4-Amino­pyridinium cis-2-carb­oxy­cyclo­hexane-1-carboxyl­ate

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536811039547

. 2011 Sep 30;67(Pt 10):o2794. doi: 10.1107/S1600536811039547

4-Aminopyridinium cis-2-carboxycyclohexane-1-carboxylate

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

PMCID: PMC3201255 PMID: 22058823

Abstract

In the structure of the title molecular salt, C₅H₇N₂ ⁺·C₈H₁₁O₄ ⁻, the cis monoanions associate through short O—H⋯O hydrogen bonds in the carboxylic acid groups [graph set C(7)], forming zigzag chains which extend along the c axis. These are interlinked through pyridinium and amine N—H⋯O hydrogen bonds, giving a three-dimensional network structure.

Related literature

For the structure of racemic cis-cyclohexane-1,2-dicarboxylic acid, see: Benedetti et al. (1970 ▶). For the structure of the racemic ammonium and 2-aminopyridinium salts of cis-2-carboxycyclohexane-1-carboxylate, see: Smith & Wermuth (2011a ▶,b ▶). For graph-set analysis, see Etter et al. (1990 ▶).

Experimental

Crystal data

C₅H₇N₂ ⁺·C₈H₁₁O₄ ⁻
M _r = 266.29
Orthorhombic,
a = 12.1359 (3) Å
b = 9.8351 (3) Å
c = 11.1850 (3) Å
V = 1335.02 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.30 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.948, T _max = 0.990
9670 measured reflections
1709 independent reflections
1448 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.060
S = 0.99
1709 reflections
188 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811039547/fj2453sup1.cif

e-67-o2794-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039547/fj2453Isup2.hkl

e-67-o2794-Isup2.hkl^{(82.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811039547/fj2453Isup3.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
N1A—H1A⋯O12ⁱ	0.88 (2)	1.91 (2)	2.795 (2)	180 (3)
N41A—H41A⋯O12ⁱⁱ	0.86 (2)	2.14 (2)	2.989 (2)	168 (2)
N41A—H42A⋯O22	0.91 (2)	2.13 (2)	2.974 (2)	152.6 (18)
O21—H21⋯O11ⁱⁱⁱ	0.95 (3)	1.59 (3)	2.5302 (17)	170 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

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

The structures of Lewis base salts of cis-cyclohexane-1,2-dicarboxylic acid (cis-CHDC) are rare in the crystallographic literature and like the parent cis-acid (Benedetti et al., 1970), exist only in the unresolved racemic form. We have reported the structures of the 1:1 ammonium salt (Smith & Wermuth, 2011a) and the 1:1 2-aminopyridinium salt (Smith & Wermuth, 2011b) and in our parallel 1:1 stoichiometric reaction of cis-CHDC anhydride with 4-aminopyridine in 50% ethanol–water solution we also obtained minor crystals of the title compound, cis-C₅H₇N₂⁺ C₈H₁₁O₄^- (Fig. 1) and the structure is reported here.

In the structure of the title compound, the monoanions associate through strong carboxylic acid–carboxyl O—H···O hydrogen bonds (Table 1) giving zigzag chains [graph set C(7) (Etter et al., 1990)] which extend along c (Fig. 2). The cations provide links between these chains through both pyridinium and amine N—H···O_carboxyl hydrogen bonds, resulting in a three-dimensional structure (Figs. 2,3).

Experimental

The title compound was synthesized by heating a solution of 1 mmol of cyclohexane-1,2-dicarboxylic anhydride and 1 mmol of 4-aminopyridine 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 finally a residual viscous oil in which minor well formed colourless crystals of the title compound were found.