4-(4-Nitro­benz­yl)pyridinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536813000093

. 2013 Jan 9;69(Pt 2):o206. doi: 10.1107/S1600536813000093

4-(4-Nitrobenzyl)pyridinium 3-carboxy-4-hydroxybenzenesulfonate

Graham Smith ^a,^*, Urs D Wermuth ^a

PMCID: PMC3569266 PMID: 23424489

Abstract

In the title salt, C₁₂H₁₁N₂O₂ ⁺·C₇H₅O₆S⁻, the dihedral angle between the benzene and pyridine rings in the 4-(4-nitrobenzyl)pyridinium cation is 82.7 (2)°. Within the anion there is an intramolecular hydroxy-O—H⋯O(carboxylic acid) bond. In the crystal, the cation forms a single N⁺—H⋯O_sulfonate hydrogen bond with the anion. These cation–anion pairs interact through duplex anion carboxylic acid O—H⋯O_sulfonate hydrogen bonds, giving a centrosymmetric cyclic association [graph set R ₂ ²(16)]. The crystals studied were non-merohedrally twinned.

Related literature

For data on 4-(4-nitrobenzyl)pyridine adduct and salt structures, see: Smith et al. (1997 ▶); Smith & Wermuth (2010 ▶). For examples of the structures of salts of 5-sulfosalicylic acid, see: Raj et al. (2003 ▶); Smith et al. (2004 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶). graphic file with name e-69-0o206-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₁N₂O₂ ⁺·C₇H₅O₆S⁻
M _r = 432.41
Monoclinic,
a = 7.4154 (7) Å
b = 12.8896 (10) Å
c = 19.649 (2) Å
β = 92.848 (9)°
V = 1875.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 200 K
0.25 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.916, T _max = 0.980
14534 measured reflections
3671 independent reflections
2631 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.173
S = 1.21
3671 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(26.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000093/bh2470sup1.cif

e-69-0o206-sup1.cif^{(26.5KB, cif)}

Click here for additional data file.^{(180KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000093/bh2470Isup2.hkl

e-69-0o206-Isup2.hkl^{(180KB, hkl)}

Click here for additional data file.^{(7.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000093/bh2470Isup3.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—H1⋯O51A	0.86	1.88	2.732 (5)	172
O2A—H2A⋯O12A	0.95	1.70	2.613 (5)	159
O11A—H11A⋯O53A ⁱ	0.94	1.65	2.583 (4)	172

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from the Australian Research Council, the Science and Engineering Faculty and the University Library, Queensland University of Technology.

supplementary crystallographic information

Comment

The Lewis base 4-(4-nitrobenzyl)pyridine (NBPY) is an analogue of 2-(2,4-dinitrobenzyl)pyridine (DNBPY) which is significant because of its unusual photochromic behaviour in the solid state, although NBPY does not possess such properties. The structure of NBPY is not known but both the structures of a 2:1 co-crystal adduct with 4-aminobenzoic acid (Smith et al., 1997) and a 5-nitrosalicylate salt (Smith & Wermuth, 2010) have been reported. Our reaction of NBPY with 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid = 5-SSA) gave the title compound, C₁₂H₁₁N₂O₂⁺ C₇H₅O₆S^-, the structure of which is reported herein. The structures of a number of 1:1 salts of 5-SSA are known (Raj et al., 2003; Smith et al., 2004).

With the title compound (Fig. 1), the dihedral angle between the phenyl and pyridine rings in the 4-(4-nitrobenzyl)pyridinium cation is 82.7 (2)° and this forms a single N⁺—H···O_sulfonate hydrogen bond with the anion. These cation–anion pairs inter-associate through duplex anion carboxylic acid O—H···O_sulfonate hydrogen bonds (Table 1, Fig. 2) giving a centrosymmetric cyclic motif [graph set R²₂(16) (Etter et al., 1990)]. Crystals of the compound are non-merohedrally twinned [BASF factor 0.3201 (Sheldrick, 2008); see Refinement section].

In the 5-SSA monoanion, the usual intramolecular phenol O–H···O_carboxyl hydrogen bond [2.613 (5) Å] is present, essentially maintaining coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2A—C1A—C11A—O11A, -176.6 (4)°] (Raj et al., 2003; Smith et al., 2004).

Experimental

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of 4-(4-nitrobenzyl)pyridine with 5-sulfosalicylic acid in 50 ml of 50% ethanol–water. After concentration to ca. 30 ml, partial room temperature evaporation of the hot-filtered solution gave colourless crystals from which a block section was cleaved for the X-ray analysis.