4-Amino-3-ammonio­pyridinium dichloride

Jian-Hua Qin; Jian-Ge Wang

doi:10.1107/S1600536808041962

. 2008 Dec 17;65(Pt 1):o131. doi: 10.1107/S1600536808041962

4-Amino-3-ammoniopyridinium dichloride

Jian-Hua Qin ^a,^*, Jian-Ge Wang ^a

PMCID: PMC2968050 PMID: 21581592

Abstract

The anions and cations of the title compound, C₅H₉N₃ ²⁺·2Cl⁻, are connected by two chloride-bridged three-centered N—H⋯Cl hydrogen bonds into a three-dimensional network. The aromatic rings are not involved in stacking interactions.

Related literature

For bond distances and angles in pyridine, derived from microwave spectra, see: Sørensen et al. (1974 ▶). For details of the N—H⋯Cl hydrogen bond in 4,4′-bipyridine compounds, see: Iyere et al. (2003 ▶). For N—H⋯Cl and secondary interactions in pyridinium chlorides, see: Jones et al. (2002 ▶); in 4-acetylpyridinium chloride, see: Kochel (2005 ▶). For N—H⋯Cl and O—H⋯Cl contacts in a triphenyl-pyridinium chloride (1/1) adduct, see: Sykora & Cioffi (2007 ▶).

Experimental

Crystal data

C₅H₉N₃ ²⁺·2Cl⁻
M _r = 182.05
Monoclinic,
a = 8.362 (2) Å
b = 7.3218 (19) Å
c = 13.239 (3) Å
β = 92.065 (4)°
V = 810.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 296 (2) K
0.41 × 0.31 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.734, T _max = 0.948
3949 measured reflections
1494 independent reflections
1345 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.068
S = 1.14
1494 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041962/si2142sup1.cif

e-65-0o131-sup1.cif^{(12.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041962/si2142Isup2.hkl

e-65-0o131-Isup2.hkl^{(73.7KB, 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
N1—H1A⋯Cl2ⁱ	0.89	2.22	3.1142 (15)	178
N1—H1B⋯Cl2ⁱⁱ	0.89	2.37	3.1754 (16)	151
N1—H1C⋯Cl1ⁱⁱⁱ	0.89	2.23	3.0790 (16)	160
N2—H2A⋯Cl1ⁱⁱ	0.86	2.39	3.2188 (17)	163
N2—H2B⋯Cl1^iv	0.86	2.42	3.2672 (17)	168
N3—H3⋯Cl2	0.86	2.59	3.2499 (16)	135
N3—H3⋯Cl2^v	0.86	2.70	3.3198 (16)	130

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

Acknowledgments

The authors thank Luo Yang Normal University for supporting this work.

supplementary crystallographic information

Comment

The title compound is a salt containing a diprotonated 3,4-diaminopyridine cation and two Cl^- anions (Fig. 1). The C1—N3—C5 bond angle is wider than that in pyridine (116.94 (3)°; Sørensen et al., 1974) which indicates that the pyridine ring N atom is protonated (Table 1). Also, the 4-amino N atom is protonated. The projection of the crystal packing along the b axis is shown in Fig. 2. The Cl^- anions and the 3,4-diaminopyridinium cations in the title compound are bonded by two chlorine-bridged, three-centered N—H···Cl hydrogen bonds into a three-dimensional network (Fig. 2, Table 2). Example structures of related compounds with two- and three-centered N—H···Cl hydrogen bonds are discussed by Iyere et al. (2003); Jones et al. (2002); Kochel (2005) and Sykora & Cioffi (2007).

Experimental

3,4-diaminopyridine (0.01 mmol) and HCl (0.02 mmol) in 10 ml ethanol. Suitable crystals for X-ray analysis, were grown by allowing the solution to slowly evaporate for 15 days, and were subsequently filtered off, washed with methanol and dried under air.