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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1774.
Published online 2009 July 4. doi:  10.1107/S1600536809025082
PMCID: PMC2977169

1-[2,6-Dichloro-4-(trifluoro­meth­yl)phen­yl]-5-iodo-4-trifluoro­methyl­sulfinyl-1H-pyrazole-3-carbonitrile

Abstract

In the title compound, C12H2Cl2F6IN3OS, the dihedral angle between the planes of the benzene and pyrazole rings is 77.8 (2)°. In the crystal, a short I(...)N contact of 2.897 (5) Å occurs.

Related literature

For related structures containing phenylpyrazole, see: Shi et al. (2009 [triangle]); Tang, Zhong, Li & Hu (2005 [triangle]). Tang, Zhong, Lin, Hu & Shi (2005 [triangle]).

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Object name is e-65-o1774-scheme1.jpg

Experimental

Crystal data

  • C12H2Cl2F6IN3OS
  • M r = 548.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1774-efi1.jpg
  • a = 9.5879 (3) Å
  • b = 13.7798 (4) Å
  • c = 14.3145 (5) Å
  • β = 107.400 (3)°
  • V = 1804.68 (10) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 18.41 mm−1
  • T = 100 K
  • 0.45 × 0.27 × 0.19 mm

Data collection

  • Oxford Diffraction Gemini (Cu) X-ray Ultra diffractometer
  • Absorption correction: analytical (CrysAlis RED; Oxford Diffraction 2006 [triangle]) T min = 0.016, T max = 0.213
  • 8203 measured reflections
  • 3132 independent reflections
  • 3065 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.111
  • S = 1.13
  • 3132 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.77 e Å−3
  • Δρmin = −1.25 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction 2006 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction 2006 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEX (McArdle, 1995 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025082/bt2972sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025082/bt2972Isup2.hkl

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

Acknowledgments

This project was sponsored by the Key Project of the Chinese Ministry of Education (No. 209092) and the President’s Fund of South China Agricultural University (No. 2008 K038).

supplementary crystallographic information

Comment

The molecular structure of title compound, C12H2Cl2F6IN3OS, is shown in Fig.1. The dihedral angle between the benzene ring and the pyrazole ring is 77.8 (2)°, while the corresponding ones in the two related compounds,C12H4Cl2F6N4S (Tang, Zhong, Li & Hu, 2005) and C22H8Cl4F6N8S2 (Tang, Zhong, Lin, Hu & Shi, 2005), are 83.2 (1)° and 88.2 (1)°, respectively.

Experimental

98% Fipronil (4.4 g, 10 mmol) was resolved in 40 ml chloroform in a 100 ml round bottom flask equipped with magnetic stirrer and a calcium chloride tube. Then iodine (3.6 g,14 mmol) was added into the solution. Half an hour later tert-butyl nitrite(1.43 g) was added into the solution and the mixture was heated under reflux for 2 h. Then it was left at room temperature overnight. The reaction mixture was filtered. Then the filtrate was evaporated in vacuo. The solid residue was purified by chromatography eluting using petroleum/ethyl acetate (4:1) and further recrystallized from toluene/hexane to afford colourless crystals. Yield: 4.70 g (86%).

Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitary radii.

Crystal data

C12H2Cl2F6IN3OSF(000) = 1040
Mr = 548.03Dx = 2.017 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 3132 reflections
a = 9.5879 (3) Åθ = 4.6–67.0°
b = 13.7798 (4) ŵ = 18.41 mm1
c = 14.3145 (5) ÅT = 100 K
β = 107.400 (3)°Prism, colorless
V = 1804.68 (10) Å30.45 × 0.27 × 0.19 mm
Z = 4

Data collection

Oxford Diffraction Gemini (Cu) X-ray Ultra diffractometer3132 independent reflections
Radiation source: fine-focus sealed tube3065 reflections with I > 2σ(I)
mirrorRint = 0.041
ω and π scansθmax = 67.0°, θmin = 4.6°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction 2006)h = −10→11
Tmin = 0.016, Tmax = 0.213k = −16→15
8203 measured reflectionsl = −17→16

