Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020715/cv2236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020715/cv2236Isup2.hkl |
CCDC reference: 654861
Following the method of Hatton et al. (1993), reaction of 2,6-dichloro-4-trifluoromethylamine(0.01 mol) with a suspension of nitrosyl sulfuric acid, followed by reaction with a solution of ethyl 2,3-dicyanopropionate(0.01 mol) in acetic acid, gave 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (about 0.005 mol) (product 1). Further, in accordance with the method of Gong et al. (2006), acetyl chloride (0.007 mol) with dry potassium thiocyanate(0.1 mol)was refluxed in anhydrous CH3CN for 2 h at the temperature 80, then filtrated to obtain acylisothiocyanate solution (product 2). The obtained products 1 and 2 were then reacted in anhydrous CH3CN for about 4 h to get the title compound(I). Single crystals suitable for X-ray analysis were obtained by slow evaporation of the solution in acetone (m.p. 473–475 K). IR (KBr, ν cm-1): 3253, 2244, 1698, 1610,1530, 1310; 1H NMR (CD3COCD3, δ, p.p.m.): 13.19 (s,1H), 10.87 (s, 1H), 8.21 (S, 2H), 7.74(s, 1H), 2.16(s, 3H); 13C NMR (CD3COCD3, δ, p.p.m.): 178.0(1 C), 173.9(1 C), 140.2(1 C), 136.1(2 C), 135.9 (1 C, J═28.7 Hz),134.8(1 C), 127.0(1 C), 126.9(2 C),123.2(1 C, J═271 Hz),113.0(1 C), 103.2(1 C),23.0(1 C).
The H atoms were positioned geometrically [C—H 0.93–0.97 Å, N—H 0.86 Å] and allowed to ride on their parent atoms with Uiso=1.5Ueq(parent atom).
Acyl thiourea derivatives show good bioactivities and may be used in many fields, such as in antimicrobial, sterilization, insecticide and herbicidal (Guo, 2004; Sun et al., 2006). Futhermore, the pyrazoles with the groups of chloride and trifluoromethyl, like 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethylsulphenylpyrazole, show good bioactivities too (Hatton et al., 1993). Herewith we present the crystal structure of the title compound, (I), synthesized from 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole and acetyl chloride.
The molecular structure of the title compound,(I), is shown in Fig.1, with the atom-numbering scheme. It is an acylthioureas with an overall U-shape. In the crystal structure, the dihedral angle between the pyrazole and attached benzene ring is 72.5 (1)°. There is an intramolecular N4—H4—O1 hydrogen bond with an N4.·O1 separation of 2.577 (4) Å. Besides that, the weak intermolecular N—H···S hydrogen bonds link the molecules into centrosymmetric dimers. The crystal packing is further stabilized by the van der Waals forces.
For related literature, see: Gong et al. (2006); Hatton et al. (1993); Guo (2004); Sun et al. (2006).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing the atom numbering scheme and displacement ellipsoids at the 50% probability level. |
