3-Chloro-6-(1H-pyrazol-1-yl)pyridazine

Ather, A.Q.; Tahir, M.N.; Khan, M.A.; Athar, M.M.; Bueno, E.A.S.

doi:10.1107/S1600536810027121

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2016

https://doi.org/10.1107/S1600536810027121

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3-Chloro-6-(1H-pyrazol-1-yl)pyridazine

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

^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

(Received 20 June 2010; accepted 8 July 2010; online 14 July 2010)

The title compound, C₇H₅ClN₄, is almost planar (r.m.s. deviation = 0.022 Å). The dihedral angle between the aromatic rings is 2.82 (5)°. The packing results in polymeric chains extending along the a axis. In the crystal, molecules are connected to each other through intermolecular C—H⋯N hydrogen bonds, resulting in R₂²(10) ring motifs.

Related literature

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

Experimental

Crystal data

C₇H₅ClN₄
M_r = 180.60
Triclinic, $[P \overline 1]$
a = 5.684 (3) Å
b = 6.526 (3) Å
c = 11.130 (6) Å
α = 83.00 (3)°
β = 77.64 (2)°
γ = 88.04 (3)°
V = 400.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 296 K
0.30 × 0.14 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.982, T_max = 0.988
5550 measured reflections
1422 independent reflections
774 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.154
S = 1.08
1422 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N2ⁱ	0.93	2.46	3.321 (6)	154
C5—H5⋯N4ⁱⁱ	0.93	2.55	3.468 (7)	169
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

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/S1600536810027121/vm2034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027121/vm2034Isup2.hkl

checkCIF report

Comment top

The title compound (I, Fig. 1) has been prepared as nucleous to synthesize a series of pyrazolylpyridazine derivatives. In this context, we have already reported some compounds (Ather et al., 2009, 2010a, 2010b).

The title compound is essentially planar. The r. m. s. deviation of all heavy atoms from the mean square plane is 0.0223 Å. The angle between the heterocyclic aromatic rings is 2.82 (5)°. Each molecule is connected to the adjacent molecules through C—H···N intermolecular H-bonds (Table 1, Fig. 2) and R₂²(10) ring motifs (Bernstein et al., 1995) are formed. In this way the packing forms one dimensional polymeric chains extending along the crystallographic a axis.

Related literature top

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

Experimental top

3-Chloro-6-hydrazinylpyridazine (0.5 g, 3.46 mmol) was dissolved in ethanol (15 ml) and malon dialdehyde bis-(diethylacetal) (0.327 g, 3.46 mmol) was added dropwise under continuous stirring. Few drops of acetic acid were also added in the reaction mixture as catalyst and the solution was refluxed for 2 h. The reaction was monitored by TLC. After completion, the reaction mixture was precipitated by adding water. The filtered precipitate was dried and colorless needles of (I) appeared on the walls of the beaker due to evaporation.

Structure description top

For related structures, see: Ather et al. (2009, 2010a,b). 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 thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Packing diagram of the title compound (PLATON: Spek, 2009) showing that the molecules form polymeric chains extending along the a axis.

