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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2429.
Published online 2008 November 22. doi:  10.1107/S160053680803883X
PMCID: PMC2959869

4-(4-Nitro­benzene­sulfonamido)pyridinium nitrate

Abstract

A short C—N distance [1.394 (2) Å] in the title compound, C11H10N3O4S+·NO3 , is indicative of some conjugation of the sulfonamide π electrons with those of the pyridinium ring. The crystal structure is stabilized by N—H(...)O hydrogen bonds.

Related literature

For zwitterionic forms of N-aryl­benzene­sulfonamides, see: Li et al. (2007 [triangle]); Yu & Li (2007 [triangle]). For reference geometrical data, see: Allen et al. (1987 [triangle]). Damiano et al. (2007 [triangle]) describe the use of pyridinium derivatives for the construction of supra­molecular architectures.

An external file that holds a picture, illustration, etc.
Object name is e-64-o2429-scheme1.jpg

Experimental

Crystal data

  • C11H10N3O4S+·NO3
  • M r = 342.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2429-efi1.jpg
  • a = 36.516 (7) Å
  • b = 5.3742 (11) Å
  • c = 13.964 (3) Å
  • β = 99.54 (3)°
  • V = 2702.5 (10) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 113 (2) K
  • 0.20 × 0.12 × 0.04 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.94, T max = 0.99
  • 11804 measured reflections
  • 3203 independent reflections
  • 2648 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.107
  • S = 1.09
  • 3203 reflections
  • 216 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 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/S160053680803883X/bg2225sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803883X/bg2225Isup2.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), the structure of the title compound was determined by X-ray diffraction. In the cations of the title compound the short C—N distance [N2—C1 = 1.394 (2) Å] has a value between those of a typical C=N double and C—N single bond (1.47–1.50 Å and 1.34–1.38 Å, respectively; Allen et al., 1987). This might be indicative of a slight conjugation of the sulfonamide π electrons with those of the pyridinium ring. The dihedral angle between the benzene and the pyridinium rings is 81.3 (1) °, while the the one between the nitro group and the benzene ring is 16.1 (1) °.

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 60.5%. A colorless single-crystal suitable for X-ray analysis was obtained by slow evaporation of an nitric acid (10%) solution at room temperature over a period of a week.

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 =0.93 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+·NO3F000 = 1408
Mr = 342.29Dx = 1.683 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4207 reflections
a = 36.516 (7) Åθ = 2.3–27.9º
b = 5.3742 (11) ŵ = 0.29 mm1
c = 13.964 (3) ÅT = 113 (2) K
β = 99.54 (3)ºBlock, colorless
V = 2702.5 (10) Å30.20 × 0.12 × 0.04 mm
Z = 8

