1,5 Di­methyl 4 {[(E) 3 oxo 3 (2 thienyl) 1 (tri­fluoro­methyl) 1 propenyl]­amino} 2 phenyl 1,2 di­hydro 3H pyrazol 3 one

organic papers

o1182

Yu, Wang and Miao C₁₉H₁₆F₃N₃O₂S DOI: 10.1107/S1600536802017348 Acta Cryst.(2002). E58, o1182±o1184 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

1,5-Dimethyl-4-{[(

E

)-3-oxo-3-(2-thienyl)-

1-(trifluoromethyl)-1-propenyl]amino}-2-phenyl-1,2-dihydro-3

H

-pyrazol-3-one

Ming Yu,a_{Jin-Ling Wang}b_{* and} Fang-Ming Miaob

a_{Department of Scientific Technology, The}

Scientific and Technology University of Tianjin, Tianjin 300222, People's Republic of China, andb_{College of Chemical and Life Science,} Tianjin Normal University, Tianjin 300074, People's Republic of China

Correspondence e-mail: wangjinling43@eyou.com

Key indicators Single-crystal X-ray study T= 297 K

Mean(C±C) = 0.005 AÊ Disorder in main residue Rfactor = 0.056 wRfactor = 0.172

Data-to-parameter ratio = 11.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound, C19H16F3N3O2S, the side-chain

carbonyl group, the adjacent double bond and the amine N atom are essentially coplanar, with the largest deviation from the mean plane being 0.010 (2) AÊ. A strong intramolecular

NÐH O hydrogen bond [N O 2.702 (3) AÊ and NÐH O

139 (3)_{] is observed, leading to an enamine tautomer in the}

solid state.

Comment

Schiff base ligands derived from 4-aminoantipyrine, such as salicylidene-4-aminoantipyrine, 5-chlorosalicylidene-4-amino-antipyrine, 2,4-dihydroxybenzylidene-4-amino5-chlorosalicylidene-4-amino-antipyrine, 1-naphthylidene-4-aminoantipyrine and 2-hydroxy-acetophenonylidene-4-aminoantipyrine, have been reported by McLendon & Martell (1976) and by Radhakrishnan & Joseph (1976). In order to study the coordination properties of Schiff base compounds, we have synthesized some of these compounds, and we report here the structure of the title compound, (I).

A view of the molecule of (I) is shown in Fig. 1. Atoms C6, C7, C8 and O1 of the thenoyltri¯uoroacetone moiety and atom N3 of 4-aminoantipyrine are essentially coplanar, the largest deviation from the mean plane being 0.010 (2) AÊ for atom C6; the dihedral angle between this plane and the thienyl plane is 22.48 (3)_{. The bond lengths within this part of the}

molecule [N3ÐC6 = 1.340 (4) AÊ, C6ÐC7 = 1.401 (4) AÊ, C7Ð C8 = 1.396 (4) AÊ and C8ÐO1 = 1.235 (4) AÊ] lie between the classical double- and single-bond lengths. These results clearly indicate that there is electron delocalization over this segment. An intramolecular hydrogen bond is observed (Table 1), which indicates that the molecule exists as the enamine tautomer. This situation is completely different from that of 3- (2,3-dihydro-1,5-dimethyl-3-oxo-2-phenylpyrazol-4-ylimino)-4,4,4-tri¯uoro-1-(2-thienyl)butane-1,2-dione (Wang et al., 2002), but similar to that of pyrazolinehydrazide (Liuet al., 2001). The displacements of atoms C5 and C21 from the

pyrazolinone ring are 0.454 (7) and ÿ0.479 (5) AÊ, respec-tively, showing that the methyl group bonded to N1 and the phenyl group bonded to N2 are on opposite sides of the ring. Intermolecular contact distances of interest are: O2 S1i ₌

3.040 (4) AÊ, C4ÐH41 O1i _{= 3.380 (4) AÊ [angle of}

135.01 (4) _{at H41], C4ÐH41 F2}i _{= 2.930 (4) AÊ [angle of}

138.96 (4) _{at H41], C5ÐH53 F2A}i_{= 3.418 (5) AÊ [angle of}

163.71 (5) _{at H53], C4ÐH42 O1}ii_{= 3.380 (4) AÊ [angle of}

135.01 (5) _{at H42], and C4ÐH43 F2A}iii _{= 3.366 (5) AÊ}

[angle of 116.32 (5)_{at H43] [symmetry codes: (i) 1ÿx,ÿy,}

1ÿz; (ii)ÿ1 +x, y, z; (iii)ÿx,ÿy, 1ÿz].

