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

Jiang, D.-X.; Xu, H.-H.

doi:10.1107/S1600536809025082

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1774

doi:10.1107/S1600536809025082

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

Ding-Xin Jiang ^a and Han-Hong Xu ^a ^*

^aKey Laboratory of Natural Pesticides and Chemical Biology of the Ministry of, Education, South China Agricultural University, Guangzhou 510642, People's Republic of China
^*Correspondence e-mail: hhxu@scau.edu.cn

(Received 15 June 2009; accepted 29 June 2009; online 4 July 2009)

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 ); Tang, Zhong, Li & Hu (2005 ). Tang, Zhong, Lin, Hu & Shi (2005 ).

Experimental

Crystal data

C₁₂H₂Cl₂F₆IN₃OS
M_r = 548.03
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) 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[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.13
3132 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −1.25 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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,C₁₂H₄C_l2F₆N₄S (Tang, Zhong, Li & Hu, 2005) and C₂₂H₈C_l4F₆N₈S₂ (Tang, Zhong, Lin, Hu & Shi, 2005), are 83.2 (1)° and 88.2 (1)°, respectively.

Related literature top

For related structures containing diphenic acid, see: Shi et al. (2009); Tang, Zhong, Li & Hu (2005). Tang, Zhong, Lin, Hu & Shi (2005).

Experimental top

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%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction 2006); cell refinement: CrysAlis RED (Oxford Diffraction 2006); data reduction: CrysAlis RED (Oxford Diffraction 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97/2 (Sheldrick, 2008).

Figures top

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.

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

Crystal data top

C₁₂H₂Cl₂F₆IN₃OS	F(000) = 1040
M_r = 548.03	D_x = 2.017 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3132 reflections
a = 9.5879 (3) Å	θ = 4.6–67.0°
b = 13.7798 (4) Å	µ = 18.41 mm⁻¹
c = 14.3145 (5) Å	T = 100 K
β = 107.400 (3)°	Prism, colorless
V = 1804.68 (10) Å³	0.45 × 0.27 × 0.19 mm
Z = 4

Data collection top

Oxford Diffraction Gemini (Cu) X-ray Ultra diffractometer	3132 independent reflections
Radiation source: fine-focus sealed tube	3065 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.041
ω and π scans	θ_max = 67.0°, θ_min = 4.6°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction 2006)	h = −10→11
T_min = 0.016, T_max = 0.213	k = −16→15
8203 measured reflections	l = −17→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0636P)² + 4.9895P] where P = (F_o² + 2F_c²)/3
3132 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −1.25 e Å⁻³

Crystal data top

C₁₂H₂Cl₂F₆IN₃OS	V = 1804.68 (10) Å³
M_r = 548.03	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.5879 (3) Å	µ = 18.41 mm⁻¹
b = 13.7798 (4) Å	T = 100 K
c = 14.3145 (5) Å	0.45 × 0.27 × 0.19 mm
β = 107.400 (3)°

Data collection top

Oxford Diffraction Gemini (Cu) X-ray Ultra diffractometer	3132 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction 2006)	3065 reflections with I > 2σ(I)
T_min = 0.016, T_max = 0.213	R_int = 0.041
8203 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.13	Δρ_max = 0.77 e Å⁻³
3132 reflections	Δρ_min = −1.25 e Å⁻³
235 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

