In the title compound, C13H11N5OS2, the dihedral angle between the planes of the phenyl and pyrazole rings is 25.62 (2)°. The crystal packing is stablized by intra- and intermolecular hydrogen bonds which link the molecules into a three-dimensional network.
Supporting information
CCDC reference: 601239
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.037
- wR factor = 0.095
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.09 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.76 Ratio
PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C4 ... 1.42 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 3
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
1-Benzoyl-3-(4-cyano-5-methylsulfanyl-1
H-pyrazol-3-yl)thiourea
top
Crystal data top
C13H11N5OS2 | F(000) = 656 |
Mr = 317.39 | Dx = 1.454 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3337 reflections |
a = 7.6970 (11) Å | θ = 2.6–26.2° |
b = 15.892 (2) Å | µ = 0.37 mm−1 |
c = 12.0775 (17) Å | T = 294 K |
β = 100.999 (2)° | Plate, light yellow |
V = 1450.2 (3) Å3 | 0.34 × 0.28 × 0.24 mm |
Z = 4 | |
Data collection top
Bruker SMART 1000 CCD area-detector diffractometer | 2938 independent reflections |
Radiation source: fine-focus sealed tube | 2287 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 26.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→9 |
Tmin = 0.882, Tmax = 0.914 | k = −19→19 |
8039 measured reflections | l = −15→14 |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.7311P] where P = (Fo2 + 2Fc2)/3 |
2938 reflections | (Δ/σ)max = 0.001 |
212 parameters | Δρmax = 0.30 e Å−3 |
20 restraints | Δρmin = −0.34 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.88574 (9) | 0.39786 (4) | 0.61584 (7) | 0.0688 (2) | |
S2 | 0.20987 (6) | 0.27316 (3) | 0.37905 (5) | 0.03952 (16) | |
O1 | 0.33366 (17) | −0.00581 (8) | 0.41396 (13) | 0.0420 (4) | |
N1 | 0.8393 (2) | 0.25986 (11) | 0.48282 (16) | 0.0420 (4) | |
N2 | 0.7313 (2) | 0.19593 (10) | 0.43960 (15) | 0.0377 (4) | |
N3 | 0.4438 (2) | 0.15222 (10) | 0.45187 (14) | 0.0327 (4) | |
H3 | 0.471 (3) | 0.0999 (14) | 0.4560 (17) | 0.037 (6)* | |
N4 | 0.1561 (2) | 0.10974 (10) | 0.38200 (14) | 0.0334 (4) | |
H4 | 0.057 (3) | 0.1259 (13) | 0.3480 (18) | 0.037 (6)* | |
N5 | 0.3860 (3) | 0.34654 (14) | 0.66339 (18) | 0.0588 (5) | |
C1 | 0.7680 (3) | 0.31268 (12) | 0.54738 (18) | 0.0392 (5) | |
C2 | 0.5990 (2) | 0.28199 (12) | 0.54778 (17) | 0.0347 (4) | |
C3 | 0.5847 (2) | 0.21005 (11) | 0.47907 (16) | 0.0313 (4) | |
C4 | 0.4775 (3) | 0.31706 (13) | 0.60991 (18) | 0.0406 (5) | |
C5 | 0.7599 (10) | 0.4839 (3) | 0.5434 (13) | 0.093 (3) | 0.80 (3) |
H5A | 0.7754 | 0.4854 | 0.4664 | 0.139* | 0.80 (3) |
H5B | 0.8004 | 0.5359 | 0.5798 | 0.139* | 0.80 (3) |
H5C | 0.6368 | 0.4763 | 0.5454 | 0.139* | 0.80 (3) |
C5' | 0.734 (3) | 0.4834 (13) | 0.588 (3) | 0.074 (7) | 0.20 (3) |
H5'A | 0.6929 | 0.4981 | 0.6556 | 0.111* | 0.20 (3) |
H5'B | 0.6344 | 0.4670 | 0.5309 | 0.111* | 0.20 (3) |
H5'C | 0.7913 | 0.5309 | 0.5618 | 0.111* | 0.20 (3) |
C6 | 0.2776 (2) | 0.17441 (11) | 0.40699 (16) | 0.0301 (4) | |
C7 | 0.1860 (2) | 0.02368 (12) | 0.38411 (16) | 0.0310 (4) | |
C8 | 0.0260 (2) | −0.02926 (11) | 0.34655 (15) | 0.0302 (4) | |
C9 | −0.1456 (2) | −0.00075 (13) | 0.34472 (17) | 0.0371 (5) | |
H9 | −0.1647 | 0.0543 | 0.3658 | 0.045* | |
C10 | −0.2875 (3) | −0.05441 (14) | 0.31153 (19) | 0.0459 (5) | |
H10 | −0.4021 | −0.0354 | 0.3104 | 0.055* | |
C11 | −0.2593 (3) | −0.13603 (14) | 0.28015 (19) | 0.0502 (6) | |
H11 | −0.3551 | −0.1719 | 0.2580 | 0.060* | |
C12 | −0.0900 (3) | −0.16441 (14) | 0.2816 (2) | 0.0529 (6) | |
H12 | −0.0716 | −0.2194 | 0.2601 | 0.064* | |
C13 | 0.0523 (3) | −0.11168 (13) | 0.31484 (18) | 0.0422 (5) | |
H13 | 0.1665 | −0.1313 | 0.3161 | 0.051* | |
H1 | 0.936 (3) | 0.2632 (15) | 0.4668 (19) | 0.049 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0526 (4) | 0.0480 (4) | 0.0980 (6) | −0.0173 (3) | −0.0057 (4) | −0.0157 (3) |
S2 | 0.0287 (3) | 0.0291 (3) | 0.0585 (3) | −0.00116 (19) | 0.0026 (2) | 0.0062 (2) |
O1 | 0.0273 (7) | 0.0330 (7) | 0.0631 (10) | 0.0022 (6) | 0.0017 (6) | −0.0031 (7) |
N1 | 0.0249 (9) | 0.0418 (10) | 0.0603 (12) | −0.0047 (8) | 0.0107 (8) | 0.0010 (8) |
N2 | 0.0295 (8) | 0.0356 (9) | 0.0481 (10) | −0.0014 (7) | 0.0077 (7) | −0.0020 (7) |
N3 | 0.0249 (8) | 0.0256 (8) | 0.0458 (10) | −0.0002 (6) | 0.0021 (7) | −0.0009 (7) |
N4 | 0.0232 (8) | 0.0277 (8) | 0.0461 (10) | −0.0014 (6) | −0.0012 (7) | 0.0024 (7) |
N5 | 0.0529 (12) | 0.0686 (14) | 0.0547 (12) | 0.0084 (10) | 0.0099 (10) | −0.0187 (11) |
C1 | 0.0314 (10) | 0.0328 (10) | 0.0507 (13) | −0.0027 (8) | 0.0007 (9) | 0.0004 (9) |
