3-Méthyl-1-(pyridin-2-yl)-4-(1-pyridin-2-yl-3-méthyl-1H-pyrazol-5-yl)-2H-3-pyrazolin-5(1H)-one

Djerrari, B.; Essassi, E.M.; Fifani, J.; Pierrot, M.

doi:10.1107/S1600536801018062

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3-Méthyl-1-(pyridin-2-yl)-4-(1-pyridin-2-yl-3-méthyl-1H-pyrazol-5-yl)-2H-3-pyrazolin-5(1H)-one

B. Djerrari, E. M. Essassi, J. Fifani et M. Pierrot

The structure of the title compound, C₁₈H₁₆N₆O, has been established by X-ray crystallographic study. The structure corresponds to the NH tautomer of the pyrazolinone moiety.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801018062/dn6006sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801018062/dn6006Isup2.hkl Contains datablock I

CCDC reference: 176044

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.056
wR factor = 0.127
Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.37
         From the CIF: _reflns_number_total               3198
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3388
         Completeness (_total/calc)             94.39%
          Alert C: < 95% complete

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.37
         From the CIF: _reflns_number_total               3198
         From the CIF: _diffrn_reflns_limit_ max hkl   22.    9.   12.
         From the CIF: _diffrn_reflns_limit_ min hkl    0.    0.  -12.
         TEST1: Expected hkl limits for theta max
         Calculated maximum hkl   22.    9.   14.
         Calculated minimum hkl  -22.   -9.  -14.
          ALERT: Expected hkl max differ from CIF values


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Les pyrazoles comptent parmi les composés hétérocycliques ayant recu la plus grande attention du fait de leurs applications dans des domaines aussi variés que la pharmacologie (Wakhsumov et al., 1986; Soliman et al., 2001; Baraldi at al., 2001), l'industrie (Clark et al., 1985) ou l'agrochimie (Kato et al., 1988). En outre, les hétérocycles à six chaînons de type pyridine sont connus pour l'étendue de leurs activités biologiques, antimicrobiennes et antibiotiques (Sebat et al., 2001), ainsi que pour leurs propriétés complexantes avec les métaux de transition, conduisant à des complexes stables à bas degré d'oxydation (Elfring & Crosby, 1981; Smothers & Wrightong, 1983). De ce fait, l'association de ces deux types d'hétérocycles permet d'élaborer de nouveaux composés hétérocycliques à visée thérapeutique susceptibles de présenter également des propriétés complexantes importantes. En effet, les ligands polyazotés sont des systèmes appropriés pour complexer les cations à couche incomplète (El Azzaoui et al., 1999). La 1-pyridine-2-yl-3-méthyl-4(1-pyridine-2-yl-3-méthyl-1H-pyrazol-5-yl)- 2H-3-pyrazoline-5-one est obtenue par action de l'acide déhydracétique sur le chlorhydrate de la 2-hydrazinopyridine au reflux de l'éthanol pendant deux nuits. Sa structure a été établie sur la base des données spectrales RMN ¹H, ¹³C et masse, puis confirmée par une étude structurale par diffraction des rayons X.

Les distances et angles trouvés dans cette molécule correspondent bien à la forme tautomère NH du fragment pyrazolinone (Kumar et al., 1995). Les distances C5—O6 = 1.242 (2) Å e t C5—N1 = 1.397 (2) Å sont typiques de ce tautomère. L'angle de torsion des cycles pyrazoles, défini par les atomes C5—C4—C15—C14 est 119.1 (3)°. Les deux cycles N1/N2/C3/C4/C5 et N7/C16/C17/C18/C19/C20 sont coplanaires [angle dièdre: 1,2(3)°] alors que les cycles N11/N12/C13/C14/C15 et N8/C21/C22/C23/C24/C25 font un angle dièdre de 29.9 (3)°. L'empilement des molécules dans le cristal est renforcé par la liaison hydrogène N2—H2···O6 qui forme une chaîne infinie dans la direction de l'axe c.

Experimental top

On chauffe à reflux pendant deux nuits dans 50 ml d'éthanol absolu 0,01 mol du chlorhydrate de la 2-hydrazinopyridine et 0,005 mol d'acide déhydracétique. Après concentration, le résidu solide est repris par l'eau, neutralisé par une solution de carbonate de sodium, le produit qui précipite est essoré puis recristallisé dans l'éthanol.

Computing details top

Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus (Mackay et al., 1999).

Figures top

Fig. 1. Dessin ORTEPII (Johnson, 1976) de la molécule. Les ellipsoides de vibration des atomes ont une probabilité de 50%.

1-(Pyridin-2-yl)-3-méthyl-4-(1-pyridin-2-yl-3-méthyl-1H-pyrazol-5-yl) -2H-3-pyrazoline-5(1H)-one top

Crystal data top

C₁₈H₁₆N₆O	F(000) = 696
M_r = 332.37	D_x = 1.335 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.297 (2) Å	Cell parameters from 10014 reflections
b = 7.7645 (9) Å	θ = 1–26.4°
c = 11.9280 (8) Å	µ = 0.09 mm⁻¹
β = 102.681 (7)°	T = 298 K
V = 1653.2 (3) Å³	Prism, colourless
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	R_int = 0.041
Radiation source: fine-focus sealed tube	θ_max = 26.4°
ϕ scans	h = 0→22
10014 measured reflections	k = 0→9
3198 independent reflections	l = −12→12
2463 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0434P)² + 0.5981P] where P = (F_o² + 2F_c²)/3
3198 reflections	(Δ/σ)_max = 0.006
228 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₈H₁₆N₆O	V = 1653.2 (3) Å³
M_r = 332.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.297 (2) Å	µ = 0.09 mm⁻¹
b = 7.7645 (9) Å	T = 298 K
c = 11.9280 (8) Å	0.30 × 0.15 × 0.10 mm
β = 102.681 (7)°

