rac-cis-Cyclo­hexane-1,2-dicarb­oxy­lic acid–isoquinoline (1/1)

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536811030613

. 2011 Aug 6;67(Pt 9):o2261. doi: 10.1107/S1600536811030613

rac-cis-Cyclohexane-1,2-dicarboxylic acid–isoquinoline (1/1)

Graham Smith ^a,^*, Urs D Wermuth ^a

PMCID: PMC3200759 PMID: 22058919

Abstract

In the crystal structure of the title molecular adduct, C₉H₇N·C₈H₁₂O₄, the two species are linked through a carboxylic acid–isoquinoline O—H⋯N hydrogen bond. These molecular pairs then inter-associate through the second acid group of the cis-cyclohexane-1,2-dicarboxylic acid molecules, forming a classic centrosymmetric cyclic head-to-head carboxylic acid–carboxyl O—H⋯O hydrogen-bonding association [graph-set R ₂ ²(8)], giving a zero-dimensional (cluster) structure, consisting of two of each species.

Related literature

For the structure of racemic cis-cyclohexane-1,2-dicarboxylic acid, see: Benedetti et al. (1970 ▶). For the structures of the racemic 1:1 ammonium and 2-aminopyridinium salts of this acid, see: Smith & Wermuth (2011a ▶,b ▶). For the structure of the 1:1 adduct with 4,4′-bipyridine, see: Bhogala et al. (2005 ▶). For hydrogen bonding in carboxylic acids and graph-set analysis, see: Leiserowitz (1976 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

C₉H₇N·C₈H₁₂O₄
M _r = 301.33
Triclinic,
a = 6.2459 (3) Å
b = 11.4238 (6) Å
c = 11.9970 (6) Å
α = 64.082 (5)°
β = 77.793 (4)°
γ = 82.756 (4)°
V = 751.95 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.40 × 0.28 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.974, T _max = 0.990
9094 measured reflections
2952 independent reflections
2463 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.090
S = 1.02
2952 reflections
207 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811030613/nk2108sup1.cif

e-67-o2261-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030613/nk2108Isup2.hkl

e-67-o2261-Isup2.hkl^{(141.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811030613/nk2108Isup3.cml

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
O11—H11⋯O12ⁱ	0.96 (2)	1.68 (2)	2.6362 (14)	171.7 (18)
O22—H22⋯N2A	0.98 (2)	1.69 (2)	2.670 (2)	174.5 (19)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from the Australian Research Council, the Faculty of Science and Technology and the University Library, Queensland University of Technology.

supplementary crystallographic information

Comment

Although the structure of racemic cis-cyclohexane-1,2-dicarboxylic acid is known (Benedetti et al., 1970), together with its 1:1 adduct with 4,4'-bipyridine (Bhogala et al., 2005), there are few examples of salts of this cis-acid in the crystallographic literature. We have previously reported the structures of the anhydrous 1:1 ammonium salt (Smith & Wermuth, 2011a) and the 2-aminopyridinium salt (Smith & Wermuth, 2011b). Our 1:1 stoichiometric interaction of cyclohexane-1,2-dicarboxylic anhydride with isoquinoline in 50% ethanol–water solution gave minor crystals of the 1:1 adduct C₈H₁₂O₄. C₉H₇N, formed in a residual oil, and the structure is reported here.

In the structure of the title adduct (Fig. 1), the two molecular species are interlinked through a carboxylic acid O—H···N_isoquinoline hydrogen bond (Table 1). The molecule pairs then associate through the second acid group, forming a classic centrosymmetric cyclic head-to-head carboxylic acid–carboxyl O—H···O hydrogen-bonding interaction (Leiserowitz, 1976) [graph set R²₂(8) (Etter et al., 1990)] giving a zero-dimensional structure (Fig. 2).

Experimental

The title compound was synthesized by heating a solution of 1 mmol of cyclohexane-1,2-dicarboxylic anhydride and 1 mmol of isoquinoline in 50 ml of 1:1 ethanol–water under reflux for 10 min. After concentration to 30 ml the solution was allowed to evaporate at room temperature, giving a viscous oil which eventually gave minor colourless crystals (m.p. 439–441 K) from which a specimen was cleaved for the X-ray analysis.