C2 | 0.0279 (10) | 0.0332 (10) | 0.0419 (11) | −0.0002 (8) | 0.0037 (8) | −0.0030 (8) |
C3 | 0.0255 (9) | 0.0305 (10) | 0.0363 (10) | 0.0002 (7) | 0.0015 (8) | 0.0024 (8) |
C4 | 0.0356 (11) | 0.0396 (11) | 0.0434 (12) | −0.0011 (9) | −0.0007 (9) | −0.0070 (9) |
C5 | 0.096 (4) | 0.040 (2) | 0.143 (6) | 0.000 (2) | 0.026 (4) | 0.002 (3) |
C5' | 0.076 (10) | 0.067 (9) | 0.079 (11) | −0.006 (7) | 0.016 (7) | −0.010 (7) |
C6 | 0.0276 (9) | 0.0299 (9) | 0.0331 (10) | −0.0020 (7) | 0.0067 (8) | −0.0006 (8) |
C7 | 0.0304 (10) | 0.0305 (10) | 0.0319 (10) | 0.0000 (7) | 0.0055 (8) | 0.0000 (8) |
C8 | 0.0326 (10) | 0.0284 (9) | 0.0295 (9) | −0.0018 (7) | 0.0055 (8) | −0.0003 (7) |
C9 | 0.0337 (10) | 0.0332 (10) | 0.0457 (12) | −0.0024 (8) | 0.0106 (9) | −0.0025 (9) |
C10 | 0.0315 (11) | 0.0518 (13) | 0.0547 (13) | −0.0065 (9) | 0.0088 (9) | −0.0002 (10) |
C11 | 0.0458 (13) | 0.0477 (13) | 0.0530 (14) | −0.0199 (10) | −0.0010 (10) | −0.0039 (10) |
C12 | 0.0590 (15) | 0.0351 (11) | 0.0589 (15) | −0.0054 (10) | −0.0032 (12) | −0.0141 (10) |
C13 | 0.0388 (11) | 0.0376 (11) | 0.0478 (12) | 0.0025 (9) | 0.0019 (9) | −0.0082 (9) |
Geometric parameters (Å, º) top
S1—C1 | 1.747 (2) | C5—H5A | 0.9600 |
S1—C5' | 1.784 (10) | C5—H5B | 0.9600 |
S1—C5 | 1.803 (5) | C5—H5C | 0.9600 |
S2—C6 | 1.6677 (19) | C5'—H5'A | 0.9600 |
O1—C7 | 1.219 (2) | C5'—H5'B | 0.9600 |
N1—C1 | 1.333 (3) | C5'—H5'C | 0.9600 |
N1—N2 | 1.353 (2) | C7—C8 | 1.489 (2) |
N1—H1 | 0.80 (2) | C8—C13 | 1.390 (3) |
N2—C3 | 1.325 (2) | C8—C9 | 1.393 (3) |
N3—C6 | 1.338 (2) | C9—C10 | 1.383 (3) |
N3—C3 | 1.412 (2) | C9—H9 | 0.9300 |
N3—H3 | 0.86 (2) | C10—C11 | 1.380 (3) |
N4—C6 | 1.383 (2) | C10—H10 | 0.9300 |
N4—C7 | 1.386 (2) | C11—C12 | 1.376 (3) |
N4—H4 | 0.83 (2) | C11—H11 | 0.9300 |
N5—C4 | 1.143 (3) | C12—C13 | 1.377 (3) |
C1—C2 | 1.390 (3) | C12—H12 | 0.9300 |
C2—C3 | 1.405 (3) | C13—H13 | 0.9300 |
C2—C4 | 1.420 (3) | | |
| | | |
C1—S1—C5' | 103.7 (9) | S1—C5'—H5'B | 109.5 |
C1—S1—C5 | 100.1 (3) | H5'A—C5'—H5'B | 109.5 |
C1—N1—N2 | 114.01 (17) | S1—C5'—H5'C | 109.5 |
C1—N1—H1 | 127.0 (17) | H5'A—C5'—H5'C | 109.5 |
N2—N1—H1 | 119.0 (17) | H5'B—C5'—H5'C | 109.5 |
C3—N2—N1 | 103.70 (16) | N3—C6—N4 | 116.55 (16) |
C6—N3—C3 | 123.75 (16) | N3—C6—S2 | 124.58 (14) |
C6—N3—H3 | 118.7 (14) | N4—C6—S2 | 118.86 (14) |
C3—N3—H3 | 117.0 (14) | O1—C7—N4 | 121.81 (17) |
