4-Nitro-N-(4-pyrid­yl)benzene­sulfonamide

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.

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

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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

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S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2 U_eq(C and N) was applied.

Computing details

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

	Fig. 1. A view of (I) with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
	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.
	Fig. 3. The tautomerization in the title compound.

4-Nitro-N-(4-pyridyl)benzenesulfonamide

Crystal data

C11H9N3O4S	F(000) = 576
Mr = 279.27	Dx = 1.600 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1893 reflections
a = 13.978 (3) Å	θ = 3.1–25.0°
b = 7.5376 (15) Å	µ = 0.29 mm^−1
c = 12.176 (2) Å	T = 113 K
β = 115.34 (3)°	Block, yellow
V = 1159.4 (4) Å^3	0.16 × 0.14 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	2262 independent reflections
Radiation source: fine-focus sealed tube	1889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 7.31 pixels mm^-1	θmax = 26.0°, θmin = 1.6°
ω scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −9→9
Tmin = 0.954, Tmax = 0.966	l = −13→15
9190 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)] = 0.046	Hydrogen site location: difmap and geom
wR(F^2) = 0.176	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.1054P)^2] where P = (Fo^2 + 2Fc^2)/3
2262 reflections	(Δ/σ)max = 0.002
173 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.65 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	0.16805 (5)	0.66565 (9)	0.10514 (6)	0.0152 (3)
O1	0.17183 (16)	0.6925 (2)	0.22344 (19)	0.0202 (5)
O2	0.11008 (16)	0.7935 (2)	0.01426 (18)	0.0185 (5)
O3	0.68036 (19)	0.5905 (4)	0.2563 (3)	0.0529 (9)
O4	0.63460 (19)	0.7324 (4)	0.0894 (3)	0.0476 (8)
N1	0.13602 (18)	0.4652 (3)	0.0713 (2)	0.0148 (5)
N2	0.11262 (18)	0.2208 (3)	−0.2411 (2)	0.0150 (5)
H2A	0.1072	0.1577	−0.3077	0.018*
N3	0.6147 (2)	0.6614 (4)	0.1659 (3)	0.0351 (8)
C1	0.1198 (2)	0.1267 (4)	−0.1438 (2)	0.0159 (6)
H1	0.1211	0.0008	−0.1462	0.019*
C2	0.1250 (2)	0.2084 (4)	−0.0440 (3)	0.0167 (6)
H2	0.1292	0.1392	0.0231	0.020*
C3	0.1245 (2)	0.3942 (4)	−0.0360 (3)	0.0142 (6)
C4	0.1143 (2)	0.4876 (4)	−0.1408 (3)	0.0163 (6)
H4	0.1110	0.6135	−0.1421	0.020*
C5	0.1091 (2)	0.3984 (4)	−0.2388 (3)	0.0163 (6)
H5	0.1028	0.4632	−0.3085	0.020*
C6	0.3010 (2)	0.6735 (3)	0.1231 (3)	0.0159 (6)
C7	0.3796 (2)	0.6078 (4)	0.2301 (3)	0.0251 (7)
H7	0.3625	0.5661	0.2932	0.030*
C8	0.4834 (3)	0.6038 (4)	0.2442 (3)	0.0295 (8)
H8	0.5384	0.5597	0.3169	0.035*
C9	0.5048 (2)	0.6640 (4)	0.1521 (3)	0.0239 (7)
C10	0.4278 (2)	0.7273 (4)	0.0444 (3)	0.0264 (7)
H10	0.4456	0.7664	−0.0187	0.032*
C11	0.3243 (2)	0.7329 (4)	0.0300 (3)	0.0236 (7)
H11	0.2698	0.7771	−0.0431	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0197 (4)	0.0117 (4)	0.0171 (5)	−0.0007 (2)	0.0107 (3)	−0.0005 (3)
O1	0.0291 (12)	0.0163 (10)	0.0213 (12)	−0.0018 (8)	0.0165 (9)	−0.0049 (8)
O2	0.0224 (11)	0.0125 (9)	0.0222 (12)	0.0026 (8)	0.0111 (9)	0.0029 (8)
O3	0.0219 (14)	0.067 (2)	0.062 (2)	0.0105 (12)	0.0109 (13)	0.0292 (16)
O4	0.0268 (13)	0.074 (2)	0.0473 (17)	−0.0041 (14)	0.0207 (13)	0.0090 (16)
N1	0.0216 (12)	0.0114 (11)	0.0166 (13)	−0.0014 (9)	0.0133 (10)	−0.0031 (9)
N2	0.0171 (12)	0.0154 (12)	0.0140 (12)	0.0002 (9)	0.0081 (10)	−0.0012 (10)
N3	0.0210 (15)	0.0327 (16)	0.050 (2)	−0.0023 (12)	0.0140 (15)	0.0035 (14)
C1	0.0161 (14)	0.0119 (13)	0.0198 (16)	−0.0013 (10)	0.0076 (12)	−0.0023 (11)
C2	0.0153 (14)	0.0137 (13)	0.0219 (16)	0.0000 (10)	0.0086 (12)	0.0043 (12)
C3	0.0109 (13)	0.0150 (13)	0.0162 (15)	−0.0005 (10)	0.0054 (11)	0.0007 (11)
C4	0.0165 (14)	0.0130 (13)	0.0217 (16)	0.0017 (10)	0.0105 (12)	0.0027 (11)
C5	0.0168 (14)	0.0165 (14)	0.0173 (15)	0.0007 (11)	0.0089 (12)	0.0012 (12)
C6	0.0203 (15)	0.0129 (13)	0.0157 (15)	−0.0022 (10)	0.0088 (12)	−0.0030 (11)
C7	0.0274 (17)	0.0270 (16)	0.0202 (16)	−0.0018 (13)	0.0097 (13)	0.0054 (14)
C8	0.0206 (16)	0.0281 (17)	0.0329 (19)	−0.0011 (13)	0.0049 (14)	0.0087 (15)
C9	0.0163 (16)	0.0236 (16)	0.0308 (19)	−0.0031 (12)	0.0090 (14)	−0.0024 (13)
C10	0.0271 (17)	0.0342 (18)	0.0204 (17)	−0.0049 (14)	0.0126 (14)	0.0042 (14)
C11	0.0196 (15)	0.0300 (17)	0.0202 (16)	−0.0010 (13)	0.0077 (13)	0.0036 (14)

