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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2702–o2703.
Published online 2009 October 10. doi:  10.1107/S1600536809040380
PMCID: PMC2971122

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

Abstract

In the title compound, C12H15BrF3N3O3S, which has potential herbicidal activity, the mol­ecule is twisted, as indicated by the C—S—C—C torsion angle of 67.86 (19)° for the atoms linking the ring systems. An intra­molecular C—H(...)F short contact occurs and inter­molecular C—H(...)O inter­actions link the mol­ecules in the crystal.

Related literature

For background to pyrazoles and their pharmacological and pharmaceutical applications, see: Aiello et al. (2000 [triangle]); Hirai et al. (2002 [triangle]); Lahm et al. (2007 [triangle]); Meegalla et al. (2004 [triangle]); Ohno et al. (2004 [triangle]); Shiga et al. (2003 [triangle]); Sivaprasad et al. (2006 [triangle]); Vicentini et al. (2005 [triangle]); Waldrep et al. (1990 [triangle]). The trifluoro­methyl group is present in many biologically active pharmaceutical and agrochemical compounds, presumably due to its increased lipophilicity, electronegativity and relatively small size, see: Welch (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2702-scheme1.jpg

Experimental

Crystal data

  • C12H15BrF3N3O3S
  • M r = 418.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2702-efi1.jpg
  • a = 16.127 (3) Å
  • b = 5.4356 (11) Å
  • c = 19.135 (4) Å
  • β = 106.85 (3)°
  • V = 1605.3 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.74 mm−1
  • T = 173 K
  • 0.16 × 0.15 × 0.05 mm

Data collection

  • Rigaku MM007HF + CCD (Saturn724+) diffractometer
  • Absorption correction: numerical (CrystalClear; Rigaku, 2008 [triangle]) T min = 0.668, T max = 0.875
  • 11131 measured reflections
  • 3614 independent reflections
  • 3353 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.093
  • S = 1.14
  • 3614 reflections
  • 211 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: CrystalClear (Rigaku, 2008 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536809040380/hb5125sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040380/hb5125Isup2.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

Pyrazole derivatives represent one of the most important classes of organic heterocyclic compounds, possessing a wide spectrum of biological activities in agrochemicals such as insecticidal (Lahm et al., 2007; Meegalla et al., 2004; Shiga et al., 2003), fungicidal (Aiello et al., 2000; Sivaprasad et al., 2006), herbicidal (Ohno et al., 2004; Vicentini et al., 2005; Waldrep et al., 1990) activities. Some pyrazole derivatives are in use as herbicides such as pyrazolate, pyrazoxyfen, benzofenap, pyraflufen-ethyl, fluazolate and pyrazosulfuron-ethyl (Hirai et al.,2002). The trifluoromethyl moiety is particularly encountered in many biologically active pharmaceutical and agrochemical compounds presumably due to its increased lipophilicity, electronegativity and relatively small size (Welch 1987). Recently, we introduced trifluoromethyl to forming a novel title compound (I) with high herbicidal activity that has not been reported in literatures. The crystal structure of the title compound is shown in Fig. 1.

Experimental

4-Bromo-5-[(5,5-dimethyl-4,5-dihydroisoxazol-3-yl)sulfonylmethyl]-3-methyl-1-(2,2,2-trifluoroethyl)-1H-pyrazole (0.2 g) was dissolved in acetone (50 ml) at room temperature. Colourless crystals of the title compound (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 were included in the refinement in the riding model approximation with Uiso(H) set to 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

C12H15BrF3N3O3SF(000) = 840
Mr = 418.24Dx = 1.730 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5465 reflections
a = 16.127 (3) Åθ = 1.5–27.5°
b = 5.4356 (11) ŵ = 2.74 mm1
c = 19.135 (4) ÅT = 173 K
β = 106.85 (3)°Slab, colourless
V = 1605.3 (6) Å30.16 × 0.15 × 0.05 mm
Z = 4

