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

Ather, A.Q.; Tahir, M.N.; Khan, M.A.; Athar, M.M.

doi:10.1107/S1600536810016697

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1327

https://doi.org/10.1107/S1600536810016697

Open

access

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

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

^aDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan, ^bApplied Chemistry Research Center, PCSIR Laboratories complex, Lahore 54600, Pakistan, ^cDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^dInstitute of Chemistry, University of the Punjab, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 25 April 2010; accepted 6 May 2010; online 12 May 2010)

The molecule of title compound, C₁₃H₁₁N₅, is essentially planar (r.m.s. deviation = 0.0440 Å) and an intramolecular C—H⋯N hydrogen bond generates an S(6) motif. In the crystal, molecules are connected into chains by intermolecular N—H⋯N and C—H⋯N hydrogen bonds. In addition, π–π stacking interactions are observed between the pyrazole and pyridazine rings [interplanar distance = 3.6859 (10) Å].

Related literature

For a related structure, see: Ather et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₁N₅
M_r = 237.27
Orthorhombic, P b c a
a = 11.3533 (7) Å
b = 9.4214 (5) Å
c = 21.6603 (14) Å
V = 2316.9 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.30 × 0.22 × 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
10085 measured reflections
2754 independent reflections
1571 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 0.99
2754 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N5ⁱ	0.86	2.22	3.071 (2)	173
C6—H6⋯N2	0.93	2.37	2.966 (3)	122
C8—H8⋯N3ⁱⁱ	0.93	2.60	3.265 (2)	129
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810016697/gk2271sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016697/gk2271Isup2.hkl

checkCIF report

Comment top

In continuation of our studies on pyrazolylpyridazine derivatives (Ather et al., 2009), the structure of title compound ( Fig. 1) is reported here.

The title compound contains pyrazole, pyridazine and benzene rings. The r. m. s. deviation of 0.044 Å shows that the molecule of title compound is essentially planar. There exist S(6) ring motif (Bernstein et al., 1995) due to C–H···N intramolecular H-bonding (Fig. 1). The molecules are stabilized in the form of infinite polymeric chains due to intermolecular H-bondings (Table 1) extending along the crystallographic b-axis (Fig. 2). The π–π interactions between the pyrazol and pyridazine ring are present at a distance of 3.6859 (10) Å.

Related literature top

For a related structure, see: Ather et al. (2009). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

3-Chloro-6-(1H-pyrazole-1-yl)pyridazine (1 g, 5.5 mmol) was dissolved in xylene (15 ml). Aniline (0.516 g, 5.5 mmol) was added to the solution and refluxed for 12 h. The reaction was monitored by TLC. After the completion, the reaction mixture was concentrated under vacuum. Distilled water (50 ml) was added to the resulting concentrated mixture, which give rise to precipitate. The filtered precipitate was dried and recrystallized from chloroform to obtain the title compound (I).

Structure description top

In continuation of our studies on pyrazolylpyridazine derivatives (Ather et al., 2009), the structure of title compound ( Fig. 1) is reported here.

For a related structure, see: Ather et al. (2009). For graph-set notation, see: Bernstein et al. (1995).

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 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii. The dotted line indicates the intramolecular hydrogen bond.
	Fig. 2. Packing diagram of the title compound (PLATON: Spek, 2009) showing that infinite polymeric chains extend along the b-axis.

N-Phenyl-6-(1H-pyrazol-1-yl)pyridazin-3-amine top

Crystal data top

C₁₃H₁₁N₅	F(000) = 992
M_r = 237.27	D_x = 1.360 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2920 reflections
a = 11.3533 (7) Å	θ = 2.6–27.9°
b = 9.4214 (5) Å	µ = 0.09 mm⁻¹
c = 21.6603 (14) Å	T = 296 K
V = 2316.9 (2) Å³	Prismatic, pale brown
Z = 8	0.30 × 0.22 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2754 independent reflections
Radiation source: fine-focus sealed tube	1571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 7.50 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
ω scan	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→8
T_min = 0.982, T_max = 0.988	l = −17→28
10085 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0546P)² + 0.0495P] where P = (F_o² + 2F_c²)/3
2754 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₃H₁₁N₅	V = 2316.9 (2) Å³
M_r = 237.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.3533 (7) Å	µ = 0.09 mm⁻¹
b = 9.4214 (5) Å	T = 296 K
c = 21.6603 (14) Å	0.30 × 0.22 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2754 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1571 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.045
10085 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 0.99	Δρ_max = 0.13 e Å⁻³
2754 reflections	Δρ_min = −0.15 e Å⁻³
163 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 > 2sigma(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	0.22072 (14)	−0.09114 (16)	0.11333 (7)	0.0450 (4)
C2	0.17051 (16)	−0.18861 (17)	0.07303 (8)	0.0588 (5)
H2	0.0892	−0.2008	0.0729	0.071*
C3	0.23913 (19)	−0.2677 (2)	0.03321 (9)	0.0685 (5)
H3	0.2040	−0.3327	0.0066	0.082*
C4	0.35859 (18)	−0.2505 (2)	0.03286 (9)	0.0676 (5)
H4	0.4052	−0.3027	0.0059	0.081*
C5	0.40882 (17)	−0.1552 (2)	0.07273 (9)	0.0694 (5)
H5	0.4902	−0.1440	0.0727	0.083*
C6	0.34133 (15)	−0.07516 (18)	0.11315 (9)	0.0579 (5)
H6	0.3772	−0.0112	0.1399	0.069*
C7	0.15904 (13)	0.08370 (16)	0.19601 (7)	0.0432 (4)
C8	0.05780 (14)	0.14252 (16)	0.22366 (8)	0.0499 (4)
H8	−0.0169	0.1139	0.2113	0.060*
C9	0.07086 (14)	0.24049 (17)	0.26820 (8)	0.0499 (4)
H9	0.0066	0.2824	0.2876	0.060*
C10	0.18694 (13)	0.27585 (16)	0.28379 (7)	0.0422 (4)
C11	0.31668 (15)	0.42876 (18)	0.34775 (9)	0.0561 (5)
H11	0.3892	0.4055	0.3305	0.067*
C12	0.29780 (17)	0.52176 (19)	0.39459 (9)	0.0608 (5)
H12	0.3537	0.5748	0.4159	0.073*
C13	0.17754 (17)	0.52036 (18)	0.40374 (8)	0.0596 (5)
H13	0.1392	0.5750	0.4333	0.072*
N1	0.14245 (11)	−0.01684 (14)	0.15110 (6)	0.0493 (4)
H1	0.0698	−0.0383	0.1450	0.059*
N2	0.26728 (11)	0.12101 (13)	0.21296 (6)	0.0473 (4)
N3	0.27965 (11)	0.22007 (14)	0.25801 (6)	0.0468 (3)
N4	0.21109 (11)	0.37648 (13)	0.33089 (6)	0.0452 (3)
N5	0.12287 (12)	0.43206 (15)	0.36555 (7)	0.0558 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0436 (9)	0.0463 (9)	0.0452 (9)	0.0013 (7)	−0.0012 (8)	0.0076 (8)
C2	0.0529 (10)	0.0656 (11)	0.0579 (11)	−0.0040 (9)	−0.0040 (9)	−0.0029 (10)
C3	0.0790 (14)	0.0682 (12)	0.0583 (12)	−0.0014 (11)	−0.0065 (11)	−0.0114 (10)
C4	0.0691 (14)	0.0739 (13)	0.0599 (12)	0.0118 (11)	0.0068 (10)	−0.0065 (10)
C5	0.0490 (11)	0.0843 (13)	0.0748 (13)	0.0052 (10)	0.0041 (10)	−0.0132 (12)
C6	0.0465 (10)	0.0645 (11)	0.0627 (12)	−0.0005 (9)	0.0009 (9)	−0.0095 (9)
C7	0.0336 (8)	0.0461 (9)	0.0499 (9)	−0.0005 (7)	−0.0016 (7)	0.0067 (8)
C8	0.0290 (8)	0.0585 (10)	0.0621 (11)	−0.0005 (7)	−0.0047 (8)	−0.0022 (9)
C9	0.0313 (8)	0.0592 (10)	0.0593 (11)	0.0049 (7)	0.0002 (8)	−0.0038 (9)
C10	0.0340 (8)	0.0457 (9)	0.0468 (9)	0.0011 (7)	−0.0031 (7)	0.0051 (8)
C11	0.0400 (9)	0.0635 (11)	0.0648 (12)	−0.0036 (8)	−0.0072 (8)	−0.0002 (10)
C12	0.0606 (12)	0.0602 (11)	0.0617 (12)	−0.0044 (9)	−0.0155 (10)	−0.0052 (10)
C13	0.0632 (12)	0.0617 (11)	0.0540 (11)	0.0092 (9)	−0.0080 (10)	−0.0076 (9)
N1	0.0329 (7)	0.0563 (8)	0.0585 (9)	−0.0031 (6)	−0.0016 (6)	−0.0046 (7)
N2	0.0337 (7)	0.0552 (8)	0.0531 (8)	−0.0003 (6)	−0.0012 (6)	−0.0023 (7)
N3	0.0308 (7)	0.0557 (8)	0.0539 (8)	0.0006 (6)	−0.0015 (6)	−0.0007 (7)
N4	0.0347 (7)	0.0517 (8)	0.0491 (8)	0.0031 (6)	−0.0038 (6)	0.0038 (7)
N5	0.0435 (8)	0.0649 (9)	0.0589 (10)	0.0100 (7)	0.0008 (7)	−0.0042 (8)

Geometric parameters (Å, º) top

C1—C6	1.378 (2)	C8—H8	0.9300
C1—C2	1.389 (2)	C9—C10	1.401 (2)
C1—N1	1.3961 (19)	C9—H9	0.9300
C2—C3	1.381 (2)	C10—N3	1.3022 (19)
C2—H2	0.9300	C10—N4	1.4194 (19)
C3—C4	1.366 (3)	C11—N4	1.3465 (19)
C3—H3	0.9300	C11—C12	1.358 (2)
C4—C5	1.370 (2)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.380 (3)
C5—C6	1.387 (2)	C12—H12	0.9300
C5—H5	0.9300	C13—N5	1.327 (2)
C6—H6	0.9300	C13—H13	0.9300
C7—N2	1.3300 (18)	N1—H1	0.8600
C7—N1	1.371 (2)	N2—N3	1.3574 (17)
C7—C8	1.410 (2)	N4—N5	1.3570 (17)
C8—C9	1.343 (2)

C6—C1—C2	118.58 (16)	C8—C9—C10	116.13 (15)
C6—C1—N1	125.41 (15)	C8—C9—H9	121.9
C2—C1—N1	116.01 (15)	C10—C9—H9	121.9
C3—C2—C1	121.18 (18)	N3—C10—C9	124.14 (15)
C3—C2—H2	119.4	N3—C10—N4	114.93 (13)
C1—C2—H2	119.4	C9—C10—N4	120.92 (14)
C4—C3—C2	119.97 (18)	N4—C11—C12	107.35 (16)
C4—C3—H3	120.0	N4—C11—H11	126.3
C2—C3—H3	120.0	C12—C11—H11	126.3
C3—C4—C5	119.20 (18)	C11—C12—C13	104.92 (16)
C3—C4—H4	120.4	C11—C12—H12	127.5
C5—C4—H4	120.4	C13—C12—H12	127.5
C4—C5—C6	121.63 (18)	N5—C13—C12	112.29 (16)
C4—C5—H5	119.2	N5—C13—H13	123.9
C6—C5—H5	119.2	C12—C13—H13	123.9
C1—C6—C5	119.44 (17)	C7—N1—C1	132.45 (13)
C1—C6—H6	120.3	C7—N1—H1	113.8
C5—C6—H6	120.3	C1—N1—H1	113.8
N2—C7—N1	120.37 (14)	C7—N2—N3	118.41 (13)
N2—C7—C8	122.16 (15)	C10—N3—N2	120.13 (13)
N1—C7—C8	117.46 (14)	C11—N4—N5	111.46 (14)
C9—C8—C7	119.03 (15)	C11—N4—C10	127.68 (14)
C9—C8—H8	120.5	N5—N4—C10	120.86 (13)
C7—C8—H8	120.5	C13—N5—N4	103.98 (14)

C6—C1—C2—C3	−0.4 (2)	C6—C1—N1—C7	−1.0 (3)
N1—C1—C2—C3	179.63 (15)	C2—C1—N1—C7	178.96 (16)
C1—C2—C3—C4	−0.2 (3)	N1—C7—N2—N3	−179.41 (13)
C2—C3—C4—C5	0.6 (3)	C8—C7—N2—N3	−0.6 (2)
C3—C4—C5—C6	−0.5 (3)	C9—C10—N3—N2	0.0 (2)
C2—C1—C6—C5	0.5 (3)	N4—C10—N3—N2	179.08 (12)
N1—C1—C6—C5	−179.48 (15)	C7—N2—N3—C10	0.3 (2)
C4—C5—C6—C1	−0.1 (3)	C12—C11—N4—N5	−0.26 (19)
N2—C7—C8—C9	0.6 (2)	C12—C11—N4—C10	179.96 (14)
N1—C7—C8—C9	179.46 (14)	N3—C10—N4—C11	6.3 (2)
C7—C8—C9—C10	−0.3 (2)	C9—C10—N4—C11	−174.63 (16)
C8—C9—C10—N3	0.0 (2)	N3—C10—N4—N5	−173.47 (13)
C8—C9—C10—N4	−179.01 (13)	C9—C10—N4—N5	5.6 (2)
N4—C11—C12—C13	0.03 (19)	C12—C13—N5—N4	−0.37 (19)
C11—C12—C13—N5	0.2 (2)	C11—N4—N5—C13	0.39 (18)
N2—C7—N1—C1	−4.1 (3)	C10—N4—N5—C13	−179.82 (14)
C8—C7—N1—C1	177.09 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5ⁱ	0.86	2.22	3.071 (2)	173
C6—H6···N2	0.93	2.37	2.966 (3)	122
C8—H8···N3ⁱⁱ	0.93	2.60	3.265 (2)	129

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₅
M_r	237.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	11.3533 (7), 9.4214 (5), 21.6603 (14)
V (Å³)	2316.9 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.982, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	10085, 2754, 1571
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 0.99
No. of reflections	2754
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.15

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5ⁱ	0.86	2.22	3.071 (2)	173
C6—H6···N2	0.93	2.37	2.966 (3)	122
C8—H8···N3ⁱⁱ	0.93	2.60	3.265 (2)	129

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1/2, y, −z+1/2.

Acknowledgements

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

References

Ather, A. Q., Tahir, M. N., Khan, M. A. & Athar, M. M. (2009). Acta Cryst. E65, o1628. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar