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The title compound, C11H10N2O2S, crystallizes as a zwitterionic tautomer, N-(4-pyridinio)benzene­sulfonamidate, with the pyridine N atom protonated and the amide N atom deprotonated. There is evidence for conjugation between the anionic N atom and the pyridinium ring. In the crystal structure, inter­molecular N—H...N hydrogen bonds link the mol­ecules into chains along the c axis. Weak C—H...O and C—H...π inter­actions further stabilize the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037713/lh2469sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037713/lh2469Isup2.hkl
Contains datablock I

CCDC reference: 660220

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • Disorder in main residue
  • R factor = 0.044
  • wR factor = 0.124
  • Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT301_ALERT_3_B Main Residue Disorder ......................... 27.00 Perc.
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT480_ALERT_4_C Long H...A H-Bond Reported H4 .. O1 .. 2.61 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 73
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 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 2 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

Comment top

In the solid state N-(4-pyridyl)benzenesulfonamide exists as a zwitterion with the pyridine N protonated and the amide N deprotonated, Fig. 1. The short N2—C3 bond, 1.333 (3) Å, indicates a degree of conjugation between the deprotonated N atom and the pyridinium ring. The angle between the pyridinium ring and the major disorder component of the benzene ring is 84.5 (3)°. Aryl sulphonamides with the amide N atom deprotonated have been reported previously, both as salts with suitable cations (Heren et al., 2006; Hannan & Talukdar, 1992) and in zwitterionic forms (Amendola et al., 2005.; Lindley et al., 1977; Schaumann et al., 1975).

Intermolecular N—H···N hydrogen bonds link the molecules into chains along the c axis. Weak C—H···O interactions and a C9—H9···Cg π-interaction (C9···Cg = 3.603 (8) Å, C9—H9···Cg = 161°) further stabilize the structure (Cg is the centroid of the pyridinium ring).

Related literature top

For the preparation of the compound see Li (2007). Aryl sulfonamides with the amide N atom deprotonated have been reported previously, both as salts with suitable cations (Heren et al., 2006; Hannan & Talukdar, 1992) and in zwitterionic forms (Amendola et al., 2005; Lindley et al., 1977; Schaumann et al., 1975).

Experimental top

The title compound was prepared using the method of Li (2007). Colourless single crystals were grown by slow evaporation of a solution in methanol.

Refinement top

All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å and with Uiso(H) = 1.2 Ueq(C). The H atom on the N atom of the pyridinium ring was located in a difference map and refined with the distance restraint N—H =0.82 (3) Å and with Uiso(H) = 1.5 Ueq(N). The benzene ring is disordered and the two disorder components were refined as rigid groups; their site occupancies refined to 0.56 (4) and 0.44 (4) respectively.

Structure description top

In the solid state N-(4-pyridyl)benzenesulfonamide exists as a zwitterion with the pyridine N protonated and the amide N deprotonated, Fig. 1. The short N2—C3 bond, 1.333 (3) Å, indicates a degree of conjugation between the deprotonated N atom and the pyridinium ring. The angle between the pyridinium ring and the major disorder component of the benzene ring is 84.5 (3)°. Aryl sulphonamides with the amide N atom deprotonated have been reported previously, both as salts with suitable cations (Heren et al., 2006; Hannan & Talukdar, 1992) and in zwitterionic forms (Amendola et al., 2005.; Lindley et al., 1977; Schaumann et al., 1975).

Intermolecular N—H···N hydrogen bonds link the molecules into chains along the c axis. Weak C—H···O interactions and a C9—H9···Cg π-interaction (C9···Cg = 3.603 (8) Å, C9—H9···Cg = 161°) further stabilize the structure (Cg is the centroid of the pyridinium ring).

