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The title compound, C11H9N3O4S, exists as its zwitterion tautomer in the solid state. The mol­ecules are linked by N—H...N hydrogen-bond inter­actions into supra­molecular chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032096/hb2464sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032096/hb2464Isup2.hkl
Contains datablock I

CCDC reference: 657683

Key indicators

  • Single-crystal X-ray study
  • T = 113 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.046
  • wR factor = 0.176
  • Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.85 Ratio PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), contains both an acid and a base centre, thus displays a zwitterion structure in the solid state (Fig. 1), i.e. nominal proton transfer from the sulfonamide N—H group to the pyridine N atom. The short C3—N1 distance [1.356 (4) Å] indicates that the N1 lone-pair electrons conjugate with pyridinium ring which correlates with the formal contribution of a second, uncharged, tautomer (see scheme) to the overall structure of the molecule. The benzene ring forms an angle of 81.71 (15)° with the pyridinium ring.

In the crystal of (I), molecules are linked by intermolecular N—H···N hydrogen bonds (Table 1), forming chains as shown in Fig. 2, two of which pack face to face to produce an independent molecular layer.

Experimental top

A solution of 4-nitrobenzenesulfonyl chloride in CH2Cl2 was added dropwise to a suspension of 4-aminopyridine in CH2Cl2 at room temperature with stirring. The reaction mixture continued stirring overnight. The yellow solid obtained was washed with warm water in a yield of 77.9%. Yellow blocks of (I) were grown by diffusion of (iPr)2O into a DMSO solution.

Refinement top

The N-bound H atom was located in a difference map and refined as riding in its as-found relative position. The C-bound H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding atoms. The constraint Uiso(H) = 1.2 Ueq(C and N) was applied.

Structure description top

The title compound, (I), contains both an acid and a base centre, thus displays a zwitterion structure in the solid state (Fig. 1), i.e. nominal proton transfer from the sulfonamide N—H group to the pyridine N atom. The short C3—N1 distance [1.356 (4) Å] indicates that the N1 lone-pair electrons conjugate with pyridinium ring which correlates with the formal contribution of a second, uncharged, tautomer (see scheme) to the overall structure of the molecule. The benzene ring forms an angle of 81.71 (15)° with the pyridinium ring.

