3-[(2E)-2-(Butan-2-yl­idene)hydrazin­yl]-6-chloro­pyridazine

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

doi:10.1107/S160053681003504X

3-[(2E)-2-(Butan-2-ylidene)hydrazinyl]-6-chloropyridazine

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

The asymmetric unit of the title compound, C₈H₁₁ClN₄, contains two independent molecules (A and B) with slightly different conformations: the dihedral angles between the 3-chloro-6-hydrazinylpyridazine units and butyl side chains are 4.5 (2) and 11.98 (16)°. In the crystal, the A and B molecules are linked by a pair of N—H

N hydogen bonds, generating an R₂²(8) loop.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681003504X/hb5623sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681003504X/hb5623Isup2.hkl Contains datablock I

CCDC reference: 797717

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.035
wR factor = 0.099
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         30
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In continuation of our studies of pyrazolylpyridazine derivatives (Ather et al., 2009, 2010), the title compound (I, Fig. 1) is being reported here.

The title compound (I), consists of two independent molecules. In one molecule, the 3-chloro-6-hydrazinylpyridazine moiety A (C1—C4/N1—N4/CL1) and the butane group B (C5—C8) is planar with r. m. s. deviation of 0.0217 and 0.0130 Å. The dihedral angle between A/B is 4.53 (24)°. In second molecule, the 3-chloro-6-hydrazinylpyridazine moiety C (C9—C12/N5—N8/CL2) and the butane group D (C13—C16) is planar with r. m. s. deviation of 0.0453 and 0.0446 Å. The dihedral angle between C/D is 11.98 (16)°. The title compound consists of dimers due to N—H···N type of H-bonding (Table 1, Fig. 2) with R₂²(8) ring motif (Bernstein et al., 1995).

Related literature top

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

Experimental top

3-Chloro-6-hydrazinylpyridazine (0.5 g, 3.46 mmol), dissolved in ethyl-methylketone was refluxed for 30 min. The unreacted ethyl-methylketone was distilled off yielding the crude material. The product was re-crystallized in alcohol to affoard colorless needles of (I).

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. Two independent molecules of (I) with 50% probability displacement ellipsoids. Dashed lines denote intermolecular hydrogen bonds, forming a dimer: the N6 moleucle shown is generated by the symmetry operation (1–x, 1–y, –z) from the asymmetric atoms.

