Bis(2-amino-3-carb­oxy­pyridinium) sulfate trihydrate

Fadila Berrah; Amira Ouakkaf; Sofiane Bouacida; Thierry Roisnel

doi:10.1107/S1600536811010191

. 2011 Mar 23;67(Pt 4):o953–o954. doi: 10.1107/S1600536811010191

Bis(2-amino-3-carboxypyridinium) sulfate trihydrate

Fadila Berrah ^a,^*,^‡, Amira Ouakkaf ^a, Sofiane Bouacida ^b,^‡, Thierry Roisnel ^c

PMCID: PMC3099893 PMID: 21754219

Abstract

In the title compound, 2C₆H₇N₂O₂ ⁺·SO₄ ²⁻·3H₂O, there are two independent cations which are connected into N—H⋯O hydrogen-bonded dimers. In the crystal, O—H⋯O hydrogen-bonded sulfate–water sheets run parallel to (001) and are linked into a three-dimensional network via intermolecular N—H⋯O and O—H⋯O hydrogen bonds through the 2-aminonicotinium dimers. Further stabilization is provided by weak intermolecular C—H⋯O hydrogen bonds. R ₄ ³(10) and R ₂ ²(8) graph-set rings are observed. The crystal studied was an inversion twin with refined components of 0.45 (6) and 0.55 (6).

Related literature

For related compounds, see: Athimoolam & Rajaram (2005 ▶); Berrah et al. (2005, ▶ 2011a ▶,b ▶); Dobson & Gerkin (1997 ▶); Giantsidis & Turnbull (2000 ▶); Pawlukojc et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶). For background to hydrogen bonding, see: Desiraju (2003 ▶).

Experimental

Crystal data

2C₆H₇N₂O₂ ⁺·SO₄ ²⁻·3H₂O
M _r = 428.39
Orthorhombic,
a = 6.5372 (5) Å
b = 12.3141 (10) Å
c = 23.0274 (19) Å
V = 1853.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 150 K
0.58 × 0.13 × 0.04 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.845, T _max = 0.970
23588 measured reflections
4229 independent reflections
3669 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.079
S = 1.06
4229 reflections
274 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ▶), 1790 Friedel pairs
Flack parameter: 0.45 (6)

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010191/lh5219sup1.cif

e-67-0o953-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010191/lh5219Isup2.hkl

e-67-0o953-Isup2.hkl^{(203.1KB, 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
O1A—H1A⋯O3Wⁱ	0.84	1.69	2.5152 (18)	167
O1B—H1B⋯O1W	0.84	1.69	2.5138 (18)	168
O1W—H1W⋯O2Wⁱⁱ	0.82 (4)	1.93 (3)	2.754 (2)	177 (4)
O3W—H5W⋯O2W	0.77 (3)	1.98 (3)	2.750 (2)	176 (3)
O1W—H2W⋯O4	0.75 (4)	2.03 (4)	2.752 (2)	164 (3)
O2W—H3W⋯O3ⁱⁱⁱ	0.80 (3)	1.92 (3)	2.7151 (19)	169 (3)
O2W—H4W⋯O4	0.90 (3)	1.87 (3)	2.7675 (19)	175 (3)
O3W—H6W⋯O2^iv	0.84 (2)	1.88 (2)	2.720 (2)	171 (3)
N2A—H2A⋯O1	0.88	1.92	2.7681 (18)	163
N2B—H2B⋯O1^v	0.88	1.88	2.7419 (19)	167
N1A—H11A⋯O4	0.88	2.05	2.915 (2)	166
N1B—H11B⋯O2^v	0.88	1.94	2.817 (2)	173
N1A—H12A⋯O2A	0.88	2.09	2.726 (2)	129
N1A—H12A⋯O2B	0.88	2.27	2.979 (2)	138
N1B—H12B⋯O2A	0.88	2.25	2.963 (2)	138
N1B—H12B⋯O2B	0.88	2.10	2.733 (2)	128
C4A—H4A⋯O3^vi	0.95	2.46	3.143 (2)	129
C4B—H4B⋯O3^vii	0.95	2.31	3.169 (2)	150

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

Acknowledgments

We are grateful to the LCATM laboratory, Université Larbi Ben M’Hidi, Oum El Bouaghi, Algeria, for financial support.

supplementary crystallographic information

Comment

Hydrogen bonds are the object of several studies, which aim to elucidate their influence on crystal construction and compounds propreties (Desiraju, 2003). Pyridine and its derivatives well known for their various chemical and biological activities, have proved their aptitude to built new edifices involving original hydrogen-bonding patterns due to their variety of potential hydrogen donors and acceptors (Athimoolam et al., 2005; Dobson & Gerkin, 1997; Giantsidis & Turnbull, 2000). The title compound was obtained from 2-aminonicotinic acid and is a part of our search for new hybrid compounds based on protonated N-heterocyclic compounds and inorganic acids (Berrah et al., 2005;2011a,b).

As shown in figure 1, the asymmetric unit includes two crystallographically independent 2-aminonicotinium cations (A and B), one sulfate anion and three water molecules. The cation geometry is similar to that reported for the structure of 2-aminonicotinic acid (Dobson & Gerkin, 1997; Pawlukojc et al., 2007) except for C—O distances in the carboxylic group. In the 2-aminonicotinic acid structure, the two C—O distances are 1.234 (2) and 1.266 (2)Å since the carboxylic group transfers its proton to the hetero-ring nitrogen atom leading to a zwitterionic molecule.

The crystal packing of the title compound (Fig. 2) results from sulfate-water sheets extending parallel to (001) (Fig. 3) and linked together via 2-aminonicotinium dimers (Fig. 4). In one sheet, sulfate anions and H₂O2W molecules alternate, leading to infinite chains running parallel to the a axis. These chains are further connected through H₂O1W and H₂O3W molecules in a way that R³₄(10) rings are formed (Fig. 3). The structure is stabilized via N—H···O, O—H···O and C—H···O Hydrogen bonds that link each dimer to its neighbors (Table 1, Fig. 4). R³₄ (10) and R²₂(8) graph-set rings are observed (Fig. 4)(Etter et al., 1990; Bernstein et al., 1995).

Experimental

Colorless crystal of the title compound was obtained by slow evaporation of an aqueous solution of 2-amino-pyridine-3-carboxylic acid and sulfuric acid in 2:1 stoichiometric ratio.