Bis(3-hydroxy­pyridinium) fumarate

Lan Shen; Jun-Hua Li; Jing-Jing Nie; Duan-Jun Xu

doi:10.1107/S1600536809023800

. 2009 Jun 24;65(Pt 7):o1679. doi: 10.1107/S1600536809023800

Bis(3-hydroxypyridinium) fumarate

Lan Shen ^a, Jun-Hua Li ^b, Jing-Jing Nie ^b, Duan-Jun Xu ^b,^*

PMCID: PMC2969193 PMID: 21582938

Abstract

The crystal structure of the title compound, 2C₅H₆NO₂ ⁺·C₄H₂O₄ ²⁻, consists of 3-hydroxypyridinium cations and fumarate dianions. The dianion is located on an inversion center and the cation is linked to it by O—H⋯O and N—H⋯O hydrogen bonds. The cation is twisted with respect to the anion by 24.83 (5)°.

Related literature

For general background, see: Thomas et al. (2007 ▶); Fidler et al. (2003 ▶); Zhang et al. (2004 ▶). For the ionization of hydropyridine in the solution, see: Lezina et al. (1981 ▶). For 3-hydropyridinium salts, see: Aakeroy & Nieuwenhuyzen (1994 ▶); Fukunaga et al. (2004 ▶). For co-crystals of neutral pyridine derivatives and neutral fumaric acid, see: Bowes et al. (2003 ▶); Aakeroy et al. (2002 ▶); Haynes et al. (2006 ▶); Bu et al. (2007 ▶); Xu et al. (2009 ▶). For C—O bond distances in the deprotonated carboxyl groups of fumarates, see: Liu et al. (2003 ▶); Liu & Xu (2004 ▶); Xu et al. (2009 ▶).

Experimental

Crystal data

2C₅H₆NO⁺·C₄H₂O₄ ²⁻
M _r = 306.27
Monoclinic,
a = 3.8037 (5) Å
b = 10.4798 (13) Å
c = 17.423 (2) Å
β = 90.360 (5)°
V = 694.52 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 294 K
0.32 × 0.28 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: none
7561 measured reflections
1359 independent reflections
1237 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.100
S = 1.07
1359 reflections
107 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023800/ng2594sup1.cif

e-65-o1679-sup1.cif^{(13.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023800/ng2594Isup2.hkl

e-65-o1679-Isup2.hkl^{(65.7KB, 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—H1⋯O1	0.893 (12)	1.687 (12)	2.5774 (14)	175.2 (18)
O3—H3A⋯O2ⁱ	0.839 (14)	1.751 (15)	2.5831 (15)	171.5 (16)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The work was supported by the ZIJIN Project of Zhejiang University, China.

supplementary crystallographic information

Comment

The hydropyridine derivatives and the fumaric acid have been extensively applied in biological and medicine fields (Zhang et al., 2004; Thomas et al., 2007; Fidler et al., 2003). Although the carboxyl group of the fumaric acid is usually deprotonated while the pyridine derivatives are protonated in the solution (Lezina et al., 1981), some crystal structures showed that they also exist as co-crystal of neutral molecules (Bowes et al. 2003; Aakeroy et al., 2002; Haynes et al. 2006; Xu et al. 2009). Herein we report the crystal structure of the title compound containing pyridine derivative and fumaric acid components.

The crystal structure of the title compond consists of fumarate anions and 3-hydroxypyridinium cations (Fig. 1). The planar fumarate anion is located in an inversion center. The C1—O1 bond distance of 1.2603 (15) Å is similar to C1—O2 bond distance of 1.2452 (15) Å, it agrees with those found in metal complexes of fumarate (Liu et al. 2003; Liu & Xu, 2004).

The 3-hydroxypyridine is protonated in the crystal structure, the geometry data is consistent with those in crystal structures of 3-hydroxypyridinium hydrogen L-malate (Aakeroy & Nieuwenhuyzen, 1994) and 3-hydroxypyridinium hydrogen tartronate (Fukunaga et al. 2004).

In the crystal structure the planar hydroxypyridinium cation is twisted respect to the planar fumarate with a dihedral angle of 24.83 (5)°, and links with the fumarate anions via N—H···O and O—H···O hydrogen bonding (Table 1 and Fig. 2).

Experimental

Reagents and solvent were used as purchased without further purification. 3-Hydroxypyridine (2 mmol) and fumaric acid (1 mmol) were dissolved in ethanol (5 ml) at room temperature. The single crystals were obtained from the solution after one week.