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The title compound, C14H15ClN2O2, is of pharmacological interest. It contains an oxopyridazine heterocycle, carrying a methyl group in the position para to the oxo group, a hydroxy­ethyl group at one of the N atoms and a 2-chloro­benzyl residue in the position meta to the oxo group. The dihedral angle between the two rings is 85.71 (5)°. In the crystal structure, the mol­ecules form hydrogen-bonded centrosymmetric dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011462/wn6158sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011462/wn6158Isup2.hkl
Contains datablock I

CCDC reference: 217612

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.036
  • wR factor = 0.078
  • Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

Many pyridazine compounds have been reported to be anticonvulsive agents (Rubat et al., 1990; Foussard-Blanc & Lacroix, 1991). Furthermore, Gehrlein et al. (1981) have described the antihypertensive effects of novel hydroxyethylpyridazine compounds. In continuation of this line of investigation, we have synthesized compound (I); it will be subjected to further pharmacological investigations, especially tests of its anticancer activity. Compound (I) is stable at room temperature, and its structure has been determined by IR, MS and NMR (1H and 13C) spectroscopy. Since these techniques did not provide sufficient information about the conformation of the reaction product, we have carried out an X-ray structure analysis. The bond lengths and angles of (I) are normal (Table 1). The dihedral angle between the two rings is 85.71 (5)°. In the crystal structure, molecules of (I) form hydrogen-bonded centrosymmetric dimers (Table 2).

The structure of a very similar compound, (II), in which the N atom carries a H atom instead of a 2-hydroxyethyl group, has been determined by Moreau et al. (1995). However, the conformations of the two compounds are completely different, as can be seen by the torsion angle C12—C11—C7—C1, which is 84.6 (2)° in the title compound and 149.6° in (II). The reason for this difference may be due to the different packing patterns. Whereas the title compound crystallizes as centrosymmetric hydrogen-bonded dimers, compound (II) contains hydrogen-bonded zigzag chains.

Experimental top

A mixture of levulinic acid and o-chlorobenzaldehyde, containing HCl at room temperature, gave the phenylmethyllevulinic acid, which was treated with hydrazine in boiling ethanol to give 5-(o-chlorobenzylidene)-6-methylpyridazin-3-one. Addition of 2-bromoethanol, in the presence of potassium carbonate in boiling tetrahydrofuran, yielded 5-(2-chlorobenzyl)-2-(2-hydroxyethyl)-6-methylpyridazin-3(2H)-one. Single crystals were obtained by recrystallization from ethanol.

Refinement top

All H atoms were located in a difference Fourier synthesis and were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl)], using a riding model with C—H(aromatic) = 0.95 Å, CH(methyl) = 0.98 Å and CH(methylene) = 0.99 Å. The methyl group was allowed to rotate but not to tip. The hydroxy H atom was refined isotropically.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Perspective view of (I), with the atom-numbering scheme; displacement ellipsoids are drawn at the 50% probability level.
(I) top
Crystal data top
C14H15ClN2O2F(000) = 584
Mr = 278.73Dx = 1.306 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5126 reflections
a = 10.6426 (13) Åθ = 3.5–25.1°
b = 7.3564 (8) ŵ = 0.27 mm1
c = 18.467 (2) ÅT = 173 K
β = 101.409 (9)°Block, colourless
V = 1417.2 (3) Å30.29 × 0.15 × 0.14 mm
Z = 4
Data collection top
Stoe IPDS-II two-circle
diffractometer
2526 independent reflections
Radiation source: fine-focus sealed tube1680 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω scansθmax = 25.2°, θmin = 3.6°
Absorption correction: empirical (using intensity measurements)
(MULABS; Spek, 1990; Blessing, 1995)
h = 1212
Tmin = 0.936, Tmax = 0.970k = 88
9173 measured reflectionsl = 2022
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 0.88 w = 1/[σ2(Fo2) + (0.0382P)2]
where P = (Fo2 + 2Fc2)/3
2526 reflections(Δ/σ)max < 0.001
177 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C14H15ClN2O2V = 1417.2 (3) Å3
Mr = 278.73Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.6426 (13) ŵ = 0.27 mm1
b = 7.3564 (8) ÅT = 173 K
c = 18.467 (2) Å0.29 × 0.15 × 0.14 mm
β = 101.409 (9)°
Data collection top
Stoe IPDS-II two-circle
diffractometer
2526 independent reflections
Absorption correction: empirical (using intensity measurements)
(MULABS; Spek, 1990; Blessing, 1995)
1680 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.970Rint = 0.063
9173 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 0.88Δρmax = 0.17 e Å3
2526 reflectionsΔρmin = 0.25 e Å3
177 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
xyzUiso*/Ueq
C10.38571 (18)0.4615 (2)0.65428 (9)0.0235 (4)
C20.33171 (19)0.5641 (2)0.59548 (9)0.0274 (4)
H20.24100.56820.58120.033*
C30.4085 (2)0.6675 (2)0.55394 (10)0.0294 (4)
O30.36219 (15)0.7598 (2)0.49852 (8)0.0443 (4)
N40.53815 (17)0.6559 (2)0.57966 (8)0.0285 (4)
N50.59594 (16)0.5555 (2)0.63933 (8)0.0276 (4)
C60.52376 (19)0.4621 (2)0.67516 (9)0.0244 (4)
C610.5932 (2)0.3547 (3)0.74023 (11)0.0317 (4)
H61A0.58050.22450.73010.048*
H61B0.55940.38660.78420.048*
H61C0.68490.38300.74880.048*
C70.31126 (19)0.3526 (3)0.70088 (10)0.0286 (4)
H7A0.33840.22400.70060.034*
H7B0.33440.39660.75250.034*
C80.6310 (2)0.7559 (3)0.54534 (11)0.0347 (5)
H8A0.58450.82310.50170.042*
H8B0.68940.66840.52810.042*
C90.7088 (2)0.8882 (3)0.59861 (10)0.0342 (5)
H9A0.75510.82080.64220.041*
H9B0.77340.94700.57450.041*
O90.63120 (18)1.02425 (19)0.62231 (8)0.0433 (4)
H90.612 (3)1.100 (4)0.5903 (17)0.078 (10)*
C110.16773 (19)0.3608 (2)0.67672 (10)0.0283 (4)
C120.1004 (2)0.2468 (3)0.62183 (11)0.0327 (5)
Cl120.18342 (6)0.08265 (8)0.58149 (3)0.04721 (17)
C130.0316 (2)0.2588 (3)0.59889 (13)0.0444 (6)
H130.07490.18160.56080.053*
C140.0994 (2)0.3828 (4)0.63147 (14)0.0554 (7)
H140.18980.39090.61610.066*
C150.0361 (3)0.4955 (3)0.68653 (15)0.0535 (6)
H150.08320.58020.70950.064*
C160.0957 (2)0.4855 (3)0.70835 (12)0.0403 (5)
H160.13820.56530.74570.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0308 (11)0.0200 (8)0.0199 (8)0.0025 (7)0.0054 (8)0.0035 (7)
C20.0313 (11)0.0268 (9)0.0229 (9)0.0054 (8)0.0029 (8)0.0001 (8)
C30.0407 (13)0.0252 (9)0.0215 (9)0.0076 (9)0.0043 (9)0.0005 (8)
O30.0527 (11)0.0481 (9)0.0289 (8)0.0121 (8)0.0001 (7)0.0168 (7)
N40.0381 (10)0.0268 (8)0.0230 (8)0.0066 (7)0.0121 (7)0.0010 (6)
N50.0315 (9)0.0259 (8)0.0271 (8)0.0006 (7)0.0098 (7)0.0006 (7)
C60.0343 (11)0.0186 (8)0.0218 (9)0.0007 (8)0.0094 (8)0.0021 (7)
C610.0319 (12)0.0281 (9)0.0343 (10)0.0015 (8)0.0043 (9)0.0061 (8)
C70.0308 (11)0.0298 (9)0.0250 (9)0.0073 (8)0.0044 (8)0.0035 (7)
C80.0457 (13)0.0357 (10)0.0271 (10)0.0126 (10)0.0181 (10)0.0022 (8)
