Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039748/cs2041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039748/cs2041Isup2.hkl |
CCDC reference: 660310
Perhydropyridazine-1-carboxylic acid (3-trifluoromethylphenyl)-amide was prepared as described by Li et al. (2007). To a solution of perhydropyridazine-1-carboxylic acid (3-trifluoromethylphenyl)-amide (1.37 g, 5 mmol) in 1.2-dichloroethane (10 ml) were added the solution of bis(trichloromethyl)carbonate (0.59 g, 2 mmol) and pyridine (0.79 g, 10 mmol) in 1.2-dichloroethane (10 ml). The mixture was stirred at room temperature for 24 h. After the completion of the reaction, the mixture was washed with water and extracted with diethyl ether. The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (eluant: petroleum ether-ethyl acetate, 1:1). Single crystals were obtained by slow evaporation of a petroleum ether-ethyl acetate solution (v/v: 1/1) (m.p. 417–418 K).
All H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). The trifluoromethyl group was treated as disordered between two orientations with refined occupancies of 0.52 (2) and 0.48 (2), respectively. All C—F bonds lengths were restrained to 1.33 (1) Å and the displacement parameters of the disordered F atoms were restrained to an approximately isotropic behaviour. The large values of atomic displacement parameters for the disordered F atoms indicate further unresolved disorder of the trifluoromethyl group. The high value of Rint is due to the poor quality of the crystal.
The title compound, (I), shows pesticidal activity. X-ray analysis was undertaken in order to establish its structure. The tetrahydropyridazine ring adopts a chair conformation and the five-membered ring lies close to the plane of the molecule. The C1—N1—C7—C12 torsion angle is 27.3 (2)°.
For related literature, see: Li et al. (2007).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
Fig. 1. The molecular structure of (I), showing the atom-labelling scheme with only one disorder component of the –CF3 group. Displacement ellipsoids are drawn at the 30% probability level. |
C13H12F3N3O2 | F(000) = 308 |
Mr = 299.26 | Dx = 1.514 Mg m−3 |
Triclinic, P1 | Melting point: 417 K |
a = 6.8348 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.0756 (11) Å | Cell parameters from 1670 reflections |
c = 12.0770 (17) Å | θ = 6.0–53.0° |
α = 90.994 (2)° | µ = 0.13 mm−1 |
β = 98.153 (2)° | T = 293 K |
γ = 95.630 (3)° | Prism, colourless |
V = 656.34 (15) Å3 | 0.50 × 0.37 × 0.30 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 2409 independent reflections |