For the preparation of the compound see Li (2007). Aryl sulfonamides with the amide N atom deprotonated have been reported previously, both as salts with suitable cations (Heren et al., 2006; Hannan & Talukdar, 1992) and in zwitterionic forms (Amendola et al., 2005; Lindley et al., 1977; Schaumann et al., 1975).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS (Sheldrick, 1997); program(s) used to refine structure: SHELXL (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure with the atom-numbering scheme and 30% probability displacement ellipsoids. Only the major component of the disordered benzene ring is shown.
[Figure 2] Fig. 2. Packing diagram with hydrogen bonds drawn as dashed lines.
N-(4-pyridinio)benzenesulfonamidate top
Crystal data top
C11H10N2O2SF(000) = 488
Mr = 234.27Dx = 1.498 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2352 reflections
a = 12.238 (6) Åθ = 3.3–26.5°
b = 7.459 (4) ŵ = 0.30 mm1
c = 12.124 (6) ÅT = 294 K
β = 110.231 (7)°Block, colourless
V = 1038.5 (8) Å30.20 × 0.16 × 0.12 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2139 independent reflections
Radiation source: fine-focus sealed tube1685 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 26.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1511
Tmin = 0.943, Tmax = 0.965k = 97
5733 measured reflectionsl = 1415
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0572P)2 + 0.6075P]
where P = (Fo2 + 2Fc2)/3
2139 reflections(Δ/σ)max = 0.001
180 parametersΔρmax = 0.40 e Å3
73 restraintsΔρmin = 0.32 e Å3
Crystal data top
C11H10N2O2SV = 1038.5 (8) Å3
Mr = 234.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.238 (6) ŵ = 0.30 mm1
b = 7.459 (4) ÅT = 294 K
c = 12.124 (6) Å0.20 × 0.16 × 0.12 mm
β = 110.231 (7)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2139 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1685 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.965Rint = 0.033
5733 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04473 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.40 e Å3
2139 reflectionsΔρmin = 0.32 e Å3
180 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*/UeqOcc. (<1)
S10.31544 (6)0.16315 (8)0.92018 (5)0.0360 (2)
O10.37860 (16)0.2910 (2)1.00505 (15)0.0434 (5)
O20.31798 (19)0.1853 (2)0.80497 (15)0.0525 (5)
N10.37226 (18)0.2772 (3)1.26144 (18)0.0359 (5)
N20.35106 (17)0.0376 (3)0.95349 (16)0.0335 (5)
C60.1697 (5)0.1746 (11)0.9082 (8)0.030 (3)0.59 (4)
C70.0798 (9)0.0865 (11)0.8225 (7)0.053 (2)0.59 (4)
H70.09530.02060.76440.063*0.59 (4)
C80.0333 (7)0.0967 (12)0.8235 (11)0.061 (3)0.59 (4)
H80.09340.03770.76620.074*0.59 (4)
C90.0565 (4)0.1951 (14)0.9103 (13)0.058 (2)0.59 (4)
H90.13210.20200.91100.069*0.59 (4)
C100.0334 (9)0.2833 (14)0.9960 (9)0.064 (2)0.59 (4)
H100.01790.34921.05410.077*0.59 (4)
C110.1465 (6)0.2731 (11)0.9950 (7)0.060 (3)0.59 (4)
H110.20660.33211.05230.072*0.59 (4)
C10.3656 (2)0.1014 (3)1.2553 (2)0.0374 (6)
H10.36500.03701.32070.045*
C20.3596 (2)0.0120 (3)1.15722 (19)0.0342 (5)
H20.35450.11251.15530.041*
