Structure and ferroelectric properties of C

3
N
2
H
5

5
Bi
2
Cl
11
R. Jakubas,
1
A. Piecha,
1
A. Pietraszko,
2
and G. Bator
1
1
Faculty of Chemistry, University of Wrocaw, Joliot-Curie 14, 50-383 Wrocaw, Poland
2
Institute of Low Temperature and Structure Research, Polish Academy of Science, Oklna 2, 50-950 Wrocaw 2, PO Box 937, Poland
Received 18 April 2005; published 16 September 2005
Pentakis imidazolium undecachlorodibismuthateIII, C
3
N
2
H
5

5
Bi
2
Cl
11
, has been synthesized and studied
by means of the x-ray, differential scanning calorimetry DSC, and dielectric methods over a wide temperature
range. The room temperature crystal structure has been determined as monoclinic, space group P2
1
/ n with
a=13.616 , b=14.684 , c=9.045 , and =96.85. Two solidsolid phase transitions: P4

n2
360 K
P2
1
/ n
I II, and P2
1
/ n
166 K
P2
1
IIIII, discontinuous and continuous in nature, respectively, have been re-
vealed. The dielectric and pyroelectric measurements allow us to characterize the lowest temperature phase
III as ferroelectric with the Curie point at 166 K and saturated spontaneous polarization value of the order of
610
3
C m
2
along the b axis. The ferroelectric phase transition mechanism is governed by the dynamics of
imidazolium cations. The room temperature, paraelectric phase II demonstrates additionally the ferroelastic
properties.
DOI: 10.1103/PhysRevB.72.104107 PACS numbers: 77.80.e, 77.70.a, 61.10.i
I. INTRODUCTION
The discovery of ferroelectricity in alkylammonium halo-
genoantimonatesIII and halogenobismuthatesIII of the
general formula R
a
M
b
X
3b+a
where R=organic cations, M
=Sb, Bi, X=Cl, Br, I has generated considerable interest in
this class of materials. The most attractive, among these
crystals, appear to be the salts with the R
3
M
2
X
9
and R
5
M
2
X
11
compositions.
14
The R
3
M
2
X
9
subgroup usually adopts three
different types of anionic structure, for which the octahedra
are connected with each other as: i zigzag double innite
chains,
5
ii two dimensional layers,
6
and iii discrete con-
facial bioctahedra.
7
The appearance of ferroelectricity is lim-
ited to salts having the layer anionic structure type ii and
incorporating small-sized cations like: CH
3
NH
3
+
,
CH
3

2
NH
2
+
, and CH
3

3
NH
+
.
810
The ferroelectric
phase transitions in this family of crystals are attributed to
the reorientations of the alkylammonium cations. The experi-
mental studies on mixed crystals, R
3
Sb
21x
Bi
2x
X
9
, showed
the ferroelectricity is strictly connected with a presence of
the two-dimensional layer anionic sublattice.
11
In recent contribution from our laboratories we have de-
scribed a ferroelectric crystal, 4-aminopyridinium tetrachlo-
roantimonate III-4-NH
2
C
5
H
4
NHSbCl
4
.
12,13
Its structure
is composed of the SbCl
4

ions, which form innite chains

through the crystal via chloride linkages. This crystal under-
goes complex sequence of phase transitions with various in-
termediate phases of an incommensurate type. The ferroelec-
tric phase transition at 270.5 K of the incommensurate
commensurate-type is found to exhibit both the order
disorder and displacive contributions. It should be added that
it is the only example of the RMX
4
composition among the
ferroelectric halogenoantimonatesIII and halogenobis-
muthatesIII.
The salts with R
5
M
2
X
11
composition are being found
quite rarely, and only three derivatives with such a stoichi-
ometry have been reported to date.
14,15
The characteristic
feature of the R
5
M
2
X
11
salts R may be either the methylam-
monium or pyridinium cation is a presence of discrete
Bi
2
X
11
5
anions, in which two octahedra are connected with
each other by one bridging halogen atom. The ferroelectric
phase transition mechanism of the orderdisorder type in
these crystals is believed to be governed by the dynamics of
the organic cations. However, the role of the discrete
Bi
2
X
11
5
counterions in the generation of ferroelectric prop-
erties persists still unclear. To understand better the nature
the ferroelectric phase transition in the R
5
M
2
X
11
subgroup,
especially the relationship between the distorted structure of
the M
2
X
11
5
moieties and their great polarizability, we made
an effort to search for a new member of this family of crys-
tals with this composition. We have synthesized a molecular-
ionic salt containing the imidazolium cations in the structure:
pentakis imidazolium undecachlorodibismuthateIII. Its
crystal structure contains the discrete Bi
2
Cl
11
5
counterion
characteristic of the ferroelectric salts with R
5
Bi
2
X
11
compo-
sition.
Here, we describe the crystal structures of a ferroelectric
crystal, C
3
N
2
H
5