Radiation source: fine-focus sealed tube | 1887 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.131 |
φ and ω scans | θmax = 25.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→8 |
Tmin = 0.751, Tmax = 1.000 | k = −9→9 |
3486 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.148 | w = 1/[σ2(Fo2) + (0.0885P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.021 |
2409 reflections | Δρmax = 0.28 e Å−3 |
219 parameters | Δρmin = −0.27 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.37 (3) |
C13H12F3N3O2 | γ = 95.630 (3)° |
Mr = 299.26 | V = 656.34 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8348 (9) Å | Mo Kα radiation |
b = 8.0756 (11) Å | µ = 0.13 mm−1 |
c = 12.0770 (17) Å | T = 293 K |
α = 90.994 (2)° | 0.50 × 0.37 × 0.30 mm |
β = 98.153 (2)° |
Bruker SMART APEX diffractometer | 2409 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1887 reflections with I > 2σ(I) |
Tmin = 0.751, Tmax = 1.000 | Rint = 0.131 |
3486 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 6 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.28 e Å−3 |
2409 reflections | Δρmin = −0.27 e Å−3 |
219 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
F1 | 0.0262 (13) | 0.720 (3) | 0.0498 (10) | 0.156 (5) | 0.48 (2) |
F2 | −0.188 (2) | 0.8924 (8) | 0.0078 (9) | 0.145 (4) | 0.48 (2) |
F3 | −0.2579 (15) | 0.6501 (15) | −0.0441 (6) | 0.095 (3) | 0.48 (2) |
F1' | 0.0267 (11) | 0.7751 (13) | 0.0497 (7) | 0.099 (3) | 0.52 (2) |
F2' | −0.2280 (14) | 0.8564 (18) | −0.0211 (9) | 0.151 (4) | 0.52 (2) |
F3' | −0.185 (3) | 0.599 (2) | −0.0220 (14) | 0.164 (5) | 0.52 (2) |
O1 | 0.1920 (2) | 0.91691 (18) | 0.39839 (12) | 0.0596 (5) | |
O2 | −0.2422 (2) | 0.56464 (18) | 0.56622 (13) | 0.0639 (5) | |
N1 | −0.0668 (2) | 0.73406 (17) | 0.45001 (12) | 0.0402 (4) | |
N2 | 0.1823 (2) | 0.83107 (19) | 0.57773 (13) | 0.0468 (4) | |
N3 | 0.0621 (2) | 0.70819 (19) | 0.62498 (13) | 0.0478 (4) | |
C1 | 0.1134 (3) | 0.8360 (2) | 0.46708 (15) | 0.0429 (5) | |
C2 | −0.1003 (3) | 0.6587 (2) | 0.54966 (16) | 0.0444 (5) | |
C3 | 0.3904 (3) | 0.8445 (3) | 0.62633 (17) | 0.0532 (5) | |
H3A | 0.4637 | 0.9350 | 0.5931 | 0.064* | |
H3B | 0.4471 | 0.7422 | 0.6119 | 0.064* | |
C4 | 0.4049 (3) | 0.8771 (3) | 0.75127 (17) | 0.0573 (6) | |
H4A | 0.5414 | 0.8740 | 0.7860 | 0.069* | |
H4B | 0.3666 | 0.9872 | 0.7651 | 0.069* | |
C5 | 0.2722 (4) | 0.7491 (3) | 0.80320 (17) | 0.0581 (6) | |
H5A | 0.2747 | 0.7795 | 0.8815 | 0.070* | |
H5B | 0.3234 | 0.6416 | 0.7995 | 0.070* | |