C14H8Cl2F3N5OS | F(000) = 848 |
Mr = 422.21 | Dx = 1.633 Mg m−3 |
Monoclinic, P21/n | Melting point: 473 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0015 (8) Å | Cell parameters from 2413 reflections |
b = 14.3443 (13) Å | θ = 2.9–24.1° |
c = 13.3019 (12) Å | µ = 0.55 mm−1 |
β = 90.803 (2)° | T = 298 K |
V = 1717.4 (3) Å3 | Block, colourless |
Z = 4 | 0.31 × 0.15 × 0.11 mm |
Bruker APEX area-detector diffractometer | 3084 independent reflections |
Radiation source: fine-focus sealed tube | 2820 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 25.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −10→9 |
Tmin = 0.849, Tmax = 0.943 | k = −17→17 |
8974 measured reflections | l = −14→15 |
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)] = 0.078 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.28 | w = 1/[σ2(Fo2) + (0.0397P)2 + 2.7124P] where P = (Fo2 + 2Fc2)/3 |
3084 reflections | (Δ/σ)max = 0.001 |
236 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C14H8Cl2F3N5OS | V = 1717.4 (3) Å3 |
Mr = 422.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0015 (8) Å | µ = 0.55 mm−1 |
b = 14.3443 (13) Å | T = 298 K |
c = 13.3019 (12) Å | 0.31 × 0.15 × 0.11 mm |
β = 90.803 (2)° |
Bruker APEX area-detector diffractometer | 3084 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2820 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.943 | Rint = 0.036 |
8974 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.28 | Δρmax = 0.37 e Å−3 |
3084 reflections | Δρmin = −0.28 e Å−3 |
236 parameters |
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 | ||
Cl1 | 0.19256 (12) | 0.07962 (8) | −0.07071 (9) | 0.0462 (3) | |
Cl2 | −0.15095 (15) | 0.25247 (10) | 0.19982 (9) | 0.0594 (4) | |
S1 | 0.49154 (13) | 0.38450 (9) | 0.11126 (9) | 0.0471 (3) | |
F1 | −0.3483 (3) | 0.1067 (3) | −0.2227 (2) | 0.0727 (10) | |
F2 | −0.4383 (4) | 0.0369 (3) | −0.0978 (3) | 0.1039 (15) | |
O1 | 0.1254 (4) | 0.3302 (2) | −0.1182 (2) | 0.0486 (8) | |
F3 | −0.4768 (4) | 0.1812 (3) | −0.1170 (3) | 0.0994 (13) | |
N1 | 0.1295 (4) | 0.1653 (2) | 0.1297 (2) | 0.0315 (8) | |
N2 | 0.1306 (4) | 0.1098 (2) | 0.2123 (3) | 0.0400 (9) | |
N3 | 0.3220 (6) | 0.0631 (4) | 0.4320 (4) | 0.095 (2) | |
N4 | 0.2570 (4) | 0.2851 (2) | 0.0481 (2) | 0.0356 (8) | |
H4 | 0.1922 | 0.2771 | 0.0008 | 0.043* | |
N5 | 0.3241 (4) | 0.4064 (2) | −0.0514 (2) | 0.0361 (8) | |
H5 | 0.3856 | 0.4508 | −0.0632 | 0.043* | |
C1 | −0.3749 (6) | 0.1154 (4) | −0.1262 (4) | 0.0534 (13) | |
C2 | −0.2382 (5) | 0.1359 (3) | −0.0640 (3) | 0.0379 (10) | |
C3 | −0.1013 (5) | 0.1057 (3) | −0.0955 (3) | 0.0353 (10) | |
H3 | −0.0910 | 0.0777 | −0.1581 | 0.042* | |
C4 | 0.0206 (4) | 0.1179 (3) | −0.0325 (3) | 0.0320 (9) | |
