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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1044.
Published online 2008 May 10. doi:  10.1107/S1600536808013342
PMCID: PMC2961364

Methyl 3-(4-{6-methyl-4-[3-(trifluoro­meth­yl)phen­yl]pyridazin-3-yl­oxy}phen­yl)propanoate

Abstract

In the title compound, C22H19F3N2O3, the benzene rings of the trifluoro­methyl­phenyl and benzoyl­phenyl groups form dihedral angles of 41.89 (10) and 67.44 (10)°, respectively, with the pyridazine ring. The methyl­propanoate group is nearly coplanar with the attached benzene ring [dihedral angle = 3.9 (2)°]. The trifluoro­methyl group is disordered over two positions; the site-occupancy factors are ca 0.64 and 0.36. In the crystal structure, inversion-related mol­ecules are linked through C—H(...)O hydrogen bonds and C—H(...)π inter­actions.

Related literature

For the biological activities of pyridazine derivatives, see: Heinisch & Kopelent (1992 [triangle]); Kolar & Tisler (1999 [triangle]).

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Object name is e-64-o1044-scheme1.jpg

Experimental

Crystal data

  • C22H19F3N2O3
  • M r = 416.39
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1044-efi1.jpg
  • a = 9.4916 (19) Å
  • b = 10.232 (2) Å
  • c = 11.022 (2) Å
  • α = 81.70 (3)°
  • β = 65.12 (3)°
  • γ = 78.92 (3)°
  • V = 950.6 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 113 (2) K
  • 0.20 × 0.16 × 0.06 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.977, T max = 0.993
  • 5529 measured reflections
  • 3319 independent reflections
  • 1862 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.147
  • S = 1.06
  • 3319 reflections
  • 301 parameters
  • 72 restraints
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013342/ci2581sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013342/ci2581Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Key Project for Basic Research (No. 20772067).

supplementary crystallographic information

Comment

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 title molecule (Fig. 1), the C2—C7 and C13—C18 benzene rings form dihedral angles of 41.89 (10)° and 67.44 (10)°, respectively, with the central pyridazine ring (C2—C4/C12/N1/N2). The methylpropanoate group is nearly coplanar with the C13—C18 benzene ring (dihedral angle 3.9 (2)°).

The crystal packing is stabilized by C—H···O hydrogen bonds and C—H···π interactions (Table 1) involving the C2—C7 ring (centroid Cg1).

Experimental

A mixture of methyl 3-(4-hydroxyphenyl)propanoate (2.3 mmol), 3-chloro-4- (3-(trifluoromethyl)phenyl)-6-methylpyridazine (2.3 mmol) and K2CO3 (5 mmol) was stirred at 313 K for 2 h. The crude product was recrystallized from ethanol and single crystals of the title compound suitable for X-ray analysis were grown from ethyl acetate-petroleum ether (3:1 v/v) at room temperature.

Refinement

The trifluoromethyl group is disordered over two orienatations (C1/F1/F2/F3 and C1/F1'/F2'/F3') with refined occupancies of 0.636 (12) and 0.364 (12). All C—F distances were restrained to 1.34 (1) Å and the Uij components of disordered F atoms were restrained to be approximately isotropic. All H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids. Only one disorder component is shown.

Crystal data

C22H19F3N2O3Z = 2
Mr = 416.39F000 = 432
Triclinic, P1Dx = 1.455 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 9.4916 (19) ÅCell parameters from 2351 reflections
b = 10.232 (2) Åθ = 2.0–27.9º
c = 11.022 (2) ŵ = 0.12 mm1
α = 81.70 (3)ºT = 113 (2) K
β = 65.12 (3)ºPlate, colourless
γ = 78.92 (3)º0.20 × 0.16 × 0.06 mm
V = 950.6 (4) Å3

Data collection

Rigaku Saturn CCD area-detector diffractometer3319 independent reflections
Radiation source: rotating anode1862 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.054
Detector resolution: 7.31 pixels mm-1θmax = 25.0º
T = 113(2) Kθmin = 2.0º
ω and [var phi] scansh = −10→11
Absorption correction: multi-scan(CrystalClear; Rigaku/MSC, 2005)k = −12→11
Tmin = 0.977, Tmax = 0.993l = −13→11
5529 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.147  w = 1/[σ2(Fo2) + (0.0675P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.003
3319 reflectionsΔρmax = 0.40 e Å3
301 parametersΔρmin = −0.39 e Å3
72 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/UeqOcc. (<1)
F11.0340 (5)0.3434 (7)0.0132 (7)0.0359 (15)0.636 (12)
F20.8747 (11)0.3445 (7)−0.0736 (7)0.072 (2)0.636 (12)
F30.7991 (6)0.4176 (6)0.1223 (8)0.079 (3)0.636 (12)
F1'1.0297 (11)0.3418 (14)−0.0418 (14)0.071 (4)0.364 (12)
F2'0.7900 (12)0.3936 (8)−0.0042 (15)0.055 (3)0.364 (12)
F3'0.8553 (19)0.4059 (12)0.1421 (11)0.076 (4)0.364 (12)
O10.39298 (18)0.1498 (2)0.2418 (2)0.0286 (6)
O2−0.5057 (2)0.5985 (2)0.6250 (2)0.0409 (7)
O3−0.4466 (2)0.7531 (2)0.4543 (2)0.0330 (6)
N10.3114 (2)−0.1545 (3)0.1899 (3)0.0246 (7)
N20.2934 (2)−0.0267 (3)0.2179 (3)0.0251 (7)
C10.8892 (3)0.3235 (3)0.0444 (3)0.0327 (9)
C20.8618 (3)0.1868 (3)0.1025 (3)0.0228 (8)
C30.9650 (3)0.1072 (3)0.1502 (3)0.0258 (8)
H31.05180.13990.14640.031*
C40.9393 (3)−0.0202 (3)0.2033 (3)0.0266 (8)
H41.0083−0.07380.23610.032*
C50.8108 (3)−0.0688 (3)0.2079 (3)0.0241 (8)
H50.7947−0.15550.24300.029*
C60.7056 (2)0.0103 (3)0.1608 (3)0.0194 (7)
C70.7313 (3)0.1389 (3)0.1080 (3)0.0205 (7)
H70.66160.19310.07630.025*
C80.5697 (3)−0.0462 (3)0.1662 (3)0.0191 (7)
C90.5840 (3)−0.1748 (3)0.1379 (3)0.0227 (7)
H90.6818−0.22780.10920.027*
C100.4511 (3)−0.2271 (3)0.1519 (3)0.0216 (7)
C110.4609 (3)−0.3680 (3)0.1257 (3)0.0319 (9)
H11A0.3575−0.38680.14660.048*
H11B0.5055−0.42690.18060.048*
H11C0.5259−0.38110.03290.048*
C120.4159 (3)0.0228 (3)0.2087 (3)0.0202 (7)
C130.2387 (3)0.2146 (3)0.3058 (3)0.0260 (8)
C140.1408 (3)0.1712 (3)0.4317 (3)0.0353 (10)
H140.17210.09310.47430.042*
C15−0.0044 (3)0.2448 (3)0.4941 (3)0.0340 (9)
H15−0.07100.21500.57920.041*
C16−0.0543 (3)0.3619 (3)0.4340 (3)0.0215 (7)
C170.0473 (3)0.4015 (3)0.3070 (3)0.0311 (9)
H170.01680.47940.26360.037*
C180.1928 (3)0.3285 (3)0.2428 (3)0.0324 (9)
H180.25930.35680.15700.039*
C19−0.2110 (3)0.4412 (3)0.5096 (3)0.0250 (8)
H19A−0.29050.38330.53700.030*
H19B−0.21020.46730.59050.030*
C20−0.2594 (3)0.5645 (3)0.4362 (3)0.0287 (8)
