Synthesis, crystal structure, thermal and dielectric properties

of tetrapropylammonium tetrachloroantimonate(III)
N. Weslati
a,n
, I. Chaabane
a
, A. Bulou
b
, F. Hlel
a
a
University of Sfax, Condensed Matter Laboratory, Faculty of Sciences BP. 1171, 3000 Sfax, Tunisia
b
LUNAM Universit, Universit du Maine, CNRS UMR 6283,Institut des Molcules et Matriaux du Mans (IMMM),
Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
a r t i c l e i n f o
Article history:
Received 13 November 2013
Received in revised form
3 February 2014
Accepted 5 February 2014
Available online 12 February 2014
Keywords:
Tetrapropylammonium
tetrachloroantimonate(III)
X-ray diffraction
Dielectric properties
a b s t r a c t
The new organicinorganic compound, tetrapropylammonium tetrachloroantimonate(III), [N(C
3
H
7
)
4
]
[SbCl
4
], crystallizes at room temperature in the monoclinic system (P2
1
/c space group) with the following
unit cell parameters: a18.1973(5) , b15.7225(4) , c15.7225 (3) , 91.65(1)1 and Z4. The
atomic arrangement can be described by a stacking of organicinorganic layers along a direction. Each
layer is made up by two types of tetrapropylammonium cations and two types of distorted tetrachlor-
oantimonate(III) anions. Differential scanning calorimetry studies indicate a presence of two order
disorder phase transitions located at 343 K and 363 K. Besides, an analysis of the dielectric constants
0
,
and loss tangent (tan()) versus temperature, at several frequencies, shows a distribution of relaxation
times. This relaxation is probably due to the reorientational dynamics of alkyl chains.
& 2014 Elsevier B.V. All rights reserved.
1. Introduction
The prospect of creating new functional materials with tunable
properties provides a great motivation on research of organic
inorganic hybrids compound [1,2]. These materials have recently
been attracting much attention because they can be widely used in
advanced laser technology, optoelectronics, optical storage and
information processing [3]. A typical research has been focused on
the tetraethylammonium and tetramethylammonium halogenoan-
timonates(III) and halogenobismuthates(III) of the general formula
R
a
M
b
X
3ba
(where R denotes organic cations, MSb, Bi and XCl,
Br, I) are well investigated and show interesting ferroelectricity,
ferroelasticity, and low nonlinear optical properties [4,5].
These properties are induced by the dynamical ordering of
dipolar organic cations [6]. However, the tetramethylammonium
and tetraethylammonium compounds are interesting because they
exhibit phase transitions which are mostly orderdisorder type.
Moreover, elements of groups 14 and 15 as Sb(III) and Bi(III) ions
are characterized by their ns
2
electronic lone pair which can be
more or less stereochemically active. This activity may tip the
energy balance towards a ferroelectric state [7]. In an attempt to
study the effects of the alkyl chain length on the electric propriety
behavior, in this class of compounds, we have successfully synthe-
sized a new compound of formula [N(C
3
H
7
)
4
] SbCl
4
.
In the present paper, we report the synthesis, structural
characterization by X-ray diffraction, differential scanning calori-
metry (DSC) and dielectric measurements of the tetrapropylam-
monium tetrachloroantimonate(III).
2. Experimental
2.1. Synthesis
The synthesis of [(C
3
H
7
)
4
N][SbCl
4
] was performed from pre-
cursors [N(C
3
H
7
)
4
]Cl (purity 97%; FLUKA) and Sb
2
O
3
(purity 99%).
The reaction sequence for the synthesis is shown in the following
equation:
2[N(C
3
H
7
)4]Cl Sb
2
O
3
6HCl-2[N(C
3
H
7
)
4
]SbCl
4
3H
2
O
The solution was obtained by dissolving 0.767 g of [N(C
3
H
7
)
4
]Cl
and 0.147 g of Sb
2
O
3
in concentrated HCl (37%) solution in a molar
ratio 1:1. The resulting solution was then kept at room tempera-
ture. After three days, colorless parallelepiped crystals appeared.
2.2. X-ray structure determination
X-ray structural analysis was performed on a single crystal
selected with an optical microscope. The intensity data were
collected on a Bruker AXS CCD area detector system equipped
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Physica B
http://dx.doi.org/10.1016/j.physb.2014.02.005
0921-4526 & 2014 Elsevier B.V. All rights reserved.
n
Corresponding author. Tel./fax: 216 41097111.
E-mail address: najouamass3oud.18@gmail.com (N. Weslati).
Physica B 441 (2014) 4246
with graphite monochromatic MoKa radiation (0.71073 ) at room
temperature.
A total of 36,634 reections were collected using the 2 scan
technique of which 6992 have I42s(I) and were used for the
structure determination. Then the structure was solved by the
Patterson method using SHELXS-86 [8] and rened by SHELX-L97
[9] programs, which readily established the heavy atoms positions and
facilitated the identication of the light atoms from different Fourier
maps. The details of the main crystal data are summarized in Table 1.
2.3. Differential scanning calorimetry
DSC measurement was performed on 7 mg of the samples from
120 to 553 K on a NETZSCH apparatus (Model 204 Phoenix) at a
heating rate of 5 K min
1
.
2.4. Impedance spectroscopy
The electrical measurements were performed using a two gold-
electrode conguration. In fact, the [(C
3
H
7
)
4
N][SbCl
4
] sample was
pressed on pellet disks of about 8 mm in diameter and 0.7 mm in
thickness using 3 t/cm
2
uniaxial pressure. The dielectric measure-
ments were registered in the frequency range 209 Hz5 MHz with
the TEGAM 3550 ALF automatic bridge monitored by a micro-
computer. Measurements were performed over the temperature
range of 323453 K.
3. Results and discussion
3.1. Crystal structure description
The title compound crystallizes in the monoclinic system (P2
1
/c
space group); the unit cell dimensions are a18.1973(5), b
15.7225(4), c13.6491(3) and 91.650(10)1.
The crystallographic analysis of the title compound reveals that
the asymmetric unit is formed by two un-equivalent cations noted
which are [N(1)(C
3
H
7
)
4
]

