(E)-2-{[(2-Amino­pyridin-3-yl)imino]­meth­yl}-4,6-di-tert-butyl­phenol

Alexander Carreño; Sonia Ladeira; Annie Castel; Andres Vega; Ivonne Chavez

doi:10.1107/S1600536812032060

. 2012 Jul 21;68(Pt 8):o2507–o2508. doi: 10.1107/S1600536812032060

(E)-2-{[(2-Aminopyridin-3-yl)imino]methyl}-4,6-di-tert-butylphenol

Alexander Carreño ^a, Sonia Ladeira ^b, Annie Castel ^b, Andres Vega ^c, Ivonne Chavez ^d,^*

PMCID: PMC3414959 PMID: 22904946

Abstract

In the title compound, C₂₀H₂₇N₃O, the hydroxy group forms an intramolecular O—H⋯N hydrogen bond with the imino N atom. The dihedral angle between the aromatic rings is 33.09 (9)°. In the crystal, molecules form centrosymmetric dimers via pairs of N—H⋯N hydrogen bonds involving aminopyridine fragments.

Related literature

For asymmetric ligands prepared from aromatic diamines and their metal complexes exhibiting catalytic activity, e.g. metallosalphenes, see: Kleij, Kuil et al. (2005 ▶); Kleij, Tooke et al. (2005 ▶). For the synthetic procedure, see: Benisvy et al. (2003 ▶, 2004 ▶). For the related structure of 2-amino-3-salicylidenaminopyridine, see: Cimerman et al. (1992 ▶).

Experimental

Crystal data

C₂₀H₂₇N₃O
M _r = 325.45
Monoclinic,
a = 16.8457 (12) Å
b = 10.6227 (8) Å
c = 10.4817 (6) Å
β = 101.268 (4)°
V = 1839.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 193 K
0.6 × 0.06 × 0.04 mm

Data collection

Bruker Kappa APEXII Quazar area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.957, T _max = 0.997
29076 measured reflections
4532 independent reflections
2875 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.160
S = 1.03
4532 reflections
230 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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 datablock(s) global, I. DOI: 10.1107/S1600536812032060/yk2062sup1.cif

e-68-o2507-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032060/yk2062Isup2.hkl

e-68-o2507-Isup2.hkl^{(222.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032060/yk2062Isup3.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
O1—H1A⋯N1	0.84	1.87	2.6214 (19)	149
N3—H203⋯N2ⁱ	0.89 (1)	2.16 (1)	3.045 (2)	175 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from UNAB DI-28-10/I, Proyecto P07-006-F de la Iniciativa Científica Milenio del Ministerio de Economía, Fomento y Turismo and ECOS-CONICYT C08E01. AV is a member of Financiamiento Basal para Centros Científicos y Tecnológicos de Excelencia FB0807. A. Carreño acknowledges Universidad Andres Bello for a doctoral fellowship.

supplementary crystallographic information

Comment

Aromatic diamines are used as starting materials for the templated synthesis of nonsymmetric metallosalphen complexes. These are useful in homogeneous catalysis. The non-templated synthesis pathway is also possible (Kleij, Kuil et al., 2005; Kleij, Tooke et al., 2005) even using diamino pyridine in combination with salicyl aldehyde derivatives. Additionaly, partially substituted products like mono Schiff bases are possible to be isolated with good yield under the same experimental conditions.

The title compound, mono Schiff base, was prepared by the non-templated direct condensation of 1,2-diaminopyridine and 3,5-di-tert-buthyl-2-ol-benzaldehide according to a previously described method (Benisvy et al., 2003, 2004).

In the title compound, the central benzene ring is substituted at position 1 with a hydroxyl group, at positions 2 and 4 with tert-buthyl groups, and at position 6 with a [(2-aminopyridin-3-yl)imino]methyl. The vicinity of the hydroxyl and the [(2-aminopyridin-3-yl)imino]methyl substituents leads to an intramolecular hydrogen bond with O1···N1 distance of 2.621 (1) Å. The reported value for the similar molecule, 2-amino-3-salicylideneaminopyridine, is 2.649 (1) Å (Cimerman et al., 1992).

In addition to that intramolecular interaction, the molecules form dimers in the solid state via hydrogen bonds between the amino pyridine fragments, as shown in Figure 2.

Experimental

The compound was prepared by direct interaction between 1,2-diaminopyridine and 3,5-di-tert-butyl-2-ol-benzaldehide (Fig. 3) according to a previously described method (Benisvy et al., 2003, 2004), slighty modified by using ethanol as a solvent, instead of diclorometane and 24 h as reaction time. The synthesis yield was 70%.