4,5-Dichloro-2-methyl­pyridazin-3(2H)-one

Goh, J.H.; Fun, H.-K.; Rukmini, P.V.R.; Kalluraya, B.

doi:10.1107/S1600536809046947

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3055

doi:10.1107/S1600536809046947

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4,5-Dichloro-2-methylpyridazin-3(2H)-one

Jia Hao Goh,^a ‡ Hoong-Kun Fun,^a ^*§ P. V. R. Rukmini ^b and B. Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 3 November 2009; accepted 6 November 2009; online 11 November 2009)

The asymmetric unit of the title compound, C₅H₄Cl₂N₂O, contains one half-molecule: all the non-H atoms lie on a crystallographic mirror plane. In the crystal structure, molecules are linked into chains along the c axis by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background to and applications of pyridazine derivatives, see: Banerjee et al. (2009 ); Samuel & Bose (1987 ); Siddiqui & Wani (2004 ). For standard bond lengths, see: Allen et al. (1987 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₅H₄Cl₂N₂O
M_r = 179.00
Orthorhombic, C m c a
a = 6.5157 (1) Å
b = 15.9127 (4) Å
c = 13.5175 (3) Å
V = 1401.53 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 100 K
0.42 × 0.29 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.717, T_max = 0.837
13402 measured reflections
1659 independent reflections
1427 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.085
S = 1.09
1659 reflections
64 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1ⁱ	0.980 (19)	2.328 (19)	3.2988 (18)	170.6 (16)
Symmetry code: (i) $[-x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046947/lh2946sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046947/lh2946Isup2.hkl

checkCIF report

Comment top

Pyridazin-3(2H)-one derivatives represent one of the most active class of compounds possessing a wide spectrum of biological activities such as cardiovascular properties, anti-inflammatory, anti-diabetic, analgesic, anti-AIDS, anti-cancer, anti-microbial and anti-convulsant activities (Banerjee et al., 2009; Siddiqui & Wani, 2004). Effects of substituted pyridazinones on photosynthetic electron transport have been studied by various workers and are known to inhibit photosystem II (PS II) electron transport (Samuel & Bose, 1987). Herein we report the crystal structure of the title compound.

The asymmetric unit of the title compound contains one half-molecule and all atoms, with the exception of one methyl hydrogen atom [symmetry related H atom generated by 1-x, y, z], lie on a crystallographic mirror plane (Fig. 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure (Fig. 2), neighbouring molecules are linked into one-dimensional chains along the c axis by intermolecular C4—H4A···O1ⁱ hydrogen bonds (Table 1).

Related literature top

For general background to and applications of pyridazine derivatives, see: Banerjee et al. (2009); Samuel & Bose (1987); Siddiqui & Wani (2004). For standard bond lengths, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

4,5-dichloropyridazin-3(2H)-one (0.01 mol) and methanol (9.7 ml) was placed into a R.B. flask. The contents were stirred for 15 minutes. Sodium hydroxide (0.5 g) in de-mineralized water (10.0 ml) was added with constant stirring. As a clear solution is observed, the R.B. flask was cooled to 278 K. When the temperature fell below 278 K, dimethyl sulphate (0.01 mol) was added dropwise. Stirring was continued, maintaining the temperature between 288–293 K over 1 h. Excess methanol was distilled off under reduced pressure. The solid obtained was collected by filtration, washed with water and dried. The crude product obtained was purified by recrystallization from ethanol. Single crystals suitable for X-ray analysis were obtained recrystallization from a 1:2 mixture of DMF and ethanol by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme [symmetry code: 1-x, y, z for one methyl hydrogen atom not lying on the mirror plane].
	Fig. 2. Part of the crystal structure of the title compound viewed along the a axis, showing one-dimensional chains along the c axis. Hydrogen bonds are shown as dashed lines.

4,5-Dichloro-2-methylpyridazin-3(2H)-one top

Crystal data top

C₅H₄Cl₂N₂O	F(000) = 720
M_r = 179.00	D_x = 1.697 Mg m⁻³
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 6513 reflections
a = 6.5157 (1) Å	θ = 2.6–34.7°
b = 15.9127 (4) Å	µ = 0.85 mm⁻¹
c = 13.5175 (3) Å	T = 100 K
V = 1401.53 (5) Å³	Block, colourless
Z = 8	0.42 × 0.29 × 0.22 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1659 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.717, T_max = 0.837	k = −25→24
13402 measured reflections	l = −20→21

