Thermal, dielectric properties and vibrational spectra

of [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystal
J. Tarasiewicz
a
, R. Jakubas
a,
*
, J. Baran
b
, A. Pietraszko
b
a
Faculty of Chemistry, University of Wrocaw, F. Joliot Curie 14, 50-383 Wrocaw, Poland
b
Institute of Low Temperature and Structure Research of the Polish Academy of Science, Okolna 2, 50-422 Wrocaw, Poland
Received 15 October 2005; received in revised form 10 November 2005; accepted 10 November 2005
Available online 4 April 2006
Abstract
[n-C
4
H
9
NH
3
]
2
[BiBr
5
] exhibits ve solidsolid structural phase transitions; at 309 (1st order), 291 (1st), 240 (1st), 219 (close to 2nd) and at
166 K (1st). The phase transitions at 291 and 240 K are accompanied by distinct dielectric anomalies. The dielectric relaxation process was found
to appear over the phases (III) and (I). The infrared spectra for [n-C
4
H
9
NH
3
]
2
[BiBr
5
] were measured in the region of the internal vibration of the n-
butylammonium cation (4000400 cm
K1
) between 12 and 320 K. The temperature changes of wavenumbers and of a width for many of the
internal modes of the n-butylammonium clearly indicate the contribution of the organic sublattice to the phase transition mechanism.
q 2006 Elsevier B.V. All rights reserved.
Keywords: Bromobismuthates(III); Phase transition; DSC; Dielectric; IR
1. Introduction
Many crystals of the halogenoantimonates(III) and halo-
genobismuthates(III) family of crystals: R
a
M
b
X
3bCa
where M
is a metal Sb or Bi, XZCl, Br, I and RZorganic cations,
exhibit interesting physical and structural properties. Much
research effort has been devoted to those salts which possess
ferroic properties (ferroelectric and ferroelastic) [15]. The
ferroelectricity is usually encountered for salts crystallizing in
two stoichiometries: R
3
M
2
X
9
and R
5
M
2
X
11
[6,7]. The former
subgroup is characterized by two-dimensional layer structure
of the anionic sublattice, whereas the latter one possesses a
discrete bioctahedral units M
2
X
5K
11
. The ferroelectric properties
are attributed to the dynamics of the organic cations. The
crystals characterized by the R
2
MX
5
composition consist of
either discrete M
2
X
4K
10
moieties (two edge-sharing octahedra) or
innite one-dimensional chains MX
2K
5

