3-Chloro-6-[2-(propan-2-yl­idene)hydrazin­yl]pyridazine

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

doi:10.1107/S1600536810034239

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2441

https://doi.org/10.1107/S1600536810034239

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3-Chloro-6-[2-(propan-2-ylidene)hydrazinyl]pyridazine

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 23 August 2010; accepted 25 August 2010; online 28 August 2010)

In the title compound, C₇H₉ClN₄, the 3-chloro-6-hydrazinylpyridazine unit is planar (r.m.s. deviation = 0.0219 Å) and is oriented at a dihedral angle 4.66 (27)° with respect to the propan-2-ylidene group. In the crystal, the molecules are linked into non-planar dimers due to a crystallographic twofold rotation via N—H⋯N hydrogen bonds with R₂²(8) graph-set ring motifs.

Related literature

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

Experimental

Crystal data

C₇H₉ClN₄
M_r = 184.63
Monoclinic, C 2/c
a = 20.6635 (19) Å
b = 7.8202 (6) Å
c = 11.3266 (8) Å
β = 94.140 (3)°
V = 1825.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 K
0.30 × 0.15 × 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
6699 measured reflections
1658 independent reflections
1176 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.114
S = 1.02
1658 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1ⁱ	0.86	2.33	3.083 (2)	146
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: 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 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/S1600536810034239/si2291sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810034239/si2291Isup2.hkl

checkCIF report

Comment top

In continuation to 3-chloro-6-hydrazinylpyridazine derivatives (Ather et al., 2010), the title compound (I, Fig. 1) is being reported here.

In (I), the 3-chloro-6-hydrazinylpyridazine moiety A (C1—C4/N1—N4/CL1) is planar with r. m. s. deviation of 0.0219 Å. The propyl group B(C5/C6/C7) is certainly planar. The dihedral angle between A/B is 4.66 (27)°. The title compound consists of non-planar dimers due to N—H···N type of H-bonding (Table 1, Fig. 2) with R₂²(8) ring motif (Bernstein et al., 1995). The dimers are formed due to a crystallographic twofold rotation axis parallel b and located in c = 1/4.

Related literature top

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

Experimental top

3-Chloro-6-hydrazinylpyridazine (0.5 g, 3.46 mmol), dissolved in acetone was refluxed for 15 min. The unreacted acetone was distilled off yielding in crude material. The product was re-crystallized in alcohol to affoard the colorless needles of (I).

Structure description top

In continuation to 3-chloro-6-hydrazinylpyridazine derivatives (Ather et al., 2010), the title compound (I, Fig. 1) is being reported here.

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

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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 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. Perspective view of a pair of symmetry related title molecules with the N—H···N hydrogen bonds indicated by dashed lines [Symmetry code: a = - x, y, - z + 1/2].

