3-(Piperidin-1-yl)-6-(1H-pyrazol-1-yl)pyridazine

Ather, A.Q.; Şahin, O.; Khan, I.U.; Khan, M.A.; Büyükgüngör, O.

doi:10.1107/S1600536810016491

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1295

https://doi.org/10.1107/S1600536810016491

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3-(Piperidin-1-yl)-6-(1H-pyrazol-1-yl)pyridazine

Abdul Qayyum Ather,^a Onur Şahin,^b ^* Islam Ullah Khan,^c ^* Misbahul Ain Khan ^d and Orhan Büyükgüngör ^b

^aDepartment of Chemistry, Islamia University, Ba-hawalpur, Pakistan and Applied Chemistry Research Center, PCSIR Laboratories Complex, Lahore 54600, Pakistan, ^bDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, ^cMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^dInstitute of Chemistry, University of the Punjab, Lahore 54000, Pakistan
^*Correspondence e-mail: onurs@omu.edu.tr, iukhan.gcu@gmail.com

(Received 4 May 2010; accepted 5 May 2010; online 8 May 2010)

In the title compound, C₁₂H₁₅N₅, the piperidine ring adopts a chair conformation with the substituent C atom in an equatorial site and the dihedral angle between the pyridazine and pyrazole ring planes is 10.36 (2)°.

Related literature

For related structures, see: Blake et al. (2002 ); Ather et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₅N₅
M_r = 229.29
Monoclinic, P 2₁ /n
a = 5.9665 (6) Å
b = 20.189 (3) Å
c = 9.9695 (13) Å
β = 103.230 (7)°
V = 1169.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.31 × 0.25 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
11710 measured reflections
2674 independent reflections
1282 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.182
S = 1.01
2674 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810016491/hb5436sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016491/hb5436Isup2.hkl

checkCIF report

Comment top

As part of our onging studies of azolylpyridazines (Ather et al., 2009), we now report the synthesis and structure of the title compound, (I).

Compound (I) consists of a pyridazine ring with piperidine and pyrazole substituents at the 3- and 6-positions, respectively (Fig. 1). Least-squares mean-plane calculations for the pyridazine (N3/N4/C4/C5/C6/C7) and pyrazole (N1/N2/C3/C1/C2) rings show that these are approximately planar, with respective maximum deviations of 0.0042 (16)Å for atom C7 and 0.0026 (19)Å for atom C2. The dihedral angle between the pyridazine and pyrazole ring planes is 10.36 (2)°. The piperidine ring in (I) adopts a chair conformation. The N5—C7 and N2—C4 bond lengths indicate significant single-bond character, whereas the N3═C7 and N4═C4 bond lengths are indicative of significant double-bond character. The N1—N2 and N3—N4 bond lengths [1.357 (3)Å and 1.353 (3) Å, respectively] agree with the corresponding distances in 3,4,6-Tris(pyrazol-1-yl)pyridazine (Blake et al., 2002).

Related literature top

For related structures, see: Blake et al. (2002); Ather et al. (2009).

Experimental top

A mixture of 1.0 g (0.18 mmol) of 3-chloro-6-(1 H-Pyrozol-1-yl) pyridazine and 5 ml of piperidine was refluxed for 2 h, concentrated under vacuum, cooled and added to cooled water. The ppt filtered dried and recrystallized from benzene to give colourless prisms of (I) (m.p. 383-384 K).

Structure description top

As part of our onging studies of azolylpyridazines (Ather et al., 2009), we now report the synthesis and structure of the title compound, (I).

For related structures, see: Blake et al. (2002); Ather et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. A view of (I), showing 30% displacement ellipsoids.

3-(Piperidin-1-yl)-6-(1H-pyrazol-1-yl)pyridazine top

Crystal data top

C₁₂H₁₅N₅	F(000) = 488
M_r = 229.29	D_x = 1.303 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1639 reflections
a = 5.9665 (6) Å	θ = 2.3–21.3°
b = 20.189 (3) Å	µ = 0.08 mm⁻¹
c = 9.9695 (13) Å	T = 296 K
β = 103.230 (7)°	Prism, colourless
V = 1169.0 (2) Å³	0.31 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1282 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
phi and ω scans	h = −7→7
11710 measured reflections	k = −26→26
2674 independent reflections	l = −12→12

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0863P)²] where P = (F_o² + 2F_c²)/3
2674 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₅N₅	V = 1169.0 (2) Å³
M_r = 229.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.9665 (6) Å	µ = 0.08 mm⁻¹
b = 20.189 (3) Å	T = 296 K
c = 9.9695 (13) Å	0.31 × 0.25 × 0.22 mm
β = 103.230 (7)°