3-[(2E)-2-(Butan-2-ylidene)hydrazinyl]-6-chloropyridazine top

Crystal data top

C₈H₁₁ClN₄	Z = 4
M_r = 198.66	F(000) = 416
Triclinic, P1	D_x = 1.321 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0623 (4) Å	Cell parameters from 2652 reflections
b = 11.6768 (5) Å	θ = 2.1–25.3°
c = 12.1314 (5) Å	µ = 0.34 mm⁻¹
α = 113.858 (1)°	T = 296 K
β = 91.370 (2)°	Needle, colorless
γ = 104.880 (2)°	0.25 × 0.15 × 0.14 mm
V = 998.85 (8) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3585 independent reflections
Radiation source: fine-focus sealed tube	2652 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 2.1°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.982, T_max = 0.988	l = −14→11
14983 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0426P)² + 0.1867P] where P = (F_o² + 2F_c²)/3
3585 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₈H₁₁ClN₄	γ = 104.880 (2)°
M_r = 198.66	V = 998.85 (8) Å³
Triclinic, P1	Z = 4
a = 8.0623 (4) Å	Mo Kα radiation
b = 11.6768 (5) Å	µ = 0.34 mm⁻¹
c = 12.1314 (5) Å	T = 296 K
α = 113.858 (1)°	0.25 × 0.15 × 0.14 mm
β = 91.370 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3585 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2652 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.031
14983 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	Δρ_max = 0.15 e Å⁻³
3585 reflections	Δρ_min = −0.20 e Å⁻³
239 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	0.56878 (7)	1.01144 (5)	0.14461 (4)	0.0711 (2)
N1	0.65078 (7)	0.81818 (4)	−0.01826 (4)	0.0494 (5)
N2	0.69138 (9)	0.70411 (6)	−0.06328 (4)	0.0477 (5)
N3	0.73568 (11)	0.52631 (8)	−0.04789 (4)	0.0485 (5)
N4	0.75811 (18)	0.46292 (14)	0.02371 (12)	0.0446 (5)
C1	0.6218 (2)	0.86549 (17)	0.09480 (15)	0.0457 (6)
C2	0.6309 (2)	0.80724 (18)	0.17388 (15)	0.0482 (6)
C3	0.6692 (2)	0.69257 (17)	0.12939 (14)	0.0456 (6)
C4	0.6972 (2)	0.64155 (16)	0.00695 (14)	0.0403 (6)
C5	0.8018 (2)	0.35764 (18)	−0.02463 (16)	0.0446 (6)
C6	0.8294 (3)	0.29374 (19)	0.05683 (17)	0.0546 (7)
C7	0.8037 (3)	0.3631 (2)	0.18693 (18)	0.0706 (9)
C8	0.8324 (3)	0.29472 (19)	−0.15401 (16)	0.0571 (7)
Cl2	0.61890 (8)	0.92216 (5)	0.55956 (5)	0.0741 (2)
N5	0.4684 (2)	0.70148 (16)	0.37821 (14)	0.0577 (6)
N6	0.3743 (2)	0.57428 (16)	0.32230 (13)	0.0577 (6)
N7	0.2290 (2)	0.38112 (15)	0.32596 (13)	0.0557 (6)
N8	0.1391 (2)	0.31693 (16)	0.38987 (13)	0.0527 (6)
C9	0.4960 (2)	0.75931 (18)	0.49629 (16)	0.0499 (6)
C10	0.4326 (3)	0.69965 (19)	0.57130 (16)	0.0572 (7)
C11	0.3386 (3)	0.57264 (19)	0.51703 (16)	0.0560 (7)
C12	0.3135 (2)	0.51037 (18)	0.38917 (15)	0.0461 (6)
C13	0.0646 (3)	0.19453 (19)	0.33475 (16)	0.0514 (7)
C14	−0.0380 (3)	0.1305 (2)	0.40720 (18)	0.0656 (8)
C15	−0.0180 (3)	0.2152 (2)	0.5419 (2)	0.0842 (10)
C16	0.06718 (9)	0.10973 (7)	0.20380 (5)	0.0690 (8)
H2	0.61145	0.84592	0.25415	0.0578*
H3	0.67676	0.64881	0.17770	0.0547*
H3A	0.74569	0.49409	−0.12405	0.0582*
H6A	0.75051	0.20566	0.02287	0.0655*
H6B	0.94655	0.28638	0.05598	0.0655*
H7A	0.88583	0.44865	0.22347	0.1059*
H7B	0.68809	0.37098	0.18942	0.1059*
H7C	0.82074	0.31382	0.23104	0.1059*
H8A	0.72987	0.27583	−0.20780	0.0858*
H8B	0.92751	0.35314	−0.16869	0.0858*
H8C	0.85936	0.21485	−0.16845	0.0858*
H7	0.23145	0.34080	0.24923	0.0668*
H10	0.45400	0.74553	0.65567	0.0687*
H11	0.29214	0.52778	0.56265	0.0673*
H14A	−0.00369	0.05316	0.39609	0.0787*
H14B	−0.15974	0.10162	0.37404	0.0787*
H15A	0.10043	0.23887	0.57731	0.1264*
H15B	−0.09207	0.16776	0.57958	0.1264*
H15C	−0.04957	0.29300	0.55442	0.1264*
H16A	−0.00022	0.13112	0.15265	0.1035*
H16B	0.01880	0.01944	0.18790	0.1035*
H16C	0.18459	0.12428	0.18693	0.1035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1018 (5)	0.0565 (3)	0.0605 (3)	0.0378 (3)	0.0197 (3)	0.0210 (3)
N1	0.0617 (10)	0.0490 (9)	0.0437 (8)	0.0192 (8)	0.0131 (7)	0.0235 (7)
N2	0.0627 (10)	0.0477 (9)	0.0393 (8)	0.0201 (8)	0.0144 (7)	0.0222 (7)
N3	0.0670 (10)	0.0479 (9)	0.0362 (7)	0.0190 (8)	0.0112 (7)	0.0219 (7)
N4	0.0485 (9)	0.0478 (9)	0.0427 (8)	0.0109 (7)	0.0063 (7)	0.0261 (7)
C1	0.0480 (11)	0.0428 (10)	0.0437 (10)	0.0106 (8)	0.0075 (8)	0.0173 (8)
C2	0.0534 (11)	0.0505 (11)	0.0360 (9)	0.0100 (9)	0.0095 (8)	0.0167 (8)
C3	0.0521 (11)	0.0494 (11)	0.0367 (9)	0.0091 (9)	0.0078 (8)	0.0230 (8)
C4	0.0404 (10)	0.0420 (10)	0.0373 (9)	0.0066 (8)	0.0055 (7)	0.0188 (8)
C5	0.0414 (10)	0.0454 (11)	0.0467 (10)	0.0070 (8)	0.0060 (8)	0.0228 (9)
C6	0.0529 (12)	0.0582 (12)	0.0621 (12)	0.0144 (10)	0.0074 (9)	0.0358 (10)
C7	0.0867 (16)	0.0831 (16)	0.0590 (12)	0.0271 (13)	0.0127 (11)	0.0454 (12)
C8	0.0663 (13)	0.0581 (12)	0.0506 (11)	0.0227 (10)	0.0131 (9)	0.0236 (10)
Cl2	0.0911 (4)	0.0514 (3)	0.0707 (4)	0.0066 (3)	0.0057 (3)	0.0259 (3)
N5	0.0740 (12)	0.0536 (10)	0.0461 (9)	0.0099 (9)	0.0093 (8)	0.0269 (8)
N6	0.0790 (12)	0.0537 (10)	0.0401 (8)	0.0104 (9)	0.0088 (8)	0.0249 (8)
N7	0.0760 (11)	0.0497 (10)	0.0379 (8)	0.0079 (8)	0.0112 (8)	0.0213 (7)
N8	0.0610 (10)	0.0546 (10)	0.0466 (9)	0.0123 (8)	0.0115 (7)	0.0282 (8)
C9	0.0580 (12)	0.0459 (11)	0.0482 (10)	0.0162 (9)	0.0093 (9)	0.0215 (9)
C10	0.0795 (14)	0.0535 (13)	0.0373 (10)	0.0183 (11)	0.0123 (9)	0.0185 (9)
C11	0.0786 (14)	0.0534 (12)	0.0409 (10)	0.0169 (11)	0.0182 (9)	0.0256 (9)
C12	0.0540 (11)	0.0488 (11)	0.0394 (9)	0.0147 (9)	0.0086 (8)	0.0225 (9)
C13	0.0534 (12)	0.0540 (12)	0.0493 (10)	0.0128 (10)	0.0069 (9)	0.0261 (10)
C14	0.0692 (14)	0.0642 (14)	0.0642 (13)	0.0077 (11)	0.0132 (10)	0.0349 (11)
C15	0.1004 (19)	0.0848 (18)	0.0671 (15)	0.0104 (14)	0.0291 (13)	0.0410 (13)
C16	0.0818 (16)	0.0572 (13)	0.0572 (12)	0.0078 (11)	0.0125 (11)	0.0212 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.734 (2)	C6—H6B	0.9700
Cl2—C9	1.733 (2)	C6—H6A	0.9700
N1—N2	1.3504 (9)	C7—H7A	0.9600
N1—C1	1.3075 (17)	C7—H7C	0.9600
N2—C4	1.3345 (19)	C7—H7B	0.9600
N3—N4	1.3843 (18)	C8—H8A	0.9600
N3—C4	1.360 (2)	C8—H8C	0.9600
N4—C5	1.276 (3)	C8—H8B	0.9600
N3—H3A	0.8600	C9—C10	1.388 (3)
N5—C9	1.297 (2)	C10—C11	1.348 (3)
N5—N6	1.350 (3)	C11—C12	1.405 (2)
N6—C12	1.333 (3)	C13—C16	1.4981 (19)
N7—N8	1.381 (2)	C13—C14	1.505 (3)
N7—C12	1.357 (3)	C14—C15	1.508 (3)
N8—C13	1.272 (3)	C10—H10	0.9300
N7—H7	0.8600	C11—H11	0.9300
C1—C2	1.392 (3)	C14—H14A	0.9700
C2—C3	1.347 (3)	C14—H14B	0.9700
C3—C4	1.408 (2)	C15—H15A	0.9600
C5—C8	1.498 (3)	C15—H15B	0.9600
C5—C6	1.501 (3)	C15—H15C	0.9600
C6—C7	1.503 (3)	C16—H16A	0.9600
C2—H2	0.9300	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600