H20A−0.18150.62400.40940.034*
H20B−0.26150.53960.35540.034*
C21−0.4164 (3)0.6373 (3)0.5179 (3)0.0246 (8)
C22−0.5929 (3)0.8355 (3)0.5257 (4)0.0392 (9)
H22A−0.67860.79560.52980.059*
H22B−0.59420.92260.47980.059*
H22C−0.60340.84310.61500.059*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0233 (17)0.036 (2)0.049 (3)−0.0158 (15)−0.0157 (19)0.011 (3)
F20.123 (5)0.063 (4)0.071 (4)−0.058 (3)−0.075 (4)0.042 (3)
F30.041 (3)0.028 (3)0.102 (5)0.003 (2)0.027 (3)0.006 (3)
F1'0.052 (4)0.035 (4)0.069 (7)−0.004 (3)0.025 (4)0.012 (5)
F2'0.057 (4)0.035 (4)0.093 (7)−0.009 (3)−0.056 (4)0.019 (4)
F3'0.129 (8)0.040 (5)0.051 (5)−0.008 (6)−0.026 (6)−0.014 (4)
O10.0136 (9)0.0279 (13)0.0422 (15)0.0010 (8)−0.0076 (9)−0.0135 (11)
O20.0284 (11)0.0378 (15)0.0377 (16)0.0032 (10)−0.0012 (10)0.0053 (12)
O30.0283 (10)0.0297 (13)0.0279 (14)0.0109 (9)−0.0045 (9)−0.0039 (11)
N10.0212 (11)0.0294 (15)0.0253 (16)−0.0046 (11)−0.0108 (10)−0.0031 (12)
N20.0198 (11)0.0284 (16)0.0286 (16)−0.0037 (10)−0.0104 (11)−0.0046 (12)
C10.0232 (15)0.038 (2)0.037 (2)−0.0089 (15)−0.0131 (15)0.0076 (19)
C20.0160 (12)0.0280 (18)0.0207 (18)−0.0029 (11)−0.0039 (11)−0.0019 (14)
C30.0154 (12)0.0360 (19)0.0261 (19)−0.0052 (12)−0.0083 (12)−0.0008 (15)
C40.0179 (13)0.0323 (19)0.030 (2)−0.0012 (12)−0.0133 (12)0.0042 (15)
C50.0179 (12)0.0241 (17)0.0269 (19)−0.0018 (11)−0.0070 (12)0.0003 (14)
C60.0124 (12)0.0271 (17)0.0154 (16)−0.0008 (11)−0.0022 (11)−0.0053 (13)
C70.0146 (12)0.0280 (18)0.0161 (17)0.0013 (11)−0.0050 (11)−0.0031 (13)
C80.0159 (12)0.0283 (18)0.0124 (17)−0.0022 (12)−0.0054 (11)−0.0016 (14)
C90.0180 (12)0.0278 (18)0.0191 (18)0.0007 (12)−0.0059 (12)−0.0024 (14)
C100.0226 (13)0.0246 (17)0.0169 (17)−0.0042 (12)−0.0069 (12)−0.0013 (13)
C110.0278 (14)0.0296 (19)0.035 (2)−0.0048 (13)−0.0091 (14)−0.0047 (16)
C120.0156 (12)0.0246 (17)0.0194 (18)0.0002 (12)−0.0059 (11)−0.0059 (14)
C130.0140 (12)0.0303 (18)0.034 (2)−0.0019 (12)−0.0080 (12)−0.0097 (15)
C140.0269 (15)0.040 (2)0.033 (2)0.0083 (14)−0.0122 (14)0.0010 (17)
C150.0232 (14)0.041 (2)0.026 (2)0.0040 (13)−0.0049 (13)0.0035 (16)
C160.0151 (12)0.0253 (17)0.0235 (18)−0.0003 (11)−0.0064 (12)−0.0079 (14)
C170.0251 (14)0.0235 (18)0.031 (2)0.0039 (13)−0.0021 (13)0.0000 (15)
C180.0244 (14)0.0294 (19)0.031 (2)−0.0042 (13)0.0008 (13)0.0002 (16)
C190.0210 (13)0.0270 (18)0.0226 (18)0.0019 (12)−0.0057 (12)−0.0051 (14)
C200.0255 (14)0.0269 (18)0.029 (2)−0.0005 (12)−0.0073 (13)−0.0027 (15)
C210.0216 (13)0.0245 (18)0.027 (2)−0.0018 (12)−0.0091 (13)−0.0046 (15)
C220.0351 (16)0.035 (2)0.039 (2)0.0139 (14)−0.0126 (15)−0.0098 (17)

