2-Amino-5-nitro­pyridinium hydrogen oxalate

M Ambrose Rajkumar; S Stanly John Xavier; S Anbarasu; Prem Anand Devarajan; M NizamMohideen

doi:10.1107/S160053681400525X

. 2014 Mar 26;70(Pt 4):o473–o474. doi: 10.1107/S160053681400525X

2-Amino-5-nitropyridinium hydrogen oxalate

M Ambrose Rajkumar ^a, S Stanly John Xavier ^b, S Anbarasu ^a, Prem Anand Devarajan ^a,^*, M NizamMohideen ^c,^*

PMCID: PMC3998560 PMID: 24826170

Abstract

In the cation of the title molecular salt, C₅H₆N₃O₂ ⁺·C₂HO₄ ⁻, the dihedral angle between the aromatic ring and the nitro group is 3.5 (3)°; in the anion, the dihedral angle between the CO2 and CO₂H planes is 10.5 (2)°. In the crystal, the anions are linked into [100] chains by O—H⋯O hydrogen bonds. The cations cross-link the chains by way of N—H⋯O hydrogen bonds and the structure is consolidated by C—H⋯O interactions.

Related literature

For the crystal structures of related pyridine derivatives, see: Babu et al. (2014 ▶); Anderson et al. (2005 ▶); Karle et al. (2003 ▶). For simple organic–inorganic salts containing strong intermolecular hydrogen bonds, see: Fu et al. (2011 ▶); Sethuram et al. (2013a ▶,b ▶); Shihabuddeen Syed et al. (2013 ▶); Showrilu et al. (2013 ▶); Huq et al. (2013 ▶). For the structure of oxalic acid, see: Derissen & Smith (1974 ▶). For graph-set analysis, see: Bernstein et al.(1995 ▶).

Experimental

Crystal data

C₅H₆N₃O₂ ⁺·C₂HO₄ ⁻
M _r = 229.16
Triclinic,
a = 5.5609 (2) Å
b = 9.2012 (4) Å
c = 9.2305 (4) Å
α = 90.245 (2)°
β = 98.500 (2)°
γ = 100.038 (2)°
V = 459.74 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.950, T _max = 0.957
10142 measured reflections
1615 independent reflections
1417 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.110
S = 1.07
1615 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681400525X/jj2183sup1.cif

e-70-0o473-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400525X/jj2183Isup2.hkl

e-70-0o473-Isup2.hkl^{(77.9KB, hkl)}

Click here for additional data file.^{(3.9KB, cml)}

Supporting information file. DOI: 10.1107/S160053681400525X/jj2183Isup3.cml

CCDC reference: 990527

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
C2—H2⋯O5ⁱ	0.93	2.48	3.323 (2)	152
C3—H3⋯O2ⁱⁱ	0.93	2.37	3.296 (2)	178
C5—H5⋯O1ⁱⁱⁱ	0.93	2.42	3.186 (2)	140
C5—H5⋯O4^iv	0.93	2.44	2.970 (2)	116
N1—H1⋯O6^iv	0.86	1.94	2.7697 (18)	160
O4—H4⋯O5^v	0.82	1.64	2.4486 (16)	170
N2—H2A⋯O3^v	0.89 (3)	2.16 (3)	2.959 (2)	149 (2)
N2—H2A⋯O5^v	0.89 (3)	2.36 (3)	3.007 (2)	130 (2)
N2—H2B⋯O3^vi	0.89 (3)	1.99 (3)	2.870 (2)	173 (2)

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

Acknowledgments

MAR, DPA and SJX would like to thank the Board of Research in Nuclear Sciences, Department of Atomic Energy (BRNS-DAE) (file No. 2012/34/63/BRNS/2865; dated 01/03/2013), for funding this major research project.

supplementary crystallographic information

1. Comment

Simple organic–inorganic salts containing strong intermolecular hydrogen bonds have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Fu et al., 2011; Sethuram, et al., 2013a,b; Huq, et al., 2013; Shihabuddeen Syed, et al., 2013; Showrilu, et al., 2013). As part of our ongoing investigations of pyridine derivatives (Babu et al., 2014), the title compound was synthesized and we report herein on its crystal structure.

In the title salt, (C₅H₆N₃O₂)⁺, (C₂HO₄)^-, the asymmetric unit consists of an independent 2-amino-5-nitropyridinium cation, and oxalic actetate anion, which lie on an inversion symmetry. A proton transfer from the carboxyl group of oxalic acid to atom N1 of 2-amino-5-nitro pyridinine resulted in the formation of a salt. This protonation lead to the widening of the C5-N1-C1 angle of the pyridine ring to 122.79 (14)°, compared to 115.25 (13)° in the unprotonated aminopyridine (Anderson et al., 2005). This type of protonation is observed in various aminopyridine acid complexes (Babu et al., 2014; Karle et al., 2003).

The bond lengths and bond angles of the aminopyridine are comparable to the values reported earlier for aminopyridine (Babu et al., 2014; Anderson et al., 2005). The bond lengths and bond angles of the oxalate are comparable to the values reported for oxalic acid (Derissen & Smith, 1974). The non hydrogen pyridine ring, C1/C2/C3/C4/C5/N1, is planar with a maximum deviation of 0.006 (1)Å from the least squares plane for the C3 atom, with the endocyclic angles covering range of 117.88 (16) - 122.79 (14)°. The hydrogen oxalate anion O3/O4/O5/O6/C6/C7, is less planar with a maximum deviation of -0.131 (1)Å for the O3 and O6 atoms.

The crystal packing is consolidated by intermolecular N—H···O and O—H···O hydrogen bonds and weak C—H···O intermolecular interactions (Table 1 and Fig. 2). In the crystal structure, the 2-Amino-5-nitropyridinium unit is bound to acetate anions by five distinct N—H···O hydrogen bonds. The ion pairs are joined by two N—H···O hydrogen bonds in which the N atom of the 2-amino-5-nitroPyridinium unit acts as a bifurcated donor, thus generating R₁²(5) ring motifs (Bernstein et al., 1995). The hydroxyl group hydrogen atom is also hydrogen-bonded to the carboxylate oxygen atom through strong intermolecular O—H···O hydrogen bonds, with the O···O distance of 2.4486 (16)Å, which is from a chain, C(5), running along the b axis (Bernstein et al., 1995). The structure is further stabilized by weak C—H···O intermolecular inteactions, forming a three-dimensional network.

2. Experimental

Crystals of the title compound were obtained by slow evaporation of a 1:1 mol. mixture of 2-amino-5-nitropyridine and oxalic acid in methanol at room temperature.