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Acta Cryst. (2008). E64, o675    [ doi:10.1107/S1600536808005928 ]

6-Methyl-2-p-tolyl-4-[3-(trifluoromethyl)phenyl]pyridazin-3(2H)-one

Z.-X. Niu, Y.-Q. Zhu, F.-Z. Hu, X.-H. Hu and H.-Z. Yang

Abstract top

In the title molecule, C19H15F3N2O, the benzene rings of the tolyl and trifluoromethylphenyl groups form dihedral angles of 64.1 (2) and 38.5 (2)°, respectively, with the pyridazine ring. The CF3 group is disordered over two orientations, with site-occupancy factors of ca 0.56 and 0.44.

Comment top

Many pyridazine derivatives have been found to exhibit biological activities such as insecticidal, fungicidal, herbicidal, plant-growth regulatory activity, etc. (Heinisch & Kopelent, 1992). For example, pyridate, credazine and maleic hydrazide (Kolar & Tisler, 1999) have been commercialized as herbicides. In order to discover new biologically active pyridazine compounds, the title compound was synthesized and its structure is reported here.

In the molecule of the title compound (Fig. 1), the central pyridazine ring (C9—C12/N1/N2) forms dihedral angles of 64.1 (2)° and 38.5 (2)°, respectively, with the C1—C6 and C13—C18 benzene rings. The C2—C1—N1—N2, C2—C1—N1—C12, C6—C1—N1—N2, C6—C1—N1—C12, C10—C11—C13—C14, C12—C11—C13—C14, C10—C11—C13—C18 and C12—C11—C13—C18 torsion angles are -115.7 (3), 65.2 (4), 64.5 (4), -114.6 (3), -38.5 (5), 140.2 (3), 141.6 (3) and -39.7 (5)°, respectively. No significant hydrogen bonding interactions are observed in the crystal structure.

Related literature top

For related literature, see: Heinisch & Kopelent (1992); Kolar & Tisler (1999).

Experimental top

A mixture of ethyl 2-(3-trifluoromethylphenyl)-4-oxopentanoate (2.3 mmol) and 4-methylphenylhydrazine (2.3 mmol) and glacial acetic acid (1 ml) was stirred at room temperature for 2 h. The precipitate formed was filtered and recrystallized from ethanol. Single crystals suitable for X-ray analysis were grown from a ethyl acetate-petroleum ether (3:1 v/v) solution at room temperature.

