N-(2-Methyl­phen­yl)-6-(1H-pyrazol-1-yl)pyridazin-3-amine

Abdul Qayyum Ather; M Nawaz Tahir; Misbahul Ain Khan; Muhammad Makshoof Athar

doi:10.1107/S1600536809022867

. 2009 Jun 20;65(Pt 7):o1628. doi: 10.1107/S1600536809022867

N-(2-Methylphenyl)-6-(1H-pyrazol-1-yl)pyridazin-3-amine

Abdul Qayyum Ather ^a, M Nawaz Tahir ^b,^*, Misbahul Ain Khan ^c, Muhammad Makshoof Athar ^d

PMCID: PMC2969459 PMID: 21582895

Abstract

The title compound, C₁₄H₁₃N₅, crystallizes with two crystallographically independent molecules in the unit cell. The two molecules form dimers through intermolecular N—H⋯N and C—H⋯N hydrogen bonds. The hydrogen-bonding motifs are R ₂ ²(8) for both the N—H⋯N and C—H⋯N interactions. The pyrazole and pyrimidine rings form dihedral angles of 6.2 (3) and 8.3 (3)° with each other and the dihedral angles between the pyrazole and benzene rings are 54.9 (2) and 58.6 (2)°. The benzene rings of neighbouring dimers also exhibit C—H⋯π interactions.

Related literature

A docking study of pyrazololylpyridazine has shown inhibitory action against glycogen synthase kinase 3, see: Xiao et al. (2006 ▶); For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₃N₅
M _r = 251.29
Monoclinic,
a = 16.548 (5) Å
b = 19.639 (4) Å
c = 8.015 (5) Å
β = 99.619 (5)°
V = 2568.1 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.982, T _max = 0.988
13833 measured reflections
3209 independent reflections
1716 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.167
S = 1.02
3209 reflections
303 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.32 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 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022867/zl2217sup1.cif

e-65-o1628-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022867/zl2217Isup2.hkl

e-65-o1628-Isup2.hkl^{(154.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N7ⁱ	0.86	2.26	3.086 (5)	162
N6—H6A⋯N2ⁱⁱ	0.86	2.26	3.065 (6)	156
C7—H7C⋯N8ⁱ	0.96	2.53	3.482 (8)	175
C21—H21C⋯N3ⁱⁱ	0.96	2.59	3.519 (10)	163
C6—H6⋯Cg1	0.93	2.80	3.529 (6)	136

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of benzene ring (C15–C20).

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore and for technical support, respectively.

supplementary crystallographic information

Comment

Pyrazolylpyridazine derivatives are potential anticholestromic and antihypertensive agents. A docking study of pyrazololylpyridazine has shown inhibitory action against glycogen synthase kinase 3 (Xiao et al., 2006). In continuation of our work on the synthesis and reactions of azolylpyridazines, we have isolated crystals of the title compound, (Fig. 1).

The title compound contains pyrazole, pyridazine and benzene rings. In the asymmetric unit there are two molecules which differ from one another crystallographically.

In one molecule (containing C1—C14), the pyrazole ring is oriented at dihedral angles of 6.16 (30)° and 54.91 (21)° with the pyridazine and benzene rings, respectively. In the second molecule, the pyrazole ring exhibits dihedral angles of 8.26 (34)° and 58.57 (20)° with the pyridazine and benzene rings, respectively. Through intermolecular N–H···N and C–H···N hydrogen bonds the two molecules form dimers with hydrogen bonding ring motifs of R₂²(8) (Bernstein et al., 1995). C—H···π interactions between the benzene rings are also observed in the structure of the title compound (Table 1, Cg1 is the centroid of benzene ring (C15—C20)).

Experimental

3-Chloro-6-(1H-pyrazol-1-yl)pyridazine (1.68 g, 9.33 mmol) and 2-toluidine (1 g, 9.34 mmol) were refluxed in dimethylformamide (DMF) for 2 h. The reaction mixture was concentrated under vacuum and poured in cold water. The precipitates obtained were filtered, washed with distilled water and dried to give 51.28% yield. The product obtained was purified by column chromatography and recrystallized in benzene.