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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2567.
Published online 2009 September 30. doi:  10.1107/S1600536809038471
PMCID: PMC2970275

4-Chloro-5-[(5,5-dimethyl-4,5-dihydro­isoxazol-3-yl)sulfonyl­meth­yl]-3-methyl-1-(2,2,2-trifluoro­ethyl)-1H-pyrazole

Abstract

The mol­ecule of the title compound, C12H15ClF3N3O3S, is twisted, as indicated by the C—S—C—C torsion angle of 66.00 (18)° for the atoms linking the ring systems. An intra­molecular C—H(...)F short contact occurs. In the crystal, non-classical C—H(...)O inter­actions, one of which has a short H(...)O contact of 2.28 Å, link the mol­ecules.

Related literature

For background to pyrazoles and their pharmacological and pharmaceutical applications, see: Hirai et al. (2002 [triangle]); Shiga et al. (2003 [triangle]); Ohno et al. (2004 [triangle]); Sabbagh et al. (2009 [triangle]); Sridhar et al. (2004 [triangle]); Zheng et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2567-scheme1.jpg

Experimental

Crystal data

  • C12H15ClF3N3O3S
  • M r = 373.78
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2567-efi1.jpg
  • a = 16.034 (3) Å
  • b = 5.4319 (11) Å
  • c = 19.069 (4) Å
  • β = 106.71 (3)°
  • V = 1590.7 (6) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 3.83 mm−1
  • T = 173 K
  • 0.39 × 0.26 × 0.25 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: numerical (NUMABS; Higashi, 2003 [triangle]) T min = 0.317, T max = 0.448
  • 11348 measured reflections
  • 2891 independent reflections
  • 2568 reflections with I > 2σ(I)
  • R int = 0.073

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.097
  • S = 1.09
  • 2891 reflections
  • 212 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2001 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038471/hb5103sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038471/hb5103Isup2.hkl

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

Acknowledgments

This work was supported by the Major State Basic Research Development Program of China (No. 2010CB126106 and No. 2006CB101907), and the 863 high-tech key project of China (2006AA10A203).

supplementary crystallographic information

Comment

Pyrazoles are an important class of compounds, which possess widespread pharmacological properties in pharmaceuticals (Sridhar et al., 2004; Zheng et al., 2009; Sabbagh et al., 2009) and agrochemicals (Shiga et al., 2003; Ohno et al., 2004). Various pyrazole derivatives with potent herbicidal activity have been synthesized and some are in use as herbicides such as pyrazolate, pyrazoxyfen, benzofenap, pyraflufen-ethyl, fluazolate and pyrazosulfuron-ethyl (Hirai et al., 2002). Recently, the new title compound (I) was synthesized in our group with high herbicidal activity. The crystal structure of the title compound is shown in Fig. 1.

Experimental

The title compound (0.2 g) was dissolved in acetone (50 ml) at room temperature. Colourless blocks of (I) were obtained through slow evaporation after two weeks.

Refinement

The H atoms were placed at calculated positions, with C—H = 0.93–0.98 Å, and refined as riding with Uiso(H) = 1.2–1.5Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C12H15ClF3N3O3SF(000) = 768
Mr = 373.78Dx = 1.561 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 11348 reflections
a = 16.034 (3) Åθ = 3.2–68.2°
b = 5.4319 (11) ŵ = 3.83 mm1
c = 19.069 (4) ÅT = 173 K
β = 106.71 (3)°Block, colourless
V = 1590.7 (6) Å30.39 × 0.26 × 0.25 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer2891 independent reflections
Radiation source: rotating anode2568 reflections with I > 2σ(I)
graphiteRint = 0.073
ω scansθmax = 68.2°, θmin = 3.2°
Absorption correction: numerical (NUMABS; Higashi, 2003)h = −16→19
Tmin = 0.317, Tmax = 0.448k = −6→5
11348 measured reflectionsl = −22→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.097w = 1/[σ2(Fo2) + (0.0203P)2 + 1.0073P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2891 reflectionsΔρmax = 0.39 e Å3
212 parametersΔρmin = −0.36 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0054 (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 (Å2)

xyzUiso*/Ueq
Cl10.44152 (4)0.93466 (11)0.09341 (4)0.03950 (19)
S10.36881 (3)0.46279 (10)0.24281 (3)0.02353 (17)
F10.10868 (10)0.5476 (3)0.06789 (10)0.0610 (5)
F20.05756 (9)0.1893 (3)0.03398 (9)0.0584 (5)
F30.09944 (9)0.4206 (3)−0.04032 (8)0.0519 (5)
O10.35709 (10)0.2075 (3)0.22345 (9)0.0320 (4)
O20.34961 (10)0.5475 (3)0.30760 (9)0.0355 (4)
O30.60616 (9)0.5020 (3)0.23839 (9)0.0295 (4)
N10.29777 (12)0.3998 (4)−0.01380 (10)0.0308 (5)
N20.27450 (11)0.4064 (3)0.04952 (10)0.0252 (4)
N30.52262 (11)0.4070 (3)0.22312 (10)0.0273 (4)
C10.37126 (13)0.6956 (4)0.06043 (13)0.0286 (5)
C20.35682 (14)0.5758 (5)−0.00755 (13)0.0311 (5)
C30.31789 (13)0.5852 (4)0.09606 (12)0.0238 (5)
C40.39748 (17)0.6278 (6)−0.06716 (14)0.0478 (7)
H4A0.37370.5148−0.10810.072*
H4B0.46060.6049−0.04860.072*
H4C0.38480.7979−0.08400.072*
C50.20776 (14)0.2398 (4)0.05769 (12)0.0277 (5)
H5A0.21920.19680.11010.033*
H5B0.21020.08610.03040.033*
C60.11822 (15)0.3496 (5)0.03000 (14)0.0358 (6)
C70.30537 (13)0.6436 (4)0.16871 (12)0.0252 (5)
H7A0.24310.62110.16540.030*
H7B0.31970.81930.17980.030*
C80.47791 (13)0.5464 (4)0.25218 (11)0.0217 (5)
C90.61812 (13)0.6994 (4)0.29469 (12)0.0262 (5)
C100.52374 (13)0.7681 (4)0.29159 (13)0.0280 (5)
H10A0.51610.78440.34110.034*
H10B0.50450.92140.26350.034*
C110.66650 (17)0.5831 (5)0.36693 (14)0.0415 (7)
H11A0.72120.51210.36320.062*
H11B0.63060.45310.37900.062*
H11C0.67910.70870.40550.062*
C120.66893 (16)0.9029 (5)0.27166 (17)0.0426 (7)
H12A0.72490.83820.26880.064*
H12B0.67911.03650.30770.064*
H12C0.63570.96580.22360.064*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0318 (3)0.0362 (4)0.0491 (4)−0.0112 (2)0.0094 (3)0.0061 (3)
S10.0209 (3)0.0256 (3)0.0244 (3)−0.0035 (2)0.0071 (2)−0.0022 (2)
F10.0316 (8)0.0694 (12)0.0759 (13)0.0110 (8)0.0057 (8)−0.0260 (10)
F20.0300 (8)0.0797 (13)0.0579 (10)−0.0223 (8)0.0005 (7)0.0141 (9)
F30.0366 (8)0.0723 (12)0.0408 (9)0.0071 (8)0.0018 (7)0.0211 (8)
O10.0305 (9)0.0225 (9)0.0404 (10)−0.0064 (7)0.0060 (7)−0.0002 (7)
O20.0297 (9)0.0528 (12)0.0271 (9)−0.0028 (8)0.0132 (7)−0.0060 (8)
O30.0204 (8)0.0306 (9)0.0379 (10)−0.0020 (6)0.0091 (7)−0.0091 (7)
N10.0277 (10)0.0423 (12)0.0227 (10)0.0014 (9)0.0077 (8)0.0003 (9)
N20.0234 (9)0.0295 (10)0.0227 (10)−0.0022 (8)0.0066 (8)0.0004 (8)
N30.0219 (9)0.0281 (10)0.0308 (10)−0.0018 (8)0.0060 (8)−0.0038 (8)
C10.0193 (11)0.0307 (13)0.0338 (13)−0.0010 (9)0.0047 (9)0.0068 (10)
C20.0226 (11)0.0424 (14)0.0279 (13)0.0016 (10)0.0068 (10)0.0081 (10)
C30.0207 (10)0.0237 (11)0.0262 (12)0.0025 (8)0.0053 (9)0.0014 (9)
C40.0345 (14)0.079 (2)0.0333 (15)−0.0023 (14)0.0147 (11)0.0113 (14)
C50.0269 (11)0.0280 (12)0.0261 (12)−0.0059 (9)0.0043 (9)0.0015 (9)
C60.0242 (12)0.0444 (15)0.0368 (14)−0.0086 (11)0.0054 (10)0.0017 (12)
C70.0212 (10)0.0238 (11)0.0309 (12)0.0018 (9)0.0080 (9)−0.0027 (9)
C80.0198 (10)0.0211 (11)0.0231 (11)0.0010 (8)0.0043 (9)−0.0008 (8)
C90.0221 (11)0.0208 (11)0.0335 (13)−0.0012 (9)0.0048 (9)−0.0038 (9)
C100.0221 (11)0.0248 (12)0.0365 (13)−0.0030 (9)0.0076 (9)−0.0079 (10)
C110.0348 (14)0.0444 (16)0.0367 (15)0.0013 (11)−0.0034 (11)−0.0013 (12)
C120.0295 (13)0.0306 (14)0.070 (2)−0.0011 (10)0.0186 (13)0.0039 (13)

Geometric parameters (Å, °)

Cl1—C11.716 (2)C4—H4B0.9800
S1—O21.4324 (16)C4—H4C0.9800
S1—O11.4333 (16)C5—C61.503 (3)
S1—C81.766 (2)C5—H5A0.9900
S1—C71.780 (2)C5—H5B0.9900
F1—C61.329 (3)C7—H7A0.9900
F2—C61.324 (3)C7—H7B0.9900
F3—C61.344 (3)C8—C101.496 (3)
O3—N31.386 (2)C9—C121.511 (3)
O3—C91.490 (3)C9—C111.511 (3)
N1—C21.327 (3)C9—C101.543 (3)
N1—N21.363 (2)C10—H10A0.9900
N2—C31.364 (3)C10—H10B0.9900
N2—C51.444 (3)C11—H11A0.9800
N3—C81.274 (3)C11—H11B0.9800
C1—C31.374 (3)C11—H11C0.9800
C1—C21.409 (3)C12—H12A0.9800
C2—C41.491 (3)C12—H12B0.9800
C3—C71.490 (3)C12—H12C0.9800
C4—H4A0.9800
O2—S1—O1119.23 (10)F2—C6—C5111.2 (2)
O2—S1—C8106.40 (10)F1—C6—C5112.21 (19)
O1—S1—C8109.12 (10)F3—C6—C5112.4 (2)
O2—S1—C7106.96 (10)C3—C7—S1114.93 (15)
O1—S1—C7109.07 (10)C3—C7—H7A108.5
C8—S1—C7105.17 (10)S1—C7—H7A108.5
N3—O3—C9109.60 (15)C3—C7—H7B108.5
C2—N1—N2105.74 (19)S1—C7—H7B108.5
N1—N2—C3112.16 (18)H7A—C7—H7B107.5
N1—N2—C5118.62 (18)N3—C8—C10116.13 (19)
C3—N2—C5129.16 (19)N3—C8—S1117.92 (16)
C8—N3—O3108.56 (17)C10—C8—S1125.96 (16)
C3—C1—C2107.0 (2)O3—C9—C12106.57 (19)
C3—C1—Cl1125.86 (19)O3—C9—C11106.36 (18)
C2—C1—Cl1127.13 (18)C12—C9—C11113.1 (2)
N1—C2—C1109.9 (2)O3—C9—C10103.00 (16)
N1—C2—C4121.7 (2)C12—C9—C10114.63 (19)
C1—C2—C4128.5 (2)C11—C9—C10112.1 (2)
N2—C3—C1105.2 (2)C8—C10—C999.16 (17)
N2—C3—C7125.2 (2)C8—C10—H10A111.9
C1—C3—C7129.5 (2)C9—C10—H10A111.9
C2—C4—H4A109.5C8—C10—H10B111.9
C2—C4—H4B109.5C9—C10—H10B111.9
H4A—C4—H4B109.5H10A—C10—H10B109.6
C2—C4—H4C109.5C9—C11—H11A109.5
H4A—C4—H4C109.5C9—C11—H11B109.5
H4B—C4—H4C109.5H11A—C11—H11B109.5
N2—C5—C6112.07 (19)C9—C11—H11C109.5
N2—C5—H5A109.2H11A—C11—H11C109.5
C6—C5—H5A109.2H11B—C11—H11C109.5
N2—C5—H5B109.2C9—C12—H12A109.5
C6—C5—H5B109.2C9—C12—H12B109.5
H5A—C5—H5B107.9H12A—C12—H12B109.5
F2—C6—F1107.5 (2)C9—C12—H12C109.5
F2—C6—F3106.76 (19)H12A—C12—H12C109.5
F1—C6—F3106.4 (2)H12B—C12—H12C109.5
C2—N1—N2—C30.1 (2)N2—C3—C7—S186.0 (2)
C2—N1—N2—C5177.64 (19)C1—C3—C7—S1−95.8 (3)
C9—O3—N3—C811.2 (2)O2—S1—C7—C3178.87 (16)
N2—N1—C2—C10.0 (2)O1—S1—C7—C3−50.91 (19)
N2—N1—C2—C4−179.3 (2)C8—S1—C7—C366.00 (18)
C3—C1—C2—N1−0.2 (3)O3—N3—C8—C101.4 (3)
Cl1—C1—C2—N1180.00 (17)O3—N3—C8—S1−178.52 (13)
C3—C1—C2—C4179.0 (2)O2—S1—C8—N3148.32 (18)
Cl1—C1—C2—C4−0.8 (4)O1—S1—C8—N318.5 (2)
N1—N2—C3—C1−0.2 (2)C7—S1—C8—N3−98.41 (19)
C5—N2—C3—C1−177.4 (2)O2—S1—C8—C10−31.6 (2)
N1—N2—C3—C7178.34 (19)O1—S1—C8—C10−161.43 (18)
C5—N2—C3—C71.2 (3)C7—S1—C8—C1081.7 (2)
C2—C1—C3—N20.2 (2)N3—O3—C9—C12−139.32 (18)
Cl1—C1—C3—N2−179.92 (16)N3—O3—C9—C1199.8 (2)
C2—C1—C3—C7−178.3 (2)N3—O3—C9—C10−18.3 (2)
Cl1—C1—C3—C71.6 (3)N3—C8—C10—C9−12.4 (3)
N1—N2—C5—C6−89.8 (2)S1—C8—C10—C9167.48 (16)
C3—N2—C5—C687.3 (3)O3—C9—C10—C817.0 (2)
N2—C5—C6—F2176.34 (19)C12—C9—C10—C8132.3 (2)
N2—C5—C6—F1−63.3 (3)C11—C9—C10—C8−96.9 (2)
N2—C5—C6—F356.7 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7A···F10.992.443.229 (3)136
C4—H4A···O3i0.982.603.325 (3)131
C5—H5A···O2ii0.992.313.146 (3)141
C7—H7B···O1iii0.992.283.265 (3)171

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5103).

References

  • Higashi, T. (2003). NUMABS Rigaku Corporation, Tokyo, Japan.
  • Hirai, K., Uchida, A. & Ohno, R. (2002). Herbicide Classes in Development, edited by P. Boger, K. Hirai & K. Wakabyashi, pp. 179–289. Heidelberg: Springer-Verlag.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Ohno, R., Watanabe, A., Nagaoka, M., Ueda, T., Sakurai, H., Hori, M. & Hirai, K. (2004). J Pestic Sci 29, 15–26.
  • Rigaku (2001). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sabbagh, O. I., Raraka, M. M., Ibrahim, S. M., Pannecouque, C., Andrei, G., Snoeck, R., Balzarini, J. & Rashad, A. A. (2009). Eur J Med Chem 44, 3746–3753. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shiga, Y., Okada, I., Ikeda, Y., Takizawa, E. & Fukuchi, T. (2003). J Pestic Sci 28, 313–314.
  • Sridhar, R., Perumal, P. T., Etti, S., Shanmugam, G., Ponnuswamy, M. N., Prabayathy, V. R. & Mathivanan, N. (2004). Bioorg Med Chem Lett 14, 6035–6040. [PubMed]
  • Zheng, L. W., Wu, L. L., Zhao, B. X., Dong, W. L. & Miao, J. Y. (2009). Bioorg Med Chem 17, 1957–1962. [PubMed]

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