4-Nitro-N-(4-pyridinio)benzene­sulfonamidate monohydrate

Chen, Y.-Z.; Gao, H.; Li, G.; Chen, X.-J.; Niu, S.-Y.

doi:10.1107/S1600536808032273

organic compounds

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Volume 64| Part 11| November 2008| Page o2109

doi:10.1107/S1600536808032273

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4-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate

Yu-Zhen Chen,^a ^* Han Gao,^b Gang Li,^b Xiao-Jing Chen ^c and Sheng-Yang Niu ^b

^aDepartment of Mathematics, Henan Institute of Science and Technology, Xinxiang 453003, People's Republic of China, ^bSchool of Food Science, Henan Institute of Science and Technology, Xinxiang 453003, People's Republic of China, and ^cXinke College, Henan Institute of Science and Technology, Xinxiang 453003, People's Republic of China
^*Correspondence e-mail: chen_yuzhen@yahoo.cn

(Received 27 September 2008; accepted 7 October 2008; online 11 October 2008)

The title compound, C₁₁H₉N₃O₄S·H₂O, contains both an acid and a base centre, and displays a zwitterionic structure in the solid state. The benzene ring makes an angle of 109.1 (2)° with the pyridinium ring. The crystal structure is stabilized by O—H⋯N, O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Allen et al. (1987 ); Li et al. (2007 ); Damiano et al. (2007 ); Yu & Li (2007 ).

Experimental

Crystal data

C₁₁H₉N₃O₄S·H₂O
M_r = 297.29
Monoclinic, P 2₁ /n
a = 6.7766 (14) Å
b = 8.3932 (17) Å
c = 21.717 (4) Å
β = 92.35 (3)°
V = 1234.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 113 (2) K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.932, T_max = 0.963
9708 measured reflections
2908 independent reflections
2022 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.136
S = 1.17
2908 reflections
193 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯N2	0.85 (4)	1.97 (4)	2.813 (3)	167 (4)
O5—H5B⋯O2ⁱ	0.85 (5)	2.07 (5)	2.895 (3)	164 (4)
N1—H1A⋯O5ⁱⁱ	0.92 (4)	1.82 (4)	2.728 (3)	170 (4)
Symmetry codes: (i) -x+2, -y, -z; (ii) x, y+1, z.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032273/at2641sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032273/at2641Isup2.hkl

checkCIF report

Comment top

Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Teresa 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 (I) was determined by X-ray diffraction.

In the cations of (I) (Fig. 1), the short C—N distance [N2—C1 = 1.370 (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 π electron conjugation of the sulphonamide N with the pyridinium ring. The benzene ring exhibits an angle of 109.1 (2) ° with the pyridinium ring. The dihedral angle between the nitro group and the benzene ring is 2.2 (1) °.

The crystal structure is stabilized by O—H···N, O—H···O and N—H···O hydrogen bonds (Table 1).

Related literature top

For related literature, see: Allen et al. (1987); Li et al. (2007); Teresa et al. (2007); Yu & Li (2007).

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 55.3%. A colourless single-crystal suitable for X-ray analysis was obtained by slow evaporation of an acetic acid solution at room temperature over a period of a week.