N
(corner-sharing
octahedra). For the salts with the R
2
MX
5
composition no
ferroelectric properties were found so far. Nevertheless, the
analogs containing n-alkylammonium cations long in size (e.g.
n-butylammonium) appeared to have interesting dynamic
properties [812]. The complicated reorientational motion of
the n-butylammonium cations are the source of a rich sequence
of phase transitions in [n-C
4
H
9
NH
3
]
2
[SbBr
5
] [13]. This
compound undergoes seven solidsolid phase transitions and
some of the intermediate phases are incommensurately
modulated. Therefore, it seems to be interesting to extend the
studies on bismuth analogs with the same cation[n-
C
4
H
9
NH
3
]
2
[BiBr
5
].
The present work is a part of our project of searching for
new molecularionic salts exhibiting polar properties. The title
novel compound, [n-C
4
H
9
NH
3
]
2
[BiBr
5
], was synthesized and
extensively studied. We measured and analysed IR spectra of
polycrystalline [n-C
4
H
9
NH
3
]
2
[BiBr
5
]. The IR spectra were
measured as a function of temperature (down to 10 K).
Differential scanning calorimetry (DSC) and dilatometric
measurements in a broad temperature range were carried out
to elucidate the complex sequence of the phase transitions as
well. Dielectric dispersion measurements in radio-frequency
region were done to explain the motion of dipolar groups in the
title crystal.
2. Experimental details
Deep yellow transparent crystals of [n-C
4
H
9
NH
3
]
2
[BiBr
5
]
were synthesized by the addition of n-butylammine (Aldrich,
99.5%) to a solution of antimony(III) oxide (Aldrich, 99.9%) in
concentrated hydrobromic acid (Aldrich, 48%). The obtained
polycrystalline material was recrystallized twice from the
solution. Single crystals were grown by a slow evaporation of
Journal of Molecular Structure 792793 (2006) 265273
www.elsevier.com/locate/molstruc
0022-2860/$ - see front matter q 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2005.11.046
* Corresponding author. Tel.: C48 71 320 4236; fax: C48 71 328 2348.
E-mail address: rj@wchuwr.chem.uni.wroc.pl (R. Jakubas).
an aqueous solution at room temperature. The elementary
chemical analysis performed gave: C: 12.58 (theor. 12.67), H:
2.59 (theor. 3.17), N: 3.56 (theor. 3.70).
Differential scanning calorimetry (DSC) measurements
were carried out with a PerkinElmer DSC-7 between 100
and 400 K at a heating/cooling rate of 2, 5, 10 and 20 K/min.
Linear thermal expansion was measured using a
thermomechanical analyserPerkinElmer TMA-7. The
samples used in the measurements were prepared in the
form of thin plates (5!3!1 mm
3
). The anomalies in
dilatation of single crystals in the vicinity of the phase
transitions were always reproducible within 10% for each
sample. The accuracy of thermal expansion determination
was about 3%.
The complex electric permittivity, 3*, for a single crystal of
[n-C
4
H
9
NH
3
]
2
[BiBr
5
] along the a-axis was measured by an HP
4285A Precision LCR Meter at frequency range between
75 kHz and 12 MHz and an HP 4284A Precision LCR Meter at
a frequency range between 130 Hz and 1 MHz from 120 to
370 K at a cooling rate of 0.5 K/min. Samples for dielectric
measurements were typically of size 4!3!1 mm
3
. The
accuracy of the measured electric permittivity value was
about 5%.
The pyroelectric charge was measured with a KEITHLEY
617 electrometer.
Infrared spectra of the powder sample [n-C
4
H
9
NH
3
]
2
[BiBr
5
]
(in Nujol with NaCl windows) in the temperature range between
12 and 320 K were recorded with a BRUKER IFS-88 FT-IR
spectrometer with a resolution of 1 cm
K1
. The Displex Model
CS-202 system of the APD Cryogenic Inc. provided sample
cooling temperatures in the range 10350 K. The temperature
was stabilized by the Scientic Instruments Model 5500
temperature controller.
3. Results
3.1. X-ray studies
The structural results at room temperature indicate that the
phase II appears to be incommensurate modulated. The lattice
parameters of the unit cell for the average structure are as
follows: the monoclinic system, space group KP2/m, aZ
15.582, bZ63.277, cZ16.810 A

, bZ92.528. The results

indicate that the [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystal is isomorphic
to the [n-C
4
H
9
NH
3
]
2
[SbBr
5
] crystal [13]. The preliminary
optical observations of single crystals under polarizing
microscope suggest that the low temperature phases possess
the ferroelastic properties.
Numerous studies on various salts with R
5
MX
5
composition
showed that the anionic sublattice may be built up either of
discrete M
2
X
4K
10
moieties (two edge-sharing octahedra) or of
innite one-dimensional chains (corner-sharing octahedra).
The salts containing large in size and bulky cations have some
tendency to form discrete M
2
X
4K
10
ions in the crystal lattice [11].
3.2. Thermal measurementsdifferential scanning calorimetry
(DSC) and dilatometry
DSC thermograms of the [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystals
(Fig. 1) show up to ve reversible solidsolid phase transitions
below the melting point. The high temperature phase transition
(II/I) at 322 K is hardly visible during the heating scan. The
shape of the observed anomalies and value of the temperature
hysteresis (extrapolated linearly to the zero scanning rate) of
the peak at 309, 291, 240 and 166 K (on cooling) clearly
indicate the rstorder phase transitions. A characteristic
change in the slope of the basic line at 224 K (the heating scan)
Fig. 1. DSC thermograms of the [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystals for the cooling and heating runs between 110 and 340 K (10 K /min, mZ6.034 mg).
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 266
is typical for the phase transition close to a second order. The
entropy change accompanying the phase transition at 240 K is
estimated to be ca. 10.1 J/mol K (zR ln 3.4). Such a great
value of the transition entropy may be explained in the increase
of the reorientational motion of alkyl group of the dipropy-
lammonium cations. Thus, an orderdisorder mechanism of
this phase transition is suggested. For the all remaining phase
transitions (DS!1 J/mol K) a dispacive mechanism is
postulated. The parameters characterizing the phase transitions
in [n-C
4
H
9
NH
3
]
2
[BiBr
5
] are collected in Table 1.
The temperature dependency of the linear thermal
expansion along the crystallographic axis of the [n-C
4
H
9-
NH
3
]
2
[BiBr
5
] monoclinic crystal upon cooling runs is shown in
Fig. 2. The dilatometric anomalies correspond well to the phase
transition disclosed by the calorimetric studies. The biggest
changes in dilation of the crystal are observed close to T
c3
Z
240 K. A similar tendency in the dilation is seen around T
c5
,
however, the anomalies are signicantly smaller. The other
phase transitions are hardly visible in the linear thermal
expansion.
3.3. Dielectric measurements
The dielectric measurements were done at the frequencies
between 300 Hz and 12 MHz. The temperature dependence of
the real part (3
0
) of the complex electric permittivity, 3

