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access3-Chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)pyridazine
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, dInstitute of Chemistry, University of the Punjab, Lahore, Pakistan, and eInstituto de Quimica, Universidade Estadual de Londrina, Londrina, Pr., Brazil
*Correspondence e-mail: dmntahir_uos@yahoo.com
In the title compound, C9H9ClN4, the dihedral angle between the aromatic rings is 6.25 (9)°. The whole molecule is approximately planar (r.m.s. deviation = 0.070 Å). In the crystal, π–π interactions between the centroids of the pyridazine rings [separation = 3.5904 (10) Å] occur.
Related literature
For background to pyrazolylpyridazine derivatives and for related crystal structures, see: Ather et al. (2010a![[Ather, A. Q., Tahir, M. N., Khan, M. A. & Athar, M. M. (2010a). Acta Cryst. E66, o1327.]](../../../../../../logos/arrows/e_arr.gif "Ather, A. Q., Tahir, M. N., Khan, M. A. & Athar, M. M. (2010a). Acta Cryst. E66, o1327.")
,b,c). For hydrogen-bond motifs, see: Bernstein et al. (1995).
![[Scheme 1]](hb5625scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536810034756/hb5625sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810034756/hb5625Isup2.hkl
3-Chloro-6-hydrazinylpyridazine (1 g, 6.92 mmol) was dissolved in 5 ml of ethanol. To this solution acetylacetone (8 mmol) and acetic acid (0.7 ml) were added and heated for 30 min. The unreacted acetic acid was removed under vacuum and charged to 25 ml of distilled water and filtered. The final product was re-crystallized in ethanol to obtain colourless prisms of (I).
The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and were included in the in the riding model approximation, with Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for aryl H-atoms.
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./hb5625fig1thm.gif) | Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radius. |
| C9H9ClN4 | F(000) = 432 |
| Mr = 208.65 | Dx = 1.438 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1514 reflections |
| a = 11.2773 (3) Å | θ = 3.1–25.3° |
| b = 8.4181 (2) Å | µ = 0.36 mm−1 |
| c = 11.3501 (3) Å | T = 296 K |
| β = 116.529 (1)° | Prism, colourless |
| V = 964.05 (4) Å3 | 0.32 × 0.24 × 0.20 mm |
| Z = 4 |
| Bruker Kappa APEXII CCD diffractometer | 1727 independent reflections |
| Radiation source: fine-focus sealed tube | 1514 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.022 |
| Detector resolution: 8.10 pixels mm-1 | θmax = 25.3°, θmin = 3.1° |
| ω scans | h = −13→13 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −10→10 |
| Tmin = 0.903, Tmax = 0.932 | l = −13→13 |
| 6922 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0405P)2 + 0.3389P] where P = (Fo2 + 2Fc2)/3 |
| 1727 reflections | (Δ/σ)max < 0.001 |
| 129 parameters | Δρmax = 0.16 e Å−3 |
| 0 restraints | Δρmin = −0.19 e Å−3 |
| C9H9ClN4 | V = 964.05 (4) Å3 |
| Mr = 208.65 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.2773 (3) Å | µ = 0.36 mm−1 |
| b = 8.4181 (2) Å | T = 296 K |
| c = 11.3501 (3) Å | 0.32 × 0.24 × 0.20 mm |
| β = 116.529 (1)° |
| Bruker Kappa APEXII CCD diffractometer | 1727 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1514 reflections with I > 2σ(I) |
| Tmin = 0.903, Tmax = 0.932 | Rint = 0.022 |
| 6922 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.16 e Å−3 |
| 1727 reflections | Δρmin = −0.19 e Å−3 |
| 129 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.76089 (4) | 0.97122 (6) | 0.60328 (4) | 0.0581 (2) | |
