Solid State Communications 150 (2010) 2005–2010
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Solid State Communications
journal homepage: www.elsevier.com/locate/ssc
Magneto-structural studies of the bis (1,4-bis (3-aminopropylamine)
piperazinium) chloride pentachlorocuprate (II) trihydrate
I. Baccar
a
, F. Issaoui
b
, F. Zouari
a
, M. Hussein
c
, E. Dhahri
b,*
, M.A. Valente
d
a
Laboratoire des Sciences des Matériaux et d’Environnement, Faculté des Sciences de Sfax, 3000 Sfax, Tunisia
b
Laboratoire de Physique Appliquée, Faculté des Sciences de Sfax, Sfax 3000, Tunisia
c
Physics Department, Faculty of Science, Zagazig University, Zagazig, Egypt
d
I3N and Physics Department, University of Aveiro, 3810-193 Aveiro, Portugal
article info
Article history:
Received 24 June 2010
Received in revised form
2 August 2010
Accepted 17 August 2010
by C. Lacroix
Available online 8 September 2010
Keywords:
C. Crystal structure
D. Magnetic properties
E. Differential scanning calorimetric
E. Raman spectroscopy
abstract
Bis (1,4-bis (3-aminopropylamine) piperazinium) chloride pentachlorocuprate (II) trihydrate (C
10
H
26
N
4
)
2
Cl CuCl
5
.3H
2
O has been prepared and characterized by various physicochemical techniques including
Raman spectroscopy and magnetic properties. A preliminary single crystal X-ray diffraction structural
analysis reveals that the title compound belongs to the orthorhombic system with space group Pnma.
The unit cell dimensions are: a = 8.216(9), b = 13.006(8), c = 21.376(20) Å, with Z = 4. Its crystal
structure was determined and refined down to R = 0.028. The structure of this compound consists of
diprotonated (1,4 bis (3-aminopropyl) piperazinium) cations, polynuclear anions and water molecules.
These entities are interconnected by means of hydrogen bonding contacts [N–H. . . O(Cl), O(W)–H. . . Cl and
O(W)–H. . . O] forming a three-dimensional network.
Differential scanning calorimetry study was carried out. The Raman of polycristalline samples, have
been recorded at different temperatures between 263 and 300 K. A low temperature phase transition at
283 K of order–disorder type was found.
The temperature dependence of the magnetic susceptibility was measured in the temperature range
of 2–120 K at different magnetic field intensities. The experimental effective magnetic moment coincides
with theoretical one. The results indicate that the complex exhibit weak antiferromagnetic coupling
between the copper (II) centers. The ferromagnetic ordering is further confirmed by the presence of
hysteresis loops with rapid saturation in the (C
10
H
26
N
4
)
2
Cl CuCl
5
.3H
2
O compounds.
© 2010 Elsevier Ltd. All rights reserved.
1. Introduction
Halide transition-metal complexes represent a growing class
of compounds whose chemistry is currently a topic of intense
research.These types of materials are used in microwave devices
[1,2] due to their high resistivity, high permittivity and low
losses. The hybrid organoammonium halometallate (II) have
played a significant role in the development of the understanding
of low dimensional magnetic systems and, more recently, of
semiconducting materials [3]. With M = Mn
2+
, the systems
behave as classical two dimensional antiferromagnets [4], while
with M = Cr
2+
and Cu
2+
, the spins in the layers order
ferromagnetically [5]. The magnetic susceptibility is an important
tool for the magnetic characterization of the materials.
One of the best studied groups, both in solution and the solid
state, are the halocuprate complexes [6,7]. The large structural
*
Corresponding author. Tel.: +216 98373734; fax: +216 74274437.
E-mail address: essebti@yahoo.com (E. Dhahri).
variability of Cu (II) due to the presence of an active Jahn–Teller
effect in the d
9
electronic system and the relative flatness of the
potential surfaces make the thermochromism in chlorocuprates
of continual interest. These compounds and their properties are
of interest not only in inorganic chemistry but also in fields
ranging from solid-state physics to bioinorganic chemistry. Among
solid-state physicists and chemists, there is a great interest in
the copper (II) halides owing to the plasticity of the metal
coordination sphere which leads to a great variety of crystalline
architectures with different coordination numbers, geometries
and nuclearties, and makes copper systems excellent candidates
for analysing correlations between structural parameters and
magnetic properties [8,9].
In this paper, we report the preparation, crystal structure
and solid-state properties of the compound bis (1,4-bis (3-
aminopropylamine) piperazinium) chloride pentachlorocuprate
(II) trihydrate. The choice of 1,4-bis (3-aminopropylamine) piper-
azine base was determined by the presence of two amino groups
capable of etablishing strong hydrogen bonds, which involve the
chlorine and water oxygen atoms as acceptors and stabilize the
0038-1098/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2010.08.018