Data collection

Rigaku Saturn CCD area-detector diffractometer3203 independent reflections
Radiation source: Rotating anode2648 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.037
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 2.3º
ω and [var phi] scansh = −47→46
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −7→7
Tmin = 0.94, Tmax = 0.99l = −14→18
11804 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)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0612P)2 + 0.5371P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3203 reflectionsΔρmax = 0.30 e Å3
216 parametersΔρmin = −0.41 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
S10.133115 (11)0.62515 (7)0.45086 (3)0.01800 (13)
O10.12702 (3)0.8195 (2)0.51613 (8)0.0246 (3)
O20.14580 (3)0.6801 (2)0.36175 (8)0.0256 (3)
O30.25592 (4)−0.2298 (3)0.63494 (9)0.0323 (3)
O40.22026 (4)−0.2269 (2)0.74432 (8)0.0285 (3)
N10.06215 (5)−0.1019 (3)0.23971 (11)0.0287 (4)
N20.09333 (4)0.4790 (2)0.42774 (10)0.0167 (3)
N30.22946 (4)−0.1490 (3)0.66941 (10)0.0211 (3)
C10.08430 (4)0.2815 (3)0.36372 (10)0.0158 (3)
C20.05600 (4)0.1211 (3)0.38117 (11)0.0186 (3)
H2A0.04410.14530.43610.022*
C30.04565 (5)−0.0704 (3)0.31855 (12)0.0259 (4)
H30.0268−0.18220.33040.031*
C40.08911 (5)0.0488 (3)0.22111 (12)0.0280 (4)
H40.10000.02220.16480.034*
C50.10119 (5)0.2409 (3)0.28211 (11)0.0223 (4)
H50.12080.34560.26940.027*
C60.16389 (4)0.4066 (3)0.51584 (11)0.0170 (3)
C70.18870 (5)0.2755 (3)0.46944 (11)0.0199 (3)
H70.19050.30980.40370.024*
C80.21072 (5)0.0943 (3)0.52069 (11)0.0203 (3)
H80.22790.00170.49090.024*
C90.20707 (4)0.0509 (3)0.61656 (11)0.0178 (3)
C100.18289 (5)0.1823 (3)0.66407 (11)0.0196 (3)
H100.18130.14920.73010.023*
C110.16114 (5)0.3626 (3)0.61267 (11)0.0195 (3)
H110.14430.45680.64320.023*
O50.06125 (3)0.4370 (2)0.58801 (8)0.0229 (3)
O60.01603 (3)0.5377 (2)0.66295 (8)0.0261 (3)
O70.02485 (4)0.7446 (2)0.53506 (8)0.0284 (3)
N40.03315 (4)0.5777 (2)0.59463 (9)0.0187 (3)
H10.0541 (7)−0.225 (5)0.1953 (16)0.050 (7)*
H20.0832 (6)0.483 (4)0.4735 (16)0.035 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0163 (2)0.0161 (2)0.0213 (2)−0.00180 (15)0.00217 (14)0.00219 (14)
O10.0227 (6)0.0169 (6)0.0324 (6)−0.0003 (5)−0.0007 (5)−0.0045 (5)
O20.0219 (6)0.0286 (7)0.0270 (6)−0.0035 (5)0.0062 (5)0.0110 (5)
O30.0306 (7)0.0354 (7)0.0299 (7)0.0162 (6)0.0023 (5)−0.0040 (6)
O40.0333 (7)0.0257 (7)0.0257 (6)0.0001 (6)0.0029 (5)0.0056 (5)
N10.0367 (10)0.0211 (8)0.0229 (7)0.0070 (7)−0.0106 (6)−0.0066 (6)
N20.0157 (7)0.0185 (7)0.0168 (6)−0.0016 (5)0.0049 (5)−0.0014 (5)
N30.0216 (8)0.0185 (7)0.0216 (7)0.0016 (6)−0.0012 (5)−0.0035 (5)
C10.0171 (7)0.0150 (7)0.0142 (7)0.0036 (6)−0.0009 (5)0.0020 (6)
C20.0167 (8)0.0189 (8)0.0192 (7)−0.0012 (6)0.0000 (6)0.0033 (6)
C30.0232 (9)0.0214 (9)0.0296 (9)−0.0017 (7)−0.0062 (7)0.0016 (7)
C40.0365 (11)0.0289 (9)0.0174 (8)0.0103 (8)0.0013 (7)−0.0014 (7)
C50.0253 (9)0.0247 (9)0.0174 (7)0.0052 (7)0.0052 (6)0.0030 (6)
C60.0149 (8)0.0173 (8)0.0185 (7)−0.0030 (6)0.0015 (5)−0.0006 (6)
C70.0179 (8)0.0243 (9)0.0183 (7)−0.0018 (7)0.0055 (6)0.0005 (6)
C80.0169 (8)0.0237 (9)0.0212 (8)0.0016 (7)0.0058 (6)−0.0039 (6)
C90.0155 (8)0.0177 (8)0.0193 (7)−0.0017 (6)0.0004 (6)−0.0023 (6)
C100.0210 (8)0.0220 (8)0.0158 (7)−0.0015 (7)0.0032 (6)−0.0023 (6)
C110.0192 (8)0.0212 (9)0.0185 (7)0.0004 (6)0.0048 (6)−0.0046 (6)
O50.0238 (6)0.0257 (6)0.0203 (6)0.0055 (5)0.0068 (4)0.0010 (5)
O60.0281 (7)0.0321 (7)0.0211 (6)0.0029 (5)0.0125 (5)0.0057 (5)
O70.0311 (7)0.0268 (7)0.0281 (6)0.0048 (6)0.0070 (5)0.0132 (5)
N40.0208 (7)0.0192 (7)0.0165 (6)−0.0017 (6)0.0040 (5)0.0008 (5)

Geometric parameters (Å, °)