C30.36113 (19)0.1056 (3)1.05825 (19)0.0289 (5)
C40.3726 (2)0.2902 (3)1.0710 (2)0.0353 (5)
H40.37770.35871.00890.042*
C50.3765 (2)0.3719 (3)1.1703 (2)0.0347 (5)
H50.38230.49611.17560.042*
C6'0.1758 (6)0.180 (2)0.9147 (12)0.057 (7)0.41 (4)
C7'0.1019 (13)0.090 (2)0.8167 (11)0.066 (4)0.41 (4)
H7'0.13200.03480.76460.079*0.41 (4)
C8'0.0169 (11)0.0831 (17)0.7966 (13)0.071 (4)0.41 (4)
H8'0.06640.02320.73100.086*0.41 (4)
C9'0.0619 (5)0.1657 (18)0.8744 (17)0.051 (3)0.41 (4)
H9'0.14140.16100.86100.062*0.41 (4)
C10'0.0120 (11)0.2552 (18)0.9724 (13)0.043 (3)0.41 (4)
H10'0.01810.31051.02450.051*0.41 (4)
C11'0.1309 (9)0.2622 (16)0.9925 (9)0.034 (3)0.41 (4)
H11'0.18030.32211.05810.041*0.41 (4)
H1A0.375 (3)0.329 (4)1.322 (3)0.057 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0568 (4)0.0243 (3)0.0332 (3)0.0001 (3)0.0234 (3)0.0018 (2)
O10.0572 (11)0.0299 (9)0.0479 (10)0.0077 (8)0.0244 (9)0.0067 (8)
O20.0938 (15)0.0371 (10)0.0399 (10)0.0064 (10)0.0401 (10)0.0112 (8)
N10.0484 (13)0.0345 (11)0.0257 (10)0.0010 (9)0.0141 (9)0.0041 (9)
N20.0531 (12)0.0253 (10)0.0277 (10)0.0026 (9)0.0210 (9)0.0008 (8)
C60.039 (3)0.020 (3)0.028 (3)0.002 (2)0.008 (2)0.003 (2)
C70.051 (4)0.057 (4)0.046 (3)0.002 (3)0.011 (3)0.012 (3)
C80.051 (3)0.076 (4)0.052 (4)0.006 (3)0.011 (3)0.016 (3)
C90.055 (3)0.062 (4)0.051 (4)0.001 (3)0.013 (3)0.009 (3)
C100.055 (4)0.060 (4)0.072 (4)0.003 (3)0.014 (3)0.010 (3)
C110.056 (4)0.061 (5)0.068 (5)0.001 (3)0.028 (3)0.002 (3)
C10.0530 (15)0.0360 (13)0.0255 (11)0.0030 (11)0.0165 (10)0.0040 (10)
C20.0491 (14)0.0263 (11)0.0291 (12)0.0019 (10)0.0161 (10)0.0033 (9)
C30.0338 (12)0.0280 (11)0.0269 (11)0.0011 (9)0.0130 (9)0.0004 (9)
C40.0520 (15)0.0292 (12)0.0282 (11)0.0031 (10)0.0184 (10)0.0021 (10)
C50.0454 (14)0.0276 (12)0.0327 (12)0.0033 (10)0.0156 (10)0.0009 (10)
C6'0.068 (8)0.048 (8)0.049 (8)0.001 (5)0.015 (4)0.003 (4)
C7'0.055 (5)0.071 (6)0.068 (6)0.006 (4)0.017 (4)0.001 (4)
C8'0.064 (5)0.080 (5)0.073 (5)0.002 (4)0.028 (4)0.007 (4)
C9'0.045 (4)0.058 (4)0.048 (5)0.001 (3)0.012 (3)0.006 (4)
C10'0.035 (4)0.042 (4)0.051 (5)0.003 (3)0.016 (3)0.012 (3)
C11'0.032 (4)0.032 (4)0.039 (4)0.003 (3)0.011 (3)0.010 (3)
Geometric parameters (Å, º) top
S1—O21.4174 (19)C1—C21.343 (3)
S1—O11.4195 (18)C1—H10.9300
S1—N21.573 (2)C2—C31.394 (3)
S1—C6'1.692 (5)C2—H20.9300
S1—C61.742 (4)C3—C41.387 (3)
N1—C11.315 (3)C4—C51.335 (3)
N1—C51.328 (3)C4—H40.9300
N1—H1A0.82 (3)C5—H50.9300
N2—C31.333 (3)C6'—C7'1.3900
C6—C71.3900C6'—C11'1.3900
C6—C111.3900C7'—C8'1.3900
C7—C81.3900C7'—H7'0.9300
C7—H70.9300C8'—C9'1.3900
C8—C91.3900C8'—H8'0.9300
C8—H80.9300C9'—C10'1.3900
C9—C101.3900C9'—H9'0.9300
C9—H90.9300C10'—C11'1.3900
C10—C111.3900C10'—H10'0.9300
C10—H100.9300C11'—H11'0.9300
C11—H110.9300
O2—S1—O1116.35 (12)N1—C1—H1119.0
O2—S1—N2105.41 (11)C2—C1—H1119.0
O1—S1—N2114.85 (11)C1—C2—C3120.0 (2)
O2—S1—C6'108.6 (5)C1—C2—H2120.0
O1—S1—C6'105.6 (4)C3—C2—H2120.0
N2—S1—C6'105.4 (5)N2—C3—C4117.2 (2)
O2—S1—C6106.4 (3)N2—C3—C2127.2 (2)
O1—S1—C6108.2 (3)C4—C3—C2115.6 (2)
N2—S1—C6104.7 (3)C5—C4—C3121.6 (2)
C1—N1—C5120.2 (2)C5—C4—H4119.2
