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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1430.
Published online 2009 May 29. doi:  10.1107/S1600536809019205
PMCID: PMC2969619

2-(Benzene­sulfonamido)pyridinium perchlorate

Abstract

In the title compound, C11H11N2O2S+·ClO4 , the dihedral angle between the benzene and pyridinium rings is 87.33 (10)°. An intra­molecular N—H(...)O inter­action, with an S=O-bonded O atom as receptor, occurs in the cation. In the crystal structure, ion pairs occur, being linked by strong N—H(...)O hydrogen bonds. The perchlorate anion plays a further role in the mol­ecular packing by accepting several weak C—H(...)O inter­actions.

Related literature

For the synthesis, see: Li, Yang et al. (2008 [triangle]). For a related structure containing the same cation, see: Li & Li (2009 [triangle]). For related structures, see: Li et al. (2008a [triangle],b [triangle]). For applications of pyridinium salts, see: Li et al. (2007 [triangle]); Li, Fan et al. (2008 [triangle]); Miyashita et al. (1977 [triangle]); Ganeshpure et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1430-scheme1.jpg

Experimental

Crystal data

  • C11H11N2O2S+·ClO4
  • M r = 334.73
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1430-efi1.jpg
  • a = 5.6594 (11) Å
  • b = 7.5996 (15) Å
  • c = 16.157 (3) Å
  • α = 83.21 (3)°
  • β = 83.70 (3)°
  • γ = 73.84 (3)°
  • V = 660.6 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.48 mm−1
  • T = 113 K
  • 0.20 × 0.10 × 0.08 mm

Data collection

  • Rigaku Saturn CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.911, T max = 0.963
  • 5339 measured reflections
  • 3051 independent reflections
  • 2473 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.092
  • S = 1.07
  • 3051 reflections
  • 198 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019205/hb2972sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019205/hb2972Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Organic pyridinium salts have been used as not only supramolecular guests (Li et al., 2007; Li, Fan, Fan et al., 2008), but also catalysts and/or media for esterification (Ganeshpure et al.2007; Miyashita et al. 1977). To seek a new pyridinium catalyst for biodiesel transformation, the title compound, (I), was synthesized and further determined by X-ray diffraction.

The title compound, (I), consists of a pyridinium cation and a perchlorate anion (Fig. 1). In the cation, the distance [1.383 (2) Å] between the pyridinum C atom and its connected amino N atom is slightly longer than the nitrate [1.378 (2) Å] (Li et al. 2009), also showing some conjugation of amino group with pyridinium ring. The benzene ring constructs an angle of 87.33 (10)° with the pyridinium ring, similar to the nitrate [87.59 (8)°]. The cation structure is stabilized by an intramolecular N—H···O hydrogen bond (Table 1), with S=O oxygen as H-bonding receptor, different from by C—H···O interaction in the nitrate.

Like the nitrate, in the crystal structure, a strong N—H···O hydrogen bond link the cation and anion (Table 1). The anion ClO4 plays a great important role in the molecular packing via weak C—H···O interactions (Table 1).

Experimental

The title compound was prepared according to the reported literature (Li, Yang et al. 2008). Colourless needles of (I) were obtained by evaporation of a perchloric acid solution of the sulfonamide.

Refinement

The H atoms bound to C were positioned geometrically (C—H = 0.95 Å)and refined as riding with Uiso(H) = 1.2 Ueq(C)]. The N—H hydrogen atoms were refined with their isotropic displacement parameters, and N—H distances are restrained to 0.82 (2) and 0.81 (2) Å, respectively.

Figures

Fig. 1.
View of the molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level and H atoms shown as small spheres of arbitrary radius. Dashed lines indicate hydrogen bonds.

Crystal data

C11H11N2O2S+·ClO4Z = 2
Mr = 334.73F(000) = 344
Triclinic, P1Dx = 1.683 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.6594 (11) ÅCell parameters from 2172 reflections
b = 7.5996 (15) Åθ = 2.8–27.9°
c = 16.157 (3) ŵ = 0.48 mm1
α = 83.21 (3)°T = 113 K
β = 83.70 (3)°Needle, colourless
γ = 73.84 (3)°0.20 × 0.10 × 0.08 mm
V = 660.6 (2) Å3

Data collection

Rigaku Saturn CCD diffractometer3051 independent reflections
Radiation source: rotating anode2473 reflections with I > 2σ(I)
confocalRint = 0.024
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.8°
ω and [var phi] scansh = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −7→9
Tmin = 0.911, Tmax = 0.963l = −19→21
5339 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0383P)2 + 0.3333P] where P = (Fo2 + 2Fc2)/3
3051 reflections(Δ/σ)max = 0.001
198 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = −0.42 e Å3

