2-(Ethyl­sulfin­yl)imidazo[1,2-a]pyridine-3-sulfonamide

Gong, Y.; Ma, H.; Li, J.

doi:10.1107/S1600536812013992

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1342

doi:10.1107/S1600536812013992

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2-(Ethylsulfinyl)imidazo[1,2-a]pyridine-3-sulfonamide

Yaling Gong,^a Haixia Ma ^b and Jing Li ^b ^*

^aInstitute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: lxf7777@sxu.edu.cn

(Received 23 March 2012; accepted 31 March 2012; online 13 April 2012)

The supramolecular structure of the title compound, C₉H₁₁N₃O₃S₂, is defined by two intermolecular hydrogen bonds. Pairs of N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers and N—H⋯O hydrogen bonds link the dimers into a tubular chain structure running parallel to the a axis.

Related literature

The title compound is a derivative of sulfosulfuron [systematic name: 1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-ylsulfonyl)urea], a high-performance sulfonylurea herbicide used to control several grassy weeds in wheat, see: Maxwell et al. (2005 ).

Experimental

Crystal data

C₉H₁₁N₃O₃S₂
M_r = 273.33
Triclinic, $[P \overline 1]$
a = 8.3761 (9) Å
b = 8.5438 (9) Å
c = 9.1083 (10) Å
α = 88.832 (2)°
β = 75.376 (1)°
γ = 65.170 (1)°
V = 569.67 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.873, T_max = 0.912
6015 measured reflections
2001 independent reflections
1793 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.068
S = 1.06
2001 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱ	0.83	2.07	2.888 (2)	171
N3—H3B⋯N1ⁱⁱ	0.82	2.24	3.026 (2)	161
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013992/go2050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013992/go2050Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013992/go2050Isup3.cml

checkCIF report

Comment top

Sulfosulfuron,1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo [1,2-a]pyridin-3-ylsulfonyl)urea, is high-performance sulfonylurea herbicide, and can effectively control several grassy weeds in wheat (Maxwell, et al.2005). In the course of exploring its derivatives, we obtained the compound C₉H₁₁N₃O₃S₂, Figure, 1.

The supramolecular structure is defined by the N3—H3B···N1 hydrogen bond which links the molecules into centrosymmetric dimers lying across the centre-of-symmetry at (0.5,0.5,0.5) and the N3–H3B···O1 hydrogen bond which links the dimers into tubular chains which run parallel to the a-axis, Table 1 and Figure 2.

Related literature top

Experimental top

m-chloroperoxybenzoic acid (1.88 g, 8.22 mmol) in 100 ml CH₂Cl₂ was added dropwise to a solution of 2-ethylthioimidazo[1,2-a]pyridine-3-sulfonamide (2.2 g, 8.22 mmol) in 200 ml CH₂Cl₂ in an ice water bath. The suspension was stirred at 0–5°C for more than 3 h, and filtered. After removing the solvent, and the crude product was recrystallized in MeOH to give white crystalline product (1.24 g, 55% yield)). The melting point of the product was 203–205°C.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of (1) with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of compound, showing the tubular chain structure which runs parallel to the a-axis. Hydrogen atoms not involved in the motifs are not included.