Data collection top

Nonius KappaCCD diffractometer	2463 reflections with I > 2σ(I)
10014 measured reflections	R_int = 0.041
3198 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.24 e Å⁻³
3198 reflections	Δρ_min = −0.23 e Å⁻³
228 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O6	0.21581 (8)	0.7957 (2)	0.15539 (12)	0.0662 (5)
N1	0.19078 (8)	0.7370 (2)	0.33412 (12)	0.0423 (4)
N2	0.22963 (9)	0.6618 (2)	0.43448 (13)	0.0443 (4)
H2	0.2131	0.6476	0.4960	0.053*
N7	0.09083 (9)	0.7782 (2)	0.41894 (14)	0.0513 (4)
N8	0.25259 (9)	0.3708 (2)	0.13833 (15)	0.0555 (5)
N11	0.36059 (8)	0.5378 (2)	0.15296 (13)	0.0414 (4)
N12	0.42648 (9)	0.5433 (2)	0.11567 (15)	0.0477 (4)
C3	0.29760 (10)	0.6145 (2)	0.42001 (16)	0.0393 (4)
C4	0.30302 (10)	0.6503 (2)	0.30970 (15)	0.0398 (4)
C5	0.23555 (10)	0.7331 (3)	0.25319 (15)	0.0440 (5)
C9	0.35265 (12)	0.5354 (3)	0.51676 (17)	0.0527 (5)
H9A	0.3277	0.5029	0.5765	0.079*	0.60
H9B	0.3915	0.6172	0.5464	0.079*	0.60
H9C	0.3743	0.4352	0.4898	0.079*	0.60
H9D	0.4047	0.5304	0.5023	0.079*	0.40
H9E	0.3565	0.6088	0.5864	0.079*	0.40
H9F	0.3307	0.4246	0.5360	0.079*	0.40
C10	0.55199 (12)	0.6615 (3)	0.1839 (2)	0.0705 (7)
H10A	0.5588	0.6101	0.1138	0.106*
H10B	0.5871	0.6127	0.2477	0.106*
H10C	0.5601	0.7835	0.1815	0.106*
C13	0.47371 (11)	0.6276 (3)	0.19777 (19)	0.0486 (5)
C14	0.43901 (11)	0.6780 (3)	0.28619 (18)	0.0489 (5)
H14	0.4609	0.7384	0.3524	0.059*
C15	0.36651 (10)	0.6208 (2)	0.25591 (16)	0.0404 (4)
C16	0.11759 (10)	0.7980 (2)	0.32488 (16)	0.0411 (4)
C17	0.07751 (11)	0.8710 (3)	0.22330 (19)	0.0528 (5)
H17	0.0981	0.8814	0.1590	0.063*
C18	0.00598 (12)	0.9270 (3)	0.2223 (2)	0.0633 (6)
H18	−0.0230	0.9761	0.1561	0.076*
C19	−0.02265 (13)	0.9105 (3)	0.3191 (2)	0.0676 (7)
H19	−0.0706	0.9493	0.3200	0.081*
C20	0.02120 (13)	0.8357 (3)	0.4140 (2)	0.0626 (6)
H20	0.0015	0.8239	0.4792	0.075*
C21	0.29970 (10)	0.4469 (2)	0.08349 (16)	0.0404 (4)
C22	0.29414 (12)	0.4379 (3)	−0.03348 (17)	0.0528 (5)
H22	0.3287	0.4933	−0.0677	0.063*
C23	0.23590 (14)	0.3445 (3)	−0.0983 (2)	0.0693 (7)
H23	0.2306	0.3345	−0.1774	0.083*
C24	0.18584 (14)	0.2664 (3)	−0.0441 (2)	0.0736 (7)
H24	0.1458	0.2033	−0.0859	0.088*
C25	0.19600 (13)	0.2829 (3)	0.0720 (2)	0.0683 (7)
H25	0.1615	0.2300	0.1076	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O6	0.0659 (10)	0.1047 (13)	0.0312 (9)	0.0195 (9)	0.0174 (6)	0.0154 (8)
N1	0.0445 (9)	0.0556 (10)	0.0283 (9)	0.0032 (7)	0.0111 (6)	0.0006 (7)
N2	0.0531 (9)	0.0532 (10)	0.0297 (9)	0.0042 (8)	0.0159 (7)	0.0043 (7)
N7	0.0522 (10)	0.0592 (11)	0.0477 (11)	−0.0001 (8)	0.0219 (7)	−0.0085 (8)
N8	0.0522 (10)	0.0676 (12)	0.0494 (11)	−0.0110 (9)	0.0168 (8)	−0.0090 (8)
N11	0.0414 (8)	0.0488 (10)	0.0380 (9)	−0.0003 (7)	0.0171 (6)	−0.0058 (7)
N12	0.0441 (9)	0.0542 (10)	0.0506 (11)	0.0006 (8)	0.0227 (7)	−0.0039 (8)
C3	0.0483 (10)	0.0368 (10)	0.0335 (11)	−0.0010 (8)	0.0107 (7)	−0.0039 (7)
C4	0.0455 (10)	0.0452 (11)	0.0304 (11)	0.0000 (8)	0.0120 (7)	−0.0058 (8)
C5	0.0498 (11)	0.0561 (13)	0.0284 (11)	0.0007 (9)	0.0137 (8)	−0.0032 (8)
C9	0.0620 (12)	0.0557 (13)	0.0392 (12)	0.0050 (10)	0.0086 (9)	0.0029 (9)
C10	0.0488 (12)	0.0744 (17)	0.094 (2)	−0.0067 (11)	0.0284 (12)	−0.0024 (14)
C13	0.0442 (10)	0.0484 (12)	0.0565 (13)	0.0007 (9)	0.0180 (9)	0.0032 (9)
C14	0.0491 (11)	0.0500 (12)	0.0472 (12)	−0.0039 (9)	0.0101 (8)	−0.0047 (9)
C15	0.0470 (10)	0.0424 (11)	0.0336 (11)	0.0011 (8)	0.0126 (7)	−0.0026 (8)
C16	0.0448 (10)	0.0403 (11)	0.0402 (11)	−0.0027 (8)	0.0133 (8)	−0.0068 (8)
C17	0.0537 (12)	0.0532 (13)	0.0515 (14)	0.0021 (10)	0.0118 (9)	0.0046 (9)
C18	0.0544 (13)	0.0545 (14)	0.0783 (18)	0.0070 (10)	0.0084 (11)	0.0098 (12)
C19	0.0536 (13)	0.0590 (15)	0.095 (2)	0.0107 (11)	0.0272 (13)	−0.0004 (13)
C20	0.0601 (13)	0.0653 (15)	0.0711 (17)	0.0049 (11)	0.0334 (12)	−0.0075 (12)
C21	0.0432 (10)	0.0405 (11)	0.0384 (11)	0.0061 (8)	0.0108 (7)	−0.0060 (8)
C22	0.0643 (13)	0.0539 (13)	0.0412 (13)	0.0097 (10)	0.0136 (9)	−0.0023 (9)
C23	0.0807 (17)	0.0780 (17)	0.0419 (14)	0.0117 (14)	−0.0026 (11)	−0.0171 (11)
C24	0.0607 (15)	0.0752 (18)	0.0757 (19)	−0.0012 (13)	−0.0049 (12)	−0.0246 (14)
C25	0.0538 (13)	0.0764 (17)	0.0745 (18)	−0.0162 (12)	0.0138 (11)	−0.0165 (13)

