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Acta Cryst. (2008). E64, o2091    [ doi:10.1107/S1600536808032054 ]

4-(4-Nitrobenzenesulfonamido)pyridinium chloride

H. Zhang, Y.-X. Ma, L. Zhou and H.-Z. Mo

Abstract top

In the title compound, C11H10N3O4S+·Cl-, the benzene ring makes an angle of 89.2 (1)° with the pyridinium ring. The dihedral angle between the nitro group and the benzene ring is 15.7 (1)°. The crystal structure is stabilized by N-H...Cl hydrogen bonds.

Comment top

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 (3) 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 sulphonamide π electrons N with those of the pyridinium ring. The benzene ring exhibits an angle of 89.2 (1)° with the pyridinium ring. The dihedral angle between the nitro group and the benzene ring is 164.3 (1)°. The crystal packing is stabilized by N—H···Cl hydrogen bonds (Table 1). Fig. 2 showing supramolecular chains linked by N—H···Cl hydrogen bonds.

Related literature top

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

Experimental top

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 61.6%. A colorless single-crystal suitable for X-ray analysis was obtained by slow evaporation of an hydrochloric acid (10%) solution at room temperature over a period of a week. Analysis calculated for C11H10N3O4SCl: C 41.84, H 3.19, N 13.31%; found: C 41.95, H 3.52, N 13.69%.