C6 | 0.0601 (3) | 0.7350 (3) | 0.74499 (16) | 0.0558 (5) | |
H6A | −0.0170 | 0.6425 | 0.7738 | 0.067* | |
H6B | 0.0001 | 0.8362 | 0.7582 | 0.067* | |
C7 | −0.1960 (3) | 0.7115 (2) | 0.34650 (15) | 0.0397 (4) | |
C8 | −0.3976 (3) | 0.6728 (2) | 0.34434 (18) | 0.0488 (5) | |
H8 | −0.4502 | 0.6599 | 0.4110 | 0.059* | |
C9 | −0.5213 (3) | 0.6532 (2) | 0.24317 (19) | 0.0550 (5) | |
H9 | −0.6568 | 0.6252 | 0.2421 | 0.066* | |
C10 | −0.4459 (3) | 0.6747 (2) | 0.14363 (18) | 0.0533 (5) | |
H10 | −0.5299 | 0.6633 | 0.0757 | 0.064* | |
C11 | −0.2447 (3) | 0.7132 (2) | 0.14634 (16) | 0.0465 (5) | |
C12 | −0.1173 (3) | 0.7311 (2) | 0.24693 (15) | 0.0431 (5) | |
H12 | 0.0187 | 0.7558 | 0.2478 | 0.052* | |
C13 | −0.1607 (4) | 0.7390 (3) | 0.03994 (19) | 0.0678 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.080 (6) | 0.239 (15) | 0.068 (4) | 0.077 (8) | 0.036 (4) | 0.025 (7) |
F2 | 0.181 (12) | 0.073 (4) | 0.084 (5) | −0.024 (5) | 0.068 (6) | 0.030 (3) |
F3 | 0.101 (4) | 0.137 (6) | 0.034 (2) | −0.039 (3) | 0.004 (2) | −0.019 (3) |
F1' | 0.076 (5) | 0.169 (5) | 0.045 (3) | −0.041 (5) | 0.018 (3) | 0.015 (2) |
F2' | 0.131 (5) | 0.163 (13) | 0.069 (4) | 0.063 (6) | 0.011 (3) | 0.082 (5) |
F3' | 0.162 (13) | 0.134 (7) | 0.110 (7) | −0.058 (7) | 0.102 (7) | −0.063 (6) |
O1 | 0.0457 (8) | 0.0851 (10) | 0.0442 (8) | −0.0150 (7) | 0.0069 (6) | 0.0176 (7) |
O2 | 0.0486 (9) | 0.0841 (10) | 0.0579 (9) | −0.0113 (7) | 0.0145 (7) | 0.0199 (8) |
N1 | 0.0305 (8) | 0.0538 (9) | 0.0377 (8) | 0.0042 (6) | 0.0091 (6) | 0.0052 (6) |
N2 | 0.0362 (9) | 0.0661 (10) | 0.0383 (8) | −0.0009 (7) | 0.0095 (6) | 0.0085 (7) |
N3 | 0.0411 (9) | 0.0651 (10) | 0.0384 (9) | 0.0008 (7) | 0.0121 (7) | 0.0101 (7) |
C1 | 0.0336 (10) | 0.0569 (11) | 0.0391 (10) | 0.0034 (7) | 0.0083 (7) | 0.0050 (8) |
C2 | 0.0355 (10) | 0.0562 (10) | 0.0434 (10) | 0.0045 (8) | 0.0122 (8) | 0.0092 (8) |
C3 | 0.0367 (11) | 0.0726 (13) | 0.0494 (12) | 0.0034 (9) | 0.0046 (8) | 0.0050 (9) |
C4 | 0.0580 (13) | 0.0657 (12) | 0.0454 (11) | 0.0077 (10) | −0.0032 (9) | 0.0039 (9) |
C5 | 0.0684 (15) | 0.0678 (12) | 0.0393 (11) | 0.0164 (10) | 0.0048 (9) | 0.0073 (9) |
C6 | 0.0599 (13) | 0.0737 (13) | 0.0381 (11) | 0.0107 (10) | 0.0174 (9) | 0.0105 (9) |
C7 | 0.0339 (9) | 0.0452 (9) | 0.0413 (10) | 0.0065 (7) | 0.0079 (7) | 0.0036 (7) |
C8 | 0.0353 (10) | 0.0599 (11) | 0.0533 (12) | 0.0066 (8) | 0.0122 (8) | 0.0029 (9) |
C9 | 0.0312 (10) | 0.0677 (12) | 0.0643 (13) | 0.0034 (8) | 0.0027 (9) | 0.0014 (10) |
C10 | 0.0460 (11) | 0.0588 (12) | 0.0514 (12) | 0.0056 (8) | −0.0056 (9) | 0.0014 (9) |
C11 | 0.0458 (11) | 0.0500 (10) | 0.0431 (11) | 0.0041 (8) | 0.0043 (8) | 0.0031 (8) |
C12 | 0.0340 (10) | 0.0532 (10) | 0.0425 (10) | 0.0036 (7) | 0.0079 (8) | 0.0032 (8) |
C13 | 0.0696 (17) | 0.0860 (17) | 0.0429 (13) | −0.0120 (13) | 0.0051 (11) | 0.0021 (12) |
F1—C13 | 1.290 (9) | C4—C5 | 1.511 (3) |
F2—C13 | 1.327 (7) | C4—H4A | 0.9700 |
F3—C13 | 1.295 (7) | C4—H4B | 0.9700 |
F1'—C13 | 1.273 (7) | C5—C6 | 1.511 (3) |
F2'—C13 | 1.291 (7) | C5—H5A | 0.9700 |
F3'—C13 | 1.326 (10) | C5—H5B | 0.9700 |
O1—C1 | 1.217 (2) | C6—H6A | 0.9700 |
O2—C2 | 1.214 (2) | C6—H6B | 0.9700 |
N1—C2 | 1.396 (2) | C7—C8 | 1.380 (3) |
N1—C1 | 1.400 (2) | C7—C12 | 1.390 (2) |
N1—C7 | 1.422 (2) | C8—C9 | 1.381 (3) |
N2—C1 | 1.355 (3) | C8—H8 | 0.9300 |
N2—N3 | 1.406 (2) | C9—C10 | 1.381 (3) |
N2—C3 | 1.453 (3) | C9—H9 | 0.9300 |
N3—C2 | 1.354 (3) | C10—C11 | 1.376 (3) |
N3—C6 | 1.464 (3) | C10—H10 | 0.9300 |
C3—C4 | 1.515 (3) | C11—C12 | 1.387 (3) |
C3—H3A | 0.9700 | C11—C13 | 1.490 (3) |
C3—H3B | 0.9700 | C12—H12 | 0.9300 |
C2—N1—C1 | 109.80 (15) | C8—C7—C12 | 120.05 (18) |
C2—N1—C7 | 125.31 (15) | C8—C7—N1 | 120.65 (16) |
C1—N1—C7 | 124.89 (15) | C12—C7—N1 | 119.29 (16) |
C1—N2—N3 | 108.32 (15) | C7—C8—C9 | 119.93 (19) |
C1—N2—C3 | 125.36 (15) | C7—C8—H8 | 120.0 |
N3—N2—C3 | 114.04 (15) | C9—C8—H8 | 120.0 |
C2—N3—N2 | 109.04 (14) | C10—C9—C8 | 120.72 (19) |
C2—N3—C6 | 124.67 (16) | C10—C9—H9 | 119.6 |
N2—N3—C6 | 113.84 (17) | C8—C9—H9 | 119.6 |
O1—C1—N2 | 126.13 (18) | C11—C10—C9 | 119.07 (19) |
O1—C1—N1 | 127.85 (18) | C11—C10—H10 | 120.5 |
N2—C1—N1 | 106.00 (15) | C9—C10—H10 | 120.5 |
O2—C2—N3 | 126.31 (18) | C10—C11—C12 | 121.19 (18) |
O2—C2—N1 | 127.89 (19) | C10—C11—C13 | 119.88 (18) |
N3—C2—N1 | 105.78 (15) | C12—C11—C13 | 118.92 (18) |
N2—C3—C4 | 108.52 (15) | C11—C12—C7 | 119.03 (17) |
N2—C3—H3A | 110.0 | C11—C12—H12 | 120.5 |
C4—C3—H3A | 110.0 | C7—C12—H12 | 120.5 |
N2—C3—H3B | 110.0 | F1'—C13—F1 | 19.8 (11) |
C4—C3—H3B | 110.0 | F1'—C13—F2' | 102.7 (6) |
H3A—C3—H3B | 108.4 | F1—C13—F2' | 119.0 (9) |
C5—C4—C3 | 111.21 (18) | F1'—C13—F3 | 121.8 (6) |
C5—C4—H4A | 109.4 | F1—C13—F3 | 110.6 (8) |
C3—C4—H4A | 109.4 | F2'—C13—F3 | 80.6 (6) |
C5—C4—H4B | 109.4 | F1'—C13—F3' | 101.7 (9) |
C3—C4—H4B | 109.4 | F1—C13—F3' | 85.2 (8) |
H4A—C4—H4B | 108.0 | F2'—C13—F3' | 108.5 (8) |
C4—C5—C6 | 112.16 (17) | F3—C13—F3' | 31.0 (10) |
C4—C5—H5A | 109.2 | F1'—C13—F2 | 90.1 (7) |
C6—C5—H5A | 109.2 | F1—C13—F2 | 109.1 (9) |
C4—C5—H5B | 109.2 | F2'—C13—F2 | 21.3 (6) |
C6—C5—H5B | 109.2 | F3—C13—F2 | 101.7 (5) |
H5A—C5—H5B | 107.9 | F3'—C13—F2 | 128.5 (8) |