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

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

4-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate top

Crystal data top

C₁₁H₉N₃O₄S·H₂O	F(000) = 616
M_r = 297.29	D_x = 1.600 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3340 reflections
a = 6.7766 (14) Å	θ = 1.9–27.9°
b = 8.3932 (17) Å	µ = 0.29 mm⁻¹
c = 21.717 (4) Å	T = 113 K
β = 92.35 (3)°	Block, colourless
V = 1234.2 (4) Å³	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2908 independent reflections
Radiation source: rotating anode	2022 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.061
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 1.9°
ω and ϕ scans	h = −8→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −11→10
T_min = 0.932, T_max = 0.963	l = −19→28
9708 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.031P)² + 1.5168P] where P = (F_o² + 2F_c²)/3
2908 reflections	(Δ/σ)_max = 0.002
193 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₁H₉N₃O₄S·H₂O	V = 1234.2 (4) Å³
M_r = 297.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7766 (14) Å	µ = 0.29 mm⁻¹
b = 8.3932 (17) Å	T = 113 K
c = 21.717 (4) Å	0.20 × 0.18 × 0.12 mm
β = 92.35 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2908 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2022 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.963	R_int = 0.061
9708 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.35 e Å⁻³
2908 reflections	Δρ_min = −0.45 e Å⁻³
193 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.89206 (11)	0.18818 (8)	0.12547 (3)	0.01574 (18)
N1	0.7145 (4)	0.7176 (3)	0.00969 (13)	0.0228 (6)
H1A	0.707 (6)	0.823 (5)	−0.0019 (19)	0.048 (12)*
N2	0.8061 (4)	0.2477 (3)	0.06005 (11)	0.0166 (5)
N3	0.2350 (4)	0.1341 (3)	0.29976 (12)	0.0236 (6)
O1	1.0378 (3)	0.2937 (2)	0.15368 (9)	0.0197 (5)
O2	0.9523 (3)	0.0240 (2)	0.11577 (10)	0.0208 (5)
O3	0.2477 (4)	0.2106 (3)	0.34777 (10)	0.0332 (6)
O4	0.0934 (4)	0.0497 (3)	0.28506 (13)	0.0401 (7)
C1	0.7738 (4)	0.4058 (3)	0.04742 (13)	0.0151 (6)
C2	0.7618 (5)	0.5312 (3)	0.09068 (14)	0.0203 (6)
H2	0.7736	0.5099	0.1336	0.024*
C3	0.7329 (5)	0.6835 (4)	0.06978 (16)	0.0259 (7)
H3	0.7257	0.7677	0.0989	0.031*
C4	0.7199 (5)	0.6006 (4)	−0.03300 (14)	0.0204 (6)
H4	0.7053	0.6265	−0.0755	0.024*
C5	0.7463 (4)	0.4454 (3)	−0.01543 (14)	0.0176 (6)
H5	0.7462	0.3638	−0.0458	0.021*
C6	0.6953 (4)	0.1762 (3)	0.17671 (13)	0.0150 (6)
C7	0.5306 (5)	0.0811 (3)	0.16067 (13)	0.0182 (6)
H7	0.5230	0.0275	0.1221	0.022*
C8	0.3798 (5)	0.0659 (3)	0.20114 (14)	0.0180 (6)
H8	0.2678	0.0013	0.1912	0.022*
C9	0.3961 (4)	0.1475 (3)	0.25685 (13)	0.0171 (6)
C10	0.5550 (5)	0.2447 (3)	0.27298 (14)	0.0199 (6)
H10	0.5598	0.3011	0.3109	0.024*
C11	0.7072 (5)	0.2580 (3)	0.23239 (13)	0.0189 (6)
H11	0.8189	0.3226	0.2426	0.023*
O5	0.7268 (4)	0.0224 (2)	−0.03361 (11)	0.0216 (5)
H5A	0.763 (6)	0.079 (5)	−0.003 (2)	0.046 (13)*
H5B	0.815 (7)	0.027 (5)	−0.060 (2)	0.049 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0176 (4)	0.0143 (3)	0.0154 (3)	0.0017 (3)	0.0016 (3)	0.0006 (3)
N1	0.0216 (15)	0.0139 (11)	0.0326 (15)	−0.0023 (10)	−0.0021 (12)	0.0047 (11)
N2	0.0213 (14)	0.0133 (11)	0.0152 (11)	0.0014 (10)	0.0005 (10)	0.0005 (9)
N3	0.0253 (15)	0.0227 (13)	0.0231 (14)	0.0026 (11)	0.0061 (12)	0.0037 (11)
O1	0.0175 (11)	0.0213 (10)	0.0203 (11)	−0.0013 (9)	−0.0007 (8)	−0.0004 (9)
O2	0.0254 (12)	0.0151 (10)	0.0222 (11)	0.0054 (8)	0.0056 (9)	0.0025 (8)
O3	0.0445 (16)	0.0358 (13)	0.0202 (11)	−0.0024 (11)	0.0134 (11)	−0.0026 (10)
O4	0.0294 (15)	0.0468 (15)	0.0452 (16)	−0.0171 (12)	0.0146 (13)	−0.0081 (13)
C1	0.0116 (15)	0.0138 (12)	0.0201 (14)	−0.0010 (10)	0.0029 (12)	0.0012 (11)
C2	0.0251 (17)	0.0172 (13)	0.0184 (14)	0.0024 (12)	−0.0027 (13)	−0.0017 (12)
C3	0.0309 (19)	0.0169 (14)	0.0292 (17)	0.0010 (13)	−0.0068 (14)	−0.0050 (13)
C4	0.0158 (16)	0.0244 (14)	0.0211 (15)	0.0013 (12)	0.0026 (12)	0.0048 (12)
C5	0.0135 (15)	0.0199 (13)	0.0196 (14)	0.0005 (11)	0.0037 (12)	−0.0003 (12)
C6	0.0155 (15)	0.0147 (12)	0.0148 (13)	0.0028 (11)	0.0008 (11)	0.0019 (11)
C7	0.0204 (16)	0.0189 (13)	0.0150 (13)	0.0013 (12)	−0.0024 (12)	−0.0021 (11)
C8	0.0164 (16)	0.0166 (13)	0.0207 (14)	0.0005 (11)	−0.0012 (12)	−0.0003 (12)
C9	0.0180 (15)	0.0170 (13)	0.0165 (14)	0.0022 (11)	0.0033 (12)	0.0033 (11)
C10	0.0241 (17)	0.0205 (13)	0.0151 (13)	0.0021 (12)	0.0000 (12)	−0.0035 (12)
C11	0.0221 (16)	0.0190 (13)	0.0156 (13)	−0.0026 (12)	−0.0008 (12)	−0.0012 (11)
O5	0.0292 (14)	0.0158 (10)	0.0199 (11)	−0.0026 (9)	0.0037 (10)	−0.0011 (9)

