4-Carbamoylpiperidinium 5-nitro­salicylate

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536810050129

. 2010 Dec 15;67(Pt 1):o122. doi: 10.1107/S1600536810050129

4-Carbamoylpiperidinium 5-nitrosalicylate

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

PMCID: PMC3050397 PMID: 21522633

Abstract

In the crystal structure of the title compound, C₆H₁₃N₂O⁺·C₇H₄NO₅ ⁻, the isonipecotamide cations and the 5-nitrosalicylate anions form hydrogen-bonded chain substructures through head-to-tail piperidinium–carboxylate N—H⋯O hydrogen bonds and through centrosymmetric cyclic head-to-head amide–amide hydrogen-bonding associations [graph set R ₂ ²(8)]. These chains are cross-linked by amide–carboxylate N—H⋯O and piperidinium–nitro N—H⋯O associations, giving a sheet structure.

Related literature

For structural data on isonipecotamide salts, see: Smith et al. (2010 ▶); Smith & Wermuth (2010a ▶,b ▶,c ▶,d ▶). For structures of 5-nitrosalicylates, see: Smith et al. (2005 ▶). For hydrogen-bonding graph-set and motif classification, see: Etter et al. (1990 ▶); Allen et al. (1998 ▶).

Experimental

Crystal data

C₆H₁₃N₂O⁺·C₇H₄NO₅ ⁻
M _r = 311.30
Monoclinic,
a = 15.0442 (10) Å
b = 5.5851 (3) Å
c = 17.1939 (10) Å
β = 91.466 (6)°
V = 1444.22 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 200 K
0.40 × 0.25 × 0.16 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.912, T _max = 0.980
9191 measured reflections
2833 independent reflections
1850 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.092
S = 0.95
2833 reflections
219 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.17 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 datablocks global, I. DOI: 10.1107/S1600536810050129/bt5426sup1.cif

e-67-0o122-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050129/bt5426Isup2.hkl

e-67-0o122-Isup2.hkl^{(136.3KB, hkl)}

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⋯O12ⁱ	1.00 (2)	1.71 (2)	2.688 (2)	164.2 (18)
N1A—H12A⋯O11	0.95 (2)	1.80 (2)	2.747 (2)	173.9 (17)
N41A—H41A⋯O52ⁱⁱ	0.83 (2)	2.39 (2)	3.216 (2)	170.8 (19)
N41A—H42A⋯O41Aⁱⁱⁱ	0.99 (2)	1.91 (2)	2.873 (2)	164.8 (18)
O2—H2⋯O12	0.96 (2)	1.58 (2)	2.4897 (18)	156 (2)

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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, and the School of Biomolecular and Physical Sciences, Griffith University.

supplementary crystallographic information

Comment

The structures of a number of salts of the amide piperidine-4-carboxamide (isonipecotamide, INIPA) with a range of carboxylic acids, mainly aromatic, are now known (Smith & Wermuth, 2010a, 2010b, 2010c, Smith & Wermuth, 2010d,; Smith et al., 2010). The title compound C₆H₁₃N₂O⁺ C₇H₄NO₅^- (I) was obtained from the 1:1 stoichiometric reaction of 5-nitrosalicylic acid with INIPA in methanol and the structure is reported here.

In (I) (Fig. 1) the cations and anions form hydrogn-bonded chain substructures through head-to-tail piperidinium N—H···O_carboxyl hydrogen bonds and through centrosymmetric cyclic head-to-head amide–amide hydrogen-bonding associations [graph set R²₂(8) (Etter et al., 1990)]. These chains are cross linked by amide N—H···O_carboxyl and piperidinium N—H···O_nitro associations to giving a two-dimensional sheet structure (Fig. 2). The amide-amide dimer association [the 'amide motif' (Allen et al., 1998)] is relatively common among the INIPA salts (Smith & Wermuth, 2010b; Smith et al., 2010).

The 5-nitrosalicylate anions are essentially planar [torsion angles for the carboxyl group (C2–C1–C11–O11), 178.30 (16)° and the nitro group (C4–C5–N5–O52), -175.57 (16)°], which is the usual conformation for this anion in its proton-transfer compounds (Smith et al., 2005).

Experimental

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of piperidine-4-carboxamide (isonipecotamide) and 5-nitrosalicylic acid in 50 ml of methanol. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave pale yellow prisms of the title compound from which a specimen was cleaved for the X-ray analysis.