Journal of Molecular Structure 1034 (2013) 183188

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Synthesis, structural, electronic and magnetic studies of [Cu(II)(saleanN3H3)]

Ma. Guadalupe Quintero-Tllez a, Mara de Jess Rosales Hoz b, Sylvain Berns c, Rafael Zamorano-Ulloa d,
Daniel Ramrez-Rosales d, Jos Luis Alcntara-Flores e, Yasmi Reyes-Ortega e,
a

Facultad de Ciencias Fsico Matemticas, Universidad Autnoma de Puebla, CU San Manuel, Puebla, Pue. 72570, Mexico
Departamento de Qumica, Centro de Investigacin y de Estudios Avanzados, Instituto Politcnico Nacional, Av. Instituto Politcnico Nacional 2508, San Pedro Zacatenco, DF,
Mxico 07360, Mexico
c
Facultad de Ciencias Qumicas, UANL, Guerrero y Progreso S/N, Col. Trevio, Monterrey, NL 64570, Mexico
d
Departamento de Fsica, ESFM, IPN, Av. Instituto Politcnico Nacional S/N, Edif 9, UP Zacatenco, Col. San Pedro Zacatenco, DF, Mxico 07738, Mexico
e
Centro de Qumica, Instituto de Ciencias, Edif 103F, Complejo de Ciencias, CU San Manuel, Puebla, Pue. 72570, Mexico
b

h i g h l i g h t s
" [Cu(II)(saleanN3H3)] shows a interesting 1D zigzag chains supramolecular structure.
" 1D zigzag chains supramolecular structure correlate well with the magnetic results.
" UVVis/IR spectra of [Cu(II)(saleanN3H3)] link perfectly with the Cu(II) coordination.
" ESR at 300 K/77 K spectra and J value are consistent with antiferromagnetic interaction.
" The 1D chain magnetic model ts well the magnetic data of [Cu(II)(saleanN3H3)].

a r t i c l e

i n f o

Article history:
Available online 12 September 2012
Keywords:
Cu(II) complex
Magnetic studies
1D-chain
Crystal structure
UVVis
IR studies

a b s t r a c t
[Cu(II)(saleanN3H3)] 1 (saleanN3H3 = N,N0 0 -bis(2-oxybenzyl)-diethylenetriamine dianion) is obtained by
direct synthesis. 1 crystallizes in orthorhombic space group Pbca. The crystalline network features
one-dimensional (1D) columns of zigzag chains well separated in the [1 0 0] direction. Each column is
a supramolecular structure, with triangles formed among the Cu(II) ions of the chain. Local Cu(II) geometry in 1 is intermediate between square-pyramidal and trigonalbipyramidal conformations. UVVis
spectrum, IR, and NMR 1H spectra prove the formation of 1. X-band ESR spectra at 77 K/300 K of a polycrystalline sample show a broad singlet with temperature independent values g||/g\ = 2.1967/2.1074. An
area ratio A77/A300 of 1.63 suggests an incomplete antiferromagnetic (AF) coupling of the copper ions. The
X-band ESR spectra at 77 K in solution show typical hyperne interactions of monomer paramagnetic
copper ions. The linear chain model ts well the magnetic susceptibility data vs temperature from 2 to
300 K and is consistent with antiferromagnetic exchange interaction.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The chemistry of metal complexes with Schiff base ligands has
attracted sustained and extensive attention due to biological modeling and applications, designing molecular ferromagnets, catalysis,
liquid crystals and applications in the eld of optoelectronic technologies [14]. By reducing Schiff bases, a new class of amine ligands
can be obtained. As compared to the corresponding Schiff bases, this
class of ligands has better conformational exibility and better ability to form hydrogen bonds involving the amino groups [5]. On the
other hand, studies of the properties of the Cu(II)-phenolato compounds are important because of their involvement in a range of biological and catalytic processes [6,7]. An interesting synthetic
Corresponding author. Fax: +52 22 295551.
E-mail address: yasmi.reyes@correo.buap.mx (Y. Reyes-Ortega).
0022-2860/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.08.041