Geometric parameters (Å, º)

S1—O2	1.429 (2)	C3—C4	1.410 (4)
S1—O1	1.433 (2)	C4—C5	1.345 (4)
S1—N1	1.580 (2)	C4—H4	0.9500
S1—C6	1.776 (3)	C5—H5	0.9500
O3—N3	1.214 (4)	C6—C11	1.381 (4)
O4—N3	1.206 (4)	C6—C7	1.388 (4)
N1—C3	1.356 (4)	C7—C8	1.387 (4)
N2—C5	1.340 (4)	C7—H7	0.9500
N2—C1	1.348 (4)	C8—C9	1.357 (5)
N2—H2A	0.9151	C8—H8	0.9500
N3—C9	1.472 (4)	C9—C10	1.377 (4)
C1—C2	1.336 (4)	C10—C11	1.382 (4)
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.404 (4)	C11—H11	0.9500
C2—H2	0.9500
O2—S1—O1	116.62 (12)	C5—C4—H4	120.0
O2—S1—N1	116.06 (12)	C3—C4—H4	120.0
O1—S1—N1	106.36 (12)	N2—C5—C4	122.0 (3)
O2—S1—C6	106.82 (13)	N2—C5—H5	119.0
O1—S1—C6	106.57 (14)	C4—C5—H5	119.0
N1—S1—C6	103.20 (12)	C11—C6—C7	121.1 (3)
C3—N1—S1	122.2 (2)	C11—C6—S1	120.8 (2)
C5—N2—C1	119.8 (2)	C7—C6—S1	118.0 (2)
C5—N2—H2A	123.3	C8—C7—C6	119.3 (3)
C1—N2—H2A	116.9	C8—C7—H7	120.3
O4—N3—O3	124.1 (3)	C6—C7—H7	120.3
O4—N3—C9	118.7 (3)	C9—C8—C7	118.7 (3)
O3—N3—C9	117.2 (3)	C9—C8—H8	120.7
C2—C1—N2	120.8 (3)	C7—C8—H8	120.7
C2—C1—H1	119.6	C8—C9—C10	122.9 (3)
N2—C1—H1	119.6	C8—C9—N3	119.3 (3)
C1—C2—C3	121.5 (3)	C10—C9—N3	117.7 (3)
C1—C2—H2	119.2	C9—C10—C11	118.7 (3)
C3—C2—H2	119.2	C9—C10—H10	120.6
N1—C3—C2	117.3 (2)	C11—C10—H10	120.6
N1—C3—C4	126.8 (3)	C6—C11—C10	119.2 (3)
C2—C3—C4	115.9 (3)	C6—C11—H11	120.4
C5—C4—C3	120.0 (3)	C10—C11—H11	120.4
O2—S1—N1—C3	48.1 (3)	O1—S1—C6—C7	34.0 (3)
O1—S1—N1—C3	179.6 (2)	N1—S1—C6—C7	−77.8 (3)
C6—S1—N1—C3	−68.4 (2)	C11—C6—C7—C8	0.7 (5)
C5—N2—C1—C2	−1.0 (4)	S1—C6—C7—C8	176.7 (2)
N2—C1—C2—C3	−0.7 (4)	C6—C7—C8—C9	−0.2 (5)
S1—N1—C3—C2	162.8 (2)	C7—C8—C9—C10	−0.8 (5)
S1—N1—C3—C4	−15.6 (4)	C7—C8—C9—N3	179.7 (3)
C1—C2—C3—N1	−176.4 (2)	O4—N3—C9—C8	−172.1 (3)
C1—C2—C3—C4	2.2 (4)	O3—N3—C9—C8	6.1 (4)
N1—C3—C4—C5	176.4 (3)	O4—N3—C9—C10	8.3 (5)
C2—C3—C4—C5	−2.1 (4)	O3—N3—C9—C10	−173.5 (3)
C1—N2—C5—C4	1.1 (4)	C8—C9—C10—C11	1.2 (5)
C3—C4—C5—N2	0.5 (4)	N3—C9—C10—C11	−179.3 (3)
O2—S1—C6—C11	−24.7 (3)	C7—C6—C11—C10	−0.3 (4)
O1—S1—C6—C11	−150.0 (2)	S1—C6—C11—C10	−176.2 (2)
N1—S1—C6—C11	98.2 (2)	C9—C10—C11—C6	−0.6 (5)
O2—S1—C6—C7	159.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1^i	0.92	1.92	2.816 (3)	165

Symmetry code: (i) x, −y+1/2, z−1/2.