(E)-4-[(4-Amino-5-bromo­pyridin-3-yl)­iminometh­yl]phenol

Mingjian Cai; Mingjie Zhang; Yongliang Hu

doi:10.1107/S160053680800812X

. 2008 May 10;64(Pt 6):o1053. doi: 10.1107/S160053680800812X

(E)-4-[(4-Amino-5-bromopyridin-3-yl)iminomethyl]phenol

Mingjian Cai ^a, Mingjie Zhang ^a,^*, Yongliang Hu ^a

PMCID: PMC2961383 PMID: 21202572

Abstract

In the molecule of the title compound, C₁₂H₁₀BrN₃O, the pyridine and benzene rings are oriented at a dihedral angle of 34.93 (3)°. Intramolecular N—H⋯N and N—H⋯Br hydrogen bonds result in the formation of two non-planar five-membered rings. In the crystal structure, intermolecular O—H⋯N and N—H⋯O hydrogen bonds link the molecules to form a three-dimensional network.

Related literature

For general background, see: Liu et al. (2002 ▶).

Experimental

Crystal data

C₁₂H₁₀BrN₃O
M _r = 292.14
Monoclinic,
a = 4.9607 (10) Å
b = 15.586 (3) Å
c = 14.906 (3) Å
β = 95.65 (3)°
V = 1146.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.57 mm⁻¹
T = 113 (2) K
0.10 × 0.08 × 0.06 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.717, T _max = 0.814
14191 measured reflections
2739 independent reflections
2123 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.100
S = 1.02
2739 reflections
163 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800812X/hk2438sup1.cif

e-64-o1053-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800812X/hk2438Isup2.hkl

e-64-o1053-Isup2.hkl^{(134.5KB, 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⋯N1ⁱ	0.82	1.88	2.688 (3)	167
N3—H3A⋯Br1	0.877 (18)	2.72 (3)	3.125 (4)	110.0 (19)
N3—H3A⋯O1ⁱⁱ	0.877 (18)	2.54 (2)	2.967 (5)	111.0 (19)
N3—H3B⋯N2	0.889 (16)	2.28 (3)	2.700 (5)	109 (2)

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

supplementary crystallographic information

Comment

Schiff bases, as substrates, are important organic intermediates. Their recent applications in asymmetric catalytic hydrogenation, asymmetric chemical reduction and oxidation and asymmetric alkylidation of carbon atom, as well as reactions with Lawessen regent are very active (Liu et al., 2002). We have recently synthesized the novel title compound, (I), and report herein its crystal structure.

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges. Rings A (N1/C1–C5) and B (C7–C12) are, of course, planar and the dihedral angle between them is A/B = 34.93 (3)°. The intramolecular N—H···N and N—H···Br hydrogen bonds (Table 1) result in the formation of two non-planar five-membered rings; C (N2/C4/C5/N3/H3B) and D (Br1/C1/C5/N3/H3A).

In the crystal structure, intermolecular O—H···N and N—H···O hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

5-bromopyridine-3,4-diamine (1.88 g, 10 mmol) was added to a solution of 4-hydroxybenzaldehyde (1.22 g, 10 mmol)in MeOH (50 ml). The solution was refluxed for 10 h, and then dried over magnesium sulfate, filtered and the volatiles were removed under reduced pressure. The crude product was further purified and recystallized from MeOH affording yellow crystals of (I) (yield; 70%).