2-(Ethylsulfinyl)imidazo[1,2-a]pyridine-3-sulfonamide top

Crystal data top

C₉H₁₁N₃O₃S₂	Z = 2
M_r = 273.33	F(000) = 284
Triclinic, P1	D_x = 1.593 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3761 (9) Å	Cell parameters from 3732 reflections
b = 8.5438 (9) Å	θ = 2.6–30.8°
c = 9.1083 (10) Å	µ = 0.47 mm⁻¹
α = 88.832 (2)°	T = 296 K
β = 75.376 (1)°	Block, colourless
γ = 65.170 (1)°	0.30 × 0.20 × 0.20 mm
V = 569.67 (11) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	2001 independent reflections
Radiation source: fine-focus sealed tube	1793 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.873, T_max = 0.912	k = −10→10
6015 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0298P)² + 0.3093P] where P = (F_o² + 2F_c²)/3
2001 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₉H₁₁N₃O₃S₂	γ = 65.170 (1)°
M_r = 273.33	V = 569.67 (11) Å³
Triclinic, P1	Z = 2
a = 8.3761 (9) Å	Mo Kα radiation
b = 8.5438 (9) Å	µ = 0.47 mm⁻¹
c = 9.1083 (10) Å	T = 296 K
α = 88.832 (2)°	0.30 × 0.20 × 0.20 mm
β = 75.376 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2001 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1793 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.912	R_int = 0.017
6015 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.06	Δρ_max = 0.29 e Å⁻³
2001 reflections	Δρ_min = −0.30 e Å⁻³
155 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
S1	0.85430 (6)	0.27576 (6)	0.34364 (5)	0.02656 (13)
S2	0.45246 (6)	0.23968 (6)	0.29742 (5)	0.02731 (13)
O1	0.96772 (17)	0.30562 (18)	0.43380 (16)	0.0388 (3)
O2	0.59485 (18)	0.2537 (2)	0.18084 (15)	0.0431 (4)
O3	0.4246 (2)	0.08604 (17)	0.29993 (17)	0.0435 (4)
N1	0.64659 (19)	0.30840 (18)	0.63394 (16)	0.0267 (3)
N2	0.39592 (19)	0.28563 (17)	0.61067 (15)	0.0235 (3)
N3	0.2631 (2)	0.39803 (19)	0.29715 (17)	0.0303 (3)
H3A	0.1735	0.3815	0.3436	0.036*
H3B	0.2634	0.4922	0.3130	0.036*
C1	0.4861 (2)	0.3112 (2)	0.7099 (2)	0.0255 (4)
C2	0.4020 (3)	0.3362 (2)	0.8674 (2)	0.0335 (4)
H2B	0.4593	0.3540	0.9364	0.040*
C3	0.2362 (3)	0.3342 (3)	0.9171 (2)	0.0373 (4)
H3D	0.1791	0.3512	1.0210	0.045*
C4	0.1494 (3)	0.3065 (3)	0.8128 (2)	0.0355 (4)
H4A	0.0354	0.3060	0.8490	0.043*
C5	0.2291 (2)	0.2807 (2)	0.6613 (2)	0.0292 (4)
H5A	0.1726	0.2601	0.5930	0.035*
C6	0.5075 (2)	0.2671 (2)	0.46454 (19)	0.0240 (4)
C7	0.6586 (2)	0.2806 (2)	0.48511 (19)	0.0241 (4)
C8	0.9606 (2)	0.0468 (2)	0.2813 (2)	0.0322 (4)
H8A	0.9966	−0.0194	0.3646	0.039*
H8B	0.8738	0.0151	0.2517	0.039*
C9	1.1260 (3)	0.0039 (3)	0.1481 (2)	0.0439 (5)
H9A	1.1791	−0.1173	0.1144	0.066*
H9B	1.2138	0.0309	0.1787	0.066*
H9C	1.0904	0.0707	0.0663	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0231 (2)	0.0276 (2)	0.0309 (2)	−0.01298 (18)	−0.00662 (17)	0.00240 (17)
S2	0.0250 (2)	0.0318 (2)	0.0257 (2)	−0.01139 (19)	−0.00860 (17)	−0.00373 (17)
O1	0.0293 (7)	0.0504 (8)	0.0445 (8)	−0.0243 (6)	−0.0095 (6)	−0.0045 (6)
O2	0.0311 (7)	0.0691 (10)	0.0259 (7)	−0.0202 (7)	−0.0042 (6)	−0.0020 (6)
O3	0.0475 (8)	0.0297 (7)	0.0593 (9)	−0.0152 (6)	−0.0261 (7)	−0.0046 (6)
N1	0.0272 (8)	0.0276 (8)	0.0286 (8)	−0.0128 (6)	−0.0113 (6)	0.0025 (6)
N2	0.0234 (7)	0.0236 (7)	0.0245 (7)	−0.0107 (6)	−0.0071 (6)	0.0021 (6)
N3	0.0278 (8)	0.0316 (8)	0.0358 (9)	−0.0140 (7)	−0.0134 (7)	0.0019 (6)
C1	0.0273 (9)	0.0232 (8)	0.0282 (9)	−0.0106 (7)	−0.0118 (7)	0.0031 (7)
C2	0.0408 (11)	0.0353 (10)	0.0262 (9)	−0.0162 (9)	−0.0121 (8)	0.0028 (8)
C3	0.0425 (11)	0.0388 (11)	0.0262 (10)	−0.0176 (9)	−0.0019 (8)	0.0022 (8)
C4	0.0298 (10)	0.0388 (11)	0.0366 (11)	−0.0174 (8)	−0.0023 (8)	0.0050 (8)
C5	0.0259 (9)	0.0302 (9)	0.0343 (10)	−0.0145 (8)	−0.0087 (7)	0.0044 (7)
C6	0.0233 (8)	0.0267 (9)	0.0234 (9)	−0.0116 (7)	−0.0066 (7)	0.0012 (7)
C7	0.0231 (8)	0.0228 (8)	0.0269 (9)	−0.0095 (7)	−0.0082 (7)	0.0016 (7)
C8	0.0314 (10)	0.0276 (9)	0.0356 (10)	−0.0109 (8)	−0.0084 (8)	0.0000 (8)
C9	0.0352 (11)	0.0488 (13)	0.0414 (12)	−0.0154 (10)	−0.0033 (9)	−0.0085 (9)

Geometric parameters (Å, º) top

S1—O1	1.4993 (13)	C2—C3	1.355 (3)
S1—C7	1.7965 (17)	C2—H2B	0.9300
S1—C8	1.8082 (18)	C3—C4	1.410 (3)
S2—O3	1.4255 (14)	C3—H3D	0.9300
S2—O2	1.4281 (14)	C4—C5	1.349 (3)
S2—N3	1.5954 (15)	C4—H4A	0.9300
S2—C6	1.7448 (17)	C5—H5A	0.9300
N1—C1	1.338 (2)	C6—C7	1.376 (2)
N1—C7	1.352 (2)	C8—C9	1.506 (3)
N2—C5	1.375 (2)	C8—H8A	0.9700
N2—C1	1.388 (2)	C8—H8B	0.9700
N2—C6	1.388 (2)	C9—H9A	0.9600
N3—H3A	0.83	C9—H9B	0.9600
N3—H3B	0.82	C9—H9C	0.9600
C1—C2	1.406 (2)