C90.0444 (13)0.0329 (10)0.0282 (10)0.0102 (10)0.0143 (9)0.0002 (8)
O90.0750 (12)0.0285 (7)0.0291 (8)0.0010 (8)0.0171 (8)0.0037 (6)
C110.0331 (12)0.0285 (9)0.0242 (9)0.0057 (8)0.0081 (8)0.0053 (7)
C120.0350 (12)0.0358 (10)0.0294 (10)0.0103 (9)0.0113 (9)0.0002 (8)
Cl120.0564 (4)0.0474 (3)0.0415 (3)0.0104 (3)0.0186 (3)0.0148 (3)
C130.0350 (14)0.0584 (14)0.0389 (12)0.0169 (11)0.0050 (11)0.0029 (10)
C140.0319 (13)0.0766 (18)0.0578 (15)0.0006 (13)0.0091 (12)0.0144 (14)
C150.0489 (16)0.0545 (14)0.0613 (16)0.0143 (12)0.0211 (13)0.0055 (12)
C160.0458 (14)0.0377 (11)0.0387 (11)0.0015 (10)0.0112 (10)0.0027 (9)
Geometric parameters (Å, º) top
C1—C21.354 (3)C8—H8A0.9900
C1—C61.443 (3)C8—H8B0.9900
C1—C71.510 (2)C9—O91.421 (3)
C2—C31.443 (3)C9—H9A0.9900
C2—H20.9500C9—H9B0.9900
C3—O31.246 (2)O9—H90.81 (3)
C3—N41.370 (3)C11—C161.395 (3)
N4—N51.367 (2)C11—C121.399 (3)
N4—C81.472 (2)C12—C131.387 (3)
N5—C61.304 (2)C12—Cl121.748 (2)
C6—C611.504 (3)C13—C141.374 (3)
C61—H61A0.9800C13—H130.9500
C61—H61B0.9800C14—C151.380 (4)
C61—H61C0.9800C14—H140.9500
C7—C111.506 (3)C15—C161.383 (4)
C7—H7A0.9900C15—H150.9500
C7—H7B0.9900C16—H160.9500
C8—C91.509 (3)
C2—C1—C6117.45 (17)C9—C8—H8A109.3
C2—C1—C7124.44 (18)N4—C8—H8B109.3
C6—C1—C7118.07 (15)C9—C8—H8B109.3
C1—C2—C3121.66 (19)H8A—C8—H8B107.9
C1—C2—H2119.2O9—C9—C8112.17 (18)
C3—C2—H2119.2O9—C9—H9A109.2
O3—C3—N4121.78 (18)C8—C9—H9A109.2
O3—C3—C2123.4 (2)O9—C9—H9B109.2
N4—C3—C2114.86 (16)C8—C9—H9B109.2
N5—N4—C3125.06 (15)H9A—C9—H9B107.9
N5—N4—C8112.57 (16)C9—O9—H9110 (2)
C3—N4—C8122.36 (16)C16—C11—C12116.9 (2)
C6—N5—N4118.51 (16)C16—C11—C7120.73 (18)
N5—C6—C1122.44 (16)C12—C11—C7122.37 (18)
N5—C6—C61115.88 (17)C13—C12—C11121.7 (2)
C1—C6—C61121.68 (16)C13—C12—Cl12118.73 (17)
C6—C61—H61A109.5C11—C12—Cl12119.54 (16)
C6—C61—H61B109.5C14—C13—C12119.8 (2)
H61A—C61—H61B109.5C14—C13—H13120.1
C6—C61—H61C109.5C12—C13—H13120.1
H61A—C61—H61C109.5C13—C14—C15120.0 (2)
H61B—C61—H61C109.5C13—C14—H14120.0
C11—C7—C1115.23 (15)C15—C14—H14120.0
C11—C7—H7A108.5C14—C15—C16120.1 (2)
C1—C7—H7A108.5C14—C15—H15119.9
C11—C7—H7B108.5C16—C15—H15119.9
C1—C7—H7B108.5C15—C16—C11121.5 (2)
H7A—C7—H7B107.5C15—C16—H16119.3
N4—C8—C9111.71 (15)C11—C16—H16119.3
N4—C8—H8A109.3
C6—C1—C2—C31.3 (3)C6—C1—C7—C11178.97 (15)
C7—C1—C2—C3178.96 (16)N5—N4—C8—C960.6 (2)
C1—C2—C3—O3178.21 (18)C3—N4—C8—C9118.4 (2)
C1—C2—C3—N41.3 (3)N4—C8—C9—O962.3 (2)
O3—C3—N4—N5179.01 (17)C1—C7—C11—C1694.8 (2)
C2—C3—N4—N50.5 (3)C1—C7—C11—C1284.6 (2)
O3—C3—N4—C82.1 (3)C16—C11—C12—C131.1 (3)
C2—C3—N4—C8178.41 (16)C7—C11—C12—C13178.41 (18)
C3—N4—N5—C60.2 (2)C16—C11—C12—Cl12178.18 (14)
C8—N4—N5—C6179.24 (15)C7—C11—C12—Cl122.4 (2)
N4—N5—C6—C10.2 (2)C11—C12—C13—C141.3 (3)
N4—N5—C6—C61179.98 (15)Cl12—C12—C13—C14177.91 (17)
C2—C1—C6—N50.5 (2)C12—C13—C14—C150.4 (4)
C7—C1—C6—N5178.33 (15)C13—C14—C15—C160.8 (4)
C2—C1—C6—C61179.20 (16)C14—C15—C16—C111.1 (4)
C7—C1—C6—C611.4 (2)C12—C11—C16—C150.2 (3)
C2—C1—C7—C111.4 (3)C7—C11—C16—C15179.63 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O3i0.81 (3)2.00 (3)2.751 (2)154 (3)
Symmetry code: (i) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC14H15ClN2O2
Mr278.73
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)10.6426 (13), 7.3564 (8), 18.467 (2)
β (°) 101.409 (9)
V3)1417.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.29 × 0.15 × 0.14
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.936, 0.970
No. of measured, independent and
observed [I > 2σ(I)] reflections
9173, 2526, 1680
Rint0.063
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.078, 0.88
No. of reflections2526
No. of parameters177
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.25

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.

Selected geometric parameters (Å, º) top
C3—N41.370 (3)N5—C61.304 (2)
N4—N51.367 (2)C9—O91.421 (3)
N4—C81.472 (2)C12—Cl121.748 (2)
N5—N4—C3125.06 (15)C3—N4—C8122.36 (16)
N5—N4—C8112.57 (16)C6—N5—N4118.51 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O3i0.81 (3)2.00 (3)2.751 (2)154 (3)
Symmetry code: (i) x+1, y+2, z+1.
 

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