3-Chloro-6-(1H-pyrazol-1-yl)pyridazine top

Crystal data top

C₇H₅ClN₄	Z = 2
M_r = 180.60	F(000) = 184
Triclinic, P1	D_x = 1.499 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.684 (3) Å	Cell parameters from 774 reflections
b = 6.526 (3) Å	θ = 3.2–25.1°
c = 11.130 (6) Å	µ = 0.42 mm⁻¹
α = 83.00 (3)°	T = 296 K
β = 77.64 (2)°	Needle, colourless
γ = 88.04 (3)°	0.30 × 0.14 × 0.14 mm
V = 400.2 (4) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1422 independent reflections
Radiation source: fine-focus sealed tube	774 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 8.20 pixels mm^-1	θ_max = 25.1°, θ_min = 3.2°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −7→7
T_min = 0.982, T_max = 0.988	l = −13→13
5550 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0381P)² + 0.276P] where P = (F_o² + 2F_c²)/3
1422 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₇H₅ClN₄	γ = 88.04 (3)°
M_r = 180.60	V = 400.2 (4) Å³
Triclinic, P1	Z = 2
a = 5.684 (3) Å	Mo Kα radiation
b = 6.526 (3) Å	µ = 0.42 mm⁻¹
c = 11.130 (6) Å	T = 296 K
α = 83.00 (3)°	0.30 × 0.14 × 0.14 mm
β = 77.64 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	774 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.071
5550 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.08	Δρ_max = 0.22 e Å⁻³
1422 reflections	Δρ_min = −0.22 e Å⁻³
109 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.0311 (2)	0.6902 (2)	0.86426 (11)	0.0772 (6)
N1	−0.0066 (6)	0.7294 (6)	0.6368 (3)	0.0586 (14)
N2	0.0752 (6)	0.7486 (6)	0.5126 (3)	0.0525 (14)
N3	0.3753 (6)	0.7757 (5)	0.3384 (3)	0.0449 (14)
N4	0.6127 (6)	0.7910 (6)	0.2806 (3)	0.0576 (16)
C1	0.1521 (8)	0.7182 (7)	0.7066 (4)	0.0503 (17)
C2	0.4010 (7)	0.7237 (7)	0.6628 (4)	0.0506 (17)
C3	0.4819 (7)	0.7451 (6)	0.5399 (4)	0.0450 (16)
C4	0.3094 (7)	0.7556 (6)	0.4674 (4)	0.0417 (16)
C5	0.2316 (9)	0.7798 (8)	0.2556 (4)	0.0676 (19)
C6	0.3770 (10)	0.7966 (9)	0.1421 (5)	0.078 (2)
C7	0.6095 (9)	0.8042 (8)	0.1617 (5)	0.0701 (19)
H2	0.50643	0.71294	0.71672	0.0608*
H3	0.64564	0.75254	0.50460	0.0538*
H5	0.06440	0.77251	0.27366	0.0814*
H6	0.33112	0.80200	0.06646	0.0928*
H7	0.74672	0.81708	0.09857	0.0841*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0676 (9)	0.1105 (13)	0.0459 (8)	−0.0045 (8)	0.0038 (6)	−0.0068 (7)
N1	0.040 (2)	0.084 (3)	0.047 (2)	−0.002 (2)	0.0002 (19)	−0.005 (2)
N2	0.028 (2)	0.076 (3)	0.051 (2)	−0.0027 (17)	−0.0050 (16)	−0.003 (2)
N3	0.0321 (19)	0.055 (3)	0.044 (2)	−0.0020 (17)	−0.0012 (16)	−0.0033 (18)
N4	0.041 (2)	0.076 (3)	0.049 (3)	−0.0033 (19)	0.0048 (17)	−0.005 (2)
C1	0.046 (3)	0.061 (3)	0.040 (3)	−0.004 (2)	0.002 (2)	−0.009 (2)
C2	0.040 (3)	0.060 (3)	0.052 (3)	−0.001 (2)	−0.011 (2)	−0.005 (2)
C3	0.031 (2)	0.049 (3)	0.052 (3)	−0.0045 (19)	−0.004 (2)	−0.001 (2)
C4	0.039 (2)	0.038 (3)	0.046 (3)	0.0016 (19)	−0.003 (2)	−0.008 (2)
C5	0.058 (3)	0.097 (4)	0.051 (3)	−0.002 (3)	−0.021 (3)	−0.004 (3)
C6	0.079 (4)	0.104 (5)	0.050 (3)	−0.009 (3)	−0.015 (3)	−0.006 (3)
C7	0.061 (3)	0.089 (4)	0.051 (3)	−0.008 (3)	0.008 (2)	−0.005 (3)

Geometric parameters (Å, º) top

Cl1—C1	1.732 (5)	C2—C3	1.338 (6)
N1—N2	1.353 (5)	C3—C4	1.392 (6)
N1—C1	1.306 (6)	C5—C6	1.348 (7)
N2—C4	1.319 (5)	C6—C7	1.388 (8)
N3—N4	1.366 (5)	C2—H2	0.9300
N3—C4	1.395 (5)	C3—H3	0.9300
N3—C5	1.354 (6)	C5—H5	0.9300
N4—C7	1.320 (6)	C6—H6	0.9300
C1—C2	1.394 (6)	C7—H7	0.9300

