2-Chloro-3-[(E)-(hydrazin-1-yl­idene)meth­yl]-6-meth­oxy­quinoline

Sofiane Bouacida; Abdelmalek Bouraiou; Nassima Benhamoud; Thierry Roisnel; Ali Belfaitah

doi:10.1107/S1600536812017977

. 2012 Apr 28;68(Pt 5):o1548. doi: 10.1107/S1600536812017977

2-Chloro-3-[(E)-(hydrazin-1-ylidene)methyl]-6-methoxyquinoline

Sofiane Bouacida ^a,^*, Abdelmalek Bouraiou ^b, Nassima Benhamoud ^a, Thierry Roisnel ^c, Ali Belfaitah ^b

PMCID: PMC3344647 PMID: 22590409

Abstract

In the title compound, C₁₁H₁₀ClN₃O, the quinoline ring system is essentially planar, the r.m.s. deviation for the non-H atoms being 0.014 (2) Å with a maximum deviation from the mean plane of 0.0206 (14) Å for the C atom bonded to the –CH—N=NH₂ group. In the crystal, molecules are linked via N—H⋯O and N—H⋯N hydrogen bonds, forming zigzag layers parallel to (010).

Related literature

For previous work on molecules with a quinolyl moiety, see: Benzerka et al. (2011 ▶); Belfaitah et al. (2006 ▶) Bouraiou et al. (2008 ▶, 2011 ▶); Ladraa et al. (2009 ▶). For applications of pyrazole and its derivatives, see: Mali et al. (2010 ▶); Paul et al. (2001 ▶).

Experimental

Crystal data

C₁₁H₁₀ClN₃O
M _r = 235.67
Orthorhombic,
a = 3.8949 (2) Å
b = 12.0510 (5) Å
c = 21.9910 (9) Å
V = 1032.20 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 150 K
0.28 × 0.15 × 0.14 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.898, T _max = 0.952
15777 measured reflections
2352 independent reflections
2044 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.073
S = 1.06
2352 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ▶), 922 Friedel pairs
Flack parameter: 0.00 (6)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT (Bruker, 2004 ▶); program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017977/fj2545sup1.cif

e-68-o1548-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017977/fj2545Isup2.hkl

e-68-o1548-Isup2.hkl^{(113.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017977/fj2545Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13A⋯O14ⁱ	0.88	2.34	3.219 (2)	178
N13—H13B⋯N13ⁱⁱ	0.88	2.19	3.058 (2)	169

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We are grateful to the PHYSYNOR laboratory, Université Mentouri-Constantine, Algeria for assistance. Thanks are also due to the Ministére de l’Enseignement Supérieur et de la Recherche Scientifique and the Agence Nationale pour le Développement de la Recherche Universitaire for financial support via the PNR programm.

supplementary crystallographic information

Comment

Pyrazole and its derivatives are gaining importance in medicinal and organic chemistry. They have displayed broad spectrum of pharmacological and biological activities such as anti-bacterial, anti-depressant, and anti-hyperglycemic (Mali et al., 2010). Pyrazolo[3,4-b]quinolines have displayed bioactivities such as antiviral, antimalarial, lowering of serum cholesterol (Paul et al., 2001), but no metal complexes of such drugs have been reported in the past which might possibly have better pharmaceutical effect. Therefore, studies of the metal complexes are important in the search for new drugs. In previous works, we were interested in the design and synthesis of new molecules that contain a quinolyl moiety (Belfaitah et al., 2006; Bouraiou et al., 2008, 2011; Ladraa et al., 2009 and Benzerka et al., 2011). In this paper, we report the structure determination of compound resulting from an unwanted reaction of the 6-methoxy-1H-pyrazolo[3,4-b]quinoline with RuCl₃ in acidic conditions. Our attempt to synthesis the pyrazolo[3,4-b]quinoline/Ruthenium complex was failed and led to (E)-1-((2-chloro-6-methylquinolin-3-yl)methylene)hydrazine (I).

The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. In the asymetric unit of title molecule, (C₁₁ H₁₀ Cl N₃ O), the chloro-quinolyl unit is linked to methoxy and methylenehydrazine group. The quinoline ring system is essentially planar; the r.m.s. deviation for the non-H atoms is 0.014 (2) Å with a maximum deviation from the mean plane of 0.0206 (14) Å for the C atom bonded to the –CH—N═NH₂ group. The crystal packing can be described as layers in zigzag parallel to the (010) plane (Fig. 2). It is stabilized by N—H···O and N—H···N intermolecular hydrogen bonds (Fig. 2). These interaction bonds link the molecules within the layers and also link the layers together, reinforcing the cohesion of the structure. Hydrogen-bonding parameters are listed in table 1.

Experimental

First, 6-methoxy-1H-pyrazolo[3,4-b]quinoline was prepared from 2-chloro-6-methoxyquinoline-3-carbaldehyde and hydrazine hydrate in refluxing ethanol in a one-pot synthesis. Next, a mixture of 6-methoxy-1H-pyrazolo[3,4-b]quinoline(5 mmol)and RuCl₃(5 mmol) in aqueous HCl(10 ml) was stirred at 50°C for 1 h. Under these conditions, compound I was successfully obtained. Single crystals suitable for X-ray diffraction analysis were obtained by dissolving the corresponding compound in methanol solution and letting it for slow evaporation at room temperature.