method is the direct synthesis, which is based on the use of zerovalent metals as starting materials, providing a suitable environment
for the synthesis of different complexes of Cu(II). It has resulted a
suitable way for preparing complexes of Cu(II) without residual salt.
This is important in order to reach better conditions for crystallization process of the synthesized complex [811]. In this work, the
synthesis, the structural, electronic and magnetic studies of the
[Cu(II)(saleanN3H3)] 1 complex are presented.
2. Experimental
2.1. Materials and instrumentation
The N,N00 -bis(2-hydroxybenzyl)-diethylenetriamine (saleanN3H5)
ligand is prepared as previously reported [12,13]. All reagents for
synthesis and analyses were of analytical grade.

184

Ma. Guadalupe Quintero-Tllez et al. / Journal of Molecular Structure 1034 (2013) 183188

2.2. Synthesis
The copper complex has been prepared by direct synthesis
[811]. Equimolar amounts (1.15 mmol) of copper and neutral
base saleanN3H5 in DMSO (3.7 ml) were placed in a ask and the
mixture was kept under magnetic stirring at 80 C for 26 h and
then ltered. Light green single-crystals of [Cu(II) {N,N00 -bis(2oxybenzyl)-diethylenetriamine}] were obtained by crystallization
(41.3 mg, 10%), mp 195 C (from MeOH). UVVis kmax/e (MeOH)
nm/mM1cm1: 216/24569, 237/13593, 277/9145, 382/779, 598/
156. IR mmax (KBr) cm1: 3303 (NH), 468 and 420 (CuN), 447
(CuO). X-band ESR polycrystalline sample at 300/77 K g|| =
2.1967/2.1967, g\ = 2.1074/2.1074; A77K/300K = 1.63; X-band ESR
MeOH
frozen-solution
sample,
ca = 17 mM g|| = 2.2153,
g\ = 2.0563, A|| = 192.8  104 cm1. Mass spectrum (FAB+): m/z
377 (M+, 45%).
2.3. Instruments
Melting point is obtained on a SEV melting point meter apparatus. UVVis spectrum (1901100 nm) is recorded in a Shimadzu
UV-3100S spectrophotometer in methanol solution for 1 of ca
0.13 mM and 0.707 mM at 25 C, respectively. Calibration curves
at concentration used in this study and at kmax of 268 nm,
378 nm and 600 nm show an absorbance-concentration linear
relation satisfying the LambertBeer law. IR spectrum (4000
400 cm1) is obtained in a Nicolet Magna-IR 750 spectrophotometer using KBr pellet. The 1H NMR spectra is recorded at 25 C on a
JEOL ECLIPSE 400 MHz spectrometer using methanol-d solutions in
the 100 to 100 ppm range. Powder X-band ESR spectra at 300 K
and 77 K and methanol solutions of 1 at four different concentrations ca from 17 mM to 41 mM are recorded on a JEOL JES-RES
3X spectrometer. Magnetic measurement is recorded on a Quantum Design MPMS SQUID magnetometer from 2 K to 300 K.

Fig. 1. Molecular and crystal structures of 1. (a) ORTEP-like view of 1, with

displacement ellipsoids for non-H atoms at 30% probability level. (b) View of the
arrangement of molecules in the [1 0 0] direction, with intermolecular NAH  O
hydrogen bonds and NAH  p interactions represented as dashes lines. H atoms not
involved in hydrogen bonding have been omitted for clarity.

