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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3055.
Published online 2009 November 11. doi:  10.1107/S1600536809046947
PMCID: PMC2971970

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

Abstract

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 [triangle]); Samuel & Bose (1987 [triangle]); Siddiqui & Wani (2004 [triangle]). For standard bond lengths, see: Allen et al. (1987 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

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Object name is e-65-o3055-scheme1.jpg

Experimental

Crystal data

  • C5H4Cl2N2O
  • M r = 179.00
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3055-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.085
  • S = 1.09
  • 1659 reflections
  • 64 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The hydrogen atom H4A was located from difference Fourier map and allowed to refine freely. The hydrogen atoms bound to atom C5 were located geometrically and refined using a riding model with C—H = 0.96 Å and Uiso(H) = 1.5 Ueq(C).

Figures

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.

Crystal data

C5H4Cl2N2OF(000) = 720
Mr = 179.00Dx = 1.697 Mg m3
Orthorhombic, CmcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2Cell parameters from 6513 reflections
a = 6.5157 (1) Åθ = 2.6–34.7°
b = 15.9127 (4) ŵ = 0.85 mm1
c = 13.5175 (3) ÅT = 100 K
V = 1401.53 (5) Å3Block, colourless
Z = 80.42 × 0.29 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer1659 independent reflections
Radiation source: fine-focus sealed tube1427 reflections with I > 2σ(I)
graphiteRint = 0.029
[var phi] and ω scansθmax = 35.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −10→10
Tmin = 0.717, Tmax = 0.837k = −25→24
13402 measured reflectionsl = −20→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0513P)2 + 0.3383P] where P = (Fo2 + 2Fc2)/3
1659 reflections(Δ/σ)max < 0.001
64 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.50000.152043 (19)0.19640 (2)0.01834 (9)
Cl20.50000.07981 (2)0.41860 (3)0.02540 (10)
O10.50000.33799 (6)0.19775 (7)0.0221 (2)
N10.50000.35316 (6)0.36546 (8)0.0182 (2)
N20.50000.32435 (8)0.45961 (9)0.0194 (2)
C10.50000.30554 (8)0.28034 (9)0.0159 (2)
C20.50000.21504 (8)0.29869 (10)0.0152 (2)
C30.50000.18537 (8)0.39241 (10)0.0173 (2)
C40.50000.24313 (9)0.47317 (11)0.0190 (2)
C50.50000.44471 (9)0.35542 (13)0.0296 (3)
H5A0.50000.47000.41990.044*
H5B0.62030.46210.31990.044*
H4A0.50000.2257 (12)0.5427 (14)0.016 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02167 (15)0.01747 (14)0.01587 (16)0.0000.000−0.00382 (10)
Cl20.03383 (19)0.01782 (15)0.02456 (19)0.0000.0000.00717 (11)
O10.0344 (6)0.0193 (4)0.0124 (4)0.0000.0000.0030 (3)
N10.0257 (5)0.0156 (4)0.0133 (5)0.0000.000−0.0007 (4)
N20.0235 (5)0.0218 (5)0.0129 (5)0.0000.000−0.0014 (4)
C10.0192 (5)0.0152 (5)0.0132 (5)0.0000.0000.0005 (4)
C20.0165 (5)0.0156 (5)0.0134 (5)0.0000.000−0.0007 (4)
C30.0193 (5)0.0173 (5)0.0155 (5)0.0000.0000.0019 (4)
C40.0214 (5)0.0224 (6)0.0132 (6)0.0000.0000.0012 (4)
C50.0503 (10)0.0160 (5)0.0224 (7)0.0000.000−0.0012 (5)

Geometric parameters (Å, °)

Cl1—C21.7078 (13)C1—C21.4613 (18)
Cl2—C31.7166 (13)C2—C31.3520 (19)
O1—C11.2301 (15)C3—C41.427 (2)
N1—N21.3528 (16)C4—H4A0.980 (18)
N1—C11.3778 (16)C5—H5A0.9599
N1—C51.4631 (17)C5—H5B0.9600
N2—C41.3053 (19)
N2—N1—C1126.82 (11)C2—C3—C4119.46 (12)
N2—N1—C5115.13 (11)C2—C3—Cl2122.34 (11)
C1—N1—C5118.04 (11)C4—C3—Cl2118.20 (11)
C4—N2—N1117.88 (11)N2—C4—C3122.03 (13)
O1—C1—N1121.81 (11)N2—C4—H4A114.5 (11)
O1—C1—C2124.60 (11)C3—C4—H4A123.5 (11)
N1—C1—C2113.59 (11)N1—C5—H5A109.5
C3—C2—C1120.22 (12)N1—C5—H5B109.5
C3—C2—Cl1123.62 (10)H5A—C5—H5B109.5
C1—C2—Cl1116.16 (9)
C1—N1—N2—C40.0N1—C1—C2—Cl1180.0
C5—N1—N2—C4180.0C1—C2—C3—C40.0
N2—N1—C1—O1180.0Cl1—C2—C3—C4180.0
C5—N1—C1—O10.0C1—C2—C3—Cl2180.0
N2—N1—C1—C20.0Cl1—C2—C3—Cl20.0
C5—N1—C1—C2180.0N1—N2—C4—C30.0
O1—C1—C2—C3180.0C2—C3—C4—N20.0
N1—C1—C2—C30.0Cl2—C3—C4—N2180.0
O1—C1—C2—Cl10.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4A···O1i0.98 (2)2.33 (2)3.2988 (18)171 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2946).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Banerjee, P. S., Sharma, P. K. & Nema, R. K. (2009). Int. J. Chem. Technol. Res 1, 522–525.
  • Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
  • Samuel, K. & Bose, S. (1987). J. Biosci. 12, 211–218.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siddiqui, A. A. & Wani, S. M. (2004). Indian J. Chem. Sect. B, 43, 1574–1579.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography