4-Amino-3-ammonio­pyridinium dinitrate

Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536810005556

. 2010 Feb 17;66(Pt 3):o639–o640. doi: 10.1107/S1600536810005556

4-Amino-3-ammoniopyridinium dinitrate

Madhukar Hemamalini ^a, Hoong-Kun Fun ^a,^*,^‡

PMCID: PMC2983652 PMID: 21580395

Abstract

In the crystal structure of the title compound, C₅H₉N₃ ²⁺·2NO₃ ⁻, the cations and anions are connected by intermolecular N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π⋯π interactions between pyridinium rings [centroid–centroid distance = 3.775 (4) Å].

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Abu Zuhri & Cox (1989 ▶). For related structures, see: Fun & Balasubramani (2009 ▶); Rubin-Preminger & Englert (2007 ▶); Qin & Wang (2009 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₅H₉N₃ ²⁺·2NO₃ ⁻
M _r = 235.17
Monoclinic,
a = 12.3008 (5) Å
b = 10.5086 (5) Å
c = 7.1411 (3) Å
β = 97.546 (1)°
V = 915.09 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.65 × 0.37 × 0.28 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.906, T _max = 0.958
18234 measured reflections
4796 independent reflections
4129 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.096
S = 1.06
4796 reflections
181 parameters
All H-atom parameters refined
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005556/rz2419sup1.cif

e-66-0o639-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005556/rz2419Isup2.hkl

e-66-0o639-Isup2.hkl^{(230.2KB, 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—H1N1⋯O2ⁱ	0.874 (13)	2.001 (13)	2.7750 (7)	147.0 (12)
N2—H1N2⋯O5	0.935 (14)	2.105 (15)	2.9070 (8)	143.1 (12)
N2—H1N2⋯O2ⁱⁱ	0.935 (14)	2.211 (14)	2.7767 (7)	118.1 (11)
N2—H2N2⋯O3ⁱⁱⁱ	0.881 (14)	2.193 (14)	3.0006 (7)	152.3 (12)
N2—H2N2⋯O3^iv	0.881 (14)	2.482 (14)	2.9231 (7)	111.6 (11)
N3—H1N3⋯O4	0.844 (16)	2.054 (16)	2.8653 (8)	161.0 (14)
N3—H2N3⋯O6^v	0.827 (12)	2.130 (12)	2.9442 (7)	168.0 (12)
N2—H3N2⋯O5^iv	0.871 (12)	1.963 (12)	2.8227 (8)	169.0 (12)
N2—H3N2⋯O6^iv	0.871 (12)	2.494 (12)	3.1217 (7)	129.5 (10)
C2—H2⋯O3ⁱⁱⁱ	0.910 (11)	2.439 (11)	3.0489 (8)	124.6 (9)
C2—H2⋯O1^vi	0.910 (11)	2.552 (11)	3.1834 (8)	127.0 (9)
C2—H2⋯O3^iv	0.910 (11)	2.570 (11)	3.1277 (8)	120.2 (9)
C3—H3⋯O6ⁱ	0.979 (12)	2.253 (12)	3.1170 (8)	146.6 (10)
C4—H4⋯O4^v	0.926 (12)	2.559 (12)	3.4274 (8)	156.3 (10)

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

Acknowledgments

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. MH thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). In particular, diaminopyridines play an important role in the preparation of aromatic azo dyes, the subject of many polarographic investigations (Abu Zuhri & Cox, 1989). Pyridine and its substituted derivatives are often involved in hydrogen-bond interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). The crystal structures of 3,4-diaminopyridine (Rubin-Preminger & Englert, 2007), 3,4-diaminopyridinium hydrogen succinate (Fun & Balasubramani, 2009) and 4-amino-3-ammoniopyridinium dichloride (Qin & Wang, 2009) have been reported in the literature. In order to study some interesting hydrogen bonding interactions, the synthesis and structure of the title salt is presented here.

The asymmetric unit of the title compound (Fig. 1) consists of a diprotonated 3,4-diaminopyridine cation and two nitrate anions. In the 3,4-diaminopyridinium cation, protonation at atom N1 has lead to a slight increase in the C2—N1—C3 angle to 121.45 (5)° compared to those of an unprotonated structure (Rubin-Preminger & Englert, 2007). The 3-amino N atom (N2) is also protonated. This type of protonation has also been observed in the crystal structure of 4-amino-3-ammoniopyridinium dichloride (Qin & Wang, 2009). The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal structure (Fig. 2), the anions and cations are connected by intermolecular strong N—H···O and weak C—H···O hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π···π interactions between the pyridinium rings (N1/C1–C5) [centroid-to-centroid (x, 3/2-y, -1/2+z and x, 3/2-y, 1/2+z) distance = 3.775 (4)Å].

Experimental

To a hot methanol solution (20 ml) of 3,4-diaminopyridine (27 mg, Aldrich) was added a few drops of nitric acid. The solution was warmed over a water bath for a few minutes. The resulting solution was allowed to cool slowly to room temperature. Crystals of the title compound appeared from the mother liquor after a few days.