2.4. X-ray crystallographic studies

A green crystal of 1 with 0.32  0.15  0.1 mm3 size is mounted
at random orientation on a glass ber. Data are collected on a EnrafNonius
CCD
diffractometer
using
Mo Ka
radiation
(k = 0.71073 ) at 295(2) K; programs used solve and rene the
structure: SHELXS-97 [14] and SHELXL-97. The structure of 1 is
solved by direct methods and rened by full-matrix least squares
on F2. Theta range for data collection 2.0427.49; reections collected 13550; independent reections 3591 [R(int) = 0.0618]; completeness to theta = 27.49, 91.5%; zero restraints; absorption
correction: semi-empirical from equivalents. Max. and min. transmission: 0.95 and 0.74. H-atom parameters constrained. All H
atoms were placed in idealized positions, and were allowed to ride
on their carrier atoms, with CAH bond lengths xed to 0.93 (aromatic CH) and 0.97 (methylene CH2). The atomic coordinates
have been deposited with the Cambridge Crystallographic Data
Centre. The coordinates can be obtained, on request from the
Director, Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK. Deposition number: CCDC 826049.
3. Results and discussion
3.1. Crystal structure
The neutral complex [Cu(II)(saleanN3H3)] 1 is built from one
unit of [saleanN3H3]2 where all heteroatoms of the base are coordinated to the Cu(II) ion, which displays a highly distorted pentacoordinated structure, Fig. 1a. The packing index value for 1 is
67.1% and the complex is isomorphous to the Zn(II) analogue [5].

Fig. 2. Crystal structure of 1 viewed down the [0 0 1] direction. All C-bonded H

atoms have been omitted for clarity, and dashed lines represent NAH  O
intermolecular hydrogen bonds.

Relevant crystallographic data of 1 are listed in Table 1. Addison

and co-workers [15] reported the trigonality index as s = (b  a)/
60 with a value of s = 1 when the structure is a perfect trigonal
bipyramidal (tbp), and with a value of s = 0 when the structure is
perfectly square pyramidal (sp). Molecular structure of 1 displays
s = 0.51, in the middle of the two structures, tbp and sp, which
shows that 1 has a highly distorted structure.

185

Ma. Guadalupe Quintero-Tllez et al. / Journal of Molecular Structure 1034 (2013) 183188

(b)

2
2
dx-y
dz2
dxz, yz

898 nm

695 nm

330 nm
642 nm

0.06

627 nm

1.5

216 nm

0.12

Absorbance

Absorbance

3.0

237 nm

(a)

0.00

600

750

900

381 nm

dxy
1050

(nm)
0.00

200

400

600

800

1000

(nm)

(c)

Fig. 3. (a) UVVis spectrum of 1. Inset shows the simulation of the dd transitions with four Gaussian functions at kmax of 627, 642, 695 and 898 nm. The experimental curve (solid
line) is offset by +0.005 absorbance units in order to match the simulated curve (dashed line). (b) Molecular orbital diagram corresponding to sp geometry. (c) IR spectrum of 1.
Table 1
Summary of crystal data, intensity data collection and structure renement of 1.
Empirical Formula

CuC18H23N3O2

Formula weight
Crystal system
Space group
Crystal size (mm3)
Crystal color and shape
a ()
b ()
c ()
Volume (3)
Z
q(calcd) (Mg/m3)
F000
Theta range for data collection
Temperature (K)
Reections collected
Independent reections
Rint
Parameters
Goodness-of-t on F2
Final R ndices [I>2sigmaI]a
R indices (all data)

376.92
Orthorhombic
Pbca
0.32 0.15 0.1
Green block
9.5603(6)
17.9503(13)
19.9588(16)
3425.0(4)
8
1.454
1576.0
2.04 to 27.49
295(2)
13550
3591
0.0618
221
1.081
R1 = 0.0567, wR2 = 0.1307
R1 = 0.1290, wR2 = 0.1663

R1

r
P
P 2 22
wF 0 F c
jjF 0 jjF c jj
P
P
, wR2
2 2
jF j
0

wF 0

20

15

10

-5

ppm

100

80

60

40

20

-20

-40

ppm
Fig. 4. 1H NMR spectrum of 1.

-60

-80

186

Ma. Guadalupe Quintero-Tllez et al. / Journal of Molecular Structure 1034 (2013) 183188

Fig. 5. One way of modeling the magnetic exchange interactions is to consider the trapezoid and triangles pathways along 1D-chains for 1. Separations are given in (top)
and angles in (bottom). A and A0 are dummy atoms placed on the centroids of noncovalent intermolecular separations (N1  O1) and (N2  O2).

Fig. 3a shows the UVVis spectrum of 1 in solution with one

broad band which corresponds to dd transition at 600 nm. This
band is consistent with that of other similar ve-coordinated Cu(II)
compounds reported with sp geometry Fig. 3b [11,2127]. Spectrum shows two bands of charge transfer transitions, one at
kmax = 382 nm (e = 779 mM1 cm1) p ? d ligandmetal transition,
other at 330 nm d ? p metalligand transition. At 216 nm
(e = 24569 mM1 cm1) occurs the p ? p transition, and at 237,
277 nm (e = 13593, 9145 mM1 cm1) the n ? p transitions, both
characteristic of saleanN3H5 [28]. Spectral data of 1 are summarized in Table 2 and shows molar absorptivity and oscillator
strength values typical of transitions where parity forbidden Laporte selection rules are relaxed by lowered symmetry [2932].
The dd band is satisfactorily tted with four Gaussian functions.
Oscillator strengths, f, of each Gaussian band is calculated from

Table 2
Assignments of the optical spectra of 1.

3.3. 1H NMR spectroscopy

The 1H NMR spectrum of 1 is typical of paramagnetic compounds characterized by base line deformation due to the efcient
nuclear relaxation of Cu(II) ions [11,35] The isotropic chemical
shifts observed in the spectrum are broadened either by the dipolar
relaxation of protons which are at 45 of the ion, and/or by the
contact relaxation of protons belonging to ligand residues with
relaxation times shorter than 5 ns [11,35,36]. Chemical shifts for
1 appear from 100 to 100 ppm and it is not possible to quantify
and to assign the proton signals, Fig. 4.
3.4. Magnetic behavior
The MYM bridging angle, h, with Y atom bridge, is a key
structural parameter. For h, the angles close to 90 or less favor
minimum overlap, leading to ferromagnetic interactions owing to
accidental orthogonality of the orbitals [37]. For CuAOACu = h
0.20
1.0

0.8
0.10
0.6

0.00

k(nm)

Dm1/2(nm)

e(cm2/mmol)

627
642
695
898

102.69
326.32
179.31
239.53

26.82
80.42
41.28
24.20

1.269E-5
1.209E-4
3.412E-5
2.672E-5

MT (emu K/mol)

3.2. UVVis, IR spectroscopies

R
the relationship f = 4.325  109 e(m)dm  4.610  109emaxDm1/2;
where emax is the molar absorptivity of the peak maximum and
Dm is half the intensity bandwidth [30,33]. The four Gaussian
bands (Fig. 3a) have been assigned to the dx2 y2 ! dz2 ; dxz ; dyz ; dxy ,
positive hole transitions for sp, and dx2 y2 ! dxy ; dz2 ; dxz ; dyz positive
hole transitions for tbp structure (Fig. 3b) [34]. Far IR spectrum of 1
(Fig. 3c) shows saleanN3H5 typical vibrations m/cm1 1591 (C@C)
and 3303 (NH) [26]. Metalligand vibrations are observed at
m/cm1 447 (CuO), two bands 420 and 468 (CuN), in agreement
with the X-ray structure determination [10,11,19,34].

M (emu/mol)

The apical bond distances values Cu(1)N(1) = 1.998(4) and

Cu(1)N(2) = 2.017(4) are shorter than the equatorial distance
value Cu(1)N(3) = 2.217(4) , showing a less common Cu(II) axial
compression, bringing to the more electronegative oxygen groups
to occupy the equatorial positions and breaking the Benn rule
[16]. Fig. 1a shows the ve-members CuN2C2 chelato ring highly
distorted as reected in the torsion angles. One chelato ring formed
by Cu1, N2, N3, C10 and C11 shows a torsion angle of 25.6(4),
and the another chelato ring formed by Cu1, N1, N3, C8 and C9
shows the torsion angle of 55.5(4).
Dipolar Coulomb interactions between mononuclear molecules
are observed through N(2)H(2A)  O(2) and N(1)H(1A)  O(1),
forming regular chains in a 1D-supramolecular structure [17,18]
with separations H(2A)  O(2) of 1.892(3) and H(1A)  O(1) of
2.049(3) , Figs. 1b and 2. Theoretical investigations show that
the hydrogen atoms play an essential structural role by holding
these oxygen atoms in close proximity [19]. Other important interaction, which produces a high stability for structure 1 is N3AH  pcloud of phenolato group Fig. 1b [19,20].