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 (Å2)

xyzUiso*/Ueq
S10.22811 (8)0.24398 (6)0.16564 (3)0.01285 (12)
O10.3752 (3)0.36817 (19)0.13565 (8)0.0188 (3)
O2−0.0260 (2)0.2927 (2)0.14890 (8)0.0195 (3)
N10.5339 (3)0.3703 (2)0.28668 (10)0.0146 (3)
N20.2351 (3)0.2162 (2)0.26820 (9)0.0142 (3)
C10.6774 (3)0.4261 (3)0.33434 (12)0.0178 (4)
H10.77750.50300.30960.021*
C20.6782 (4)0.3717 (3)0.41768 (12)0.0202 (4)
H20.78150.40720.45130.024*
C30.5244 (4)0.2628 (3)0.45284 (12)0.0214 (4)
H30.52080.22550.51110.026*
C40.3781 (4)0.2091 (3)0.40365 (11)0.0167 (4)
H40.27290.13530.42760.020*
C50.3861 (3)0.2644 (3)0.31822 (11)0.0133 (4)
C60.3713 (3)0.0251 (2)0.13242 (11)0.0122 (3)
C70.6069 (3)−0.0679 (3)0.15558 (11)0.0167 (4)
H70.6874−0.01720.19150.020*
C80.7216 (4)−0.2369 (3)0.12480 (11)0.0185 (4)
H80.8823−0.30310.13970.022*
C90.6018 (4)−0.3089 (3)0.07244 (12)0.0179 (4)
H90.6818−0.42410.05140.021*
C100.3665 (4)−0.2150 (3)0.05020 (12)0.0193 (4)
H100.2865−0.26590.01420.023*
C110.2487 (3)−0.0472 (3)0.08060 (11)0.0157 (4)
H110.08690.01750.06630.019*
H1A0.536 (4)0.398 (3)0.2358 (15)0.022 (6)*
H2A0.152 (4)0.150 (3)0.2905 (14)0.019 (6)*
Cl10.06395 (8)−0.20083 (6)0.34300 (3)0.01538 (12)
O30.0680 (3)−0.3209 (2)0.28027 (10)0.0267 (3)
O4−0.0763 (2)−0.01507 (19)0.31513 (9)0.0209 (3)
O50.3112 (3)−0.1954 (2)0.35352 (9)0.0243 (3)
O6−0.0508 (3)−0.2619 (3)0.42029 (10)0.0415 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0155 (2)0.0101 (2)0.0123 (2)−0.00192 (17)−0.00278 (15)−0.00055 (15)
O10.0296 (8)0.0140 (7)0.0144 (6)−0.0102 (6)−0.0003 (5)0.0011 (5)
O20.0169 (7)0.0168 (7)0.0220 (7)0.0020 (6)−0.0067 (5)−0.0018 (5)
N10.0152 (8)0.0138 (8)0.0152 (8)−0.0041 (6)−0.0009 (6)−0.0024 (6)
N20.0156 (8)0.0148 (8)0.0139 (7)−0.0075 (7)0.0006 (6)−0.0008 (6)
C10.0127 (9)0.0145 (10)0.0268 (10)−0.0023 (7)−0.0014 (7)−0.0081 (8)
C20.0169 (9)0.0203 (10)0.0245 (10)−0.0014 (8)−0.0065 (7)−0.0104 (8)
C30.0230 (10)0.0221 (11)0.0165 (9)0.0006 (9)−0.0036 (7)−0.0052 (8)
C40.0190 (9)0.0148 (10)0.0152 (8)−0.0032 (8)0.0002 (7)−0.0017 (7)
C50.0122 (8)0.0097 (9)0.0166 (8)0.0003 (7)−0.0012 (6)−0.0029 (7)
C60.0149 (9)0.0099 (9)0.0119 (8)−0.0035 (7)−0.0007 (6)−0.0004 (6)
C70.0171 (9)0.0160 (10)0.0173 (9)−0.0032 (8)−0.0056 (7)−0.0020 (7)
C80.0179 (9)0.0169 (10)0.0170 (9)0.0010 (8)−0.0017 (7)−0.0002 (7)
C90.0246 (10)0.0108 (9)0.0171 (9)−0.0043 (8)0.0017 (7)−0.0009 (7)
C100.0241 (10)0.0181 (10)0.0187 (9)−0.0088 (8)−0.0029 (7)−0.0049 (7)
C110.0152 (9)0.0167 (10)0.0159 (8)−0.0051 (8)−0.0032 (7)−0.0005 (7)
Cl10.0175 (2)0.0130 (2)0.0159 (2)−0.00511 (18)−0.00268 (16)0.00102 (16)
O30.0278 (8)0.0179 (8)0.0367 (8)−0.0036 (7)−0.0096 (6)−0.0113 (6)
O40.0163 (7)0.0104 (7)0.0344 (8)−0.0002 (6)−0.0049 (6)−0.0012 (6)
O50.0179 (7)0.0235 (8)0.0331 (8)−0.0049 (6)−0.0116 (6)−0.0018 (6)
O60.0476 (11)0.0515 (12)0.0251 (8)−0.0225 (10)0.0047 (7)0.0133 (8)

