2-(Benzene­sulfonamido)pyridinium perchlorate

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.092
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl O4

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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).

Related literature

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

S2. 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.

S3. Refinement

The H atoms bound to C were positioned geometrically (C—H = 0.95 Å)and refined as riding with U_iso(H) = 1.2 U_eq(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.

Computing details

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: CrystalStructure (Rigaku/MSC, 2005).

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.

2-(Benzenesulfonamido)pyridinium perchlorate

Crystal data

C11H11N2O2S^+·ClO4^−	Z = 2
Mr = 334.73	F(000) = 344
Triclinic, P1	Dx = 1.683 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6594 (11) Å	Cell parameters from 2172 reflections
b = 7.5996 (15) Å	θ = 2.8–27.9°
c = 16.157 (3) Å	µ = 0.48 mm^−1
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) Å^3

Data collection

Rigaku Saturn CCD diffractometer	3051 independent reflections
Radiation source: rotating anode	2473 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.024
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.8°
ω and ϕ scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −7→9
Tmin = 0.911, Tmax = 0.963	l = −19→21
5339 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.3333P] where P = (Fo^2 + 2Fc^2)/3
3051 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.42 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	0.22811 (8)	0.24398 (6)	0.16564 (3)	0.01285 (12)
O1	0.3752 (3)	0.36817 (19)	0.13565 (8)	0.0188 (3)
O2	−0.0260 (2)	0.2927 (2)	0.14890 (8)	0.0195 (3)
N1	0.5339 (3)	0.3703 (2)	0.28668 (10)	0.0146 (3)
N2	0.2351 (3)	0.2162 (2)	0.26820 (9)	0.0142 (3)
C1	0.6774 (3)	0.4261 (3)	0.33434 (12)	0.0178 (4)
H1	0.7775	0.5030	0.3096	0.021*
C2	0.6782 (4)	0.3717 (3)	0.41768 (12)	0.0202 (4)
H2	0.7815	0.4072	0.4513	0.024*
C3	0.5244 (4)	0.2628 (3)	0.45284 (12)	0.0214 (4)
H3	0.5208	0.2255	0.5111	0.026*
C4	0.3781 (4)	0.2091 (3)	0.40365 (11)	0.0167 (4)
H4	0.2729	0.1353	0.4276	0.020*
C5	0.3861 (3)	0.2644 (3)	0.31822 (11)	0.0133 (4)
C6	0.3713 (3)	0.0251 (2)	0.13242 (11)	0.0122 (3)
C7	0.6069 (3)	−0.0679 (3)	0.15558 (11)	0.0167 (4)
H7	0.6874	−0.0172	0.1915	0.020*
C8	0.7216 (4)	−0.2369 (3)	0.12480 (11)	0.0185 (4)
H8	0.8823	−0.3031	0.1397	0.022*
C9	0.6018 (4)	−0.3089 (3)	0.07244 (12)	0.0179 (4)
H9	0.6818	−0.4241	0.0514	0.021*
C10	0.3665 (4)	−0.2150 (3)	0.05020 (12)	0.0193 (4)
H10	0.2865	−0.2659	0.0142	0.023*
C11	0.2487 (3)	−0.0472 (3)	0.08060 (11)	0.0157 (4)
H11	0.0869	0.0175	0.0663	0.019*
H1A	0.536 (4)	0.398 (3)	0.2358 (15)	0.022 (6)*
H2A	0.152 (4)	0.150 (3)	0.2905 (14)	0.019 (6)*
Cl1	0.06395 (8)	−0.20083 (6)	0.34300 (3)	0.01538 (12)
O3	0.0680 (3)	−0.3209 (2)	0.28027 (10)	0.0267 (3)
O4	−0.0763 (2)	−0.01507 (19)	0.31513 (9)	0.0209 (3)
O5	0.3112 (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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0155 (2)	0.0101 (2)	0.0123 (2)	−0.00192 (17)	−0.00278 (15)	−0.00055 (15)
O1	0.0296 (8)	0.0140 (7)	0.0144 (6)	−0.0102 (6)	−0.0003 (5)	0.0011 (5)
O2	0.0169 (7)	0.0168 (7)	0.0220 (7)	0.0020 (6)	−0.0067 (5)	−0.0018 (5)
N1	0.0152 (8)	0.0138 (8)	0.0152 (8)	−0.0041 (6)	−0.0009 (6)	−0.0024 (6)
N2	0.0156 (8)	0.0148 (8)	0.0139 (7)	−0.0075 (7)	0.0006 (6)	−0.0008 (6)
C1	0.0127 (9)	0.0145 (10)	0.0268 (10)	−0.0023 (7)	−0.0014 (7)	−0.0081 (8)
C2	0.0169 (9)	0.0203 (10)	0.0245 (10)	−0.0014 (8)	−0.0065 (7)	−0.0104 (8)
C3	0.0230 (10)	0.0221 (11)	0.0165 (9)	0.0006 (9)	−0.0036 (7)	−0.0052 (8)
C4	0.0190 (9)	0.0148 (10)	0.0152 (8)	−0.0032 (8)	0.0002 (7)	−0.0017 (7)
C5	0.0122 (8)	0.0097 (9)	0.0166 (8)	0.0003 (7)	−0.0012 (6)	−0.0029 (7)
C6	0.0149 (9)	0.0099 (9)	0.0119 (8)	−0.0035 (7)	−0.0007 (6)	−0.0004 (6)
C7	0.0171 (9)	0.0160 (10)	0.0173 (9)	−0.0032 (8)	−0.0056 (7)	−0.0020 (7)
C8	0.0179 (9)	0.0169 (10)	0.0170 (9)	0.0010 (8)	−0.0017 (7)	−0.0002 (7)
C9	0.0246 (10)	0.0108 (9)	0.0171 (9)	−0.0043 (8)	0.0017 (7)	−0.0009 (7)
C10	0.0241 (10)	0.0181 (10)	0.0187 (9)	−0.0088 (8)	−0.0029 (7)	−0.0049 (7)
C11	0.0152 (9)	0.0167 (10)	0.0159 (8)	−0.0051 (8)	−0.0032 (7)	−0.0005 (7)
Cl1	0.0175 (2)	0.0130 (2)	0.0159 (2)	−0.00511 (18)	−0.00268 (16)	0.00102 (16)
O3	0.0278 (8)	0.0179 (8)	0.0367 (8)	−0.0036 (7)	−0.0096 (6)	−0.0113 (6)
O4	0.0163 (7)	0.0104 (7)	0.0344 (8)	−0.0002 (6)	−0.0049 (6)	−0.0012 (6)
O5	0.0179 (7)	0.0235 (8)	0.0331 (8)	−0.0049 (6)	−0.0116 (6)	−0.0018 (6)
O6	0.0476 (11)	0.0515 (12)	0.0251 (8)	−0.0225 (10)	0.0047 (7)	0.0133 (8)