In the crystal of (I), molecules are linked by intermolecular N—H···N hydrogen bonds (Table 1), forming chains as shown in Fig. 2, two of which pack face to face to produce an independent molecular layer.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. A view of (I) with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. The packing of (I), view down the b axis, showing supramolecular chains linked by N—H···N hydrogen bonds which are indicated by dashed lines.
[Figure 3] Fig. 3. The tautomerization in the title compound.
4-Nitro-N-(4-pyridyl)benzenesulfonamide top
Crystal data top
C11H9N3O4SF(000) = 576
Mr = 279.27Dx = 1.600 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1893 reflections
a = 13.978 (3) Åθ = 3.1–25.0°
b = 7.5376 (15) ŵ = 0.29 mm1
c = 12.176 (2) ÅT = 113 K
β = 115.34 (3)°Block, yellow
V = 1159.4 (4) Å30.16 × 0.14 × 0.12 mm
Z = 4
Data collection top
Rigaku Saturn
diffractometer
2262 independent reflections
Radiation source: fine-focus sealed tube1889 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 7.31 pixels mm-1θmax = 26.0°, θmin = 1.6°
ω scansh = 1717
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 99
Tmin = 0.954, Tmax = 0.966l = 1315
9190 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)] = 0.046Hydrogen site location: difmap and geom
wR(F2) = 0.176H-atom parameters constrained
S = 1.18 w = 1/[σ2(Fo2) + (0.1054P)2]
where P = (Fo2 + 2Fc2)/3
2262 reflections(Δ/σ)max = 0.002
173 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
C11H9N3O4SV = 1159.4 (4) Å3
Mr = 279.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.978 (3) ŵ = 0.29 mm1
b = 7.5376 (15) ÅT = 113 K
c = 12.176 (2) Å0.16 × 0.14 × 0.12 mm
β = 115.34 (3)°
Data collection top
Rigaku Saturn
diffractometer
2262 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
1889 reflections with I > 2σ(I)
Tmin = 0.954, Tmax = 0.966Rint = 0.050
9190 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.176H-atom parameters constrained
S = 1.18Δρmax = 0.46 e Å3
2262 reflectionsΔρmin = 0.65 e Å3
173 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
xyzUiso*/Ueq
S10.16805 (5)0.66565 (9)0.10514 (6)0.0152 (3)
O10.17183 (16)0.6925 (2)0.22344 (19)0.0202 (5)
O20.11008 (16)0.7935 (2)0.01426 (18)0.0185 (5)
O30.68036 (19)0.5905 (4)0.2563 (3)0.0529 (9)
O40.63460 (19)0.7324 (4)0.0894 (3)0.0476 (8)
N10.13602 (18)0.4652 (3)0.0713 (2)0.0148 (5)
N20.11262 (18)0.2208 (3)0.2411 (2)0.0150 (5)
H2A0.10720.15770.30770.018*
N30.6147 (2)0.6614 (4)0.1659 (3)0.0351 (8)
C10.1198 (2)0.1267 (4)0.1438 (2)0.0159 (6)
H10.12110.00080.14620.019*
C20.1250 (2)0.2084 (4)0.0440 (3)0.0167 (6)
H20.12920.13920.02310.020*
C30.1245 (2)0.3942 (4)0.0360 (3)0.0142 (6)
C40.1143 (2)0.4876 (4)0.1408 (3)0.0163 (6)
H40.11100.61350.14210.020*
C50.1091 (2)0.3984 (4)0.2388 (3)0.0163 (6)
H50.10280.46320.30850.020*
C60.3010 (2)0.6735 (3)0.1231 (3)0.0159 (6)
C70.3796 (2)0.6078 (4)0.2301 (3)0.0251 (7)
H70.36250.56610.29320.030*
C80.4834 (3)0.6038 (4)0.2442 (3)0.0295 (8)
H80.53840.55970.31690.035*
C90.5048 (2)0.6640 (4)0.1521 (3)0.0239 (7)
C100.4278 (2)0.7273 (4)0.0444 (3)0.0264 (7)
H100.44560.76640.01870.032*
C110.3243 (2)0.7329 (4)0.0300 (3)0.0236 (7)
H110.26980.77710.04310.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0197 (4)0.0117 (4)0.0171 (5)0.0007 (2)0.0107 (3)0.0005 (3)
O10.0291 (12)0.0163 (10)0.0213 (12)0.0018 (8)0.0165 (9)0.0049 (8)
O20.0224 (11)0.0125 (9)0.0222 (12)0.0026 (8)0.0111 (9)0.0029 (8)
O30.0219 (14)0.067 (2)0.062 (2)0.0105 (12)0.0109 (13)0.0292 (16)
O40.0268 (13)0.074 (2)0.0473 (17)0.0041 (14)0.0207 (13)0.0090 (16)
N10.0216 (12)0.0114 (11)0.0166 (13)0.0014 (9)0.0133 (10)0.0031 (9)
N20.0171 (12)0.0154 (12)0.0140 (12)0.0002 (9)0.0081 (10)0.0012 (10)