Refinement top

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).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] 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).
[Figure 2] Fig. 2. The packing of title compound, view down the b axis, showing supramolecular chains linked by N—H···Cl hydrogen bonds which are indicated by dashed lines.
4-(4-Nitrobenzenesulfonamido)pyridinium chloride top
Crystal data top
C11H10N3O4S+·Cl−F(000) = 1296
Mr = 315.73Dx = 1.614 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 37.942 (8) ÅCell parameters from 3179 reflections
b = 5.2446 (10) Åθ = 2.6–27.1°
c = 13.713 (3) ŵ = 0.47 mm−1
β = 107.77 (3)°T = 113 K
V = 2598.5 (9) Å3Block, colourless
Z = 80.12 × 0.10 × 0.08 mm
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2865 independent reflections
Radiation source: Rotating anode2330 reflections with I > 2σ(I)
confocalRint = 0.043
Detector resolution: 7.21 pixels mm-1θmax = 27.1°, θmin = 2.3°
ω and φ scansh = −35→48
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −6→6
Tmin = 0.932, Tmax = 0.963l = −17→13
9693 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0506P)2 + 1.967P]
where P = (Fo2 + 2Fc2)/3
2865 reflections(Δ/σ)max = 0.001
189 parametersΔρmax = 0.39 e Å−3
0 restraintsΔρmin = −0.48 e Å−3
Crystal data top
C11H10N3O4S+·Cl−V = 2598.5 (9) Å3
Mr = 315.73Z = 8
Monoclinic, C2/cMo Kα radiation
a = 37.942 (8) ŵ = 0.47 mm−1
b = 5.2446 (10) ÅT = 113 K
c = 13.713 (3) Å0.12 × 0.10 × 0.08 mm
β = 107.77 (3)°
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2865 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		2330 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.963Rint = 0.043
9693 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107Δρmax = 0.39 e Å−3
S = 1.06Δρmin = −0.48 e Å−3
2865 reflectionsAbsolute structure: ?
189 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
S10.130148 (12)0.37275 (10)0.40268 (4)0.02104 (16)
O10.12396 (4)0.1690 (3)0.32996 (12)0.0268 (4)
O20.14305 (4)0.3226 (3)0.51052 (12)0.0271 (4)
O30.21998 (4)1.2270 (3)0.21517 (12)0.0320 (4)
O40.25562 (4)1.2246 (3)0.37259 (12)0.0334 (4)
N10.05555 (5)1.1001 (4)0.52726 (16)0.0297 (5)
N20.09049 (4)0.5214 (4)0.37499 (15)0.0215 (4)
N30.22877 (5)1.1462 (3)0.30326 (14)0.0246 (4)
C10.08046 (5)0.7177 (4)0.42979 (16)0.0217 (4)
C20.10010 (6)0.7864 (4)0.52953 (17)0.0253 (5)
H20.12270.70320.56450.030*
C30.08643 (6)0.9760 (4)0.57664 (18)0.0284 (5)
H30.09921.01960.64560.034*
C40.03605 (6)1.0410 (5)0.43021 (19)0.0323 (5)
H40.01411.13270.39660.039*
C50.04777 (5)0.8496 (4)0.38013 (18)0.0277 (5)
H50.03380.80600.31200.033*
C60.16110 (5)0.5922 (4)0.37472 (16)0.0190 (4)
C70.15830 (5)0.6369 (4)0.27247 (16)0.0221 (5)
H70.14090.54460.21960.027*
C80.18104 (5)0.8169 (4)0.24842 (16)0.0225 (4)
H80.17970.84990.17930.027*
C90.20570 (5)0.9469 (4)0.32797 (16)0.0196 (4)
C100.20940 (5)0.9012 (4)0.43010 (16)0.0229 (5)
H100.22720.99140.48270.028*
C110.18659 (5)0.7207 (4)0.45380 (16)0.0223 (4)
H110.18840.68560.52310.027*
Cl10.038070 (13)0.52540 (11)0.65583 (4)0.02598 (16)
H10.0477 (8)1.233 (6)0.561 (2)0.058 (9)*
H2A0.0771 (8)0.504 (6)0.310 (2)0.059 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0197 (2)0.0190 (3)0.0238 (3)0.00150 (18)0.00570 (19)0.0027 (2)
O10.0272 (7)0.0204 (8)0.0333 (9)0.0011 (6)0.0101 (6)−0.0028 (7)
O20.0281 (7)0.0289 (9)0.0233 (9)0.0018 (6)0.0062 (6)0.0100 (7)
O30.0388 (8)0.0284 (9)0.0310 (10)−0.0013 (7)0.0137 (7)0.0059 (8)
O40.0313 (8)0.0372 (10)0.0321 (10)−0.0125 (7)0.0103 (7)−0.0109 (8)
N10.0333 (10)0.0246 (11)0.0368 (12)−0.0034 (8)0.0190 (9)−0.0056 (9)
N20.0189 (8)0.0234 (10)0.0207 (10)0.0006 (7)0.0038 (7)−0.0008 (8)
