4-[(2,4-Difluoro-phen-yl)hydrazinyl-idene]-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title compound, C(11)H(9)F(2)N(5)OS, the pyrazole ring forms a dihedral angle of 16.42 (6)° with the benzene ring. Intra-molecular N-H⋯O hydrogen bonds generate two S(6) ring motifs. In the crystal, an R(2) (2)(8) ring motif is formed by a pair of inter-molecular N-H⋯S hydrogen bonds. Inter-molecular C-H⋯F hydrogen bonds further link the mol-ecules into a three-dimensional network.

Related literature

For the biological activity of pyrazole derivatives, see: Isloor et al. (2009 ▶); Rai et al. (2008 ▶); Bradbury & Pucci (2008 ▶); Girisha et al. (2010 ▶). For a related structure, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986) ▶.

Experimental

Crystal data

C11H9F2N5OS

M = 297.29

Triclinic,

a = 7.9003 (1) Å

b = 8.2400 (1) Å

c = 10.1378 (1) Å

α = 103.409 (1)°

β = 99.864 (1)°

γ = 99.372 (1)°

V = 618.18 (1) Å3

Z = 2

Mo Kα radiation

μ = 0.29 mm−1

T = 100 K

0.41 × 0.23 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.890, T max = 0.977

15661 measured reflections

4211 independent reflections

3546 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.091

S = 1.06

4211 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811044576/is2796sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044576/is2796Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811044576/is2796Isup3.cml

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

C11H9F2N5OS	Z = 2
Mr = 297.29	F(000) = 304
Triclinic, P1	Dx = 1.597 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9003 (1) Å	Cell parameters from 7383 reflections
b = 8.2400 (1) Å	θ = 2.6–31.9°
c = 10.1378 (1) Å	µ = 0.29 mm−1
α = 103.409 (1)°	T = 100 K
β = 99.864 (1)°	Block, green
γ = 99.372 (1)°	0.41 × 0.23 × 0.08 mm
V = 618.18 (1) Å3

Bruker SMART APEXII CCD area-detector diffractometer	4211 independent reflections
Radiation source: fine-focus sealed tube	3546 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 31.9°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.890, Tmax = 0.977	k = −12→12
15661 measured reflections	l = −15→15