5
Bi
2
Cl
11
. The sequence of phase transitions
have been examined by the differential scanning calorimetry
DSC and temperature dependence x-ray methods. The di-
electric response and pyroelectric techniques are used to
evaluate the polar properties of the title crystal. The mecha-
nism of the ferroelectric phase transition is discussed.
II. EXPERIMENT
The powder of C
3
N
2
H
5

5
Bi
2
Cl
11
was prepared by reac-
tion of imidazole and Bi
2
O
3
in a concentrated hydrochloric
acid. The salts obtained were twice recrystallized and char-
acterized by an elemental analysis C:15.82% theor. 15.60,
H:2.06% theor. 2.17, N:11.84% theor. 12.14. The large
single crystals were grown by a slow evaporation of an aque-
ous solution. Differential scanning calorimetry DSC runs
were recorded using a Perkin Elmer DSC-7 in the tempera-
ture range 100450 K.
PHYSICAL REVIEW B 72, 104107 2005
1098-0121/2005/7210/1041078/$23.00 2005 The American Physical Society 104107-1
The TGA and DTA measurements were performed on a
Setaram SETSYS 16/ 18 instrument in the temperature range
300700 K with a ramp rate 2 K min
1
. The scan was per-
formed in owing nitrogen ow rate: 1 dm
3
h
1
.
The dilatometric measurements were performed by a ther-
momechanical analyzer Perkin Elmer TMA-7 in the tem-
perature range 140300 K. The dimensions of the sample
were of the order of 531 mm
3
.
The complex dielectric permittivity,
*
=i, was
measured with the HP 4285A and Agilent 4284A Precision
LCR Meters in the frequency range between 100 Hz and
25 MHz and in the temperature range between 200 and
450 K. The dimensions of the sample were of the order of
531 mm
3
. The plates were silver painted. The overall
error in estimation of the real and imaginary parts of the
complex electric permittivity was about 5%.
The pyroelectric charge was measured by a KEITHLEY
617 electrometer.
The single crystal for the x-ray measurements was se-
lected as a monodomain one at room temperature using the
polarizing microscope. The x-ray diffraction data were col-
lected using an automatic x-ray four-circle Kuma Diffraction
diffractometer and an Excalibur diffractometer with CCD
area detectors. Graphite monochromated Mo K radiation
=0.071 073 nm was generated at 50 kV and 25 mA. A
single image for 1 rotation around the axis was obtained
during 30 s and the full set of x-ray diffraction in the 2
angle was collected over the range from 3 to 93. The in-
tensities of the reections were recorded in 1200 frames. The
lattice parameters were calculated for renement of positions
all measured reections. The measurements were performed
at high temperature range up to 400 K with a KUMA Dif-
fraction temperature stage, the temperature of which was sta-
bilized within 0.5 K. In the low temperature region, down to
80 K, the Oxford Cryosystem was used. Data reduction was
performed using the Kuma 161DAT-RED system with ana-
lytic absorption correction. The crystal structure at all tem-
perature points was solved using the direct method-program
SHELXL-97.
16
The same program was used for the succes-
sive renement cycles of the crystal structure.
Crystallographic data for the structures reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Centre.
17
III. RESULTS
Crystallographic data and details on the structure determi-
nations of C
3
N
2
H
5