Geometric parameters (Å, °)

F1—C11.319 (5)C8—C121.405 (3)
F2—C11.347 (5)C9—C101.405 (4)
F3—C11.304 (7)C9—H90.93
F1'—C11.302 (8)C10—C111.489 (4)
F2'—C11.320 (6)C11—H11A0.96
F3'—C11.357 (9)C11—H11B0.96
O1—C121.353 (4)C11—H11C0.96
O1—C131.405 (3)C13—C181.363 (4)
O2—C211.192 (3)C13—C141.372 (4)
O3—C211.333 (3)C14—C151.375 (4)
O3—C221.442 (3)C14—H140.93
N1—C101.316 (3)C15—C161.384 (4)
N1—N21.348 (4)C15—H150.93
N2—C121.317 (3)C16—C171.380 (4)
C1—C21.475 (4)C16—C191.502 (4)
C2—C31.379 (3)C17—C181.379 (4)
C2—C71.393 (4)C17—H170.93
C3—C41.372 (4)C18—H180.93
C3—H30.93C19—C201.501 (4)
C4—C51.382 (4)C19—H19A0.97
C4—H40.93C19—H19B0.97
C5—C61.388 (3)C20—C211.491 (4)
C5—H50.93C20—H20A0.97
C6—C71.382 (4)C20—H20B0.97
C6—C81.488 (4)C22—H22A0.96
C7—H70.93C22—H22B0.96
C8—C91.364 (4)C22—H22C0.96
C12—O1—C13119.0 (2)C10—C11—H11A109.5
C21—O3—C22116.2 (2)C10—C11—H11B109.5
C10—N1—N2119.7 (2)H11A—C11—H11B109.5
C12—N2—N1119.3 (2)C10—C11—H11C109.5
F1'—C1—F3119.9 (8)H11A—C11—H11C109.5
F3—C1—F1105.4 (5)H11B—C11—H11C109.5
F1'—C1—F2'106.9 (7)N2—C12—O1117.9 (2)
F3—C1—F2'69.2 (6)N2—C12—C8124.8 (3)
F1—C1—F2'126.6 (5)O1—C12—C8117.2 (2)
F1'—C1—F276.7 (7)C18—C13—C14120.7 (3)
F3—C1—F2109.6 (4)C18—C13—O1117.6 (2)
F1—C1—F2103.9 (4)C14—C13—O1121.6 (2)
F1'—C1—F3'104.6 (9)C13—C14—C15119.1 (3)
F1—C1—F3'82.7 (7)C13—C14—H14120.5
F2'—C1—F3'95.6 (7)C15—C14—H14120.5
F2—C1—F3'132.0 (6)C14—C15—C16122.0 (3)
F1'—C1—C2118.4 (6)C14—C15—H15119.0
F3—C1—C2114.6 (4)C16—C15—H15119.0
F1—C1—C2112.6 (4)C17—C16—C15117.1 (3)
F2'—C1—C2117.7 (4)C17—C16—C19123.3 (2)
F2—C1—C2110.1 (4)C15—C16—C19119.5 (2)
F3'—C1—C2110.7 (6)C18—C17—C16121.6 (3)
C3—C2—C7120.5 (3)C18—C17—H17119.2
C3—C2—C1120.2 (2)C16—C17—H17119.2
C7—C2—C1119.4 (2)C13—C18—C17119.6 (3)
C4—C3—C2119.8 (2)C13—C18—H18120.2
C4—C3—H3120.1C17—C18—H18120.2
C2—C3—H3120.1C20—C19—C16116.4 (2)
C3—C4—C5120.0 (2)C20—C19—H19A108.2
C3—C4—H4120.0C16—C19—H19A108.2
C5—C4—H4120.0C20—C19—H19B108.2
C4—C5—C6120.8 (3)C16—C19—H19B108.2
C4—C5—H5119.6H19A—C19—H19B107.3
C6—C5—H5119.6C21—C20—C19113.1 (2)
C7—C6—C5119.1 (2)C21—C20—H20A109.0
C7—C6—C8121.7 (2)C19—C20—H20A109.0
C5—C6—C8119.2 (2)C21—C20—H20B109.0