Geometric parameters (Å, º) top

O6—C5	1.242 (2)	C10—C13	1.501 (3)
N1—N2	1.380 (2)	C10—H10A	0.9600
N1—C5	1.397 (2)	C10—H10B	0.9600
N1—C16	1.402 (2)	C10—H10C	0.9600
N2—C3	1.344 (2)	C13—C14	1.401 (3)
N2—H2	0.8600	C14—C15	1.370 (3)
N7—C16	1.328 (2)	C14—H14	0.9300
N7—C20	1.339 (3)	C16—C17	1.392 (3)
N8—C21	1.330 (2)	C17—C18	1.377 (3)
N8—C25	1.343 (3)	C17—H17	0.9300
N11—C15	1.370 (2)	C18—C19	1.375 (3)
N11—N12	1.374 (2)	C18—H18	0.9300
N11—C21	1.421 (2)	C19—C20	1.365 (3)
N12—C13	1.328 (3)	C19—H19	0.9300
C3—C4	1.370 (3)	C20—H20	0.9300
C3—C9	1.488 (3)	C21—C22	1.378 (3)
C4—C5	1.423 (3)	C22—C23	1.378 (3)
C4—C15	1.463 (2)	C22—H22	0.9300
C9—H9A	0.9600	C23—C24	1.373 (4)
C9—H9B	0.9600	C23—H23	0.9300
C9—H9C	0.9600	C24—C25	1.363 (4)
C9—H9D	1.0052	C24—H24	0.9300
C9—H9E	0.9971	C25—H25	0.9300
C9—H9F	0.9970

N2—N1—C5	108.77 (14)	H10A—C10—H10B	109.5
N2—N1—C16	120.81 (14)	C13—C10—H10C	109.5
C5—N1—C16	130.39 (16)	H10A—C10—H10C	109.5
C3—N2—N1	108.62 (14)	H10B—C10—H10C	109.5
C3—N2—H2	125.7	N12—C13—C14	111.34 (17)
N1—N2—H2	125.7	N12—C13—C10	119.19 (19)
C16—N7—C20	116.60 (19)	C14—C13—C10	129.4 (2)
C21—N8—C25	115.8 (2)	C15—C14—C13	106.47 (18)
C15—N11—N12	111.90 (15)	C15—C14—H14	126.8
C15—N11—C21	130.82 (15)	C13—C14—H14	126.8
N12—N11—C21	117.26 (15)	C14—C15—N11	105.69 (16)
C13—N12—N11	104.59 (15)	C14—C15—C4	130.51 (17)
N2—C3—C4	109.39 (16)	N11—C15—C4	123.54 (16)
N2—C3—C9	120.10 (16)	N7—C16—C17	124.14 (18)
C4—C3—C9	130.51 (17)	N7—C16—N1	114.67 (17)
C3—C4—C5	107.96 (16)	C17—C16—N1	121.18 (17)
C3—C4—C15	128.42 (17)	C18—C17—C16	117.1 (2)
C5—C4—C15	123.55 (17)	C18—C17—H17	121.5
O6—C5—N1	123.15 (17)	C16—C17—H17	121.5
O6—C5—C4	131.65 (17)	C19—C18—C17	120.0 (2)
N1—C5—C4	105.18 (16)	C19—C18—H18	120.0
C3—C9—H9A	109.5	C17—C18—H18	120.0
C3—C9—H9B	109.5	C20—C19—C18	118.2 (2)
H9A—C9—H9B	109.5	C20—C19—H19	120.9
C3—C9—H9C	109.5	C18—C19—H19	120.9
H9A—C9—H9C	109.5	N7—C20—C19	124.0 (2)
H9B—C9—H9C	109.5	N7—C20—H20	118.0
C3—C9—H9D	112.9	C19—C20—H20	118.0
H9A—C9—H9D	137.7	N8—C21—C22	124.30 (19)
H9B—C9—H9D	55.7	N8—C21—N11	116.34 (17)
H9C—C9—H9D	55.6	C22—C21—N11	119.33 (18)
C3—C9—H9E	108.8	C23—C22—C21	118.1 (2)
H9A—C9—H9E	59.3	C23—C22—H22	120.9
H9B—C9—H9E	53.4	C21—C22—H22	120.9
H9C—C9—H9E	141.6	C24—C23—C22	118.8 (2)
H9D—C9—H9E	105.6	C24—C23—H23	120.6
C3—C9—H9F	107.2	C22—C23—H23	120.6
H9A—C9—H9F	47.3	C25—C24—C23	118.7 (2)
H9B—C9—H9F	142.0	C25—C24—H24	120.6
H9C—C9—H9F	66.0	C23—C24—H24	120.6
H9D—C9—H9F	116.8	N8—C25—C24	124.2 (2)
H9E—C9—H9F	105.1	N8—C25—H25	117.9
C13—C10—H10A	109.5	C24—C25—H25	117.9
C13—C10—H10B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6ⁱ	0.86	1.94	2.722 (2)	150

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₆O
M_r	332.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	18.297 (2), 7.7645 (9), 11.9280 (8)
β (°)	102.681 (7)
V (Å³)	1653.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10014, 3198, 2463
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.127, 1.12
No. of reflections	3198
No. of parameters	228
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.23

Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), maXus (Mackay et al., 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6ⁱ	0.86	1.94	2.722 (2)	150.0

Symmetry code: (i) x, −y+3/2, z+1/2.

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