Refinement top

The trifluoromethyl group is disordered over two orienatations (C19/F1/F2/F3 and C19/F1'/F2'/F3') with refined occupancies of 0.564 (15) and 0.436 (15). All C—F distances were restrained to be equal and the Uij components of disordered F atoms were restrained to be approximately isotropic. The H atoms were positioned geometrically (C—H = 0.93 or 0.96 Å) and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. Only one disorder component is shown.
6-Methyl-2-p-tolyl-4-[3-(trifluoromethyl)phenyl]pyridazin- 3(2H)-one top
Crystal data top
C19H15F3N2OF000 = 1424
Mr = 344.33Dx = 1.382 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2694 reflections
a = 20.902 (6) Åθ = 2.2–26.2º
b = 4.2898 (13) ŵ = 0.11 mm−1
c = 37.683 (11) ÅT = 294 (2) K
β = 101.534 (5)ºBlock, colourless
V = 3310.6 (17) Å30.52 × 0.20 × 0.16 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		2907 independent reflections
Radiation source: fine-focus sealed tube1988 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 294(2) Kθmax = 25.0º
φ and ω scansθmin = 1.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −24→17
Tmin = 0.945, Tmax = 0.983k = −5→4
7702 measured reflectionsl = −36→44
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.170  w = 1/[σ2(Fo2) + (0.0755P)2 + 3.8729P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2907 reflectionsΔρmax = 0.20 e Å−3
256 parametersΔρmin = −0.25 e Å−3
51 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C19H15F3N2OV = 3310.6 (17) Å3
Mr = 344.33Z = 8
Monoclinic, C2/cMo Kα
a = 20.902 (6) ŵ = 0.11 mm−1
b = 4.2898 (13) ÅT = 294 (2) K
c = 37.683 (11) Å0.52 × 0.20 × 0.16 mm
β = 101.534 (5)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2907 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1988 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.983Rint = 0.035
7702 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05951 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.05Δρmax = 0.20 e Å−3
2907 reflectionsΔρmin = −0.25 e Å−3
256 parameters
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
xyzUiso*/UeqOcc. (<1)
O10.15529 (10)0.4998 (7)0.16676 (6)0.0680 (8)
N10.22749 (11)0.2163 (6)0.14191 (6)0.0444 (6)
N20.24743 (11)0.0589 (6)0.11419 (7)0.0474 (7)
C10.27804 (13)0.2541 (8)0.17437 (8)0.0423 (7)
C20.27033 (14)0.1120 (9)0.20615 (8)0.0529 (9)
H20.2336−0.00920.20670.064*
C30.31796 (14)0.1520 (9)0.23731 (8)0.0530 (9)
H30.31270.05670.25870.064*
C40.37291 (14)0.3305 (8)0.23708 (8)0.0498 (8)
C50.37977 (15)0.4657 (9)0.20447 (9)0.0583 (9)
H50.41700.58230.20370.070*
C60.33258 (14)0.4312 (8)0.17308 (8)0.0514 (8)
H60.33770.52560.15160.062*
C70.42303 (18)0.3813 (12)0.27183 (9)0.0780 (12)
H7A0.40270.35200.29230.117*
H7B0.44000.58940.27210.117*
H7C0.45810.23440.27300.117*
C80.22624 (17)−0.1579 (10)0.05424 (9)0.0675 (10)
H8A0.2697−0.23530.06270.101*
H8B0.2261−0.01660.03450.101*
H8C0.1974−0.32910.04620.101*
C90.20357 (14)0.0106 (8)0.08460 (8)0.0471 (8)
C100.13750 (14)0.1112 (8)0.08120 (8)0.0475 (8)
H100.10750.06700.06000.057*
C110.11739 (13)0.2704 (8)0.10827 (8)0.0432 (7)
C120.16574 (13)0.3414 (8)0.14129 (8)0.0469 (8)
C130.04906 (13)0.3800 (8)0.10537 (8)0.0445 (8)
C140.01367 (14)0.4972 (7)0.07268 (8)0.0463 (8)
H140.03330.50830.05260.056*
C15−0.05036 (14)0.5971 (8)0.06965 (9)0.0488 (8)
C16−0.08032 (16)0.5813 (9)0.09917 (10)0.0613 (10)
H16−0.12330.64680.09720.074*
C17−0.04563 (16)0.4667 (11)0.13184 (10)0.0695 (11)
H17−0.06560.45520.15170.083*
C180.01841 (15)0.3695 (10)0.13515 (9)0.0599 (10)
H180.04130.29660.15730.072*
C19−0.08649 (16)0.7180 (8)0.03406 (11)0.0651 (10)
F1−0.0909 (6)0.5095 (13)0.00586 (14)0.100 (3)0.564 (15)
F2−0.1439 (3)0.841 (3)0.0327 (3)0.119 (4)0.564 (15)
F3−0.0530 (5)0.943 (2)0.0207 (3)0.083 (3)0.564 (15)
F1'−0.1325 (6)0.5147 (17)0.0190 (3)0.100 (4)0.436 (15)
F2'−0.1258 (5)0.955 (2)0.0415 (3)0.080 (3)0.436 (15)
F3'−0.0510 (6)0.834 (3)0.0126 (3)0.095 (4)0.436 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0453 (12)0.105 (2)0.0480 (14)0.0123 (13)−0.0030 (10)−0.0287 (14)
N10.0358 (12)0.0615 (17)0.0327 (13)0.0009 (12)−0.0004 (10)−0.0072 (12)
N20.0439 (14)0.0591 (17)0.0378 (14)0.0016 (12)0.0047 (11)−0.0052 (12)
C10.0339 (14)0.056 (2)0.0336 (16)0.0044 (14)−0.0004 (12)−0.0054 (14)
C20.0406 (16)0.071 (2)0.0455 (19)−0.0073 (16)0.0049 (14)0.0000 (17)
C30.0484 (18)0.072 (2)0.0375 (17)0.0012 (17)0.0049 (14)0.0023 (16)
C40.0384 (16)0.067 (2)0.0390 (18)0.0033 (15)−0.0039 (13)−0.0042 (16)
C50.0400 (16)0.081 (3)0.050 (2)−0.0136 (17)−0.0008 (15)0.0027 (18)
C60.0443 (17)0.067 (2)0.0405 (17)−0.0022 (16)0.0029 (14)0.0062 (16)
C70.061 (2)0.117 (4)0.046 (2)−0.017 (2)−0.0133 (17)0.003 (2)
C80.066 (2)0.085 (3)0.050 (2)0.006 (2)0.0058 (17)−0.019 (2)
C90.0447 (17)0.056 (2)0.0370 (16)−0.0016 (15)0.0000 (13)−0.0030 (15)
C100.0441 (16)0.057 (2)0.0360 (17)−0.0083 (15)−0.0044 (13)−0.0038 (15)
C110.0370 (15)0.0545 (19)0.0344 (16)−0.0029 (14)−0.0021 (12)0.0016 (14)
C120.0371 (15)0.064 (2)0.0374 (17)0.0014 (15)0.0011 (13)−0.0063 (16)
C130.0344 (15)0.058 (2)0.0372 (16)−0.0064 (14)−0.0019 (13)−0.0015 (15)
C140.0399 (16)0.0546 (19)0.0419 (17)−0.0078 (14)0.0021 (13)−0.0041 (15)
C150.0392 (16)0.052 (2)0.0497 (19)−0.0034 (14)−0.0043 (14)−0.0023 (15)
C160.0383 (16)0.079 (3)0.065 (2)0.0013 (17)0.0052 (16)−0.009 (2)
C170.0475 (19)0.107 (3)0.055 (2)−0.001 (2)0.0135 (16)0.000 (2)
C180.0441 (17)0.090 (3)0.0422 (18)−0.0023 (18)0.0011 (14)0.0086 (19)
C190.059 (2)0.055 (2)0.071 (3)0.0049 (19)−0.010 (2)0.002 (2)
F10.141 (7)0.080 (3)0.056 (3)−0.001 (4)−0.034 (3)0.005 (2)
F20.044 (3)0.190 (9)0.117 (6)0.025 (4)0.004 (3)0.065 (6)
F30.098 (5)0.083 (4)0.065 (5)−0.008 (4)0.012 (3)0.011 (3)
F1'0.098 (6)0.079 (4)0.091 (6)−0.012 (4)−0.055 (5)−0.008 (4)
F2'0.066 (5)0.069 (4)0.094 (5)0.021 (4)−0.011 (4)0.005 (3)
F3'0.087 (5)0.155 (9)0.044 (5)0.050 (6)0.016 (4)0.024 (6)
Geometric parameters (Å, °) top
O1—C121.231 (4)C9—C101.428 (4)
N1—N21.377 (3)C10—C111.362 (4)
N1—C121.394 (4)C10—H100.93
N1—C11.457 (3)C11—C121.470 (4)
N2—C91.311 (4)C11—C131.487 (4)
C1—C61.379 (4)C13—C141.398 (4)
C1—C21.382 (4)C13—C181.400 (4)
C2—C31.390 (4)C14—C151.388 (4)
C2—H20.93C14—H140.93
C3—C41.382 (5)C15—C161.383 (5)
C3—H30.93C15—C191.494 (5)
C4—C51.392 (5)C16—C171.388 (5)
C4—C71.520 (4)C16—H160.93
C5—C61.388 (4)C17—C181.384 (5)
C5—H50.93C17—H170.93
C6—H60.93C18—H180.93
C7—H7A0.96C19—F3'1.300 (7)
C7—H7B0.96C19—F21.303 (6)
