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Acta Cryst. (2007). E63, o4057    [ doi:10.1107/S1600536807044054 ]

4-(2-Chlorobenzylidenehydrazinocarbonyl)-2-methyl-2H-pyrazole-3-sulfonamide

J.-J. Wei, W.-D. Wang, W.-Y. Li and H.-W. He

Abstract top

In the title compound, C12H12ClN5O3S, the pyrazole ring and the benzene ring are approximately coplanar. The mean plane of the pyrazole ring makes a dihedral angle of 12.82 (13)° with the mean plane of the benzene ring. The crystal packing is stabilized by intramolecular N-H...O and intermolecular N-H...O and N-H...N hydrogen bonds.

Comment top

Pyrazole derivatives are important compounds with versatile industrial and medical applications (Liang & He, 2005; Wang et al., 2004). We report here the molecular structure of (I). In the title compound, all bond lengths and angles are within normal ranges (Allen et al., 1987) and the molecules are stabilized by intra and intermolecular hydrogen bonds (Table 1). Short intermolecular distances between the centroids, Cg1, of two adjacent pyrazole ring suggest π— π stacking interactions [Cg1···Cg1iii = 3.4664 (13) Å, iii = 2 − x, 2 − y, −z].

Related literature top

For biological and pharmaceutical activity of pyrazoles, see: Liang & He (2005); Wang et al. (2004). For the preparation of derivatives of pyrazoles, see: Zou et al. (2005). For reference structural data, see: Allen et al. (1987).

Experimental top

In a 50 mL flask provided with magnetic stirrer were placed 4-hydrazinocarbonyl-2-methyl-2H-pyrazole-3-sulfonic acid amide (1.10 g, 5 mmol), 2-chloro-benzaldehyde (0.84 g, 6 mmol) and anhydrous ethanol (10 mL). The reaction mixture was heated to reflux for 3 h, allowed to cool to room temperature. The white solid was filtered and recrystallized from a dimethylformamide-ethanol mixture to give the title compound (yield 94%). Colourless crystals of (I) suitable for X-ray structure analysis were grown from the mixture of tetrahydrofuran and petroleum ether (v/v, 1:6).

