4-(4-Nitro­benzene­sulfonamido)pyri­dinium chloride

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.042
• wR factor = 0.107
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   113.000
            Value of melting point given =     0.000
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C11 H10 Cl N3 O4 S
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         88.00     88.00    0.00
           H         80.00     80.00    0.00
           Cl         0.00      8.00   -8.00
           N         24.00     24.00    0.00
           O         32.00     32.00    0.00
           S          8.00      8.00    0.00

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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 (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

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.

S2. 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 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%.

S3. Refinement

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

Computing details

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

	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).
	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

Crystal data

C11H10N3O4S^+·Cl^−	F(000) = 1296
Mr = 315.73	Dx = 1.614 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 37.942 (8) Å	Cell parameters from 3179 reflections
b = 5.2446 (10) Å	θ = 2.6–27.1°
c = 13.713 (3) Å	µ = 0.47 mm^−1
β = 107.77 (3)°	T = 113 K
V = 2598.5 (9) Å^3	Block, colourless
Z = 8	0.12 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer	2865 independent reflections
Radiation source: Rotating anode	2330 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.043
Detector resolution: 7.21 pixels mm^-1	θmax = 27.1°, θmin = 2.3°
ω and ϕ scans	h = −35→48
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −6→6
Tmin = 0.932, Tmax = 0.963	l = −17→13
9693 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0506P)^2 + 1.967P] where P = (Fo^2 + 2Fc^2)/3
2865 reflections	(Δ/σ)max = 0.001
189 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.130148 (12)	0.37275 (10)	0.40268 (4)	0.02104 (16)
O1	0.12396 (4)	0.1690 (3)	0.32996 (12)	0.0268 (4)
O2	0.14305 (4)	0.3226 (3)	0.51052 (12)	0.0271 (4)
O3	0.21998 (4)	1.2270 (3)	0.21517 (12)	0.0320 (4)
O4	0.25562 (4)	1.2246 (3)	0.37259 (12)	0.0334 (4)
N1	0.05555 (5)	1.1001 (4)	0.52726 (16)	0.0297 (5)
N2	0.09049 (4)	0.5214 (4)	0.37499 (15)	0.0215 (4)
N3	0.22877 (5)	1.1462 (3)	0.30326 (14)	0.0246 (4)
C1	0.08046 (5)	0.7177 (4)	0.42979 (16)	0.0217 (4)
C2	0.10010 (6)	0.7864 (4)	0.52953 (17)	0.0253 (5)
H2	0.1227	0.7032	0.5645	0.030*
C3	0.08643 (6)	0.9760 (4)	0.57664 (18)	0.0284 (5)
H3	0.0992	1.0196	0.6456	0.034*
C4	0.03605 (6)	1.0410 (5)	0.43021 (19)	0.0323 (5)
H4	0.0141	1.1327	0.3966	0.039*
C5	0.04777 (5)	0.8496 (4)	0.38013 (18)	0.0277 (5)
H5	0.0338	0.8060	0.3120	0.033*
C6	0.16110 (5)	0.5922 (4)	0.37472 (16)	0.0190 (4)
C7	0.15830 (5)	0.6369 (4)	0.27247 (16)	0.0221 (5)
H7	0.1409	0.5446	0.2196	0.027*
C8	0.18104 (5)	0.8169 (4)	0.24842 (16)	0.0225 (4)
H8	0.1797	0.8499	0.1793	0.027*
C9	0.20570 (5)	0.9469 (4)	0.32797 (16)	0.0196 (4)
C10	0.20940 (5)	0.9012 (4)	0.43010 (16)	0.0229 (5)
H10	0.2272	0.9914	0.4827	0.028*
C11	0.18659 (5)	0.7207 (4)	0.45380 (16)	0.0223 (4)
H11	0.1884	0.6856	0.5231	0.027*
Cl1	0.038070 (13)	0.52540 (11)	0.65583 (4)	0.02598 (16)
H1	0.0477 (8)	1.233 (6)	0.561 (2)	0.058 (9)*
H2A	0.0771 (8)	0.504 (6)	0.310 (2)	0.059 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0197 (2)	0.0190 (3)	0.0238 (3)	0.00150 (18)	0.00570 (19)	0.0027 (2)
O1	0.0272 (7)	0.0204 (8)	0.0333 (9)	0.0011 (6)	0.0101 (6)	−0.0028 (7)
O2	0.0281 (7)	0.0289 (9)	0.0233 (9)	0.0018 (6)	0.0062 (6)	0.0100 (7)
O3	0.0388 (8)	0.0284 (9)	0.0310 (10)	−0.0013 (7)	0.0137 (7)	0.0059 (8)
O4	0.0313 (8)	0.0372 (10)	0.0321 (10)	−0.0125 (7)	0.0103 (7)	−0.0109 (8)
N1	0.0333 (10)	0.0246 (11)	0.0368 (12)	−0.0034 (8)	0.0190 (9)	−0.0056 (9)
N2	0.0189 (8)	0.0234 (10)	0.0207 (10)	0.0006 (7)	0.0038 (7)	−0.0008 (8)
N3	0.0261 (8)	0.0216 (10)	0.0287 (11)	−0.0001 (7)	0.0124 (7)	−0.0033 (8)
C1	0.0194 (9)	0.0231 (11)	0.0246 (11)	−0.0038 (8)	0.0097 (8)	0.0007 (9)
C2	0.0272 (10)	0.0249 (12)	0.0236 (12)	−0.0005 (8)	0.0074 (8)	0.0023 (10)
C3	0.0326 (11)	0.0301 (13)	0.0249 (12)	−0.0068 (9)	0.0126 (9)	−0.0016 (10)
C4	0.0261 (10)	0.0329 (14)	0.0392 (15)	0.0050 (9)	0.0117 (10)	−0.0031 (11)
C5	0.0209 (9)	0.0322 (13)	0.0281 (13)	0.0016 (8)	0.0046 (8)	−0.0034 (10)
C6	0.0185 (8)	0.0186 (11)	0.0195 (11)	0.0033 (7)	0.0055 (7)	0.0012 (8)
C7	0.0227 (9)	0.0222 (12)	0.0205 (11)	0.0000 (8)	0.0050 (8)	−0.0036 (9)
C8	0.0260 (9)	0.0239 (12)	0.0183 (11)	0.0013 (8)	0.0081 (8)	−0.0001 (9)
C9	0.0181 (8)	0.0205 (11)	0.0213 (11)	0.0009 (7)	0.0078 (7)	−0.0003 (9)
C10	0.0193 (9)	0.0277 (12)	0.0197 (11)	0.0008 (8)	0.0030 (8)	−0.0008 (9)
C11	0.0206 (9)	0.0275 (12)	0.0176 (11)	0.0011 (8)	0.0041 (7)	0.0013 (9)
Cl1	0.0256 (3)	0.0283 (3)	0.0228 (3)	0.00156 (19)	0.0056 (2)	−0.0007 (2)

