4-Bromo-5-[(5,5-dimethyl-4,5-dihydro-isoxazol-3-yl)sulfonyl-meth-yl]-3-methyl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazole.

In the title compound, C(12)H(15)BrF(3)N(3)O(3)S, which has potential herbicidal activity, the mol-ecule is twisted, as indicated by the C-S-C-C torsion angle of 67.86 (19)° for the atoms linking the ring systems. An intra-molecular C-H⋯F short contact occurs and inter-molecular C-H⋯O inter-actions link the mol-ecules in the crystal.

Related literature

For background to pyrazoles and their pharmacological and pharmaceutical applications, see: Aiello et al. (2000 ▶); Hirai et al. (2002 ▶); Lahm et al. (2007 ▶); Meegalla et al. (2004 ▶); Ohno et al. (2004 ▶); Shiga et al. (2003 ▶); Sivaprasad et al. (2006 ▶); Vicentini et al. (2005 ▶); Waldrep et al. (1990 ▶). 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 ▶).

Experimental

Crystal data

C12H15BrF3N3O3S

M = 418.24

Monoclinic,

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 ▶) 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 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

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

C12H15BrF3N3O3S	F(000) = 840
Mr = 418.24	Dx = 1.730 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5465 reflections
a = 16.127 (3) Å	θ = 1.5–27.5°
b = 5.4356 (11) Å	µ = 2.74 mm−1
c = 19.135 (4) Å	T = 173 K
β = 106.85 (3)°	Slab, colourless
V = 1605.3 (6) Å3	0.16 × 0.15 × 0.05 mm
Z = 4

Rigaku MM007HF + CCD (Saturn724+) diffractometer	3614 independent reflections
Radiation source: Rotating Anode	3353 reflections with I > 2σ(I)
Confocal	Rint = 0.040
Detector resolution: 28.5714 pixels mm-1	θmax = 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 = 0.875	l = −21→24
11131 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0399P)2 + 1.0315P] where P = (Fo2 + 2Fc2)/3
3614 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.50 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.445686 (15)	0.94374 (5)	0.090555 (14)	0.03063 (10)
S1	0.36847 (3)	0.46277 (11)	0.24140 (3)	0.01880 (13)
F1	0.05557 (10)	0.1917 (4)	0.03774 (10)	0.0506 (5)
F2	0.10792 (11)	0.5508 (4)	0.06883 (11)	0.0533 (5)
F3	0.09624 (11)	0.4150 (4)	−0.03880 (9)	0.0446 (5)
O1	0.34862 (11)	0.5488 (4)	0.30560 (9)	0.0302 (4)
O2	0.35701 (10)	0.2071 (3)	0.22232 (9)	0.0278 (4)
O3	0.60544 (10)	0.5023 (3)	0.23928 (9)	0.0247 (4)
N1	0.29249 (12)	0.3877 (4)	−0.01482 (10)	0.0245 (4)
N2	0.27115 (12)	0.4000 (4)	0.04901 (10)	0.0202 (4)
N3	0.52217 (12)	0.4076 (4)	0.22290 (11)	0.0218 (4)
C1	0.36847 (14)	0.6842 (4)	0.05707 (12)	0.0215 (5)
C2	0.35194 (15)	0.5606 (5)	−0.01018 (12)	0.0233 (5)
C3	0.31611 (14)	0.5796 (4)	0.09432 (12)	0.0190 (4)
C4	0.39090 (17)	0.6042 (6)	−0.07062 (14)	0.0352 (6)
H4A	0.3649	0.4916	−0.1110	0.053*
H4B	0.4535	0.5753	−0.0531	0.053*
H4C	0.3800	0.7745	−0.0876	0.053*
C5	0.20495 (14)	0.2363 (5)	0.05891 (12)	0.0235 (5)
H5A	0.2172	0.1966	0.1114	0.028*
H5B	0.2064	0.0809	0.0323	0.028*
C6	0.11590 (16)	0.3492 (5)	0.03153 (14)	0.0306 (6)
C7	0.30517 (14)	0.6434 (5)	0.16676 (12)	0.0203 (4)
H7A	0.2433	0.6247	0.1641	0.024*
H7B	0.3206	0.8188	0.1770	0.024*
C8	0.47706 (14)	0.5475 (4)	0.25141 (12)	0.0180 (4)
C9	0.52301 (14)	0.7679 (5)	0.29165 (13)	0.0242 (5)
H9A	0.5152	0.7824	0.3409	0.029*
H9B	0.5041	0.9221	0.2641	0.029*
C10	0.61659 (14)	0.6997 (4)	0.29502 (13)	0.0221 (5)
C11	0.66758 (17)	0.9027 (5)	0.27253 (17)	0.0347 (6)
H11A	0.7229	0.8370	0.2691	0.052*
H11B	0.6786	1.0347	0.3090	0.052*
H11C	0.6343	0.9682	0.2249	0.052*
C12	0.66479 (18)	0.5845 (5)	0.36726 (15)	0.0359 (6)
H12A	0.7202	0.5188	0.3643	0.054*
H12B	0.6300	0.4508	0.3786	0.054*
H12C	0.6754	0.7093	0.4058	0.054*