C1—N1—H1A120 (2)C3—C4—H4119.2
C5—N1—H1A119 (2)N1—C5—C4120.5 (2)
C3—N2—S1122.23 (16)N1—C5—H5119.7
C7—C6—C11120.0C4—C5—H5119.7
C7—C6—S1124.2 (6)C7'—C6'—C11'120.0
C11—C6—S1115.7 (6)C7'—C6'—S1110.4 (9)
C6—C7—C8120.0C11'—C6'—S1129.6 (9)
C6—C7—H7120.0C8'—C7'—C6'120.0
C8—C7—H7120.0C8'—C7'—H7'120.0
C7—C8—C9120.0C6'—C7'—H7'120.0
C7—C8—H8120.0C7'—C8'—C9'120.0
C9—C8—H8120.0C7'—C8'—H8'120.0
C8—C9—C10120.0C9'—C8'—H8'120.0
C8—C9—H9120.0C10'—C9'—C8'120.0
C10—C9—H9120.0C10'—C9'—H9'120.0
C11—C10—C9120.0C8'—C9'—H9'120.0
C11—C10—H10120.0C9'—C10'—C11'120.0
C9—C10—H10120.0C9'—C10'—H10'120.0
C10—C11—C6120.0C11'—C10'—H10'120.0
C10—C11—H11120.0C10'—C11'—C6'120.0
C6—C11—H11120.0C10'—C11'—H11'120.0
N1—C1—C2122.0 (2)C6'—C11'—H11'120.0
O2—S1—N2—C3178.12 (19)S1—N2—C3—C210.0 (3)
O1—S1—N2—C348.7 (2)C1—C2—C3—N2177.0 (2)
C6'—S1—N2—C367.1 (5)C1—C2—C3—C41.9 (3)
C6—S1—N2—C369.8 (3)N2—C3—C4—C5176.1 (2)
O2—S1—C6—C745.2 (5)C2—C3—C4—C52.9 (4)
O1—S1—C6—C7170.9 (4)C1—N1—C5—C40.9 (4)
N2—S1—C6—C766.2 (5)C3—C4—C5—N11.6 (4)
C6'—S1—C6—C7173 (18)O2—S1—C6'—C7'41.3 (6)
O2—S1—C6—C11137.9 (4)O1—S1—C6'—C7'166.7 (5)
O1—S1—C6—C1112.1 (5)N2—S1—C6'—C7'71.3 (6)
N2—S1—C6—C11110.8 (4)C6—S1—C6'—C7'3 (17)
C6'—S1—C6—C114 (17)O2—S1—C6'—C11'140.4 (9)
C11—C6—C7—C80.0O1—S1—C6'—C11'14.9 (11)
S1—C6—C7—C8176.9 (6)N2—S1—C6'—C11'107.0 (9)
C6—C7—C8—C90.0C6—S1—C6'—C11'179 (18)
C7—C8—C9—C100.0C11'—C6'—C7'—C8'0.0
C8—C9—C10—C110.0S1—C6'—C7'—C8'178.5 (10)
C9—C10—C11—C60.0C6'—C7'—C8'—C9'0.0
C7—C6—C11—C100.0C7'—C8'—C9'—C10'0.0
S1—C6—C11—C10177.1 (6)C8'—C9'—C10'—C11'0.0
C5—N1—C1—C21.9 (4)C9'—C10'—C11'—C6'0.0
N1—C1—C2—C30.4 (4)C7'—C6'—C11'—C10'0.0
S1—N2—C3—C4168.89 (18)S1—C6'—C11'—C10'178.2 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.82 (3)1.99 (3)2.795 (3)170 (3)
C2—H2···O2ii0.932.523.168 (3)128
C5—H5···O1iii0.932.603.221 (3)125
C4—H4···O1iii0.932.613.232 (3)125
C5—H5···O2i0.932.433.075 (3)126
C9—H9···Cgiv0.932.713.603 (8)161
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y1, z; (iv) x, y, z+2.

Experimental details

Crystal data
Chemical formulaC11H10N2O2S
Mr234.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)12.238 (6), 7.459 (4), 12.124 (6)
β (°) 110.231 (7)
V3)1038.5 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.20 × 0.16 × 0.12
Data collection
DiffractometerBruker SMART 1K CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.943, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
5733, 2139, 1685
Rint0.033
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.124, 1.07
No. of reflections2139
No. of parameters180
No. of restraints73
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS (Sheldrick, 1997), SHELXL (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.82 (3)1.99 (3)2.795 (3)170 (3)
C2—H2···O2ii0.932.523.168 (3)127.5
C5—H5···O1iii0.932.603.221 (3)125.0
C4—H4···O1iii0.932.613.232 (3)124.5
C5—H5···O2i0.932.433.075 (3)126.1
C9—H9···Cgiv0.932.713.603 (8)161.1
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y1, z; (iv) x, y, z+2.
 

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