and [N(2)(C
3
H
7
)
4
]

and two un-equivalent

tetrachloroantimonate(III) anions noted which are [Sb(1)Cl
4
]

and
[Sb(2)Cl
4
]

, as shown in Fig. 1. The structural arrangement of the title

compound can be described by stacked organicinorganic layers
along a direction (Fig. 2). The crystal package is provided by Van Der
Waals and electrostatic interaction.
The tetrachloroantimonate(III) anions in [(C
3
H
7
)
4
N][SbCl
4
] exhi-
bit a distorted tetrahedral geometry. The angles ClSbCl vary
between 86.71(7)1 and 178.55(7)1. The SbCl bond lengths are in
the range 2.342.81 . The high error value of the angle and the
bond length may be due to the stereochemical activity of the Sb
(5s
2
) lone pair (E). These lengths fall within the range of total
observation of antimonyhalide distances reported by Bujak and
Zaleski [10]. For Sb(1)Cl
4
and Sb(2)Cl
4
anions the Sb atom is located
at the edge formed by Cl12Cl13 and Cl21Cl23, respectively. In
fact, the angles Cl12Sb1Cl13 and Cl21Sb2Cl23 are around 1801
and the corresponding SbCl bond lengths are signicantly longer
(Fig. 3 (a)). The difference between the SbCl bond lengths can be
due to the presence of the lone electron pair (E) carried by Sb(III).
As already observed, the coordination sphere of Sb(III) [11,12].
Moreover, SbCl
4
E present a trigonal bi-pyramid geometry. A recent
bibliographic investigation shows that this geometry was observed
for the rst time in [N(C
3
H
7
)
4
]SbCl
4
compound.
The distortion indices of [Sb(1)Cl
4
]

and [Sb(2)Cl
4
]

tetrahedra
are about 0.75 and 0.23 for bond and angles, respectively. The high
value of distortion indices may be due to the stereochemical
activity of the Sb (5s
2
) lone pair (E).
The geometry of [N(1)(C
3
H
7
)
4
]

and [N(2)(C
3
H
7
)
4
]

cations is
shown in Fig. 3(b). The rst cation, [N(1)(C
3
H
7
)
4
]