C6—N4—C7 | 128.73 (17) | O1—C7—C8 | 122.90 (17) |
C6—N4—H4 | 113.2 (14) | N4—C7—C8 | 115.28 (16) |
C7—N4—H4 | 116.5 (14) | C13—C8—C9 | 119.33 (18) |
N1—C1—C2 | 105.74 (17) | C13—C8—C7 | 117.45 (17) |
N1—C1—S1 | 122.02 (15) | C9—C8—C7 | 123.21 (17) |
C2—C1—S1 | 132.20 (17) | C10—C9—C8 | 119.86 (19) |
C1—C2—C3 | 104.57 (17) | C10—C9—H9 | 120.1 |
C1—C2—C4 | 125.12 (18) | C8—C9—H9 | 120.1 |
C3—C2—C4 | 130.26 (18) | C11—C10—C9 | 120.2 (2) |
N2—C3—C2 | 111.98 (16) | C11—C10—H10 | 119.9 |
N2—C3—N3 | 118.36 (17) | C9—C10—H10 | 119.9 |
C2—C3—N3 | 129.60 (17) | C12—C11—C10 | 120.1 (2) |
N5—C4—C2 | 176.9 (2) | C12—C11—H11 | 119.9 |
S1—C5—H5A | 109.5 | C10—C11—H11 | 119.9 |
S1—C5—H5B | 109.5 | C11—C12—C13 | 120.2 (2) |
H5A—C5—H5B | 109.5 | C11—C12—H12 | 119.9 |
S1—C5—H5C | 109.5 | C13—C12—H12 | 119.9 |
H5A—C5—H5C | 109.5 | C12—C13—C8 | 120.3 (2) |
H5B—C5—H5C | 109.5 | C12—C13—H13 | 119.9 |
S1—C5'—H5'A | 109.5 | C8—C13—H13 | 119.9 |
| | | |
C1—N1—N2—C3 | 0.3 (2) | C3—N3—C6—N4 | 178.03 (17) |
N2—N1—C1—C2 | 0.0 (2) | C3—N3—C6—S2 | −1.5 (3) |
N2—N1—C1—S1 | 177.84 (14) | C7—N4—C6—N3 | −8.7 (3) |
C5'—S1—C1—N1 | 133.9 (13) | C7—N4—C6—S2 | 170.84 (16) |
C5—S1—C1—N1 | 114.3 (5) | C6—N4—C7—O1 | 2.5 (3) |
C5'—S1—C1—C2 | −48.9 (13) | C6—N4—C7—C8 | −176.96 (18) |
C5—S1—C1—C2 | −68.5 (6) | O1—C7—C8—C13 | −18.2 (3) |
N1—C1—C2—C3 | −0.3 (2) | N4—C7—C8—C13 | 161.26 (18) |
S1—C1—C2—C3 | −177.81 (17) | O1—C7—C8—C9 | 160.12 (19) |
N1—C1—C2—C4 | 177.4 (2) | N4—C7—C8—C9 | −20.4 (3) |
S1—C1—C2—C4 | −0.1 (3) | C13—C8—C9—C10 | 0.0 (3) |
N1—N2—C3—C2 | −0.5 (2) | C7—C8—C9—C10 | −178.28 (18) |
N1—N2—C3—N3 | −178.19 (16) | C8—C9—C10—C11 | −0.1 (3) |
C1—C2—C3—N2 | 0.5 (2) | C9—C10—C11—C12 | −0.1 (4) |
C4—C2—C3—N2 | −177.0 (2) | C10—C11—C12—C13 | 0.3 (4) |
C1—C2—C3—N3 | 177.90 (19) | C11—C12—C13—C8 | −0.3 (4) |
C4—C2—C3—N3 | 0.4 (4) | C9—C8—C13—C12 | 0.2 (3) |
C6—N3—C3—N2 | −127.9 (2) | C7—C8—C13—C12 | 178.58 (19) |
C6—N3—C3—C2 | 54.9 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.86 (2) | 2.00 (2) | 2.662 (2) | 133.9 (18) |
N3—H3···O1i | 0.86 (2) | 2.46 (2) | 3.149 (2) | 137.5 (18) |
N4—H4···N5ii | 0.83 (2) | 2.40 (2) | 3.111 (3) | 143.1 (19) |
N1—H1···S2iii | 0.80 (2) | 2.54 (2) | 3.334 (2) | 170 (2) |
C9—H9···N2iv | 0.93 | 2.60 | 3.521 (2) | 169 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1, y, z; (iv) x−1, y, z. |