Geometric parameters (Å, º)

S1—O1	1.4311 (16)	C2—H2	0.9500
S1—O2	1.4331 (16)	C3—H3	0.9500
S1—N2	1.6332 (17)	C4—C5	1.365 (3)
S1—C6	1.768 (2)	C4—H4	0.9500
O3—N3	1.226 (2)	C5—H5	0.9500
O4—N3	1.233 (2)	C6—C11	1.388 (3)
N1—C3	1.330 (3)	C6—C7	1.393 (3)
N1—C4	1.347 (3)	C7—C8	1.385 (3)
N1—H1	0.93 (3)	C7—H7	0.9500
N2—C1	1.394 (3)	C8—C9	1.381 (3)
N2—H2A	0.89 (3)	C8—H8	0.9500
N3—C9	1.468 (3)	C9—C10	1.385 (3)
C1—C2	1.391 (3)	C10—C11	1.387 (3)
C1—C5	1.402 (3)	C10—H10	0.9500
C2—C3	1.371 (3)	C11—H11	0.9500
O1—S1—O2	120.92 (10)	N1—C4—C5	120.1 (2)
O1—S1—N2	104.52 (10)	N1—C4—H4	120.0
O2—S1—N2	109.13 (10)	C5—C4—H4	120.0
O1—S1—C6	108.27 (10)	C4—C5—C1	119.6 (2)
O2—S1—C6	107.63 (10)	C4—C5—H5	120.2
N2—S1—C6	105.35 (9)	C1—C5—H5	120.2
C3—N1—C4	121.6 (2)	C11—C6—C7	121.73 (19)
C3—N1—H1	118.5 (18)	C11—C6—S1	119.82 (16)
C4—N1—H1	119.9 (18)	C7—C6—S1	118.42 (15)
C1—N2—S1	127.65 (15)	C8—C7—C6	119.50 (19)
C1—N2—H2A	117 (2)	C8—C7—H7	120.3
S1—N2—H2A	112.8 (19)	C6—C7—H7	120.3
O3—N3—O4	123.83 (19)	C9—C8—C7	118.0 (2)
O3—N3—C9	118.12 (18)	C9—C8—H8	121.0
O4—N3—C9	118.04 (18)	C7—C8—H8	121.0
C2—C1—N2	124.68 (19)	C8—C9—C10	123.26 (19)
C2—C1—C5	118.6 (2)	C8—C9—N3	118.51 (19)
N2—C1—C5	116.69 (19)	C10—C9—N3	118.22 (18)
C3—C2—C1	119.0 (2)	C9—C10—C11	118.50 (19)
C3—C2—H2	120.5	C9—C10—H10	120.8
C1—C2—H2	120.5	C11—C10—H10	120.8
N1—C3—C2	121.1 (2)	C10—C11—C6	118.97 (19)
N1—C3—H3	119.5	C10—C11—H11	120.5
C2—C3—H3	119.5	C6—C11—H11	120.5
O1—S1—N2—C1	172.50 (18)	O2—S1—C6—C7	168.84 (15)
O2—S1—N2—C1	41.8 (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—C8	176.94 (15)
S1—N2—C1—C5	167.25 (16)	C6—C7—C8—C9	−0.4 (3)
N2—C1—C2—C3	−177.14 (19)	C7—C8—C9—C10	1.8 (3)
C5—C1—C2—C3	1.5 (3)	C7—C8—C9—N3	−177.26 (17)
C4—N1—C3—C2	1.5 (3)	O3—N3—C9—C8	15.3 (3)
C1—C2—C3—N1	−2.4 (3)	O4—N3—C9—C8	−165.44 (18)
C3—N1—C4—C5	0.1 (3)	O3—N3—C9—C10	−163.75 (18)
N1—C4—C5—C1	−1.0 (4)	O4—N3—C9—C10	15.5 (3)
C2—C1—C5—C4	0.1 (3)	C8—C9—C10—C11	−1.7 (3)
N2—C1—C5—C4	178.9 (2)	N3—C9—C10—C11	177.29 (17)
O1—S1—C6—C11	−145.42 (16)	C9—C10—C11—C6	0.3 (3)
O2—S1—C6—C11	−13.15 (19)	C7—C6—C11—C10	1.1 (3)
N2—S1—C6—C11	103.20 (18)	S1—C6—C11—C10	−176.88 (15)
O1—S1—C6—C7	36.57 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1^i	0.93 (3)	2.12 (3)	3.039 (2)	171 (3)
N2—H2A···Cl1^ii	0.89 (3)	2.18 (3)	3.066 (2)	173 (3)

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