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0513P)² + 0.3383P] where P = (F_o² + 2F_c²)/3
1659 reflections	(Δ/σ)_max < 0.001
64 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₅H₄Cl₂N₂O	V = 1401.53 (5) Å³
M_r = 179.00	Z = 8
Orthorhombic, Cmca	Mo Kα radiation
a = 6.5157 (1) Å	µ = 0.85 mm⁻¹
b = 15.9127 (4) Å	T = 100 K
c = 13.5175 (3) Å	0.42 × 0.29 × 0.22 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1659 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1427 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.837	R_int = 0.029
13402 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.55 e Å⁻³
1659 reflections	Δρ_min = −0.40 e Å⁻³
64 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.5000	0.152043 (19)	0.19640 (2)	0.01834 (9)
Cl2	0.5000	0.07981 (2)	0.41860 (3)	0.02540 (10)
O1	0.5000	0.33799 (6)	0.19775 (7)	0.0221 (2)
N1	0.5000	0.35316 (6)	0.36546 (8)	0.0182 (2)
N2	0.5000	0.32435 (8)	0.45961 (9)	0.0194 (2)
C1	0.5000	0.30554 (8)	0.28034 (9)	0.0159 (2)
C2	0.5000	0.21504 (8)	0.29869 (10)	0.0152 (2)
C3	0.5000	0.18537 (8)	0.39241 (10)	0.0173 (2)
C4	0.5000	0.24313 (9)	0.47317 (11)	0.0190 (2)
C5	0.5000	0.44471 (9)	0.35542 (13)	0.0296 (3)
H5A	0.5000	0.4700	0.4199	0.044*
H5B	0.6203	0.4621	0.3199	0.044*
H4A	0.5000	0.2257 (12)	0.5427 (14)	0.016 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02167 (15)	0.01747 (14)	0.01587 (16)	0.000	0.000	−0.00382 (10)
Cl2	0.03383 (19)	0.01782 (15)	0.02456 (19)	0.000	0.000	0.00717 (11)
O1	0.0344 (6)	0.0193 (4)	0.0124 (4)	0.000	0.000	0.0030 (3)
N1	0.0257 (5)	0.0156 (4)	0.0133 (5)	0.000	0.000	−0.0007 (4)
N2	0.0235 (5)	0.0218 (5)	0.0129 (5)	0.000	0.000	−0.0014 (4)
C1	0.0192 (5)	0.0152 (5)	0.0132 (5)	0.000	0.000	0.0005 (4)
C2	0.0165 (5)	0.0156 (5)	0.0134 (5)	0.000	0.000	−0.0007 (4)
C3	0.0193 (5)	0.0173 (5)	0.0155 (5)	0.000	0.000	0.0019 (4)
C4	0.0214 (5)	0.0224 (6)	0.0132 (6)	0.000	0.000	0.0012 (4)
C5	0.0503 (10)	0.0160 (5)	0.0224 (7)	0.000	0.000	−0.0012 (5)

Geometric parameters (Å, º) top

Cl1—C2	1.7078 (13)	C1—C2	1.4613 (18)
Cl2—C3	1.7166 (13)	C2—C3	1.3520 (19)
O1—C1	1.2301 (15)	C3—C4	1.427 (2)
N1—N2	1.3528 (16)	C4—H4A	0.980 (18)
N1—C1	1.3778 (16)	C5—H5A	0.9599
N1—C5	1.4631 (17)	C5—H5B	0.9600
N2—C4	1.3053 (19)

N2—N1—C1	126.82 (11)	C2—C3—C4	119.46 (12)
N2—N1—C5	115.13 (11)	C2—C3—Cl2	122.34 (11)
C1—N1—C5	118.04 (11)	C4—C3—Cl2	118.20 (11)
C4—N2—N1	117.88 (11)	N2—C4—C3	122.03 (13)
O1—C1—N1	121.81 (11)	N2—C4—H4A	114.5 (11)
O1—C1—C2	124.60 (11)	C3—C4—H4A	123.5 (11)
N1—C1—C2	113.59 (11)	N1—C5—H5A	109.5
C3—C2—C1	120.22 (12)	N1—C5—H5B	109.5
C3—C2—Cl1	123.62 (10)	H5A—C5—H5B	109.5
C1—C2—Cl1	116.16 (9)

C1—N1—N2—C4	0.0	N1—C1—C2—Cl1	180.0
C5—N1—N2—C4	180.0	C1—C2—C3—C4	0.0
N2—N1—C1—O1	180.0	Cl1—C2—C3—C4	180.0
C5—N1—C1—O1	0.0	C1—C2—C3—Cl2	180.0
N2—N1—C1—C2	0.0	Cl1—C2—C3—Cl2	0.0
C5—N1—C1—C2	180.0	N1—N2—C4—C3	0.0
O1—C1—C2—C3	180.0	C2—C3—C4—N2	0.0
N1—C1—C2—C3	0.0	Cl2—C3—C4—N2	180.0
O1—C1—C2—Cl1	0.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.98 (2)	2.33 (2)	3.2988 (18)	171 (2)

Symmetry code: (i) −x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₄Cl₂N₂O
M_r	179.00
Crystal system, space group	Orthorhombic, Cmca
Temperature (K)	100
a, b, c (Å)	6.5157 (1), 15.9127 (4), 13.5175 (3)
V (Å³)	1401.53 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.42 × 0.29 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.717, 0.837
No. of measured, independent and observed [I > 2σ(I)] reflections	13402, 1659, 1427
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.808

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.09
No. of reflections	1659
No. of parameters	64
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.980 (19)	2.328 (19)	3.2988 (18)	170.6 (16)

Symmetry code: (i) −x+1, −y+1/2, z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: C-7576-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and JHG thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

References

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