The torsion angle C21ÐN2ÐN1ÐC5 is 51.2 (4)_{, close to}

the values of 55.6 (3) and 55.7 (3) _{for the compounds}

4-(salicylideneamino)-2-3-dimethyl-1-phenyl-3-pyrazolin-5-one

(Chumakov et al., 2000) and 4-{[(1E)-(2-hydroxyphenyl)

methylidene]amino}-1,5-dimethyl-2-phenyl-2,3-dihydro-1H -pyrazol-3-one (HoÈkeleket al., 2001). By contrast, conjugation leads to a small torsion angle of 7.75 _in

4-(antipyrin-4-yl-iminomethyl)benzoic acid (Zhanget al., 2002).

The mean plane through the side-chain carbonyl group, the adjacent double bond and the amino N atom is nearly perpendicular to the pyrazolinone ring, with a dihedral angle of 84.10 (6)_{, close to the value of 82.43 (8)reported by Wang} et al. (2002). However, the dihedral angle between the pyrazolinone ring and the phenyl ring is 115.26 (5)_{, quite}

different from the value of 41.7 (5)_in

4-(salicylideneamino)-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (Chumakov et al., 2000). These results indicate that the compounds may have quite different coordination properties as ligands to metal ions.

Experimental

Ethanol solutions of 0.1 mol of 4-aminoantipyrine and 0.1 mol of thenoyltri¯uoroacetone were re¯uxed together for 4 h over a steam bath. The excess solvent was removed by evaporation and the concentrated solution was cooled in an ice bath, with stirring. The title compound separated out as a cream-colored powder, which was collected and dried in air (m.p. 434 K). It was recrystallized from

ethanol and dried in a vacuum over CaCl2. The product is stable in

air, and soluble in acetone and ethanol. Elemental analysis for C19H16F3N3O2S, calculated: C 56.01, H 10.31, N 3.96%; found: C

55.87, H 10.16, N 3.94%. Bright-yellow single crystals suitable for X-ray analysis were obtained by slow cooling of a warmed solution in dimethyl sulfoxide.

Crystal data

C19H16F3N3O2S Mr= 407.42

Triclinic,P1

a= 5.8063 (10) AÊ

b= 10.9254 (17) AÊ

c= 15.288 (2) AÊ = 74.790 (3)

= 97.463 (3)

= 94.731 (4) V= 926.7 (2) AÊ3

Z= 2

Dx= 1.460 Mg mÿ3

MoKradiation Cell parameters from 3101

re¯ections = 1.5±25.1

= 0.22 mmÿ1 T= 297 (2) K Prism, yellow 0.350.300.25 mm

Data collection

Bruker SMART 1000 CCD diffractometer

!scans

Absorption correction: multi-scan (SADABS; Bruker, 1999)

Tmin= 0.926,Tmax= 0.946 3860 measured re¯ections

3245 independent re¯ections 2229 re¯ections withI> 2(I)

Rint= 0.018 max= 25.0 h=ÿ5!6

k=ÿ12!8

l=ÿ18!17

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.057} wR(F2_{) = 0.173} S= 1.04 3245 re¯ections 286 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0983P)2

+ 0.1991P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.002 max= 0.33 e AÊÿ3 min=ÿ0.45 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.011 (4)

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N3ÐH3 O1 0.81 (4) 2.04 (4) 2.702 (3) 139 (3)

Some rather high residual electron densities close to the CF3group

and staggered with respect to the F atoms appeared in a difference Fourier map. A disordered distribution of the F atoms was re®ned with geometrical restraints; this led to much lower residual electron density and to lowerRandwR2 values.

Data collection:SMART(Bruker, 1999); cell re®nement:SAINT

(Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

This work was supported by the Foundation of Tianjin Scienti®c Committee (003601711).

References

Bruker (1999).SADABS, SMARTandSAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chumakov, Yu. M., Antosyak, B. Ya., Mazus, M. D., Tsapkov, V. I. & Samus, N. N. (2000).Zh. Strukt. Khim.41, 1095±1997.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.