0.4
0

100

200

300

T (K)
Fig. 6. Temperature dependence of vMT (h), vM (s), solid line is the best-tting
results for linear chain for 1.

187

Ma. Guadalupe Quintero-Tllez et al. / Journal of Molecular Structure 1034 (2013) 183188

(a)

(b)
g = 2.1967

c.a. = 0.1 mM

||

c.a. = 1.14 mM
g || = 2.2153

g = 2.1074

-4

A || = 192.8x10 cm

g = 2.0563

-1

dpph
c.a. = 16.98 mM

dpph

c.a. = 33.5 mM

77 K
300 K

c.a. = 40.78 mM

H (kG)

H (kG)

Fig. 7. (a) X-band ESR of polycrystalline sample of 1 at 300 K (dashed line) and 77 K (solid line). (b) Hyperne splitting of 1 in frozen methanol solution at different
concentrations.

angle the principal structural changes concern varies from 95.6 to

104.1, antiferromagnetic behavior occurs to >104 [37,38]. The
antiferromagnetic behavior is expected for CuANACu for angles
between 97.5 and 108.5 [3941]. It has been proposed
[37,40,42] that when the J values are plotted vs the ratio h/R, where
R is the distance from Cu to the bridging group, the h/R value of
28.55 1 corresponds to a J maximum value. Hence, bridging angles close to 90 or less and h/R < 28.556 1 are taken as evidence
of ferromagnetism coupling.
Structural analysis of 1 shows that there are several magnetic
pathway types: CuAN  OACu with irregular trapezium structures
with magnetic unit CuAN and CuAO; Cu  OACu and CuN  Cu
as triangles magnetic structure pathways. In addition Fig. 5 shows
the bridging angles 101.3 and 108 for CuAOACu and 100.4 and
107.9 for CuANACu (h/R = 2428 1) giving rise to the possibility of antiferromagnetic or ferromagnetic exchange interaction
[38,43,44]. Fig. 5 (top and bottom) shows in the middle of the line
joining atoms N  O (point A) of the trapezium that there is an angle that there is an angle CuAAACu = h > 90, h/R > 28 1 (in fact
h/R around 43 1) indicating possibility of antiferromagnetic exchange interactions[38,45,46].
The magnetic susceptibility of a polycrystalline sample of 1 is
measured under an applied eld of 1 kOe, in the temperature range
2300 K. Diamagnetic corrections were applied by using Pascals
constants 149.61  106 emu/mol. 1 shows at room temperature
a vMT value of 1.06 emu K mol1, much higher than the value expected for an isolated spin Cu(II) ion (for g = 2) for spin only paramagnets (0.374 emu K mol1), Fig. 6. When the temperature is
decreased gradually, the vMT values also decrease gradually; at
2 K vMT is 0.415 emu K mol1. These two observations imply dominant antiferromagnetic interactions between copper centers. The
vT product of 1 shows no evidence of spincanting behavior, which
would be manifested by a slight increase of vT at low temperature
[47].
Analysis of the temperature variation of susceptibility with use
of the CurieWeiss law yields a h value of 0.02 K (giso = 2.1372
t), suggesting a very small exchange coupling constant [48]. From
X-rays results the distance Cu  Cu is 5.016 for all Cu(II) magnetic centers. The innite linear chain should be able to account
for the observed susceptibility. The spin Hamiltonian adapted to
describe the isotropic interaction between nearest neighbor ion

for a magnetic chain of an array equally spaced Cu(II) ions is

^ J P Si Si1 . The magnetic data have been analyzed using the
H
Eq. (1) as quadratic/cubic function [37]:

Ng 2 b2
A Bx Cx2
kT D Ex Fx2 Gx3

where A = 0.25, B = 0.074975, C = 0.075235, D = 1.00, E = 0.9931,

F = 0.172135, G = 0.757825, x = |J|/kT and J is the exchange coupling
parameter describing the magnetic interaction between any two
nearest neighbor S = 1/2 spins. The g-factor is tted to giso = 2.1372,
the
J
value
is
-0.06868 cm1
with
R = 1.41  102
P
2 P 2
(R vobs  vcalc = vobs ). The small value of J is indicative of
a weak antiferromagnetism interaction; this result is in agreement
with the ESR result and the CurieWeiss adjustment [48].
3.5. ESR spectroscopy
X-band ESR spectra of polycrystalline sample of 1 were recorded at 300 K and 77 K. The spectra show a broad (34.2 Gauss
line width) singlet with the same values of g||(300 K) =
g||(77 K) = 2.1967 and g\(300 K) = g\(77 K) = 2.1074 without
hyperne splitting, indicating exchange narrowing, Fig. 7a. The
powdered sample of 1 does not show additional resonances at
zero-eld or any other absorption at any gain. Hence, DMs = 2
(Ms = double quantum spin ip), and zero-eld transitions do not
occur in this system [49]. The areas ratio value (arv) A77/300 =
1.63 suggest an incomplete [50,51] antiferromagnetic behavior.
Identical values of gs at 300 K and 77 K indicate that the atomicmagnetic structure is not signicantly modied with temperature.
ESR spectra of 1 in frozen solution at different concentrations, ca
0.1, 1.14, 16.98, 33.48, 40.78 mM, are carried out at 77 K, Fig. 7b.
Hyperne splitting emerges when the magnetic exchange
interactions disappear. The frozen solution spectra are rationalized
= g || bH z S z +
according to the simplied spin Hamiltonian H
g\b(HxSx + HySy) + A||SzIz + A\(SxIx + SyIy). Here all symbols have
their usual meanings [33]. ESR of 1 in solution shows axial spectra
with g values of g || = 2.2153, g\ = 2.0563, hyperne interaction
with A|| = 192.8  104 cm1 (186.4 G) and A\ (68.4 G) is not
resolved in frozen solution. The two forms sp or tbp can be
recognized from the ESR spectra, since g \ > g ||  2.00 and
|A|| |  |A\|  (60100)  10 4 cm1 for tbp and g || > g\ and

188

Ma. Guadalupe Quintero-Tllez et al. / Journal of Molecular Structure 1034 (2013) 183188

|A\| << |A|||  (120150)  104 cm1 for sp complexes [52], thus 1
is a sp complex. The values of the gs with g|| > g\ > 2.0023 indicate
that the unpaired electron is in the dx2 y2 ground state [15,22,53],
in accord with the UVVis spectrum. The electron conguration
is characteristic of a sp or tbp local geometry around each Cu(II)
ion.
4. Conclusions
We report the direct synthesis and the supramolecular crystalline-structure network forming one-dimensional 1D columns of
Cu(II) ions in zigzag arrangement of 1. The UVVis study of 1 in
solution is consistent with local coordination sphere, highly distorted between sp and tbp geometries, around Cu(II) ion shown
by crystalline study. Magnetic results, ESR spectra of powder samples of 1 and supramolecular structure are consistent with the
weak antiferromagnetic constant value J obtained. In solution, 1
is more stable in sp geometry according with UVVis and ESR
studies.
Acknowledgments
Yurij Mozharivskyj, Ph.D. Associate Professor of Chemistry,
Department of Chemistry and Chemical Biology, Ontario, Canada,
L8S 4M1, acknowledged for magnetization measurements. Present
work has been supported by Secretara de Educacin Pblica, Subsecretara de Educacin Superior, and Vicerrectora de Investigacin y Estudios de Posgrado from BUAP, Project No. REOMNAT08/2009-G.
References
[1] R.J.P. Corriu, E. Lancelle-Beltran, A. Mehdi, C. Rey, S. Brands, R. Guilard, Chem.
Mater. 15 (2003) 3152.
[2] C. Biswas, M.G.B. Drew, A. Ghosh, Inorg. Chem. 47 (2008) 4513.
[3] S. Adsule, V. Barve, D. Chen, F. Ahmed, Q.P. Dou, S. Padhye, F.H. Sarkar, J. Med.
Chem. 49 (2006) 7242.
[4] J. Gradinaru, A. Forni, V. Druta, F. Tessore, S. Zecchin, S. Quici, N. Garbalau,
Inorg. Chem. 46 (2007) 884.
[5] Y.S. Xie, Y. Xue, F.P. Kou, R.S. Lin, Q.L. Liu, J. Coord. Chem. 53 (2001) 91.
[6] B.A. Jazdzewski, P.L. Holland, M. Pink, V.G. Young, D.J.E. Spencer, W.B. Tolman,
Inorg. Chem. 40 (2001) 6097.
[7] S. Ghosh, J. Cirera, M.A. Vance, T. Ono, K. Fujisawa, E.I. Solomon, J. Am. Chem.
Soc. 130 (2008) 16262.
[8] A.D. Garnovskii, B.I. Kharisov, G. Gojon-Zorrila, D.A. Garnovskii, Russ. Chem.
Rev. 64 (1995) 201.
[9] B.I. Kharisov, A.D. Garnovskii, G. Gojon-Zorrilla, S.S. Berdonosov, Rev. Soc.
Qum. Mx. 40 (1996) 173.
[10] R. Gutierrez, J. Vzquez, R.A. Vzquez, Y. Reyes, R.A. Toscano, M. Martnez, C.
lvarez, J. Coord. Chem. 5 (2001) 313.
[11] J.L. Alcntara-Flores, J.J. Vzquez-Bravo, R. Gutirrez-Prez, D. RamrezRosales, S. Berns, J.G. Prez-Ramrez Bokhimi, R. Zamorano-Ulloa, Y. ReyesOrtega, J. Mol. Struct. 657 (2003) 137.
[12] R. Luna Garca, D thesis, Universidad Autnoma del Estado de Morelos, 2005.
[13] E.A. El-Ghany, F.F. Attia, F. Marzouk, M.T. El-Kolaly, J. Radioanal. Nucl. Chem.
245 (2000) 237.
[14] G.M. Sheldrick, Acta Cryst. A64 (2008) 112.

[15] A.W. Addison, T.N. Rao, J. van Reedijk, J. Van Rijn, G.C. Verschoor, J. Chem. Soc.
Dalton Trans. (1984) 1349.
[16] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry: Principles of Structure
and Reactivity, fourth ed., Harper Collins College Publishers, USA, 1993.
[17] B.K. Das, S.J. Bora, M. Chakrabortty, L. Kalita, R. Chakrabarty, R. Barman, J.
Chem. Sci. 118 (2006) 487.
[18] D. Braga, F. Grepioni, Acc. Chem. Res. 33 (2000) 601.
[19] C. Desplanches, E. Ruiz, A. Rodrguez-Fortea, S. Alvarez, J. Am. Chem. Soc. 124
(2002) 5197.
[20] C. Bissantz, B. Kuhn, M. Stahl, J. Med. Chem. 53 (2010) 5061.
[21] Y. Reyes-Ortega, J.L. Alcntara-Flores, M.C. Hernndez-Galindo, R. GutirrezPrez, D. Ramrez-Rosales, S. Berns, B.M. Cabrera-Vivas, A. Durn-Hernndez,
R. Zamorano-Ulloa, J. Mol. Struct. 788 (2006) 145.
[22] M. Du, Y.M. Guo, S.T. Chen, X.H. Bu, J. Mol. Struct. 641 (2002) 29.
[23] E.T. Roth, Inorg. Chem. 46 (2007) 4362.
[24] L. Kozlevcar, G. Glazar, Z. Pirc, A. Jaglicic, P. Golobic, Polyhedron 26 (2007) 11.
[25] S. Noro, N. Yanai, S. Kitagawa, T. Akutagawa, T. Nakamura, Inorg. Chem. 47
(2008) 7360.
[26] H. Brzel, P. Comba, K.S. Hagen, M. Kerscher, H. Pritzkow, M. Schatz, S.
Schindler, O. Walter, Inorg. Chem. 41 (2002) 5440.
[27] J.M. Rowland, M.M. Olmstead, P.K. Mascharak, Inorg. Chem. 39 (2000) 5326.
[28] E. Pretsch, P. Bhlmann, C. Affolter, Structure Determination of Organic
Compounds, Tables of Spectral Data, Springer, USA, 2000.
[29] S.T. Spees, J.R. Perumareddi, A.W. Adamson, J. Phys. Chem. 72 (1968) 1822.
[30] G. Park, J. Shao, F.H. Lu, R.D. Rogers, N.D. Chasteen, M.W. Brechbiel, R.P.
Planalp, Inorg. Chem. 40 (2001) 4167.
[31] S. Tirado-Guerra, N.A. Cuevas-Garibay, M.E. Sosa-Torres, R. Zamorano-Ulloa, J.
Chem. Soc. Dalton Trans. (1998) 2431.
[32] R. Rossi, R. Hoffmann, Inorg. Chem. 14 (1975) 365.
[33] R.S. Drago, Physical Methods in Chemistry, Saunders College Publishing, USA,
1977.
[34] J.L. Alcntara-Flores, D. Ramrez-Rosales, S. Berns, J.G. Prez-Ramrez, A.
Durn-Hernndez, R. Gutirrez-Prez, R. Zamorano-Ulloa, Y. Reyes-Ortega, J.
Mol. Struct. 693 (2004) 125.
[35] G.M. Godziela, H.M. Goff, J. Am. Chem. Soc. 108 (1986) 2237.
[36] S. Bertini, A. Ciurli, R. Dikiy, C. Gasanov, G. Luchinat, J. Am. Chem. Soc. 121
(1999) 2037.
[37] O. Kahn, Molecular Magnetism, VCH Publisher, USA, 1993.
[38] V.H. Crawford, H.W. Richarson, J.R. Wasson, D.J. Hodgson, W.E. Hateld, Inorg.
Chem. 15 (1976) 2107.
[39] E. Ruiz, J. Cano, S. Alvarez, P. Alemany, J. Am. Chem. Soc. 120 (1998) 11122.
[40] X.-H. Bu, M. Du, Z.-L. Shang, R.-H. Zhang, D.-Z. Liao, M. Shionoya, T. Clifford,
Inorg. Chem. 39 (2000) 4190.
[41] S.S. Tandon, L.K. Thompson, M.E. Manuel, J.N. Bridson, Inorg. Chem. 33 (1994)
5555.
[42] R.D. Willet, D. Gateschi, O. Kahn (Eds.), Magneteto-Structural Correlations in
Exchange Coupled Systems, Reidel, Dordrecht, The Netherlands, 1985.
[43] J.B. Goodenough, Phys. Rev. 100 (1955) 564.
[44] X.-H. Bu, M. Du, L. Zhang, Z.-L. Shang, R.-H. Zhang, M. Shionoya, J. Chem. Soc.
Dalton Trans. (2001) 729.
[45] Y.-F. Zeng, X. Hu, F.C. Liu, X.-H. Bu, Chem. Soc. Rev. 38 (2009) 469.
[46] X.-H. Bu, M. Du, Z.-L. Shang, L. Zhang, Q.-H. Zhao, R.-H. Zhang, M. Shionoya,
Eur. J. Inorg. Chem. (2001) 1551.
[47] T. Birk, K.S. Perderson, S. Piligkos, C.A. Thuesen, H. Weihe, J. Bendix, Inorg.
Chem. 50 (2011) 5312.
[48] W.E. Marsh, K.C. Patel, W.W. Hateld, D.J. Hodgson, Inorg. Chem. 22 (1983)
511.
[49] G. Feher, Electron Paramagnetic Resonance with Applications to Selected
Problems in Biology, Gordon & Breach, USA, 1970.
[50] G. Alvarez, R. Font, J. Portelles, R. Valenzuela, R. Zamorano, Physica B 384
(2006) 322.
[51] G. Alvarez, R. Zamorano, J. Heiras, M. Castellanos, R. Valenzuela, J. Magn. Magn.
Mater. 316 (2007) e695.
[52] I. Bencini, D. Bertini, Inorg. Chem. 17 (1978) 3195.
[53] E. Lamour, S. Routier, J.-L. Bernier, J.-P. Catteau, C. Bailly, H. Vezin, J. Am. Chem.
Soc. 121 (1999) 1862.