0022-4766/06/4705-0998 2006 Springer Science+Business Media, Inc.

998
Journal of Structural Chemistry. Vol. 47, No. 5, pp. 998-1001, 2006
Original Russian Text Copyright 2006 by L. Xu, Yu. V. Mironov, X. Qi, and S.-J. Kim
A NEW Co(II) COMPLEX WITH N,O-DONOR SCHIFF BASE:
SYNTHESIS, STRUCTURE AND CHARACTERIZATION
L. Xu,
1,2
Yu. V. Mironov,
2,3
X. Qi,
2
and S.-J. Kim
2
UDC 538.736
A new Co(II) complex with tridentate Schiff base ligand with a N,N,O donor set has been synthesized and
characterized by single X-ray technique and spectroscopic techniques. The thermochemical properties have
been studied. X-ray structure analysis of the title compound Co(II)L
2
[HL = 2-methyl-6-(2'-hydroxy-
benzylideneamino)pyridine] shows that the polyhedron around Co(II) is a distorted tetrahedron, and the
self-assembly via intermolecular tt interactions leads to a three-dimensional network. Crystal data for
the title complex C
26
H
22
CoN
4
O
2
: Monoclinic, space group Ia, a = 11.741(7) , b = 8.149(5) , c =
22.764(16) , | = 98.530(12), V = 2154(2)
3
, Z = 4.
Keywords: Schiff base ligand, Co(II) complex, crystal structure, weight loss.
Multidentate Schiff base ligands and their metal complexes have been extensively studied for many years [1-4].
These complexes play an important role in the development of coordination chemistry [5-6] and possess characterized by
important properties, such as biological activity [7-8], catalytic activity [9] and photochromic properties [10]. The Schiff base
ligands, such as bis-(salicylaldehyde)ethylenediimine (salenH
2
), N-salicylidene-2-hydroxyaniline (shaH
2
) and salicyli-
deneimine-2-anisole (salanH), have catalytic characteristics, especially for epoxidation reactions [11], and their metal
complexes were found to provide important effect on biological systems [12]. In recent years, we have been interested in
Schiff base ligands [13], their metal complexes [14] and cluster complexes [15]. As a continuation of our previous work, the
structure of the title new Co(II)Schiff base complex is reported here.
Experimental. All commercially available chemicals were of analytical grade and used without further purification.
Elemental analyses for C, H, N were performed on Perkin-Elmer 240C Instrument. Infrared spectra were recorded in the
range of 400-4000 cm
1
on a BIO RAD FTS 135 spectrometer. Thermal analysis was carried out on a SETARAM TG-
DTA/DSC thermal analyzer under argon atmosphere with a heating rate of 10 C/min.
1
H NMR spectra was recorded on a
Bruker 250 in CDCl
3
with TMS as internal standard.
Synthesis. 1. Schiff base ligand L [2-methyl-6-(2'-hydroxybenzylideneamino)pyridine] (see schema) was synthesized
by condensation of salicylaldehyde and 6-methyl-2-aminopyridine as follows: a mixture of salicylaldehyde (2 mmol) and 6-
methyl-2-aminopyridine (2 mmol) in EtOH (10 ml) was refluxed for 1.5 h under N
2
atmosphere. A yellow product collected
1
Information College of Science and Technology, Nanjing Forestry University, Nanjing 210037, P. R. China.
2
Department of Chemistry and Division of Nano Science, Ewha Womans University, Seoul 120-750, Seoul, Korea;
xuliqby@163.com, sjkim@ewha.ac.kr.
3
A. V. Nikolaev Institute of Inorganic Chemistry, Novosibirsk. Translated from
Zhurnal Strukturnoi Khimii, Vol. 47, No. 5, pp. 1003-1006, September-October, 2006. Original article submitted April 25, 2006.
999
after removing solvent was purified by recrystallization from EtOH.
1
H NMR (CDCl3, ppm): 1.57, 3H; 9.44, 1H;
7.66-6.68, 7H.
2.Co(ClO
4
)6H
2
O (0.5 mmol) was dissolved in a minimum amount of EtOH and then added into ethanol solution of
L (1.0 mmol). During this operation, the colour of the solution changed to orange-red, and than slowly to brown. It was
allowed to stand at room temperature overnight after refluxing for 75 min. The yellow solid product was collected by
filtration and washed with EtOH. Single crystals suitable for X-ray diffraction were obtained by evaporation of the filtrate.
(Yield: 68%). Elemental analysis: found, %: C 64.90, H 4.58, N 11.68; calculated for C
26
H
22
CoN
4
O
2
, %: C 64.87, H 4.61,
N 11.64.
Crystallographic studies. Single-crystal X-ray diffraction data were collected on a yellow block crystal of the title
compound with the use of graphite-monochromotized MoK
o
radiation ( = 0.71073 ) at 298(2) K on a Bruker Smart AXS
diffractometer with the program SMART. [18] Crystal decay was monitored by recollecting 50 initial frames at the end of
data collection. Cell refinement and data reduction were carried out with the use of the program SAINT. [18] The structure
was solved by direct methods and difference Fourier maps. Full matrix least-squares refinements were carried out with
anisotropy thermal parameters for all nonhydrogen atoms. Hydrogen atoms were placed in calculated positions with CH
distances of 0.93-0.97 with isotropic thermal parameters and were included in the refinement in riding motion
approximation with U
iso
= 1.2U
eq
(C) or U
iso
= 1.5U
eq
(C), where C is a parent C-atom to which the H-atom is attached.
Crystal data and refinement parameters: C
26
H
22
CoN
4
O
2
(M = 481.41), monoclinic, space group Ia, a = 11.741(7) ,
b = 8.149(5) , c = 22.764(16) , | = 98.530(12), V = 2154(2)
3
, Z = 4, (MoK
o
) = 27.495 mm
1
, d
calc
= 1.485 g/cm
3
.
Final R indices: R = 0.054 and wR
2
= 0.106 for 1729 observed reflections with intensities greater than 2o (refinement on F
2
),
280 parameters, 2 restraints; R = 0.100 and wR
2
= 0.126 for all 2631 reflections collected; GOOF = 0.984.
Results and discussion. Molecular and crystal structure. The structure of the title complex is shown in Fig. 1,
selected bond distances and angles are given in Table 1. In the title compound, Co(II) center is chelated by two Schiff base
ligands and has a distorted tetrahedron coordination geometry. Two imine N atoms (N2 and N4) and two O atoms (O1 and
O2) from the two ligands define the four vertexes of the tetrahedron. The average chelate bite angle in the six-membered
rings formed by imine-N and phenolate-O about of 93.87 is far from the ideal value of 10928''. The long distances of Co
N1 (2.708(16) ) and CoN3 (2.625(16) ) suggest that N atoms (N1 and N3) of pyridine rings are not coordinated to
Fig. 1. Molecular structure of the title complex.
Displacement ellipsoids 50% probability and the
atom numbering scheme are shown.
1000
TABLE 1. Selected Bond Lengths () and Angles (deg) for Co(II)L
2
C2N1 1.29(3) C19N4 1.45(2) N3C19N4 103.9(16) O2Co1N2 109.8(6)
C6N1 1.33(2) C20N4 1.33(2) O2Co1O1 108.05(17) O2Co1N4 94.9(6)
C6N2 1.39(2) C26O2 1.27(2) O1Co1N2 92.7(6) N2Co1N4 137.5(2)
C7N2 1.27(3) Co1O2 1.923(14) O1Co1N4 112.3(6) C7N2C6 122.8(18)
C13O1 1.33(2) Co1O1 1.964(12) C2N1C6 124.3(17) C6N2Co1 111.9(12)
C15N3 1.41(2) Co1N2 1.972(16) C7N2Co1 125.2(15) C20N4C19 121.3(16)
C19N3 1.36(2) Co1N4 1.978(13) C19N3C15 110.5(16) C19N4Co1 113.4(12)
C20N4Co1 125.2(13) C26O2Co1 126.6(13)
C13O1Co1 125.6(13)
Fig. 2. The packing of the complex in the unit cell (a); the geometry of tt intermolecular interactions (b).
Co(II), which is quit different from Ni compound (NiL
2
) [21] with the same ligand. In the Ni compound (NiL
2
), L is a
tridentate ligand and gives octahedral NiL
2
.
Atoms O1, N2, C1, C7 and two aromatic rings (N1C2, C3, C4, C5, C6 and N2C8, C9, C10, C11, C12, C13) are
planar with average deviation of 0.076 , and atoms O2, N4, C14, C20 and other two aromatic ring (N3C15, C16, C17,
C18, C19 and N4C21, C22, C23, C24, C25, C26) are planar with average deviation of 0.069 . The dihedral angle between
the two planes is 75.31(16).
There are weak tt intermolecular interactions between phenyl rings and pyridyl rings; t-stacked rings are parallel
with the distances of 3.557(12) and 3.610(12) . The self-assembly via intermolecular t-t interactions leads to a three-
dimensional network (Fig. 2).
Infrared spectral characteristics. In infrared spectrum, a strong peak at ca. 1600 cm
1
is attributable to the imine
[16]. There are two bands, at 435 cm
1
and 524 cm
1
from CoO and CoN bonds, respectively [17], which suggest that
Schiff base ligand coordinated to cobalt atom via phenolic oxygen and nitrogen atoms. Medium to strong bands in the range
of 1557~1443 cm
1
are, possibly, due to vibrations associated with the aromatic C=C fragments of the ligands [22].
Thermal analysis. In order to give more insight into the structure of the complex, the thermal study of the complex
was carried out from 50C to 700C. The TG curve exhibits multi-stage weight loss. At the first stage, from 105C to 140 C,
the weight loss is ca. 4%. The most reasonable explanation for this is the presence of same amounts of water in the bulk mass
of compound. Then starting from 308C begins the slow decomposition of the compound up to 700C with the summary
weight loss of about 59%. The resulting residue is presumed to be CoO (15.6%) and the part of first ligand (CH
3
)C
5
H
3
N(N=)
(22%), which means that Schiff base ligands are not decomposed completely up to 700C. Similarly, for compound
W
2
O
5
(shaH
2
)
2
[17], 22.61% of Schiff base ligand (N-salicylidene-2-hydroxyaniline) was not decomposed up to 735C.
1001
This work was supported by the Korea Research Foundation Grant (KRF 2004 005 C00093), Research
Innovation Program of Nanjing Forestry University, P. R. China (CX03-070-1) and Research Foundation for Talent of
Nanjing Forestry University, P. R. China.
Supplementary material. CCDC 279885 contains the supplementary crystallographic data for this paper. These data
can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data
Center (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033; e-mail: deposit@ccdc.cam.ac.uk].
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