	x	y	z	U_iso*/U_eq
I1	0.32209 (3)	0.65606 (2)	0.31318 (2)	0.02325 (15)
Cl1	0.49232 (14)	0.42087 (8)	0.14823 (9)	0.0336 (3)
Cl2	0.37074 (16)	0.80256 (8)	0.09630 (9)	0.0364 (3)
S1	0.70639 (13)	0.70720 (8)	0.47083 (8)	0.0257 (3)
O1	0.8422 (4)	0.7630 (3)	0.4932 (3)	0.0360 (8)
N1	0.5348 (4)	0.6307 (3)	0.1980 (3)	0.0215 (8)
N2	0.6758 (4)	0.6311 (4)	0.1956 (3)	0.0312 (10)
N3	1.0327 (6)	0.6582 (4)	0.3373 (4)	0.0474 (15)
C1	0.1794 (5)	0.5669 (3)	−0.0465 (3)	0.0238 (10)
C2	0.2659 (5)	0.4911 (3)	0.0021 (3)	0.0230 (9)
H2A	0.2448	0.4273	−0.0183	0.028*
C3	0.3855 (5)	0.5134 (3)	0.0823 (3)	0.0219 (9)
C4	0.4171 (5)	0.6096 (3)	0.1111 (3)	0.0217 (9)
C5	0.3304 (6)	0.6833 (4)	0.0603 (4)	0.0263 (10)
C6	0.2084 (6)	0.6628 (3)	−0.0189 (4)	0.0279 (11)
H6A	0.1480	0.7124	−0.0523	0.034*
C7	0.0517 (6)	0.5443 (4)	−0.1351 (4)	0.0304 (11)
C8	0.5210 (5)	0.6523 (3)	0.2870 (4)	0.0182 (9)
C9	0.6611 (5)	0.6671 (3)	0.3484 (4)	0.0228 (10)
C10	0.7517 (6)	0.6527 (3)	0.2873 (4)	0.0276 (11)
C11	0.9089 (6)	0.6571 (4)	0.3153 (5)	0.0350 (14)
C12	0.7590 (6)	0.5852 (4)	0.5261 (4)	0.0391 (13)
F1	0.0028 (4)	0.4545 (3)	−0.1333 (3)	0.0488 (9)
F2	0.0883 (4)	0.5527 (3)	−0.2176 (2)	0.0439 (8)
F3	−0.0603 (4)	0.6042 (3)	−0.1430 (3)	0.0487 (9)
F4	0.6443 (4)	0.5270 (2)	0.4989 (3)	0.0503 (9)
F5	0.7988 (5)	0.5949 (3)	0.6227 (3)	0.0585 (11)
F6	0.8683 (4)	0.5472 (3)	0.5007 (3)	0.0624 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0165 (2)	0.0296 (2)	0.0220 (2)	−0.00092 (10)	0.00320 (13)	−0.00227 (10)
Cl1	0.0314 (6)	0.0221 (6)	0.0387 (7)	0.0056 (5)	−0.0026 (5)	0.0011 (5)
Cl2	0.0574 (8)	0.0171 (6)	0.0285 (6)	−0.0045 (5)	0.0033 (5)	−0.0014 (4)
S1	0.0264 (6)	0.0222 (6)	0.0230 (6)	−0.0021 (4)	−0.0008 (4)	−0.0002 (4)
O1	0.038 (2)	0.0290 (19)	0.036 (2)	−0.0106 (16)	0.0032 (16)	−0.0038 (16)
N1	0.0142 (18)	0.0247 (19)	0.0225 (19)	−0.0027 (16)	0.0008 (15)	−0.0014 (16)
N2	0.025 (2)	0.034 (2)	0.035 (2)	−0.0073 (17)	0.010 (2)	−0.0099 (19)
N3	0.021 (3)	0.064 (4)	0.058 (3)	−0.011 (2)	0.013 (2)	−0.035 (3)
C1	0.025 (2)	0.024 (2)	0.021 (2)	−0.0014 (19)	0.0050 (19)	−0.0004 (19)
C2	0.024 (2)	0.019 (2)	0.024 (2)	−0.0002 (18)	0.0043 (19)	−0.0038 (18)
C3	0.022 (2)	0.020 (2)	0.023 (2)	−0.0009 (18)	0.0050 (18)	−0.0004 (18)
C4	0.019 (2)	0.023 (2)	0.021 (2)	−0.0055 (18)	0.0039 (18)	−0.0053 (18)
C5	0.040 (3)	0.018 (2)	0.020 (2)	−0.002 (2)	0.007 (2)	−0.0022 (19)
C6	0.034 (3)	0.022 (2)	0.024 (2)	0.0029 (19)	0.002 (2)	0.0020 (18)
C7	0.025 (2)	0.031 (3)	0.030 (3)	0.003 (2)	0.000 (2)	−0.004 (2)
C8	0.010 (2)	0.018 (2)	0.025 (2)	0.0004 (15)	0.0038 (18)	0.0011 (16)
C9	0.021 (2)	0.017 (2)	0.027 (3)	−0.0013 (17)	0.002 (2)	−0.0014 (17)
C10	0.019 (3)	0.027 (3)	0.036 (3)	−0.0075 (18)	0.007 (2)	−0.009 (2)
C11	0.025 (3)	0.038 (3)	0.043 (3)	−0.008 (2)	0.012 (2)	−0.022 (2)
C12	0.034 (3)	0.029 (3)	0.042 (3)	−0.002 (2)	−0.008 (2)	0.009 (2)
F1	0.047 (2)	0.0386 (18)	0.0447 (19)	−0.0169 (16)	−0.0112 (15)	−0.0053 (15)
F2	0.0371 (18)	0.069 (2)	0.0202 (14)	0.0001 (16)	−0.0001 (12)	−0.0055 (15)
F3	0.0321 (17)	0.055 (2)	0.048 (2)	0.0130 (16)	−0.0052 (15)	−0.0163 (16)
F4	0.056 (2)	0.0313 (17)	0.053 (2)	−0.0147 (16)	0.0008 (17)	0.0124 (15)
F5	0.070 (3)	0.054 (2)	0.0337 (18)	−0.0074 (19)	−0.0127 (17)	0.0158 (16)
F6	0.047 (2)	0.049 (2)	0.084 (3)	0.0264 (18)	0.009 (2)	0.021 (2)

