cis-Cyclo­hexane-1,4-dicarboxylic acid

Wang, Y.-Q.; Weng, J.-B.

doi:10.1107/S1600536809016110

organic compounds

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Volume 65| Part 6| June 2009| Page o1293

doi:10.1107/S1600536809016110

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cis-Cyclohexane-1,4-dicarboxylic acid

Yan-Qin Wang ^a ^* and Jia-Bao Weng ^a

^aFujian Provincial Key Laboratory for Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350007, People's Republic of China
^*Correspondence e-mail: yqwang@fjnu.edu.cn

(Received 8 March 2009; accepted 29 April 2009; online 14 May 2009)

In the title compound, C₈H₁₂O₄, the two carboxyl groups are on the same side of the cyclohexane ring and the ring adopts a chair conformation. Adjacent molecules related by an inversion centre are linked by pairs of O—H⋯O hydrogen bonds, forming a zigzag chain along [1 $[\overline{1}]$ $[\overline{1}]$ ].

Related literature

For related structures, see: Bi et al. (2003 , 2004 ); Chen et al. (2006 ); Du et al. (2006 ); Dunitz & Strickler (1966 ); Kurmoo et al. (2003 , 2006 ); Luger et al. (1972 ).

Experimental

Crystal data

C₈H₁₂O₄
M_r = 172.18
Triclinic, $[P \overline 1]$
a = 5.2912 (6) Å
b = 6.2611 (6) Å
c = 13.1851 (18) Å
α = 82.505 (10)°
β = 80.309 (11)°
γ = 81.875 (10)°
V = 423.70 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.979, T_max = 0.989
9807 measured reflections
1925 independent reflections
1222 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.129
S = 1.05
1925 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1⋯O1ⁱ	0.88 (4)	1.81 (4)	2.684 (2)	178 (4)
O3—H8⋯O4ⁱⁱ	1.01 (4)	1.65 (4)	2.658 (2)	175 (4)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+2, -y, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016110/is2399sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016110/is2399Isup2.hkl

checkCIF report

Comment top

According to the literatures, there are a few structures incorporating 1,4-cis-Cyclohexane dicarboxylic acid (Bi et al., 2004). Although the structures of its isomer in trans conformation have been described for more than 40 years (Dunitz & Strickler, 1996; Luger et al., 1972), the structure of the title compound, (I), has only been reported as a co-crystal by Du et al. (2006).

According to the results of single X-ray diffraction analysis, there is one complete molecule in the asymmetric unit, and the molecule is in a general position (Fig. 1). The geometry of the molecule is similar to the one observed by Du et al. (2006). The bond lengths are comparable to those in its isomers in trans conformations (Bi et al., 2003; Chen et al., 2006; Kurmoo et al., 2003, 2006).

Strong hydrogen bonds between two adjacent carboxylate groups link molecules into a zigzag chain along the [111] direction. The zigzag chains are packed into three-dimensional motif (Fig. 2).

Related literature top

For related structures, see: Bi et al. (2003, 2004); Chen et al. (2006); Du et al. (2006); Dunitz & Strickler (1966); Kurmoo et al. (2003, 2006); Luger et al. (1972).

Experimental top

C₈H₁₂O₄ (1 mmol, 172 mg; mixture of trans- and cis-ACROS) was disloved into 50 ml of CD₃OD. The solution was stirring and refluxing for 12 h, and the clear solution was allowed to evaporate slowly in the inert atmosphere. Nice plate crystals of the title compound were obtained after 5 days. The crystals were filtered, washed by cool EtOH and dried in the air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure showing 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram viewed down the b axis, The H-bonds are shown as dotted lines.

cis-Cyclohexane-1,4-dicarboxylic acid top

Crystal data top

C₈H₁₂O₄	Z = 2
M_r = 172.18	F(000) = 184
Triclinic, P1	D_x = 1.350 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2912 (6) Å	Cell parameters from 3560 reflections
b = 6.2611 (6) Å	θ = 2.6–26.9°
c = 13.1851 (18) Å	µ = 0.11 mm⁻¹
α = 82.505 (10)°	T = 296 K
β = 80.309 (11)°	Plate, colorless
γ = 81.875 (10)°	0.24 × 0.20 × 0.10 mm
V = 423.70 (9) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1925 independent reflections
Radiation source: fine-focus sealed tube	1222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.979, T_max = 0.989	k = −7→8
9807 measured reflections	l = −17→17

