organic compounds
N-Phenyl-6-(1H-pyrazol-1-yl)pyridazin-3-amine
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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
https://doi.org/10.1107/S1600536810016697/gk2271sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016697/gk2271Isup2.hkl
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).
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.
For a related structure, see: Ather et al. (2009). For graph-set notation, see: Bernstein et al. (1995).
Data collection: APEX2 (Bruker, 2007); cell
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).C13H11N5 | F(000) = 992 |
Mr = 237.27 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 2754 independent reflections |
Radiation source: fine-focus sealed tube | 1571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 7.50 pixels mm-1 | θmax = 27.9°, θmin = 2.6° |
ω scan | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −12→8 |
Tmin = 0.982, Tmax = 0.988 | l = −17→28 |
10085 measured reflections |
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(Fo2) + (0.0546P)2 + 0.0495P] where P = (Fo2 + 2Fc2)/3 |
2754 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C13H11N5 | V = 2316.9 (2) Å3 |
Mr = 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 |
Bruker Kappa APEXII CCD diffractometer | 2754 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1571 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.988 | Rint = 0.045 |
10085 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.13 e Å−3 |
2754 reflections | Δρmin = −0.15 e Å−3 |
163 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.982, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10085, 2754, 1571 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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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.