| N1 | 0.56592 (14) | 0.81330 (18) | 0.60486 (13) | 0.0495 (5) | |
| N2 | 0.45739 (14) | 0.71964 (18) | 0.55421 (13) | 0.0487 (5) | |
| N3 | 0.29683 (12) | 0.57550 (16) | 0.38434 (12) | 0.0419 (4) | |
| N4 | 0.25369 (14) | 0.50746 (16) | 0.26163 (13) | 0.0465 (4) | |
| C1 | 0.62272 (15) | 0.84978 (19) | 0.53015 (15) | 0.0427 (5) | |
| C2 | 0.58063 (16) | 0.7982 (2) | 0.40156 (16) | 0.0480 (5) | |
| C3 | 0.47217 (16) | 0.7034 (2) | 0.35066 (15) | 0.0460 (5) | |
| C4 | 0.41180 (14) | 0.66847 (18) | 0.43182 (14) | 0.0389 (5) | |
| C5 | 0.21463 (16) | 0.5362 (2) | 0.44074 (16) | 0.0449 (5) | |
| C6 | 0.11915 (17) | 0.4428 (2) | 0.35130 (17) | 0.0510 (6) | |
| C7 | 0.14674 (16) | 0.4269 (2) | 0.24272 (16) | 0.0464 (5) | |
| C8 | 0.07365 (19) | 0.3310 (3) | 0.12074 (19) | 0.0620 (7) | |
| C9 | 0.23144 (19) | 0.5897 (3) | 0.57258 (17) | 0.0589 (6) | |
| H2 | 0.62480 | 0.82738 | 0.35258 | 0.0576* | |
| H3 | 0.43929 | 0.66322 | 0.26555 | 0.0551* | |
| H6 | 0.04831 | 0.39741 | 0.36007 | 0.0612* | |
| H8A | 0.11672 | 0.34089 | 0.06480 | 0.0930* | |
| H8B | −0.01582 | 0.36889 | 0.07498 | 0.0930* | |
| H8C | 0.07304 | 0.22143 | 0.14400 | 0.0930* | |
| H9A | 0.15789 | 0.55308 | 0.58622 | 0.0883* | |
| H9B | 0.23501 | 0.70358 | 0.57665 | 0.0883* | |
| H9C | 0.31225 | 0.54673 | 0.63974 | 0.0883* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0593 (3) | 0.0588 (3) | 0.0592 (3) | −0.0085 (2) | 0.0291 (2) | −0.0040 (2) |
| N1 | 0.0543 (8) | 0.0585 (9) | 0.0412 (7) | −0.0008 (7) | 0.0264 (6) | −0.0005 (6) |
| N2 | 0.0513 (8) | 0.0624 (9) | 0.0396 (7) | −0.0016 (7) | 0.0268 (6) | 0.0009 (6) |
| N3 | 0.0427 (7) | 0.0509 (8) | 0.0372 (7) | 0.0059 (6) | 0.0223 (6) | 0.0047 (6) |
| N4 | 0.0480 (8) | 0.0545 (8) | 0.0410 (7) | 0.0031 (6) | 0.0234 (6) | −0.0009 (6) |
| C1 | 0.0446 (8) | 0.0435 (8) | 0.0429 (9) | 0.0066 (7) | 0.0222 (7) | 0.0050 (7) |
| C2 | 0.0487 (9) | 0.0617 (10) | 0.0422 (9) | 0.0029 (8) | 0.0280 (7) | 0.0064 (7) |
| C3 | 0.0471 (9) | 0.0607 (10) | 0.0356 (8) | 0.0041 (7) | 0.0234 (7) | 0.0025 (7) |
| C4 | 0.0408 (8) | 0.0433 (8) | 0.0369 (8) | 0.0105 (6) | 0.0213 (6) | 0.0084 (6) |
| C5 | 0.0443 (9) | 0.0525 (9) | 0.0456 (9) | 0.0093 (7) | 0.0269 (7) | 0.0098 (7) |
| C6 | 0.0443 (9) | 0.0581 (10) | 0.0564 (10) | 0.0033 (8) | 0.0277 (8) | 0.0084 (8) |
| C7 | 0.0438 (9) | 0.0474 (9) | 0.0484 (9) | 0.0069 (7) | 0.0209 (7) | 0.0053 (7) |
| C8 | 0.0608 (11) | 0.0638 (12) | 0.0592 (11) | −0.0047 (9) | 0.0249 (9) | −0.0061 (9) |
| C9 | 0.0569 (10) | 0.0818 (13) | 0.0511 (10) | −0.0020 (10) | 0.0360 (9) | 0.0010 (9) |
| Cl1—C1 | 1.7340 (18) | C5—C9 | 1.492 (3) |
| N1—N2 | 1.350 (2) | C6—C7 | 1.406 (3) |
| N1—C1 | 1.307 (2) | C7—C8 | 1.493 (3) |
| N2—C4 | 1.320 (2) | C2—H2 | 0.9300 |
| N3—N4 | 1.3781 (18) | C3—H3 | 0.9300 |
| N3—C4 | 1.400 (2) | C6—H6 | 0.9300 |
| N3—C5 | 1.382 (2) | C8—H8A | 0.9600 |
| N4—C7 | 1.315 (2) | C8—H8B | 0.9600 |
| C1—C2 | 1.388 (2) | C8—H8C | 0.9600 |
| C2—C3 | 1.355 (3) | C9—H9A | 0.9600 |
| C3—C4 | 1.400 (2) | C9—H9B | 0.9600 |
| C5—C6 | 1.353 (2) | C9—H9C | 0.9600 |
| N2—N1—C1 | 118.35 (14) | C6—C7—C8 | 128.16 (18) |
| N1—N2—C4 | 119.46 (15) | C1—C2—H2 | 122.00 |
| N4—N3—C4 | 118.01 (14) | C3—C2—H2 | 122.00 |
| N4—N3—C5 | 111.21 (14) | C2—C3—H3 | 121.00 |
| C4—N3—C5 | 130.79 (13) | C4—C3—H3 | 121.00 |
| N3—N4—C7 | 105.27 (14) | C5—C6—H6 | 126.00 |
| Cl1—C1—N1 | 115.08 (12) | C7—C6—H6 | 126.00 |
| Cl1—C1—C2 | 120.01 (14) | C7—C8—H8A | 109.00 |
| N1—C1—C2 | 124.91 (16) | C7—C8—H8B | 109.00 |
| C1—C2—C3 | 116.90 (17) | C7—C8—H8C | 109.00 |
| C2—C3—C4 | 117.07 (15) | H8A—C8—H8B | 109.00 |
