3-{[5-(4-Chloro-phen-yl)-3-methyl-1H-pyrazol-1-yl]meth-yl}-4-m-tolyl-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C20H18ClN5S, the toluene and triazole rings are oriented almost perpendicular to each other, making a dihedral angle of 89.97 (9)°, whereas the dihedral angle between cholorophenyl and pyrazole rings is 54.57 (11)°. In the crystal, pairs of N-H⋯N hydrogen bonds link the mol-ecules into inversion dimers. Weaker C-H⋯S and C-H⋯Cl inter-actions are also present.

Related literature

For medicinal applications of 1, 2, 4-triazoles, see: Lipinski (1983 ▶); Ram & Vlietinck (1988 ▶); Akahoshi et al. (1998 ▶); Young et al. (2001 ▶); Ouyang et al. (2005 ▶); Dolzhenko et al. (2007 ▶). For general background to the coordination chemistry of triazoles, see: Mishra et al. (1989 ▶); Klingele & Brooker (2003 ▶); Beckmann & Brooker (2003 ▶); Ferrer et al. (2004 ▶); Castineiras & Garcia-Santos (2008 ▶).

Experimental

Crystal data

C20H18ClN5S

M = 395.90

Monoclinic,

a = 8.328 (5) Å

b = 16.407 (5) Å

c = 14.759 (5) Å

β = 99.509 (5)°

V = 1988.9 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 296 K

0.61 × 0.53 × 0.52 mm

Data collection

Bruker APEXII CCD detector diffractometer

Absorption correction: analytical {SADABS; Bruker, 2009 ▶) T min = 0.833, T max = 0.855

38237 measured reflections

3914 independent reflections

3207 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.112

S = 1.04

3914 reflections

250 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013494/gw2132sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013494/gw2132Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813013494/gw2132Isup3.cml

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

C20H18ClN5S	F(000) = 824
Mr = 395.90	Dx = 1.322 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 143 reflections
a = 8.328 (5) Å	θ = 1.9–26.5°
b = 16.407 (5) Å	µ = 0.31 mm−1
c = 14.759 (5) Å	T = 296 K
β = 99.509 (5)°	Block, colourless
V = 1988.9 (15) Å3	0.61 × 0.53 × 0.52 mm
Z = 4

Bruker APEXII CCD detector diffractometer	3914 independent reflections
Radiation source: fine-focus sealed tube	3207 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω and φ scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: analytical {SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.833, Tmax = 0.855	k = −20→20
38237 measured reflections	l = −18→18

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0474P)2 + 0.8662P] where P = (Fo2 + 2Fc2)/3
3914 reflections	(Δ/σ)max = 0.008
250 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.26 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
S1	0.89331 (8)	0.45028 (4)	0.23277 (4)	0.0738 (2)
Cl1	0.87201 (11)	−0.10903 (4)	0.56431 (6)	0.1018 (3)
N2	0.83576 (17)	0.30784 (8)	0.58288 (10)	0.0420 (3)
N3	0.91296 (16)	0.36199 (8)	0.39136 (10)	0.0402 (3)
N1	0.76919 (18)	0.38104 (9)	0.59822 (10)	0.0460 (3)
N4	1.08074 (19)	0.46017 (9)	0.40066 (11)	0.0474 (4)
N5	1.10761 (18)	0.42403 (9)	0.48545 (11)	0.0468 (4)
C12	1.00462 (19)	0.36448 (10)	0.47753 (11)	0.0396 (4)
C14	0.78212 (19)	0.30653 (10)	0.35998 (11)	0.0388 (4)
C15	0.6269 (2)	0.32639 (10)	0.37306 (12)	0.0438 (4)
H19	0.6080	0.3758	0.4003	0.053*
C4	0.7762 (2)	0.15886 (10)	0.58340 (12)	0.0453 (4)
C13	0.9620 (2)	0.42534 (10)	0.34117 (13)	0.0457 (4)
C11	0.9930 (2)	0.30522 (11)	0.55227 (12)	0.0457 (4)
H11A	1.0112	0.2507	0.5307	0.055*
H11B	1.0780	0.3168	0.6040	0.055*
C20	0.8140 (2)	0.23434 (11)	0.31944 (13)	0.0492 (4)
H14	0.9187	0.2219	0.3097	0.059*
C9	0.6232 (2)	0.36378 (11)	0.61886 (13)	0.0506 (4)
C16	0.4988 (2)	0.27320 (12)	0.34583 (13)	0.0491 (4)
C18	0.5317 (2)	0.20020 (12)	0.30670 (13)	0.0548 (5)
H16	0.4474	0.1634	0.2889	0.066*
C7	0.7349 (2)	0.24523 (10)	0.59382 (12)	0.0445 (4)
C6	0.9473 (3)	0.04243 (13)	0.62598 (15)	0.0643 (6)
H6	1.0406	0.0195	0.6597	0.077*
C8	0.5974 (2)	0.27957 (11)	0.61661 (14)	0.0529 (5)
H8	0.5050	0.2523	0.6283	0.063*
C5	0.9165 (3)	0.12459 (12)	0.63229 (13)	0.0564 (5)
H5	0.9907	0.1574	0.6698	0.068*
C19	0.6871 (3)	0.18060 (12)	0.29343 (14)	0.0574 (5)
H15	0.7066	0.1310	0.2668	0.069*
C3	0.6710 (2)	0.10971 (11)	0.52508 (14)	0.0551 (5)
H3	0.5775	0.1321	0.4910	0.066*
C2	0.7034 (3)	0.02772 (12)	0.51691 (16)	0.0640 (6)
H2	0.6342	−0.0049	0.4763	0.077*
C1	0.8389 (3)	−0.00466 (12)	0.56953 (16)	0.0605 (5)
C17	0.3290 (3)	0.29548 (17)	0.3590 (2)	0.0794 (7)
H17A	0.2554	0.2525	0.3357	0.119*
H17B	0.2966	0.3450	0.3264	0.119*
H17C	0.3266	0.3032	0.4232	0.119*
C10	0.5133 (3)	0.43051 (14)	0.64055 (19)	0.0749 (7)
H10A	0.5713	0.4813	0.6453	0.112*
H10B	0.4776	0.4189	0.6978	0.112*
H10C	0.4206	0.4341	0.5925	0.112*
HN4	1.130 (2)	0.5065 (14)	0.3917 (14)	0.056 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0868 (4)	0.0712 (4)	0.0609 (3)	−0.0027 (3)	0.0045 (3)	0.0243 (3)
Cl1	0.1391 (7)	0.0416 (3)	0.1352 (7)	0.0167 (3)	0.0533 (5)	0.0124 (3)
N2	0.0469 (8)	0.0364 (7)	0.0430 (8)	−0.0039 (6)	0.0086 (6)	−0.0001 (6)
N3	0.0405 (7)	0.0361 (7)	0.0437 (7)	−0.0015 (6)	0.0060 (6)	0.0015 (6)
N1	0.0528 (9)	0.0380 (7)	0.0480 (8)	−0.0046 (6)	0.0106 (7)	−0.0024 (6)
N4	0.0500 (8)	0.0369 (8)	0.0580 (9)	−0.0073 (7)	0.0169 (7)	−0.0003 (7)
N5	0.0456 (8)	0.0439 (8)	0.0518 (9)	−0.0070 (6)	0.0110 (7)	−0.0043 (7)
C12	0.0371 (8)	0.0379 (8)	0.0443 (9)	0.0000 (7)	0.0081 (7)	−0.0030 (7)
C14	0.0411 (8)	0.0350 (8)	0.0391 (8)	−0.0011 (6)	0.0033 (6)	0.0012 (6)
C15	0.0457 (9)	0.0398 (9)	0.0463 (9)	0.0016 (7)	0.0083 (7)	−0.0041 (7)
C4	0.0549 (10)	0.0377 (9)	0.0444 (9)	−0.0048 (8)	0.0117 (8)	0.0039 (7)
C13	0.0480 (9)	0.0367 (8)	0.0545 (10)	0.0030 (7)	0.0147 (8)	0.0030 (7)
C11	0.0425 (9)	0.0477 (10)	0.0461 (10)	−0.0012 (7)	0.0050 (7)	0.0030 (7)
C20	0.0498 (10)	0.0450 (10)	0.0523 (10)	0.0062 (8)	0.0071 (8)	−0.0048 (8)
C9	0.0540 (10)	0.0464 (10)	0.0536 (11)	−0.0045 (8)	0.0151 (8)	−0.0054 (8)
C16	0.0445 (9)	0.0555 (11)	0.0470 (10)	−0.0047 (8)	0.0067 (8)	0.0019 (8)
C18	0.0605 (11)	0.0508 (11)	0.0496 (10)	−0.0170 (9)	−0.0005 (9)	−0.0017 (8)
C7	0.0523 (10)	0.0402 (9)	0.0409 (9)	−0.0078 (8)	0.0078 (7)	0.0016 (7)
C6	0.0717 (13)	0.0574 (12)	0.0630 (13)	0.0118 (11)	0.0093 (11)	0.0171 (10)
C8	0.0533 (10)	0.0478 (10)	0.0609 (11)	−0.0107 (8)	0.0192 (9)	−0.0012 (9)
C5	0.0649 (12)	0.0531 (11)	0.0485 (10)	−0.0038 (9)	0.0014 (9)	0.0046 (9)
C19	0.0731 (13)	0.0392 (9)	0.0575 (11)	−0.0003 (9)	0.0036 (10)	−0.0106 (8)
C3	0.0544 (11)	0.0431 (10)	0.0653 (12)	−0.0049 (8)	0.0026 (9)	0.0015 (9)
C2	0.0693 (13)	0.0439 (11)	0.0789 (15)	−0.0115 (10)	0.0124 (11)	−0.0084 (10)
C1	0.0747 (14)	0.0390 (10)	0.0729 (14)	0.0043 (9)	0.0268 (11)	0.0095 (9)
C17	0.0482 (12)	0.0956 (18)	0.0968 (18)	−0.0064 (12)	0.0191 (12)	−0.0075 (15)
C10	0.0723 (14)	0.0598 (13)	0.0986 (19)	0.0036 (11)	0.0323 (13)	−0.0114 (12)

