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

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) Å. A strong intramolecular N—H...O hydrogen bond [N...O 2.702 (3) Å and N—H...O 139 (3)°] is observed, leading to an en­amine tautomer in the solid state.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.056
• wR factor = 0.172
• Data-to-parameter ratio = 11.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_213  Alert B Atom F1A     has ADP max/min Ratio ...........       4.70 oblate

PLAT_213  Alert B Atom F3A     has ADP max/min Ratio ...........       4.20 oblate


 Alert Level C:



PLAT_031  Alert C Refined Extinction Parameter within Range ....       2.75 Sigma


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

C19H16F3N3O2S	F(000) = 420
Mr = 407.42	Dx = 1.460 Mg m^−3
Triclinic, P1	Melting point: 161° K
a = 5.8063 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9254 (17) Å	Cell parameters from 3101 reflections
c = 15.288 (2) Å	θ = 1.5–25.1°
α = 74.790 (3)°	µ = 0.22 mm^−1
β = 97.463 (3)°	T = 297 K
γ = 94.731 (4)°	Prism, yellow
V = 926.7 (2) Å^3	0.35 × 0.30 × 0.25 mm
Z = 2

Data collection

Bruker SMART 1000 CCD diffractometer	3245 independent reflections
Radiation source: fine-focus sealed tube	2229 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999)	h = −5→6
Tmin = 0.926, Tmax = 0.946	k = −12→8
3860 measured reflections	l = −18→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.173	w = 1/[σ^2(Fo^2) + (0.0983P)^2 + 0.1991P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
3245 reflections	Δρmax = 0.33 e Å^−3
286 parameters	Δρmin = −0.45 e Å^−3
338 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (4)

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 (Ų)