3-Chloro-6-[2-(propan-2-ylidene)hydrazinyl]pyridazine top

Crystal data top

C₇H₉ClN₄	F(000) = 768
M_r = 184.63	D_x = 1.344 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1176 reflections
a = 20.6635 (19) Å	θ = 2.0–25.3°
b = 7.8202 (6) Å	µ = 0.37 mm⁻¹
c = 11.3266 (8) Å	T = 296 K
β = 94.140 (3)°	Needle, colorless
V = 1825.5 (3) Å³	0.30 × 0.15 × 0.14 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	1658 independent reflections
Radiation source: fine-focus sealed tube	1176 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 2.0°
ω scans	h = −23→24
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→8
T_min = 0.982, T_max = 0.988	l = −11→13
6699 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0466P)² + 1.083P] where P = (F_o² + 2F_c²)/3
1658 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₉ClN₄	V = 1825.5 (3) Å³
M_r = 184.63	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.6635 (19) Å	µ = 0.37 mm⁻¹
b = 7.8202 (6) Å	T = 296 K
c = 11.3266 (8) Å	0.30 × 0.15 × 0.14 mm
β = 94.140 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1658 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1176 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.034
6699 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
1658 reflections	Δρ_min = −0.26 e Å⁻³
111 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	0.24961 (3)	0.56355 (11)	0.22863 (7)	0.0864 (3)
N1	0.08033 (8)	0.3556 (2)	0.21840 (14)	0.0503 (6)
N2	0.13843 (9)	0.4249 (2)	0.25439 (15)	0.0547 (7)
N3	0.00430 (8)	0.2720 (2)	0.07587 (14)	0.0528 (6)
N4	−0.01436 (9)	0.2424 (2)	−0.04230 (13)	0.0497 (6)
C1	0.06381 (10)	0.3389 (3)	0.10295 (16)	0.0429 (7)
C2	0.10598 (11)	0.3850 (3)	0.01608 (18)	0.0519 (8)
C3	0.16374 (12)	0.4516 (3)	0.0531 (2)	0.0583 (9)
C4	0.17733 (11)	0.4706 (3)	0.1745 (2)	0.0537 (8)
C5	−0.06866 (11)	0.1693 (3)	−0.06689 (17)	0.0469 (7)
C6	−0.08681 (12)	0.1354 (3)	−0.19521 (18)	0.0628 (9)
C7	−0.11442 (12)	0.1098 (3)	0.0200 (2)	0.0663 (9)
H2	0.09422	0.36991	−0.06405	0.0622*
H3	0.19359	0.48381	−0.00039	0.0699*
H3A	−0.02122	0.24848	0.13034	0.0634*
H6A	−0.05590	0.18936	−0.24248	0.0942*
H6B	−0.12926	0.18084	−0.21605	0.0942*
H6C	−0.08688	0.01439	−0.20933	0.0942*
H7A	−0.09286	0.02922	0.07329	0.0994*
H7B	−0.15116	0.05591	−0.02135	0.0994*
H7C	−0.12876	0.20582	0.06396	0.0994*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0588 (5)	0.1068 (6)	0.0929 (6)	−0.0195 (4)	0.0002 (3)	−0.0051 (4)
N1	0.0506 (11)	0.0648 (12)	0.0357 (10)	−0.0027 (9)	0.0055 (8)	0.0008 (8)
N2	0.0537 (12)	0.0650 (12)	0.0451 (10)	−0.0025 (9)	0.0026 (9)	−0.0020 (9)
N3	0.0547 (12)	0.0714 (12)	0.0332 (9)	−0.0086 (10)	0.0089 (8)	−0.0016 (9)
N4	0.0558 (12)	0.0615 (11)	0.0321 (9)	0.0040 (9)	0.0046 (8)	−0.0021 (8)
C1	0.0483 (13)	0.0454 (11)	0.0355 (11)	0.0028 (9)	0.0062 (9)	−0.0001 (9)
C2	0.0598 (15)	0.0606 (14)	0.0363 (11)	−0.0014 (11)	0.0109 (10)	0.0009 (10)
C3	0.0591 (16)	0.0653 (15)	0.0527 (14)	−0.0003 (12)	0.0197 (11)	0.0042 (12)
C4	0.0485 (14)	0.0565 (13)	0.0562 (14)	0.0010 (10)	0.0056 (10)	0.0012 (11)
C5	0.0535 (14)	0.0484 (12)	0.0389 (11)	0.0056 (10)	0.0040 (10)	−0.0003 (10)
C6	0.0659 (16)	0.0787 (17)	0.0431 (12)	0.0017 (13)	−0.0011 (11)	−0.0038 (12)
C7	0.0731 (17)	0.0757 (16)	0.0507 (14)	−0.0198 (14)	0.0088 (12)	−0.0024 (12)

Geometric parameters (Å, º) top

Cl1—C4	1.733 (2)	C5—C6	1.498 (3)
N1—N2	1.353 (2)	C5—C7	1.488 (3)
N1—C1	1.334 (2)	C2—H2	0.9300
N2—C4	1.303 (3)	C3—H3	0.9300
N3—N4	1.385 (2)	C6—H6A	0.9600
N3—C1	1.351 (3)	C6—H6B	0.9600
N4—C5	1.272 (3)	C6—H6C	0.9600
N3—H3A	0.8600	C7—H7A	0.9600
C1—C2	1.408 (3)	C7—H7B	0.9600
C2—C3	1.341 (3)	C7—H7C	0.9600
C3—C4	1.391 (3)

