Soc.91, 4072–4074.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Koningsveld, H. van (1984). Acta Cryst. C40, 1857–1863.
  • Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography