3-[(3,5-Dimethyl-1H-pyrazol-1-yl)meth­yl]-4-(4-methyl­phen­yl)-4,5-di­hydro-1H-1,2,4-triazole-5-thione

With the pyrazolyl and p-tolyl groups lying to one side of the plane through the linking 1,2,4-triazole-5-thione residue [forming dihedral angles of 87.05 (8) and 81.41 (7)°, respectively], the title mol­ecule, C₁₅H₁₇N₅S, adopts a `pincer' conformation stabilized in part by two intra­molecular C—H...π(ring) inter­actions. A three-dimensional network structure is generated by a combination of inter­molecular N—H...N and C—H...S hydrogen bonds, as well as C—H...π(ring) inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.033
• wR factor = 0.091
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  S1      ..       2.93 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10A   ..  S1      ..       2.93 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         46 Report

Alert level G
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         20 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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).

3-[(3,5-Dimethyl-1H-pyrazol-1-yl)methyl]-4-(4-methylphenyl)-4,5-dihydro-1H-1,2,4-triazole-5-thione

Crystal data

C15H17N5S	F(000) = 632
Mr = 299.39	Dx = 1.254 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 7.9322 (2) Å	Cell parameters from 9878 reflections
b = 15.2415 (4) Å	θ = 2.9–72.4°
c = 13.6694 (4) Å	µ = 1.81 mm^−1
β = 106.316 (1)°	T = 150 K
V = 1586.06 (7) Å^3	Thick plate, colourless
Z = 4	0.15 × 0.15 × 0.07 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3070 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2812 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 10.4167 pixels mm^-1	θmax = 72.4°, θmin = 4.5°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −18→18
Tmin = 0.82, Tmax = 0.89	l = −16→16
11791 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 0.6677P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.033	(Δ/σ)max < 0.001
wR(F^2) = 0.091	Δρmax = 0.24 e Å^−3
S = 1.05	Δρmin = −0.21 e Å^−3
3070 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
191 parameters	Extinction coefficient: 0.0040 (3)
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.92398 (17)	0.37412 (8)	0.35362 (10)	0.0212 (2)
C2	1.00943 (17)	0.35248 (9)	0.52192 (10)	0.0212 (2)
C3	0.77405 (17)	0.25167 (9)	0.41923 (9)	0.0204 (3)
C4	0.82341 (19)	0.16998 (9)	0.39224 (11)	0.0268 (3)
H4	0.9348	0.1617	0.3805	0.032*
C5	0.7066 (2)	0.10048 (10)	0.38268 (12)	0.0341 (4)
H5	0.7370	0.0442	0.3631	0.041*
C6	0.5455 (2)	0.11329 (11)	0.40169 (11)	0.0341 (4)
H6	0.4673	0.0651	0.3957	0.041*
C7	0.49608 (19)	0.19490 (11)	0.42931 (10)	0.0290 (3)
C8	0.61277 (17)	0.26505 (9)	0.43697 (10)	0.0230 (3)
H8	0.5812	0.3219	0.4544	0.028*
C9	0.3242 (2)	0.20843 (14)	0.45340 (13)	0.0435 (4)
H9A	0.2501	0.1564	0.4327	0.065*
H9B	0.2644	0.2598	0.4163	0.065*
H9C	0.3461	0.2178	0.5268	0.065*
C10	1.01710 (18)	0.31858 (10)	0.62551 (10)	0.0257 (3)
H10A	1.0425	0.2549	0.6284	0.031*
H10B	1.1139	0.3481	0.6768	0.031*
C11	0.74452 (19)	0.27428 (9)	0.67525 (10)	0.0245 (3)
C12	0.6022 (2)	0.32088 (10)	0.68573 (11)	0.0273 (3)
H12	0.5029	0.2982	0.7032	0.033*
C13	0.63305 (19)	0.40877 (9)	0.66543 (11)	0.0263 (3)
C14	0.7851 (2)	0.17859 (10)	0.68567 (12)	0.0327 (3)
H14A	0.7884	0.1549	0.6196	0.049*
H14B	0.6940	0.1482	0.7086	0.049*
H14C	0.8995	0.1698	0.7357	0.049*
C15	0.5202 (2)	0.48732 (11)	0.66467 (15)	0.0405 (4)
H15A	0.5736	0.5388	0.6424	0.061*
H15B	0.5095	0.4975	0.7335	0.061*
H15C	0.4034	0.4772	0.6177	0.061*
N1	0.89554 (14)	0.32359 (7)	0.43150 (8)	0.0202 (2)
N2	1.10763 (15)	0.41591 (8)	0.50617 (9)	0.0250 (3)
N3	1.05596 (15)	0.42747 (8)	0.40224 (9)	0.0238 (3)
H3N	1.093 (2)	0.4738 (12)	0.3762 (13)	0.029*
N4	0.85295 (15)	0.33364 (7)	0.65030 (8)	0.0223 (2)
N5	0.78636 (15)	0.41691 (7)	0.64379 (9)	0.0242 (3)
S1	0.81896 (4)	0.36931 (2)	0.22924 (2)	0.02550 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0196 (4)	0.0185 (5)	0.0261 (5)	0.0009 (3)	0.0076 (4)	−0.0015 (3)
C2	0.0196 (4)	0.0185 (5)	0.0261 (5)	0.0009 (3)	0.0076 (4)	−0.0015 (3)
C3	0.0216 (6)	0.0199 (6)	0.0190 (6)	−0.0040 (5)	0.0045 (5)	0.0010 (5)
C4	0.0271 (7)	0.0236 (7)	0.0307 (7)	−0.0008 (5)	0.0099 (6)	−0.0023 (6)
C5	0.0444 (9)	0.0219 (7)	0.0356 (8)	−0.0068 (6)	0.0106 (7)	−0.0046 (6)
C6	0.0377 (8)	0.0338 (8)	0.0283 (7)	−0.0171 (7)	0.0052 (6)	0.0003 (6)
C7	0.0227 (7)	0.0417 (9)	0.0206 (6)	−0.0085 (6)	0.0031 (5)	0.0032 (6)
C8	0.0209 (6)	0.0272 (7)	0.0200 (6)	−0.0003 (5)	0.0042 (5)	0.0013 (5)
C9	0.0254 (8)	0.0717 (13)	0.0345 (8)	−0.0139 (8)	0.0098 (6)	−0.0007 (8)
C10	0.0222 (7)	0.0287 (7)	0.0245 (7)	0.0012 (5)	0.0037 (5)	0.0025 (5)
C11	0.0310 (7)	0.0229 (7)	0.0181 (6)	−0.0058 (5)	0.0046 (5)	0.0018 (5)
C12	0.0311 (7)	0.0281 (8)	0.0249 (7)	−0.0085 (6)	0.0114 (6)	−0.0027 (6)
C13	0.0263 (7)	0.0256 (7)	0.0270 (7)	−0.0052 (5)	0.0077 (6)	−0.0060 (6)
C14	0.0397 (9)	0.0235 (8)	0.0328 (8)	−0.0026 (6)	0.0069 (7)	0.0069 (6)
C15	0.0316 (8)	0.0315 (9)	0.0593 (11)	−0.0026 (6)	0.0141 (8)	−0.0134 (8)
N1	0.0187 (5)	0.0188 (6)	0.0232 (5)	−0.0019 (4)	0.0062 (4)	−0.0005 (4)
N2	0.0227 (6)	0.0247 (6)	0.0273 (6)	−0.0029 (4)	0.0062 (5)	−0.0020 (5)
N3	0.0254 (6)	0.0202 (6)	0.0272 (6)	−0.0047 (4)	0.0094 (5)	−0.0004 (5)
N4	0.0237 (6)	0.0209 (6)	0.0213 (5)	−0.0012 (4)	0.0047 (4)	0.0018 (4)
N5	0.0253 (6)	0.0198 (6)	0.0267 (6)	−0.0026 (4)	0.0059 (5)	−0.0008 (4)
S1	0.0306 (2)	0.0232 (2)	0.02287 (19)	−0.00195 (12)	0.00779 (14)	0.00007 (12)

