2-[(4-Chloro­phen­yl)imino­meth­yl]hydro­quinone

Serap Yazıcı; Ferda Erşahin; Erbil Ağar; İsmet Şenel; Orhan Büyükgüngör

doi:10.1107/S1600536809015396

. 2009 Apr 30;65(Pt 5):o1155. doi: 10.1107/S1600536809015396

2-[(4-Chlorophenyl)iminomethyl]hydroquinone

Serap Yazıcı ^a, Ferda Erşahin ^b, Erbil Ağar ^b, İsmet Şenel ^a, Orhan Büyükgüngör ^a,^*

PMCID: PMC2977821 PMID: 21583958

Abstract

The title compound, C₁₃H₁₀ClNO₂, exists in the phenol–imine form in the crystal, and the aromatic rings are oriented at a dihedral angle of 2.82 (9)°. An intramolecular O—H⋯N hydrogen bond results in the formation of a planar six-membered ring. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules into chains.

Related literature

For general background to o-hydroxy Schiff bases, see: Calligaris et al. (1972 ▶); Hadjoudis et al. (1987 ▶); Hökelek et al. (2004 ▶); Maslen & Waters (1975 ▶); Moustakali-Mavridis et al. (1980 ▶); Xu et al. (1994 ▶). For related structures, see: Filarowski et al. (2003 ▶); Karadayı et al. (2003 ▶); Yıldız et al. (1998 ▶).

Experimental

Crystal data

C₁₃H₁₀ClNO₂
M _r = 247.67
Monoclinic,
a = 20.3347 (14) Å
b = 4.5848 (2) Å
c = 12.0383 (9) Å
β = 98.231 (6)°
V = 1110.78 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.80 × 0.40 × 0.06 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.819, T _max = 0.978
15373 measured reflections
2185 independent reflections
1575 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 0.95
2185 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-RED32 (Stoe & Cie, 2002 ▶); 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/S1600536809015396/hk2670sup1.cif

e-65-o1155-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015396/hk2670Isup2.hkl

e-65-o1155-Isup2.hkl^{(105.2KB, 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	1.90	2.6270 (18)	147
O2—H2⋯O2ⁱ	0.82	2.04	2.7631 (13)	147

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

o-Hydroxy Schiff bases derived from the reactions of o-hydroxyaldehydes with aniline have been examined extensively (Calligaris et al., 1972; Maslen & Waters, 1975). In general, o-hydroxy Schiff bases exhibit two possible tautomeric forms, namely, phenol-imine and keto-amine. Naphthaldimine and salicylaldimine can also exist in the phenol-imine and keto-amine forms, respectively depending on the stereochemistry of the molecule and the type of nitrogen substituents in naphthaldimine and salicylaldimine Schiff bases (Hökelek et al., 2004). Schiff base compounds display interesting photochromic and thermochromic features and can be classified in terms of these ( Moustakali-Mavridis et al., 1980; Hadjoudis et al., 1987). Photo- and thermochromism arise via H atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994).

In the title compound (Fig. 1), the phenol-imine form is favored over the keto-amine form, as indicated by C13-O1 [1.356 (2) Å] and C7-N1 [1.280 (2) Å] bonds, which are in accordance with the corresponding values in a similar compound [C-O = 1.352 (3) and C-N = 1.280 (4) Å; Karadayı et al., 2003]. As a common feature of o-hydroxysalicylidene systems, the title compound displays a strong hydrogen bond between atoms N1 and O1 (Filarowski et al., 2003; Yıldız et al., 1998).

It is known that Schiff bases may exhibit thermochromism or photochromism, depending on the planarity or non-planarity of the molecule, respectively. Therefore, one can expect thermochromic properties in the title compound caused by planarity of the molecule; the dihedral angle between rings A (C1-C6) and B (C8-C13) is 2.82 (9)°. Intramolecular O-H···N hydrogen bond (Table 1) results in the formation of a planar six-membered ring C (O1/N1/C7/C8/C13/H1), which is oriented with respect to rings A and B at dihedral angles of A/C = 2.97 (8) and B/C = 1.35 (8) °. So, they are nearly coplanar.

In the crystal structure, intermolecular O-H···O hydrogen bonds (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared by refluxing a mixture of a solution containing 2,5-dihydroxybenzaldehyde (0.034 g 0.246 mmol) in ethanol (20 ml) and a solution containing 4-chloroaniline (0.031 g 0.246 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Crystals suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield; 69%; m.p. 439-441 K).