a
, at
300 Hz (treated as a static electric permittivity) along the a
direction on cooling for [n-C
4
H
9
NH
3
]
2
[BiBr
5
] is shown in
Fig. 3. It should be noticed that only the (II/III) and (III/IV)
phase transitions are active in the dielectric measurements. The
3
0
a
value approaching these transitions are quite large. The 3
0
peak positions for 300 Hz appear at 283 and 252 K, they are
shifted with respect to the phase transition points 291 and
240 K, respectively. These features are unclear at this moment.
The electric permittivity increases rapidly by about 27 units
(10/37) through (II/III) transition. Such a dielectric
response is encountered in the improper ferroelectrics.
Approaching the T
c3
Z240 K the 3
0
falls abruptly from 23 to
6 units. The source of the dielectric anomaly, especially of that
close to 240 K, is undoubtedly connected with the freezing of
dipolar groups, i.e. both the rigid n-butylammonium cations or
some fragment of the alkyl group.
Table 1
Phase transitions in n-butylammonium bromobismuthate(III) crystal
T (K) DT (K) DH (kJ/mol) DS (J/mol/K) Order of phase
transition
Cooling Heating 0 K/min 20 K/min
T
c1
309 322 ?
a
12 0.16 0.51 I
T
c2
291 311 ?
a
19 0.03 0.10 I
T
c3
240 264 24 35 2.33 10.09 I
T
c4
219 224 5 5 Close to II
T
c5
166 181 10 15 0.15 0.90 I
a
Hardly visible at slow rates of the scan.
Fig. 2. Temperature dependence of the linear thermal expansion along the a, b
and c-axis upon cooling.
Fig. 3. Temperature dependence of the real part of 3* measured along the a-axis
at 300 Hz (on cooling).
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 267
The temperature dependencies of the real and imaginary
parts of the complex electric permittivity, 3

a
, between 75 kHz
and 12 MHz along the a direction performed on cooling for
[n-C
4
H
9
NH
3
]
2
[BiBr
5
] are shown in Fig. 4(a) and (b). These
results clearly indicate that the relaxation process in a radio-
frequency region is observed over the temperatures covering
the phases (I), (II) and (III).
It was shown that the dielectric relaxation in the [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystal in the phases (I) and (III) is well
described by the ColeCole relation
3

u Z3
0
uKi3
00
u Z3
N
C
D3
1 Ciut
1Ka
; (1)
where D3Z3
0
K3
N
, 3
0
and 3
N
denote the low and high
frequency limits of the electric permittivity, u is an angular
frequency, t is the macroscopic relaxation time and a is a
parameter which represents a measure of the distribution of
the relaxation times. 3
0
, 3
N
, t and a are the t parameters for
each temperature independently. The Argand diagrams at
selected temperatures of phase (III) are displayed in
Fig. 5(a).
The macroscopic relaxation times t changes with tempera-
ture, from 6.9!10
K9
s at 256 K to 9.6!10
K9
s at 248 K. The
parameter a estimated with Eq. (1) changes from 0.25 (at
248 K) to 0.53 (at 256 K). The temperature dependence of the
macroscopic relaxation time in this temperature phase
fulls the Arrhenius relation, with the activation energy E
a
Z
24.5 kJ/mol. The dielectric response in phase (I) is described
by the ColeCole relation as well (Fig. 5(b)). The estimated
macroscopic relaxation time for temperatures above T
c(I/II)
increases signicantly from 7.7$10
K7
s at 345 K to 13$10
K7
s
at 328 K. The parameter a within phase (I) is characterized by
relatively large value: 0.40 at 328 K and 0.54 at 345 K, which