Cl1···Cl1ⁱ	3.632 (3)	C3···N2^vi	3.321 (6)
Cl1···H7ⁱⁱ	2.9500	C3···C3^iv	3.411 (6)
N1···C2ⁱⁱⁱ	3.318 (6)	C3···C3^v	3.339 (6)
N1···C3ⁱⁱⁱ	3.305 (6)	C3···C4^iv	3.442 (6)
N2···C3ⁱⁱⁱ	3.321 (6)	C3···C4^v	3.491 (6)
N4···C2^iv	3.342 (6)	C4···C3^iv	3.442 (6)
N4···C2^v	3.299 (6)	C4···C3^v	3.491 (6)
N1···H2ⁱⁱⁱ	2.7200	C7···H5^vi	3.0900
N1···H3ⁱⁱⁱ	2.7000	H2···N1^vi	2.7200
N2···H3ⁱⁱⁱ	2.4600	H3···N1^vi	2.7000
N2···H5	2.6600	H3···N2^vi	2.4600
N4···H5^vi	2.5500	H3···N4	2.5200
N4···H3	2.5200	H5···N2	2.6600
C2···N1^vi	3.318 (6)	H5···N4ⁱⁱⁱ	2.5500
C2···N4^iv	3.342 (6)	H5···C7ⁱⁱⁱ	3.0900
C2···N4^v	3.299 (6)	H7···Cl1^vii	2.9500
C3···N1^vi	3.305 (6)

N2—N1—C1	117.9 (4)	N3—C5—C6	106.9 (5)
N1—N2—C4	119.1 (3)	C5—C6—C7	105.7 (5)
N4—N3—C4	120.1 (3)	N4—C7—C6	112.0 (5)
N4—N3—C5	111.4 (3)	C1—C2—H2	121.00
C4—N3—C5	128.5 (4)	C3—C2—H2	121.00
N3—N4—C7	104.0 (4)	C2—C3—H3	122.00
Cl1—C1—N1	114.7 (3)	C4—C3—H3	122.00
Cl1—C1—C2	120.4 (3)	N3—C5—H5	126.00
N1—C1—C2	124.9 (4)	C6—C5—H5	127.00
C1—C2—C3	117.2 (4)	C5—C6—H6	127.00
C2—C3—C4	116.9 (4)	C7—C6—H6	127.00
N2—C4—N3	114.7 (4)	N4—C7—H7	124.00
N2—C4—C3	124.0 (4)	C6—C7—H7	124.00
N3—C4—C3	121.3 (4)

C1—N1—N2—C4	−0.1 (6)	N4—N3—C5—C6	0.4 (6)
N2—N1—C1—Cl1	−179.1 (3)	C4—N3—C5—C6	−178.6 (4)
N2—N1—C1—C2	−0.3 (7)	N3—N4—C7—C6	−0.3 (6)
N1—N2—C4—N3	−180.0 (4)	Cl1—C1—C2—C3	179.8 (3)
N1—N2—C4—C3	−0.2 (6)	N1—C1—C2—C3	1.0 (7)
C4—N3—N4—C7	179.0 (4)	C1—C2—C3—C4	−1.3 (6)
C5—N3—N4—C7	0.0 (5)	C2—C3—C4—N2	1.0 (6)
N4—N3—C4—N2	178.0 (4)	C2—C3—C4—N3	−179.3 (4)
N4—N3—C4—C3	−1.7 (6)	N3—C5—C6—C7	−0.6 (6)
C5—N3—C4—N2	−3.1 (6)	C5—C6—C7—N4	0.6 (7)
C5—N3—C4—C3	177.2 (4)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1, y, z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z; (vii) x+1, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2^vi	0.9300	2.4600	3.321 (6)	154.00
C5—H5···N4ⁱⁱⁱ	0.9300	2.5500	3.468 (7)	169.00

Symmetry codes: (iii) x−1, y, z; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₅ClN₄
M_r	180.60
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.684 (3), 6.526 (3), 11.130 (6)
α, β, γ (°)	83.00 (3), 77.64 (2), 88.04 (3)
V (Å³)	400.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.30 × 0.14 × 0.14

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	5550, 1422, 774
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.154, 1.08
No. of reflections	1422
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

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
C3—H3···N2ⁱ	0.9300	2.4600	3.321 (6)	154.00
C5—H5···N4ⁱⁱ	0.9300	2.5500	3.468 (7)	169.00

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

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, Pakistan.

References

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