Refinement top

The H atom bound to N3 was found in a difference Fourier map and its coordinates were refined with Uiso(H) = 1.2Ueq(N). All other H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top
[Figure 1] Fig. 1. The structure of (I). showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of (I) with hydrogen bonds drawn as dashed lines.
4-(2-Chlorobenzylidenehydrazinocarbonyl)-2-methyl-2H-pyrazole-3-sulfonic acid amide top
Crystal data top
C12H12ClN5O3SZ = 2
Mr = 341.78F000 = 352
Triclinic, P1Dx = 1.545 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.4272 (6) ÅCell parameters from 2721 reflections
b = 9.0905 (7) Åθ = 2.2–28.3º
c = 10.4381 (7) ŵ = 0.42 mm−1
α = 89.525 (1)ºT = 292 (2) K
β = 66.852 (1)ºBlock, colorless
γ = 87.722 (1)º0.10 × 0.10 × 0.08 mm
V = 734.66 (9) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2421 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.051
Monochromator: graphiteθmax = 26.0º
T = 297(2) Kθmin = 2.1º
φ and ω scansh = −10→9
Absorption correction: Nonek = −11→11
4684 measured reflectionsl = −12→8
2843 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.136  w = 1/[σ2(Fo2) + (0.0737P)2 + 0.1888P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.011
2843 reflectionsΔρmax = 0.32 e Å−3
209 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C12H12ClN5O3Sγ = 87.722 (1)º
Mr = 341.78V = 734.66 (9) Å3
Triclinic, P1Z = 2
a = 8.4272 (6) ÅMo Kα
b = 9.0905 (7) ŵ = 0.42 mm−1
c = 10.4381 (7) ÅT = 292 (2) K
α = 89.525 (1)º0.10 × 0.10 × 0.08 mm
β = 66.852 (1)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2843 independent reflections
Absorption correction: None2421 reflections with I > 2σ(I)
4684 measured reflectionsRint = 0.051
Refinement top
R[F2 > 2σ(F2)] = 0.043209 parameters
wR(F2) = 0.136H atoms treated by a mixture of
independent and constrained refinement
S = 1.11Δρmax = 0.32 e Å−3
2843 reflectionsΔρmin = −0.29 e Å−3
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 > 2sigma(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*/Ueq
C11.4090 (3)0.9541 (3)−0.1318 (3)0.0513 (6)
H1A1.45231.0053−0.21880.077*
H1B1.48960.8758−0.13320.077*
H1C1.39441.0214−0.05720.077*
C21.1438 (3)0.8013 (2)−0.0105 (2)0.0305 (4)
C30.9973 (3)0.7766 (2)−0.0376 (2)0.0324 (5)
C41.0236 (3)0.8610 (3)−0.1570 (2)0.0403 (5)
H40.94600.8673−0.20040.048*
C50.8395 (3)0.6899 (2)0.0232 (2)0.0356 (5)
C60.6552 (3)0.4574 (3)0.3040 (2)0.0414 (5)
H60.73860.46290.34110.050*
C70.5040 (3)0.3680 (3)0.3721 (2)0.0425 (5)
C80.4960 (4)0.2636 (3)0.4734 (3)0.0520 (7)
C90.3514 (5)0.1801 (3)0.5337 (3)0.0724 (10)
H90.34830.11040.60030.087*
C100.2140 (5)0.1986 (4)0.4970 (4)0.0782 (11)
H100.11850.14080.53730.094*
C110.2164 (4)0.3036 (4)0.3995 (3)0.0703 (9)
H110.12140.31820.37600.084*
C120.3606 (3)0.3868 (3)0.3372 (3)0.0521 (6)
H120.36200.45650.27100.062*