Geometric parameters (Å, º)

C1—N3	1.3446 (17)	C9—H9C	0.9800
C1—N1	1.3830 (17)	C10—N4	1.4528 (18)
C1—S1	1.6716 (14)	C10—H10A	0.9900
C2—N2	1.2969 (18)	C10—H10B	0.9900
C2—N1	1.3821 (17)	C11—N4	1.3562 (17)
C2—C10	1.4925 (18)	C11—C12	1.375 (2)
C3—C8	1.3825 (19)	C11—C14	1.492 (2)
C3—C4	1.3860 (19)	C12—C13	1.403 (2)
C3—N1	1.4378 (16)	C12—H12	0.9500
C4—C5	1.389 (2)	C13—N5	1.3356 (19)
C4—H4	0.9500	C13—C15	1.493 (2)
C5—C6	1.387 (2)	C14—H14A	0.9800
C5—H5	0.9500	C14—H14B	0.9800
C6—C7	1.388 (2)	C14—H14C	0.9800
C6—H6	0.9500	C15—H15A	0.9800
C7—C8	1.399 (2)	C15—H15B	0.9800
C7—C9	1.504 (2)	C15—H15C	0.9800
C8—H8	0.9500	N2—N3	1.3749 (16)
C9—H9A	0.9800	N3—H3N	0.877 (18)
C9—H9B	0.9800	N4—N5	1.3680 (16)
N3—C1—N1	103.24 (11)	C2—C10—H10B	109.3
N3—C1—S1	128.72 (11)	H10A—C10—H10B	108.0
N1—C1—S1	128.04 (10)	N4—C11—C12	106.20 (12)
N2—C2—N1	111.18 (12)	N4—C11—C14	122.77 (13)
N2—C2—C10	123.31 (12)	C12—C11—C14	131.03 (13)
N1—C2—C10	125.47 (12)	C11—C12—C13	106.16 (12)
C8—C3—C4	121.58 (13)	C11—C12—H12	126.9
C8—C3—N1	119.34 (12)	C13—C12—H12	126.9
C4—C3—N1	119.06 (12)	N5—C13—C12	110.66 (13)
C3—C4—C5	118.64 (14)	N5—C13—C15	120.36 (13)
C3—C4—H4	120.7	C12—C13—C15	128.98 (14)
C5—C4—H4	120.7	C11—C14—H14A	109.5
C6—C5—C4	120.01 (15)	C11—C14—H14B	109.5
C6—C5—H5	120.0	H14A—C14—H14B	109.5
C4—C5—H5	120.0	C11—C14—H14C	109.5
C5—C6—C7	121.50 (14)	H14A—C14—H14C	109.5
C5—C6—H6	119.3	H14B—C14—H14C	109.5
C7—C6—H6	119.3	C13—C15—H15A	109.5
C6—C7—C8	118.28 (13)	C13—C15—H15B	109.5
C6—C7—C9	121.68 (14)	H15A—C15—H15B	109.5
C8—C7—C9	120.03 (15)	C13—C15—H15C	109.5
C3—C8—C7	119.98 (13)	H15A—C15—H15C	109.5
C3—C8—H8	120.0	H15B—C15—H15C	109.5
C7—C8—H8	120.0	C2—N1—C1	107.70 (11)
C7—C9—H9A	109.5	C2—N1—C3	126.55 (11)
C7—C9—H9B	109.5	C1—N1—C3	125.71 (11)
H9A—C9—H9B	109.5	C2—N2—N3	104.38 (11)
C7—C9—H9C	109.5	C1—N3—N2	113.45 (11)
H9A—C9—H9C	109.5	C1—N3—H3N	126.1 (11)
H9B—C9—H9C	109.5	N2—N3—H3N	119.0 (11)
N4—C10—C2	111.49 (11)	C11—N4—N5	112.00 (11)
N4—C10—H10A	109.3	C11—N4—C10	128.80 (12)
C2—C10—H10A	109.3	N5—N4—C10	119.10 (11)
N4—C10—H10B	109.3	C13—N5—N4	104.98 (11)
C8—C3—C4—C5	0.2 (2)	N3—C1—N1—C3	−175.76 (12)
N1—C3—C4—C5	178.65 (12)	S1—C1—N1—C3	4.15 (19)
C3—C4—C5—C6	−1.1 (2)	C8—C3—N1—C2	82.53 (16)
C4—C5—C6—C7	0.7 (2)	C4—C3—N1—C2	−95.92 (16)
C5—C6—C7—C8	0.5 (2)	C8—C3—N1—C1	−100.26 (15)
C5—C6—C7—C9	−177.92 (14)	C4—C3—N1—C1	81.29 (16)
C4—C3—C8—C7	1.0 (2)	N1—C2—N2—N3	−0.52 (15)
N1—C3—C8—C7	−177.44 (11)	C10—C2—N2—N3	−178.55 (12)
C6—C7—C8—C3	−1.3 (2)	N1—C1—N3—N2	−2.35 (15)
C9—C7—C8—C3	177.12 (13)	S1—C1—N3—N2	177.75 (10)
N2—C2—C10—N4	115.87 (14)	C2—N2—N3—C1	1.86 (15)
N1—C2—C10—N4	−61.87 (17)	C12—C11—N4—N5	−0.22 (15)
N4—C11—C12—C13	0.25 (15)	C14—C11—N4—N5	179.05 (12)
C14—C11—C12—C13	−178.93 (14)	C12—C11—N4—C10	−176.50 (12)
C11—C12—C13—N5	−0.21 (16)	C14—C11—N4—C10	2.8 (2)
C11—C12—C13—C15	179.17 (15)	C2—C10—N4—C11	121.63 (14)
N2—C2—N1—C1	−0.89 (15)	C2—C10—N4—N5	−54.42 (16)
C10—C2—N1—C1	177.09 (12)	C12—C13—N5—N4	0.08 (15)
N2—C2—N1—C3	176.74 (12)	C15—C13—N5—N4	−179.37 (13)
C10—C2—N1—C3	−5.3 (2)	C11—N4—N5—C13	0.09 (14)
N3—C1—N1—C2	1.89 (14)	C10—N4—N5—C13	176.77 (11)
S1—C1—N1—C2	−178.20 (10)

Hydrogen-bond geometry (Å, º)

Cg1, Cg2 and Cg3 are the centroids of the N1–N3/C1/C2, N4/N5/C11–C13 and C3–C8 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg2	0.95	2.81	3.2544 (14)	110
C14—H14A···Cg3	0.98	2.79	3.6130 (17)	143
N3—H3N···N5^i	0.878 (18)	1.978 (18)	2.8334 (17)	164.5 (16)
C15—H15C···N2^ii	0.98	2.59	3.550 (2)	168
C9—H9B···Cg1^ii	0.98	2.88	3.637 (2)	135
C5—H5···S1^iii	0.95	2.93	3.824 (2)	157
C10—H10A···S1^iv	0.99	2.93	3.747 (1)	140

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2.