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0469P)2 + 0.1483P] where P = (Fo2 + 2Fc2)/3
4211 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.21061 (4)	0.24608 (3)	0.56219 (3)	0.01893 (8)
F1	−0.53111 (10)	0.91062 (10)	−0.26133 (8)	0.02844 (17)
F2	−0.43017 (9)	0.41257 (8)	−0.13817 (7)	0.02208 (15)
O1	−0.14398 (10)	0.30354 (10)	0.16468 (8)	0.01952 (16)
N1	−0.15277 (12)	0.58736 (12)	0.06501 (10)	0.01746 (17)
N2	−0.00803 (12)	0.66676 (12)	0.15852 (9)	0.01665 (17)
N3	0.08671 (12)	0.38926 (11)	0.36455 (9)	0.01611 (17)
N4	0.22017 (12)	0.53670 (11)	0.43282 (10)	0.01660 (17)
N5	−0.06153 (13)	0.11880 (12)	0.34770 (11)	0.02077 (19)
C1	−0.19357 (15)	0.85108 (14)	0.00178 (12)	0.0202 (2)
H1A	−0.0949	0.9165	0.0722	0.024*
C2	−0.29073 (16)	0.93080 (15)	−0.08133 (13)	0.0229 (2)
H2A	−0.2603	1.0507	−0.0681	0.027*
C3	−0.43254 (15)	0.83195 (15)	−0.18365 (12)	0.0208 (2)
C4	−0.48169 (14)	0.65643 (14)	−0.21030 (12)	0.0190 (2)
H4A	−0.5768	0.5907	−0.2839	0.023*
C5	−0.38454 (14)	0.58275 (13)	−0.12371 (11)	0.01665 (19)
C6	−0.24060 (14)	0.67551 (13)	−0.01797 (11)	0.01630 (19)
C7	−0.01793 (13)	0.40835 (13)	0.24639 (11)	0.01574 (19)
C8	0.05592 (13)	0.58088 (13)	0.24210 (11)	0.01541 (18)
C9	0.20256 (14)	0.64684 (13)	0.36007 (11)	0.01583 (19)
C10	0.32130 (15)	0.81794 (13)	0.39924 (12)	0.0200 (2)
H10A	0.4110	0.8292	0.4825	0.030*
H10B	0.2529	0.9064	0.4184	0.030*
H10C	0.3783	0.8311	0.3227	0.030*
C11	0.07145 (14)	0.24765 (13)	0.41963 (11)	0.01608 (19)
H1N1	−0.198 (2)	0.482 (2)	0.0569 (18)	0.036 (5)*
H1N5	−0.078 (2)	0.032 (2)	0.3780 (19)	0.036 (4)*
H2N5	−0.138 (2)	0.126 (2)	0.2763 (18)	0.030 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.01932 (13)	0.01622 (12)	0.01939 (14)	0.00185 (9)	−0.00104 (10)	0.00627 (10)
F1	0.0254 (4)	0.0287 (4)	0.0295 (4)	0.0030 (3)	−0.0064 (3)	0.0154 (3)
F2	0.0226 (3)	0.0156 (3)	0.0241 (3)	−0.0004 (2)	0.0008 (3)	0.0039 (3)
O1	0.0175 (4)	0.0184 (4)	0.0183 (4)	−0.0008 (3)	−0.0013 (3)	0.0032 (3)
N1	0.0172 (4)	0.0165 (4)	0.0164 (4)	0.0018 (3)	−0.0009 (3)	0.0044 (3)
N2	0.0170 (4)	0.0175 (4)	0.0143 (4)	0.0034 (3)	0.0018 (3)	0.0032 (3)
N3	0.0164 (4)	0.0135 (4)	0.0161 (4)	0.0005 (3)	−0.0002 (3)	0.0041 (3)
N4	0.0164 (4)	0.0134 (4)	0.0170 (4)	0.0000 (3)	0.0003 (3)	0.0027 (3)
N5	0.0211 (5)	0.0163 (4)	0.0216 (5)	−0.0015 (3)	−0.0015 (4)	0.0068 (4)
C1	0.0194 (5)	0.0186 (5)	0.0185 (5)	0.0011 (4)	−0.0028 (4)	0.0038 (4)
C2	0.0238 (5)	0.0183 (5)	0.0236 (6)	0.0020 (4)	−0.0022 (4)	0.0067 (4)
C3	0.0195 (5)	0.0231 (5)	0.0193 (5)	0.0038 (4)	−0.0010 (4)	0.0089 (4)
C4	0.0159 (5)	0.0220 (5)	0.0164 (5)	0.0005 (4)	0.0002 (4)	0.0046 (4)
C5	0.0166 (5)	0.0160 (4)	0.0157 (5)	0.0009 (4)	0.0030 (4)	0.0031 (4)
C6	0.0165 (4)	0.0176 (4)	0.0146 (4)	0.0036 (4)	0.0023 (4)	0.0046 (4)
C7	0.0152 (4)	0.0163 (4)	0.0147 (4)	0.0028 (3)	0.0022 (4)	0.0033 (4)
C8	0.0156 (4)	0.0146 (4)	0.0146 (4)	0.0018 (3)	0.0018 (4)	0.0030 (4)
C9	0.0164 (4)	0.0146 (4)	0.0152 (4)	0.0025 (3)	0.0022 (4)	0.0030 (4)
C10	0.0219 (5)	0.0148 (4)	0.0197 (5)	−0.0006 (4)	0.0005 (4)	0.0037 (4)
C11	0.0164 (4)	0.0143 (4)	0.0170 (5)	0.0030 (3)	0.0029 (4)	0.0041 (4)

S1—C11	1.6633 (11)	C1—C2	1.3893 (15)
F1—C3	1.3557 (12)	C1—C6	1.3914 (15)
F2—C5	1.3564 (12)	C1—H1A	0.9500
O1—C7	1.2366 (13)	C2—C3	1.3810 (16)
N1—N2	1.3159 (13)	C2—H2A	0.9500
N1—C6	1.4016 (13)	C3—C4	1.3840 (16)
N1—H1N1	0.866 (17)	C4—C5	1.3772 (15)
N2—C8	1.3122 (13)	C4—H4A	0.9500
N3—C7	1.3905 (13)	C5—C6	1.3949 (15)
N3—C11	1.4026 (13)	C7—C8	1.4597 (14)
N3—N4	1.4176 (12)	C8—C9	1.4445 (14)
N4—C9	1.3051 (13)	C9—C10	1.4858 (14)
N5—C11	1.3334 (14)	C10—H10A	0.9800
N5—H1N5	0.840 (18)	C10—H10B	0.9800
N5—H2N5	0.878 (17)	C10—H10C	0.9800
N2—N1—C6	120.34 (9)	F2—C5—C6	117.21 (9)
N2—N1—H1N1	120.6 (12)	C4—C5—C6	123.13 (10)
C6—N1—H1N1	119.0 (12)	C1—C6—C5	118.51 (10)
C8—N2—N1	116.66 (9)	C1—C6—N1	123.27 (10)
C7—N3—C11	127.86 (9)	C5—C6—N1	118.20 (9)
C7—N3—N4	112.25 (8)	O1—C7—N3	127.95 (10)
C11—N3—N4	119.89 (9)	O1—C7—C8	128.37 (10)
C9—N4—N3	106.61 (8)	N3—C7—C8	103.68 (9)
C11—N5—H1N5	117.8 (12)	N2—C8—C9	126.25 (9)
C11—N5—H2N5	122.4 (11)	N2—C8—C7	127.47 (10)
H1N5—N5—H2N5	119.5 (16)	C9—C8—C7	105.88 (9)
C2—C1—C6	120.11 (10)	N4—C9—C8	111.56 (9)
C2—C1—H1A	119.9	N4—C9—C10	122.26 (10)
C6—C1—H1A	119.9	C8—C9—C10	126.18 (9)
C3—C2—C1	118.57 (10)	C9—C10—H10A	109.5
C3—C2—H2A	120.7	C9—C10—H10B	109.5
C1—C2—H2A	120.7	H10A—C10—H10B	109.5
F1—C3—C2	118.52 (10)	C9—C10—H10C	109.5
F1—C3—C4	117.86 (10)	H10A—C10—H10C	109.5
C2—C3—C4	123.62 (10)	H10B—C10—H10C	109.5
C5—C4—C3	116.00 (10)	N5—C11—N3	114.10 (9)
C5—C4—H4A	122.0	N5—C11—S1	124.50 (8)
C3—C4—H4A	122.0	N3—C11—S1	121.40 (8)
F2—C5—C4	119.65 (10)
C6—N1—N2—C8	172.87 (9)	N4—N3—C7—O1	179.75 (10)
C7—N3—N4—C9	−0.44 (12)	C11—N3—C7—C8	178.66 (10)
C11—N3—N4—C9	−179.57 (9)	N4—N3—C7—C8	−0.38 (11)
C6—C1—C2—C3	−0.58 (18)	N1—N2—C8—C9	−173.72 (10)
C1—C2—C3—F1	177.63 (10)	N1—N2—C8—C7	−2.03 (16)
C1—C2—C3—C4	−1.39 (19)	O1—C7—C8—N2	7.81 (18)
F1—C3—C4—C5	−176.26 (10)	N3—C7—C8—N2	−172.05 (10)
C2—C3—C4—C5	2.77 (17)	O1—C7—C8—C9	−179.15 (10)
C3—C4—C5—F2	176.48 (10)	N3—C7—C8—C9	0.98 (11)
C3—C4—C5—C6	−2.30 (16)	N3—N4—C9—C8	1.11 (12)
C2—C1—C6—C5	1.00 (17)	N3—N4—C9—C10	−179.47 (9)
C2—C1—C6—N1	−177.62 (10)	N2—C8—C9—N4	171.79 (10)
F2—C5—C6—C1	−178.30 (10)	C7—C8—C9—N4	−1.35 (12)
C4—C5—C6—C1	0.50 (16)	N2—C8—C9—C10	−7.61 (17)
F2—C5—C6—N1	0.39 (14)	C7—C8—C9—C10	179.24 (10)
C4—C5—C6—N1	179.20 (10)	C7—N3—C11—N5	−0.44 (16)
N2—N1—C6—C1	−6.89 (16)	N4—N3—C11—N5	178.53 (9)
N2—N1—C6—C5	174.49 (9)	C7—N3—C11—S1	179.35 (8)
C11—N3—C7—O1	−1.21 (18)	N4—N3—C11—S1	−1.67 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.863 (17)	2.080 (17)	2.7605 (13)	135.2 (15)
N5—H1N5···S1i	0.842 (17)	2.607 (17)	3.4279 (11)	165.5 (15)
N5—H2N5···O1	0.880 (17)	2.048 (17)	2.7208 (13)	132.5 (14)
C10—H10A···F1ii	0.98	2.47	3.3016 (14)	143.
C10—H10C···F1iii	0.98	2.53	3.2775 (14)	133.
C10—H10C···F2iv	0.98	2.55	3.2145 (14)	125.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	0.863 (17)	2.080 (17)	2.7605 (13)	135.2 (15)
N5—H1N5⋯S1i	0.842 (17)	2.607 (17)	3.4279 (11)	165.5 (15)
N5—H2N5⋯O1	0.880 (17)	2.048 (17)	2.7208 (13)	132.5 (14)
C10—H10A⋯F1ii	0.98	2.47	3.3016 (14)	143
C10—H10C⋯F1iii	0.98	2.53	3.2775 (14)	133
C10—H10C⋯F2iv	0.98	2.55	3.2145 (14)	125

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .