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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2308.
Published online 2008 November 13. doi:  10.1107/S1600536808035265
PMCID: PMC2960076

4-(4-Nitro­benzene­sulfonamido)pyridinium bromide

Abstract

In the title compound, C11H10N3O4S+·Br, the benzene ring makes an angle of 88.4 (2)° with the pyridinium ring. The dihedral angle between the nitro group and the benzene ring is 16.5 (2)°. The ions in the crystal structure are linked by a combination of inter­molecular N—H(...)Br and non-conventional C—H(...)Br and C—H(...)O hydrogen bonds, forming a three-dimensional network.

Related literature

For zwitterionic forms of N-aryl­benzene­sulfonamides, see: Li et al. (2007 [triangle]); Yu & Li (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For non-conventional hydrogen bonds, see: Desiraju & Steiner (2001 [triangle]). For the use of pyridinium derivatives in the construction of supra­molecular architectures, see: Damiano et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2308-scheme1.jpg

Experimental

Crystal data

  • C11H10N3O4S+·Br
  • M r = 360.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2308-efi1.jpg
  • a = 38.242 (8) Å
  • b = 5.2852 (11) Å
  • c = 13.941 (3) Å
  • β = 108.18 (3)°
  • V = 2677.0 (11) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.24 mm−1
  • T = 113 (2) K
  • 0.10 × 0.04 × 0.02 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.710, T max = 0.938
  • 10460 measured reflections
  • 3174 independent reflections
  • 2635 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.076
  • S = 1.05
  • 3174 reflections
  • 189 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035265/si2122sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035265/si2122Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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), an X-ray structure analysis of the title compound has been performed. In the cations of the title compound the short C—N distance [N2—C3 = 1.387 (3) Å] has a value between those of a typical C=N double and C—N single bond (1.34–1.38 Å and 1.47–1.50 Å, respectively; Allen et al., 1987). This might be indicative of a slight conjugation of the sulphonamide π electrons N with those of the pyridinium ring. The benzene ring makes an angle of 88.4 (2) ° with the pyridinium ring. The dihedral angle between the nitro group and the benzene ring is 163.5 (2) °. The S atom has a tetrahedral geometry and the Br anion link the cationic molecule into chains along the c axis. The ions in the crystal structure are linked by a combination of intermolecular N—H···Br and non-conventional C—H···Br and C—H···O hydrogen bonds (Table 1) to form a three-dimensional network (Desiraju & Steiner, 2001).

Experimental

A solution of 4-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 60.6%. A colorless single-crystal suitable for X-ray analysis was obtained by slow evaporation of an hydrobromic acid (5%) solution at room temperature over a period of a week. Analysis calculated for C11H10N3O4SBr: C 36.68, H 2.80, N 11.67%; found: C 36.70, H 2.52, N 11.98%.

Refinement

The N-bound H atoms were located in a difference map and their coordinates were refined with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned geometrically (C—H =0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of one molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level (arbitrary spheres for the H atoms).

Crystal data

C11H10N3O4S+·BrF000 = 1440
Mr = 360.19Dx = 1.787 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3479 reflections
a = 38.242 (8) Åθ = 2.2–27.9º
b = 5.2852 (11) ŵ = 3.24 mm1
c = 13.941 (3) ÅT = 113 (2) K
β = 108.18 (3)ºNeedle, colorless
V = 2677.0 (11) Å30.10 × 0.04 × 0.02 mm
Z = 8