Refinement top

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.038P)² + 0.2496P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1925 reflections	Δρ_max = 0.27 e Å⁻³
118 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.057 (12)

Crystal data top

C₈H₁₂O₄	γ = 81.875 (10)°
M_r = 172.18	V = 423.70 (9) Å³
Triclinic, P1	Z = 2
a = 5.2912 (6) Å	Mo Kα radiation
b = 6.2611 (6) Å	µ = 0.11 mm⁻¹
c = 13.1851 (18) Å	T = 296 K
α = 82.505 (10)°	0.24 × 0.20 × 0.10 mm
β = 80.309 (11)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1925 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1222 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.989	R_int = 0.038
9807 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.27 e Å⁻³
1925 reflections	Δρ_min = −0.19 e Å⁻³
118 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.4359 (3)	0.5154 (3)	0.88398 (12)	0.0583 (5)
O2	0.2703 (4)	0.2964 (3)	1.01503 (13)	0.0620 (5)
O3	0.7370 (4)	−0.1284 (3)	0.57741 (15)	0.0709 (6)
O4	0.8260 (3)	0.2120 (3)	0.55122 (14)	0.0632 (5)
C1	0.2929 (4)	0.3798 (3)	0.91784 (16)	0.0386 (5)
C2	0.1278 (4)	0.2898 (4)	0.85544 (16)	0.0420 (5)
H2	−0.0488	0.3021	0.8932	0.050*
C3	0.2176 (4)	0.0476 (3)	0.84796 (17)	0.0457 (6)
H3A	0.2410	−0.0240	0.9161	0.055*
H3B	0.0853	−0.0174	0.8242	0.055*
C4	0.1185 (4)	0.4153 (4)	0.74843 (17)	0.0493 (6)
H4A	−0.0264	0.3782	0.7208	0.059*
H4B	0.0878	0.5694	0.7557	0.059*
C5	0.4695 (4)	0.0121 (3)	0.77409 (16)	0.0411 (5)
H5A	0.5175	−0.1420	0.7694	0.049*
H5B	0.6056	0.0664	0.8006	0.049*
C6	0.3638 (4)	0.3713 (4)	0.67093 (17)	0.0457 (6)
H6A	0.3350	0.4396	0.6028	0.055*
H6B	0.5029	0.4346	0.6907	0.055*
C7	0.4420 (4)	0.1286 (3)	0.66664 (16)	0.0411 (5)
H7	0.3028	0.0710	0.6423	0.049*
C8	0.6862 (4)	0.0769 (4)	0.59270 (16)	0.0432 (5)
H1	0.369 (7)	0.355 (6)	1.048 (3)	0.106 (12)*
H8	0.898 (8)	−0.163 (6)	0.526 (3)	0.128 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0785 (12)	0.0610 (11)	0.0431 (9)	−0.0335 (10)	−0.0145 (8)	−0.0002 (8)
O2	0.0795 (13)	0.0717 (12)	0.0413 (10)	−0.0360 (10)	−0.0111 (9)	0.0020 (8)
O3	0.0759 (13)	0.0525 (11)	0.0741 (13)	−0.0054 (9)	0.0251 (10)	−0.0191 (9)
O4	0.0571 (11)	0.0595 (11)	0.0685 (12)	−0.0124 (9)	0.0167 (9)	−0.0190 (9)
C1	0.0371 (11)	0.0377 (11)	0.0396 (12)	−0.0004 (9)	−0.0016 (9)	−0.0091 (9)
C2	0.0299 (10)	0.0512 (13)	0.0452 (12)	−0.0048 (9)	0.0017 (9)	−0.0163 (10)
C3	0.0454 (12)	0.0447 (13)	0.0476 (13)	−0.0145 (10)	0.0045 (10)	−0.0131 (10)
C4	0.0422 (12)	0.0544 (14)	0.0531 (14)	0.0066 (10)	−0.0150 (10)	−0.0168 (11)
C5	0.0437 (12)	0.0358 (11)	0.0422 (12)	−0.0034 (9)	0.0003 (9)	−0.0084 (9)
C6	0.0490 (13)	0.0490 (13)	0.0378 (12)	0.0017 (10)	−0.0098 (10)	−0.0038 (10)
C7	0.0377 (11)	0.0491 (13)	0.0383 (11)	−0.0058 (9)	−0.0051 (9)	−0.0122 (9)
C8	0.0450 (12)	0.0483 (14)	0.0366 (11)	−0.0024 (10)	−0.0057 (9)	−0.0097 (10)