	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)
C2	0.1757 (5)	0.1935 (3)	0.3212 (2)	0.0338 (7)
C3	0.0161 (6)	0.2407 (3)	0.3591 (2)	0.0356 (7)
C4	−0.1157 (7)	0.1759 (3)	0.4377 (2)	0.0497 (9)
H4A	−0.0422	0.1993	0.4929	0.075*
H4B	−0.1147	0.0837	0.4471	0.075*
H4C	−0.2765	0.2022	0.4246	0.075*
C5	−0.1055 (8)	0.4595 (3)	0.3469 (3)	0.0601 (11)
H5A	−0.2471	0.4277	0.3759	0.090*
H5B	−0.1397	0.5342	0.2962	0.090*
H5C	0.0147	0.4828	0.3917	0.090*
C7	0.2821 (6)	−0.1372 (3)	0.3234 (2)	0.0396 (8)
H7	0.2253	−0.1996	0.2918	0.059*
C11	−0.0193 (6)	−0.0004 (3)	0.2273 (2)	0.0387 (7)
C12	−0.0580 (7)	−0.0707 (4)	0.1581 (3)	0.0610 (11)
H12	0.0423	−0.1294	0.1487	0.092*
C13	−0.2800 (8)	−0.0340 (4)	0.1060 (3)	0.0712 (12)
H13	−0.3451	−0.0695	0.0572	0.107*
C14	−0.3875 (6)	0.0537 (4)	0.1312 (2)	0.0541 (9)
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0454 (5)	0.0621 (6)	0.0496 (5)	0.0149 (4)	−0.0043 (4)	−0.0163 (4)
O1	0.0502 (14)	0.0355 (13)	0.0545 (14)	0.0100 (11)	−0.0085 (11)	−0.0145 (11)
O2	0.0507 (15)	0.0500 (15)	0.0598 (15)	0.0203 (12)	0.0192 (12)	−0.0029 (12)
C6	0.0345 (16)	0.0312 (16)	0.0366 (16)	0.0048 (13)	0.0039 (13)	−0.0077 (13)
N1	0.0469 (16)	0.0315 (14)	0.0419 (14)	0.0114 (12)	0.0104 (12)	−0.0096 (11)
N2	0.0434 (16)	0.0320 (14)	0.0468 (15)	0.0106 (12)	0.0107 (12)	−0.0037 (11)
N3	0.0417 (16)	0.0281 (14)	0.0391 (15)	0.0125 (12)	−0.0057 (13)	−0.0085 (11)
C8	0.0387 (17)	0.0271 (16)	0.0470 (18)	0.0074 (13)	0.0049 (14)	−0.0072 (14)
C9	0.058 (2)	0.040 (2)	0.072 (3)	0.0153 (17)	−0.010 (2)	−0.0170 (18)
F1	0.091 (2)	0.0428 (17)	0.137 (3)	0.0269 (15)	−0.046 (2)	−0.0447 (19)
F2	0.0594 (19)	0.079 (2)	0.207 (4)	0.0249 (16)	0.021 (2)	−0.067 (3)
F3	0.185 (4)	0.047 (2)	0.090 (2)	0.041 (2)	−0.012 (2)	0.0043 (16)
F1A	0.13 (2)	0.066 (17)	0.118 (14)	0.062 (16)	−0.002 (14)	−0.058 (14)
F2A	0.061 (13)	0.074 (18)	0.093 (15)	0.035 (11)	−0.019 (12)	0.018 (15)
F3A	0.112 (17)	0.017 (8)	0.14 (2)	−0.021 (11)	−0.016 (15)	−0.017 (13)
C1	0.0347 (17)	0.0303 (16)	0.0456 (18)	0.0095 (13)	0.0025 (14)	−0.0086 (13)
C2	0.0368 (17)	0.0265 (15)	0.0371 (16)	0.0071 (13)	−0.0029 (13)	−0.0081 (12)
C3	0.0405 (17)	0.0309 (16)	0.0353 (16)	0.0044 (13)	0.0001 (13)	−0.0091 (13)
C4	0.060 (2)	0.044 (2)	0.0447 (19)	0.0062 (17)	0.0161 (17)	−0.0057 (15)
C5	0.077 (3)	0.043 (2)	0.070 (2)	0.0205 (19)	0.026 (2)	−0.0163 (18)
C7	0.0442 (19)	0.0314 (17)	0.0453 (18)	0.0061 (14)	0.0002 (14)	−0.0145 (14)
C11	0.0420 (18)	0.0378 (18)	0.0359 (16)	0.0086 (14)	0.0006 (13)	−0.0085 (13)
C12	0.071 (3)	0.056 (2)	0.053 (2)	0.0165 (19)	−0.0298 (19)	−0.0215 (18)
C13	0.082 (3)	0.073 (3)	0.060 (2)	0.014 (2)	−0.023 (2)	−0.031 (2)
C14	0.048 (2)	0.061 (2)	0.049 (2)	0.0085 (18)	−0.0104 (17)	−0.0134 (17)
C21	0.0459 (19)	0.0275 (16)	0.0448 (18)	0.0103 (13)	0.0079 (14)	−0.0072 (13)
C22	0.048 (2)	0.042 (2)	0.057 (2)	0.0071 (16)	0.0057 (16)	−0.0094 (16)
C23	0.061 (2)	0.059 (2)	0.051 (2)	0.0210 (19)	−0.0017 (18)	−0.0074 (18)
C24	0.082 (3)	0.045 (2)	0.050 (2)	0.023 (2)	0.013 (2)	0.0029 (17)
C25	0.068 (3)	0.043 (2)	0.066 (2)	−0.0006 (19)	0.017 (2)	0.0052 (18)
C26	0.050 (2)	0.043 (2)	0.060 (2)	0.0032 (16)	0.0069 (17)	−0.0056 (16)