N1···N3ⁱ	3.083 (2)	H3A···C7	2.4700
N2···C2ⁱⁱ	3.425 (3)	H3A···H7A	2.3300
N3···N1ⁱ	3.083 (2)	H3A···H7C	2.3200
N1···H3Aⁱ	2.3300	H3A···N1ⁱ	2.3300
N1···H6Cⁱⁱⁱ	2.9000	H6A···H6A^vii	2.3300
N1···H7Cⁱ	2.8500	H6B···H7B	2.4800
N2···H7Cⁱ	2.7000	H6B···C4^v	2.9500
N2···H2ⁱⁱ	2.8100	H6C···N1ⁱⁱⁱ	2.9000
N3···H7A	2.7600	H6C···C1ⁱⁱⁱ	3.0400
N3···H7C	2.7900	H6C···H7A^vi	2.4800
N4···H2	2.4800	H7A···N3	2.7600
C2···N2^iv	3.425 (3)	H7A···H3A	2.3300
C3···C5^v	3.566 (3)	H7A···C6^viii	2.9200
C5···C3^v	3.566 (3)	H7A···H6C^viii	2.4800
C1···H6Cⁱⁱⁱ	3.0400	H7B···H6B	2.4800
C3···H7C^v	3.0500	H7C···N3	2.7900
C4···H6B^v	2.9500	H7C···H3A	2.3200
C6···H7A^vi	2.9200	H7C···N1ⁱ	2.8500
C7···H3A	2.4700	H7C···N2ⁱ	2.7000
H2···N4	2.4800	H7C···C3^v	3.0500
H2···N2^iv	2.8100

N2—N1—C1	119.56 (17)	C1—C2—H2	121.00
N1—N2—C4	118.63 (17)	C3—C2—H2	121.00
N4—N3—C1	117.99 (16)	C2—C3—H3	121.00
N3—N4—C5	117.79 (16)	C4—C3—H3	121.00
N4—N3—H3A	121.00	C5—C6—H6A	109.00
C1—N3—H3A	121.00	C5—C6—H6B	109.00
N1—C1—N3	115.14 (17)	C5—C6—H6C	109.00
N1—C1—C2	122.19 (19)	H6A—C6—H6B	109.00
N3—C1—C2	122.66 (17)	H6A—C6—H6C	109.00
C1—C2—C3	117.56 (19)	H6B—C6—H6C	109.00
C2—C3—C4	117.5 (2)	C5—C7—H7A	109.00
Cl1—C4—C3	120.12 (18)	C5—C7—H7B	109.00
N2—C4—C3	124.5 (2)	C5—C7—H7C	109.00
Cl1—C4—N2	115.37 (17)	H7A—C7—H7B	109.00
C6—C5—C7	117.4 (2)	H7A—C7—H7C	110.00
N4—C5—C6	116.55 (19)	H7B—C7—H7C	109.00
N4—C5—C7	126.04 (18)

C1—N1—N2—C4	−1.3 (3)	N3—N4—C5—C6	−178.64 (18)
N2—N1—C1—N3	−178.55 (17)	N3—N4—C5—C7	−0.8 (3)
N2—N1—C1—C2	2.5 (3)	N1—C1—C2—C3	−1.7 (3)
N1—N2—C4—Cl1	178.26 (14)	N3—C1—C2—C3	179.5 (2)
N1—N2—C4—C3	−0.7 (3)	C1—C2—C3—C4	−0.3 (3)
C1—N3—N4—C5	175.6 (2)	C2—C3—C4—Cl1	−177.43 (19)
N4—N3—C1—N1	−176.46 (17)	C2—C3—C4—N2	1.5 (4)
N4—N3—C1—C2	2.5 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.86	2.33	3.083 (2)	146

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₉ClN₄
M_r	184.63
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	20.6635 (19), 7.8202 (6), 11.3266 (8)
β (°)	94.140 (3)
V (Å³)	1825.5 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.30 × 0.15 × 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	6699, 1658, 1176
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 1.02
No. of reflections	1658
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.26

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
N3—H3A···N1ⁱ	0.86	2.33	3.083 (2)	146

Symmetry code: (i) −x, y, −z+1/2.

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

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