Pyridinium 5-nitro­thio­phene-2-carboxyl­ate

Xiao-Yan Yang; Ning Xu; Shan Liu

doi:10.1107/S1600536810016089

. 2010 May 8;66(Pt 6):o1287. doi: 10.1107/S1600536810016089

Pyridinium 5-nitrothiophene-2-carboxylate

Xiao-Yan Yang ^a, Ning Xu ^a, Shan Liu ^a,^*

PMCID: PMC2979441 PMID: 21579385

Abstract

The anion of the title compound, C₅H₆N⁺·C₅H₂NO₄S⁻, is approximately planar, with the carboxylate and nitro group planes forming dihedral angles of 7.5 (3) and 3.5 (3)°, respectively, with the thiophene ring. In the crystal structure, the cations and anions are linked into a two-dimensional network parallel to (011) by N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the uses of 5-nitrothiophene-2-carboxylic acid, see: Cao et al. (2003 ▶). For the synthesis, see: Marques et al. (2002 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₅H₆N⁺·C₅H₂NO₄S⁻
M _r = 252.24
Triclinic,
a = 6.0940 (12) Å
b = 7.3390 (15) Å
c = 13.296 (3) Å
α = 77.30 (3)°
β = 81.52 (3)°
γ = 71.00 (3)°
V = 546.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.915, T _max = 0.971
2194 measured reflections
1990 independent reflections
1657 reflections with I > 2σ(I)
R _int = 0.019
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.080
S = 1.00
1990 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536810016089/ci5088sup1.cif

e-66-o1287-sup1.cif^{(15.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016089/ci5088Isup2.hkl

e-66-o1287-Isup2.hkl^{(97.9KB, 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—H6⋯O2	0.86	1.74	2.594 (3)	176
C3—H3⋯O1	0.93	2.49	3.156 (3)	129
C1—H1⋯O3ⁱ	0.93	2.55	3.254 (3)	133
C4—H4⋯O1ⁱⁱ	0.93	2.44	3.210 (3)	141

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

supplementary crystallographic information

Comment

5-Nitrothiophene-2-carboxylic acid is an important intermediate used to synthesize raltitrexed (trade name Tomudex), an antimetabolite drug used in cancer chemotherapy (Cao et al., 2003). We report here the crystal structure of the title compound (Fig. 1).

Bond lengths and angles in both cation and anion are within normal ranges (Allen et al., 1987). The anion is approximately planar; the C6/O1/O2 and N2/O3/O4 planes form dihedral angles of 7.5 (3)° and 3.5 (3)°, respectively, with the thiophene ring. In the crystal structure, the cations and anions are linked into a two-dimensional network (Fig. 2) by N—H···O and C—H···O hydrogen bonds.

Experimental

5-Nitrothiophene-2-carboxylic acid was prepared by the method reported in literature (Marques et al., 2002). Single crystals were obtained by dissolving 5-nitrothiophene-2-carboxylic acid (0.5 g, 2.89 mmol) in pyridine (50 ml) and evaporating the solvent slowly at room temperature for about 20 d.