5
Bi
2
Cl
11
at room temperature are given
in Table I. The selected bond lengths and angles for the sake
of brevity of this paper limited to anionic Bi
2
Cl
11
5
geom-
etry are listed in Table II. The structure of the Bi
2
Cl
11
5
anion with nonequivalent imidazolium cations and the
atomic numbering scheme is presented in Fig. 1. The projec-
tion of the unit-cell content along the c axis is shown in Fig.
2. The crystal structure consists of discrete Bi
2
Cl
11
5
anions
and four kinds of nonequivalent imidazolium cations. The
Bi
2
Cl
11
5
moieties form a distorted bioctahedron with one
bridging Cl5 atom located at the inversion center. Among
ve imidazolium cations two cations labeled as type A,
placed in general positions, are ordered. The other three cat-
ions B, C, and D types occupy positions on an inversion
center and reveal a signicant dynamical disorder. These
three cations are distributed between two positions with the
occupancy factors 0.5 the 180 reorientation model within
the pentagonal ring. The imidazolium cations are connected
to the Bi
2
Cl
11
5
moieties by quite weak NuH. . . Cl hydro-
gen bonds. Specic hydrogen bonds are listed in Table III.
The crystal structure was determined at 180 K phase II as
well. The comparison of the hydrogen bonds system at 180
and 293 K revealed that the most important NuH. . . Cl
bonds experiences an important shortening N1A
H1ACl6, N2AH2ACl1, N1C
H1CCl3 as large as 0.1 . It means that the changes in
the hydrogen bonds conguration with decreasing tempera-
ture may be a decisive parameter leading to the freezing out
or ordering of the imidazolium cations below 166 K.
The lattice parameters of the unit cell and the space group
at four temperatures for the phases I, II, III, and IV are given
in Table IV. The temperature x-ray studies clearly show that
the C
3
N
2
H
5

5
Bi
2
Cl
11
crystals undergo the polymorphic
phase transitions from tetragonal system above 360 K
through an intermediate monoclinic phase to a low tempera-
ture monoclinic one. Thus the sequence of the phase transi-
tions is following:
TABLE I. Crystal data and structure renement for
C
3
H
5
N
2

5
Bi
2
Cl
11
.
Empirical formula C
3
H
5
N
2

5
Bi
2
Cl
11
Formula weight 1153.36
Temperature K 2932
Wavelength 0.71073
Crystal system monoclinic
space group P2
1
/ n
Unit cell dimensions a=13.6163
b=14.6843
c=9.045417
=96.853 deg
Volume
3
1795.66
Z 2
Calculated density g cm
3
2.133
Absorption coefcient mm
1
10.631
F000 1076
Crystal size mm 0.360.260.23
Theta range for data collection 4.2236.31
Ranges of h, k, l 2122, 2417,1315
Reections collected/unique 25177/ 8080
Renement method Full-matrix least-squares on F
2
Data/restraints/parameters 8080/ 21/ 246
Goodness-of-t on F
2
0.842
Final R
1
/ wR
2
indices I 2I 0.0521/ 0.1128
R
1
/ wR
2
indices all data 0.1388/ 0.1297
Largest diff. peak/hole e
3
2.950/ 1.378
JAKUBAS et al. PHYSICAL REVIEW B 72, 104107 2005
104107-2
Phase IIIP2
1

166 K
166 K
Phase IIP2
1
/n
360 K
365 K
Phase IP4

n2,
The crystal structure was determined at four temperatures
362 K-phase I, 293 K and 180 K-phase II and
130 K-phase III. In this paper the structure determination
of phase II at 293 K is presented, whereas those of the
tetragonal phase I and monoclinic phase III will be re-
ported elsewhere.
The optical observations under the polarizing microscope
along the c-axis disclosed a ferroelastic domain structure in
the room temperature phase II. According to Sapriels ap-
proach the phase transition I II 4

n2P2
1
/ n and corre-
sponding point group: 4

2m2/ m in C
3
N
2
H
5

5
Bi
2
Cl
11
does not belong to the ferroelastic species.
18
For the fer-
roelastic point group 2/ m the 4

2m one is not a prototypic

phase. It means that the paraelastic prototypic
ferroelastic phase transition is expected to appear above
T
c1
365/ 360 K. Thus the phase I is believed to have fer-
roelastic properties. The preliminary optical observation con-
rms this suggestion.
Figure 3a shows the DSC runs for C
3
N
2
H
5