C6—C7—C2119.8 (2)C19—C20—H20B109.0
C6—C7—H7120.1H20A—C20—H20B107.8
C2—C7—H7120.1O2—C21—O3123.5 (3)
C9—C8—C12114.3 (2)O2—C21—C20125.7 (2)
C9—C8—C6121.7 (2)O3—C21—C20110.9 (2)
C12—C8—C6123.9 (3)O3—C22—H22A109.5
C8—C9—C10120.0 (2)O3—C22—H22B109.5
C8—C9—H9120.0H22A—C22—H22B109.5
C10—C9—H9120.0O3—C22—H22C109.5
N1—C10—C9121.7 (3)H22A—C22—H22C109.5
N1—C10—C11116.6 (2)H22B—C22—H22C109.5
C9—C10—C11121.7 (2)
C10—N1—N2—C12−1.1 (4)N2—N1—C10—C11178.8 (3)
F1'—C1—C2—C346.6 (11)C8—C9—C10—N11.2 (4)
F3—C1—C2—C3−104.0 (6)C8—C9—C10—C11−178.3 (3)
F1—C1—C2—C316.5 (6)N1—N2—C12—O1−177.8 (2)
F2'—C1—C2—C3177.6 (8)N1—N2—C12—C82.6 (4)
F2—C1—C2—C3131.9 (6)C13—O1—C12—N211.0 (4)
F3'—C1—C2—C3−74.0 (8)C13—O1—C12—C8−169.4 (2)
F1'—C1—C2—C7−133.2 (10)C9—C8—C12—N2−2.1 (4)
F3—C1—C2—C776.3 (6)C6—C8—C12—N2−178.0 (3)
F1—C1—C2—C7−163.2 (5)C9—C8—C12—O1178.3 (3)
F2'—C1—C2—C7−2.2 (9)C6—C8—C12—O12.5 (4)
F2—C1—C2—C7−47.8 (6)C12—O1—C13—C18−119.9 (3)
F3'—C1—C2—C7106.2 (8)C12—O1—C13—C1464.9 (4)
C7—C2—C3—C40.2 (5)C18—C13—C14—C15−0.4 (5)
C1—C2—C3—C4−179.6 (3)O1—C13—C14—C15174.6 (3)
C2—C3—C4—C50.5 (5)C13—C14—C15—C16−0.4 (5)
C3—C4—C5—C6−0.8 (5)C14—C15—C16—C170.9 (5)
C4—C5—C6—C70.5 (5)C14—C15—C16—C19−177.2 (3)
C4—C5—C6—C8179.4 (3)C15—C16—C17—C18−0.5 (5)
C5—C6—C7—C20.2 (5)C19—C16—C17—C18177.4 (3)
C8—C6—C7—C2−178.7 (3)C14—C13—C18—C170.7 (5)
C3—C2—C7—C6−0.5 (5)O1—C13—C18—C17−174.5 (3)
C1—C2—C7—C6179.3 (3)C16—C17—C18—C13−0.3 (5)
C7—C6—C8—C9139.4 (3)C17—C16—C19—C204.1 (5)
C5—C6—C8—C9−39.5 (4)C15—C16—C19—C20−178.0 (3)
C7—C6—C8—C12−45.0 (4)C16—C19—C20—C21179.8 (3)
C5—C6—C8—C12136.1 (3)C22—O3—C21—O23.2 (5)
C12—C8—C9—C100.1 (4)C22—O3—C21—C20−177.6 (3)
C6—C8—C9—C10176.1 (2)C19—C20—C21—O2−7.7 (5)
N2—N1—C10—C9−0.8 (4)C19—C20—C21—O3173.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11B···O2i0.962.573.467 (4)156
C22—H22C···Cg1ii0.962.733.486 (4)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2581).

References

  • Heinisch, G. & Kopelent, H. (1992). Prog. Med. Chem.29, 141–183. [PubMed]
  • Kolar, P. & Tisler, M. (1999). Adv. Heterocycl. Chem.75, 167–241.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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