Fig. 4. Temperature dependence of the real (a) and imaginary (b) parts of 3*
measured along the a-axis for the frequencies between 75 kHz and 12 MHz (on
cooling).
Fig. 5. The Argand diagrams at selected temperatures; (a) phase (III), (b) phase (I).
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 268
is quite similar to that found in the phase (III). The energy of
activation estimated from the Arhennius law, for the relaxation
process in the phase (I) is found to be ca. 28 kJ/mol.
The change in the pyroelectric charge was measured on
cooling and heating. The spontaneous polarization of the order
of 3$10
K5
C$m
K2
appears in the vicinity of IV/III phase
transition (264 K, upon heating). The spontaneous polarization
is not reversed under an external DC electric eld. It can be
concluded that [n-C
4
H
9
NH
3
]
2
[BiBr
5
] may be classied as a
pyroelectric crystal over the phases (IV), (V) and (VI).
3.4. Infrared studies
The temperature dependence of the infrared studies
have been undertaken to clarify the cationic dynamics
contribution to the phase transition mechanisms in [n-C
4
H
9-
NH
3
]
2
[BiBr
5
]. The infrared spectra of the polycrystalline [n-
C
4
H
9
NH
3
]
2
[BiBr
5
] between 4000 and 500 cm
K1
in Nujol at
two temperatures, 12 and 300 K, infrared spectrum in
uorolube (at 300 K), and far infrared spectrum (at 300 K)
are presented in Fig. 6.
The wavenumbers and the assignments of the bands at 12
and 320 K are collected in Table 2. This assignment is based on
comparison with the IR spectra of n-butylamine [14] and
n-propylamine [15] and alkylammonium bromobismuthate-
s(III) salts as well [16,17]. The low frequency vibrational
spectra of bromobismuthates(III) and iodobismuthates(III) and
assignments of the MX
2K
5
anions are reported in [18].
The detailed analysis is made for the bands for which a
noticeable temperature changes are observed. A number of the
bands exhibiting the anomalous changes in the wavenumbers
and bandwidths around 264 and 311 K (in heating cycle),
which could conrm the dynamics role of the organic cations in
the mechanism of the phase transitions.
The temperature evolutions of the infrared bands in the
region of the u(CH
2
) deformation vibrations are shown in
Fig. 7(a). At low temperatures seven bands are observed. The
intensities of the bands decrease and they become broad at high
temperatures and at 320 K only four bands one can distinguish.
Temperature dependence of bands maxima assigned to the
u(CH
2
) vibrations is presented in Fig. 7(b). The positions of the
bands at 1327 and 1317 cm
K1
(12 K) shift to lower
wavenumbers approaching the T
c2
, whereas the band at
1348 cm
K1
(12 K) slightly shifts to higher wavenumbers
around this phase transition temperature. A linear increase
with temperature reveals the FWHM of 1327 cm
K1
band over
the phases VI, V and IV, next approaching the IV/III
transition it increases rapidly (Fig. 7(c)). This behaviour of the
1327 cm
K1
mode may be explained in terms of the releasing of
some type of motion by a long alkyl chain of cations.
The temperature evolution of the infrared spectra in the
region of the deformation vibrations r(CH
2
), r(CH
2
)C
r(CH
3
), and stretching vibrations n
s
(CC) and temperature
dependence of the wavenumbers of the modes observed in
this wavenumbers region are displayed in Fig. 8(a) and (b).
At 12 K nine components can be distinguished in this
region. Three of them (908, 896 and 888 cm
K1
) disappear
at high temperature of phase VI. The changes in the
position of some bands arising from r(CH
2
) vibrations are
observed close to T
c5
Z181, T
c3
Z264 and T
c2
Z311 K.
Three bands (924, 910 and 904 cm
K1
observed at 12 K)
shift their positions toward lower wavenumbers in the
high temperature of phase VI. The bands at 904 and
910 cm
K1
shift to higher wavenumbers close to T
c5
. At T
c3
Fig. 6. The infrared spectra of the powdered [n-C
4
H
9
NH
3
]
2
[BiBr
5
] sample in Nujol in the wavenumber range between 4000 and 500 cm
K1
at 12 and 300 K, the IR
spectra in uorolube at 300 K and FIR spectra.
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 269
Table 2
Wavenumbers, intensity and tentative assignments of the bands observed in the IR spectra in (n-C
4
H
9
NH
3
)
2
BiBr
5
at 12 and 320 K
12 K 320 K Assignments 12 K 320 K Assignments 12 K 320 K Assignments
3211 s
n
a
NH
C
3

