Crystal structure of 4-amino-3-(3-methyl-5-phenyl-1H-pyrazol-1-yl)-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C12H12N6S, the dihedral angles between the central pyrazole ring and the pendant triazole and benzene rings are 68.01 (4) and 59.83 (9)°, respectively. In the crystal, mol-ecules are linked by N-H⋯N and N-H⋯S hydrogen bonds, generating (10-1) sheets.

Related literature

For the bio-activities of amino­triazoles, see: Jin et al. (2007 ▸); Joung et al. (2000 ▸). For amino­triazoles as block-building synthons, see: Curtis (2004 ▸).

Experimental

Crystal data

C12H12N6S

M = 272.34

Monoclinic,

a = 11.3278 (4) Å

b = 8.3970 (3) Å

c = 15.4427 (5) Å

β = 109.053 (1)°

V = 1388.43 (8) Å3

Z = 4

Cu Kα radiation

μ = 2.04 mm−1

T = 150 K

0.24 × 0.18 × 0.10 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.77, T max = 0.82

10355 measured reflections

2683 independent reflections

2515 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.102

S = 1.09

2683 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500938X/hb7427sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500938X/hb7427Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500938X/hb7427Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500938X/hb7427fig1.tif

The title mol­ecule showing labeling scheme and 50% probability ellipsoids.

Click here for additional data file.

b . DOI: 10.1107/S205698901500938X/hb7427fig2.tif

Packing viewed down the b axis. N—H⋯N and N—H⋯S hydrogen bonds are shown, respectively, as blue and purple dotted lines.

CCDC reference: 1401505

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H12N6S	F(000) = 568
Mr = 272.34	Dx = 1.303 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.3278 (4) Å	Cell parameters from 8668 reflections
b = 8.3970 (3) Å	θ = 4.3–72.3°
c = 15.4427 (5) Å	µ = 2.04 mm−1
β = 109.053 (1)°	T = 150 K
V = 1388.43 (8) Å3	Block, colourless
Z = 4	0.24 × 0.18 × 0.10 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2683 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2515 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.4167 pixels mm-1	θmax = 72.3°, θmin = 4.2°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −9→10
Tmin = 0.77, Tmax = 0.82	l = −19→19
10355 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)] = 0.036	Hydrogen site location: mixed
wR(F2) = 0.102	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0581P)2 + 0.5187P] where P = (Fo2 + 2Fc2)/3
2683 reflections	(Δ/σ)max = 0.002
173 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.28 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. H-atoms attached to carbonwere placed in calculated positions (C—H = 0.95 - 0.98 Å) while thoseattached to nitrogen were placed in locations derived from a differencemap and their parameters adjusted to give N—H = 0.91 Å. All wereincluded as riding contributions with isotropic displacementparameters 1.2 - 1.5 times those of the attached atoms.

	x	y	z	Uiso*/Ueq
S1	1.06212 (3)	0.49379 (4)	0.36297 (2)	0.02864 (14)
N1	0.52909 (11)	0.54447 (14)	0.29113 (8)	0.0249 (3)
N2	0.60148 (11)	0.41615 (13)	0.33081 (8)	0.0235 (3)
N3	0.86566 (11)	0.29657 (15)	0.28254 (8)	0.0263 (3)
H3A	0.9039	0.2256	0.2559	0.032*
N4	0.74091 (11)	0.27516 (15)	0.27154 (9)	0.0273 (3)
N5	0.81912 (11)	0.48358 (13)	0.35855 (8)	0.0205 (3)
N6	0.81859 (11)	0.61690 (14)	0.41236 (8)	0.0262 (3)
H6A	0.8704	0.5948	0.4699	0.031*
H6B	0.8512	0.6973	0.3878	0.031*
C1	0.60875 (14)	0.17810 (17)	0.42641 (9)	0.0251 (3)
C2	0.72215 (17)	0.1972 (2)	0.49645 (11)	0.0399 (4)
H2	0.7559	0.3009	0.5120	0.048*
C3	0.78631 (19)	0.0666 (2)	0.54370 (13)	0.0469 (5)
H3	0.8636	0.0807	0.5914	0.056*
C4	0.73738 (18)	−0.0845 (2)	0.52122 (12)	0.0392 (4)
H4	0.7808	−0.1744	0.5538	0.047*
C5	0.62567 (16)	−0.10472 (18)	0.45161 (11)	0.0344 (4)
H5	0.5927	−0.2088	0.4362	0.041*
C6	0.56078 (15)	0.02533 (18)	0.40384 (11)	0.0292 (3)
H6	0.4839	0.0102	0.3559	0.035*
C7	0.54349 (13)	0.31865 (17)	0.37531 (9)	0.0239 (3)
C8	0.43020 (14)	0.38690 (19)	0.36366 (10)	0.0287 (3)
H8	0.3670	0.3482	0.3862	0.034*
C9	0.42509 (14)	0.52643 (18)	0.31143 (10)	0.0262 (3)
C10	0.71675 (13)	0.39120 (16)	0.31857 (9)	0.0218 (3)
C11	0.91672 (13)	0.42285 (16)	0.33429 (9)	0.0222 (3)
C12	0.32313 (15)	0.6470 (2)	0.28071 (13)	0.0386 (4)
H12A	0.3481	0.7316	0.2466	0.058*
H12B	0.3074	0.6928	0.3343	0.058*
H12C	0.2469	0.5957	0.2411	0.058*

	U11	U22	U33	U12	U13	U23
S1	0.0210 (2)	0.0357 (2)	0.0290 (2)	−0.00344 (13)	0.00779 (15)	−0.00294 (13)
N1	0.0233 (6)	0.0232 (6)	0.0304 (6)	0.0020 (5)	0.0120 (5)	0.0040 (5)
N2	0.0235 (6)	0.0206 (6)	0.0301 (6)	0.0012 (4)	0.0136 (5)	0.0031 (4)
N3	0.0235 (6)	0.0263 (6)	0.0330 (6)	−0.0013 (5)	0.0145 (5)	−0.0075 (5)
N4	0.0242 (6)	0.0270 (6)	0.0340 (6)	−0.0030 (5)	0.0141 (5)	−0.0049 (5)
N5	0.0224 (6)	0.0193 (5)	0.0210 (5)	0.0013 (4)	0.0088 (5)	−0.0009 (4)
N6	0.0311 (7)	0.0225 (6)	0.0248 (6)	0.0018 (5)	0.0089 (5)	−0.0048 (4)
C1	0.0288 (7)	0.0241 (7)	0.0251 (7)	−0.0021 (5)	0.0125 (6)	0.0010 (5)
C2	0.0459 (10)	0.0302 (8)	0.0355 (8)	−0.0082 (7)	0.0019 (7)	0.0026 (6)
C3	0.0468 (11)	0.0443 (10)	0.0382 (9)	−0.0008 (8)	−0.0018 (8)	0.0085 (8)
C4	0.0500 (10)	0.0327 (9)	0.0369 (8)	0.0094 (7)	0.0168 (7)	0.0099 (6)
C5	0.0477 (10)	0.0223 (7)	0.0372 (8)	0.0004 (6)	0.0195 (7)	−0.0018 (6)
C6	0.0316 (8)	0.0262 (7)	0.0313 (8)	−0.0027 (6)	0.0122 (6)	−0.0033 (6)
C7	0.0258 (7)	0.0230 (7)	0.0242 (6)	−0.0061 (5)	0.0101 (5)	−0.0012 (5)
C8	0.0246 (7)	0.0313 (8)	0.0333 (7)	−0.0045 (6)	0.0136 (6)	0.0045 (6)
C9	0.0223 (7)	0.0283 (7)	0.0294 (7)	−0.0019 (5)	0.0104 (6)	0.0014 (6)
C10	0.0217 (7)	0.0208 (6)	0.0242 (6)	0.0001 (5)	0.0094 (5)	0.0018 (5)
C11	0.0244 (7)	0.0229 (7)	0.0207 (6)	0.0014 (5)	0.0091 (5)	0.0014 (5)
C12	0.0262 (8)	0.0422 (9)	0.0521 (10)	0.0079 (7)	0.0193 (7)	0.0143 (8)