5
Bi
2
Cl
11
on
cooling and heating at the rate 10 K/ min. The calorimetric
TABLE II. Selected bond lengths and angles deg for
C
3
N
2
H
5

5
Bi
2
Cl
11
at 293 K.
Bi1 uCl4 2.574713 Cl4 uBi1 uCl2 90.765
Bi1 uCl2 2.616413 Cl4 uBi1 uCl6 91.975
Bi1 uCl6 2.678013 Cl2 uBi1 uCl6 91.374
Bi1 uCl3 2.720814 Cl4 uBi1 uCl3 90.295
Bi1 uCl1 2.799113 Cl2 uBi1 uCl3 90.254
Bi1 uCl5 2.87654 Cl6 uBi1 uCl3 177.204
Cl5 uBi1#1 2.87654 Cl4 uBi1 uCl1 88.765
Cl2 uBi1 uCl1 179.104
Cl6 uBi1 uCl1 89.414
Cl3 uBi1 uCl1 88.994
Cl4 uBi1 uCl5 172.633
Cl2 uBi1 uCl5 96.623
Cl6 uBi1 uCl5 87.863
Cl3 uBi1 uCl5 89.683
Cl1 uBi1 uCl5 83.873
Bi1 uCl5 uBi1#1 180.005
Symmetry transformations used to generate equivalent atoms: No. 1
x+2, y, z.
FIG. 1. Color online. Molecular structure with atom labeling scheme of C
3
N
2
H
5

5
Bi
2
Cl
11
.
STRUCTURE AND FERROELECTRIC PROPERTIES OF PHYSICAL REVIEW B 72, 104107 2005
104107-3
measurements clearly reveal an existence of two solid-solid
reversible phase transitions. The strong rst order phase tran-
sition at high temperatures 365/ 360 K is accompanied by a
quite large transition entropy, S
tr
=24 J/ mol K Rln18,
which may indicate the orderdisorder mechanism for this
transition. The thermal hysteresis is indicative of the rst
order transition. The S value was estimated as an average
value for the cooling and heating scans for several samples.
The error in the estimation of H and S value is as large as
15%20%. The lower temperature phase transition at about
166 K is characterized by the relatively small temperature
hysteresis, T1 K. This transition has a long tail on the
lower temperature side of the thermal anomaly. It indicates
that this transformation is close to the second order transi-
tion. The estimated transition entropy, being of about
9.0 J/ mol K, proves also the orderdisorder character of the
low temperature transition.
To characterize the thermal stability of the
C
3
N
2
H
5

5
Bi
2
Cl
11
crystal the TGA and DTA thermograms
were performed between 300 and 700 K see Fig. 3b. It is
clearly seen that the title crystal is stable up to about 520 K.
The TGA curve shows a total weight loss of 87% when the
crystal is heated between 520 and 630 K. The rst endother-
mic dip in the DTA curve at 330 K invisible in the DSC
measurements is accompanied by a slight loss of the mass
below 0.5%. We ascribe it to the amine loss on the sample
surface. The next anomaly, at 364 K, corresponds to the re-
versible structural phase transition detected by the DSC
method. The third endothermic peak at about 520 K may be
due to the structural transformation. This thermal anomaly is
not conrmed by the DSC experiment since it is rather close
to the onset of decomposition of the sample.
The noncompatibility of the DSC results with the DTA
ones over 300380 K is due to the experimental conditions.
In both experiments the sample is encapsulated in different
way. In contrast to the DTA experiment during the DSC mea-
surements the sample is hermetically closed in an ampoule
so the surface effects are not manifested. The sample is pro-
tected against decomposition at 330 K and no thermal
anomaly is observed.
Figures 4a and 4b present the unit cell parameters as a
function of temperature obtained from x-ray measurements
between 90 and 380 K. They clearly show that
C
3
N
2
H
5

