rac-4-Carbamoylpiperidinium cis-2-car­boxy­cyclo­hexane-1-carboxyl­ate

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536812004710

. 2012 Feb 10;68(Pt 3):o660. doi: 10.1107/S1600536812004710

rac-4-Carbamoylpiperidinium cis-2-carboxycyclohexane-1-carboxylate

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

PMCID: PMC3295451 PMID: 22412562

Abstract

In the title racemic salt, C₆H₁₃N₂O⁺·C₈H₁₁O₄ ⁻, formed from the reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with isonipecotamide, the cations are linked into duplex chain substructures through both centrosymmetric cyclic head-to-head ‘amide motif’ hydrogen-bonding associations [graph set R ₂ ²(8)] and ‘side-by-side’ R ₂ ²(14) associations. The anions are incorporated into the chains through cyclic R ₄ ³(10) interactions involving amide and piperidinium N—H⋯O_carboxyl hydrogen bonds which, together with inter-anion carboxylic acid O—H⋯O_carboxyl hydrogen bonds, give a two-dimensional layered structure extending along (011).

Related literature

For examples of structures of 1:1 Lewis base salts of cis-cyclohexane-1,2-dicarboxylic acid, see: Smith & Wermuth (2011a ▶,b ▶). For examples of isonipecotamide proton-transfer salts, see: Smith & Wermuth (2010 ▶). For graph-set analysis, see: Etter et al. (1990 ▶). For hydrogen-bonding motifs, see: Allen et al. (1998 ▶).

Experimental

Crystal data

C₆H₁₃N₂O⁺·C₈H₁₁O₄ ⁻
M _r = 300.35
Monoclinic,
a = 19.0097 (14) Å
b = 9.0667 (7) Å
c = 9.1999 (8) Å
β = 92.022 (7)°
V = 1584.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.40 × 0.35 × 0.10 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.86, T _max = 0.98
10518 measured reflections
3100 independent reflections
2146 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.075
wR(F ²) = 0.182
S = 1.06
3100 reflections
210 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.20 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/S1600536812004710/nk2139sup1.cif

e-68-0o660-sup1.cif^{(20KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004710/nk2139Isup2.hkl

e-68-0o660-Isup2.hkl^{(149KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812004710/nk2139Isup3.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—H11A⋯O41Aⁱ	0.97 (3)	1.95 (3)	2.861 (3)	155 (2)
N1A—H12A⋯O11	0.99 (4)	1.64 (4)	2.588 (4)	158 (3)
N41A—H41A⋯O41Aⁱⁱ	0.86 (3)	2.14 (4)	2.996 (3)	174 (2)
N41A—H42A⋯O12ⁱⁱⁱ	0.77 (3)	2.11 (3)	2.882 (4)	177 (3)
O22—H22⋯O12^iv	0.93 (5)	1.64 (5)	2.571 (3)	173 (4)

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

Acknowledgments

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

supplementary crystallographic information

Comment

cis-Cyclohexane-1,2-dicarboxylic anhydride (cis-CHDC anhydride) forms racemic 1:1 salts with some Lewis bases and the structures of a few of these have been reported, e.g. with 2-aminopyridine (Smith & Wermuth, 2011a) and 4-aminopyridine (Smith & Wermuth, 2011b). The 1:1 stoichiometric reaction of cis-CHDC anhydride with piperidine-4-carboxamide (isonipecotamide) also gave a racemic salt, the title compound, C₆H₁₂N₂O⁺.C₈H₁₁O₄^- and the structure is reported here.

In this compound (Fig. 1) the cis-configuration of the anion is found as expected, with the cations linked into duplex ribbon substructures through both centrosymmetric cyclic head-to-head hydrogen-bonding associations [the `amide' motif (Allen et al., 1998)] [graph set R₂²(8) (Etter et al., 1990)] and `side-by-side' R₂²(14) associations (Table 1, Fig. 2). Both of these associations have been found in the structures of Lewis base salts of isonipecotamide (Smith & Wermuth, 2010). In the present structure, the monoanions are incorporated into the ribbons through cyclic R³₄(10) amide and piperidinium N—H···O_carboxyl associations and together with inter-anion carboxylic acid O—H···O_carboxyl hydrogen bonds down c (Fig. 3), give a two-dimensional layered structure extending along (011).

Experimental

The title compound was synthesized by heating together under reflux for 15 min, 1 mmol quantities of cyclohexane-1,2-dicarboxylic anhydride and piperidine-4-carboxamide (isonipecotamide) in 50 ml of methanol. After volume reduction to 30 ml, the hot-filtered solution was allowed evaporate to dryness at room temperature, giving a white amorphous powder. Minor colourless crystal plates were obtained in the residual viscous residue after evaporation of a solution of the compound in 80% propane-2-ol–water.