N30.0210 (15)0.0327 (16)0.050 (2)0.0023 (12)0.0140 (15)0.0035 (14)
C10.0161 (14)0.0119 (13)0.0198 (16)0.0013 (10)0.0076 (12)0.0023 (11)
C20.0153 (14)0.0137 (13)0.0219 (16)0.0000 (10)0.0086 (12)0.0043 (12)
C30.0109 (13)0.0150 (13)0.0162 (15)0.0005 (10)0.0054 (11)0.0007 (11)
C40.0165 (14)0.0130 (13)0.0217 (16)0.0017 (10)0.0105 (12)0.0027 (11)
C50.0168 (14)0.0165 (14)0.0173 (15)0.0007 (11)0.0089 (12)0.0012 (12)
C60.0203 (15)0.0129 (13)0.0157 (15)0.0022 (10)0.0088 (12)0.0030 (11)
C70.0274 (17)0.0270 (16)0.0202 (16)0.0018 (13)0.0097 (13)0.0054 (14)
C80.0206 (16)0.0281 (17)0.0329 (19)0.0011 (13)0.0049 (14)0.0087 (15)
C90.0163 (16)0.0236 (16)0.0308 (19)0.0031 (12)0.0090 (14)0.0024 (13)
C100.0271 (17)0.0342 (18)0.0204 (17)0.0049 (14)0.0126 (14)0.0042 (14)
C110.0196 (15)0.0300 (17)0.0202 (16)0.0010 (13)0.0077 (13)0.0036 (14)
Geometric parameters (Å, º) top
S1—O21.429 (2)C3—C41.410 (4)
S1—O11.433 (2)C4—C51.345 (4)
S1—N11.580 (2)C4—H40.9500
S1—C61.776 (3)C5—H50.9500
O3—N31.214 (4)C6—C111.381 (4)
O4—N31.206 (4)C6—C71.388 (4)
N1—C31.356 (4)C7—C81.387 (4)
N2—C51.340 (4)C7—H70.9500
N2—C11.348 (4)C8—C91.357 (5)
N2—H2A0.9151C8—H80.9500
N3—C91.472 (4)C9—C101.377 (4)
C1—C21.336 (4)C10—C111.382 (4)
C1—H10.9500C10—H100.9500
C2—C31.404 (4)C11—H110.9500
C2—H20.9500
O2—S1—O1116.62 (12)C5—C4—H4120.0
O2—S1—N1116.06 (12)C3—C4—H4120.0
O1—S1—N1106.36 (12)N2—C5—C4122.0 (3)
O2—S1—C6106.82 (13)N2—C5—H5119.0
O1—S1—C6106.57 (14)C4—C5—H5119.0
N1—S1—C6103.20 (12)C11—C6—C7121.1 (3)
C3—N1—S1122.2 (2)C11—C6—S1120.8 (2)
C5—N2—C1119.8 (2)C7—C6—S1118.0 (2)
C5—N2—H2A123.3C8—C7—C6119.3 (3)
C1—N2—H2A116.9C8—C7—H7120.3
O4—N3—O3124.1 (3)C6—C7—H7120.3
O4—N3—C9118.7 (3)C9—C8—C7118.7 (3)
O3—N3—C9117.2 (3)C9—C8—H8120.7
C2—C1—N2120.8 (3)C7—C8—H8120.7
C2—C1—H1119.6C8—C9—C10122.9 (3)
N2—C1—H1119.6C8—C9—N3119.3 (3)
C1—C2—C3121.5 (3)C10—C9—N3117.7 (3)
C1—C2—H2119.2C9—C10—C11118.7 (3)
C3—C2—H2119.2C9—C10—H10120.6
N1—C3—C2117.3 (2)C11—C10—H10120.6
N1—C3—C4126.8 (3)C6—C11—C10119.2 (3)
C2—C3—C4115.9 (3)C6—C11—H11120.4
C5—C4—C3120.0 (3)C10—C11—H11120.4
O2—S1—N1—C348.1 (3)O1—S1—C6—C734.0 (3)
O1—S1—N1—C3179.6 (2)N1—S1—C6—C777.8 (3)
C6—S1—N1—C368.4 (2)C11—C6—C7—C80.7 (5)
C5—N2—C1—C21.0 (4)S1—C6—C7—C8176.7 (2)
N2—C1—C2—C30.7 (4)C6—C7—C8—C90.2 (5)
S1—N1—C3—C2162.8 (2)C7—C8—C9—C100.8 (5)
S1—N1—C3—C415.6 (4)C7—C8—C9—N3179.7 (3)
C1—C2—C3—N1176.4 (2)O4—N3—C9—C8172.1 (3)
C1—C2—C3—C42.2 (4)O3—N3—C9—C86.1 (4)
N1—C3—C4—C5176.4 (3)O4—N3—C9—C108.3 (5)
C2—C3—C4—C52.1 (4)O3—N3—C9—C10173.5 (3)
C1—N2—C5—C41.1 (4)C8—C9—C10—C111.2 (5)
C3—C4—C5—N20.5 (4)N3—C9—C10—C11179.3 (3)
O2—S1—C6—C1124.7 (3)C7—C6—C11—C100.3 (4)
O1—S1—C6—C11150.0 (2)S1—C6—C11—C10176.2 (2)
N1—S1—C6—C1198.2 (2)C9—C10—C11—C60.6 (5)
O2—S1—C6—C7159.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.921.922.816 (3)165
Symmetry code: (i) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC11H9N3O4S
Mr279.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)113
a, b, c (Å)13.978 (3), 7.5376 (15), 12.176 (2)
β (°) 115.34 (3)
V3)1159.4 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.16 × 0.14 × 0.12
Data collection
DiffractometerRigaku Saturn
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2005)
Tmin, Tmax0.954, 0.966
No. of measured, independent and
observed [I > 2σ(I)] reflections
9190, 2262, 1889
Rint0.050
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.176, 1.18
No. of reflections2262
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.65

Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), CrystalStructure (Rigaku/MSC, 2005).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.921.922.816 (3)165
Symmetry code: (i) x, y+1/2, z1/2.
 

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