| N2—C4—N3 | 116.49 (15) | H8A—C8—H8C | 109.00 |
| N2—C4—C3 | 123.29 (16) | H8B—C8—H8C | 109.00 |
| N3—C4—C3 | 120.22 (13) | C5—C9—H9A | 109.00 |
| N3—C5—C6 | 105.38 (15) | C5—C9—H9B | 109.00 |
| N3—C5—C9 | 125.57 (16) | C5—C9—H9C | 109.00 |
| C6—C5—C9 | 129.05 (19) | H9A—C9—H9B | 109.00 |
| C5—C6—C7 | 107.42 (17) | H9A—C9—H9C | 109.00 |
| N4—C7—C6 | 110.72 (15) | H9B—C9—H9C | 109.00 |
| N4—C7—C8 | 121.10 (17) | ||
| C1—N1—N2—C4 | −0.2 (2) | C4—N3—C5—C6 | −179.65 (16) |
| N2—N1—C1—Cl1 | 179.72 (12) | C4—N3—C5—C9 | 0.8 (3) |
| N2—N1—C1—C2 | −0.6 (3) | N3—N4—C7—C6 | 0.49 (19) |
| N1—N2—C4—N3 | −178.28 (14) | N3—N4—C7—C8 | −177.82 (16) |
| N1—N2—C4—C3 | 1.5 (3) | Cl1—C1—C2—C3 | 179.88 (13) |
| C4—N3—N4—C7 | 179.37 (14) | N1—C1—C2—C3 | 0.2 (3) |
| C5—N3—N4—C7 | −0.21 (18) | C1—C2—C3—C4 | 0.9 (2) |
| N4—N3—C4—N2 | −173.89 (14) | C2—C3—C4—N2 | −1.8 (3) |
| N4—N3—C4—C3 | 6.4 (2) | C2—C3—C4—N3 | 177.92 (15) |
| C5—N3—C4—N2 | 5.6 (3) | N3—C5—C6—C7 | 0.43 (19) |
| C5—N3—C4—C3 | −174.15 (16) | C9—C5—C6—C7 | 179.98 (19) |
| N4—N3—C5—C6 | −0.15 (19) | C5—C6—C7—N4 | −0.6 (2) |
| N4—N3—C5—C9 | −179.73 (17) | C5—C6—C7—C8 | 177.56 (19) |
Experimental details
| Crystal data | |
| Chemical formula | C9H9ClN4 |
| Mr | 208.65 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 296 |
| a, b, c (Å) | 11.2773 (3), 8.4181 (2), 11.3501 (3) |
| β (°) | 116.529 (1) |
| V (Å3) | 964.05 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.36 |
| Crystal size (mm) | 0.32 × 0.24 × 0.20 |
| Data collection | |
| Diffractometer | Bruker Kappa APEXII CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
| Tmin, Tmax | 0.903, 0.932 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6922, 1727, 1514 |
| Rint | 0.022 |
| (sin θ/λ)max (Å−1) | 0.600 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.04 |
| No. of reflections | 1727 |
| No. of parameters | 129 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.16, −0.19 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Acknowledgements
The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. They also acknowledge the technical support provided by Bana International, Karachi, Pakistan.
References
Ather, A. Q., Tahir, M. N., Khan, M. A. & Athar, M. M. (2010a). Acta Cryst. E66, o1327. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ather, A. Q., Tahir, M. N., Khan, M. A., Athar, M. M. & Bueno, E. A. S. (2010b). Acta Cryst. E66, o1900. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ather, A. Q., Tahir, M. N., Khan, M. A., Athar, M. M. & Bueno, E. A. S. (2010c). Acta Cryst. E66, o2016. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). 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
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
In continuation of our studies of pyrazolylpyridazine derivatives (Ather et al., 2010a,b,c), the title compound (I, Fig. 1) is being reported here.
In the title compound, the 3-chloro-pyridazine group A (C1—C4/N1/N2/CL1) and 3,5-dimethyl-pyrazol moiety B (N3/N4/C5—C9) are planar with r. m. s. deviation of 0.0057 and 0.0121 Å, respectively. The dihedral angle between A/B is 6.40 (9)°. The title compound essentially consists of monomers. The molecules are stabilized due to π–π interactions. There exist π–π interactions between the centroids of pyridazine rings at a distance of 3.5904 (10) Å [symmetry code: 1 - x, 1 - y, 1 - z]. The centroids of pyridazine and pyrazol rings are separated at 4.1319 (9) Å [symmetry code: 1 - x, 1 - y, 1 - z] and 4.4233 (9)Å [symmetry code: 1 - x, 2 - y, 1 - z].