S1—C13	1.659 (2)	C20—H14	0.9300
Cl1—C1	1.738 (2)	C9—C8	1.398 (3)
N2—C7	1.353 (2)	C9—C10	1.495 (3)
N2—N1	1.357 (2)	C16—C18	1.377 (3)
N2—C11	1.455 (2)	C16—C17	1.504 (3)
N3—C12	1.372 (2)	C18—C19	1.379 (3)
N3—C13	1.377 (2)	C18—H16	0.9300
N3—C14	1.436 (2)	C7—C8	1.367 (3)
N1—C9	1.332 (2)	C6—C1	1.363 (3)
N4—C13	1.337 (2)	C6—C5	1.378 (3)
N4—N5	1.369 (2)	C6—H6	0.9300
N4—HN4	0.89 (2)	C8—H8	0.9300
N5—C12	1.293 (2)	C5—H5	0.9300
C12—C11	1.486 (2)	C19—H15	0.9300
C14—C20	1.373 (2)	C3—C2	1.381 (3)
C14—C15	1.377 (2)	C3—H3	0.9300
C15—C16	1.385 (2)	C2—C1	1.367 (3)
C15—H19	0.9300	C2—H2	0.9300
C4—C3	1.382 (3)	C17—H17A	0.9600
C4—C5	1.387 (3)	C17—H17B	0.9600
C4—C7	1.472 (2)	C17—H17C	0.9600
C11—H11A	0.9700	C10—H10A	0.9600
C11—H11B	0.9700	C10—H10B	0.9600
C20—C19	1.381 (3)	C10—H10C	0.9600
C7—N2—N1	111.89 (14)	C15—C16—C17	120.32 (19)
C7—N2—C11	128.53 (15)	C16—C18—C19	121.26 (17)
N1—N2—C11	119.43 (13)	C16—C18—H16	119.4
C12—N3—C13	107.90 (14)	C19—C18—H16	119.4
C12—N3—C14	126.46 (14)	N2—C7—C8	106.16 (16)
C13—N3—C14	125.54 (14)	N2—C7—C4	123.88 (16)
C9—N1—N2	105.27 (14)	C8—C7—C4	129.96 (16)
C13—N4—N5	113.98 (15)	C1—C6—C5	118.9 (2)
C13—N4—HN4	125.5 (13)	C1—C6—H6	120.5
N5—N4—HN4	119.9 (13)	C5—C6—H6	120.5
C12—N5—N4	103.82 (14)	C7—C8—C9	106.34 (16)
N5—C12—N3	111.46 (15)	C7—C8—H8	126.8
N5—C12—C11	123.46 (16)	C9—C8—H8	126.8
N3—C12—C11	125.05 (15)	C6—C5—C4	120.8 (2)
C20—C14—C15	121.24 (16)	C6—C5—H5	119.6
C20—C14—N3	119.76 (15)	C4—C5—H5	119.6
C15—C14—N3	118.99 (15)	C18—C19—C20	120.32 (18)
C14—C15—C16	120.39 (16)	C18—C19—H15	119.8
C14—C15—H19	119.8	C20—C19—H15	119.8
C16—C15—H19	119.8	C4—C3—C2	120.66 (19)
C3—C4—C5	118.72 (18)	C4—C3—H3	119.7
C3—C4—C7	119.44 (17)	C2—C3—H3	119.7
C5—C4—C7	121.82 (17)	C1—C2—C3	118.9 (2)
N4—C13—N3	102.84 (15)	C1—C2—H2	120.5
N4—C13—S1	128.86 (14)	C3—C2—H2	120.5
N3—C13—S1	128.28 (14)	C6—C1—C2	121.89 (19)
N2—C11—C12	112.56 (14)	C6—C1—Cl1	119.44 (18)
N2—C11—H11A	109.1	C2—C1—Cl1	118.67 (18)
C12—C11—H11A	109.1	C16—C17—H17A	109.5
N2—C11—H11B	109.1	C16—C17—H17B	109.5
C12—C11—H11B	109.1	H17A—C17—H17B	109.5
H11A—C11—H11B	107.8	C16—C17—H17C	109.5
C14—C20—C19	118.55 (17)	H17A—C17—H17C	109.5