S1—O11.4277 (12)C4—C51.364 (2)
S1—O21.4286 (12)C4—H40.9500
S1—N21.6358 (14)C5—H50.9500
S1—C61.7687 (17)C6—C71.389 (2)
O3—N31.2281 (18)C6—C111.393 (2)
O4—N31.2243 (17)C7—C81.385 (2)
N1—C41.333 (3)C7—H70.9500
N1—C31.350 (2)C8—C91.387 (2)
N1—H10.92 (2)C8—H80.9500
N2—C11.392 (2)C9—C101.383 (2)
N2—H20.79 (2)C10—C111.377 (2)
N3—C91.472 (2)C10—H100.9500
C1—C21.398 (2)C11—H110.9500
C1—C51.400 (2)O5—N41.2902 (17)
C2—C31.363 (2)O6—N41.2427 (16)
C2—H2A0.9500O7—N41.2270 (17)
C3—H30.9500
O1—S1—O2120.81 (7)C5—C4—H4119.6
O1—S1—N2104.46 (7)C4—C5—C1119.05 (16)
O2—S1—N2109.44 (8)C4—C5—H5120.5
O1—S1—C6108.14 (7)C1—C5—H5120.5
O2—S1—C6108.30 (8)C7—C6—C11121.62 (15)
N2—S1—C6104.51 (7)C7—C6—S1120.35 (12)
C4—N1—C3121.75 (15)C11—C6—S1117.96 (12)
C4—N1—H1118.0 (14)C8—C7—C6118.90 (14)
C3—N1—H1120.2 (14)C8—C7—H7120.5
C1—N2—S1126.95 (11)C6—C7—H7120.5
C1—N2—H2116.5 (16)C7—C8—C9118.47 (15)
S1—N2—H2110.4 (16)C7—C8—H8120.8
O4—N3—O3123.99 (14)C9—C8—H8120.8
O4—N3—C9118.02 (14)C10—C9—C8123.25 (15)
O3—N3—C9117.99 (13)C10—C9—N3118.54 (14)
N2—C1—C2117.50 (13)C8—C9—N3118.19 (14)
N2—C1—C5123.52 (15)C11—C10—C9117.92 (14)
C2—C1—C5118.95 (14)C11—C10—H10121.0
C3—C2—C1119.22 (15)C9—C10—H10121.0
C3—C2—H2A120.4C10—C11—C6119.82 (15)
C1—C2—H2A120.4C10—C11—H11120.1
N1—C3—C2120.27 (17)C6—C11—H11120.1
N1—C3—H3119.9O7—N4—O6123.22 (14)
C2—C3—H3119.9O7—N4—O5119.33 (13)
N1—C4—C5120.74 (16)O6—N4—O5117.45 (13)
N1—C4—H4119.6
O1—S1—N2—C1176.50 (13)O2—S1—C6—C11167.74 (12)
O2—S1—N2—C145.81 (15)N2—S1—C6—C11−75.67 (14)
C6—S1—N2—C1−69.99 (14)C11—C6—C7—C81.1 (2)
S1—N2—C1—C2154.93 (12)S1—C6—C7—C8−175.84 (12)
S1—N2—C1—C5−27.1 (2)C6—C7—C8—C90.0 (2)
N2—C1—C2—C3178.18 (14)C7—C8—C9—C10−1.0 (2)
C5—C1—C2—C30.1 (2)C7—C8—C9—N3177.55 (15)
C4—N1—C3—C20.9 (3)O4—N3—C9—C1015.6 (2)
C1—C2—C3—N1−1.1 (2)O3—N3—C9—C10−165.41 (15)
C3—N1—C4—C50.4 (3)O4—N3—C9—C8−163.03 (15)
N1—C4—C5—C1−1.4 (3)O3—N3—C9—C816.0 (2)
N2—C1—C5—C4−176.80 (15)C8—C9—C10—C110.8 (2)
C2—C1—C5—C41.2 (2)N3—C9—C10—C11−177.68 (14)
O1—S1—C6—C7−147.78 (13)C9—C10—C11—C60.3 (2)
O2—S1—C6—C7−15.24 (16)C7—C6—C11—C10−1.2 (2)
N2—S1—C6—C7101.35 (14)S1—C6—C11—C10175.76 (13)
O1—S1—C6—C1135.21 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O50.79 (2)1.92 (2)2.7020 (19)171 (2)
N1—H1···O5i0.92 (2)1.93 (2)2.7764 (19)151 (2)
N1—H1···O6i0.92 (2)2.18 (3)2.979 (2)144.6 (19)

Symmetry codes: (i) x, −y, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2225).

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]
  • 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 (2005). CrystalClear Rigaku/MSC Inc., 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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