5-{[5-(4-Chloro­phen­yl)-3-methyl-1H-pyrazol-1-yl]meth­yl}-1,3,4-oxa­diazole-2(3H)-thione

In the title compound, C₁₃H₁₁ClN₄OS, the oxa­diazo­lethione ring is inclined to the pyrazole ring by 79.2 (2)°. The 4-chloro­phenyl ring is rotationally disordered, with the two fragments inclined to one another by 27.1 (4)°, and to the pyrazole ring by 43.1 (3) and 68.6 (3)°. In the crystal, mol­ecules are linked by pairs of N—H...N hydrogen bonds, forming inversion dimers, enclosing an R₂²(14) ring motif. The dimers are linked by C—H...N hydrogen bonds, forming ribbons propagating along the a-axis direction and enclosing R₂²(8) ring motifs. The ribbons are linked by C—H...Cl hydrogen bonds, forming a three-dimensional supra­molecular structure.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.068
• wR factor = 0.195
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00675 Ang.
PLAT397_ALERT_2_C Deviating  C-O-C  Angle from 120 Deg for  O1          105.8 Degree
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.635 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         14 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.11 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          7 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1)..         35 % Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Note

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 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) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

5-{[5-(4-Chlorophenyl)-3-methyl-1H-pyrazol-1-yl]methyl}-1,3,4-oxadiazole-2(3H)-thione

Crystal data

C13H11ClN4OS	F(000) = 632
Mr = 306.77	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 4.9309 (2) Å	Cell parameters from 4259 reflections
b = 17.1173 (8) Å	θ = 3.7–69.9°
c = 16.6517 (7) Å	µ = 3.81 mm^−1
β = 91.189 (3)°	T = 150 K
V = 1405.16 (11) Å^3	Needles, colourless
Z = 4	0.20 × 0.05 × 0.02 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2632 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1759 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.080
Detector resolution: 10.4167 pixels mm^-1	θmax = 70.1°, θmin = 3.7°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −20→18
Tmin = 0.63, Tmax = 0.92	l = −20→20
10669 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.195	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.106P)^2 + 0.4524P] where P = (Fo^2 + 2Fc^2)/3
2632 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 0.51 e Å^−3
2 restraints	Δρmin = −0.49 e Å^−3

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.