C14—C20—H14	120.7	H17B—C17—H17C	109.5
C19—C20—H14	120.7	C9—C10—H10A	109.5
N1—C9—C8	110.33 (17)	C9—C10—H10B	109.5
N1—C9—C10	120.48 (18)	H10A—C10—H10B	109.5
C8—C9—C10	129.19 (19)	C9—C10—H10C	109.5
C18—C16—C15	118.22 (17)	H10A—C10—H10C	109.5
C18—C16—C17	121.46 (18)	H10B—C10—H10C	109.5
C7—N2—N1—C9	−0.24 (19)	C14—C15—C16—C18	0.8 (3)
C11—N2—N1—C9	175.82 (15)	C14—C15—C16—C17	−179.16 (19)
C13—N4—N5—C12	1.10 (19)	C15—C16—C18—C19	−1.0 (3)
N4—N5—C12—N3	−0.47 (18)	C17—C16—C18—C19	178.9 (2)
N4—N5—C12—C11	177.59 (15)	N1—N2—C7—C8	0.4 (2)
C13—N3—C12—N5	−0.25 (19)	C11—N2—C7—C8	−175.26 (16)
C14—N3—C12—N5	−176.79 (15)	N1—N2—C7—C4	−178.73 (15)
C13—N3—C12—C11	−178.27 (15)	C11—N2—C7—C4	5.7 (3)
C14—N3—C12—C11	5.2 (3)	C3—C4—C7—N2	−127.2 (2)
C12—N3—C14—C20	−91.4 (2)	C5—C4—C7—N2	54.4 (3)
C13—N3—C14—C20	92.6 (2)	C3—C4—C7—C8	54.0 (3)
C12—N3—C14—C15	87.3 (2)	C5—C4—C7—C8	−124.4 (2)
C13—N3—C14—C15	−88.7 (2)	N2—C7—C8—C9	−0.3 (2)
C20—C14—C15—C16	0.4 (3)	C4—C7—C8—C9	178.69 (18)
N3—C14—C15—C16	−178.24 (16)	N1—C9—C8—C7	0.2 (2)
N5—N4—C13—N3	−1.22 (19)	C10—C9—C8—C7	−179.6 (2)
N5—N4—C13—S1	−179.74 (13)	C1—C6—C5—C4	1.1 (3)
C12—N3—C13—N4	0.86 (17)	C3—C4—C5—C6	−2.7 (3)
C14—N3—C13—N4	177.44 (14)	C7—C4—C5—C6	175.69 (18)
C12—N3—C13—S1	179.39 (14)	C16—C18—C19—C20	0.0 (3)
C14—N3—C13—S1	−4.0 (3)	C14—C20—C19—C18	1.1 (3)
C7—N2—C11—C12	129.99 (18)	C5—C4—C3—C2	1.2 (3)
N1—N2—C11—C12	−45.3 (2)	C7—C4—C3—C2	−177.28 (18)
N5—C12—C11—N2	117.51 (18)	C4—C3—C2—C1	1.9 (3)
N3—C12—C11—N2	−64.7 (2)	C5—C6—C1—C2	2.1 (3)
C15—C14—C20—C19	−1.3 (3)	C5—C6—C1—Cl1	−177.48 (16)
N3—C14—C20—C19	177.29 (16)	C3—C2—C1—C6	−3.6 (3)
N2—N1—C9—C8	0.0 (2)	C3—C2—C1—Cl1	175.96 (17)
N2—N1—C9—C10	179.80 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N4—HN4···N1i	0.88 (2)	2.02 (2)	2.888 (2)	166 (2)
C5—H5···C16ii	0.93	2.83	3.536 (3)	134
C6—H6···S1ii	0.93	3.00	3.790 (3)	144
C2—H2···C2iii	0.93	2.85	3.464 (4)	124
C20—H14···Cl1iv	0.93	2.98	3.537 (4)	120

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—HN4⋯N1i	0.88 (2)	2.02 (2)	2.888 (2)	166 (2)
C6—H6⋯S1ii	0.93	3.00	3.790 (3)	144
C20—H14⋯Cl1iii	0.93	2.98	3.537 (4)	120

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