2-{[(4-{[(2-Hy­droxy­phen­yl)(phen­yl)methyl­idene]amino}­phen­yl)imino](phen­yl)meth­yl}phenol

Anita Blagus; Branko Kaitner

doi:10.1107/S1600536811046988

. 2011 Nov 9;67(Pt 12):o3252. doi: 10.1107/S1600536811046988

2-{[(4-{[(2-Hydroxyphenyl)(phenyl)methylidene]amino}phenyl)imino](phenyl)methyl}phenol

Anita Blagus ^a,^*, Branko Kaitner ^b

PMCID: PMC3238908 PMID: 22199761

Abstract

The title molecule, C₃₂H₂₄N₂O₂, has a crystallographically imposed inversion centre and exists in the crystal as an enol–imine tautomer. The molecular structure is stabilized by two strong intramolecular O—H⋯N hydrogen bonds. The dihedral angles between the central benzene ring and the mean planes of the phenyl substituents are 59.99 (1) and 62.79 (2)°. In the crystal, the molecules are arranged into (010) layers via C—H⋯π interactions.

Related literature

For general background to Schiff bases, see: Blagus et al. (2010 ▶). For similar structures derived from p-phenylenediamine, see: Al-Douh et al. (2009 ▶); Hoshino et al. (1988 ▶); Inabe et al. (1994 ▶).

Experimental

Crystal data

C₃₂H₂₄N₂O₂
M _r = 468.53
Orthorhombic,
a = 17.383 (4) Å
b = 14.595 (3) Å
c = 9.476 (2) Å
V = 2404.1 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.6 × 0.5 × 0.3 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer
18421 measured reflections
2361 independent reflections
1559 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.149
S = 1.03
2361 reflections
166 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2003 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶) and Mercury (Macrae et al., 2006 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046988/gk2425sup1.cif

e-67-o3252-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046988/gk2425Isup2.hkl

e-67-o3252-Isup2.hkl^{(113.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811046988/gk2425Isup3.cml

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

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

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.91 (2)	1.73 (2)	2.569 (2)	152 (2)
C15—H15⋯Cgⁱ	0.93	2.93	3.748 (2)	148

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support by the Ministry of Science, Education and Sport of the Republic of Croatia is gratefully acknowledged (grant No. 119–1193079–3069).

supplementary crystallographic information

Comment

There is constant interest in investigation of solid-state structures and properties of Schiff bases and their metal complexes (Blagus et al., 2010 and references therein). The title Schiff base is derived from p-phenylenediamine and the structures of three Schiff bases derived from p-phenylenediamine and different aldehydes [(i) vanillin (Al-Douh et al., 2009), (ii) salicylaldehyde (Hoshino et al., 1988) and(iii) 2-OH-1-naphthaldehyde (Inabe et al., 1994)] were published since 1988. Two main features that define the shape of the title molecule are: (i) strong intramolecular O–H···N hydrogen bond and (ii) spatial orientation of four terminal aromatic rings with respect to the central one (Fig. 1). The C1–C6 ring and pseudo-aromatic O1–H1–N1–C1–C2–C7 ring are almost co-planar with a dihedral angle of 1.79 (1)° and the displacement of H1 atom from the best plane of pseudo-aromatic ring of 0.016 Å. The bond distances characterizing the enol-imine tautomeric form of (I) are as expected. Taking the central ring C14–C14ⁱ–C15–C15ⁱ–C16–C16ⁱ [(i): –x, –y, –z+1] as the pivotal one, the interplanar angles between this ring and the rings C1–C6 and C8–C13 are 59.99 (1) and 62.79 (2)°, respectively. The latter rings intersect at an angle of 67.74 (1)°. In crystal packing some weak C–H···π interactions can be observed that organize the molecules into (0 1 0) layers shown in Fig. 2.

Experimental

The title compound was prepared by the condensation reaction of the aromatic diamine and aromatic 2-OH-ketone in molar ratio 1: 2. Ethanolic solutions of 2-hydroxybenzophenone (10 mmol) and o-phenylenediamine (5 mmol) were stirred for 3 h. The resulting brown resinous product was dissolved in ether and overlaid with the same volume of n-hexane. After one month, red-brown crystals suitable for single-crystal X-ray analysis were obtained by slow evaporation from the solution. IR spectrum was recorded on Shimadzu FTIR-8400 spectrophotometer cm^-1: 3378, 1625, 1486, 1335, 1246, 759, 702.