N2—N1—C1	118.43 (10)	H8A—C8—H8C	109.00
N1—N2—C4	119.67 (8)	C5—C8—H8A	109.00
N4—N3—C4	117.38 (10)	H8B—C8—H8C	109.00
N3—N4—C5	118.39 (13)	H8A—C8—H8B	109.00
C4—N3—H3A	121.00	C5—C8—H8C	109.00
N4—N3—H3A	121.00	C5—C8—H8B	109.00
N6—N5—C9	119.09 (18)	Cl2—C9—C10	119.98 (14)
N5—N6—C12	119.53 (15)	Cl2—C9—N5	115.69 (16)
N8—N7—C12	117.28 (14)	N5—C9—C10	124.3 (2)
N7—N8—C13	119.01 (15)	C9—C10—C11	117.37 (17)
N8—N7—H7	121.00	C10—C11—C12	117.67 (19)
C12—N7—H7	121.00	N7—C12—C11	122.28 (19)
N1—C1—C2	124.75 (16)	N6—C12—N7	115.75 (15)
Cl1—C1—C2	119.92 (13)	N6—C12—C11	121.96 (19)
Cl1—C1—N1	115.33 (13)	N8—C13—C14	116.84 (17)
C1—C2—C3	117.28 (16)	N8—C13—C16	125.68 (18)
C2—C3—C4	117.42 (17)	C14—C13—C16	117.47 (17)
N2—C4—N3	114.99 (12)	C13—C14—C15	115.48 (19)
N3—C4—C3	122.59 (16)	C9—C10—H10	121.00
N2—C4—C3	122.41 (16)	C11—C10—H10	121.00
C6—C5—C8	117.44 (18)	C10—C11—H11	121.00
N4—C5—C8	125.76 (19)	C12—C11—H11	121.00
N4—C5—C6	116.78 (16)	C13—C14—H14A	108.00
C5—C6—C7	115.54 (19)	C13—C14—H14B	108.00
C3—C2—H2	121.00	C15—C14—H14A	108.00
C1—C2—H2	121.00	C15—C14—H14B	108.00
C4—C3—H3	121.00	H14A—C14—H14B	107.00
C2—C3—H3	121.00	C14—C15—H15A	109.00
C5—C6—H6A	108.00	C14—C15—H15B	109.00
C7—C6—H6B	108.00	C14—C15—H15C	109.00
C5—C6—H6B	108.00	H15A—C15—H15B	110.00
H6A—C6—H6B	107.00	H15A—C15—H15C	109.00
C7—C6—H6A	108.00	H15B—C15—H15C	110.00
H7A—C7—H7B	110.00	C13—C16—H16A	109.00
H7A—C7—H7C	109.00	C13—C16—H16B	109.00
C6—C7—H7C	109.00	C13—C16—H16C	109.00
H7B—C7—H7C	109.00	H16A—C16—H16B	109.00
C6—C7—H7B	109.00	H16A—C16—H16C	109.00
C6—C7—H7A	109.00	H16B—C16—H16C	109.00

