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Acta Cryst. (2009). E65, o1228    [ doi:10.1107/S1600536809015670 ]

2-(Benzenesulfonamido)pyridinium nitrate

J.-S. Li and X. Li

Abstract top

In the title compound, C11H11N2O2S+·NO3-, the dihedral angle between the benzene and pyridinium rings is 87.59 (8)°. An intramolecular C-H...O interaction occurs in the cation. In the crystal structure, ion pairs occur, being linked by two strong N-H...O interactions, forming R22(8) loops. The packing is further stabilized by weak C-H...O interactions.

Comment top

Organic pyridinium salts have been widely used as guests for construction of supramolecular complexes. As part of our ongoing studies of host–guest chemistry involving the pyridinium salts (Li et al., 2007; Li, Fan, Fan et al., 2008), the structure of the title compound was determined by X-ray diffraction. For related structures, see: Li et al. (2008a,b).

The title compound, (I), consists of a pyridinium cation and a nitrate anion (Fig. 1). In the cation, the C—N distance [1.378 (2) Å] is short enough to display significant double-bond character (typical C=N = 1.34–1.38 Å), despite the presence of the strong electron-withdrawing sulfonyl group. This could be attributed to the ortho N+ atom in the pyridinium ring. The benzene ring constructs an angle of 87.59 (8)° with the pyridinium ring.

In the crystal structure, two strong N—H···O hydrogen bonds (R22(8)) link the cation and anion, and weak C—H···O interactions (Table 1) help establishing the packing as well as significant ion-dipolar interactions [N2—O2 3.020 at (x - 1, y, z), N2—O3 3.006, N2—O4 3.581, N2—O5 3.377 at (-x + 3/2, y + 3/2, -z + 1/2)]. Besides, one short intramolecular C—H···O contact also occurs in the cation.

Related literature top

For the synthesis, see: Li, Yang et al. (2008). For related structures, see: Li et al. (2008a,b). For background studies of supramolecular chemistry involving pyridinium rings, see: Li et al. (2007); Li, Fan, Fan et al. (2008).

Experimental top

The title compound was prepared according to the reported literature (Li, Yang et al. 2008). Colourless blocks of (I) were obtained by evaporation of a nitric acid solution of the sulfonamide.

Refinement top

The H atoms bound to C were positioned geometrically (C—H = 0.95Å) and refined as riding with Uiso(H) = 1.2 Ueq(C). The N—H hydrogen atoms were refined with their isotropic displacement parameters, and N—H distances are restrained to 0.86 (2) and 0.91 (2) Å, respectively.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: CrystalStructure (Rigaku, 2005).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius. Dashed lines indicates H-bonding.
2-(Benzenesulfonamido)pyridinium nitrate top
Crystal data top
C11H11N2O2S+·NO3–F000 = 616
Mr = 297.29Dx = 1.544 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3934 reflections
a = 5.3309 (11) Åθ = 2.6–27.9º
b = 10.067 (2) ŵ = 0.28 mm−1
c = 23.837 (5) ÅT = 113 K
β = 90.44 (3)ºBlock, colourless
V = 1279.2 (5) Å30.20 × 0.16 × 0.12 mm
Z = 4
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2959 independent reflections
Radiation source: rotating anode2547 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.027
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113 Kθmin = 2.7º
ω and φ scansh = −6→7
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −13→10
Tmin = 0.947, Tmax = 0.968l = −27→31
9882 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0535P)2 + 0.6301P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2959 reflectionsΔρmax = 0.39 e Å−3
189 parametersΔρmin = −0.50 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C11H11N2O2S+·NO3–V = 1279.2 (5) Å3
Mr = 297.29Z = 4
Monoclinic, P21/nMo Kα
a = 5.3309 (11) ŵ = 0.28 mm−1
b = 10.067 (2) ÅT = 113 K
c = 23.837 (5) Å0.20 × 0.16 × 0.12 mm
β = 90.44 (3)º
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2959 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2547 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.968Rint = 0.027
9882 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041189 parameters
wR(F2) = 0.107H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.39 e Å−3
2959 reflectionsΔρmin = −0.50 e Å−3
Special details top