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)
C14—S1—C11	92.11 (17)	H4A—C4—H4C	109.5
N3—C6—C7	119.5 (3)	H4B—C4—H4C	109.5
N3—C6—C11	121.5 (3)	N1—C5—H5A	109.5
C7—C6—C11	119.0 (3)	N1—C5—H5B	109.5
C3—N1—N2	107.5 (2)	H5A—C5—H5B	109.5
C3—N1—C5	126.6 (3)	N1—C5—H5C	109.5
N2—N1—C5	118.2 (3)	H5A—C5—H5C	109.5
C1—N2—N1	109.1 (2)	H5B—C5—H5C	109.5
C1—N2—C21	123.7 (3)	C8—C7—C6	123.1 (3)
N1—N2—C21	118.4 (2)	C8—C7—H7	118.5
C6—N3—C2	125.5 (3)	C6—C7—H7	118.5
C6—N3—H3	116 (3)	C12—C11—C6	123.3 (3)
C2—N3—H3	119 (3)	C12—C11—S1	112.6 (2)
O1—C8—C7	128.5 (3)	C6—C11—S1	124.0 (2)
O1—C8—C9	115.2 (3)	C11—C12—C13	106.6 (3)
C7—C8—C9	116.4 (3)	C11—C12—H12	126.7
F2A—C9—F1A	106.8 (9)	C13—C12—H12	126.7
F2A—C9—F3A	104.9 (9)	C14—C13—C12	115.6 (3)
F1A—C9—F3A	111.5 (9)	C14—C13—H13	122.2
F2—C9—F1	107.6 (4)	C12—C13—H13	122.2
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
C3—N1—N2—C1	8.5 (3)	N3—C2—C3—N1	−173.5 (3)
C5—N1—N2—C1	160.0 (3)	C1—C2—C3—N1	1.7 (4)
C3—N1—N2—C21	157.2 (3)	N3—C2—C3—C4	3.5 (5)
C5—N1—N2—C21	−51.2 (4)	C1—C2—C3—C4	178.7 (3)
C7—C6—N3—C2	170.8 (3)	O1—C8—C7—C6	0.9 (6)
C11—C6—N3—C2	−10.3 (5)	C9—C8—C7—C6	179.8 (3)
O1—C8—C9—F2A	−6.3 (8)	N3—C6—C7—C8	−1.9 (5)
C7—C8—C9—F2A	174.7 (7)	C11—C6—C7—C8	179.2 (3)
O1—C8—C9—F1A	−125.2 (7)	N3—C6—C11—C12	159.8 (3)
C7—C8—C9—F1A	55.7 (7)	C7—C6—C11—C12	−21.3 (5)
O1—C8—C9—F2	−63.5 (5)	N3—C6—C11—S1	−24.4 (4)
C7—C8—C9—F2	117.5 (4)	C7—C6—C11—S1	154.5 (3)
O1—C8—C9—F3A	110.5 (7)	C14—S1—C11—C12	3.1 (3)
C7—C8—C9—F3A	−68.6 (7)	C14—S1—C11—C6	−173.1 (3)
O1—C8—C9—F1	172.5 (4)	C6—C11—C12—C13	173.1 (3)
C7—C8—C9—F1	−6.6 (5)	S1—C11—C12—C13	−3.1 (4)
O1—C8—C9—F3	50.2 (5)	C11—C12—C13—C14	1.6 (6)
C7—C8—C9—F3	−128.9 (4)	C12—C13—C14—S1	0.7 (6)
N1—N2—C1—O2	171.5 (3)	C11—S1—C14—C13	−2.2 (4)
C21—N2—C1—O2	24.7 (5)	C1—N2—C21—C22	97.4 (4)
N1—N2—C1—C2	−7.1 (3)	N1—N2—C21—C22	−46.5 (4)
C21—N2—C1—C2	−153.9 (3)	C1—N2—C21—C26	−81.1 (4)
C6—N3—C2—C3	101.0 (4)	N1—N2—C21—C26	135.0 (3)
C6—N3—C2—C1	−73.6 (4)	C26—C21—C22—C23	0.3 (5)
O2—C1—C2—C3	−175.0 (3)	N2—C21—C22—C23	−178.2 (3)
N2—C1—C2—C3	3.4 (3)	C21—C22—C23—C24	−0.1 (6)
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
N3—H3···O1	0.81 (4)	2.04 (4)	2.702 (3)	139 (3)