5-(4-Fluoro-phen-yl)-3-[5-methyl-1-(4-methyl-phen-yl)-1H-1,2,3-triazol-4-yl]-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title compound, C(20)H(19)FN(6)S, the pyrazole ring has an envelope conformation, with the methine C atom being the flap atom. The dihedral angle between the least-squares plane through the pyrazole and triazole rings is 7.59 (9)°, and the triazole and attached benzene ring form a dihedral angle of 74.79 (9)°. The thio-urea group is coplanar with the pyrazole ring [N-N-C-S torsion angle = -179.93 (11)°], which enables the formation of an intra-molecular N-H⋯N hydrogen bond. In the crystal, inversion-related mol-ecules associate via N-H⋯S hydrogen bonds and eight-membered {⋯HNCS}(2) synthons feature in the crystal packing. These synthons are connected into supra-molecular chains along the a axis via N-H⋯F hydrogen bonds, and the chains are consolidated into layers in the ab plane via C-H⋯S and C-H⋯F contacts.

Related literature

For the biological activity of pyrazolyl-1,2,3-triazoles, see: Abdel-Wahab et al. (2012a ▶); Booth & Ross (1982 ▶); Curran (1982 ▶). For a related pyrazolyl-1,2,3-triazole structure, see: Abdel-Wahab et al. (2012b ▶).

Experimental

Crystal data

C20H19FN6S

M = 394.47

Monoclinic,

a = 9.4388 (4) Å

b = 6.5476 (3) Å

c = 32.1483 (18) Å

β = 91.288 (4)°

V = 1986.31 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 100 K

0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.855, T max = 1.000

7765 measured reflections

4551 independent reflections

3809 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.109

S = 1.02

4551 reflections

263 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024245/su2439sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024245/su2439Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812024245/su2439Isup3.cml

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

C20H19FN6S	F(000) = 824
Mr = 394.47	Dx = 1.319 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3598 reflections
a = 9.4388 (4) Å	θ = 2.2–27.5°
b = 6.5476 (3) Å	µ = 0.19 mm−1
c = 32.1483 (18) Å	T = 100 K
β = 91.288 (4)°	Prism, light-brown
V = 1986.31 (17) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	4551 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3809 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.5°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→8
Tmin = 0.855, Tmax = 1.000	l = −23→41
7765 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.045P)2 + 1.138P] where P = (Fo2 + 2Fc2)/3
4551 reflections	(Δ/σ)max = 0.002
263 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
S1	0.32997 (4)	1.28074 (6)	0.507140 (13)	0.01661 (12)
F1	−0.23235 (10)	1.32770 (17)	0.39047 (3)	0.0253 (3)
N1	0.53882 (15)	1.2902 (2)	0.45302 (5)	0.0181 (3)
N2	0.38250 (13)	1.0266 (2)	0.44567 (4)	0.0137 (3)
N3	0.45951 (13)	0.9562 (2)	0.41184 (4)	0.0145 (3)
N4	0.40790 (15)	0.4715 (2)	0.35943 (5)	0.0212 (3)
N5	0.47668 (16)	0.3904 (2)	0.32855 (5)	0.0224 (3)
N6	0.57249 (14)	0.5319 (2)	0.31626 (4)	0.0161 (3)
C1	0.42324 (16)	1.1970 (2)	0.46636 (5)	0.0139 (3)
C2	0.25153 (16)	0.9101 (2)	0.45166 (5)	0.0139 (3)
H2	0.2393	0.8789	0.4818	0.017*
C3	0.28474 (17)	0.7137 (3)	0.42742 (5)	0.0162 (3)
H3A	0.3146	0.6017	0.4463	0.019*
H3B	0.2023	0.6684	0.4102	0.019*
C4	0.40479 (16)	0.7836 (3)	0.40082 (5)	0.0145 (3)
C5	0.12296 (16)	1.0241 (2)	0.43419 (5)	0.0136 (3)
C6	0.13589 (17)	1.1894 (3)	0.40729 (5)	0.0170 (3)
H6	0.2272	1.2330	0.3992	0.020*
C7	0.01603 (17)	1.2911 (3)	0.39217 (5)	0.0183 (4)
H7	0.0241	1.4039	0.3738	0.022*
C8	−0.11438 (17)	1.2240 (3)	0.40457 (5)	0.0177 (4)
C9	−0.13193 (17)	1.0592 (3)	0.43024 (5)	0.0200 (4)
H9	−0.2238	1.0148	0.4376	0.024*
C10	−0.01149 (17)	0.9592 (3)	0.44518 (5)	0.0176 (3)
H10	−0.0210	0.8450	0.4631	0.021*
C11	0.45981 (17)	0.6634 (3)	0.36697 (5)	0.0157 (3)
C12	0.56581 (17)	0.7042 (3)	0.33933 (5)	0.0158 (3)
C13	0.65699 (19)	0.8859 (3)	0.33351 (6)	0.0245 (4)
H13A	0.6911	0.8880	0.3049	0.037*
H13B	0.7380	0.8799	0.3531	0.037*
H13C	0.6021	1.0100	0.3387	0.037*
C14	0.66475 (17)	0.4832 (3)	0.28258 (5)	0.0167 (3)
C15	0.77454 (18)	0.3469 (3)	0.28951 (5)	0.0204 (4)
H15	0.7917	0.2913	0.3165	0.025*
C16	0.85941 (19)	0.2924 (3)	0.25663 (6)	0.0229 (4)
H16	0.9354	0.1995	0.2613	0.027*
C17	0.83530 (18)	0.3714 (3)	0.21690 (5)	0.0207 (4)
C18	0.72555 (19)	0.5103 (3)	0.21112 (6)	0.0260 (4)
H18	0.7092	0.5685	0.1844	0.031*
C19	0.63922 (19)	0.5658 (3)	0.24361 (5)	0.0234 (4)
H19	0.5635	0.6594	0.2391	0.028*
C20	0.9250 (2)	0.3050 (3)	0.18119 (6)	0.0324 (5)
H20A	1.0108	0.2375	0.1920	0.049*
H20B	0.9514	0.4247	0.1648	0.049*
H20C	0.8710	0.2096	0.1635	0.049*
H1N	0.5662 (19)	1.407 (3)	0.4648 (6)	0.020 (5)*
H2N	0.574 (2)	1.255 (3)	0.4297 (7)	0.027 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0194 (2)	0.0157 (2)	0.0149 (2)	−0.00300 (17)	0.00448 (15)	−0.00283 (16)
F1	0.0177 (5)	0.0359 (6)	0.0223 (5)	0.0063 (5)	−0.0003 (4)	0.0081 (5)
N1	0.0174 (7)	0.0180 (8)	0.0191 (8)	−0.0041 (6)	0.0050 (6)	−0.0068 (6)
N2	0.0125 (6)	0.0151 (7)	0.0137 (7)	−0.0008 (5)	0.0024 (5)	−0.0030 (6)
N3	0.0149 (6)	0.0154 (7)	0.0132 (7)	0.0016 (6)	0.0022 (5)	−0.0015 (6)
N4	0.0287 (8)	0.0162 (7)	0.0190 (7)	−0.0038 (6)	0.0068 (6)	−0.0044 (6)
N5	0.0291 (8)	0.0177 (7)	0.0208 (8)	−0.0071 (6)	0.0080 (6)	−0.0044 (6)
N6	0.0203 (7)	0.0133 (7)	0.0147 (7)	−0.0028 (6)	0.0027 (5)	−0.0007 (6)
C1	0.0145 (7)	0.0131 (8)	0.0141 (8)	0.0020 (6)	−0.0026 (6)	0.0011 (6)
C2	0.0159 (8)	0.0118 (7)	0.0142 (8)	−0.0031 (6)	0.0014 (6)	0.0004 (6)
C3	0.0180 (8)	0.0137 (8)	0.0170 (8)	−0.0008 (7)	0.0025 (6)	−0.0006 (7)
C4	0.0155 (7)	0.0143 (8)	0.0138 (8)	0.0019 (6)	0.0001 (6)	0.0013 (6)
C5	0.0153 (7)	0.0136 (8)	0.0121 (7)	−0.0015 (6)	0.0011 (6)	−0.0023 (6)
C6	0.0150 (8)	0.0186 (8)	0.0174 (8)	−0.0042 (7)	0.0019 (6)	−0.0003 (7)
C7	0.0204 (8)	0.0179 (8)	0.0166 (8)	−0.0010 (7)	0.0004 (6)	0.0041 (7)
C8	0.0148 (8)	0.0230 (9)	0.0152 (8)	0.0036 (7)	−0.0012 (6)	0.0003 (7)
C9	0.0142 (8)	0.0270 (10)	0.0189 (8)	−0.0034 (7)	0.0033 (6)	0.0027 (7)
C10	0.0182 (8)	0.0187 (8)	0.0161 (8)	−0.0029 (7)	0.0017 (6)	0.0021 (7)
C11	0.0180 (8)	0.0132 (8)	0.0157 (8)	−0.0006 (6)	0.0001 (6)	−0.0010 (6)
C12	0.0188 (8)	0.0137 (8)	0.0150 (8)	0.0003 (7)	0.0000 (6)	−0.0032 (7)
C13	0.0273 (9)	0.0177 (9)	0.0290 (10)	−0.0070 (8)	0.0093 (8)	−0.0067 (8)
C14	0.0204 (8)	0.0151 (8)	0.0148 (8)	−0.0022 (7)	0.0033 (6)	−0.0033 (7)
C15	0.0252 (9)	0.0213 (9)	0.0148 (8)	0.0012 (7)	0.0008 (7)	0.0016 (7)
C16	0.0236 (9)	0.0239 (9)	0.0214 (9)	0.0059 (8)	0.0021 (7)	0.0015 (8)
C17	0.0239 (9)	0.0207 (9)	0.0177 (8)	0.0020 (7)	0.0039 (7)	−0.0039 (7)
C18	0.0330 (10)	0.0292 (10)	0.0158 (9)	0.0075 (8)	0.0030 (7)	0.0024 (8)
C19	0.0272 (9)	0.0240 (9)	0.0192 (9)	0.0104 (8)	0.0020 (7)	0.0019 (8)
C20	0.0372 (11)	0.0379 (12)	0.0223 (10)	0.0130 (9)	0.0089 (8)	0.0000 (9)

S1—C1	1.6873 (17)	C7—C8	1.374 (2)
F1—C8	1.3724 (19)	C7—H7	0.9500
N1—C1	1.329 (2)	C8—C9	1.371 (2)
N1—H1N	0.89 (2)	C9—C10	1.389 (2)
N1—H2N	0.86 (2)	C9—H9	0.9500
N2—C1	1.350 (2)	C10—H10	0.9500
N2—N3	1.3996 (18)	C11—C12	1.379 (2)
N2—C2	1.469 (2)	C12—C13	1.483 (2)
N3—C4	1.289 (2)	C13—H13A	0.9800
N4—N5	1.311 (2)	C13—H13B	0.9800
N4—C11	1.368 (2)	C13—H13C	0.9800
N5—N6	1.360 (2)	C14—C19	1.381 (2)
N6—C12	1.352 (2)	C14—C15	1.382 (2)
N6—C14	1.441 (2)	C15—C16	1.387 (2)
C2—C5	1.521 (2)	C15—H15	0.9500
C2—C3	1.539 (2)	C16—C17	1.392 (2)
C2—H2	1.0000	C16—H16	0.9500
C3—C4	1.506 (2)	C17—C18	1.388 (3)
C3—H3A	0.9900	C17—C20	1.505 (2)
C3—H3B	0.9900	C18—C19	1.387 (2)
C4—C11	1.449 (2)	C18—H18	0.9500
C5—C10	1.391 (2)	C19—H19	0.9500
C5—C6	1.392 (2)	C20—H20A	0.9800
C6—C7	1.391 (2)	C20—H20B	0.9800
C6—H6	0.9500	C20—H20C	0.9800
C1—N1—H1N	119.3 (12)	C8—C9—C10	118.08 (15)
C1—N1—H2N	119.6 (14)	C8—C9—H9	121.0
H1N—N1—H2N	119.4 (19)	C10—C9—H9	121.0
C1—N2—N3	120.50 (13)	C9—C10—C5	120.82 (16)
C1—N2—C2	126.55 (13)	C9—C10—H10	119.6
N3—N2—C2	112.60 (12)	C5—C10—H10	119.6
C4—N3—N2	106.88 (13)	N4—C11—C12	109.01 (14)
N5—N4—C11	108.96 (14)	N4—C11—C4	119.94 (15)
N4—N5—N6	106.73 (13)	C12—C11—C4	131.01 (16)
C12—N6—N5	111.69 (13)	N6—C12—C11	103.62 (14)
C12—N6—C14	129.31 (14)	N6—C12—C13	124.45 (15)
N5—N6—C14	119.00 (13)	C11—C12—C13	131.93 (16)
N1—C1—N2	116.57 (15)	C12—C13—H13A	109.5
N1—C1—S1	123.20 (13)	C12—C13—H13B	109.5
N2—C1—S1	120.23 (12)	H13A—C13—H13B	109.5
N2—C2—C5	111.32 (13)	C12—C13—H13C	109.5
N2—C2—C3	100.70 (12)	H13A—C13—H13C	109.5
C5—C2—C3	113.13 (13)	H13B—C13—H13C	109.5
N2—C2—H2	110.4	C19—C14—C15	120.95 (16)
C5—C2—H2	110.4	C19—C14—N6	119.95 (15)
C3—C2—H2	110.4	C15—C14—N6	119.05 (15)
C4—C3—C2	101.42 (13)	C14—C15—C16	119.14 (16)
C4—C3—H3A	111.5	C14—C15—H15	120.4
C2—C3—H3A	111.5	C16—C15—H15	120.4
C4—C3—H3B	111.5	C15—C16—C17	121.23 (17)
C2—C3—H3B	111.5	C15—C16—H16	119.4
H3A—C3—H3B	109.3	C17—C16—H16	119.4
N3—C4—C11	122.33 (15)	C18—C17—C16	118.19 (16)
N3—C4—C3	114.34 (14)	C18—C17—C20	121.20 (17)
C11—C4—C3	123.26 (15)	C16—C17—C20	120.61 (16)
C10—C5—C6	119.23 (15)	C19—C18—C17	121.34 (17)
C10—C5—C2	118.75 (15)	C19—C18—H18	119.3
C6—C5—C2	122.02 (14)	C17—C18—H18	119.3
C7—C6—C5	120.48 (15)	C14—C19—C18	119.14 (17)
C7—C6—H6	119.8	C14—C19—H19	120.4
C5—C6—H6	119.8	C18—C19—H19	120.4
C8—C7—C6	118.18 (16)	C17—C20—H20A	109.5
C8—C7—H7	120.9	C17—C20—H20B	109.5