Data collection

Rigaku MM007HF + CCD (Saturn724+) diffractometer3614 independent reflections
Radiation source: Rotating Anode3353 reflections with I > 2σ(I)
ConfocalRint = 0.040
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 1.5°
ω scans at fixed χ = 45°h = −20→18
Absorption correction: numerical (CrystalClear; Rigaku, 2008)k = −7→6
Tmin = 0.668, Tmax = 0.875l = −21→24
11131 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0399P)2 + 1.0315P] where P = (Fo2 + 2Fc2)/3
3614 reflections(Δ/σ)max = 0.001
211 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = −0.50 e Å3

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
Br10.445686 (15)0.94374 (5)0.090555 (14)0.03063 (10)
S10.36847 (3)0.46277 (11)0.24140 (3)0.01880 (13)
F10.05557 (10)0.1917 (4)0.03774 (10)0.0506 (5)
F20.10792 (11)0.5508 (4)0.06883 (11)0.0533 (5)
F30.09624 (11)0.4150 (4)−0.03880 (9)0.0446 (5)
O10.34862 (11)0.5488 (4)0.30560 (9)0.0302 (4)
O20.35701 (10)0.2071 (3)0.22232 (9)0.0278 (4)
O30.60544 (10)0.5023 (3)0.23928 (9)0.0247 (4)
N10.29249 (12)0.3877 (4)−0.01482 (10)0.0245 (4)
N20.27115 (12)0.4000 (4)0.04901 (10)0.0202 (4)
N30.52217 (12)0.4076 (4)0.22290 (11)0.0218 (4)
C10.36847 (14)0.6842 (4)0.05707 (12)0.0215 (5)
C20.35194 (15)0.5606 (5)−0.01018 (12)0.0233 (5)
C30.31611 (14)0.5796 (4)0.09432 (12)0.0190 (4)
C40.39090 (17)0.6042 (6)−0.07062 (14)0.0352 (6)
H4A0.36490.4916−0.11100.053*
H4B0.45350.5753−0.05310.053*
H4C0.38000.7745−0.08760.053*
C50.20495 (14)0.2363 (5)0.05891 (12)0.0235 (5)
H5A0.21720.19660.11140.028*
H5B0.20640.08090.03230.028*
C60.11590 (16)0.3492 (5)0.03153 (14)0.0306 (6)
C70.30517 (14)0.6434 (5)0.16676 (12)0.0203 (4)
H7A0.24330.62470.16410.024*
H7B0.32060.81880.17700.024*
C80.47706 (14)0.5475 (4)0.25141 (12)0.0180 (4)
C90.52301 (14)0.7679 (5)0.29165 (13)0.0242 (5)
H9A0.51520.78240.34090.029*
H9B0.50410.92210.26410.029*
C100.61659 (14)0.6997 (4)0.29502 (13)0.0221 (5)
C110.66758 (17)0.9027 (5)0.27253 (17)0.0347 (6)
H11A0.72290.83700.26910.052*
H11B0.67861.03470.30900.052*
H11C0.63430.96820.22490.052*
C120.66479 (18)0.5845 (5)0.36726 (15)0.0359 (6)
H12A0.72020.51880.36430.054*
H12B0.63000.45080.37860.054*
H12C0.67540.70930.40580.054*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02683 (15)0.02743 (17)0.03790 (17)−0.00740 (9)0.00979 (11)0.00368 (10)
S10.0184 (3)0.0222 (3)0.0175 (3)−0.00311 (19)0.0078 (2)−0.0020 (2)
F10.0246 (8)0.0738 (14)0.0495 (10)−0.0205 (8)0.0044 (7)0.0103 (9)
F20.0288 (9)0.0612 (13)0.0659 (13)0.0097 (8)0.0074 (8)−0.0243 (10)
F30.0334 (9)0.0640 (13)0.0331 (9)0.0067 (8)0.0043 (7)0.0170 (8)
O10.0277 (9)0.0473 (12)0.0192 (8)−0.0046 (8)0.0126 (7)−0.0057 (8)
O20.0285 (9)0.0204 (9)0.0328 (9)−0.0056 (7)0.0065 (7)0.0001 (7)
O30.0180 (8)0.0272 (9)0.0307 (9)−0.0019 (6)0.0098 (7)−0.0084 (7)
N10.0237 (10)0.0334 (12)0.0174 (9)0.0014 (8)0.0076 (8)−0.0002 (8)
N20.0185 (9)0.0257 (10)0.0173 (9)−0.0007 (7)0.0065 (7)−0.0004 (8)
N30.0187 (9)0.0221 (10)0.0251 (10)−0.0013 (7)0.0070 (8)−0.0031 (8)
C10.0183 (10)0.0239 (12)0.0220 (11)0.0001 (8)0.0055 (8)0.0036 (9)
C20.0204 (11)0.0320 (14)0.0185 (11)0.0040 (9)0.0072 (9)0.0041 (9)
C30.0180 (10)0.0201 (11)0.0187 (10)0.0014 (8)0.0047 (8)0.0009 (8)
C40.0289 (13)0.0569 (19)0.0236 (13)−0.0009 (12)0.0133 (10)0.0072 (12)
C50.0231 (11)0.0254 (12)0.0219 (11)−0.0066 (9)0.0066 (9)0.0003 (9)
C60.0242 (12)0.0373 (15)0.0295 (13)−0.0075 (11)0.0067 (10)0.0009 (11)
C70.0190 (10)0.0207 (12)0.0217 (11)0.0008 (8)0.0067 (8)−0.0028 (9)
C80.0181 (10)0.0189 (11)0.0170 (10)−0.0008 (8)0.0049 (8)−0.0015 (8)
C90.0199 (11)0.0235 (12)0.0298 (12)−0.0028 (9)0.0083 (9)−0.0064 (10)
C100.0208 (11)0.0183 (12)0.0261 (12)−0.0002 (8)0.0053 (9)−0.0037 (9)
C110.0256 (13)0.0256 (14)0.0546 (18)−0.0013 (10)0.0141 (12)0.0048 (12)
C120.0350 (14)0.0383 (16)0.0277 (14)0.0000 (11)−0.0014 (11)0.0005 (11)