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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.13w = 1/[σ2(Fo2) + (0.0636P)2 + 4.9895P] where P = (Fo2 + 2Fc2)/3
3132 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = −1.25 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
I10.32209 (3)0.65606 (2)0.31318 (2)0.02325 (15)
Cl10.49232 (14)0.42087 (8)0.14823 (9)0.0336 (3)
Cl20.37074 (16)0.80256 (8)0.09630 (9)0.0364 (3)
S10.70639 (13)0.70720 (8)0.47083 (8)0.0257 (3)
O10.8422 (4)0.7630 (3)0.4932 (3)0.0360 (8)
N10.5348 (4)0.6307 (3)0.1980 (3)0.0215 (8)
N20.6758 (4)0.6311 (4)0.1956 (3)0.0312 (10)
N31.0327 (6)0.6582 (4)0.3373 (4)0.0474 (15)
C10.1794 (5)0.5669 (3)−0.0465 (3)0.0238 (10)
C20.2659 (5)0.4911 (3)0.0021 (3)0.0230 (9)
H2A0.24480.4273−0.01830.028*
C30.3855 (5)0.5134 (3)0.0823 (3)0.0219 (9)
C40.4171 (5)0.6096 (3)0.1111 (3)0.0217 (9)
C50.3304 (6)0.6833 (4)0.0603 (4)0.0263 (10)
C60.2084 (6)0.6628 (3)−0.0189 (4)0.0279 (11)
H6A0.14800.7124−0.05230.034*
C70.0517 (6)0.5443 (4)−0.1351 (4)0.0304 (11)
C80.5210 (5)0.6523 (3)0.2870 (4)0.0182 (9)
C90.6611 (5)0.6671 (3)0.3484 (4)0.0228 (10)
C100.7517 (6)0.6527 (3)0.2873 (4)0.0276 (11)
C110.9089 (6)0.6571 (4)0.3153 (5)0.0350 (14)
C120.7590 (6)0.5852 (4)0.5261 (4)0.0391 (13)
F10.0028 (4)0.4545 (3)−0.1333 (3)0.0488 (9)
F20.0883 (4)0.5527 (3)−0.2176 (2)0.0439 (8)
F3−0.0603 (4)0.6042 (3)−0.1430 (3)0.0487 (9)
F40.6443 (4)0.5270 (2)0.4989 (3)0.0503 (9)
F50.7988 (5)0.5949 (3)0.6227 (3)0.0585 (11)
F60.8683 (4)0.5472 (3)0.5007 (3)0.0624 (11)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.0165 (2)0.0296 (2)0.0220 (2)−0.00092 (10)0.00320 (13)−0.00227 (10)
Cl10.0314 (6)0.0221 (6)0.0387 (7)0.0056 (5)−0.0026 (5)0.0011 (5)
Cl20.0574 (8)0.0171 (6)0.0285 (6)−0.0045 (5)0.0033 (5)−0.0014 (4)
S10.0264 (6)0.0222 (6)0.0230 (6)−0.0021 (4)−0.0008 (4)−0.0002 (4)
O10.038 (2)0.0290 (19)0.036 (2)−0.0106 (16)0.0032 (16)−0.0038 (16)
N10.0142 (18)0.0247 (19)0.0225 (19)−0.0027 (16)0.0008 (15)−0.0014 (16)
N20.025 (2)0.034 (2)0.035 (2)−0.0073 (17)0.010 (2)−0.0099 (19)
N30.021 (3)0.064 (4)0.058 (3)−0.011 (2)0.013 (2)−0.035 (3)
C10.025 (2)0.024 (2)0.021 (2)−0.0014 (19)0.0050 (19)−0.0004 (19)
C20.024 (2)0.019 (2)0.024 (2)−0.0002 (18)0.0043 (19)−0.0038 (18)
C30.022 (2)0.020 (2)0.023 (2)−0.0009 (18)0.0050 (18)−0.0004 (18)
C40.019 (2)0.023 (2)0.021 (2)−0.0055 (18)0.0039 (18)−0.0053 (18)
C50.040 (3)0.018 (2)0.020 (2)−0.002 (2)0.007 (2)−0.0022 (19)
C60.034 (3)0.022 (2)0.024 (2)0.0029 (19)0.002 (2)0.0020 (18)
C70.025 (2)0.031 (3)0.030 (3)0.003 (2)0.000 (2)−0.004 (2)
C80.010 (2)0.018 (2)0.025 (2)0.0004 (15)0.0038 (18)0.0011 (16)
C90.021 (2)0.017 (2)0.027 (3)−0.0013 (17)0.002 (2)−0.0014 (17)
C100.019 (3)0.027 (3)0.036 (3)−0.0075 (18)0.007 (2)−0.009 (2)
C110.025 (3)0.038 (3)0.043 (3)−0.008 (2)0.012 (2)−0.022 (2)
C120.034 (3)0.029 (3)0.042 (3)−0.002 (2)−0.008 (2)0.009 (2)
F10.047 (2)0.0386 (18)0.0447 (19)−0.0169 (16)−0.0112 (15)−0.0053 (15)
F20.0371 (18)0.069 (2)0.0202 (14)0.0001 (16)−0.0001 (12)−0.0055 (15)
F30.0321 (17)0.055 (2)0.048 (2)0.0130 (16)−0.0052 (15)−0.0163 (16)
F40.056 (2)0.0313 (17)0.053 (2)−0.0147 (16)0.0008 (17)0.0124 (15)
F50.070 (3)0.054 (2)0.0337 (18)−0.0074 (19)−0.0127 (17)0.0158 (16)
F60.047 (2)0.049 (2)0.084 (3)0.0264 (18)0.009 (2)0.021 (2)

Geometric parameters (Å, °)

I1—C82.051 (4)C2—H2A0.9300
Cl1—C31.728 (5)C3—C41.394 (6)
Cl2—C51.731 (5)C4—C51.375 (7)
S1—O11.463 (4)C5—C61.392 (7)
S1—C91.764 (5)C6—H6A0.9300
S1—C121.863 (6)C7—F11.327 (6)
N1—C81.353 (6)C7—F31.332 (6)
N1—N21.363 (6)C7—F21.333 (6)
N1—C41.438 (6)C8—C91.382 (7)
N2—C101.330 (7)C9—C101.419 (7)
N3—C111.134 (8)C10—C111.440 (8)
C1—C21.384 (7)C12—F61.316 (8)
C1—C61.384 (7)C12—F41.322 (7)
C1—C71.508 (6)C12—F51.327 (7)
C2—C31.393 (7)
O1—S1—C9108.7 (2)C5—C6—H6A120.8
O1—S1—C12105.8 (2)F1—C7—F3107.4 (4)
C9—S1—C1295.4 (2)F1—C7—F2106.6 (4)
C8—N1—N2113.6 (4)F3—C7—F2106.9 (4)
C8—N1—C4126.0 (4)F1—C7—C1112.2 (4)
N2—N1—C4120.5 (4)F3—C7—C1112.0 (4)
C10—N2—N1103.3 (4)F2—C7—C1111.4 (4)
C2—C1—C6122.5 (5)N1—C8—C9106.3 (4)
C2—C1—C7118.7 (4)N1—C8—I1122.4 (3)
C6—C1—C7118.7 (5)C9—C8—I1131.3 (4)
C1—C2—C3118.0 (4)C8—C9—C10104.2 (4)
C1—C2—H2A121.0C8—C9—S1125.6 (4)
C3—C2—H2A121.0C10—C9—S1129.9 (4)
C2—C3—C4120.4 (4)N2—C10—C9112.6 (5)
C2—C3—Cl1119.7 (4)N2—C10—C11120.1 (5)
C4—C3—Cl1119.9 (4)C9—C10—C11127.2 (5)
C5—C4—C3120.2 (4)N3—C11—C10178.4 (6)
C5—C4—N1120.1 (4)F6—C12—F4109.8 (5)
C3—C4—N1119.6 (4)F6—C12—F5108.9 (5)
C4—C5—C6120.6 (4)F4—C12—F5108.8 (5)
C4—C5—Cl2119.9 (4)F6—C12—S1112.3 (4)
C6—C5—Cl2119.5 (4)F4—C12—S1109.1 (4)
C1—C6—C5118.3 (5)F5—C12—S1107.9 (4)
C1—C6—H6A120.8
C8—N1—N2—C100.7 (6)C2—C1—C7—F2−94.0 (5)
C4—N1—N2—C10−179.8 (4)C6—C1—C7—F283.8 (6)
C6—C1—C2—C30.7 (7)N2—N1—C8—C9−0.7 (5)
C7—C1—C2—C3178.4 (4)C4—N1—C8—C9179.9 (4)