5
Bi
2
Cl
11
exhibits two structural anomalies corre-
sponding to the phase transitions detected by differential
scanning calorimetry at 365 and 166 K. The rapid changes in
the unit cell parameters at 365 K conrm the discontinuous
character of the III phase transition, whereas the varia-
tions of these parameters close to the IIIII transition are
typical of the continuous transformations. The structural
changes at the high temperature transition point are relatively
large. The lattice constants, a and c, expand by about 1.14%
and 1.77%, respectively, while the lattice constant b con-
tracts by about 2% at the transition temperature. Above the
transition III a=b. It should be noticed that the struc-
tural phase transition from the tetragonal to monoclinic sym-
metry and vice versa is accompanied by an enormous dis-
tortion of the unit cell, which usually leads to a drastic
breaking of the single crystal sample. Over the monoclinic
phases, II and III, there is seen a signicant change in the
value of monoclinic distortion. The crystal of
C
3
N
2
H
5

5
Bi
2
Cl
11
experiences a continuous strong deforma-
tion with decreasing temperature over the phase II. The large
distortion is characterized by a signicant change in the
-monoclinic angle, by nearly 4. It leads to an enormous
large internal stress inside the ferroelastic sample. As a con-
sequence an important rebuilding of the domain pattern takes
place, which was observed under polarizing microscope.
This is a reason that an increase of the twinning structure
should be observed, which is reected in the larger value of
TABLE III. Hydrogen bonds for C
3
N
2
H
5

5
Bi
2
Cl
11
and deg at 293 K.
DHA dDH dHA dDA DHA
N1A uH1A . . . Cl6 1.07 2.33 3.2925 149.1
N2A uH2A . . . Cl1#5 0.825 2.645 3.3215 141.05
N1C uH1C . . . Cl3#6 1.17 2.19 3.3116 158.7
N1D uH1D . . . Cl3#7 1.05 2.38 3.4016 164.4
Symmetry transformations used to generate equivalent atoms: No. 5 x+3/ 2, y1/ 2, z1/ 2 No. 6 x
+3/ 2, y+1/ 2, z+1/ 2 No. 7 x+2, y+1, z.
FIG. 2. Color online. Packing of the crystal structure of
C
3
N
2
H
5

5
Bi
2
Cl
11
along the c axis.
JAKUBAS et al. PHYSICAL REVIEW B 72, 104107 2005
104107-4
nal R
1
=0.0648 at 180 K in comparison to that found at
290 KR
1
=0.0521. The inset in Fig. 4b shows the tem-
perature dependence of the unit cell volume over the studied
temperature range. As it is expected for the discontinuous
transition, at T
c1
a rapid decrease in the volume of the crystal
of about 1.60% is clearly observed, whereas the lower tem-
perature transition IIIII occurring at about 166 K may be
classied as a continuous one. Along the b and c-axis in the
vicinity of T
c2
a change in the slope of linear part of thermal
expansion of the crystal is observed. A change in the sign of
the linear thermal expansion coefcient is seen along the
a-axis just below T
c2
, it means that with decreasing tempera-
ture over the phase III the expansion of the sample takes
place.
Temperature dependence of the complex electric permit-
tivity,
*
=i, measured at the frequency 100 Hz along
the a, b, and c axes of the monoclinic system for
C
3
N
2
H
5

5
Bi
2
Cl
11
in the vicinity of the low temperature
phase transition IIIII is displayed in Fig. 5. Along the
b-axis
max
reaches at 166 K a value of about 440 units.
Since the imaginary part,
max
, at 100 Hz is small enough
tan 0.3 near the transition temperature, the
b
mea-
sured at this frequency may be treated as a static electric
permittivity
o
. For the remaining two directions the elec-
tric permittivity values at T
c2
are nearly by one order of
magnitude smaller than that for the b axis. It suggests that
the b axis is a polar direction over the phase III. The 1/
b
vs
temperature representation see Fig. 6 permits us to predict
both the order of the phase transition and the CurieWeiss
constants according to the formula:
o
=C
+/
/ TT
c
where
TABLE IV. Unit-cell parameters at selected temperatures in various phases of C
3
N
2
H
5