Geometric parameters (Å, °)

Br1—C11.868 (2)C4—H4B0.9800
S1—O11.4346 (17)C4—H4C0.9800
S1—O21.4351 (18)C5—C61.509 (3)
S1—C81.767 (2)C5—H5A0.9900
S1—C71.789 (2)C5—H5B0.9900
F1—C61.327 (3)C7—H7A0.9900
F2—C61.334 (3)C7—H7B0.9900
F3—C61.339 (3)C8—C91.499 (3)
O3—N31.387 (2)C9—C101.537 (3)
O3—C101.487 (3)C9—H9A0.9900
N1—C21.327 (3)C9—H9B0.9900
N1—N21.363 (3)C10—C121.511 (3)
N2—C31.366 (3)C10—C111.512 (3)
N2—C51.444 (3)C11—H11A0.9800
N3—C81.279 (3)C11—H11B0.9800
C1—C31.376 (3)C11—H11C0.9800
C1—C21.407 (3)C12—H12A0.9800
C2—C41.487 (3)C12—H12B0.9800
C3—C71.488 (3)C12—H12C0.9800
C4—H4A0.9800
O1—S1—O2119.28 (11)F1—C6—C5110.8 (2)
O1—S1—C8106.41 (11)F2—C6—C5112.2 (2)
O2—S1—C8109.30 (10)F3—C6—C5112.5 (2)
O1—S1—C7106.71 (11)C3—C7—S1114.91 (16)
O2—S1—C7109.08 (11)C3—C7—H7A108.5
C8—S1—C7105.17 (11)S1—C7—H7A108.5
N3—O3—C10109.76 (16)C3—C7—H7B108.5
C2—N1—N2105.69 (19)S1—C7—H7B108.5
N1—N2—C3112.23 (19)H7A—C7—H7B107.5
N1—N2—C5118.40 (19)N3—C8—C9115.9 (2)
C3—N2—C5129.33 (19)N3—C8—S1117.85 (17)
C8—N3—O3108.43 (18)C9—C8—S1126.24 (17)
C3—C1—C2107.1 (2)C8—C9—C1099.33 (18)
C3—C1—Br1125.64 (18)C8—C9—H9A111.9
C2—C1—Br1127.23 (18)C10—C9—H9A111.9
N1—C2—C1109.9 (2)C8—C9—H9B111.9
N1—C2—C4121.4 (2)C10—C9—H9B111.9
C1—C2—C4128.7 (2)H9A—C9—H9B109.6
N2—C3—C1105.0 (2)O3—C10—C12106.28 (19)
N2—C3—C7125.0 (2)O3—C10—C11106.6 (2)
C1—C3—C7130.0 (2)C12—C10—C11112.6 (2)
C2—C4—H4A109.5O3—C10—C9103.34 (17)
C2—C4—H4B109.5C12—C10—C9112.1 (2)
H4A—C4—H4B109.5C11—C10—C9114.9 (2)
C2—C4—H4C109.5C10—C11—H11A109.5
H4A—C4—H4C109.5C10—C11—H11B109.5
H4B—C4—H4C109.5H11A—C11—H11B109.5
N2—C5—C6111.7 (2)C10—C11—H11C109.5
N2—C5—H5A109.3H11A—C11—H11C109.5
C6—C5—H5A109.3H11B—C11—H11C109.5
N2—C5—H5B109.3C10—C12—H12A109.5
C6—C5—H5B109.3C10—C12—H12B109.5
H5A—C5—H5B107.9H12A—C12—H12B109.5
F1—C6—F2107.2 (2)C10—C12—H12C109.5
F1—C6—F3107.2 (2)H12A—C12—H12C109.5
F2—C6—F3106.7 (2)H12B—C12—H12C109.5
C2—N1—N2—C30.2 (3)N2—C3—C7—S186.0 (2)
C2—N1—N2—C5178.1 (2)C1—C3—C7—S1−96.3 (3)
C10—O3—N3—C810.9 (2)O1—S1—C7—C3−179.38 (16)
N2—N1—C2—C1−0.1 (3)O2—S1—C7—C3−49.28 (19)
N2—N1—C2—C4−179.6 (2)C8—S1—C7—C367.86 (19)
C3—C1—C2—N10.0 (3)O3—N3—C8—C91.1 (3)
Br1—C1—C2—N1−179.51 (17)O3—N3—C8—S1−177.89 (14)
C3—C1—C2—C4179.4 (2)O1—S1—C8—N3148.46 (19)
Br1—C1—C2—C40.0 (4)O2—S1—C8—N318.4 (2)
N1—N2—C3—C1−0.2 (3)C7—S1—C8—N3−98.6 (2)
C5—N2—C3—C1−177.8 (2)O1—S1—C8—C9−30.4 (2)
N1—N2—C3—C7178.0 (2)O2—S1—C8—C9−160.43 (19)
C5—N2—C3—C70.4 (4)C7—S1—C8—C982.6 (2)
C2—C1—C3—N20.2 (2)N3—C8—C9—C10−11.7 (3)
Br1—C1—C3—N2179.65 (16)S1—C8—C9—C10167.21 (17)
C2—C1—C3—C7−177.9 (2)N3—O3—C10—C12100.6 (2)
Br1—C1—C3—C71.6 (4)N3—O3—C10—C11−139.07 (19)
N1—N2—C5—C6−89.7 (2)N3—O3—C10—C9−17.6 (2)
C3—N2—C5—C687.8 (3)C8—C9—C10—O316.2 (2)
N2—C5—C6—F1176.9 (2)C8—C9—C10—C12−97.8 (2)
N2—C5—C6—F2−63.4 (3)C8—C9—C10—C11131.9 (2)
N2—C5—C6—F356.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7A···F20.992.443.229 (3)137
C5—H5A···O1i0.992.303.131 (3)141
C7—H7B···O2ii0.992.293.271 (3)169

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5125).

References

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  • Hirai, K., Uchida, A. & and Ohno, R. (2002). Herbicide Classes in Development, edited by P. Boger, K. Hirai & K. Wakabyashi, pp. 179–289. Heidelberg: Springer-Verlag.
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  • Sivaprasad, G., Perumal, P. T., Prabavathyb, V. R. & Mathivananb, N. (2006). Bioorg Med Chem Lett 16, 6302–6305. [PubMed]
  • Vicentini, C. B., Guccione, S., Giurato, L., Ciaccio, R., Mares, D. & Forlani, G. (2005). J Agric Food Chem 53, 3848–3855. [PubMed]
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  • Welch, J. T. (1987). Tetrahedron, 43, 3123–3197.

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