Acta Cryst.(2002). E58, o1182±o1184 Yu, Wang and Miao C₁₉H₁₆F₃N₃O₂S

o1183

organic papers

Figure 1

organic papers

o1184

Yu, Wang and Miao C₁₉H₁₆F₃N₃O₂S Acta Cryst.(2002). E58, o1182±o1184 HoÈkelek, T., Isiklan, M. & Kilic, Z. (2001).Acta Cryst.C57, 117±119.

Liu, L., Jia, D.-Z., Qiao, Y.-M. & Yu, K.-B. (2001).Acta Chim. Sin.59, 1495± 1501.

McLendon, G. & Martell, A. E. (1976).Coord. Chem. Rev.19, 1±39.

supporting information

sup-1 Acta Cryst. (2002). E58, o1182–o1184

supporting information

Acta Cryst. (2002). E58, o1182–o1184 [https://doi.org/10.1107/S1600536802017348]

1,5-Dimethyl-4-{[(

E

)-3-oxo-3-(2-thienyl)-1-(trifluoromethyl)-1-propenyl]amino}-2-phenyl-1,2-dihydro-3

H

-pyrazol-3-one

Ming Yu, Jin-Ling Wang and Fang-Ming Miao

(I)

Crystal data

C19H16F3N3O2S

Mr = 407.42

Triclinic, P1

a = 5.8063 (10) Å

b = 10.9254 (17) Å

c = 15.288 (2) Å

α = 74.790 (3)°

β = 97.463 (3)°

γ = 94.731 (4)°

V = 926.7 (2) Å3

Z = 2

F(000) = 420

Dx = 1.460 Mg m−3 Melting point: 161° K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3101 reflections

θ = 1.5–25.1°

µ = 0.22 mm−1

T = 297 K Prism, yellow

0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: empirical (using intensity measurements)

(SADABS; Bruker, 1999)

Tmin = 0.926, Tmax = 0.946

3860 measured reflections 3245 independent reflections 2229 reflections with I > 2σ(I)

Rint = 0.018

θmax = 25.0°, θmin = 1.4°

h = −5→6

k = −12→8

l = −18→17

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.057}

wR(F2_{) = 0.173}

S = 1.04 3245 reflections 286 parameters 338 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0983P)2 + 0.1991P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.002 Δρmax = 0.33 e Å−3 Δρmin = −0.45 e Å−3

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sup-2 Acta Cryst. (2002). E58, o1182–o1184

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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq Occ. (<1)

S1 −0.23537 (16) 0.10275 (9) 0.21827 (6) 0.0521 (3) O1 0.5666 (4) −0.0983 (2) 0.44029 (16) 0.0470 (6) O2 0.3820 (4) 0.2882 (2) 0.18883 (17) 0.0534 (7) C6 0.1737 (5) −0.0213 (3) 0.2999 (2) 0.0341 (7) N1 −0.0231 (5) 0.3609 (2) 0.31225 (18) 0.0390 (6) N2 0.1358 (5) 0.3970 (2) 0.24688 (18) 0.0409 (7) N3 0.2464 (5) 0.0669 (2) 0.34539 (19) 0.0366 (6) H3 0.347 (6) 0.046 (3) 0.387 (2) 0.046 (10)* C8 0.4698 (6) −0.1652 (3) 0.3911 (2) 0.0377 (7) C9 0.5668 (7) −0.2959 (3) 0.4084 (3) 0.0571 (10)

F1 0.4504 (6) −0.3742 (3) 0.3645 (3) 0.0903 (11) 0.90 F2 0.7836 (5) −0.2878 (3) 0.3908 (3) 0.1076 (13) 0.90 F3 0.5826 (9) −0.3552 (3) 0.4969 (2) 0.1119 (14) 0.90 F1A 0.626 (2) −0.3133 (15) 0.3328 (10) 0.097 (8) 0.10 F2A 0.750 (2) −0.3093 (18) 0.4663 (9) 0.084 (8) 0.10 F3A 0.418 (3) −0.3858 (14) 0.4452 (9) 0.095 (8) 0.10 C1 0.2518 (5) 0.2906 (3) 0.2455 (2) 0.0368 (7)

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sup-3 Acta Cryst. (2002). E58, o1182–o1184