N3—C6—C5 | 108.21 (15) | F1'—C13—C11 | 116.0 (4) |
N3—C6—H6A | 110.1 | F1—C13—C11 | 113.0 (6) |
C5—C6—H6A | 110.1 | F2'—C13—C11 | 115.8 (5) |
N3—C6—H6B | 110.1 | F3—C13—C11 | 113.8 (5) |
C5—C6—H6B | 110.1 | F3'—C13—C11 | 110.9 (6) |
H6A—C6—H6B | 108.4 | F2—C13—C11 | 107.9 (4) |
C1—N2—N3—C2 | −10.91 (19) | C2—N3—C6—C5 | 166.81 (17) |
C3—N2—N3—C2 | −155.52 (16) | N2—N3—C6—C5 | −55.5 (2) |
C1—N2—N3—C6 | −155.05 (16) | C4—C5—C6—N3 | 52.4 (2) |
C3—N2—N3—C6 | 60.3 (2) | C2—N1—C7—C8 | 28.0 (3) |
N3—N2—C1—O1 | −172.91 (17) | C1—N1—C7—C8 | −151.84 (17) |
C3—N2—C1—O1 | −33.3 (3) | C2—N1—C7—C12 | −152.87 (16) |
N3—N2—C1—N1 | 8.75 (18) | C1—N1—C7—C12 | 27.3 (2) |
C3—N2—C1—N1 | 148.32 (18) | C12—C7—C8—C9 | 0.1 (3) |
C2—N1—C1—O1 | 177.87 (19) | N1—C7—C8—C9 | 179.26 (16) |
C7—N1—C1—O1 | −2.3 (3) | C7—C8—C9—C10 | −1.1 (3) |
C2—N1—C1—N2 | −3.83 (18) | C8—C9—C10—C11 | 1.1 (3) |
C7—N1—C1—N2 | 176.00 (14) | C9—C10—C11—C12 | −0.2 (3) |
N2—N3—C2—O2 | −173.49 (18) | C9—C10—C11—C13 | −179.22 (19) |
C6—N3—C2—O2 | −34.1 (3) | C10—C11—C12—C7 | −0.8 (3) |
N2—N3—C2—N1 | 8.17 (19) | C13—C11—C12—C7 | 178.26 (18) |
C6—N3—C2—N1 | 147.51 (17) | C8—C7—C12—C11 | 0.8 (3) |
C1—N1—C2—O2 | 178.92 (19) | N1—C7—C12—C11 | −178.35 (15) |
C7—N1—C2—O2 | −0.9 (3) | C10—C11—C13—F1 | −158.8 (11) |
C1—N1—C2—N3 | −2.77 (18) | C12—C11—C13—F1 | 22.2 (12) |
C7—N1—C2—N3 | 177.40 (15) | C10—C11—C13—F3 | −31.7 (7) |
C1—N2—C3—C4 | 165.83 (17) | C12—C11—C13—F3 | 149.3 (7) |
N3—N2—C3—C4 | −56.6 (2) | C10—C11—C13—F2 | 80.4 (7) |
N2—C3—C4—C5 | 52.8 (2) | C12—C11—C13—F2 | −98.6 (7) |
C3—C4—C5—C6 | −53.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C13H12F3N3O2 |
Mr | 299.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8348 (9), 8.0756 (11), 12.0770 (17) |
α, β, γ (°) | 90.994 (2), 98.153 (2), 95.630 (3) |
V (Å3) | 656.34 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.50 × 0.37 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.751, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3486, 2409, 1887 |
Rint | 0.131 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.148, 0.97 |
No. of reflections | 2409 |
No. of parameters | 219 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.27 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
The title compound, (I), shows pesticidal activity. X-ray analysis was undertaken in order to establish its structure. The tetrahydropyridazine ring adopts a chair conformation and the five-membered ring lies close to the plane of the molecule. The C1—N1—C7—C12 torsion angle is 27.3 (2)°.