C6—C7—H7	120.9	H20A—C20—H20B	109.5
C9—C8—F1	118.69 (14)	C17—C20—H20C	109.5
C9—C8—C7	123.19 (16)	H20A—C20—H20C	109.5
F1—C8—C7	118.12 (15)	H20B—C20—H20C	109.5
C1—N2—N3—C4	174.29 (14)	C6—C5—C10—C9	−1.1 (3)
C2—N2—N3—C4	−12.04 (17)	C2—C5—C10—C9	179.58 (15)
C11—N4—N5—N6	−0.27 (19)	N5—N4—C11—C12	0.2 (2)
N4—N5—N6—C12	0.23 (19)	N5—N4—C11—C4	−177.76 (15)
N4—N5—N6—C14	179.55 (14)	N3—C4—C11—N4	172.91 (15)
N3—N2—C1—N1	−0.5 (2)	C3—C4—C11—N4	−3.8 (2)
C2—N2—C1—N1	−173.19 (15)	N3—C4—C11—C12	−4.6 (3)
N3—N2—C1—S1	−179.93 (11)	C3—C4—C11—C12	178.72 (17)
C2—N2—C1—S1	7.3 (2)	N5—N6—C12—C11	−0.08 (18)
C1—N2—C2—C5	72.6 (2)	C14—N6—C12—C11	−179.32 (16)
N3—N2—C2—C5	−100.65 (15)	N5—N6—C12—C13	179.88 (16)
C1—N2—C2—C3	−167.24 (15)	C14—N6—C12—C13	0.6 (3)
N3—N2—C2—C3	19.54 (16)	N4—C11—C12—N6	−0.08 (18)
N2—C2—C3—C4	−18.17 (15)	C4—C11—C12—N6	177.61 (17)
C5—C2—C3—C4	100.72 (15)	N4—C11—C12—C13	179.96 (18)
N2—N3—C4—C11	−178.76 (14)	C4—C11—C12—C13	−2.4 (3)
N2—N3—C4—C3	−1.78 (18)	C12—N6—C14—C19	−76.7 (2)
C2—C3—C4—N3	13.53 (18)	N5—N6—C14—C19	104.1 (2)
C2—C3—C4—C11	−169.51 (15)	C12—N6—C14—C15	106.0 (2)
N2—C2—C5—C10	−165.88 (14)	N5—N6—C14—C15	−73.2 (2)
C3—C2—C5—C10	81.57 (18)	C19—C14—C15—C16	−0.3 (3)
N2—C2—C5—C6	14.8 (2)	N6—C14—C15—C16	176.99 (16)
C3—C2—C5—C6	−97.72 (18)	C14—C15—C16—C17	−0.4 (3)
C10—C5—C6—C7	1.2 (2)	C15—C16—C17—C18	1.4 (3)
C2—C5—C6—C7	−179.49 (15)	C15—C16—C17—C20	−177.77 (18)
C5—C6—C7—C8	0.1 (3)	C16—C17—C18—C19	−1.7 (3)
C6—C7—C8—C9	−1.6 (3)	C20—C17—C18—C19	177.47 (19)
C6—C7—C8—F1	178.40 (15)	C15—C14—C19—C18	0.0 (3)
F1—C8—C9—C10	−178.27 (15)	N6—C14—C19—C18	−177.25 (16)
C7—C8—C9—C10	1.7 (3)	C17—C18—C19—C14	1.0 (3)
C8—C9—C10—C5	−0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1i	0.89 (2)	2.432 (19)	3.3159 (14)	172.7 (16)
N1—H2N···F1ii	0.86 (2)	2.29 (2)	2.9940 (18)	138.9 (17)
N1—H2N···N3	0.86 (2)	2.30 (2)	2.6554 (19)	104.9 (15)
C3—H3A···S1iii	0.99	2.87	3.8390 (19)	166
C9—H9···S1iv	0.95	2.83	3.5595 (18)	135
C15—H15···F1v	0.95	2.41	3.2502 (19)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1i	0.89 (2)	2.432 (19)	3.3159 (14)	172.7 (16)
N1—H2N⋯F1ii	0.86 (2)	2.29 (2)	2.9940 (18)	138.9 (17)
N1—H2N⋯N3	0.86 (2)	2.30 (2)	2.6554 (19)	104.9 (15)
C3—H3A⋯S1iii	0.99	2.87	3.8390 (19)	166
C9—H9⋯S1iv	0.95	2.83	3.5595 (18)	135
C15—H15⋯F1v	0.95	2.41	3.2502 (19)	148

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