2,3-Dibromo-6-meth­oxy-4-[(phenethyl­amino)­methyl­idene]cyclo­hexa-2,5-dien-1-one methanol monosolvate

Rong-Bao Ge; Yue-Hu Chen; Feng-Ting Wang; Shuang-Shuang Wang; Shao-Song Qian

doi:10.1107/S1600536811052895

. 2011 Dec 14;68(Pt 1):o117. doi: 10.1107/S1600536811052895

2,3-Dibromo-6-methoxy-4-[(phenethylamino)methylidene]cyclohexa-2,5-dien-1-one methanol monosolvate

Rong-Bao Ge ^a, Yue-Hu Chen ^a, Feng-Ting Wang ^a, Shuang-Shuang Wang ^a, Shao-Song Qian ^a,^*

PMCID: PMC3254464 PMID: 22259404

Abstract

In the title compound, C₁₆H₁₅Br₂NO₂·CH₄O, the mean planes of the substituted cyclohexa-2,5-dien-1-one and phenyl rings are almost parallel [dihedral angle = 7.84 (4)°]. The crystal packing is stabilized by N—H⋯O hydrogen bonds generating infinite [101] chains. The methanol solvent molecules are connected with the main species by O—H⋯O interactions.

Related literature

For background to bromophenols and their bioactivity, see: Liu et al. (2011 ▶). For related structures, see: Palmer et al. (1973 ▶); Li et al. (1995 ▶); Huang et al. (2006 ▶). For structural and theoretical aspects on the keto-enol equilibrium of salicylaldehyde Schiff bases, see: Chatziefthimiou et al. (2006 ▶).

Experimental

Crystal data

C₁₆H₁₅Br₂NO₂·CH₄O
M _r = 445.15
Monoclinic,
a = 8.752 (6) Å
b = 16.308 (10) Å
c = 13.001 (8) Å
β = 104.047 (6)°
V = 1800 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.52 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.337, T _max = 0.406
8282 measured reflections
3292 independent reflections
1674 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.133
S = 1.00
3292 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811052895/zq2143sup1.cif

e-68-0o117-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052895/zq2143Isup2.hkl

e-68-0o117-Isup2.hkl^{(161.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811052895/zq2143Isup3.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
N1—H1⋯O1ⁱ	0.86	1.93	2.731 (7)	154
O3—H3⋯O1ⁱⁱ	0.82	2.05	2.786 (8)	150

Open in a new tab

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

Acknowledgments

This project was sponsored by the ShanDong Province Science & Technology Innovation Foundation (People’s Republic of China).

supplementary crystallographic information

Comment

The 2,3-dibromo-4-hydroxy-5-methoxybenzaldehyde acts as an important precursor for the synthesis of bromophenols, which have been reported to possess a variety of biological activities (Liu et al., 2011). As an extension of our work on the 2,3-dibromo-4-hydroxy-5-methoxybenzaldehyde, the title compound was synthesized by condensing 2,3-dibromo-4-hydroxy-5-methoxybenzaldehyde with phenethylamine, and attempts to investigate its biological activities were carried out.

In the crystal structure of the title compound, C₁₆H₁₅Br₂NO₂.CH₄O, the mean planes of the substituted cyclohexa-2,5-dien-1-one and phenyl rings are almost parallel [dihedral angle = 7.84 (4)°]. Difference Fourier maps clearly showed that the N1 atom is protonated rather than the O1 atom indicating a methylidenecyclohexa-2,5-dien-1-one skeleton (Palmer et al., 1973; Huang et al., 2006; Chatziefthimiou et al., 2006). The N1 and O1 atoms are connected via a short intermolecular N—H···O hydrogen bond [N1···O1ⁱ = 2.731 (7) Å; (i) = x - 1/2, -y + 3/2, z - 1/2] generating infinite one-dimensional [101] chains (Chatziefthimiou et al., 2006). The solvent molecules of methanol are connected with the main species by O3—H3···O1ⁱⁱ interactions [O3···O1ⁱⁱ = 2.786 (8) Å; (ii) = x - 1, y, z].

Experimental

2,3-Dibromo-4-hydroxy-5-methoxybenzaldehyde (0.31 g) and phenethylamine (0.12 g) were dissolved in methanol (20 ml). The mixture was stirred at room temperature for 30 min to give a clear solution. Keeping the solution in air for 5 days, yellow block-shaped single crystals suitable for X-ray diffraction analysis were obtained at the bottom of the vessel.