N30.0261 (8)0.0216 (10)0.0287 (11)−0.0001 (7)0.0124 (7)−0.0033 (8)
C10.0194 (9)0.0231 (11)0.0246 (11)−0.0038 (8)0.0097 (8)0.0007 (9)
C20.0272 (10)0.0249 (12)0.0236 (12)−0.0005 (8)0.0074 (8)0.0023 (10)
C30.0326 (11)0.0301 (13)0.0249 (12)−0.0068 (9)0.0126 (9)−0.0016 (10)
C40.0261 (10)0.0329 (14)0.0392 (15)0.0050 (9)0.0117 (10)−0.0031 (11)
C50.0209 (9)0.0322 (13)0.0281 (13)0.0016 (8)0.0046 (8)−0.0034 (10)
C60.0185 (8)0.0186 (11)0.0195 (11)0.0033 (7)0.0055 (7)0.0012 (8)
C70.0227 (9)0.0222 (12)0.0205 (11)0.0000 (8)0.0050 (8)−0.0036 (9)
C80.0260 (9)0.0239 (12)0.0183 (11)0.0013 (8)0.0081 (8)−0.0001 (9)
C90.0181 (8)0.0205 (11)0.0213 (11)0.0009 (7)0.0078 (7)−0.0003 (9)
C100.0193 (9)0.0277 (12)0.0197 (11)0.0008 (8)0.0030 (8)−0.0008 (9)
C110.0206 (9)0.0275 (12)0.0176 (11)0.0011 (8)0.0041 (7)0.0013 (9)
Cl10.0256 (3)0.0283 (3)0.0228 (3)0.00156 (19)0.0056 (2)−0.0007 (2)
Geometric parameters (Å, °) top
S1—O11.4311 (16)C2—H20.9500
S1—O21.4331 (16)C3—H30.9500
S1—N21.6332 (17)C4—C51.365 (3)
S1—C61.768 (2)C4—H40.9500
O3—N31.226 (2)C5—H50.9500
O4—N31.233 (2)C6—C111.388 (3)
N1—C31.330 (3)C6—C71.393 (3)
N1—C41.347 (3)C7—C81.385 (3)
N1—H10.93 (3)C7—H70.9500
N2—C11.394 (3)C8—C91.381 (3)
N2—H2A0.89 (3)C8—H80.9500
N3—C91.468 (3)C9—C101.385 (3)
C1—C21.391 (3)C10—C111.387 (3)
C1—C51.402 (3)C10—H100.9500
C2—C31.371 (3)C11—H110.9500
O1—S1—O2120.92 (10)N1—C4—C5120.1 (2)
O1—S1—N2104.52 (10)N1—C4—H4120.0
O2—S1—N2109.13 (10)C5—C4—H4120.0
O1—S1—C6108.27 (10)C4—C5—C1119.6 (2)
O2—S1—C6107.63 (10)C4—C5—H5120.2
N2—S1—C6105.35 (9)C1—C5—H5120.2
C3—N1—C4121.6 (2)C11—C6—C7121.73 (19)
C3—N1—H1118.5 (18)C11—C6—S1119.82 (16)
C4—N1—H1119.9 (18)C7—C6—S1118.42 (15)
C1—N2—S1127.65 (15)C8—C7—C6119.50 (19)
C1—N2—H2A117 (2)C8—C7—H7120.3
S1—N2—H2A112.8 (19)C6—C7—H7120.3
O3—N3—O4123.83 (19)C9—C8—C7118.0 (2)
O3—N3—C9118.12 (18)C9—C8—H8121.0
O4—N3—C9118.04 (18)C7—C8—H8121.0
C2—C1—N2124.68 (19)C8—C9—C10123.26 (19)
C2—C1—C5118.6 (2)C8—C9—N3118.51 (19)
N2—C1—C5116.69 (19)C10—C9—N3118.22 (18)
C3—C2—C1119.0 (2)C9—C10—C11118.50 (19)
C3—C2—H2120.5C9—C10—H10120.8
C1—C2—H2120.5C11—C10—H10120.8
N1—C3—C2121.1 (2)C10—C11—C6118.97 (19)
N1—C3—H3119.5C10—C11—H11120.5
C2—C3—H3119.5C6—C11—H11120.5
O1—S1—N2—C1172.50 (18)O2—S1—C6—C7168.84 (15)
O2—S1—N2—C141.8 (2)N2—S1—C6—C7−74.81 (18)
C6—S1—N2—C1−73.5 (2)C11—C6—C7—C8−1.0 (3)
S1—N2—C1—C2−14.1 (3)S1—C6—C7—C8176.94 (15)
S1—N2—C1—C5167.25 (16)C6—C7—C8—C9−0.4 (3)
N2—C1—C2—C3−177.14 (19)C7—C8—C9—C101.8 (3)
C5—C1—C2—C31.5 (3)C7—C8—C9—N3−177.26 (17)
C4—N1—C3—C21.5 (3)O3—N3—C9—C815.3 (3)
C1—C2—C3—N1−2.4 (3)O4—N3—C9—C8−165.44 (18)
C3—N1—C4—C50.1 (3)O3—N3—C9—C10−163.75 (18)
N1—C4—C5—C1−1.0 (4)O4—N3—C9—C1015.5 (3)
C2—C1—C5—C40.1 (3)C8—C9—C10—C11−1.7 (3)
N2—C1—C5—C4178.9 (2)N3—C9—C10—C11177.29 (17)
O1—S1—C6—C11−145.42 (16)C9—C10—C11—C60.3 (3)
O2—S1—C6—C11−13.15 (19)C7—C6—C11—C101.1 (3)
N2—S1—C6—C11103.20 (18)S1—C6—C11—C10−176.88 (15)
O1—S1—C6—C736.57 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.93 (3)2.12 (3)3.039 (2)171 (3)
N2—H2A···Cl1ii0.89 (3)2.18 (3)3.066 (2)173 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.93 (3)2.12 (3)3.039 (2)171 (3)
N2—H2A···Cl1ii0.89 (3)2.18 (3)3.066 (2)173 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z−1/2.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. 1–19.

Damiano, T., Morton, D. & Nelson, A. (2007). Org. Biomol. Chem. 5, 2735—2752.

Li, J.-S., Chen, L.-G., Zhang, Y.-Y., Xu, Y.-J., Deng, Y. & Huang, P.-M. (2007). J. Chem. Res. pp. 350–352.

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

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

Yu, H.-J. & Li, J.-S. (2007). Acta Cryst. E63, o3399.