4-Aza­niumyl-2,2,6,6-tetra­methyl­piperidin-1-ium dinitrate

Hammouda Chebbi; Ridha Ben Smail; Mohamed Faouzi Zid

doi:10.1107/S1600536814009787

. 2014 May 10;70(Pt 6):o642. doi: 10.1107/S1600536814009787

4-Azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dinitrate

Hammouda Chebbi ^a,^b,^*, Ridha Ben Smail ^c,^b, Mohamed Faouzi Zid ^b

PMCID: PMC4051017 PMID: 24940229

Abstract

In the crystal structure of the title salt, C₉H₂₂N₂ ²⁺·2NO₃ ⁻, the piperidine ring of the dication adopts a chair conformation and the orientation of the C—NH₃ bond is equatorial. The ions are linked by normal and bifurcated N—H⋯O hydrogen bonds in R ₂ ²(6), two R ₄ ²(8) and R ₃ ⁴(14) graf-set motifs, generating a three-dimensional network.

Related literature

For related structures, see: Chebbi & Driss (2001 ▶); El Glaoui, Mrad, Jenneau & Ben Nasr (2010 ▶); Mrad et al. (2009 ▶); Huang & Deng (2007 ▶). For hydrogen bonding and graph-set motifs, see: Jeffrey (1997 ▶); Bernstein et al. (1995 ▶); Etter et al. (1990 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶); Spek (2009 ▶).

Experimental

Crystal data

C₉H₂₂N₂ ²⁺·2NO₃ ⁻
M _r = 282.31
Monoclinic,
a = 10.367 (2) Å
b = 11.054 (1) Å
c = 13.167 (2) Å
β = 112.45 (2)°
V = 1394.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.45 × 0.30 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.860, T _max = 0.978
2849 measured reflections
2731 independent reflections
1908 reflections with I > 2σ(I)
R _int = 0.017
2 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.121
S = 1.05
2731 reflections
261 parameters
All H-atom parameters refined
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814009787/nc2324sup1.cif

e-70-0o642-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009787/nc2324Isup2.hkl

e-70-0o642-Isup2.hkl^{(131.4KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814009787/nc2324Isup3.cml

CCDC reference: 1000438

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B⋯O1ⁱⁱ	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A⋯O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A⋯O2ⁱⁱⁱ	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B⋯O4ⁱⁱⁱ	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B⋯O3ⁱⁱⁱ	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C⋯O5ⁱ	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)

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

Acknowledgments

The authors thank Professor Dr Ahmed Driss for many helpful discussions.

supplementary crystallographic information

1. Comment

The title compound, C₉H₂₂N₂²⁺·2NO₃^-, was synthesized unexpectedly from 4-amino-2,2,6,6-tetramethylpiperidine, bismuth(III) nitrate pentahydrate and nitric acid. We report in this paper it's structure; its homologues obtained with chlorate, phosphate and tetrachlorozincate anions has been described previously (Huang & Deng, 2007; Mrad et al., 2009; El Glaoui et al., 2010).

The asymmetric unit of the title compound contains one 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dication and two nitrate anions (Fig. 1) with all atoms are located on general Wykoff position 4 e.

The piperidine ring adopts a chair conformation, with puckering parameters (calculated with PLATON (Spek, 2009)): Q = 0.535 Å, Θ = 6.63 ° and Φ = 205.565 ° (Cremer & Pople, 1975). This conformation has also been noticed in other 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium salts (Chebbi & Driss, 2001; Huang & Deng, 2007; Mrad et al., 2009; El Glaoui et al., 2010).

The three-dimensional extensive hydrogen-bonding network is built and linked through moderate hydrogen-bond interactions (Table 1) (Jeffrey, 1997) between the NH₃ and NH₂ groups of the dications and the nitrate anions, located in the vicinity of the protonated amine groups. Each organic entity is bounded to six different nitrate anions through seven N—H···O hydrogen bonds (Fig. 2). Indeed, N1—H1A···O1, N2—H2C···O5, N2—H2A···O2 and bifurcated N2—H2B···O3(O4) hydrogen bonds (Table 1) link dications and anions into chains along [010] direction, which generate R₃⁴(14) and R₂²(6) ring motifs (Etter et al., 1990; Bernstein, et al., 1995) (Fig. 3). These chains are interconnected by N1—H1B···O1 and N2—H2A···O4 hydrogen bonds (Table 1),which generate two sets of R₄²(8) ring motifs (Fig. 2). This arrangement results in the formation of a complicated three-dimensional network.

2. Experimental

The title compound was prepared by dissolving 0.096 mmol (0.36 g) of bismuth(III) nitrate pentahydrate in 20 ml of distilled water; 0.096 mmol (0.15 g) of 4-amino-2,2,6,6-tetramethylpiperidine in 15 ml of ethanol (96%) and 1 ml of concentred nitric acid were then added. The mixture was stirred for 20 minutes and the solution is allowed to stand at room temperature. Dark brown crystals were obtained after 5 days of slow evaporation of the solvent. The X-ray analysis proves that the trivalent bismuth is not part of the structure and that the obtained phase is C₉H₂₂N₂²⁺·2NO₃^-.