H14 −0.5341 0.0847 0.1028 0.081* C21 0.0796 (6) 0.4990 (3) 0.1676 (2) 0.0390 (7) C22 −0.1366 (6) 0.5035 (3) 0.1193 (3) 0.0492 (9) H22 −0.2541 0.4400 0.1388 0.074* C23 −0.1829 (7) 0.6016 (4) 0.0415 (3) 0.0580 (10) H23 −0.3323 0.6056 0.0074 0.087* C24 −0.0117 (8) 0.6924 (4) 0.0143 (3) 0.0601 (10) H24 −0.0433 0.7598 −0.0387 0.090* C25 0.2025 (8) 0.6872 (4) 0.0622 (3) 0.0622 (11) H25 0.3199 0.7504 0.0420 0.093* C26 0.2522 (7) 0.5907 (3) 0.1405 (3) 0.0522 (9) H26 0.4015 0.5878 0.1746 0.078*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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sup-4 Acta Cryst. (2002). E58, o1182–o1184

Geometric parameters (Å, º)

S1—C14 1.682 (4) C4—H4A 0.980 S1—C11 1.723 (3) C4—H4B 0.980 O1—C8 1.235 (4) C4—H4C 0.980 O2—C1 1.228 (4) C5—H5A 0.980 C6—N3 1.340 (4) C5—H5B 0.980 C6—C7 1.401 (4) C5—H5C 0.980 C6—C11 1.458 (4) C7—H7 0.950 N1—C3 1.343 (4) C11—C12 1.447 (5) N1—N2 1.406 (4) C12—C13 1.453 (5) N1—C5 1.455 (4) C12—H12 0.950 N2—C1 1.397 (4) C13—C14 1.346 (6) N2—C21 1.437 (4) C13—H13 0.950 N3—C2 1.416 (4) C14—H14 0.950 N3—H3 0.81 (4) C21—C22 1.369 (5) C8—C7 1.396 (4) C21—C26 1.380 (5) C8—C9 1.524 (5) C22—C23 1.390 (5) C9—F2A 1.285 (13) C22—H22 0.950 C9—F1A 1.311 (13) C23—C24 1.369 (6) C9—F2 1.312 (5) C23—H23 0.950 C9—F3A 1.314 (13) C24—C25 1.357 (6) C9—F1 1.315 (4) C24—H24 0.950 C9—F3 1.333 (5) C25—C26 1.388 (5) C1—C2 1.438 (4) C25—H25 0.950 C2—C3 1.356 (4) C26—H26 0.950 C3—C4 1.494 (4)

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sup-5 Acta Cryst. (2002). E58, o1182–o1184

F2—C9—F3 102.5 (4) C13—C14—S1 113.1 (3) F1—C9—F3 106.8 (4) C13—C14—H14 123.5 F2A—C9—C8 112.0 (9) S1—C14—H14 123.5 F1A—C9—C8 110.6 (8) C22—C21—C26 121.0 (3) F2—C9—C8 111.7 (3) C22—C21—N2 121.1 (3) F3A—C9—C8 111.0 (9) C26—C21—N2 117.9 (3) F1—C9—C8 116.4 (3) C21—C22—C23 119.6 (3) F3—C9—C8 110.8 (3) C21—C22—H22 120.2 O2—C1—N2 124.6 (3) C23—C22—H22 120.2 O2—C1—C2 131.6 (3) C24—C23—C22 119.5 (4) N2—C1—C2 103.8 (3) C24—C23—H23 120.2 C3—C2—N3 126.8 (3) C22—C23—H23 120.2 C3—C2—C1 109.1 (3) C25—C24—C23 120.7 (3) N3—C2—C1 123.9 (3) C25—C24—H24 119.7 N1—C3—C2 109.8 (3) C23—C24—H24 119.7 N1—C3—C4 121.1 (3) C24—C25—C26 120.8 (4) C2—C3—C4 129.0 (3) C24—C25—H25 119.6 C3—C4—H4A 109.5 C26—C25—H25 119.6 C3—C4—H4B 109.5 C21—C26—C25 118.4 (4) H4A—C4—H4B 109.5 C21—C26—H26 120.8 C3—C4—H4C 109.5 C25—C26—H26 120.8

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sup-6 Acta Cryst. (2002). E58, o1182–o1184

O2—C1—C2—N3 0.4 (6) C22—C23—C24—C25 0.3 (6) N2—C1—C2—N3 178.8 (3) C23—C24—C25—C26 −0.8 (7) N2—N1—C3—C2 −6.2 (4) C22—C21—C26—C25 −0.7 (6) C5—N1—C3—C2 −154.6 (3) N2—C21—C26—C25 177.8 (3) N2—N1—C3—C4 176.6 (3) C24—C25—C26—C21 1.0 (6) C5—N1—C3—C4 28.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A