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

Rizal, M.R.; Ng, S.W.

doi:10.1107/S1600536808012592

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o992

doi:10.1107/S1600536808012592

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

Mohd. Razali Rizal ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 21 April 2008; accepted 30 April 2008; online 3 May 2008)

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, C 2/c
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[F² > 2σ(F²)] = 0.042
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 the 1,3-cyclohexanedicarboxylic acid, see: van Koningsveld (1984). For the crystal structure of 1,4-cyclohexanedicarboxylic acid, see: Luger et al. (1972).

Experimental top

The commercially available acid was recrystallized from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	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.

trans-cyclohexane-1,2-dicarboxylic acid top

Crystal data top

C₈H₁₂O₄	F(000) = 368
M_r = 172.18	D_x = 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 = 3.6–28.2°
b = 13.840 (3) Å	µ = 0.12 mm⁻¹
c = 10.035 (2) Å	T = 100 K
β = 96.114 (3)°	Strip, colourless
V = 771.3 (3) Å³	0.38 × 0.06 × 0.04 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 2.9°
ω scans	h = −7→7
2320 measured reflections	k = −17→17
883 independent reflections	l = −13→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0635P)² + 0.2009P] where P = (F_o² + 2F_c²)/3
883 reflections	(Δ/σ)_max = 0.001
59 parameters	Δρ_max = 0.31 e Å⁻³
1 restraint	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₈H₁₂O₄	V = 771.3 (3) Å³
M_r = 172.18	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 5.585 (1) Å	µ = 0.12 mm⁻¹
b = 13.840 (3) Å	T = 100 K
c = 10.035 (2) Å	0.38 × 0.06 × 0.04 mm
β = 96.114 (3)°

Data collection top

Bruker SMART APEX diffractometer	715 reflections with I > 2σ(I)
2320 measured reflections	R_int = 0.035
883 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.31 e Å⁻³
883 reflections	Δρ_min = −0.28 e Å⁻³
59 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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 code: (ii) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₈H₁₂O₄
M_r	172.18
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	5.585 (1), 13.840 (3), 10.035 (2)
β (°)	96.114 (3)
V (Å³)	771.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.38 × 0.06 × 0.04

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2320, 883, 715
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.115, 1.07
No. of reflections	883
No. of parameters	59
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, −y+1/2, −z.

Acknowledgements

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

References

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