S1—C11	1.6697 (14)	C2—C3	1.384 (2)
N1—C9	1.3230 (19)	C2—H2	0.9500
N1—N2	1.3714 (16)	C3—C4	1.383 (3)
N2—C7	1.3670 (18)	C3—H3	0.9500
N2—C10	1.3949 (18)	C4—C5	1.377 (3)
N3—C11	1.3401 (18)	C4—H4	0.9500
N3—N4	1.3790 (17)	C5—C6	1.387 (2)
N3—H3A	0.9100	C5—H5	0.9500
N4—C10	1.2968 (18)	C6—H6	0.9500
N5—C10	1.3639 (18)	C7—C8	1.363 (2)
N5—C11	1.3759 (17)	C8—C9	1.413 (2)
N5—N6	1.3953 (15)	C8—H8	0.9500
N6—H6A	0.9101	C9—C12	1.492 (2)
N6—H6B	0.9099	C12—H12A	0.9800
C1—C2	1.392 (2)	C12—H12B	0.9800
C1—C6	1.392 (2)	C12—H12C	0.9800
C1—C7	1.477 (2)
C9—N1—N2	104.65 (11)	C4—C5—H5	119.6
C7—N2—N1	112.32 (11)	C6—C5—H5	119.6
C7—N2—C10	127.07 (12)	C5—C6—C1	119.77 (15)
N1—N2—C10	120.47 (11)	C5—C6—H6	120.1
C11—N3—N4	113.70 (11)	C1—C6—H6	120.1
C11—N3—H3A	127.7	C8—C7—N2	105.56 (12)
N4—N3—H3A	118.6	C8—C7—C1	133.80 (13)
C10—N4—N3	103.20 (11)	N2—C7—C1	120.55 (12)
C10—N5—C11	107.82 (11)	C7—C8—C9	106.58 (12)
C10—N5—N6	123.89 (11)	C7—C8—H8	126.7
C11—N5—N6	128.28 (12)	C9—C8—H8	126.7
N5—N6—H6A	107.0	N1—C9—C8	110.89 (13)
N5—N6—H6B	105.4	N1—C9—C12	120.25 (13)
H6A—N6—H6B	109.8	C8—C9—C12	128.85 (14)
C2—C1—C6	119.08 (14)	N4—C10—N5	112.16 (12)
C2—C1—C7	119.82 (13)	N4—C10—N2	124.53 (13)
C6—C1—C7	121.07 (13)	N5—C10—N2	123.26 (12)
C3—C2—C1	120.73 (16)	N3—C11—N5	103.12 (11)
C3—C2—H2	119.6	N3—C11—S1	129.55 (11)
C1—C2—H2	119.6	N5—C11—S1	127.32 (11)
C4—C3—C2	119.73 (16)	C9—C12—H12A	109.5
C4—C3—H3	120.1	C9—C12—H12B	109.5
C2—C3—H3	120.1	H12A—C12—H12B	109.5
C5—C4—C3	119.98 (16)	C9—C12—H12C	109.5
C5—C4—H4	120.0	H12A—C12—H12C	109.5
C3—C4—H4	120.0	H12B—C12—H12C	109.5
C4—C5—C6	120.70 (15)
C9—N1—N2—C7	0.12 (16)	N2—N1—C9—C8	−0.21 (16)
C9—N1—N2—C10	176.19 (12)	N2—N1—C9—C12	178.88 (14)
C11—N3—N4—C10	−0.45 (16)	C7—C8—C9—N1	0.23 (18)
C6—C1—C2—C3	−0.5 (3)	C7—C8—C9—C12	−178.76 (16)
C7—C1—C2—C3	−178.43 (16)	N3—N4—C10—N5	−0.20 (15)
C1—C2—C3—C4	0.0 (3)	N3—N4—C10—N2	−177.56 (12)
C2—C3—C4—C5	0.5 (3)	C11—N5—C10—N4	0.75 (15)
C3—C4—C5—C6	−0.4 (3)	N6—N5—C10—N4	179.53 (12)
C4—C5—C6—C1	−0.1 (2)	C11—N5—C10—N2	178.15 (12)
C2—C1—C6—C5	0.5 (2)	N6—N5—C10—N2	−3.1 (2)
C7—C1—C6—C5	178.45 (13)	C7—N2—C10—N4	64.2 (2)
N1—N2—C7—C8	0.02 (16)	N1—N2—C10—N4	−111.26 (16)
C10—N2—C7—C8	−175.74 (13)	C7—N2—C10—N5	−112.89 (16)
N1—N2—C7—C1	−176.94 (12)	N1—N2—C10—N5	71.66 (18)
C10—N2—C7—C1	7.3 (2)	N4—N3—C11—N5	0.88 (15)
C2—C1—C7—C8	−118.65 (19)	N4—N3—C11—S1	−178.60 (11)
C6—C1—C7—C8	63.4 (2)	C10—N5—C11—N3	−0.94 (14)
C2—C1—C7—N2	57.3 (2)	N6—N5—C11—N3	−179.65 (12)
C6—C1—C7—N2	−120.64 (15)	C10—N5—C11—S1	178.55 (10)
N2—C7—C8—C9	−0.14 (16)	N6—N5—C11—S1	−0.2 (2)
C1—C7—C8—C9	176.23 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1i	0.91	1.94	2.8429 (17)	169
N6—H6A···S1ii	0.91	2.55	3.4157 (13)	159
N6—H6B···N4iii	0.91	2.43	3.0059 (18)	122

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3AN1i	0.91	1.94	2.8429(17)	169
N6H6AS1ii	0.91	2.55	3.4157(13)	159
N6H6BN4iii	0.91	2.43	3.0059(18)	122

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