Synthesis and crystal structure of 1-(4-{[(E)-3,5-dibromo- 2-hydroxybenzylidene]amino}phenyl)ethanone Oxime

Article abstract of DOI:10.14233/ajchem.2013.14022

The title compound, 1-(4-{[(E)-3,5-dibromo-2-hydroxybenzylidene]amino} phenyl)ethanone oxime, was synthesized by the reaction of 3,5- dibromosalicylaldehyde with 4-amino-phenylethanone oxime in ethanol. The molecule crystallizes in the triclinic system, space group P21/c, with four crystallographically independent molecules in the unit cell. The two benzene rings form a dihedral angle of 21.63°. In the crystal structure, there are a strong intramolecular O2-H2?N2 hydrogen bond between the hydroxyl (O2-H2) group and the Schiff base nitrogen (N2) atom, with the distance between N2 and O2 is 2.580(4) ?. Moreover, a dimer is formed with another adjacent molecule by two pairs of intermolecular O1-H1?N1 hydrogen bonds.

Full text of DOI:10.14233/ajchem.2013.14022

Asian Journal of Chemistry; Vol. 25, No. 7 (2013), 4061-4063
http://dx.doi.org/10.14233/ajchem.2013.14022
Synthesis and Crystal Structure of 1-(4-{[(E)-3,5-dibromo-
2-hydroxybenzylidene]amino}phenyl)ethanone Oxime
*
LI ZHAO , XU-TAO DONG, LI WANG, QIAN CHENG and JI-XING ZHAO
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
*Corresponding author: E-mail: zhaoli_72@163.com
(Received: 7 May 2012;
Accepted: 25 January 2013)
AJC-12755
The title compound, 1-(4-{[(E)-3,5-dibromo-2-hydroxybenzylidene]amino}phenyl)ethanone oxime, was synthesized by the reaction of
3,5-dibromosalicylaldehyde with 4-amino-phenylethanone oxime in ethanol. The molecule crystallizes in the triclinic system, space
group P21/c, with four crystallographically independent molecules in the unit cell. The two benzene rings form a dihedral angle of 21.63º.
In the crystal structure, there are a strong intramolecular O2-H2···N2 hydrogen bond between the hydroxyl (O2-H2) group and the Schiff
base nitrogen (N2) atom, with the distance between N2 and O2 is 2.580(4) Å. Moreover, a dimer is formed with another adjacent
molecule by two pairs of intermolecular O1-H1···N1 hydrogen bonds.
Key Words: Oxime-type compound, Synthesis, Crystal structure.
synthesized according to an analogous method reported earlier
8,9. To an ethanolic solution of 3,5-dibromosalicylaldehyde
(560.2 mg, 2 mmol) was added an ethanolic solution of 4-
aminophenylethanone oxime (300.6 mg, 2 mmol). The mixture
solution was stirred at 328 K for 5 h. After cooling to room
temperature, the precipitate was filtered and washed succes-
sively with ethanol and n-hexane, respectively. The product
was dried under vacuum and obtained orange red microcrystal.
Yield, 77.4 %. m.p. 491-492 K.Anal. calcd. for C15H12N2O2Br2
(%): C, 43.72; H, 2.94; N, 6.80. Found (%): C, 43.98; H, 3.06;
N, 6.63. IR: ν(C=N), 1612 cm-1 and ν(O-H), 3416 cm-1.
Orange-red block-like single crystals suitable for X-ray diff-
raction studies were obtained after about 2 weeks by slow
evaporation from a ethanol/acetone solution of 1-(4-{[(E)-3,5-
dibromo-2-hydroxybenzylidene]amino}phenyl)ethanone
oxime.
X-Ray structure determination: The single crystal of
the title compound, with approximate dimensions of 0.45 mm
× 0.40 mm × 0.33 mm was placed on a Bruker Smart 1000
diffractmeter equipped withApex CCD area detector. The diff-
raction data were collected using a graphite monochromated
MoKα radition (λ = 0.71073 Å) at 298(2) K. The structure
was solved by using the program SHELXS-97 and Fourier
difference techniques and refined by full-matrix least-squares
method on F2 using SHELXL-97. Details of the data collection
and refinements of the title compound are given in Table-1.
The non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were added theoretically. CCDC: 880448.
INTRODUCTION
Schiff base compounds have been playing an important
role in the development of coordination chemistry1,2. During
the past several decades, a large number of Schiff base comp-
lexes have been studied extensively for there facile synthesis
and easily tunable steric position and application3. Many Schiff
base complexes have been structurally characterized4, but only
a relatively small number of oxime-type compounds have been
characterized5-7. Here, we report the synthesis and crystal struc-
ture of a new oxime-type compound 1-(4-{[(E)-3,5-dibromo-
2-hydroxybenzylidene]amino}phenyl) ethanone oxime.
EXPERIMENTAL
3,5-Dibromosalicylaldehyde was purchased from Alfa
Aesar and used without further purification. The other reagents
and solvents were analytical grade reagents from Tianjin
Chemical Reagent Factory. C, H and N analyses were carried
out with a GmbHVariuoELV3.00 automatic elemental analyzer.
IR spectra in the range 400-4000 cm-1 were recorded on a
VERTEX70 FT-IR spectrophotometer using KBr pellets. X-ray
single crystal structure was determined on a Bruker Smart
APEX CCD area detector. Melting points were measured by
the use of a microscopic melting point apparatus made in
Beijing Taike Instrument Limited Company and the thermo-
meter was uncorrected.
1-(4-{[(E)-3,5-dibromo-2-hydroxybenzylidene]amino}-
phenyl)ethanone oxime: 4-Aminophenylethanone oxime was

4062 Zhao et al.
Asian J. Chem.
TABLE-1
CRYSTAL DATA AND REFINEMENT PARAMETERS
FOR THE TITLE COMPOUND
Empirical formula
C15H12N2O2Br2
412.09
298(2) K
0.71073 Å
Formula weight
Temperature
Wavelength
Crystal system
Space group
Monoclinic
P21/c
Cell dimensions
a = 12.2181(11) Å, b = 15.0209(14) Å, c
= 8.6640(7) Å β = 108.232(1)
Volume
1510.3(2) Å3
Z
4
1.812 mg/m3
Fig. 1. Molecule structure of the title compound with atom numbering
scheme. Displacement ellipsoids for non-hydrogen atoms are drawn
at the 30 % probability level
Density (calculated)
Absorption coefficient
F(000)
5.372 mm-1
808
Index ranges
Reflections collected
Independent reflections
-14 ≤ h ≤ 6, -17 ≤ k ≤ 17, -9 ≤ l ≤ 10
7517 / 2651 [R(int) = 0.0751]
1402
Data/restraints/parameters 2651/0/191
Goodness of fit indicator
R [I > 2σ(I)]
1.011
R1 = 0.0514, wR2 = 0.1032
Largest diff. peak and hole 0.631 and -0.559 e. Å
RESULTS AND DISCUSSION
Fig. 2. Dimer formed by the title compounds showing the intramolecular
and intermolecular O-H···N hydrogen bonds (dashed lines). For
clarity, the H atoms not involved in the interactions have been
omitted
X-ray crystallographic analysis revealed the crystal struc-
ture of the title compound (Fig. 1). Selected bond distances
and angles are listed in Table-2. The crystal structure of the
title compound is built up by only the C15H12Br2N2O2 mole-
cules and all bond lengths and angles are in normal ranges.
The molecule crystallizes in the triclinic system, space group
P21/c, with four crystallographically independent molecules
in the unit cell. The two benzene rings form a dihedral angle
of 21.63º.
TABLE-3
INTRAMOLECULAR AND INTERMOLECULAR O-H···N
HYDROGEN-BONDING DATA [Å, º]
D-H···A
O1-H1···N1
O2-H2···N2
d(D-H)
0.82
0.82
d(H···A)
2.04
1.86
d(D···A)
2.769(3)
2.580(4)
∠D-H···A
148
147
In the crystal structure, there is a strong intramolecular
O2-H2···N2 hydrogen bond between the hydroxyl (O2-H2)
group and the Schiff base nitrogen (N2) atom, with the
distance between N2 and O2 is 2.580(4) Å. Moreover, a
dimer is formed with another adjacent molecule by two pairs
of intermolecular O1-H1···N1 hydrogen bonds (Table-3,
ACKNOWLEDGEMENTS
This work was supported by the Foundation of Preparative
Research of Jin-Chuan Corporation (No. 209125-1104) is
gratefully acknowledged.
Fig. 2)10-12
.
TABLE-2
SELECTED BOND LENGTHS (Å) AND ANGLES (º) FOR THE TITLE COMPOUND
Bond
Lengths
1.873(6)
1.911(6)
1.274(8)
1.387(6)
1.288(7)
1.411(7)
1.349(7)
1.490(9)
Angles
113.0(5)
121.9(6)
115.9(6)
123.7(6)
120.4(6)
116.5(6)
121.7(6)
121.8(6)
121.5(6)
121.0(6)
Bond
C(2)-C(3)
C(3)-C(8)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(7)-C(8)
Lengths
1.490(9)
1.371(9)
1.394(8)
1.367(8)
1.387(8)
1.372(8)
1.374(8)
1.448(8)
Angles
118.1(6)
117.0(6)
124.8(6)
120.7(6)
122.2(6)
120.8(6)
118.2(6)
120.5(6)
121.2(6)
119.5(6)
Bond
Lengths
1.400(8)
1.414(8)
1.386(8)
1.398(8)
1.372(9)
1.344(9)
Br(1)-C(12)
Br(2)-C(14)
N(1)-C(2)
N(1)-O(1)
N(2)-C(9)
N(2)-C(6)
O(2)-C(11)
C(1)-C(2)
Bond
C(2)-N(1)-O(1)
C(9)-N(2)-C(6)
N(1)-C(2)-C(3)
N(1)-C(2)-C(1)
C(3)-C(2)-C(1)
C(8)-C(3)-C(4)
C(8)-C(3)-C(2)
C(4)-C(3)-C(2)
C(5)-C(4)-C(3)
C(4)-C(5)-C(6)
C(10)-C(15)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
C(14)-C(15)
C(9)-C(10)
Bond
Bond
Angles
121.5(6)
119.0(6)
121.3(6)
119.2(5)
119.3(5)
118.2(6)
122.0(6)
119.7(5)
118.2(5)
121.3(6)
C(7)-C(6)-C(5)
C(7)-C(6)-N(2)
C(5)-C(6)-N(2)
C(6)-C(7)-C(8)
C(3) -C(8)-C(7)
N(2)-C(9)-C(10)
C(15)-C(10)-C(11)
C(15)-C(10)-C(9)
C(11)-C(10)-C(9)
O(2)-C(11)-C(12)
O(2)-C(11)-C(10)
C(12)-C(11)-C(10)
C(11)-C(12)-C(13)
C(11)-C(12)-Br(1)
C(13)-C(12)-Br(1)
C(14)-C(13)-C(12)
C(15)-C(14)-C(13)
C(15)-C(14)-Br(2)
C(13)-C(14)-Br(2)
C(14)-C(15)-C(10)

Vol. 25, No. 7 (2013)
Structure of 1-(4-{[(E)-3,5-dibromo-2-hydroxybenzylidene]amino}phenyl)ethanone Oxime 4063
7. W.K. Dong,Y.X. Sun,Y.P. Zhang, L. Li, X.N. He and X.L. Tang, Inorg.
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