Data collection top

Bruker APEXII CCD diffractometer	1282 reflections with I > 2σ(I)
11710 measured reflections	R_int = 0.054
2674 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	Δρ_max = 0.18 e Å⁻³
2674 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.3406 (6)	0.72572 (15)	0.3173 (3)	0.0738 (9)
H1	0.4014	0.6901	0.2782	0.089*
C2	0.1112 (6)	0.74333 (16)	0.2984 (3)	0.0756 (9)
H2	−0.0087	0.7203	0.2415	0.091*
C3	0.4568 (5)	0.77160 (14)	0.4052 (3)	0.0639 (8)
H3	0.6155	0.7740	0.4384	0.077*
C4	0.3331 (4)	0.86969 (12)	0.5224 (2)	0.0452 (6)
C5	0.1481 (4)	0.90081 (13)	0.5592 (3)	0.0501 (7)
H5	−0.0019	0.8857	0.5274	0.060*
C6	0.1955 (4)	0.95375 (14)	0.6429 (2)	0.0496 (7)
H6	0.0779	0.9767	0.6699	0.060*
C7	0.4275 (4)	0.97398 (12)	0.6893 (2)	0.0415 (6)
C8	0.3360 (4)	1.08147 (13)	0.7801 (3)	0.0540 (7)
H8A	0.1774	1.0665	0.7559	0.065*
H8B	0.3581	1.1125	0.7098	0.065*
C9	0.3800 (4)	1.11603 (15)	0.9163 (3)	0.0638 (8)
H9A	0.3378	1.0870	0.9840	0.077*
H9B	0.2842	1.1553	0.9085	0.077*
C10	0.6306 (4)	1.13584 (14)	0.9652 (3)	0.0674 (8)
H10A	0.6698	1.1689	0.9037	0.081*
H10B	0.6567	1.1548	1.0569	0.081*
C11	0.7792 (4)	1.07512 (14)	0.9672 (3)	0.0580 (8)
H11A	0.9401	1.0879	0.9932	0.070*
H11B	0.7501	1.0443	1.0359	0.070*
C12	0.7328 (4)	1.04124 (14)	0.8292 (3)	0.0530 (7)
H12A	0.7779	1.0702	0.7623	0.064*
H12B	0.8244	1.0012	0.8360	0.064*
N1	0.0810 (4)	0.79630 (13)	0.3697 (2)	0.0692 (7)
N2	0.2982 (4)	0.81341 (11)	0.4357 (2)	0.0536 (6)
N3	0.5964 (3)	0.94188 (11)	0.6493 (2)	0.0493 (6)
N4	0.5475 (3)	0.88877 (11)	0.5649 (2)	0.0523 (6)
N5	0.4896 (3)	1.02450 (10)	0.7825 (2)	0.0449 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.099 (3)	0.052 (2)	0.072 (2)	0.0073 (17)	0.0227 (18)	−0.0060 (17)
C2	0.093 (3)	0.063 (2)	0.070 (2)	−0.0127 (18)	0.0162 (17)	−0.0139 (18)
C3	0.0711 (19)	0.0549 (19)	0.0662 (19)	0.0141 (15)	0.0166 (15)	−0.0039 (16)
C4	0.0482 (14)	0.0451 (16)	0.0416 (14)	0.0045 (11)	0.0088 (11)	0.0059 (12)
C5	0.0386 (13)	0.0639 (19)	0.0480 (15)	0.0021 (12)	0.0104 (11)	0.0014 (14)
C6	0.0327 (12)	0.0650 (19)	0.0517 (16)	0.0071 (12)	0.0108 (10)	−0.0019 (14)
C7	0.0343 (12)	0.0508 (16)	0.0404 (14)	0.0054 (11)	0.0106 (9)	0.0055 (12)
C8	0.0348 (13)	0.0593 (18)	0.0672 (18)	0.0064 (12)	0.0104 (11)	−0.0022 (15)
C9	0.0484 (16)	0.0595 (19)	0.086 (2)	0.0036 (13)	0.0211 (13)	−0.0177 (16)
C10	0.0549 (17)	0.064 (2)	0.084 (2)	−0.0063 (14)	0.0176 (14)	−0.0157 (16)
C11	0.0395 (13)	0.071 (2)	0.0610 (18)	−0.0092 (13)	0.0070 (11)	−0.0054 (15)
C12	0.0322 (12)	0.0668 (19)	0.0600 (17)	0.0016 (12)	0.0107 (10)	0.0036 (14)
N1	0.0619 (15)	0.0732 (18)	0.0691 (17)	−0.0082 (12)	0.0077 (12)	−0.0157 (14)
N2	0.0590 (13)	0.0462 (14)	0.0545 (14)	0.0035 (11)	0.0110 (10)	0.0021 (11)
N3	0.0378 (11)	0.0543 (14)	0.0583 (13)	0.0065 (9)	0.0161 (9)	−0.0031 (11)
N4	0.0433 (12)	0.0542 (14)	0.0610 (14)	0.0082 (10)	0.0156 (10)	−0.0008 (12)
N5	0.0286 (9)	0.0566 (14)	0.0496 (12)	0.0048 (9)	0.0090 (8)	−0.0008 (11)

Geometric parameters (Å, º) top

C1—C3	1.352 (4)	C8—C9	1.496 (4)
C1—C2	1.384 (4)	C8—H8A	0.9700
C1—H1	0.9300	C8—H8B	0.9700
C2—N1	1.319 (4)	C9—C10	1.516 (3)
C2—H2	0.9300	C9—H9A	0.9700
C3—N2	1.353 (3)	C9—H9B	0.9700
C3—H3	0.9300	C10—C11	1.510 (4)
C4—N4	1.310 (3)	C10—H10A	0.9700
C4—C5	1.391 (3)	C10—H10B	0.9700
C4—N2	1.414 (3)	C11—C12	1.504 (3)
C5—C6	1.346 (3)	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700
C6—C7	1.415 (3)	C12—N5	1.458 (3)
C6—H6	0.9300	C12—H12A	0.9700
C7—N3	1.334 (3)	C12—H12B	0.9700
C7—N5	1.372 (3)	N1—N2	1.357 (3)
C8—N5	1.467 (3)	N3—N4	1.353 (3)

C3—C1—C2	104.9 (3)	C8—C9—H9B	109.3
C3—C1—H1	127.6	C10—C9—H9B	109.3
C2—C1—H1	127.6	H9A—C9—H9B	107.9
N1—C2—C1	112.8 (3)	C11—C10—C9	108.8 (2)
N1—C2—H2	123.6	C11—C10—H10A	109.9
C1—C2—H2	123.6	C9—C10—H10A	109.9
C1—C3—N2	106.9 (3)	C11—C10—H10B	109.9
C1—C3—H3	126.5	C9—C10—H10B	109.9
N2—C3—H3	126.5	H10A—C10—H10B	108.3
N4—C4—C5	123.9 (2)	C12—C11—C10	111.9 (2)
N4—C4—N2	115.5 (2)	C12—C11—H11A	109.2
C5—C4—N2	120.7 (2)	C10—C11—H11A	109.2
C6—C5—C4	117.1 (2)	C12—C11—H11B	109.2
C6—C5—H5	121.5	C10—C11—H11B	109.2
C4—C5—H5	121.5	H11A—C11—H11B	107.9
C5—C6—C7	118.9 (2)	N5—C12—C11	111.04 (19)
C5—C6—H6	120.6	N5—C12—H12A	109.4
C7—C6—H6	120.6	C11—C12—H12A	109.4
N3—C7—N5	117.3 (2)	N5—C12—H12B	109.4
N3—C7—C6	120.8 (2)	C11—C12—H12B	109.4
N5—C7—C6	121.9 (2)	H12A—C12—H12B	108.0
N5—C8—C9	111.8 (2)	C2—N1—N2	103.6 (2)
N5—C8—H8A	109.3	C3—N2—N1	111.8 (2)
C9—C8—H8A	109.3	C3—N2—C4	128.7 (2)
N5—C8—H8B	109.3	N1—N2—C4	119.4 (2)
C9—C8—H8B	109.3	C7—N3—N4	120.05 (19)
H8A—C8—H8B	107.9	C4—N4—N3	119.34 (19)
C8—C9—C10	111.7 (2)	C7—N5—C12	118.89 (18)
C8—C9—H9A	109.3	C7—N5—C8	120.04 (18)
C10—C9—H9A	109.3	C12—N5—C8	113.3 (2)

C3—C1—C2—N1	−0.5 (4)	C5—C4—N2—C3	−169.6 (2)
C2—C1—C3—N2	0.4 (3)	N4—C4—N2—N1	−169.8 (2)
N4—C4—C5—C6	0.4 (4)	C5—C4—N2—N1	11.0 (3)
N2—C4—C5—C6	179.5 (2)	N5—C7—N3—N4	175.5 (2)
C4—C5—C6—C7	−0.7 (4)	C6—C7—N3—N4	−0.9 (3)
C5—C6—C7—N3	1.0 (4)	C5—C4—N4—N3	−0.3 (4)
C5—C6—C7—N5	−175.2 (2)	N2—C4—N4—N3	−179.4 (2)
N5—C8—C9—C10	54.4 (3)	C7—N3—N4—C4	0.5 (3)
C8—C9—C10—C11	−54.9 (3)	N3—C7—N5—C12	1.6 (3)
C9—C10—C11—C12	55.6 (3)	C6—C7—N5—C12	177.9 (2)
C10—C11—C12—N5	−55.7 (3)	N3—C7—N5—C8	148.8 (2)
C1—C2—N1—N2	0.4 (3)	C6—C7—N5—C8	−34.8 (3)
C1—C3—N2—N1	−0.2 (3)	C11—C12—N5—C7	−156.3 (2)
C1—C3—N2—C4	−179.6 (2)	C11—C12—N5—C8	54.3 (3)
C2—N1—N2—C3	−0.1 (3)	C9—C8—N5—C7	157.0 (2)
C2—N1—N2—C4	179.4 (2)	C9—C8—N5—C12	−54.1 (3)
N4—C4—N2—C3	9.6 (4)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₅
M_r	229.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.9665 (6), 20.189 (3), 9.9695 (13)
β (°)	103.230 (7)
V (Å³)	1169.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.31 × 0.25 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11710, 2674, 1282
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.182, 1.01
No. of reflections	2674
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

UK thanks the Higher Education Commission of Pakistan for financial support under the project `Strengthening of the Materials Chemistry Laboratory' at GCUL.

References

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