	U11	U22	U33	U12	U13	U23
Br1	0.02683 (15)	0.02743 (17)	0.03790 (17)	−0.00740 (9)	0.00979 (11)	0.00368 (10)
S1	0.0184 (3)	0.0222 (3)	0.0175 (3)	−0.00311 (19)	0.0078 (2)	−0.0020 (2)
F1	0.0246 (8)	0.0738 (14)	0.0495 (10)	−0.0205 (8)	0.0044 (7)	0.0103 (9)
F2	0.0288 (9)	0.0612 (13)	0.0659 (13)	0.0097 (8)	0.0074 (8)	−0.0243 (10)
F3	0.0334 (9)	0.0640 (13)	0.0331 (9)	0.0067 (8)	0.0043 (7)	0.0170 (8)
O1	0.0277 (9)	0.0473 (12)	0.0192 (8)	−0.0046 (8)	0.0126 (7)	−0.0057 (8)
O2	0.0285 (9)	0.0204 (9)	0.0328 (9)	−0.0056 (7)	0.0065 (7)	0.0001 (7)
O3	0.0180 (8)	0.0272 (9)	0.0307 (9)	−0.0019 (6)	0.0098 (7)	−0.0084 (7)
N1	0.0237 (10)	0.0334 (12)	0.0174 (9)	0.0014 (8)	0.0076 (8)	−0.0002 (8)
N2	0.0185 (9)	0.0257 (10)	0.0173 (9)	−0.0007 (7)	0.0065 (7)	−0.0004 (8)
N3	0.0187 (9)	0.0221 (10)	0.0251 (10)	−0.0013 (7)	0.0070 (8)	−0.0031 (8)
C1	0.0183 (10)	0.0239 (12)	0.0220 (11)	0.0001 (8)	0.0055 (8)	0.0036 (9)
C2	0.0204 (11)	0.0320 (14)	0.0185 (11)	0.0040 (9)	0.0072 (9)	0.0041 (9)
C3	0.0180 (10)	0.0201 (11)	0.0187 (10)	0.0014 (8)	0.0047 (8)	0.0009 (8)
C4	0.0289 (13)	0.0569 (19)	0.0236 (13)	−0.0009 (12)	0.0133 (10)	0.0072 (12)
C5	0.0231 (11)	0.0254 (12)	0.0219 (11)	−0.0066 (9)	0.0066 (9)	0.0003 (9)
C6	0.0242 (12)	0.0373 (15)	0.0295 (13)	−0.0075 (11)	0.0067 (10)	0.0009 (11)
C7	0.0190 (10)	0.0207 (12)	0.0217 (11)	0.0008 (8)	0.0067 (8)	−0.0028 (9)
C8	0.0181 (10)	0.0189 (11)	0.0170 (10)	−0.0008 (8)	0.0049 (8)	−0.0015 (8)
C9	0.0199 (11)	0.0235 (12)	0.0298 (12)	−0.0028 (9)	0.0083 (9)	−0.0064 (10)
C10	0.0208 (11)	0.0183 (12)	0.0261 (12)	−0.0002 (8)	0.0053 (9)	−0.0037 (9)
C11	0.0256 (13)	0.0256 (14)	0.0546 (18)	−0.0013 (10)	0.0141 (12)	0.0048 (12)
C12	0.0350 (14)	0.0383 (16)	0.0277 (14)	0.0000 (11)	−0.0014 (11)	0.0005 (11)