C1—N1—N2—C4	1.45 (15)	N8—N7—C12—C11	12.0 (3)
N2—N1—C1—Cl1	−179.47 (8)	N7—N8—C13—C16	1.2 (3)
N2—N1—C1—C2	0.5 (2)	N7—N8—C13—C14	−177.43 (18)
N1—N2—C4—N3	178.67 (10)	N1—C1—C2—C3	−1.3 (3)
N1—N2—C4—C3	−2.6 (2)	Cl1—C1—C2—C3	178.68 (14)
C4—N3—N4—C5	−176.95 (15)	C1—C2—C3—C4	0.2 (3)
N4—N3—C4—N2	174.58 (12)	C2—C3—C4—N2	1.8 (3)
N4—N3—C4—C3	−4.1 (2)	C2—C3—C4—N3	−179.62 (16)
N3—N4—C5—C6	178.44 (15)	N4—C5—C6—C7	−0.6 (3)
N3—N4—C5—C8	0.2 (3)	C8—C5—C6—C7	177.78 (19)
C9—N5—N6—C12	−0.8 (3)	Cl2—C9—C10—C11	−179.66 (18)
N6—N5—C9—Cl2	179.70 (14)	N5—C9—C10—C11	1.1 (3)
N6—N5—C9—C10	−1.0 (3)	C9—C10—C11—C12	0.6 (3)
N5—N6—C12—N7	−176.31 (16)	C10—C11—C12—N6	−2.3 (3)
N5—N6—C12—C11	2.5 (3)	C10—C11—C12—N7	176.4 (2)
C12—N7—N8—C13	−176.99 (19)	N8—C13—C14—C15	−8.9 (3)
N8—N7—C12—N6	−169.24 (16)	C16—C13—C14—C15	172.35 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N6ⁱ	0.86	2.30	3.0674 (15)	148
N7—H7···N2ⁱ	0.86	2.24	3.0689 (15)	161

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₈H₁₁ClN₄
M_r	198.66
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.0623 (4), 11.6768 (5), 12.1314 (5)
α, β, γ (°)	113.858 (1), 91.370 (2), 104.880 (2)
V (Å³)	998.85 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.25 × 0.15 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
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	14983, 3585, 2652
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.05
No. of reflections	3585
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.20

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).