Geometric parameters (Å, º) top

I1—C8	2.051 (4)	C2—H2A	0.9300
Cl1—C3	1.728 (5)	C3—C4	1.394 (6)
Cl2—C5	1.731 (5)	C4—C5	1.375 (7)
S1—O1	1.463 (4)	C5—C6	1.392 (7)
S1—C9	1.764 (5)	C6—H6A	0.9300
S1—C12	1.863 (6)	C7—F1	1.327 (6)
N1—C8	1.353 (6)	C7—F3	1.332 (6)
N1—N2	1.363 (6)	C7—F2	1.333 (6)
N1—C4	1.438 (6)	C8—C9	1.382 (7)
N2—C10	1.330 (7)	C9—C10	1.419 (7)
N3—C11	1.134 (8)	C10—C11	1.440 (8)
C1—C2	1.384 (7)	C12—F6	1.316 (8)
C1—C6	1.384 (7)	C12—F4	1.322 (7)
C1—C7	1.508 (6)	C12—F5	1.327 (7)
C2—C3	1.393 (7)

O1—S1—C9	108.7 (2)	C5—C6—H6A	120.8
O1—S1—C12	105.8 (2)	F1—C7—F3	107.4 (4)
C9—S1—C12	95.4 (2)	F1—C7—F2	106.6 (4)
C8—N1—N2	113.6 (4)	F3—C7—F2	106.9 (4)
C8—N1—C4	126.0 (4)	F1—C7—C1	112.2 (4)
N2—N1—C4	120.5 (4)	F3—C7—C1	112.0 (4)
C10—N2—N1	103.3 (4)	F2—C7—C1	111.4 (4)
C2—C1—C6	122.5 (5)	N1—C8—C9	106.3 (4)
C2—C1—C7	118.7 (4)	N1—C8—I1	122.4 (3)
C6—C1—C7	118.7 (5)	C9—C8—I1	131.3 (4)
C1—C2—C3	118.0 (4)	C8—C9—C10	104.2 (4)
C1—C2—H2A	121.0	C8—C9—S1	125.6 (4)
C3—C2—H2A	121.0	C10—C9—S1	129.9 (4)
C2—C3—C4	120.4 (4)	N2—C10—C9	112.6 (5)
C2—C3—Cl1	119.7 (4)	N2—C10—C11	120.1 (5)
C4—C3—Cl1	119.9 (4)	C9—C10—C11	127.2 (5)
C5—C4—C3	120.2 (4)	N3—C11—C10	178.4 (6)
C5—C4—N1	120.1 (4)	F6—C12—F4	109.8 (5)
C3—C4—N1	119.6 (4)	F6—C12—F5	108.9 (5)
C4—C5—C6	120.6 (4)	F4—C12—F5	108.8 (5)
C4—C5—Cl2	119.9 (4)	F6—C12—S1	112.3 (4)
C6—C5—Cl2	119.5 (4)	F4—C12—S1	109.1 (4)
C1—C6—C5	118.3 (5)	F5—C12—S1	107.9 (4)
C1—C6—H6A	120.8