5
Bi
2
Cl
11
.
Phase T K Space group a b c deg
I 362
P4

n2
14.27503 14.27503 9.188017 90.003
II 293 P2
1
/ n 13.61584 14.68425 9.045413 96.854
II 180 P2
1
/ n 13.52904 14.60606 8.975510 98.593
III 130 P2
1
13.61663 14.52665 8.904311 99.163
FIG. 3. a DSC runs for C
3
N
2
H
5

5
Bi
2
Cl
11
on cooling and heat-
ing at the rate 10 K/ min; b TGA and DTA thermograms be-
tween 300 and 700 K.
FIG. 4. Variations of lattice parameters of a b and angle and
b a and c.
STRUCTURE AND FERROELECTRIC PROPERTIES OF PHYSICAL REVIEW B 72, 104107 2005
104107-5
C
+
and C

are constants for the paraelectric and ferroelectric

phase, respectively. It should be noticed that the CurieWeiss
law is not well obeyed. The linear part of 1/
b
T curve is
observed only within a narrow temperature region, of about
1.5 K, both above and below 166 K. The ratio C
+
/ C

2.6
is characteristic for the second order ferroelectric transitions
theoretical value C
+
/ C

=4 or 2 for the rst or second order

transition, respectively. Nevertheless, the C
+
value increases
signicantly with temperature increasing. Since the electric
permittivity was measured in the dispersion frequency region
both magnitudes, C
+
and C

, depend strongly on the fre-

quency of measuring electric eld.
Our preliminary dielectric dispersion studies between
100 Hz and 25 MHz reveal that the fundamental relaxation
process in C
3
N
2
H
5

5
Bi
2
Cl
11
above 166 K takes place in the
kilohertz frequency region. These results indicate the order
disorder mechanism of the ferroelectric transition. The full
analysis of the dielectric response function will be presented
elsewhere.
The pyroelectric current was measured after poling the
crystal while cooling from 200 K down to about 100 K. The
dc electric eld was equal to +5 kV/ cm. Then the pyroelec-
tric current, I
pyro
, was measured with temperature increasing.
The same procedure was used after poling the crystal by the
dc electric eld of the negative value of 5 kV/ cm. The
spontaneous polarization P
s
as a function of temperature is
presented in Fig. 7. From this gure it clearly results that the
spontaneous polarization is reversed by the external dc elec-
tric eld. This is a crucial proof of ferroelectric order in
phase III. The saturated P
s
value is found to be 6
10
3
C m
2
at about 100 Kdc=5 kV/ cm. The tempera-
ture evolution of P
s
over the phase III indicates that we deal
with the paraelectricferroelectric phase transition of a sec-
ond order. One can conclude also that P
s
may be considered
as an order parameter for this ferroelectric. According to the
Landau theory the order parameter P
s
is expected to fulll
the following relation:
P
s
T
c
T

. 1
FIG. 6. 1/
b
vs temperature representation The CurieWeiss
law.
FIG. 7. Spontaneous polarization P
s
as a function of tempera-
ture from the pyroelectric effect for the pooling electric eld
5 kV/ cm. The inset shows ln P
s
as a function of lnT
c
-T.
FIG. 5. Complex electric permittivity,
*
=-i, measured at
the frequency 100 Hz along the a, b, and c axes of the monoclinic
system for C
3
N
2
H
5

5
Bi
2
Cl
11
in the vicinity of the ferroelectric
phase transition IIIII.
JAKUBAS et al. PHYSICAL REVIEW B 72, 104107 2005
104107-6
Where denotes critical exponent being of the order
0.250.50 for the continuous phase transition.
The inset of Fig. 7 shows ln P
s
as a function of lnT
c
T in the temperature region of 30 K below T
c2
. A linear
dependence of this function is observed with the parameter
equal to 0.24. Thus one can conclude that the ferroelectric
phase transition for C
3
N
2
H
5

