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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044054/sj2353sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044054/sj2353Isup2.hkl
Contains datablock I

CCDC reference: 663767

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.043
  • wR factor = 0.136
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

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Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.55 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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 ππ 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

Structure description 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 ππ stacking interactions [Cg1···Cg1iii = 3.4664 (13) Å, iii = 2 - x, 2 - y, -z].

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).

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 = 341.78F(000) = 352
Triclinic, P1Dx = 1.545 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4272 (6) ÅCell parameters from 2721 reflections
b = 9.0905 (7) Åθ = 2.2–28.3°
c = 10.4381 (7) ŵ = 0.42 mm1
α = 89.525 (1)°T = 292 K
β = 66.852 (1)°Block, colorless
γ = 87.722 (1)°0.10 × 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
Graphite monochromatorθmax = 26.0°, θmin = 2.1°
φ and ω scansh = 109
4684 measured reflectionsk = 1111
2843 independent reflectionsl = 128
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0737P)2 + 0.1888P]
where P = (Fo2 + 2Fc2)/3
2843 reflections(Δ/σ)max = 0.011
209 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C12H12ClN5O3Sγ = 87.722 (1)°
Mr = 341.78V = 734.66 (9) Å3
Triclinic, P1Z = 2
a = 8.4272 (6) ÅMo Kα radiation
b = 9.0905 (7) ŵ = 0.42 mm1
c = 10.4381 (7) ÅT = 292 K
α = 89.525 (1)°0.10 × 0.10 × 0.08 mm
β = 66.852 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2421 reflections with I > 2σ(I)
4684 measured reflectionsRint = 0.051
2843 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.32 e Å3
2843 reflectionsΔρmin = 0.29 e Å3
209 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*/Ueq
C11.4090 (3)0.9541 (3)0.1318 (3)0.0513 (6)
H1A1.45231.00530.21880.077*
H1B1.48960.87580.13320.077*
H1C1.39441.02140.05720.077*
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)
H40.94600.86730.20040.048*
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, º) 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—C40.4 (2)C10—C11—C12—C70.7 (5)
S1—C2—C3—C4179.24 (18)C8—C7—C12—C110.9 (4)
N1—C2—C3—C5178.8 (2)C6—C7—C12—C11179.8 (2)
S1—C2—C3—C51.6 (4)C3—C2—N1—N20.3 (2)
C2—C3—C4—N20.3 (3)S1—C2—N1—N2179.38 (15)
C5—C3—C4—N2178.99 (19)C3—C2—N1—C1180.0 (2)
C2—C3—C5—O3177.8 (2)S1—C2—N1—C10.3 (3)
C4—C3—C5—O31.2 (3)C3—C4—N2—N10.2 (3)
C2—C3—C5—N31.8 (4)C2—N1—N2—C40.1 (3)
C4—C3—C5—N3179.2 (2)C1—N1—N2—C4179.8 (2)
N4—C6—C7—C1215.3 (3)O3—C5—N3—N41.2 (4)
N4—C6—C7—C8165.4 (2)C3—C5—N3—N4178.40 (19)
C12—C7—C8—C91.5 (4)C7—C6—N4—N3178.6 (2)
C6—C7—C8—C9179.2 (2)C5—N3—N4—C6179.1 (2)
C12—C7—C8—Cl1177.30 (19)N1—C2—S1—O249.18 (19)
C6—C7—C8—Cl12.0 (3)C3—C2—S1—O2130.4 (2)
C7—C8—C9—C100.6 (4)N1—C2—S1—O1178.13 (18)
Cl1—C8—C9—C10178.2 (3)C3—C2—S1—O11.4 (3)
C8—C9—C10—C111.0 (5)N1—C2—S1—N566.77 (19)
C9—C10—C11—C121.6 (5)C3—C2—S1—N5113.7 (2)
Hydrogen-bond geometry (Å, º) 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.

Experimental details

Crystal data
Chemical formulaC12H12ClN5O3S
Mr341.78
Crystal system, space groupTriclinic, P1
Temperature (K)292
a, b, c (Å)8.4272 (6), 9.0905 (7), 10.4381 (7)
α, β, γ (°)89.525 (1), 66.852 (1), 87.722 (1)
V3)734.66 (9)
Z2
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.10 × 0.10 × 0.08
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4684, 2843, 2421
Rint0.051
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.136, 1.11
No. of reflections2843
No. of parameters209
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2001).

Hydrogen-bond geometry (Å, º) 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.
 

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