, presents a
cross conguration, while the second, [N(2)(C
3
H
7
)
4
]

, presents a
broken cross conguration. Both cations have C
1
point group
symmetry. All bond and angles for both cations are listed in
Table 2; these results are commonly observed [13,14].
3.2. Thermal behavior of [N (C
3
H
7
)
4
]SbCl
4
The differential scanning calorimetry (DSC) curve of [N(C
3
H
7
)
4
]
SbCl
4
crystal is presented in Fig. 4. An overview of this curve
unambiguously shows the existence of three endothermic peaks.
Peaks located at 343 and 363 K correspond to the phase transition
while the third peak, at 513 K, corresponds to the melting point.
The enthalpy and entropy of the rst peak are 1.12 kJ mol
1
and
3.2 J mol
1
K
1
, respectively. However those of second peak are
12.04 kJ mol
1
and 33.10 J mol
1
K
1
, respectively. Experimen-
tally observed S
tr
can be interpreted in terms of Boltzmann's
principle: S Rln (N1/N2), where N1 and N2 are the number of
distinguishable orientations allowed in the high-temperature and
Table 1
Summary with data collection and structure renement.
Compound [(C
3
H
7
)
4
N]SbCl
4
Molecular weight 899.8438
Color/shape Colorless/ parallelepiped
System Monoclinic
Space group P2
1
/c
Temperature (K) 293(2)
Cell dimensions
a () 18.1973(5)
b () 15.7225(4)
c () 13.6491(3)
(1) 91.650(1)1
Cell volume (
3
) 3903.48
Z 4
D
calc
(g cm
3
) 0.879
Diffractometer/scan Bruker AXS CCD
Radiation, ( ) Mo K, 0.71073
Crystal dimensions (mm) 0.380.28 0.16

calc
(mm
1
) 1.945
R (int) 0.042
Unique reections 12,298
range (deg) 1.731.16
Reections with I 42s(I) 6992
Range of h, k, l 24/26, 22/21, 17/19
F(000) 1619
Weights w1/[\s
2
(Fo
2
)(0.1P)
2
0.0P]
R/Rw 0.055/0.15
GOOF 1.055

min
/
max
(
3
) 0.75/1.58
Fig. 1. Asymmetric unit with thermal ellepsoide 50%.
N. Weslati et al. / Physica B 441 (2014) 4246 43
the low-temperature phases, respectively. At T343 K and
T363 K the Nl/N21.45 and Nl/N253.65, respectively.
Taking into account the transition entropies values, both phase
transitions may be classied as orderdisorder.
3.3. Dielectric studies
The temperature dependence of the real
0
and imaginary
parts of the dielectric permittivity of tetrapropylammonium tetra-
chloroantimonate(III) at different frequencies is shown in
Figs. 5 and 6, respectively. At low temperature the variations of

0
and are less pronounced and do not change with increasing
frequency. This behavior can be explained on the basis that at
relatively low temperature, the charge carriers cannot orient
themselves with respect to the direction of applied electric eld.
Therefore, they possess a weak contribution to the polarization
and the dielectric behavior [15]. Beyond T343 K the variation of
the real part
0
shows a low intensity which is anomalous;
this may be due to a weak disorder in the material related to
the low dynamics reorientational of the alkylammonium chains
[N(C
3
H
7
)
4
]

shown by thermal analysis [16]. A rapid jump of

0
and values is shown in the vicinity of the second phase
transition.
0
and behavior is related to increasing the disorder
in the [N(C
3
H
7
)
4
]SbCl
4
compound. In fact, the thermal analysis has
shown an endothermic peak at 363 K with a height entropy value.
The corresponding disorder induced weakens forces of Van Der
Waals and electrostatic interaction. For this, charge carriers can
orient themselves with respect to the direction of applied electric
eld [17]. As a result, transition from states of low
0
and to
states of high
0
and occurs with increasing temperature.
Fig. 7 shows the variation of dielectric loss factor (tan
0 0
/
0
)
versus temperature at selected frequencies. The dielectric loss
remains constant up to certain temperatures, thereafter increases
rapidly with increasing temperature [18,19]. The temperature
dependence of dielectric loss plot shows a peak which shifts to
higher temperature with increasing frequency.
The variation of with frequency on a double logarithmic scale
at different temperatures is presented in Fig. 8. The obtained
curves are straight lines at various temperatures. According to
Guintini et al. [20], veries the equation as follows:

0

1
2
2
N
ne

0

2
kT
m
0
W
4
M

mT
This can be rewritten as B
mT
Fig. 2. Projection of the structure of compound [N(C
3
H
7
)
4
] SbCl
4
on the plane (a, b).
Fig. 3. (a) Geometry of the anionic groups and (b) geometry of the cationic groups.
N. Weslati et al. / Physica B 441 (2014) 4246 44
where n is the number of electrons that hop, N is the
concentration of localized sites,
0
and
1
are the static and optical
dielectric constants, respectively. W
M
is the maximum barrier
height (the energy required to move the electron from a site to
the innity). The power m(T) of this equation was calculated from
the negative slopes of the obtained straight lines of Fig. 8 at several
temperatures. Such a dependence of m(T) on temperature satises
the empirical law [20,21] as follows:
s
ac
B
mT
AT
sT
Table 2
Selected bond lengths () and angles (1) in cationic and anionic parts of the
[(C
3
H
7
)
4
N]SbCl
4
crystal.
Distances (A) Angles (1)
Sb(1)Cl
4
Sb(1)Cl11 2.340(18) Cl11Sb1Cl14 93.85(9)
Sb(1)Cl14 2.398(2) Cl11Sb1Cl13 90.94(7)
Sb(1)Cl13 2.517(17) Cl14Sb1Cl13 91.09(8)
Sb(1)Cl12 2.714(19) Cl11Sb1Cl12 87.63(7)
Cl14Sb1Cl12 89.25(7)
Cl13Sb1Cl12 178,55(7)
Sb(2)Cl
4
Sb(2)Cl22 2.353(17) Cl22Sb2Cl24 92.48(9)
Sb(2)Cl24 2.441(19) Cl22Sb2Cl21 91.91(7)
Sb(2)Cl21 2.469(17) Cl24Sb2Cl21 89.14(8)
Sb(2)Cl23 2.819(18) Cl22Sb2Cl23 86.71(7)
Cl24Sb2Cl23 90.31(7)
Cl21Sb2Cl23 178,49(6)
[N(1)(C
3
H
7
)
4
]
N1C11 1.518(8) C11N1C13 111.9(5)
N1C13 1.513(8) C11N1C14 112.8(5)
N1C14 1.530(8) C13N1C14 103.5(5)
N1C12 1.526(8) C11N1C12 105.1(4)
C11C15 1.520(10) C13N1C12 111.8(5)
C12C16 1.495(10) C14N1C12 112.0(5)
C13C17 1.503(10) C15C11N1 117.3(5)
C14C18 1.493(10) C16C12N1 115.8(6)
C17C111 1.527(9) N1C13C17 116.4(5)
C16C110 1.526(11) C18C14N1 116.0(5)
C18C112 1.542(11) C13C17C111 109.0(6)
C15C19 1.500(11) C12C16C110 108.7(7)
C14C18C112 107.7(6)
C11C15C19 108.4(7)
[N(2)(C
3
H
7
)
4
]
N2C21 1.515(8) C21N2C23 109.1(5)
N2C23 1.521(7) C21N2C22 110.6(5)
N2C22 1.537(8) C23N2C22 107.8(5)
N2C24 1.503(8) C21N2C24 108.4(5)
C21C25 1.491(10) C23N2C24 111.6(5)
C22C26 1.482(10) C22N2C24 109.4(5)
C23C27 1.507(10) N2C21C25 116.0(6)
C24C28 1.515(11) C26C2N2 118.0(7)
C27C291 1.508(10) N2C23C27 115.0(5)
C28C292 1.467(13) C28C24N2 116.7(6)
C26C290 1.504(12) C23C27C291 109.6(7)
C25C29 1.478(12) C292C28C24 111.3(8)
C22C26C290 110.8(8)
C29C25C21 113.9(8)
310 320 330 340 350 360 370 380 390 400
-4
-3
-2
-1
0
1
endo
H
e
a
t