C5 | 0.0069 (4) | 0.1597 (3) | 0.0609 (3) | 0.0298 (9) | |
C6 | −0.1312 (5) | 0.1933 (3) | 0.0876 (3) | 0.0360 (10) | |
C7 | −0.2547 (5) | 0.1810 (3) | 0.0264 (3) | 0.0421 (11) | |
H7 | −0.3472 | 0.2027 | 0.0459 | 0.051* | |
C8 | 0.2489 (4) | 0.2236 (3) | 0.1272 (3) | 0.0307 (9) | |
C9 | 0.3325 (5) | 0.2050 (3) | 0.2112 (3) | 0.0364 (10) | |
H9 | 0.4219 | 0.2324 | 0.2309 | 0.044* | |
C10 | 0.2538 (5) | 0.1357 (3) | 0.2605 (3) | 0.0366 (10) | |
C11 | 0.3520 (4) | 0.3560 (3) | 0.0346 (3) | 0.0329 (9) | |
C12 | 0.2119 (5) | 0.3956 (3) | −0.1205 (3) | 0.0392 (10) | |
C13 | 0.2015 (7) | 0.4701 (4) | −0.1981 (4) | 0.0686 (17) | |
H13A | 0.1269 | 0.4537 | −0.2472 | 0.103* | |
H13B | 0.2957 | 0.4766 | −0.2304 | 0.103* | |
H13C | 0.1754 | 0.5280 | −0.1668 | 0.103* | |
C14 | 0.2918 (6) | 0.0928 (4) | 0.3560 (4) | 0.0558 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0337 (6) | 0.0556 (7) | 0.0495 (7) | 0.0009 (5) | 0.0069 (5) | −0.0065 (5) |
Cl2 | 0.0590 (8) | 0.0703 (9) | 0.0489 (7) | 0.0053 (7) | 0.0012 (6) | −0.0223 (6) |
S1 | 0.0407 (7) | 0.0483 (7) | 0.0519 (7) | −0.0184 (5) | −0.0136 (5) | 0.0133 (6) |
F1 | 0.060 (2) | 0.112 (3) | 0.0456 (18) | −0.0136 (18) | −0.0190 (14) | −0.0019 (17) |
F2 | 0.080 (3) | 0.131 (3) | 0.099 (3) | −0.066 (2) | −0.044 (2) | 0.046 (2) |
O1 | 0.051 (2) | 0.050 (2) | 0.0447 (19) | −0.0142 (17) | −0.0137 (15) | 0.0100 (15) |
F3 | 0.058 (2) | 0.145 (4) | 0.094 (3) | 0.038 (2) | −0.0370 (19) | −0.022 (2) |
N1 | 0.0293 (18) | 0.0338 (18) | 0.0315 (18) | −0.0089 (15) | −0.0034 (14) | 0.0050 (15) |
N2 | 0.047 (2) | 0.037 (2) | 0.036 (2) | −0.0092 (17) | 0.0003 (17) | 0.0122 (16) |
N3 | 0.086 (4) | 0.128 (5) | 0.069 (3) | −0.039 (4) | −0.028 (3) | 0.058 (3) |
N4 | 0.0326 (19) | 0.039 (2) | 0.0347 (19) | −0.0127 (16) | −0.0074 (15) | 0.0060 (16) |
N5 | 0.039 (2) | 0.0356 (19) | 0.0337 (19) | −0.0106 (16) | −0.0001 (16) | 0.0070 (15) |
C1 | 0.042 (3) | 0.070 (4) | 0.047 (3) | −0.006 (3) | −0.013 (2) | 0.012 (3) |
C2 | 0.039 (3) | 0.037 (2) | 0.038 (2) | −0.0044 (19) | −0.0033 (19) | 0.0080 (19) |
C3 | 0.038 (2) | 0.037 (2) | 0.031 (2) | −0.0028 (19) | −0.0008 (18) | 0.0005 (18) |
C4 | 0.030 (2) | 0.031 (2) | 0.035 (2) | −0.0036 (18) | 0.0030 (17) | 0.0045 (18) |
C5 | 0.028 (2) | 0.029 (2) | 0.032 (2) | −0.0095 (17) | −0.0021 (17) | 0.0045 (17) |
C6 | 0.041 (2) | 0.035 (2) | 0.032 (2) | −0.0025 (19) | 0.0011 (19) | −0.0019 (18) |
C7 | 0.035 (2) | 0.045 (3) | 0.046 (3) | 0.004 (2) | −0.001 (2) | 0.000 (2) |
C8 | 0.030 (2) | 0.031 (2) | 0.031 (2) | −0.0049 (18) | −0.0015 (17) | 0.0004 (18) |
C9 | 0.033 (2) | 0.037 (2) | 0.039 (2) | −0.0090 (19) | −0.0077 (19) | 0.0033 (19) |
C10 | 0.035 (2) | 0.041 (2) | 0.034 (2) | −0.005 (2) | −0.0062 (18) | 0.0048 (19) |