Geometric parameters (Å, º) top

S1—O1	1.444 (2)	C4—C5	1.367 (4)
S1—O2	1.455 (2)	C4—H4	0.9500
S1—N2	1.594 (2)	C5—H5	0.9500
S1—C6	1.774 (3)	C6—C11	1.390 (4)
N1—C3	1.337 (4)	C6—C7	1.404 (4)
N1—C4	1.352 (4)	C7—C8	1.381 (4)
N1—H1A	0.92 (4)	C7—H7	0.9500
N2—C1	1.370 (3)	C8—C9	1.391 (4)
N3—O4	1.224 (4)	C8—H8	0.9500
N3—O3	1.225 (3)	C9—C10	1.385 (4)
N3—C9	1.468 (4)	C10—C11	1.388 (4)
C1—C5	1.410 (4)	C10—H10	0.9500
C1—C2	1.416 (4)	C11—H11	0.9500
C2—C3	1.368 (4)	O5—H5A	0.85 (4)
C2—H2	0.9500	O5—H5B	0.85 (5)
C3—H3	0.9500

O1—S1—O2	116.81 (13)	C5—C4—H4	119.8
O1—S1—N2	113.86 (13)	C4—C5—C1	120.4 (3)
O2—S1—N2	105.21 (12)	C4—C5—H5	119.8
O1—S1—C6	106.69 (13)	C1—C5—H5	119.8
O2—S1—C6	105.05 (13)	C11—C6—C7	120.9 (3)
N2—S1—C6	108.69 (13)	C11—C6—S1	120.0 (2)
C3—N1—C4	120.7 (3)	C7—C6—S1	119.1 (2)
C3—N1—H1A	118 (3)	C8—C7—C6	119.8 (3)
C4—N1—H1A	121 (3)	C8—C7—H7	120.1
C1—N2—S1	122.1 (2)	C6—C7—H7	120.1
O4—N3—O3	123.5 (3)	C7—C8—C9	118.2 (3)
O4—N3—C9	118.3 (3)	C7—C8—H8	120.9
O3—N3—C9	118.2 (3)	C9—C8—H8	120.9
N2—C1—C5	115.9 (2)	C10—C9—C8	122.9 (3)
N2—C1—C2	126.9 (3)	C10—C9—N3	118.4 (3)
C5—C1—C2	117.2 (3)	C8—C9—N3	118.7 (3)
C3—C2—C1	119.1 (3)	C9—C10—C11	118.5 (3)
C3—C2—H2	120.5	C9—C10—H10	120.8
C1—C2—H2	120.5	C11—C10—H10	120.8
N1—C3—C2	122.0 (3)	C10—C11—C6	119.6 (3)
N1—C3—H3	119.0	C10—C11—H11	120.2
C2—C3—H3	119.0	C6—C11—H11	120.2
N1—C4—C5	120.5 (3)	H5A—O5—H5B	109 (4)
N1—C4—H4	119.8