F
l
o
w

(
m
w
/
m
g
)
T(K)
Fig. 4. DSC thermograms of [N(C
3
H
7
)
4
]SbCl
4
compound.
300 330 360 390 420 450
0.0
5.0x10
2
1.0x10
3
1.5x10
3
2.0x10
3
209 Hz
306 Hz
655 Hz
1160 Hz
1550 Hz
2060 Hz
3010 Hz
4010 Hz
5870 Hz
T(K)
Fig. 5. Temperature dependence of the real part of the permittivity (
0
) at various
frequencies.
300 320 340 360 380 400 420 440 460
0
1x10
4
2x10
4
3x10
4
4x10
4
209 Hz
306 Hz
655 Hz
1160 Hz
1550 Hz
2060 Hz
3010 Hz
4010 Hz
5870 Hz
T(K)
Fig. 6. Temperature dependence of the imaginary part of the permittivity () at
various frequencies.
300 320 340 360 380 400 420 440 460
0
10
20
30
40
50
60
209 Hz
306 Hz
655 Hz
1160 Hz
1550 Hz
2060 Hz
3010 Hz
4010 Hz
5870 Hz
t
a
n
T(K)
Fig. 7. Temperature dependence of dielectric loss at various frequencies for
[N(C
3
H
7
)][SbCl
4
].
N. Weslati et al. / Physica B 441 (2014) 4246 45
Since the frequency exponent s(T) is temperature dependent
[22,23], m(T) should consequently depend on temperature. How-
ever, from the variation of s(T), we can determine the predominant
conduction mechanism. In fact, if s increases with the tempera-
ture, small polaron conduction is predominant [24]. If s decreases
with increasing temperature and reaches a minimum value at a
certain temperature and then continues to increase with increas-
ing temperature, it suggests that the conduction mechanism is due
to an overlapping large polaron tunneling mechanism [25]. In the
case where s is almost equal to 0.8 and temperature independent,
quantum mechanical tunneling is expected [26]. The correlated
barrier hopping is usually associated with a decrease in s with
temperature [27].
The variation of the obtained m values versus temperature is
shown in Fig. 9. It is clear, from this gure, that m decreases with
increasing temperature and reaches a minimum value at T343 K.
Afterwards, m continues to increase slightly with increasing
temperature. Since the behaviors of both exponents s(T) (ac
measurements) and m(T) (dielectric properties) have the same
temperature trend according to Guintini et al. model [20], in this
investigation the variation of m indicates the possibility of an
overlapping large polaron tunneling mechanism (OLPT).
4. Conclusion
The present work is devoted to the synthesis, X-ray character-
ization and electrical properties of tetrapropylammonium tetra-
chloroantimonate(III), [N(C
3
H
7
)
4
]SbCl
4
. The compound crystallizes,
at room temperature, in the monoclinic system (P2
1
/c space
group).
The atomic arrangement can be described by a stacking of
organicinorganic layers according to [100] direction made up of
[N(C
3
H
7
)
4
]

groups and isolated SbCl

4
E trigonal bipyramid. SbCl
4
is
highly distorted due to the stereochemical activity of the lone pair
of antimony. Differential scanning calorimetry revealed the pre-
sence of two orderdisorder phase transitions at 343 and 363 K,
resulting from the disorder of tetrapropylammonium cations.
The results of the dielectric permittivity study conrm the
conclusion drawn from the calorimetric measurements that the
orderdisorder phase transition located in the vicinity of the
temperature of the dielectric relaxation is characterized by change
in dynamical state of the cation. The dependency of m on
temperature is correlated with the ac conductivity and has been
discussed in terms of the correlated barrier large polaron tunnel-
ing mechanism (OLPT).
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7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5
0
2
4
6
8
10
323
333
343
353
363
373
383
393
403
413
423
433
343
453
L
n

'
'
Ln
Fig. 8. Variation of ln versus ln at different temperatures.
330 360 390 420 450
-1.00
-0.95
-0.90
-0.85
-0.80
-0.75
-0.70
m
T(K)
Fig. 9. The temperature dependence of the exponent m(T).
N. Weslati et al. / Physica B 441 (2014) 4246 46