5
Bi
2
Cl
11
is continuous as well
as close to a critical one.
The title crystal is characterized by a quite slow switching
process and relatively high coercive eld signicantly
higher than 67 kV/ cm at 50 Hz and this is a reason that
no ferroelectric hysteresis loop was observed using diamand-
dreck-pepinsky bridge with an electric eld of the 5010 Hz
frequency. However, an application of markedly lower fre-
quency 0.0020.005 Hz permits to observe a clearly
shaped hysteresis loops characterized by a coercive eld of
the order 7 kV/ cm at temperature 150 K 16 K below T
c
.
The existence of the hysteresis loop below 166 K is a direct
proof of ferroelectricity in C
3
N
2
H
5

5
Bi
2
Cl
11
. The results of
studies devoted to the switching of the spontaneous polariza-
tion will be published elsewhere.
19
The temperature dependence of the real part of the com-
plex electric permittivity, , along the c axis, measured be-
tween 30 kHz and 1 MHz, with temperature decreasing, is
displayed in Fig. 8. At the structural phase transition tem-
perature 360 K the permittivity drops abruptly by about 1.5
units. The dielectric response in the vicinity of the I II
phase transition is characteristic of crystals with the rotator
phase at high temperatures, which is consistent with a sig-
nicant transition entropy, S
tr
R ln 18. One can state that
some kind of imidazolium cations, performing the isotropic
rotation over the high temperature phase close to the phase
transition temperature I II, are suddenly frozen out.
Since this process is relatively fast no dielectric dispersion is
observed near 360 K up to 25 MHz the macroscopic relax-
ation time should be shorter than 110
8
10
9
s.
IV. DISCUSSION
The characteristic feature of the halogenoantimonates III
and halogenobismuthates III of the general formula
R
a
M
b
X
3b+a
is a rich diversity of the anionic structures. Up
till now there were found 29 various types of anionic
architectures.
2
However, only three of them: i R
3
M
2
X
9
, ii
RMX
4
, iii R
5
Bi
2
X
11
have revealed the ferroelectric proper-
ties.
i In the case of R
3
M
2
X
9
subgroup the ferroelectricity is
strictly connected with a presence of the layer anionic struc-
ture ve ferroelectrics
ii The RMX
4
salts, characterized by one-dimensional
chains of anions, are quite widespread, nevertheless only one
example of salt crystallizing with this stoichiometry, 4
-NH
2
PyHSbCl
4
, was found to show ferroelectric properties
The ferroelectricity appears rather accidentally in this type of
anionic stoichiometry.
iii The R
5
M
2
X
11
derivatives are encountered quite
rarely and four known derivatives crystallizing with this
composition are found to show the ferroelectricity.
For the R
3
M
2
X
9
and RMX
4
salts the ferroelectric proper-
ties were explained with a large electric polarizability of ei-
ther the anionic layers or chains consisting of octahedral
units MX
6
. For the third case iii the structural situation is
completely different since the anionic sublattice is made up
of discrete bioctahedral units, M
2
X
11
5
. It should be under-
lined the fact that such a type of anionic form and simulta-
neous appearance of ferroelectricity is limited to the systems
containing the bismuth III atoms. The question arises about
the origin of high electric polarizability of the crystals. There
is no doubt that this effect should be attributed to the pres-
ence of the 6s
2
electrons of the bismuth III atom, which are
easier polarizable than the 5s
2
electrons of the SbIII atoms.
Thus one can stress that the anionic sublattice, Bi
2
X
11
5
,
plays a primary role in the generation of ferroelectricity. The
dielectric parameters to characterize the R
5
Bi
2
X
11
salts are
summarized in Table V. Despite of obvious similarities in the
crystal structures ordered Bi
2
X
11
5
moieties and highly dis-
ordered cations the phase situation for the presented salts is
FIG. 8. Real part of the complex electric permittivity between
30 kHz and 1 MHz along the a axis for C
3
N
2
H
5