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) top
xyzUiso*/Ueq
S10.91800 (7)0.56853 (4)0.160276 (15)0.01836 (13)
O11.0236 (2)0.43908 (12)0.15364 (5)0.0236 (3)
O21.0764 (2)0.68341 (12)0.16025 (5)0.0246 (3)
N10.7169 (3)0.57948 (14)0.10753 (5)0.0202 (3)
N20.3909 (3)0.66605 (13)0.05567 (5)0.0176 (3)
C10.7348 (3)0.57165 (15)0.22140 (6)0.0172 (3)
C20.8103 (3)0.65238 (16)0.26571 (7)0.0228 (3)
H20.95340.70800.26240.027*
C30.6718 (4)0.65010 (17)0.31498 (7)0.0279 (4)
H30.72050.70420.34590.033*
C40.4630 (4)0.56891 (17)0.31892 (7)0.0274 (4)
H40.36740.56870.35240.033*
C50.3915 (3)0.48754 (17)0.27435 (7)0.0256 (4)
H50.24910.43150.27770.031*
C60.5277 (3)0.48821 (16)0.22514 (7)0.0206 (3)
H60.48060.43280.19450.025*
C70.5852 (3)0.69057 (15)0.09074 (6)0.0178 (3)
C80.6390 (3)0.82204 (16)0.10529 (7)0.0212 (3)
H80.77260.84210.13050.025*
C90.4944 (3)0.92219 (16)0.08236 (7)0.0241 (4)
H90.52981.01200.09170.029*
C100.2968 (3)0.89326 (17)0.04570 (7)0.0236 (3)
H100.19830.96250.02980.028*
C110.2475 (3)0.76278 (17)0.03302 (6)0.0209 (3)
H110.11280.74070.00840.025*
H10.666 (4)0.502 (2)0.0974 (9)0.035 (6)*
H2A0.347 (4)0.580 (2)0.0487 (9)0.030 (6)*
N30.3198 (3)0.31725 (13)0.05623 (5)0.0188 (3)
O30.2271 (2)0.41507 (11)0.02985 (5)0.0213 (3)
O40.2173 (3)0.20711 (11)0.05331 (5)0.0280 (3)
O50.5183 (2)0.33211 (12)0.08439 (5)0.0261 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0160 (2)0.0236 (2)0.01549 (19)0.00131 (14)−0.00045 (14)−0.00020 (13)
O10.0220 (7)0.0279 (6)0.0210 (6)0.0079 (5)−0.0009 (5)−0.0034 (4)
O20.0190 (6)0.0307 (6)0.0243 (6)−0.0058 (5)0.0000 (5)0.0028 (5)
N10.0244 (8)0.0196 (7)0.0166 (6)0.0031 (5)−0.0039 (5)−0.0009 (5)
N20.0177 (7)0.0199 (7)0.0153 (6)0.0003 (5)0.0005 (5)−0.0015 (5)
C10.0167 (8)0.0188 (7)0.0161 (7)0.0027 (5)−0.0007 (5)0.0010 (5)
C20.0269 (9)0.0196 (7)0.0219 (8)−0.0014 (6)−0.0019 (6)−0.0011 (6)
C30.0393 (11)0.0256 (8)0.0187 (7)0.0052 (7)−0.0012 (7)−0.0029 (6)
C40.0302 (10)0.0311 (9)0.0211 (8)0.0080 (7)0.0062 (7)0.0048 (6)
C50.0200 (9)0.0279 (9)0.0290 (8)0.0016 (6)0.0027 (7)0.0066 (7)
C60.0178 (8)0.0215 (8)0.0224 (7)0.0019 (6)−0.0030 (6)−0.0009 (6)
C70.0173 (8)0.0231 (8)0.0131 (6)0.0006 (6)0.0022 (5)0.0003 (5)
C80.0188 (9)0.0240 (8)0.0207 (7)−0.0012 (6)−0.0003 (6)−0.0023 (6)
C90.0246 (9)0.0210 (8)0.0267 (8)0.0005 (6)0.0030 (7)−0.0012 (6)
C100.0229 (9)0.0237 (8)0.0242 (8)0.0037 (6)−0.0009 (6)0.0010 (6)
C110.0163 (8)0.0272 (8)0.0191 (7)0.0033 (6)0.0001 (6)0.0014 (6)
N30.0201 (7)0.0198 (6)0.0166 (6)0.0035 (5)−0.0004 (5)−0.0015 (5)
O30.0238 (7)0.0204 (6)0.0197 (5)0.0027 (4)−0.0040 (4)0.0022 (4)
O40.0322 (8)0.0184 (6)0.0334 (7)−0.0018 (5)−0.0079 (5)0.0002 (5)
O50.0240 (7)0.0254 (6)0.0288 (6)0.0038 (5)−0.0106 (5)−0.0029 (5)
Geometric parameters (Å, °) top
S1—O11.4288 (12)C4—H40.9500
S1—O21.4322 (12)C5—C61.384 (2)
S1—N11.6498 (15)C5—H50.9500
S1—C11.7607 (16)C6—H60.9500
N1—C71.378 (2)C7—C81.397 (2)
N1—H10.86 (2)C8—C91.380 (2)
N2—C111.348 (2)C8—H80.9500
N2—C71.349 (2)C9—C101.394 (3)
N2—H2A0.91 (2)C9—H90.9500
C1—C21.390 (2)C10—C111.373 (2)
C1—C61.391 (2)C10—H100.9500
C2—C31.392 (2)C11—H110.9500
C2—H20.9500N3—O41.2378 (18)
C3—C41.385 (3)N3—O51.2580 (18)
C3—H30.9500N3—O31.2665 (17)
C4—C51.392 (3)
O1—S1—O2120.24 (8)C6—C5—C4120.12 (17)
O1—S1—N1103.35 (7)C6—C5—H5119.9
O2—S1—N1109.00 (7)C4—C5—H5119.9
O1—S1—C1109.24 (7)C5—C6—C1118.60 (15)
O2—S1—C1108.47 (7)C5—C6—H6120.7
N1—S1—C1105.54 (8)C1—C6—H6120.7
C7—N1—S1127.02 (12)N2—C7—N1114.73 (14)
C7—N1—H1119.6 (16)N2—C7—C8118.83 (15)
S1—N1—H1110.9 (15)N1—C7—C8126.41 (15)
C11—N2—C7123.13 (14)C9—C8—C7118.75 (16)
C11—N2—H2A117.8 (14)C9—C8—H8120.6
C7—N2—H2A118.9 (14)C7—C8—H8120.6
C2—C1—C6122.01 (15)C8—C9—C10120.85 (16)
C2—C1—S1118.68 (13)C8—C9—H9119.6
C6—C1—S1119.21 (12)C10—C9—H9119.6
C1—C2—C3118.62 (16)C11—C10—C9118.72 (16)
C1—C2—H2120.7C11—C10—H10120.6
C3—C2—H2120.7C9—C10—H10120.6
C4—C3—C2119.91 (16)N2—C11—C10119.71 (16)
C4—C3—H3120.0N2—C11—H11120.1
C2—C3—H3120.0C10—C11—H11120.1
C3—C4—C5120.73 (16)O4—N3—O5120.37 (13)
C3—C4—H4119.6O4—N3—O3119.89 (13)
C5—C4—H4119.6O5—N3—O3119.72 (13)
O1—S1—N1—C7−171.95 (14)C4—C5—C6—C1−0.2 (2)
O2—S1—N1—C7−42.97 (16)C2—C1—C6—C50.9 (2)
C1—S1—N1—C773.37 (15)S1—C1—C6—C5177.27 (12)
O1—S1—C1—C2114.78 (13)C11—N2—C7—N1−177.09 (13)
O2—S1—C1—C2−17.97 (15)C11—N2—C7—C81.2 (2)
N1—S1—C1—C2−134.67 (13)S1—N1—C7—N2−164.75 (11)
O1—S1—C1—C6−61.68 (14)S1—N1—C7—C817.1 (2)
O2—S1—C1—C6165.56 (12)N2—C7—C8—C9−1.3 (2)
N1—S1—C1—C648.86 (14)N1—C7—C8—C9176.77 (15)
C6—C1—C2—C3−0.7 (2)C7—C8—C9—C100.5 (3)
S1—C1—C2—C3−177.06 (13)C8—C9—C10—C110.4 (3)
C1—C2—C3—C4−0.3 (3)C7—N2—C11—C10−0.2 (2)
C2—C3—C4—C51.0 (3)C9—C10—C11—N2−0.5 (2)
C3—C4—C5—C6−0.8 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.86 (2)1.91 (2)2.760 (2)171 (2)
N2—H2A···O30.91 (2)1.84 (2)2.7417 (18)173 (2)
C8—H8···O20.952.383.009 (2)123
C3—H3···O5i0.952.523.432 (2)162
C10—H10···O4ii0.952.533.193 (2)127
C11—H11···O3iii0.952.563.434 (2)153
C11—H11···O4iii0.952.343.223 (2)154
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.86 (2)1.91 (2)2.760 (2)171 (2)
N2—H2A···O30.91 (2)1.84 (2)2.7417 (18)173 (2)
C8—H8···O20.952.383.009 (2)123
C3—H3···O5i0.952.523.432 (2)162
C10—H10···O4ii0.952.533.193 (2)127
C11—H11···O3iii0.952.563.434 (2)153
C11—H11···O4iii0.952.343.223 (2)154
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x, −y+1, −z.
Acknowledgements top

This project was supported by Changsha University of Science and Technology Talent Fund (Project No.1004214)

references
References top

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Li, J.-S., Yang, D.-W. & Liu, W.-D. (2008). Acta Cryst. E64, o204.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.