1584 vs 1580 vs
d
a
NH
C
3

1001 w n(CN)
3201 s 1580 s 997 w 996 vw
3191 s 3185 vs 1568 s d
s
NH
C
3
975 vw 974 vw
3168 s 1564 m 973 vw
3156 vs 1556 vw 958 vw, br r(CH
3
)
3143 vs 1471
a
vs d(CH
3
) 924 w 917 w r(CH
2
)
3133 vs 3134 vs 1457
a
s, sh 921 w
3122 vs 1448
a
w, sh 918 w
3108 vs 3107 vs, sh n
s
NH
C
3
1393
a
vw 910 vw
3099 vs 1378
a
vw 907 vw
3086 vs 1340 vw 1341 vw u(CH
2
) 904 vw
3078 vs 1330 vw, sh 901 m n
s
(CC)
3065 s 1327 vw 1326 vw 896 m 899 w r(CH
3
)C
r(CH
2
)
3058 s 1317 vw 1314 vw 887 vw 888 vw sh
3038 s 3035
a
s n
s
(CH
2
) and n
a
(CH
2
),
n
s
(CH
3
) and n
a
(CH
3
)
1308 vw 882 vw r(CH
2
)
3029 m, sh 1290 vw, sh 869 vw 866 vw
2960
a
s 1287 vw 1287 vw t(CH
2
) 862 vw
2930
a
s 1270 vw 844 vw
2913
a
m, sh 1265 vw 1265 vw 839 vw, sh 837 vw n
s
(CCC)
2897
a
m 1257 vw 1257 vw, sh 802 vw 799 vw
2873
a
m 1249 vw 1248 vw, sh 797 vw
uNH
C
3

2863
a
m 1245 vw 791 vw 788 vw
2791
a
w 1245 vw rNH
C
3
C
rCH
3

789 vw
2787 vw 1190 vw 1187 vw, sh 786
8
>
>
>
<
>
>
>
:
vw
2731 vw 2734 vw 1175 vw 1173 vw 781 vw
2646 vw 1167 w 748 vw
2621 vw 2620 vw 1163 w 1161 w 561 vw u(skeleton)
2606 vw 1161 w sh 478
b
vw t(skeleton)
2581 vw 1156 w 1153 w 421
b
vw d(CCN)
2560 vw 1142 vw 398
b
vw
d(CCC)
2500 vw 1076 vw sh n
a
(CC) 346
b
vw
2486 vw 1072 vw 1072 vw 275
b
vw tNH
C
3

2476 vw 1068 vw 176
b
m, sh
n
(BiBr)terminal
2462 vw 2469 vw 1041 vw n(CN) 158
b
vs
2375 vw 1037 vw 1038 vw n
a
(CCC) 125
b
vs n
(BiBr)bridge
2365 vw 2366 vw 1030 w 1031 vw, sh 105
b
vs d
(BiBr)
1598 w 1012 vw
1591 s 1009 vw 1006 vw
vs, very strong; s, strong; m, medium; w, weak; vw, very weak; sh, shoulder; br, broad.
a
Spectrum in uorolube.
b
FIR spectra.
8
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n
n
J
.
T
a
r
a
s
i
e
w
i
c
z
e
t
a
l
.
/
J
o
u
r
n
a
l
o
f
M
o
l
e
c
u
l
a
r
S
t
r
u
c
t
u
r
e
7
9
2