C1—C2—C3—C4−0.9 (7)N2—N1—C8—I1−179.5 (3)
C1—C2—C3—Cl1177.4 (4)C4—N1—C8—I11.1 (6)
C2—C3—C4—C5−0.2 (7)N1—C8—C9—C100.3 (5)
Cl1—C3—C4—C5−178.5 (4)I1—C8—C9—C10178.9 (3)
C2—C3—C4—N1175.7 (4)N1—C8—C9—S1174.4 (3)
Cl1—C3—C4—N1−2.6 (6)I1—C8—C9—S1−6.9 (6)
C8—N1—C4—C575.7 (6)O1—S1—C9—C8−149.2 (4)
N2—N1—C4—C5−103.6 (5)C12—S1—C9—C8102.1 (4)
C8—N1—C4—C3−100.2 (6)O1—S1—C9—C1023.4 (5)
N2—N1—C4—C380.4 (6)C12—S1—C9—C10−85.3 (5)
C3—C4—C5—C61.6 (7)N1—N2—C10—C9−0.5 (6)
N1—C4—C5—C6−174.3 (5)N1—N2—C10—C11178.0 (5)
C3—C4—C5—Cl2−179.8 (4)C8—C9—C10—N20.2 (6)
N1—C4—C5—Cl24.3 (6)S1—C9—C10—N2−173.6 (4)
C2—C1—C6—C50.7 (8)C8—C9—C10—C11−178.3 (5)
C7—C1—C6—C5−177.1 (5)S1—C9—C10—C117.9 (8)
C4—C5—C6—C1−1.8 (8)O1—S1—C12—F6−50.8 (5)
Cl2—C5—C6—C1179.6 (4)C9—S1—C12—F660.4 (4)
C2—C1—C7—F125.4 (6)O1—S1—C12—F4−172.7 (4)
C6—C1—C7—F1−156.8 (5)C9—S1—C12—F4−61.5 (5)
C2—C1—C7—F3146.3 (5)O1—S1—C12—F569.2 (5)
C6—C1—C7—F3−35.9 (7)C9—S1—C12—F5−179.6 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2972).

References

  • McArdle, P. (1995). J. Appl. Cryst.28, 65.
  • Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shi, A.-E., Hou, Y.-J., Zhang, Y.-M., Hou, G.-F. & Gao, J.-S. (2009). Acta Cryst. E65, o690. [PMC free article] [PubMed]
  • Tang, R.-Y., Zhong, P., Li, S.-Y. & Hu, M.-L. (2005). Acta Cryst. E61, o1564–o1565.
  • Tang, R.-Y., Zhong, P., Lin, Q.-L., Hu, M.-L. & Shi, Q. (2005). Acta Cryst. E61, o4374–o4375.

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