Data collection

Rigaku Saturn CCD area-detector diffractometer3174 independent reflections
Radiation source: rotating anode2635 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.050
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 2.2º
ω and [var phi] scansh = −45→50
Absorption correction: multi-scan(CrystalClear; Rigaku/MSC, 2005)k = −6→4
Tmin = 0.710, Tmax = 0.938l = −18→18
10460 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0332P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3174 reflectionsΔρmax = 0.68 e Å3
189 parametersΔρmin = −0.47 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.038458 (6)−0.03831 (5)0.156635 (19)0.02228 (9)
S10.134013 (15)−0.12886 (11)0.40908 (5)0.01823 (14)
O10.14776 (4)−0.1752 (3)0.51529 (13)0.0248 (4)
O20.12760 (4)−0.3323 (3)0.33820 (13)0.0240 (4)
O30.25567 (5)0.7285 (4)0.36991 (13)0.0304 (4)
O40.21939 (5)0.7239 (3)0.21551 (13)0.0277 (4)
N10.05972 (6)0.5912 (4)0.53090 (18)0.0279 (5)
N20.09433 (5)0.0162 (4)0.38299 (17)0.0191 (4)
N30.22900 (5)0.6463 (4)0.30319 (16)0.0207 (4)
C10.09132 (7)0.4746 (5)0.5789 (2)0.0271 (6)
H10.10460.52300.64600.033*
C20.10479 (6)0.2877 (5)0.53330 (18)0.0227 (5)
H20.12770.21010.56720.027*
C30.08437 (6)0.2113 (5)0.43571 (18)0.0196 (5)
C40.05109 (6)0.3348 (5)0.38843 (19)0.0261 (6)
H40.03650.28630.32240.031*
C50.03964 (7)0.5254 (5)0.4376 (2)0.0304 (6)
H50.01730.61150.40530.036*
C60.16392 (6)0.0923 (4)0.37923 (18)0.0165 (5)
C70.16066 (6)0.1306 (5)0.27787 (18)0.0192 (5)
H70.14360.03420.22680.023*
C80.18247 (6)0.3099 (5)0.25237 (17)0.0186 (5)
H80.18080.33890.18380.022*
C90.20687 (6)0.4465 (4)0.32927 (18)0.0164 (5)
C100.21101 (6)0.4056 (5)0.43050 (18)0.0188 (5)
H100.22850.49950.48150.023*
C110.18912 (6)0.2252 (5)0.45572 (17)0.0193 (5)
H110.19140.19310.52440.023*
H1A0.0529 (8)0.723 (6)0.561 (2)0.040 (8)*
H2A0.0799 (8)−0.010 (5)0.324 (2)0.018 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02226 (14)0.02479 (15)0.01857 (15)−0.00186 (10)0.00461 (11)−0.00007 (10)
S10.0162 (3)0.0167 (3)0.0210 (3)0.0022 (2)0.0046 (2)0.0039 (2)
O10.0228 (8)0.0270 (10)0.0216 (10)0.0012 (8)0.0025 (7)0.0111 (8)
O20.0219 (8)0.0179 (9)0.0323 (10)0.0006 (7)0.0085 (8)−0.0030 (8)
O30.0290 (9)0.0333 (11)0.0296 (11)−0.0136 (8)0.0099 (8)−0.0083 (9)
O40.0351 (10)0.0260 (10)0.0230 (10)−0.0022 (8)0.0105 (8)0.0055 (8)
N10.0323 (12)0.0243 (12)0.0317 (14)−0.0043 (10)0.0170 (11)−0.0065 (10)
N20.0139 (10)0.0224 (11)0.0182 (12)0.0011 (8)0.0010 (9)−0.0021 (9)
N30.0230 (10)0.0178 (10)0.0248 (12)0.0004 (9)0.0124 (9)−0.0026 (9)
C10.0280 (14)0.0316 (15)0.0234 (15)−0.0087 (11)0.0104 (12)−0.0043 (12)
C20.0209 (12)0.0261 (13)0.0209 (13)−0.0024 (10)0.0063 (11)0.0011 (11)
C30.0186 (11)0.0182 (12)0.0250 (13)−0.0050 (10)0.0109 (10)−0.0001 (10)
C40.0203 (12)0.0310 (15)0.0256 (15)0.0033 (11)0.0052 (11)−0.0009 (12)
C50.0246 (13)0.0292 (15)0.0398 (17)0.0059 (11)0.0136 (13)0.0012 (13)
C60.0137 (10)0.0182 (12)0.0163 (12)0.0017 (9)0.0029 (9)0.0013 (9)
C70.0204 (11)0.0185 (12)0.0162 (13)0.0008 (10)0.0022 (10)−0.0038 (10)
C80.0226 (11)0.0208 (12)0.0129 (11)0.0003 (10)0.0063 (10)−0.0005 (10)
C90.0172 (11)0.0146 (11)0.0194 (13)0.0029 (9)0.0087 (10)0.0011 (10)
C100.0160 (11)0.0232 (12)0.0149 (12)0.0011 (9)0.0015 (10)−0.0018 (10)
C110.0175 (11)0.0246 (13)0.0146 (12)0.0042 (10)0.0032 (9)0.0037 (10)

Geometric parameters (Å, °)