O1—S1—C7	104.42 (8)	C5—C4—C3	121.08 (17)
O1—S1—C8	106.98 (8)	C5—C4—H4A	119.5
C7—S1—C8	97.74 (8)	C3—C4—H4A	119.5
O3—S2—O2	120.44 (9)	C4—C5—N2	118.26 (17)
O3—S2—N3	107.20 (8)	C4—C5—H5A	120.9
O2—S2—N3	108.79 (9)	N2—C5—H5A	120.9
O3—S2—C6	108.41 (8)	C7—C6—N2	104.92 (14)
O2—S2—C6	103.09 (8)	C7—C6—S2	130.38 (13)
N3—S2—C6	108.43 (8)	N2—C6—S2	124.68 (12)
C1—N1—C7	105.05 (14)	N1—C7—C6	112.36 (15)
C5—N2—C1	122.26 (14)	N1—C7—S1	118.80 (12)
C5—N2—C6	131.29 (15)	C6—C7—S1	128.78 (13)
C1—N2—C6	106.45 (13)	C9—C8—S1	110.33 (14)
S2—N3—H3A	112.6	C9—C8—H8A	109.6
S2—N3—H3B	112.2	S1—C8—H8A	109.6
H3A—N3—H3B	118.8	C9—C8—H8B	109.6
N1—C1—N2	111.22 (14)	S1—C8—H8B	109.6
N1—C1—C2	130.02 (16)	H8A—C8—H8B	108.1
N2—C1—C2	118.76 (15)	C8—C9—H9A	109.5
C3—C2—C1	118.91 (17)	C8—C9—H9B	109.5
C3—C2—H2B	120.5	H9A—C9—H9B	109.5
C1—C2—H2B	120.5	C8—C9—H9C	109.5
C2—C3—C4	120.71 (17)	H9A—C9—H9C	109.5
C2—C3—H3D	119.6	H9B—C9—H9C	109.5
C4—C3—H3D	119.6

C7—N1—C1—N2	−0.09 (18)	O2—S2—C6—C7	−6.34 (19)
C7—N1—C1—C2	−179.63 (18)	N3—S2—C6—C7	−121.56 (17)
C5—N2—C1—N1	179.11 (15)	O3—S2—C6—N2	−59.80 (16)
C6—N2—C1—N1	−0.39 (18)	O2—S2—C6—N2	171.48 (14)
C5—N2—C1—C2	−1.3 (2)	N3—S2—C6—N2	56.26 (16)
C6—N2—C1—C2	179.21 (15)	C1—N1—C7—C6	0.56 (19)
N1—C1—C2—C3	179.69 (18)	C1—N1—C7—S1	177.83 (12)
N2—C1—C2—C3	0.2 (3)	N2—C6—C7—N1	−0.79 (19)
C1—C2—C3—C4	0.3 (3)	S2—C6—C7—N1	177.35 (13)
C2—C3—C4—C5	0.3 (3)	N2—C6—C7—S1	−177.72 (12)
C3—C4—C5—N2	−1.3 (3)	S2—C6—C7—S1	0.4 (3)
C1—N2—C5—C4	1.9 (3)	O1—S1—C7—N1	0.33 (15)
C6—N2—C5—C4	−178.78 (17)	C8—S1—C7—N1	110.16 (14)
C5—N2—C6—C7	−178.75 (16)	O1—S1—C7—C6	177.09 (16)
C1—N2—C6—C7	0.69 (17)	C8—S1—C7—C6	−73.08 (17)
C5—N2—C6—S2	3.0 (3)	O1—S1—C8—C9	−77.41 (15)
C1—N2—C6—S2	−177.60 (12)	C7—S1—C8—C9	174.87 (14)
O3—S2—C6—C7	122.38 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.83	2.07	2.888 (2)	171
N3—H3B···N1ⁱⁱ	0.82	2.24	3.026 (2)	161

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₃S₂
M_r	273.33
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.3761 (9), 8.5438 (9), 9.1083 (10)
α, β, γ (°)	88.832 (2), 75.376 (1), 65.170 (1)
V (Å³)	569.67 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.873, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	6015, 2001, 1793
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 1.06
No. of reflections	2001
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.83	2.07	2.888 (2)	171
N3—H3B···N1ⁱⁱ	0.82	2.24	3.026 (2)	161

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

Acknowledgements

The authors are grateful to the National Science Foundation (YG, No. 81001364) for support of this work.

References

Maxwell, B. D., Boyé, O. G. & Ohta, K. (2005). J. Label. Compd Radiopharm., 48, 397–406. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar