(E)-2-[(2,4-Dichloro­phen­yl)imino­meth­yl]benzene-1,4-diol monohydrate

Zarife Sibel Şahin; Sūmeyye Gūmūş; Mustafa Macit; Şamil Işık

doi:10.1107/S1600536809045103

. 2009 Nov 7;65(Pt 12):o3022. doi: 10.1107/S1600536809045103

(E)-2-[(2,4-Dichlorophenyl)iminomethyl]benzene-1,4-diol monohydrate

Zarife Sibel Şahin ^a,^*, Sūmeyye Gūmūş ^b, Mustafa Macit ^b, Şamil Işık ^a

PMCID: PMC2972111 PMID: 21578759

Abstract

The title compound, C₁₃H₉Cl₂NO₂·H₂O, represents a Schiff base which adopts the phenol–imine tautomeric form in the solid state. The molecule is approximately planar (r.m.s. deviation 0.0818 Å), and the dihedral angle between the two aromatic rings is 7.46 (12)°. An O—H⋯N interaction generates an S(6) ring. In the crystal, molecules are linked by intermolecular O—H⋯O hydrogen bonds involving the solvent water molecule, forming chains.

Related literature

For the biological properties of Schiff bases see: Lozier et al. (1975 ▶), Dao et al. (2000 ▶). For the coordination chemistry of Schiff bases see: Kargar et al. (2009 ▶); Yeap et al. (2009 ▶). For a discussion of Schiff bases tautomerism, see: Şahin et al. (2005 ▶); Hadjoudis et al. (1987 ▶). For a related structure, see: Zhang (2009 ▶). graphic file with name e-65-o3022-scheme1.jpg

Experimental

Crystal data

C₁₃H₉Cl₂NO₂·H₂O
M _r = 300.13
Monoclinic,
a = 4.6899 (2) Å
b = 17.4289 (6) Å
c = 16.1645 (7) Å
β = 95.923 (3)°
V = 1314.23 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.90 × 0.56 × 0.25 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.801, T _max = 0.959
11982 measured reflections
2585 independent reflections
1879 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 0.97
2585 reflections
188 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32; 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/S1600536809045103/bh2254sup1.cif

e-65-o3022-sup1.cif^{(16KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045103/bh2254Isup2.hkl

e-65-o3022-Isup2.hkl^{(124.4KB, 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
O3—H1O⋯O2ⁱ	0.85 (4)	1.94 (4)	2.774 (3)	170 (3)
O2—H2⋯N1	0.87 (4)	1.77 (3)	2.569 (2)	152 (3)
O3—H2O⋯O1ⁱⁱ	0.82 (4)	2.49 (5)	3.184 (3)	143 (4)
O1—H1⋯O3	0.87 (4)	1.79 (4)	2.659 (3)	171 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Schiff bases often exhibit various biological activities and in many cases were shown to have antibacterial, anticancer, anti-inflammatory and antitoxic properties (Lozier et al., 1975; Dao et al., 2000). Schiff bases have also been used as versatile ligands in coordination chemistry (Kargar et al., 2009; Yeap et al., 2009). There are two types of intramolecular hydrogen bonds in Schiff bases, which may be stabilized either in keto-amine (N—H···O hydrogen bond) (Şahin et al., 2005) or phenol-imine (N···H—O hydrogen bond) tautomeric forms (Hadjoudis et al., 1987). The present X-ray investigation shows that the title compound is a Schiff base and exists in the phenol-imine form in the solid-state.

An ORTEP-3 (Farrugia, 1997) plot and crystal packing of the molecule of the title compound are shown in Figs. 1 and 2, respectively. The molecule is approximately planar. The dihedral angle between the two aromatic rings is 7.46 (12)° and the C1—C7—N1—C8 torsion angle is 178.71 (16)°. All bond lengths are within normal values. An intramolecular O2—H2···N1 hydrogen bond (Table 1) is observed and this hydrogen bond produces S(6) ring. The O2···N1 separation of 2.569 (2) Å is comparable to those observed for analogous hydrogen bonds in 2-bromo-4-chloro-6-[(E)-p-tolylimino-methyl]phenol (Zhang, 2009). Molecules are linked into sheets by a combination of O—H···O hydrogen bonds (Table 1). The combination of O—H···O hydrogen bonds generates a chain of edge-fused R₆⁶(22) rings running parallel to the [100] direction (Fig. 2).

Experimental

The compound (E)-2-[(2,4-(dichloro)phenylimino)methyl]-4-hydroxyphenol monohydrate was prepared by refluxing a solution containing 2,5-dihydroxybenzaldehyde (0.03 g, 0.22 mmol) in ethanol (20 ml) and 2,4-dichloroaniline (0.035 g, 0.22 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. The crystals of the title hydrate suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield 73%; m.p. 432–435 K).