C8—N1—N2—C10	0.7 (6)	C2—C1—C7—F2	−94.0 (5)
C4—N1—N2—C10	−179.8 (4)	C6—C1—C7—F2	83.8 (6)
C6—C1—C2—C3	0.7 (7)	N2—N1—C8—C9	−0.7 (5)
C7—C1—C2—C3	178.4 (4)	C4—N1—C8—C9	179.9 (4)
C1—C2—C3—C4	−0.9 (7)	N2—N1—C8—I1	−179.5 (3)
C1—C2—C3—Cl1	177.4 (4)	C4—N1—C8—I1	1.1 (6)
C2—C3—C4—C5	−0.2 (7)	N1—C8—C9—C10	0.3 (5)
Cl1—C3—C4—C5	−178.5 (4)	I1—C8—C9—C10	178.9 (3)
C2—C3—C4—N1	175.7 (4)	N1—C8—C9—S1	174.4 (3)
Cl1—C3—C4—N1	−2.6 (6)	I1—C8—C9—S1	−6.9 (6)
C8—N1—C4—C5	75.7 (6)	O1—S1—C9—C8	−149.2 (4)
N2—N1—C4—C5	−103.6 (5)	C12—S1—C9—C8	102.1 (4)
C8—N1—C4—C3	−100.2 (6)	O1—S1—C9—C10	23.4 (5)
N2—N1—C4—C3	80.4 (6)	C12—S1—C9—C10	−85.3 (5)
C3—C4—C5—C6	1.6 (7)	N1—N2—C10—C9	−0.5 (6)
N1—C4—C5—C6	−174.3 (5)	N1—N2—C10—C11	178.0 (5)
C3—C4—C5—Cl2	−179.8 (4)	C8—C9—C10—N2	0.2 (6)
N1—C4—C5—Cl2	4.3 (6)	S1—C9—C10—N2	−173.6 (4)
C2—C1—C6—C5	0.7 (8)	C8—C9—C10—C11	−178.3 (5)
C7—C1—C6—C5	−177.1 (5)	S1—C9—C10—C11	7.9 (8)
C4—C5—C6—C1	−1.8 (8)	O1—S1—C12—F6	−50.8 (5)
Cl2—C5—C6—C1	179.6 (4)	C9—S1—C12—F6	60.4 (4)
C2—C1—C7—F1	25.4 (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—F3	146.3 (5)	O1—S1—C12—F5	69.2 (5)
C6—C1—C7—F3	−35.9 (7)	C9—S1—C12—F5	−179.6 (4)

Experimental details

Crystal data
Chemical formula	C₁₂H₂Cl₂F₆IN₃OS
M_r	548.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.5879 (3), 13.7798 (4), 14.3145 (5)
β (°)	107.400 (3)
V (Å³)	1804.68 (10)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	18.41
Crystal size (mm)	0.45 × 0.27 × 0.19

Data collection
Diffractometer	Oxford Diffraction Gemini (Cu) X-ray Ultra diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction 2006)
T_min, T_max	0.016, 0.213
No. of measured, independent and observed [I > 2σ(I)] reflections	8203, 3132, 3065
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.13
No. of reflections	3132
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −1.25

Computer programs: CrysAlis CCD (Oxford Diffraction 2006), CrysAlis RED (Oxford Diffraction 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEX (McArdle, 1995), SHELXL97/2 (Sheldrick, 2008).

Acknowledgements

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).

References

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