C7—H7C0.96C19—F1'1.337 (6)
C8—C91.508 (4)C19—F31.347 (6)
C8—H8A0.96C19—F2'1.370 (6)
C8—H8B0.96C19—F11.377 (6)
C8—H8C0.96
N2—N1—C12126.6 (2)O1—C12—N1120.5 (3)
N2—N1—C1114.4 (2)O1—C12—C11125.1 (3)
C12—N1—C1119.0 (2)N1—C12—C11114.3 (3)
C9—N2—N1117.2 (2)C14—C13—C18118.2 (3)
C6—C1—C2120.9 (3)C14—C13—C11120.7 (3)
C6—C1—N1119.9 (3)C18—C13—C11121.2 (3)
C2—C1—N1119.2 (3)C15—C14—C13121.0 (3)
C1—C2—C3119.3 (3)C15—C14—H14119.5
C1—C2—H2120.3C13—C14—H14119.5
C3—C2—H2120.3C16—C15—C14120.2 (3)
C4—C3—C2121.3 (3)C16—C15—C19120.7 (3)
C4—C3—H3119.4C14—C15—C19119.1 (3)
C2—C3—H3119.4C15—C16—C17119.4 (3)
C3—C4—C5118.0 (3)C15—C16—H16120.3
C3—C4—C7120.3 (3)C17—C16—H16120.3
C5—C4—C7121.7 (3)C18—C17—C16120.7 (3)
C6—C5—C4121.8 (3)C18—C17—H17119.6
C6—C5—H5119.1C16—C17—H17119.6
C4—C5—H5119.1C17—C18—C13120.5 (3)
C1—C6—C5118.7 (3)C17—C18—H18119.7
C1—C6—H6120.6C13—C18—H18119.7
C5—C6—H6120.6F3'—C19—F2117.1 (7)
C4—C7—H7A109.5F3'—C19—F1'115.9 (8)
C4—C7—H7B109.5F2—C19—F1'70.8 (5)
H7A—C7—H7B109.5F3'—C19—F324.5 (7)
C4—C7—H7C109.5F2—C19—F3103.7 (7)
H7A—C7—H7C109.5F1'—C19—F3133.8 (7)
H7B—C7—H7C109.5F3'—C19—F2'106.5 (8)
C9—C8—H8A109.5F2—C19—F2'28.5 (5)
C9—C8—H8B109.5F1'—C19—F2'99.3 (6)
H8A—C8—H8B109.5F3—C19—F2'85.6 (6)
C9—C8—H8C109.5F3'—C19—F174.2 (6)
H8A—C8—H8C109.5F2—C19—F1108.3 (5)
H8B—C8—H8C109.5F1'—C19—F147.0 (4)
N2—C9—C10121.9 (3)F3—C19—F197.8 (5)
N2—C9—C8116.7 (3)F2'—C19—F1133.5 (5)
C10—C9—C8121.4 (3)F3'—C19—C15116.2 (6)
C11—C10—C9121.5 (3)F2—C19—C15118.2 (5)
C11—C10—H10119.3F1'—C19—C15110.2 (5)
C9—C10—H10119.3F3—C19—C15112.1 (5)
C10—C11—C12118.4 (3)F2'—C19—C15106.8 (5)
C10—C11—C13122.6 (3)F1—C19—C15114.3 (3)
C12—C11—C13119.0 (3)
C12—N1—N2—C9−2.8 (5)C10—C11—C12—N1−4.0 (4)
C1—N1—N2—C9178.3 (3)C13—C11—C12—N1177.3 (3)
N2—N1—C1—C664.5 (4)C10—C11—C13—C14−38.5 (5)
C12—N1—C1—C6−114.6 (3)C12—C11—C13—C14140.2 (3)
N2—N1—C1—C2−115.7 (3)C10—C11—C13—C18141.6 (3)
C12—N1—C1—C265.2 (4)C12—C11—C13—C18−39.7 (5)
C6—C1—C2—C30.8 (5)C18—C13—C14—C15−0.7 (5)
N1—C1—C2—C3−178.9 (3)C11—C13—C14—C15179.3 (3)
C1—C2—C3—C4−0.1 (5)C13—C14—C15—C16−0.2 (5)
C2—C3—C4—C5−1.0 (5)C13—C14—C15—C19−179.5 (3)
C2—C3—C4—C7177.6 (3)C14—C15—C16—C170.4 (5)
C3—C4—C5—C61.6 (5)C19—C15—C16—C17179.7 (3)
C7—C4—C5—C6−177.0 (4)C15—C16—C17—C180.2 (6)
C2—C1—C6—C5−0.3 (5)C16—C17—C18—C13−1.1 (6)
N1—C1—C6—C5179.5 (3)C14—C13—C18—C171.3 (5)
C4—C5—C6—C1−0.9 (5)C11—C13—C18—C17−178.7 (3)
N1—N2—C9—C10−1.1 (5)C16—C15—C19—F3'155.1 (8)
N1—N2—C9—C8179.1 (3)C14—C15—C19—F3'−25.6 (9)
N2—C9—C10—C111.9 (5)C16—C15—C19—F27.9 (9)
C8—C9—C10—C11−178.3 (3)C14—C15—C19—F2−172.7 (8)
C9—C10—C11—C120.8 (5)C16—C15—C19—F1'−70.5 (9)
C9—C10—C11—C13179.5 (3)C14—C15—C19—F1'108.8 (8)
N2—N1—C12—O1−174.0 (3)C16—C15—C19—F3128.5 (6)
C1—N1—C12—O15.0 (5)C14—C15—C19—F3−52.2 (6)
N2—N1—C12—C115.2 (5)C16—C15—C19—F2'36.4 (7)
C1—N1—C12—C11−175.9 (3)C14—C15—C19—F2'−144.3 (6)
C10—C11—C12—O1175.2 (3)C16—C15—C19—F1−121.3 (7)
C13—C11—C12—O1−3.6 (5)C14—C15—C19—F158.0 (7)
references
References top

Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Heinisch, G. & Kopelent, H. (1992). Prog. Med. Chem. 29, 141–183.

Kolar, P. & Tisler, M. (1999). Adv. Heterocycl. Chem. 75, 167–241.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.