5
Bi
2
Cl
11
in the
vicinity of ferroelastic phase transition I II.
TABLE V. Polar properties of the crystals with R
5
Bi
2
X
11
X=Cl, Br composition.
Crystal T
c
K
Order
PT
Symmetry
change
at T
c
P
s
C m
2

max
T
c

CH
3
NH
3

5
Bi
2
Cl
11
307 II PcabPca2
1
2.010
2
2.010
4
CH
3
NH
3

5
Bi
2
Br
11
311 II PcabPca2
1
1.210
2
8.010
3
C
6
H
5
NH
5
Bi
2
Br
11
118 II P2
1
/ nP2
1
3.010
3
2.210
2
C
3
N
2
H
5

5
Bi
2
Cl
11
166 II P2
1
/ nP2
1
6.010
3
4.510
2
STRUCTURE AND FERROELECTRIC PROPERTIES OF PHYSICAL REVIEW B 72, 104107 2005
104107-7
different. The symmetry of the paraelectric phases of the
methylammonium analogs is higher orthorhombic than that
of the two remaining salts containing aromatic organic cat-
ions monoclinic. The magnitude of the spontaneous polar-
ization P
s
and electric permittivity value at T
c

max
for the
methylammonium analogs are signicantly larger than those
found for the pyridinium and imidazolium ones. It means
that the long-range dipoledipole interaction is stronger in
the case of the methylammonium cations. As a consequence
the ferroelectric phase transition temperature T
c
occurs at
higher temperatures in comparison to those found in the py-
ridinium and imidazolium analogs.
The imidazolium and pyridinium crystals appear to be
isomorphic at room temperature monoclinic, P2
1
/ n, how-
ever, their dielectric parameters P
s
,
max
T
c
and T
c
differ
signicantly. This can be explained within the magnitude of
dipole moment of cationic moieties: higher for the imi-
dazole molecule =3.67 D, lower for the pyridine one
=2.22 D. Thus, the expected stronger dipoledipole interac-
tions in C
3
N
2
H
5

5
Bi
2
Cl
11
affect the higher values of the
dielectric parameters see Table V. Dynamics of imidazo-
lium cations contributing to the orderdisorder mechanism of
ferroelectric transition is also conrmed by both the transi-
tion entropy magnitude S
tr
=9 J/ mol K and the funda-
mental ferroelectric relaxation process taking place in the
kilohertz frequency region.
Our experimental studies allow us to state that the inter-
actions between strongly polarizable anionic sublattice
Bi
2
Cl
11
5
and the dipolar imidazolium counterions is a nec-
essary condition for an appearance of ferroelectric properties
below 166 K in C
3
N
2
H
5

5
Bi
2
Cl
11
.
Recently, Pajk et al.
20
reported ferroelectric properties of
a simple 1:1 molecular-ionic salt comprising imidazolium
cations, namely C
3
N
2
H
5
BF
4
. It was postulated that the dy-
namics of the BF
4

anions exclusively contributed to the

polarization of this crystal, whereas the imidazolium moi-
eties played a minor role in it. This is in contrast to the
ferroelectric mechanism observed in the C
3
N
2
H
5

5
Bi
2
Cl
11
derivative, in which the ferroelectricity is due to the ordering
of dipolar imidazolium cations.
V. CONCLUSIONS
1 The structure of C
3
N
2
H
5

5
Bi
2
Cl
11
consists of dis-
crete Bi
2
Cl
11
5
moieties and ve imidazolium cations di-
vided into four nonequivalent types. At room temperature
three of ve organic cations reveal orientational disorder
two-site model, 180 reorientation.
2 Two solid-solid phase transitions:
P4

n2
360 K
P2
1
/nI II,
P2
1
/n
166 K
P2
1
II III,
discontinuous and continuous in nature, respectively, are dis-
closed. The phase transition at 166 K is clearly of order-
disorder type.
3 C
3
N
2
H
5

5
Bi
2
Cl
11
salt appears to be a ferroelectric
compound with the Curie point at 166 K and the spontane-
ous polarization of the order of 0.610
2
C m
2
.
4 The spontaneous polarization predominately origi-
nates from the ordering of the strongly dipolar imidazolium
cations over the phase III.
ACKNOWLEDGMENT
This work was supported by the Polish State Committee
for Scientic Research Project Register No. 3 T09A 023
26.
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CCDC No. 268505 Copies of this information may be obtained
free of charge from the Director, CCDC, 12 Union Rd., Cam-
bridge CB2 1EZ. UK fax: 44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk.
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