Cl10.66414 (13)0.23836 (9)0.52817 (8)0.0729 (3)
N11.2424 (2)0.8929 (2)−0.11050 (19)0.0377 (4)
N21.1702 (3)0.9306 (2)−0.2012 (2)0.0451 (5)
N30.8156 (3)0.6116 (2)0.1381 (2)0.0413 (5)
H3A0.894 (4)0.615 (3)0.174 (3)0.050*
N40.6715 (2)0.5276 (2)0.1936 (2)0.0393 (4)
N51.3822 (3)0.6394 (3)0.0437 (3)0.0551 (6)
H5A1.371 (4)0.572 (4)0.004 (3)0.066*
H5B1.475 (4)0.675 (4)0.028 (3)0.066*
O11.0830 (2)0.6507 (2)0.2113 (2)0.0637 (6)
O21.2641 (2)0.8658 (2)0.17484 (19)0.0550 (5)
O30.7372 (2)0.6923 (2)−0.03414 (19)0.0569 (5)
S11.21556 (7)0.74039 (6)0.12003 (6)0.0396 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0446 (14)0.0509 (14)0.0628 (16)−0.0168 (11)−0.0246 (12)0.0050 (12)
C20.0267 (10)0.0327 (10)0.0325 (10)0.0012 (8)−0.0121 (8)0.0012 (8)
C30.0299 (10)0.0334 (11)0.0344 (11)0.0002 (8)−0.0134 (9)0.0011 (9)
C40.0391 (12)0.0452 (13)0.0420 (12)−0.0045 (9)−0.0216 (10)0.0079 (10)
C50.0274 (10)0.0409 (12)0.0407 (12)−0.0031 (9)−0.0156 (9)0.0033 (9)
C60.0435 (13)0.0424 (12)0.0401 (12)−0.0063 (10)−0.0180 (10)0.0042 (10)
C70.0501 (14)0.0370 (12)0.0351 (12)−0.0075 (10)−0.0106 (10)0.0022 (9)
C80.0724 (18)0.0412 (13)0.0387 (13)−0.0043 (12)−0.0176 (12)0.0018 (11)
C90.104 (3)0.0474 (16)0.0473 (16)−0.0239 (17)−0.0087 (17)0.0134 (13)
C100.076 (2)0.069 (2)0.068 (2)−0.0373 (18)−0.0023 (18)0.0075 (16)
C110.0557 (17)0.077 (2)0.070 (2)−0.0231 (15)−0.0139 (15)0.0018 (16)
C120.0501 (15)0.0539 (15)0.0490 (15)−0.0129 (12)−0.0151 (12)0.0061 (12)
Cl10.1105 (7)0.0599 (5)0.0602 (5)0.0084 (4)−0.0475 (5)0.0067 (3)
N10.0360 (10)0.0388 (10)0.0397 (10)−0.0068 (8)−0.0161 (8)0.0026 (8)
N20.0490 (11)0.0476 (11)0.0429 (11)−0.0113 (9)−0.0219 (9)0.0111 (9)
N30.0345 (10)0.0506 (11)0.0438 (11)−0.0116 (8)−0.0200 (9)0.0111 (9)
N40.0362 (10)0.0415 (10)0.0409 (10)−0.0093 (8)−0.0153 (8)0.0044 (8)
N50.0396 (12)0.0471 (13)0.0931 (19)0.0038 (10)−0.0418 (13)−0.0099 (12)
O10.0450 (10)0.0969 (15)0.0610 (12)−0.0200 (10)−0.0326 (9)0.0362 (11)
O20.0611 (11)0.0611 (11)0.0556 (11)0.0016 (9)−0.0368 (9)−0.0085 (9)
O30.0403 (9)0.0845 (14)0.0577 (11)−0.0222 (9)−0.0305 (9)0.0270 (10)
S10.0339 (3)0.0472 (4)0.0441 (4)−0.0034 (2)−0.0224 (3)0.0067 (3)
Geometric parameters (Å, °) top
C1—N11.465 (3)C8—C91.386 (4)
C1—H1A0.9600C8—Cl11.731 (3)
C1—H1B0.9600C9—C101.360 (5)
C1—H1C0.9600C9—H90.9300
C2—N11.353 (3)C10—C111.384 (5)
C2—C31.397 (3)C10—H100.9300
C2—S11.772 (2)C11—C121.384 (4)
C3—C41.404 (3)C11—H110.9300
C3—C51.484 (3)C12—H120.9300
C4—N21.323 (3)N1—N21.347 (3)
C4—H40.9300N3—N41.381 (3)
C5—O31.227 (3)N3—H3A0.87 (3)
C5—N31.340 (3)N5—S11.575 (2)
C6—N41.274 (3)N5—H5A0.77 (3)
C6—C71.466 (3)N5—H5B0.82 (3)
C6—H60.9300O1—S11.4292 (19)
C7—C121.397 (4)O2—S11.4235 (18)
C7—C81.398 (3)
N1—C1—H1A109.5C10—C9—H9119.5
N1—C1—H1B109.5C8—C9—H9119.5
H1A—C1—H1B109.5C9—C10—C11119.9 (3)
N1—C1—H1C109.5C9—C10—H10120.0
H1A—C1—H1C109.5C11—C10—H10120.0
H1B—C1—H1C109.5C12—C11—C10119.8 (3)
