2,3-Diamino­pyridinium 6-carb­oxy­pyridine-2-carboxyl­ate

Mahsa Foroughian; Alireza Foroumadi; Behrouz Notash; Giuseppe Bruno; Hadi Amiri Rudbari; Hossein Aghabozorg

doi:10.1107/S1600536811047647

. 2011 Nov 16;67(Pt 12):o3325. doi: 10.1107/S1600536811047647

2,3-Diaminopyridinium 6-carboxypyridine-2-carboxylate

Mahsa Foroughian ^a, Alireza Foroumadi ^b,^*, Behrouz Notash ^c, Giuseppe Bruno ^d, Hadi Amiri Rudbari ^d, Hossein Aghabozorg ^a

PMCID: PMC3238974 PMID: 22199823

Abstract

The asymmetric unit of the title proton-transfer compound, C₅H₈N₃ ⁺·C₇H₄NO₄ ⁻, consists of one mono-deprotonated pyridine-2,6-dicarboxylic acid as anion and one protonated 2,3-diaminopyridine as cation. The crystal packing shows extensive O—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds. Thre are also several π–π interactions between the anions and also between the cations [centriod–centroid distances = 3.6634 (7), 3.7269 (7), 3.6705 (7) and 3.4164 (7) Å].

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008b ▶). For related structures, see: Aghabozorg et al. (2008a ▶, 2011a ▶,b ▶); Sharif et al. (2010 ▶).

Experimental

Crystal data

C₅H₈N₃ ⁺·C₇H₄NO₄ ⁻
M _r = 276.26
Triclinic,
a = 6.9138 (1) Å
b = 8.3364 (2) Å
c = 11.2358 (2) Å
α = 81.448 (1)°
β = 73.831 (1)°
γ = 82.486 (1)°
V = 612.33 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.706, T _max = 0.746
34839 measured reflections
2654 independent reflections
2348 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.107
S = 1.07
2654 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811047647/bt5705sup1.cif

e-67-o3325-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047647/bt5705Isup2.hkl

e-67-o3325-Isup2.hkl^{(127.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047647/bt5705Isup3.cml

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
N4—H⋯O1ⁱ	0.86	1.94	2.7872 (12)	167
N2—H2B⋯O3ⁱⁱ	0.87 (2)	2.329 (19)	3.1108 (14)	150.0 (15)
N3—H3A⋯O2ⁱ	0.86	2.03	2.8674 (14)	163
N3—H3B⋯O2	0.86	2.17	2.9427 (14)	149
O4—H1⋯O1ⁱⁱⁱ	0.89 (2)	1.75 (2)	2.5673 (12)	151.9 (18)
N2—H2A⋯O2	0.868 (19)	2.32 (2)	3.1290 (15)	156.0 (16)
N2—H2A⋯N1	0.868 (19)	2.491 (18)	3.0999 (14)	127.8 (15)

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

Acknowledgments

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

supplementary crystallographic information

Comment

Pyridinedicarboxylic acids are present in many natural products, such as vitamins, coenzymes, and alkaloids. Pyridine-2,6-dicarboxylic acid has been used to synthesize several proton transfer compounds in which pyridine-2,6-dicarboxylic acid acts as a monoacidic fragment (Aghabozorg et al. 2008b).In this regards, several organic bases were used such as propane-1,2-diamine (Aghabozorg et al. 2008a), N¹,N¹-dimethylpropane-1,2-diamine (Aghabozorg et al. 2011a), 2-amino-4-methylpyridinie (Sharif et al. 2010) and 2-amino-4-methylpyridine (Aghabozorg et al., 2011b).

The structure of the title compounds contains one deprotonated pyridine-2,6-dicarboxylic acid as anion and one protonated 2,3-diaminopyridine as cation (Fig.1). The cations and anions are linked by several O—H···O, N—H···O and N—H···N hydrogen bonds with D···A distances ranging from 2.5673 (12) Å to 3.1290 (15) Å (Table.1 & Fig. 2). Furthermore, there are several π-π interactions which formed between (py-2,6-dcH)^- anions and also between (dapyH)⁺ cations with centriod-to-centroid distances = 3.6634 (7), 3.7269 (7), 3.6705 (7), 3.4164 (7) Å (Fig. 3). These hydrogen bonds and π-π interactions play important role in the stabilization of crystal packing.

Experimental

The solution of pyridine-2,6-dicarboxylic acid (0.334 g, 2 mmol) in 7 ml water was added to solution of 2,3-diaminopyridine (0.218 g, 2 mmol) in 4 ml water in 1:1 molar ratios. The reaction mixture was stirred for 3hrs at room temprature. The colorless crystals of the title compound appeared after slow evaporation of solvent at room temperature.