Geometric parameters (Å, º) top

O1—C1	1.209 (2)	C3—H3B	0.9700
O2—C1	1.312 (3)	C4—C6	1.527 (3)
O2—H1	0.88 (4)	C4—H4A	0.9700
O3—C8	1.310 (3)	C4—H4B	0.9700
O3—H8	1.01 (4)	C5—C7	1.526 (3)
O4—C8	1.217 (3)	C5—H5A	0.9700
C1—C2	1.503 (3)	C5—H5B	0.9700
C2—C4	1.528 (3)	C6—C7	1.523 (3)
C2—C3	1.534 (3)	C6—H6A	0.9700
C2—H2	0.9800	C6—H6B	0.9700
C3—C5	1.520 (3)	C7—C8	1.505 (3)
C3—H3A	0.9700	C7—H7	0.9800

C1—O2—H1	110 (2)	H4A—C4—H4B	107.6
C8—O3—H8	114 (2)	C3—C5—C7	110.71 (18)
O1—C1—O2	121.6 (2)	C3—C5—H5A	109.5
O1—C1—C2	124.7 (2)	C7—C5—H5A	109.5
O2—C1—C2	113.66 (19)	C3—C5—H5B	109.5
C1—C2—C4	113.11 (18)	C7—C5—H5B	109.5
C1—C2—C3	109.99 (18)	H5A—C5—H5B	108.1
C4—C2—C3	111.41 (17)	C7—C6—C4	111.18 (19)
C1—C2—H2	107.3	C7—C6—H6A	109.4
C4—C2—H2	107.3	C4—C6—H6A	109.4
C3—C2—H2	107.3	C7—C6—H6B	109.4
C5—C3—C2	111.67 (17)	C4—C6—H6B	109.4
C5—C3—H3A	109.3	H6A—C6—H6B	108.0
C2—C3—H3A	109.3	C8—C7—C6	113.13 (18)
C5—C3—H3B	109.3	C8—C7—C5	109.85 (18)
C2—C3—H3B	109.3	C6—C7—C5	111.08 (17)
H3A—C3—H3B	107.9	C8—C7—H7	107.5
C6—C4—C2	114.13 (18)	C6—C7—H7	107.5
C6—C4—H4A	108.7	C5—C7—H7	107.5
C2—C4—H4A	108.7	O4—C8—O3	122.7 (2)
C6—C4—H4B	108.7	O4—C8—C7	123.5 (2)
C2—C4—H4B	108.7	O3—C8—C7	113.8 (2)

O1—C1—C2—C4	−10.6 (3)	C2—C4—C6—C7	51.0 (2)
O2—C1—C2—C4	169.74 (18)	C4—C6—C7—C8	−178.86 (18)
O1—C1—C2—C3	114.7 (2)	C4—C6—C7—C5	−54.8 (2)
O2—C1—C2—C3	−65.0 (2)	C3—C5—C7—C8	−175.50 (17)
C1—C2—C3—C5	−74.0 (2)	C3—C5—C7—C6	58.6 (2)
C4—C2—C3—C5	52.3 (2)	C6—C7—C8—O4	9.4 (3)
C1—C2—C4—C6	74.9 (2)	C5—C7—C8—O4	−115.3 (2)
C3—C2—C4—C6	−49.6 (2)	C6—C7—C8—O3	−171.16 (19)
C2—C3—C5—C7	−57.3 (2)	C5—C7—C8—O3	64.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1ⁱ	0.88 (4)	1.81 (4)	2.684 (2)	178 (4)
O3—H8···O4ⁱⁱ	1.01 (4)	1.65 (4)	2.658 (2)	175 (4)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂O₄
M_r	172.18
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.2912 (6), 6.2611 (6), 13.1851 (18)
α, β, γ (°)	82.505 (10), 80.309 (11), 81.875 (10)
V (Å³)	423.70 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.979, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	9807, 1925, 1222
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.129, 1.05
No. of reflections	1925
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.19

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1ⁱ	0.88 (4)	1.81 (4)	2.684 (2)	178 (4)
O3—H8···O4ⁱⁱ	1.01 (4)	1.65 (4)	2.658 (2)	175 (4)

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

Acknowledgements

The authors are grateful for funding support from the National Natural Science Foundation of China (20471015; 20874012) and the Foundation for Key Programs of the Ministry of Education, China (DB–O57).

References

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