Geometric parameters (Å, °)

S1—O21.4296 (14)C4—H40.9500
S1—O11.4352 (15)C6—C111.391 (3)
S1—N21.6488 (16)C6—C71.393 (3)
S1—C61.7540 (19)C7—C81.391 (3)
N1—C51.338 (2)C7—H70.9500
N1—C11.356 (2)C8—C91.384 (3)
N1—H1A0.82 (2)C8—H80.9500
N2—C51.383 (2)C9—C101.388 (3)
N2—H2A0.81 (2)C9—H90.9500
C1—C21.361 (3)C10—C111.384 (3)
C1—H10.9500C10—H100.9500
C2—C31.395 (3)C11—H110.9500
C2—H20.9500Cl1—O61.4315 (16)
C3—C41.376 (3)Cl1—O31.4358 (15)
C3—H30.9500Cl1—O51.4403 (15)
C4—C51.394 (2)Cl1—O41.4594 (15)
O2—S1—O1119.45 (9)N2—C5—C4119.97 (17)
O2—S1—N2106.71 (9)C11—C6—C7121.88 (18)
O1—S1—N2106.24 (9)C11—C6—S1118.51 (14)
O2—S1—C6108.52 (9)C7—C6—S1119.56 (14)
O1—S1—C6110.07 (9)C8—C7—C6118.41 (18)
N2—S1—C6104.81 (9)C8—C7—H7120.8
C5—N1—C1122.75 (17)C6—C7—H7120.8
C5—N1—H1A116.0 (17)C9—C8—C7120.05 (18)
C1—N1—H1A121.3 (17)C9—C8—H8120.0
C5—N2—S1129.79 (14)C7—C8—H8120.0
C5—N2—H2A116.6 (16)C8—C9—C10120.91 (19)
S1—N2—H2A112.8 (16)C8—C9—H9119.5
N1—C1—C2119.98 (19)C10—C9—H9119.5
N1—C1—H1120.0C11—C10—C9119.91 (18)
C2—C1—H1120.0C11—C10—H10120.0
C1—C2—C3118.80 (18)C9—C10—H10120.0
C1—C2—H2120.6C10—C11—C6118.83 (18)
C3—C2—H2120.6C10—C11—H11120.6
C4—C3—C2120.39 (18)C6—C11—H11120.6
C4—C3—H3119.8O6—Cl1—O3109.89 (11)
C2—C3—H3119.8O6—Cl1—O5110.65 (10)
C3—C4—C5119.16 (19)O3—Cl1—O5110.12 (10)
C3—C4—H4120.4O6—Cl1—O4109.52 (11)
C5—C4—H4120.4O3—Cl1—O4108.72 (9)
N1—C5—N2121.08 (16)O5—Cl1—O4107.89 (9)
N1—C5—C4118.89 (17)
O2—S1—N2—C5−141.28 (17)O1—S1—C6—C11−118.07 (15)
O1—S1—N2—C5−12.81 (19)N2—S1—C6—C11128.06 (15)
C6—S1—N2—C5103.73 (18)O2—S1—C6—C7−168.22 (15)
C5—N1—C1—C21.1 (3)O1—S1—C6—C759.37 (17)
N1—C1—C2—C3−1.7 (3)N2—S1—C6—C7−54.50 (17)
C1—C2—C3—C41.1 (3)C11—C6—C7—C80.7 (3)
C2—C3—C4—C50.2 (3)S1—C6—C7—C8−176.66 (14)
C1—N1—C5—N2177.48 (17)C6—C7—C8—C90.0 (3)
C1—N1—C5—C40.2 (3)C7—C8—C9—C10−0.3 (3)
S1—N2—C5—N19.9 (3)C8—C9—C10—C11−0.1 (3)
S1—N2—C5—C4−172.85 (14)C9—C10—C11—C60.8 (3)
C3—C4—C5—N1−0.8 (3)C7—C6—C11—C10−1.1 (3)
C3—C4—C5—N2−178.17 (17)S1—C6—C11—C10176.28 (14)
O2—S1—C6—C1114.34 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.82 (2)2.01 (2)2.694 (2)141 (2)
N2—H2A···O40.81 (2)2.02 (2)2.808 (2)165 (2)
C1—H1···O3i0.952.373.301 (3)166
C3—H3···O5ii0.952.443.303 (3)151
C7—H7···O4iii0.952.533.417 (2)156
C8—H8···O3iii0.952.583.251 (3)128

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2972).

References

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  • Li, J.-S., Fan, M.-L., Li, W.-S. & Liu, W.-D. (2008a). Acta Cryst. E64, o1459. [PMC free article] [PubMed]
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  • Li, J.-S. & Li, X. (2009). Acta Cryst. E65, o1228. [PMC free article] [PubMed]
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  • Miyashita, M., Yoshikoshi, A. & Grieco, P. A. (1977). J. Org. Chem.42, 3772–3774.
  • Rigaku/MSC (2005). CrystalClear and CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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