S1—O21.4288 (18)C2—H20.9500
S1—O11.4292 (18)C3—C41.399 (3)
S1—N21.637 (2)C4—C51.366 (4)
S1—C61.773 (2)C4—H40.9500
O3—N31.226 (3)C5—H50.9500
O4—N31.232 (3)C6—C111.385 (3)
N1—C51.333 (4)C6—C71.394 (3)
N1—C11.335 (4)C7—C81.380 (3)
N1—H1A0.89 (3)C7—H70.9500
N2—C31.387 (3)C8—C91.385 (3)
N2—H2A0.84 (3)C8—H80.9500
N3—C91.468 (3)C9—C101.387 (3)
C1—C21.359 (3)C10—C111.385 (3)
C1—H10.9500C10—H100.9500
C2—C31.400 (3)C11—H110.9500
O2—S1—O1121.05 (11)C5—C4—C3119.6 (3)
O2—S1—N2104.58 (11)C5—C4—H4120.2
O1—S1—N2109.04 (11)C3—C4—H4120.2
O2—S1—C6108.52 (10)N1—C5—C4120.3 (2)
O1—S1—C6107.48 (11)N1—C5—H5119.8
N2—S1—C6105.09 (11)C4—C5—H5119.8
C5—N1—C1121.6 (2)C11—C6—C7121.8 (2)
C5—N1—H1A120.0 (19)C11—C6—S1119.90 (17)
C1—N1—H1A118.3 (19)C7—C6—S1118.27 (18)
C3—N2—S1128.28 (19)C8—C7—C6119.4 (2)
C3—N2—H2A115.5 (17)C8—C7—H7120.3
S1—N2—H2A114.9 (18)C6—C7—H7120.3
O3—N3—O4123.7 (2)C7—C8—C9118.3 (2)
O3—N3—C9118.3 (2)C7—C8—H8120.9
O4—N3—C9117.9 (2)C9—C8—H8120.9
N1—C1—C2121.1 (3)C8—C9—C10122.8 (2)
N1—C1—H1119.4C8—C9—N3119.0 (2)
C2—C1—H1119.4C10—C9—N3118.2 (2)
C1—C2—C3119.1 (2)C11—C10—C9118.7 (2)
C1—C2—H2120.5C11—C10—H10120.7
C3—C2—H2120.5C9—C10—H10120.7
N2—C3—C4117.2 (2)C10—C11—C6119.0 (2)
N2—C3—C2124.6 (2)C10—C11—H11120.5
C4—C3—C2118.2 (2)C6—C11—H11120.5
O2—S1—N2—C3172.9 (2)O1—S1—C6—C7167.55 (17)
O1—S1—N2—C342.1 (2)N2—S1—C6—C7−76.4 (2)
C6—S1—N2—C3−72.9 (2)C11—C6—C7—C8−1.6 (3)
C5—N1—C1—C21.7 (4)S1—C6—C7—C8177.10 (17)
N1—C1—C2—C3−2.3 (4)C6—C7—C8—C9−0.2 (3)
S1—N2—C3—C4168.56 (19)C7—C8—C9—C101.9 (3)
S1—N2—C3—C2−13.2 (3)C7—C8—C9—N3−177.11 (19)
C1—C2—C3—N2−177.1 (2)O3—N3—C9—C8−164.7 (2)
C1—C2—C3—C41.1 (3)O4—N3—C9—C816.1 (3)
N2—C3—C4—C5178.9 (2)O3—N3—C9—C1016.2 (3)
C2—C3—C4—C50.5 (4)O4—N3—C9—C10−162.90 (19)
C1—N1—C5—C40.0 (4)C8—C9—C10—C11−1.8 (3)
C3—C4—C5—N1−1.1 (4)N3—C9—C10—C11177.23 (19)
O2—S1—C6—C11−146.30 (18)C9—C10—C11—C60.0 (3)
O1—S1—C6—C11−13.8 (2)C7—C6—C11—C101.7 (3)
N2—S1—C6—C11102.3 (2)S1—C6—C11—C10−176.96 (17)
O2—S1—C6—C735.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Br1i0.89 (3)2.30 (3)3.195 (2)173 (3)
N2—H2A···Br10.84 (3)2.38 (3)3.225 (3)174 (2)
C10—H10···O3ii0.952.443.301 (3)151
C5—H5···Br1iii0.952.753.676 (3)165

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1/2, −y+3/2, −z+1; (iii) −x, y+1, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2122).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Damiano, T., Morton, D. & Nelson, A. (2007). Org. Biomol. Chem.5, 2735–2752. [PubMed]
  • Desiraju & Steiner (2001). The Weak Hydrogen Bond in Structural Chemisty and Biology IUCr Monographs on Crystallography, Vol. 9. Oxford Science Publications.
  • Li, J. S., Chen, L. G., Zhang, Y. Y., Xu, Y. J., Deng, Y. & Huang, P. M. (2007). J. Chem. Res.6, 350–352.
  • Rigaku/MSC (2005). CrystalClear and CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yu, H.-J. & Li, J.-S. (2007). Acta Cryst. E63, o3399.

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