C11 | 0.031 (2) | 0.031 (2) | 0.036 (2) | −0.0022 (18) | 0.0050 (18) | −0.0031 (18) |
C12 | 0.048 (3) | 0.038 (2) | 0.032 (2) | −0.001 (2) | −0.003 (2) | 0.0011 (19) |
C13 | 0.081 (4) | 0.065 (4) | 0.059 (3) | −0.021 (3) | −0.026 (3) | 0.024 (3) |
C14 | 0.050 (3) | 0.066 (3) | 0.052 (3) | −0.020 (3) | −0.009 (2) | 0.022 (3) |
Cl1—C4 | 1.726 (4) | C1—C2 | 1.502 (6) |
Cl2—C6 | 1.729 (4) | C2—C7 | 1.375 (6) |
S1—C11 | 1.658 (4) | C2—C3 | 1.376 (6) |
F1—C1 | 1.315 (6) | C3—C4 | 1.383 (6) |
F2—C1 | 1.320 (6) | C3—H3 | 0.9300 |
O1—C12 | 1.220 (5) | C4—C5 | 1.387 (6) |
F3—C1 | 1.323 (6) | C5—C6 | 1.385 (6) |
N1—N2 | 1.356 (4) | C6—C7 | 1.380 (6) |
N1—C8 | 1.362 (5) | C7—H7 | 0.9300 |
N1—C5 | 1.426 (5) | C8—C9 | 1.364 (5) |
N2—C10 | 1.327 (5) | C9—C10 | 1.389 (6) |
N3—C14 | 1.127 (6) | C9—H9 | 0.9300 |
N4—C11 | 1.342 (5) | C10—C14 | 1.449 (6) |
N4—C8 | 1.377 (5) | C12—C13 | 1.487 (6) |
N4—H4 | 0.8600 | C13—H13A | 0.9600 |
N5—C12 | 1.365 (5) | C13—H13B | 0.9600 |
N5—C11 | 1.374 (5) | C13—H13C | 0.9600 |
N5—H5 | 0.8600 | ||
N2—N1—C8 | 112.5 (3) | C7—C6—C5 | 121.5 (4) |
N2—N1—C5 | 118.9 (3) | C7—C6—Cl2 | 118.8 (3) |
C8—N1—C5 | 128.6 (3) | C5—C6—Cl2 | 119.7 (3) |
C10—N2—N1 | 102.9 (3) | C2—C7—C6 | 118.7 (4) |
C11—N4—C8 | 129.0 (3) | C2—C7—H7 | 120.6 |
C11—N4—H4 | 115.5 | C6—C7—H7 | 120.6 |
C8—N4—H4 | 115.5 | N1—C8—C9 | 106.7 (3) |
C12—N5—C11 | 128.8 (4) | N1—C8—N4 | 117.5 (3) |
C12—N5—H5 | 115.6 | C9—C8—N4 | 135.8 (4) |
C11—N5—H5 | 115.6 | C8—C9—C10 | 104.3 (4) |
F1—C1—F2 | 106.5 (5) | C8—C9—H9 | 127.8 |
F1—C1—F3 | 107.1 (4) | C10—C9—H9 | 127.8 |
F2—C1—F3 | 106.2 (5) | N2—C10—C9 | 113.6 (4) |
F1—C1—C2 | 113.4 (4) | N2—C10—C14 | 119.4 (4) |
F2—C1—C2 | 111.3 (4) | C9—C10—C14 | 127.0 (4) |
F3—C1—C2 | 111.9 (4) | N4—C11—N5 | 113.6 (4) |
C7—C2—C3 | 121.5 (4) | N4—C11—S1 | 125.7 (3) |
C7—C2—C1 | 118.4 (4) | N5—C11—S1 | 120.7 (3) |
C3—C2—C1 | 120.1 (4) | O1—C12—N5 | 122.4 (4) |
C2—C3—C4 | 118.8 (4) | O1—C12—C13 | 122.4 (4) |
C2—C3—H3 | 120.6 | N5—C12—C13 | 115.1 (4) |
C4—C3—H3 | 120.6 | C12—C13—H13A | 109.5 |
C3—C4—C5 | 121.2 (4) | C12—C13—H13B | 109.5 |
C3—C4—Cl1 | 119.2 (3) | H13A—C13—H13B | 109.5 |
C5—C4—Cl1 | 119.5 (3) | C12—C13—H13C | 109.5 |
C6—C5—C4 | 118.1 (4) | H13A—C13—H13C | 109.5 |
C6—C5—N1 | 120.4 (4) | H13B—C13—H13C | 109.5 |
C4—C5—N1 | 121.5 (4) | N3—C14—C10 | 177.1 (6) |
C8—N1—N2—C10 | 0.1 (5) | C3—C2—C7—C6 | −2.0 (7) |
C5—N1—N2—C10 | −177.3 (4) | C1—C2—C7—C6 | 174.9 (4) |
F1—C1—C2—C7 | 155.1 (4) | C5—C6—C7—C2 | −1.5 (7) |
F2—C1—C2—C7 | −84.8 (6) | Cl2—C6—C7—C2 | 178.5 (3) |
F3—C1—C2—C7 | 33.8 (6) | N2—N1—C8—C9 | 0.5 (5) |
F1—C1—C2—C3 | −27.9 (6) | C5—N1—C8—C9 | 177.6 (4) |
F2—C1—C2—C3 | 92.1 (6) | N2—N1—C8—N4 | −178.1 (3) |
F3—C1—C2—C3 | −149.3 (4) | C5—N1—C8—N4 | −1.0 (6) |
C7—C2—C3—C4 | 2.7 (6) | C11—N4—C8—N1 | 171.3 (4) |
