2-Nitro-N-(4-pyridinio)benzene­sulfonamidate monohydrate

Liang-Bin Hu; Jian Chen; Chang-Zhong Liu

doi:10.1107/S1600536808035526

. 2008 Nov 8;64(Pt 12):o2277. doi: 10.1107/S1600536808035526

2-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate

Liang-Bin Hu ^a,^*, Jian Chen ^b, Chang-Zhong Liu ^c

PMCID: PMC2959804 PMID: 21581257

Abstract

The title compound, C₁₁H₉N₃O₄S·H₂O, contains both an acid and a base centre and displays a zwitterionic structure. There are two independent molecules and two water molecules in the asymmetric unit. The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1) and 110.7 (1)°. The dihedral angles between the nitro group and the benzene ring are 116.1 (2) and 116.7 (1)°. The crystal structure is stabilized by N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For the uses of organic pyridinium salts, see: Damiano et al. (2007 ▶). For zwitterionic forms of N-arylbenzenesulfonamides, see: Li et al. (2007 ▶); Yu & Li (2007 ▶). For reference geometric data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₁H₉N₃O₄S·H₂O
M _r = 297.29
Monoclinic,
a = 8.7206 (17) Å
b = 11.972 (2) Å
c = 12.743 (3) Å
β = 107.65 (3)°
V = 1267.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 113 (2) K
0.14 × 0.10 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.962, T _max = 0.989
10348 measured reflections
4633 independent reflections
3587 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.090
S = 1.03
4633 reflections
385 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ▶), 1560 Friedel pairs
Flack parameter: 0.52 (6)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 global, I. DOI: 10.1107/S1600536808035526/hg2431sup1.cif

e-64-o2277-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035526/hg2431Isup2.hkl

e-64-o2277-Isup2.hkl^{(226.9KB, 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
N4—H4A⋯O9	0.913 (10)	1.868 (12)	2.764 (3)	167 (3)
O9—H9A⋯O1	0.864 (10)	2.122 (11)	2.967 (3)	166 (3)
N1—H1A⋯O10ⁱ	0.918 (10)	1.843 (11)	2.757 (3)	174 (4)
O9—H9B⋯N5ⁱⁱ	0.867 (10)	2.043 (11)	2.901 (3)	170 (2)
O9—H9B⋯O6ⁱⁱ	0.867 (10)	2.56 (2)	3.125 (3)	123 (2)
O10—H10A⋯O6ⁱⁱⁱ	0.867 (10)	2.051 (11)	2.914 (3)	174 (4)
O10—H10B⋯N2^iv	0.870 (10)	2.042 (12)	2.902 (3)	170 (3)

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

supplementary crystallographic information

Comment

Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al., 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings (Li et al., 2007), the structure of the title compound was determined by X-ray diffraction. There are two independent molecules and two independent water molecules in the unit cell. In the cations of the title compound the short C—N distance [N2—C1 = 1.367 (3) Å and N5—C12 = 1.365 (3) Å] indicate the slight conjugation of the sulfonamide N with the pyridinium ring (Allen et al., 1987).

The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1)° and 110.7 (1)° respectively. And the dihedral angles between the nitro group and the benzene ring are 116.1 (2)° and 116.7 (1)° respectively. The crystal structure is stabilized by N—H···O hydrogen bonds.

Experimental

A solution of 2-nitrobenzenesulfonyl chloride (2.2 g, 10 mmol) in CH₂Cl₂ (10 ml) was added dropwise to a suspension of 4-aminopyridine (0.9 g, 10 mmol) in CH₂Cl₂ (10 ml) at room temperature with stirring. The reaction mixture was stirred overnight. The yellow solid obtained was washed with warm water to obtain the title compound in a yield of 55.7%. A colorless single crystal suitable for X-ray analysis was obtained by slow evaporation of an NaOH (10%) solution at room temperature over a period of a week.