3-[(2,4-Dichloro­phen­yl)imino­meth­yl]-2-hydr­oxy-5-methyl­benzaldehyde

Işın Kılıç; Şamil Işık; Erbil Ağar; Ferda Erşahin

doi:10.1107/S1600536809018303

. 2009 May 20;65(Pt 6):o1347. doi: 10.1107/S1600536809018303

3-[(2,4-Dichlorophenyl)iminomethyl]-2-hydroxy-5-methylbenzaldehyde

Işın Kılıç ^a,^*, Şamil Işık ^a, Erbil Ağar ^b, Ferda Erşahin ^b

PMCID: PMC2969673 PMID: 21583199

Abstract

The title compound, C₁₅H₁₁Cl₂NO₂, is a Schiff base which adopts the phenol–imine tautomeric form in the solid state, being stabilized by a strong intramolecular O—H⋯N hydrogen bond. The molecule is almost planar (r.m.s. deviation for all non-H atoms = 0.049 Å), displaying a dihedral angle of 3.1 (3)° between the planes of the two aromatic rings.

Related literature

For Schiff bases as substrates in the preparation of number of biologically active compounds, see: Siddiqui et al. (2006 ▶). For photochromism and thermochromism in these compounds, see: Hadjoudis et al. (1987 ▶); Xu et al. (1994 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Gül et al. (2007 ▶) Koşar et al. (2005 ▶).

Experimental

Crystal data

C₁₅H₁₁Cl₂NO₂
M _r = 308.15
Monoclinic,
a = 19.424 (2) Å
b = 4.6113 (3) Å
c = 15.4245 (14) Å
β = 103.946 (8)°
V = 1340.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 296 K
0.80 × 0.31 × 0.02 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED; Stoe & Cie, 2002 ▶) T _min = 0.817, T _max = 0.982
5912 measured reflections
2613 independent reflections
1228 reflections with I > 2σ(I)
R _int = 0.099

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.138
S = 0.91
2613 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018303/bt2960sup1.cif

e-65-o1347-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018303/bt2960Isup2.hkl

e-65-o1347-Isup2.hkl^{(125.7KB, hkl)}

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
O1—H1⋯N1	0.82	1.85	2.577 (4)	147

Open in a new tab

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

supplementary crystallographic information

Comment

In this paper, a new Schiff base, (I), C₁₅H₁₁Cl₂O₂N is prepared and its crystal structure is reported.

Schiff bases are synthesized from an aromatic amine and a carbonyl compound by a nucleophilic addition reaction. They are used as substrates in the preparation of number of biologically active compounds (Siddiqui et al., 2006). Photochromism and thermochromism are also characteristics of these materials and arise via H-atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994). These are two types of intra molecular hydrogen bonds in Schiff bases, in keto-amine (N—H···O) and phenol-imine (N···H—O) tautomeric forms. Our X-ray investigation shows that the title compound, (I), exists in the phenol-imine form.

An ORTEP view of the molecule of (I) is shown in Fig. 1. There is a strong O···N type intramolecular hydrogen bond and this intramolecular hydrogen bond (O1—H1···N1) can be described as an S(6) motif (Bernstein et al., 1995). The C1—O1 [1.354 (6) Å] and C7=N1 [1.272 (6) Å] bond lengths verify the enol-imine form of (I), and these distances are agree with the corresponding distances in (E)-2-[4-(Dimethylamino)phenyliminomethyl]-6-methylphenol [1.350 (3) and 1.280 (2) Å; Gül et al., 2007)] and in (E)-4-Methoxy-2- [(4-nitrophenyl)iminomethyl]phenol [1.351 (2) and 1.277 (2) Å; Koşar et al., 2005]. The molecule is almost planar and the dihedral angle between the rings formed by atoms C1—C6 and C8—C13 is 3.12(0.28)°.

Experimental

The compound 3-[(2,4-Dichlorophenyl)imino]methyl-2-hydroxy-5- methylbenzaldehyde was prepared by reflux a mixture of a solution containing 2-Hydroxy-5-methyl-1,3-benzenedicarboxaldehyde (0.05 g 0.3 mmol) in 20 ml e thanol and a solution containing 2,4-Dichloroaniline(0.049 g 0.3 mmol) in 20 ml e thanol. The reaction mixture was stirred for 1 hunder reflux. The crystals of 3-[(2,4-Dichlorophenyl)imino]methyl-2-hydroxy-5- methylbenzaldehyde suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield % 79; m.p.483–485 K).