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 ▶). 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 ▶). For the crystal structure of 1,4-cyclo­hexa­nedicarboxylic acid, see: Luger et al. (1972 ▶).

Experimental

Crystal data

• C₈H₁₂O₄

• M _r = 172.18

• Monoclinic,

• a = 5.585 (1) Å

• b = 13.840 (3) Å

• c = 10.035 (2) Å

• β = 96.114 (3)°

• V = 771.3 (3) ų

• 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

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

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

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
O1—H1o⋯O2i	0.85 (1)	1.81 (1)	2.662 (2)	178 (2)

Symmetry code: (i) .

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

C8H12O4	F000 = 368
Mr = 172.18	Dx = 1.483 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 739 reflections
a = 5.585 (1) Å	θ = 3.6–28.2º
b = 13.840 (3) Å	µ = 0.12 mm−1
c = 10.035 (2) Å	T = 100 (2) K
β = 96.114 (3)º	Strip, colourless
V = 771.3 (3) Å3	0.38 × 0.06 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Monochromator: graphite	θmax = 27.5º
T = 100(2) K	θmin = 2.9º
ω scans	h = −7→7
Absorption correction: None	k = −17→17
2320 measured reflections	l = −13→8
883 independent reflections

Refinement

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)] = 0.042	H 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 reflections	Δρmax = 0.31 e Å−3
59 parameters	Δρmin = −0.28 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
O1	0.0840 (2)	0.1596 (1)	0.0902 (1)	0.0173 (3)
O2	0.4725 (2)	0.1968 (1)	0.0869 (1)	0.0166 (3)
C1	0.3157 (3)	0.1471 (1)	0.1279 (2)	0.0122 (3)
C2	0.3668 (2)	0.0626 (1)	0.2220 (2)	0.0122 (4)
C3	0.2893 (3)	−0.0314 (1)	0.1475 (2)	0.0139 (4)
C4	0.3647 (3)	−0.1208 (1)	0.2303 (2)	0.0159 (4)
H1o	0.068 (4)	0.206 (1)	0.035 (2)	0.036 (6)*
H2	0.2676	0.0704	0.2986	0.015*
H3a	0.1121	−0.0315	0.1261	0.017*
H3b	0.3626	−0.0339	0.0620	0.017*
H4a	0.2799	−0.1218	0.3120	0.019*
H4b	0.3184	−0.1796	0.1776	0.019*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0124 (6)	0.0179 (6)	0.0205 (7)	0.0008 (4)	−0.0027 (5)	0.0074 (5)
O2	0.0149 (6)	0.0153 (6)	0.0186 (6)	−0.0017 (4)	−0.0028 (4)	0.0048 (4)
C1	0.0140 (7)	0.0112 (7)	0.0107 (8)	0.0012 (5)	−0.0025 (6)	−0.0034 (6)
C2	0.0115 (7)	0.0118 (7)	0.0126 (8)	0.0003 (5)	−0.0025 (6)	−0.0004 (6)
C3	0.0138 (7)	0.0141 (7)	0.0134 (8)	−0.0013 (5)	−0.0012 (6)	−0.0014 (6)
C4	0.0170 (8)	0.0109 (7)	0.0190 (9)	−0.0011 (5)	−0.0012 (6)	0.0003 (6)

Geometric parameters (Å, °)

O1—C1	1.321 (2)	O1—H1o	0.85 (1)
O2—C1	1.220 (2)	C2—H2	1.0000
C1—C2	1.511 (2)	C3—H3a	0.9900
C2—C2i	1.533 (3)	C3—H3b	0.9900
C2—C3	1.5397 (19)	C4—H4a	0.9900
C3—C4	1.523 (2)	C4—H4b	0.9900
C4—C4i	1.521 (3)
O2—C1—O1	123.1 (1)	C3—C2—H2	108.3
O2—C1—C2	123.6 (1)	C4—C3—H3a	109.2
O1—C1—C2	113.3 (1)	C2—C3—H3a	109.2
C1—C2—C2i	109.9 (1)	C4—C3—H3b	109.2
C1—C2—C3	109.0 (1)	C2—C3—H3b	109.2
C2i—C2—C3	112.9 (1)	H3a—C3—H3b	107.9
C4—C3—C2	112.0 (1)	C4i—C4—H4a	109.5
C4i—C4—C3	110.5 (1)	C3—C4—H4a	109.5
C1—O1—H1o	109 (1)	C4i—C4—H4b	109.5
C1—C2—H2	108.3	C3—C4—H4b	109.5
C2i—C2—H2	108.3	H4a—C4—H4b	108.1
O2—C1—C2—C2i	11.2 (2)	C1—C2—C3—C4	172.7 (1)
O1—C1—C2—C2i	−171.2 (1)	C2i—C2—C3—C4	50.2 (2)
O2—C1—C2—C3	−113.0 (2)	C2—C3—C4—C4i	−56.6 (2)
O1—C1—C2—C3	64.6 (2)

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2ii	0.85 (1)	1.81 (1)	2.662 (2)	178 (2)

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