Geometric parameters (Å, º)

S1—O2	1.4296 (14)	C4—H4	0.9500
S1—O1	1.4352 (15)	C6—C11	1.391 (3)
S1—N2	1.6488 (16)	C6—C7	1.393 (3)
S1—C6	1.7540 (19)	C7—C8	1.391 (3)
N1—C5	1.338 (2)	C7—H7	0.9500
N1—C1	1.356 (2)	C8—C9	1.384 (3)
N1—H1A	0.82 (2)	C8—H8	0.9500
N2—C5	1.383 (2)	C9—C10	1.388 (3)
N2—H2A	0.81 (2)	C9—H9	0.9500
C1—C2	1.361 (3)	C10—C11	1.384 (3)
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.395 (3)	C11—H11	0.9500
C2—H2	0.9500	Cl1—O6	1.4315 (16)
C3—C4	1.376 (3)	Cl1—O3	1.4358 (15)
C3—H3	0.9500	Cl1—O5	1.4403 (15)
C4—C5	1.394 (2)	Cl1—O4	1.4594 (15)
O2—S1—O1	119.45 (9)	N2—C5—C4	119.97 (17)
O2—S1—N2	106.71 (9)	C11—C6—C7	121.88 (18)
O1—S1—N2	106.24 (9)	C11—C6—S1	118.51 (14)
O2—S1—C6	108.52 (9)	C7—C6—S1	119.56 (14)
O1—S1—C6	110.07 (9)	C8—C7—C6	118.41 (18)
N2—S1—C6	104.81 (9)	C8—C7—H7	120.8
C5—N1—C1	122.75 (17)	C6—C7—H7	120.8
C5—N1—H1A	116.0 (17)	C9—C8—C7	120.05 (18)
C1—N1—H1A	121.3 (17)	C9—C8—H8	120.0
C5—N2—S1	129.79 (14)	C7—C8—H8	120.0
C5—N2—H2A	116.6 (16)	C8—C9—C10	120.91 (19)
S1—N2—H2A	112.8 (16)	C8—C9—H9	119.5
N1—C1—C2	119.98 (19)	C10—C9—H9	119.5
N1—C1—H1	120.0	C11—C10—C9	119.91 (18)
C2—C1—H1	120.0	C11—C10—H10	120.0
C1—C2—C3	118.80 (18)	C9—C10—H10	120.0
C1—C2—H2	120.6	C10—C11—C6	118.83 (18)
C3—C2—H2	120.6	C10—C11—H11	120.6
C4—C3—C2	120.39 (18)	C6—C11—H11	120.6
C4—C3—H3	119.8	O6—Cl1—O3	109.89 (11)
C2—C3—H3	119.8	O6—Cl1—O5	110.65 (10)
C3—C4—C5	119.16 (19)	O3—Cl1—O5	110.12 (10)
C3—C4—H4	120.4	O6—Cl1—O4	109.52 (11)
C5—C4—H4	120.4	O3—Cl1—O4	108.72 (9)
N1—C5—N2	121.08 (16)	O5—Cl1—O4	107.89 (9)
N1—C5—C4	118.89 (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—C11	128.06 (15)
C6—S1—N2—C5	103.73 (18)	O2—S1—C6—C7	−168.22 (15)
C5—N1—C1—C2	1.1 (3)	O1—S1—C6—C7	59.37 (17)
N1—C1—C2—C3	−1.7 (3)	N2—S1—C6—C7	−54.50 (17)
C1—C2—C3—C4	1.1 (3)	C11—C6—C7—C8	0.7 (3)
C2—C3—C4—C5	0.2 (3)	S1—C6—C7—C8	−176.66 (14)
C1—N1—C5—N2	177.48 (17)	C6—C7—C8—C9	0.0 (3)
C1—N1—C5—C4	0.2 (3)	C7—C8—C9—C10	−0.3 (3)
S1—N2—C5—N1	9.9 (3)	C8—C9—C10—C11	−0.1 (3)
S1—N2—C5—C4	−172.85 (14)	C9—C10—C11—C6	0.8 (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—C10	176.28 (14)
O2—S1—C6—C11	14.34 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.82 (2)	2.01 (2)	2.694 (2)	141 (2)
N2—H2A···O4	0.81 (2)	2.02 (2)	2.808 (2)	165 (2)
C1—H1···O3^i	0.95	2.37	3.301 (3)	166
C3—H3···O5^ii	0.95	2.44	3.303 (3)	151
C7—H7···O4^iii	0.95	2.53	3.417 (2)	156
C8—H8···O3^iii	0.95	2.58	3.251 (3)	128

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