N-(4-Methyl­phen­yl)-6-(pyrazol-1-yl)pyridazin-3-amine

Abdul Qayyum Ather; M Nawaz Tahir; Misbahul Ain Khan; Muhammad Makshoof Athar; Eliana Aparecida Silicz Bueno

doi:10.1107/S1600536810024700

. 2010 Jul 3;66(Pt 8):o1900. doi: 10.1107/S1600536810024700

N-(4-Methylphenyl)-6-(pyrazol-1-yl)pyridazin-3-amine

Abdul Qayyum Ather ^a, M Nawaz Tahir ^b,^*, Misbahul Ain Khan ^c, Muhammad Makshoof Athar ^d, Eliana Aparecida Silicz Bueno ^e

PMCID: PMC3007321 PMID: 21588234

Abstract

In the title compound, C₁₄H₁₃N₅, the pyrazole ring is disordered over two orientations in a 0.571 (10):0.429 (10) ratio and the dihedral angle between the pyridazine ring and the benzene ring is 28.07 (10)°. In the crystal, pairs of N—H⋯N and C—H⋯N hydrogen bonds link the molecules into dimers, with the aid of a crystallographic twofold axis. The packing is consolidated by further C—H⋯N bonds and weak C—H⋯π interactions.

Related literature

For related structures, see: Ather et al. (2009 ▶, 2010a ▶,b ▶,c ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₃N₅
M _r = 251.29
Monoclinic,
a = 31.8677 (17) Å
b = 7.9408 (5) Å
c = 10.8446 (7) Å
β = 109.715 (3)°
V = 2583.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.32 × 0.18 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.982, T _max = 0.988
9293 measured reflections
2336 independent reflections
1384 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.176
S = 1.03
2336 reflections
156 parameters
11 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.33 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/S1600536810024700/hb5514sup1.cif

e-66-o1900-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024700/hb5514Isup2.hkl

e-66-o1900-Isup2.hkl^{(112.5KB, hkl)}

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

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

Cg1 is the centroid of the N4/N5B/C12B–C14B ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.86	2.12	2.982 (3)	178
C6—H6⋯N3ⁱ	0.93	2.62	3.498 (4)	157
C14B—H14B⋯N5Bⁱⁱ	0.93	2.47	3.357 (11)	160
C5—H5⋯Cg1ⁱⁱⁱ	0.93	2.99	3.527 (5)	118

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Bana International, Karachi, Pakistan.

supplementary crystallographic information

Comment

In continuation to pyrazolylpyridazine derivatives (Ather et al., 2009, 2010a, 2010b, 2010c), the title compound (I, Fig. 1) is being reported here.

The title compound is reaction product of 3-chloro-6-(1H-pyrazol-1-yl)pyridazine and 4-toluidine. There are three cyclic rings in the final product. In (I), the pyrazole ring except adjoining N-atom and H-atoms of the only methyl group are disordered over two set of sites with occupancy ratio of 0.571 (10):0.429 (10). The majority group A (N4/N5B/C12B/C13B/C14B), the pyridazine ring B (C8—C11/N3/N2) and the 4-toludine group C (N1/C1—C7) are planar with r. m. s. deviations of 0.0431, 0.0175 and 0.0153 Å respectively. The miniority disordered group D (N4/N5A/C12A/C13A/C14A) is also planar with r. m. s. deviation of 0.0555 Å. The dihedral angle between A/B, A/C and B/C is 6.46 (24)°, 32.15 (28)° and 28.07 (10)° respectively. The dihedral angle between the disordered groups A/D is 17.72 (34)°. There exist intermolecular H-bondings of N—H···N and C—H···N types (Table 1). The molecules are stabilized in the form of dimers. In dimers, one ring motif of R₂²(8) and two ring motifs of R₂²(7) types (Bernstein et al., 1995) are present (Fig. 2). C—H···π interaction (Table 1) also play role in stabilizing the molecules.

Experimental

3-Chloro-6-(1H-pyrazol-1-yl)pyridazine (1.68 g, 9.33 mmol) and 4-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 74.0% yield. The product obtained was purified by column chromatography and recrystallized in ethanol to afford light brown needles of title compound (I).