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. The 4-chlorophenyl group is rotationally disordered by 27.1 (4)° in approximately equal amounts. The two components of the disorder were refined as rigid hexagons. H-atoms were placed in calculated positions (C—H = 0.95 - 0.9 Å; N—H = 0.88 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	1.3239 (3)	0.90840 (8)	0.71546 (7)	0.0599 (4)
O1	0.9335 (6)	0.86722 (16)	0.60987 (18)	0.0498 (7)
N1	0.9888 (7)	0.9914 (2)	0.6167 (2)	0.0491 (8)
H1	1.0495	1.0379	0.6307	0.059*
N2	0.7856 (7)	0.9795 (2)	0.5597 (2)	0.0482 (8)
N3	0.7160 (7)	0.8117 (2)	0.4491 (2)	0.0489 (9)
N4	0.8597 (7)	0.8490 (2)	0.3914 (2)	0.0511 (9)
C1	1.0829 (8)	0.9253 (2)	0.6482 (2)	0.0473 (10)
C2	0.7581 (8)	0.9051 (2)	0.5581 (3)	0.0476 (10)
C3	0.5703 (9)	0.8592 (3)	0.5072 (3)	0.0556 (11)
H3A	0.4608	0.8246	0.5415	0.067*
H3B	0.4447	0.8950	0.4782	0.067*
C4	0.7085 (9)	0.7334 (3)	0.4378 (3)	0.0526 (11)
C5	0.8504 (10)	0.7191 (3)	0.3686 (3)	0.0564 (12)
H5	0.8798	0.6700	0.3438	0.068*
C6	0.9417 (9)	0.7919 (3)	0.3426 (3)	0.0527 (11)
C7	1.1209 (10)	0.8099 (3)	0.2742 (3)	0.0613 (12)
H7A	1.0721	0.7764	0.2284	0.092*
H7B	1.3103	0.8004	0.2903	0.092*
H7C	1.0983	0.8649	0.2588	0.092*
Cl1A	0.1985 (12)	0.4995 (3)	0.6544 (5)	0.0542 (10)	0.506 (5)
C8A	0.5677 (16)	0.6786 (3)	0.4912 (5)	0.0459 (10)	0.506 (5)
C9A	0.5994 (16)	0.6831 (4)	0.5742 (5)	0.049 (2)	0.506 (5)
H9A	0.6967	0.7255	0.5979	0.059*	0.506 (5)
C10A	0.4886 (18)	0.6258 (5)	0.6227 (3)	0.0514 (17)	0.506 (5)
H10A	0.5102	0.6289	0.6794	0.062*	0.506 (5)
C11A	0.3461 (18)	0.5638 (4)	0.5881 (4)	0.0418 (16)	0.506 (5)
C12A	0.3145 (15)	0.5593 (4)	0.5051 (5)	0.0475 (15)	0.506 (5)
H12A	0.2171	0.5169	0.4815	0.057*	0.506 (5)
C13A	0.4252 (16)	0.6167 (4)	0.4567 (3)	0.0433 (18)	0.506 (5)
H13A	0.4036	0.6136	0.3999	0.052*	0.506 (5)
Cl1B	0.1220 (12)	0.5135 (4)	0.6530 (5)	0.0542 (10)	0.494 (5)
C8B	0.5833 (15)	0.6771 (4)	0.4934 (5)	0.0459 (10)	0.494 (5)
C9B	0.6805 (13)	0.6650 (5)	0.5714 (6)	0.049 (2)	0.494 (5)
H9B	0.8412	0.6906	0.5897	0.059*	0.494 (5)
C10B	0.5427 (17)	0.6154 (5)	0.6226 (4)	0.0514 (17)	0.494 (5)
H10B	0.6091	0.6072	0.6759	0.062*	0.494 (5)