7
9
3
(
2
0
0
6
)
2
6
5

2
7
3
2
7
0
two bands disappear and three others at 882, 896 and
918 cm
K1
shift to higher wavenumbers.
The temperature evolution and the temperature dependence
of the wavenumbers for the uNH
C
3
deformation modes are
shown in Fig. 9(a) and (b). Six components of these vibrations
are observed in the low-temperature phase spectrum. Four of
them disappear and only two bands are preserved at room
temperature. In this frequencies region the positions of two
Fig. 7. (a) Temperature evolution of the IR spectra in the u(CH
2
) vibrations region, (b) temperature dependence of the u(CH
2
) modes, (c) temperature dependence of
the full width at half maximum (FWHM) for 1327 cm
K1
mode.
Fig. 8. (a) Temperature evolution of the IR spectra in the r(CH
2
), r(CH
3
), and stretching n
s
(CC) vibrations region, (b) temperature dependence of the position of the
r(CH
2
), r(CH
3
), and stretching n
s
(CC) modes.
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 271
bands, 802 and 786 cm
K1
clearly change close to the T
c4
and
T
c3
phase transitions. The band at 802 cm
K1
shifts to lower
wavenumbers over the phases VI and V, next at T
c4
changes
discontinuously and around T
c3
rather continuously. The band
at 786 cm
K1
above T
c4
, in contrast to the 802 cm
K1
one,
hardens. Two bands at 797 and 789 cm
K1
disappear in phase V
on approaching the T
c4
temperature.
The important changes in the IR spectrum are observed at
224 and 264 K for some internal modes of cations. The
temperature wavenumbers changes of the other modes are
quite small. The changes around temperatures of phase
transition clearly indicate that the dynamics of the n-buty-
lammonium cations contributes signicantly to the mechanism
of phase transitions (at T
c3
and T
c4
) in [n-C
4
H
9
NH
3
]
2
[BiBr
5
].
4. Discussion
The sequence of the phase transitions in[n-C
4
H
9
NH
3
]
2
[BiBr
5
]
was found to be complicated since we observe ve solidsolid
transformations. Unfortunately, we were not able to determine
the crystal structure in any phase of this crystal. Some of these
phases appear to be incommensurately modulated. The prelimi-
nary X-ray studies indicate that [n-C
4
H
9
NH
3
]
2
[BiBr
5
] is
isomorphous at room temperature (monoclinic system, P2/m)
to the antimony analogue: [n-C
4
H
9
NH
3
]
2
[SbBr
5
]. Due to this,
both the n-butylammonium derivatives exhibit quite similar
sequence of phase transitions and nearly identical dynamic
properties observed by the dielectric and spectroscopic (IR)
method. The most characteristic feature of these crystals is the
presence, apart fromnumerous weak transitions, of one structural
phase transitionaccompanied bya great heat anomaly, namely: at
261 K in the Sb analogue and at 240 K for the Bi analogue, with
comparable transition entropy: 9.65 and 10.09 J/mol K, respect-
ively. The dielectric response in [C
4
H
9
NH
3
]
2
[BiBr
5
] exhibits
nearly the same feature as a shape of anomaly and values of the
dielectric function. The observed dielectric dispersion in both
compounds appears in the radio-frequency region. A long
macroscopic relaxation time of the order of 1$10
K7
1$10
K8
s
for both n-butylammoniumsalts is understood in terms of a huge
steric effect for a large in size alkylammonium cations.
To discuss the molecular mechanism of the phase
transition, we should consider the following possible
contributions: (i) the motion of the rigid n-butyl chain about
its long axis triggered by the ipping motion of the NH
C
3
group, (ii) the hindered motion of the CH
2
units with
respect to the long axis of the alkyl chain. Taking into account
a signicant value of the transition entropy, DS
tr(III/
IV)
z10 J/mol K at 240 K, the mentioned two kinds of motion
are believed to contribute to the mechanism of the phase
transition (III/IV). In turn, the phase (IV) is characterized
by an enhanced electric permittivity value reaching 38 units at
about 280 K. Through the (IV/V) transition the permittivity
is drastically reduced to 67 units. The discussed two kinds of
motion ((i) and (ii)) are expected to lead to a change in the
resultant dipole moment of the unit cell. That may explain the
dielectric anomalies in the vicinity of (III/IV) and (IV/V)
phase transition and conrms additionally an orderdisorder
mechanism of these transitions. The remaining transitions
at T
c1
, T
c2
and T
c5
, most likely, of a displacive type
are believed to be attributed to a change in the hydrogen bond
(N-H/Br) conguration of the system.
Fig. 9. (a) Temperature evolution of the IR spectra in the u(NH
C
3
) vibrations region, (b) temperature dependence of the wavenumbers of the maximum for the
u(NH
C
3
) deformation modes.
J. Tarasiewicz et al. / Journal of Molecular Structure 792793 (2006) 265273 272
Finally, we can state that the isomorphism of the Sb and Bi
n-butylammonium analogs is well reected in their dynamical
properties.
5. Conclusions
1. The [n-C
4
H
9
NH
3
]
2
[BiBr
5
] crystal undergoes ve solid
solid phase transitions of rst order (309, 291, 240, 219 and
at 166 K).
2. The phase transitions at 240 and 219 K of the order
disorder type are, more likely, due to the rotational motion
of the n-butyl chain around the long axis of the cation
and/or the hindered motion of the CH
2
units of the alkyl
group.
3. The low frequency dielectric relaxation is found to appear
over a wide temperature region. This process is attributed to
the dynamics of dipolar organic cations.
4. The infrared studies evidence the contribution of the
n-butylammonium moieties to the mechanism of phase
transitions in [n-C
4
H
9
NH
3
]
2
[BiBr
5
].
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