O1—S1—N2—C1	−36.5 (3)	O2—S1—C6—C7	−55.7 (3)
O2—S1—N2—C1	−165.6 (2)	N2—S1—C6—C7	56.5 (3)
C6—S1—N2—C1	82.3 (3)	C11—C6—C7—C8	−1.3 (4)
S1—N2—C1—C5	164.4 (2)	S1—C6—C7—C8	177.6 (2)
S1—N2—C1—C2	−16.8 (4)	C6—C7—C8—C9	0.5 (4)
N2—C1—C2—C3	178.6 (3)	C7—C8—C9—C10	1.0 (4)
C5—C1—C2—C3	−2.7 (5)	C7—C8—C9—N3	179.0 (3)
C4—N1—C3—C2	1.4 (5)	O4—N3—C9—C10	179.1 (3)
C1—C2—C3—N1	0.4 (5)	O3—N3—C9—C10	0.6 (4)
C3—N1—C4—C5	−0.6 (5)	O4—N3—C9—C8	0.9 (4)
N1—C4—C5—C1	−1.8 (5)	O3—N3—C9—C8	−177.6 (3)
N2—C1—C5—C4	−177.7 (3)	C8—C9—C10—C11	−1.7 (4)
C2—C1—C5—C4	3.4 (4)	N3—C9—C10—C11	−179.8 (3)
O1—S1—C6—C11	−1.5 (3)	C9—C10—C11—C6	1.0 (4)
O2—S1—C6—C11	123.1 (2)	C7—C6—C11—C10	0.5 (4)
N2—S1—C6—C11	−124.7 (2)	S1—C6—C11—C10	−178.3 (2)
O1—S1—C6—C7	179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···N2	0.85 (4)	1.97 (4)	2.813 (3)	167 (4)
O5—H5B···O2ⁱ	0.85 (5)	2.07 (5)	2.895 (3)	164 (4)
N1—H1A···O5ⁱⁱ	0.92 (4)	1.82 (4)	2.728 (3)	170 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₃O₄S·H₂O
M_r	297.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	6.7766 (14), 8.3932 (17), 21.717 (4)
β (°)	92.35 (3)
V (Å³)	1234.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.932, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	9708, 2908, 2022
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.136, 1.17
No. of reflections	2908
No. of parameters	193
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.45

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···N2	0.85 (4)	1.97 (4)	2.813 (3)	167 (4)
O5—H5B···O2ⁱ	0.85 (5)	2.07 (5)	2.895 (3)	164 (4)
N1—H1A···O5ⁱⁱ	0.92 (4)	1.82 (4)	2.728 (3)	170 (4)

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

References

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. CrossRef Web of Science Google Scholar
Damiano, T., Morton, D. & Nelson, A. (2007). Org. Biomol. Chem. 5, 2735–2752. Web of Science CrossRef PubMed CAS Google Scholar
Li, J. S., Chen, L. G., Zhang, Y. Y., Xu, Y. J., Deng, Y. & Huang, P. M. (2007). J. Chem. Res. 6, 350–352. CrossRef Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, H.-J. & Li, J.-S. (2007). Acta Cryst. E63, o3399. CSD CrossRef IUCr Journals Google Scholar

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