C1—C2—C3—C4 | −174.1 (4) | C11—N4—C8—C9 | −6.8 (8) |
C2—C3—C4—C5 | 0.0 (6) | N1—C8—C9—C10 | −0.9 (5) |
C2—C3—C4—Cl1 | 179.5 (3) | N4—C8—C9—C10 | 177.4 (5) |
C3—C4—C5—C6 | −3.3 (6) | N1—N2—C10—C9 | −0.8 (5) |
Cl1—C4—C5—C6 | 177.2 (3) | N1—N2—C10—C14 | 178.3 (4) |
C3—C4—C5—N1 | 174.6 (4) | C8—C9—C10—N2 | 1.1 (5) |
Cl1—C4—C5—N1 | −4.9 (5) | C8—C9—C10—C14 | −177.9 (5) |
N2—N1—C5—C6 | 70.7 (5) | C8—N4—C11—N5 | −177.1 (4) |
C8—N1—C5—C6 | −106.3 (5) | C8—N4—C11—S1 | 2.6 (6) |
N2—N1—C5—C4 | −107.2 (4) | C12—N5—C11—N4 | 2.6 (6) |
C8—N1—C5—C4 | 75.9 (5) | C12—N5—C11—S1 | −177.2 (4) |
C4—C5—C6—C7 | 4.1 (6) | C11—N5—C12—O1 | −7.1 (7) |
N1—C5—C6—C7 | −173.9 (4) | C11—N5—C12—C13 | 172.1 (4) |
C4—C5—C6—Cl2 | −175.9 (3) | N2—C10—C14—N3 | −128 (12) |
N1—C5—C6—Cl2 | 6.2 (5) | C9—C10—C14—N3 | 51 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1 | 0.86 | 1.85 | 2.577 (4) | 141 |
N5—H5···S1i | 0.86 | 2.69 | 3.524 (3) | 164 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H8Cl2F3N5OS |
Mr | 422.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.0015 (8), 14.3443 (13), 13.3019 (12) |
β (°) | 90.803 (2) |
V (Å3) | 1717.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.31 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.849, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8974, 3084, 2820 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.151, 1.28 |
No. of reflections | 3084 |
No. of parameters | 236 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.28 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1 | 0.86 | 1.85 | 2.577 (4) | 141 |
N5—H5···S1i | 0.86 | 2.69 | 3.524 (3) | 164 |
Symmetry code: (i) −x+1, −y+1, −z. |
Acyl thiourea derivatives show good bioactivities and may be used in many fields, such as in antimicrobial, sterilization, insecticide and herbicidal (Guo, 2004; Sun et al., 2006). Futhermore, the pyrazoles with the groups of chloride and trifluoromethyl, like 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethylsulphenylpyrazole, show good bioactivities too (Hatton et al., 1993). Herewith we present the crystal structure of the title compound, (I), synthesized from 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole and acetyl chloride.
The molecular structure of the title compound,(I), is shown in Fig.1, with the atom-numbering scheme. It is an acylthioureas with an overall U-shape. In the crystal structure, the dihedral angle between the pyrazole and attached benzene ring is 72.5 (1)°. There is an intramolecular N4—H4—O1 hydrogen bond with an N4.·O1 separation of 2.577 (4) Å. Besides that, the weak intermolecular N—H···S hydrogen bonds link the molecules into centrosymmetric dimers. The crystal packing is further stabilized by the van der Waals forces.