C11B	0.3076 (16)	0.5780 (4)	0.5958 (4)	0.0418 (16)	0.494 (5)
C12B	0.2104 (13)	0.5901 (4)	0.5178 (5)	0.0475 (15)	0.494 (5)
H12B	0.0498	0.5644	0.4995	0.057*	0.494 (5)
C13B	0.3483 (16)	0.6396 (5)	0.4666 (4)	0.0433 (18)	0.494 (5)
H13B	0.2819	0.6479	0.4134	0.052*	0.494 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0586 (7)	0.0667 (8)	0.0547 (6)	0.0081 (5)	0.0091 (5)	0.0061 (5)
O1	0.0478 (16)	0.0355 (15)	0.0665 (19)	0.0006 (12)	0.0149 (14)	−0.0005 (13)
N1	0.055 (2)	0.041 (2)	0.0515 (19)	−0.0032 (16)	0.0035 (17)	−0.0019 (15)
N2	0.051 (2)	0.042 (2)	0.052 (2)	−0.0013 (15)	0.0075 (16)	−0.0023 (14)
N3	0.049 (2)	0.0377 (19)	0.061 (2)	−0.0072 (15)	0.0139 (17)	−0.0069 (15)
N4	0.051 (2)	0.0371 (19)	0.066 (2)	−0.0013 (15)	0.0133 (17)	0.0025 (15)
C1	0.048 (2)	0.042 (2)	0.053 (2)	0.0021 (17)	0.0185 (19)	0.0016 (17)
C2	0.043 (2)	0.042 (2)	0.058 (2)	0.0014 (17)	0.0153 (19)	−0.0005 (18)
C3	0.052 (3)	0.041 (2)	0.074 (3)	−0.0029 (19)	0.014 (2)	−0.012 (2)
C4	0.050 (2)	0.042 (2)	0.066 (3)	−0.0030 (18)	0.013 (2)	−0.0052 (19)
C5	0.060 (3)	0.038 (2)	0.072 (3)	0.0026 (19)	0.023 (2)	−0.004 (2)
C6	0.051 (3)	0.041 (2)	0.066 (3)	−0.0018 (18)	0.015 (2)	0.0029 (19)
C7	0.066 (3)	0.051 (3)	0.068 (3)	0.002 (2)	0.024 (2)	0.009 (2)
Cl1A	0.069 (3)	0.0373 (19)	0.0567 (7)	0.0002 (16)	0.001 (2)	0.0098 (13)
C8A	0.038 (2)	0.036 (2)	0.064 (3)	0.0009 (16)	0.0118 (19)	−0.0029 (18)
C9A	0.025 (5)	0.070 (5)	0.053 (3)	−0.010 (4)	0.023 (3)	−0.023 (3)
C10A	0.036 (4)	0.069 (4)	0.050 (3)	−0.004 (3)	0.009 (2)	−0.008 (2)
C11A	0.046 (3)	0.028 (3)	0.052 (3)	0.007 (3)	0.009 (2)	−0.006 (2)
C12A	0.045 (4)	0.040 (4)	0.058 (4)	−0.003 (3)	0.002 (3)	0.002 (3)
C13A	0.031 (5)	0.040 (5)	0.058 (3)	0.009 (3)	−0.005 (3)	0.008 (3)
Cl1B	0.069 (3)	0.0373 (19)	0.0567 (7)	0.0002 (16)	0.001 (2)	0.0098 (13)
C8B	0.038 (2)	0.036 (2)	0.064 (3)	0.0009 (16)	0.0118 (19)	−0.0029 (18)
C9B	0.025 (5)	0.070 (5)	0.053 (3)	−0.010 (4)	0.023 (3)	−0.023 (3)
C10B	0.036 (4)	0.069 (4)	0.050 (3)	−0.004 (3)	0.009 (2)	−0.008 (2)
C11B	0.046 (3)	0.028 (3)	0.052 (3)	0.007 (3)	0.009 (2)	−0.006 (2)
C12B	0.045 (4)	0.040 (4)	0.058 (4)	−0.003 (3)	0.002 (3)	0.002 (3)
C13B	0.031 (5)	0.040 (5)	0.058 (3)	0.009 (3)	−0.005 (3)	0.008 (3)

Geometric parameters (Å, º)

S1—C1	1.642 (5)	Cl1A—C11A	1.730 (3)
O1—C2	1.371 (5)	C8A—C9A	1.3900
O1—C1	1.386 (5)	C8A—C13A	1.3900
N1—C1	1.327 (5)	C9A—C10A	1.3900
N1—N2	1.380 (5)	C9A—H9A	0.9500
N1—H1	0.8800	C10A—C11A	1.3900
N2—C2	1.282 (5)	C10A—H10A	0.9500
N3—C4	1.355 (6)	C11A—C12A	1.3900
N3—N4	1.364 (5)	C12A—C13A	1.3900
N3—C3	1.463 (5)	C12A—H12A	0.9500
N4—C6	1.339 (6)	C13A—H13A	0.9500
C2—C3	1.470 (6)	Cl1B—C11B	1.732 (3)
C3—H3A	0.9900	C8B—C9B	1.3900
C3—H3B	0.9900	C8B—C13B	1.3900
C4—C5	1.383 (6)	C9B—C10B	1.3900
C4—C8A	1.476 (5)	C9B—H9B	0.9500
C4—C8B	1.480 (5)	C10B—C11B	1.3900
C5—C6	1.396 (6)	C10B—H10B	0.9500
C5—H5	0.9500	C11B—C12B	1.3900
C6—C7	1.488 (6)	C12B—C13B	1.3900
C7—H7A	0.9800	C12B—H12B	0.9500
C7—H7B	0.9800	C13B—H13B	0.9500
C7—H7C	0.9800
C2—O1—C1	105.8 (3)	H7B—C7—H7C	109.5
C1—N1—N2	112.8 (4)	C9A—C8A—C13A	120.0
C1—N1—H1	123.6	C9A—C8A—C4	121.3 (7)
N2—N1—H1	123.6	C13A—C8A—C4	118.4 (7)
C2—N2—N1	103.7 (3)	C10A—C9A—C8A	120.0
C4—N3—N4	112.2 (3)	C10A—C9A—H9A	120.0
C4—N3—C3	129.0 (4)	C8A—C9A—H9A	120.0
N4—N3—C3	118.4 (3)	C11A—C10A—C9A	120.0
C6—N4—N3	104.8 (3)	C11A—C10A—H10A	120.0
N1—C1—O1	104.6 (4)	C9A—C10A—H10A	120.0
N1—C1—S1	131.5 (4)	C10A—C11A—C12A	120.0
O1—C1—S1	123.9 (3)	C10A—C11A—Cl1A	115.9 (6)
N2—C2—O1	113.0 (4)	C12A—C11A—Cl1A	123.9 (6)
N2—C2—C3	127.5 (4)	C13A—C12A—C11A	120.0
O1—C2—C3	119.5 (4)	C13A—C12A—H12A	120.0
N3—C3—C2	111.5 (4)	C11A—C12A—H12A	120.0
N3—C3—H3A	109.3	C12A—C13A—C8A	120.0
C2—C3—H3A	109.3	C12A—C13A—H13A	120.0
N3—C3—H3B	109.3	C8A—C13A—H13A	120.0
C2—C3—H3B	109.3	C9B—C8B—C13B	120.0
H3A—C3—H3B	108.0	C9B—C8B—C4	122.8 (7)
N3—C4—C5	106.1 (4)	C13B—C8B—C4	117.1 (7)
N3—C4—C8A	123.8 (5)	C8B—C9B—C10B	120.0
C5—C4—C8A	130.0 (5)	C8B—C9B—H9B	120.0
N3—C4—C8B	124.6 (5)	C10B—C9B—H9B	120.0
C5—C4—C8B	129.2 (5)	C11B—C10B—C9B	120.0
C4—C5—C6	105.9 (4)	C11B—C10B—H10B	120.0
C4—C5—H5	127.1	C9B—C10B—H10B	120.0
C6—C5—H5	127.1	C10B—C11B—C12B	120.0
N4—C6—C5	111.1 (4)	C10B—C11B—Cl1B	124.4 (6)
N4—C6—C7	120.3 (4)	C12B—C11B—Cl1B	115.6 (6)
C5—C6—C7	128.5 (4)	C13B—C12B—C11B	120.0
C6—C7—H7A	109.5	C13B—C12B—H12B	120.0
C6—C7—H7B	109.5	C11B—C12B—H12B	120.0
H7A—C7—H7B	109.5	C12B—C13B—C8B	120.0
C6—C7—H7C	109.5	C12B—C13B—H13B	120.0
H7A—C7—H7C	109.5	C8B—C13B—H13B	120.0
C1—N1—N2—C2	0.5 (5)	N3—C4—C8A—C9A	−46.9 (7)
C4—N3—N4—C6	0.5 (5)	C5—C4—C8A—C9A	134.3 (6)
C3—N3—N4—C6	−172.9 (4)	N3—C4—C8A—C13A	140.1 (5)
N2—N1—C1—O1	0.0 (4)	C5—C4—C8A—C13A	−38.8 (9)
N2—N1—C1—S1	178.6 (3)	C13A—C8A—C9A—C10A	0.0
C2—O1—C1—N1	−0.5 (4)	C4—C8A—C9A—C10A	−173.0 (7)
C2—O1—C1—S1	−179.2 (3)	C8A—C9A—C10A—C11A	0.0
N1—N2—C2—O1	−0.8 (4)	C9A—C10A—C11A—C12A	0.0
N1—N2—C2—C3	−179.3 (4)	C9A—C10A—C11A—Cl1A	−175.9 (7)
C1—O1—C2—N2	0.8 (4)	C10A—C11A—C12A—C13A	0.0
C1—O1—C2—C3	179.5 (3)	Cl1A—C11A—C12A—C13A	175.6 (7)
C4—N3—C3—C2	123.0 (5)	C11A—C12A—C13A—C8A	0.0
N4—N3—C3—C2	−64.9 (5)	C9A—C8A—C13A—C12A	0.0
N2—C2—C3—N3	113.1 (5)	C4—C8A—C13A—C12A	173.2 (7)
O1—C2—C3—N3	−65.3 (5)	N3—C4—C8B—C9B	−64.5 (7)
N4—N3—C4—C5	−1.0 (5)	C5—C4—C8B—C9B	111.6 (7)
C3—N3—C4—C5	171.5 (4)	N3—C4—C8B—C13B	111.0 (6)
N4—N3—C4—C8A	179.9 (6)	C5—C4—C8B—C13B	−72.9 (7)
C3—N3—C4—C8A	−7.6 (9)	C13B—C8B—C9B—C10B	0.0
N4—N3—C4—C8B	175.8 (6)	C4—C8B—C9B—C10B	175.4 (7)
C3—N3—C4—C8B	−11.7 (9)	C8B—C9B—C10B—C11B	0.0
N3—C4—C5—C6	1.1 (6)	C9B—C10B—C11B—C12B	0.0
C8A—C4—C5—C6	−179.9 (7)	C9B—C10B—C11B—Cl1B	178.6 (7)
C8B—C4—C5—C6	−175.5 (6)	C10B—C11B—C12B—C13B	0.0
N3—N4—C6—C5	0.3 (5)	Cl1B—C11B—C12B—C13B	−178.7 (7)
N3—N4—C6—C7	−176.2 (4)	C11B—C12B—C13B—C8B	0.0
C4—C5—C6—N4	−0.9 (6)	C9B—C8B—C13B—C12B	0.0
C4—C5—C6—C7	175.3 (5)	C4—C8B—C13B—C12B	−175.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4^i	0.88	2.02	2.836 (5)	153
C3—H3B···N2^ii	0.99	2.51	3.445 (6)	158
C7—H7C···Cl1B^iii	0.98	2.73	3.635 (10)	153

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