Br1—C1	1.868 (2)	C4—H4B	0.9800
S1—O1	1.4346 (17)	C4—H4C	0.9800
S1—O2	1.4351 (18)	C5—C6	1.509 (3)
S1—C8	1.767 (2)	C5—H5A	0.9900
S1—C7	1.789 (2)	C5—H5B	0.9900
F1—C6	1.327 (3)	C7—H7A	0.9900
F2—C6	1.334 (3)	C7—H7B	0.9900
F3—C6	1.339 (3)	C8—C9	1.499 (3)
O3—N3	1.387 (2)	C9—C10	1.537 (3)
O3—C10	1.487 (3)	C9—H9A	0.9900
N1—C2	1.327 (3)	C9—H9B	0.9900
N1—N2	1.363 (3)	C10—C12	1.511 (3)
N2—C3	1.366 (3)	C10—C11	1.512 (3)
N2—C5	1.444 (3)	C11—H11A	0.9800
N3—C8	1.279 (3)	C11—H11B	0.9800
C1—C3	1.376 (3)	C11—H11C	0.9800
C1—C2	1.407 (3)	C12—H12A	0.9800
C2—C4	1.487 (3)	C12—H12B	0.9800
C3—C7	1.488 (3)	C12—H12C	0.9800
C4—H4A	0.9800
O1—S1—O2	119.28 (11)	F1—C6—C5	110.8 (2)
O1—S1—C8	106.41 (11)	F2—C6—C5	112.2 (2)
O2—S1—C8	109.30 (10)	F3—C6—C5	112.5 (2)
O1—S1—C7	106.71 (11)	C3—C7—S1	114.91 (16)
O2—S1—C7	109.08 (11)	C3—C7—H7A	108.5
C8—S1—C7	105.17 (11)	S1—C7—H7A	108.5
N3—O3—C10	109.76 (16)	C3—C7—H7B	108.5
C2—N1—N2	105.69 (19)	S1—C7—H7B	108.5
N1—N2—C3	112.23 (19)	H7A—C7—H7B	107.5
N1—N2—C5	118.40 (19)	N3—C8—C9	115.9 (2)
C3—N2—C5	129.33 (19)	N3—C8—S1	117.85 (17)
C8—N3—O3	108.43 (18)	C9—C8—S1	126.24 (17)
C3—C1—C2	107.1 (2)	C8—C9—C10	99.33 (18)
C3—C1—Br1	125.64 (18)	C8—C9—H9A	111.9
C2—C1—Br1	127.23 (18)	C10—C9—H9A	111.9
N1—C2—C1	109.9 (2)	C8—C9—H9B	111.9
N1—C2—C4	121.4 (2)	C10—C9—H9B	111.9
C1—C2—C4	128.7 (2)	H9A—C9—H9B	109.6
N2—C3—C1	105.0 (2)	O3—C10—C12	106.28 (19)
N2—C3—C7	125.0 (2)	O3—C10—C11	106.6 (2)
C1—C3—C7	130.0 (2)	C12—C10—C11	112.6 (2)
C2—C4—H4A	109.5	O3—C10—C9	103.34 (17)
C2—C4—H4B	109.5	C12—C10—C9	112.1 (2)
H4A—C4—H4B	109.5	C11—C10—C9	114.9 (2)
C2—C4—H4C	109.5	C10—C11—H11A	109.5
H4A—C4—H4C	109.5	C10—C11—H11B	109.5
H4B—C4—H4C	109.5	H11A—C11—H11B	109.5
N2—C5—C6	111.7 (2)	C10—C11—H11C	109.5
N2—C5—H5A	109.3	H11A—C11—H11C	109.5
C6—C5—H5A	109.3	H11B—C11—H11C	109.5
N2—C5—H5B	109.3	C10—C12—H12A	109.5
C6—C5—H5B	109.3	C10—C12—H12B	109.5
H5A—C5—H5B	107.9	H12A—C12—H12B	109.5
F1—C6—F2	107.2 (2)	C10—C12—H12C	109.5
F1—C6—F3	107.2 (2)	H12A—C12—H12C	109.5
F2—C6—F3	106.7 (2)	H12B—C12—H12C	109.5
C2—N1—N2—C3	0.2 (3)	N2—C3—C7—S1	86.0 (2)
C2—N1—N2—C5	178.1 (2)	C1—C3—C7—S1	−96.3 (3)
C10—O3—N3—C8	10.9 (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—C3	67.86 (19)
C3—C1—C2—N1	0.0 (3)	O3—N3—C8—C9	1.1 (3)
Br1—C1—C2—N1	−179.51 (17)	O3—N3—C8—S1	−177.89 (14)
C3—C1—C2—C4	179.4 (2)	O1—S1—C8—N3	148.46 (19)
Br1—C1—C2—C4	0.0 (4)	O2—S1—C8—N3	18.4 (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—C7	178.0 (2)	O2—S1—C8—C9	−160.43 (19)
C5—N2—C3—C7	0.4 (4)	C7—S1—C8—C9	82.6 (2)
C2—C1—C3—N2	0.2 (2)	N3—C8—C9—C10	−11.7 (3)
Br1—C1—C3—N2	179.65 (16)	S1—C8—C9—C10	167.21 (17)
C2—C1—C3—C7	−177.9 (2)	N3—O3—C10—C12	100.6 (2)
Br1—C1—C3—C7	1.6 (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—C6	87.8 (3)	C8—C9—C10—O3	16.2 (2)
N2—C5—C6—F1	176.9 (2)	C8—C9—C10—C12	−97.8 (2)
N2—C5—C6—F2	−63.4 (3)	C8—C9—C10—C11	131.9 (2)
N2—C5—C6—F3	56.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···F2	0.99	2.44	3.229 (3)	137
C5—H5A···O1i	0.99	2.30	3.131 (3)	141
C7—H7B···O2ii	0.99	2.29	3.271 (3)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯F2	0.99	2.44	3.229 (3)	137
C5—H5A⋯O1i	0.99	2.30	3.131 (3)	141
C7—H7B⋯O2ii	0.99	2.29	3.271 (3)	169

Symmetry codes: (i) ; (ii) .