Bis(2-amino­pyridinium) 2,5-dicarb­oxy­benzene-1,4-dicarboxyl­ate

V H Rodrigues; Mohammad Hakimi; Elham Motieiyan

doi:10.1107/S1600536812017254

. 2012 Apr 25;68(Pt 5):o1524. doi: 10.1107/S1600536812017254

Bis(2-aminopyridinium) 2,5-dicarboxybenzene-1,4-dicarboxylate

V H Rodrigues ^a,^*, Mohammad Hakimi ^b, Elham Motieiyan ^b

PMCID: PMC3344628 PMID: 22590390

Abstract

In the title compound, 2C₅H₇N₂ ⁺·C₁₀H₄O₈ ²⁻, the 2-aminopyridinium (2-apyH) cation and 2,5-dicarboxybenzene-1,4-dicarboxylate (btcH2) anion are both nearly planar, with r.m.s. deviations of 0.015 and 0.050 Å, respectively. The angle between the latter least-squares planes is 17.68 (9)°. The overall crystal structure results from the packing of two-dimensional networks, formed by alternating 2-apyH and btcH2 linked by hydrogen bonds, parallel to (100).

Related literature

For similar and most common conformations of 2-aminopyridinium, see: Guelmami & Jouini (2011 ▶); Chitra et al. (2008 ▶); Quah et al. (2008 ▶); Bis & Zaworotko (2005 ▶); Büyükgüngör & Odabas˛ogˇlu (2002 ▶); Odabas˛ogˇlu et al. (2003 ▶); Acheson (1967 ▶). For similar and most common conformations of 2,5-dicarboxybenzene-1,4-dicarboxylate, see: Dong et al. (2011 ▶); Wang & Tang (2010 ▶). For graph-set analysis of hydrogen-bond patterns in organic crystals, see: Etter et al. (1990 ▶).

Experimental

Crystal data

2C₅H₇N₂ ⁺·C₁₀H₄O₈ ²⁻
M _r = 442.38
Monoclinic,
a = 4.0165 (1) Å
b = 10.8098 (4) Å
c = 21.4036 (7) Å
β = 99.535 (2)°
V = 916.45 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 273 K
0.3 × 0.2 × 0.15 mm

Data collection

Bruker–Nonius APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.755, T _max = 1.000
18838 measured reflections
2209 independent reflections
1652 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.102
S = 1.01
2209 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker–Nonius, 2004 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017254/bt5880sup1.cif

e-68-o1524-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017254/bt5880Isup2.hkl

e-68-o1524-Isup2.hkl^{(108.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017254/bt5880Isup3.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
N1—H1A⋯O2	0.913 (16)	1.904 (17)	2.7852 (15)	161.6 (15)
N1—H1A⋯O1	0.913 (16)	2.478 (16)	3.2413 (16)	141.4 (13)
N2—H2A⋯O3ⁱ	0.831 (19)	2.125 (19)	2.9520 (17)	173.0 (17)
N2—H2B⋯O1	0.880 (19)	2.14 (2)	2.9759 (17)	157.6 (16)
O4—H4A⋯O1	1.06 (2)	1.31 (2)	2.3766 (15)	176.8 (17)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by funds from FEDER via the COMPETE (Programa Operacional Factores de Competitividade) programme and by the FCT (Fundação para a Ciência e a Tecnologia) (project PEst-C/FIS/UI0036/2011).

supplementary crystallographic information

Comment

This work is a further contribution to the broad family of structural studies of 2-aminopyridinium (2-apyH) systems with hydrogen-bond donors. A considerable number of analogous materials formed from 2-aminopyridine and a given carboxylic acid has already been reported (Guelmami & Jouini, 2011; Chitra et al., 2008; Quah et al., 2008; Bis & Zaworotko, 2005; Büyükgüngör & Odabas&ogon;og&caron;lu, 2002; Odabas&ogon;og&caron;lu et al., 2003; etc). This is due to the fact that 2-aminopyridine is protonated in acidic solutions. It is well known that the bonding of the H atom to the ring N atom of 2-aminopyridine, and not to the amino N atom, produces an ion for which an additional resonance structure must be considered (Acheson, 1967). We have inferred the positive charge in the 2-apyH ion lies on the amino group based on a difference fourier map, a common practice when allowed by the quality of the collected intensities. The charge state, related to the hydrogen loss, in each of the two candidate carboxylic acid groups belonging to the assymetric unit was also inferred from a difference map and further reinforced by analysis of the C–O bond lengths.

Ellucidation of the numbering scheme and a view of the H-bonds giving rise to two-dimensional networks parallel to (100) are shown in Figs. 1 and 2, respectively. Both the 2-apyH cation and 2,5-dicarboxybenzene-1,4-dicarboxylate (btcH2) anion are nearly planar, with r.m.s. deviations of 0.015 and 0.050 A, respectively. The angle between the latter idealized planes is 17.68 (9)°. The two-dimensional networks are formed by alternating 2-apyH and btcH2 linked by H-bonds and include all H-bonds found. The first order network describing the H-bonding in the title compound is N₁=4DS(7), as established by applying the rules of graph-set analysis of hydrogen-bond patterns in organic crystals (Etter et al., 1990).

Similar and most common conformations of 2,5-dicarboxybenzene-1,4-dicarboxylate were described by Dong et al. (2011) and Wang & Tang (2010).

Experimental

A solution of 0.254 g (1 mmol) benzene-1,2,4,5-tetracarboxylicacid in methanol (10 ml) was added to a solution of 2-aminopyridine (0.1 g, 1 mmol) in water (15 ml), and refluxed for 1 h. The resulting solution was light yellow in colour. After slow evaporation of the solvent at room-temperature colorless prisms of the compound were obtained.