N1—C2—C3106.98 (18)C12—C11—H11120.1
N1—C2—S1119.13 (15)C10—C11—H11120.1
C3—C2—S1133.89 (16)C11—C12—C7121.1 (3)
C2—C3—C4103.20 (18)C11—C12—H12119.5
C2—C3—C5137.5 (2)C7—C12—H12119.5
C4—C3—C5119.3 (2)N2—N1—C2112.22 (17)
N2—C4—C3112.9 (2)N2—N1—C1117.85 (19)
N2—C4—H4123.6C2—N1—C1129.9 (2)
C3—C4—H4123.6C4—N2—N1104.69 (18)
O3—C5—N3122.8 (2)C5—N3—N4118.87 (19)
O3—C5—C3118.8 (2)C5—N3—H3A117.9 (18)
N3—C5—C3118.38 (19)N4—N3—H3A123.2 (18)
N4—C6—C7119.6 (2)C6—N4—N3115.7 (2)
N4—C6—H6120.2S1—N5—H5A116 (2)
C7—C6—H6120.2S1—N5—H5B117 (2)
C12—C7—C8117.7 (2)H5A—N5—H5B124 (3)
C12—C7—C6119.9 (2)O2—S1—O1119.36 (12)
C8—C7—C6122.4 (3)O2—S1—N5108.30 (12)
C9—C8—C7120.5 (3)O1—S1—N5108.40 (14)
C9—C8—Cl1118.7 (2)O2—S1—C2107.99 (10)
C7—C8—Cl1120.9 (2)O1—S1—C2105.91 (10)
C10—C9—C8120.9 (3)N5—S1—C2106.13 (12)
N1—C2—C3—C4−0.4 (2)C10—C11—C12—C7−0.7 (5)
S1—C2—C3—C4179.24 (18)C8—C7—C12—C11−0.9 (4)
N1—C2—C3—C5178.8 (2)C6—C7—C12—C11179.8 (2)
S1—C2—C3—C5−1.6 (4)C3—C2—N1—N20.3 (2)
C2—C3—C4—N20.3 (3)S1—C2—N1—N2−179.38 (15)
C5—C3—C4—N2−178.99 (19)C3—C2—N1—C1180.0 (2)
C2—C3—C5—O3−177.8 (2)S1—C2—N1—C10.3 (3)
C4—C3—C5—O31.2 (3)C3—C4—N2—N1−0.2 (3)
C2—C3—C5—N31.8 (4)C2—N1—N2—C4−0.1 (3)
C4—C3—C5—N3−179.2 (2)C1—N1—N2—C4−179.8 (2)
N4—C6—C7—C12−15.3 (3)O3—C5—N3—N41.2 (4)
N4—C6—C7—C8165.4 (2)C3—C5—N3—N4−178.40 (19)
C12—C7—C8—C91.5 (4)C7—C6—N4—N3178.6 (2)
C6—C7—C8—C9−179.2 (2)C5—N3—N4—C6−179.1 (2)
C12—C7—C8—Cl1−177.30 (19)N1—C2—S1—O249.18 (19)
C6—C7—C8—Cl12.0 (3)C3—C2—S1—O2−130.4 (2)
C7—C8—C9—C10−0.6 (4)N1—C2—S1—O1178.13 (18)
Cl1—C8—C9—C10178.2 (3)C3—C2—S1—O1−1.4 (3)
C8—C9—C10—C11−1.0 (5)N1—C2—S1—N5−66.77 (19)
C9—C10—C11—C121.6 (5)C3—C2—S1—N5113.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.87 (3)1.83 (3)2.685 (3)166 (3)
N5—H5B···O3i0.82 (3)2.05 (3)2.835 (3)160 (3)
N5—H5A···N4ii0.77 (3)2.42 (3)3.105 (3)149 (3)
N5—H5A···O3ii0.77 (3)2.58 (3)3.231 (3)144 (3)
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.87 (3)1.83 (3)2.685 (3)166 (3)
N5—H5B···O3i0.82 (3)2.05 (3)2.835 (3)160 (3)
N5—H5A···N4ii0.77 (3)2.42 (3)3.105 (3)149 (3)
N5—H5A···O3ii0.77 (3)2.58 (3)3.231 (3)144 (3)
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z.
Acknowledgements top

We gratefully acknowledge financial support of this work by the National Basic Research Program of China (2003CB114400) and the National Natural Science Foundation of China (No. 20372023).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (2001). SMART (Version 5.628) and SAINT-Plus (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA. SAINT-Plus or just SAINT as above?

Liang, Y. & He, H. W. (2005). Chin. J. Pestic. 44, 491–495.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Wang, H. Q., Liu, H. & Liu, Z. J. (2004). Chin. J. Org. Chem. 24, 797–801.

Zou, X. M., Cheng, Y. H., Ren, X. L., Hu, F. Z. & Yang, H. Z. (2005). Chin. J. Org. Chem. 25, 554–557.