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Ferroelastic phase
transitions in
triethylammonium
and piperidinium
chloroantimonate(V)
B. Bednarska-Bolek
a
, R. Jakubas
a
, G. Bator
b
& A. Pietraszko
b
a
Faculty of Chemistry , University of Wroclaw ,
50-383, Wroclaw, Poland
b
Institute of Low Temperature and Structure
Research, Polish Academy of Sciences , 50-950,
Wroclaw, Poland
Published online: 16 Mar 2011.
To cite this article: B. Bednarska-Bolek , R. Jakubas , G. Bator & A.
Pietraszko (2001) Ferroelastic phase transitions in triethylammonium and
piperidinium chloroantimonate(V), Ferroelectrics, 264:1, 145-150, DOI:
10.1080/00150190108008561
To link to this article: http://dx.doi.org/10.1080/00150190108008561
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Fer mr l n~r r r cr . 2001. Vol. 264, pp 135-150
Reprint, available directly from the publisher
Photocopying pc?rmitlcd by license only
8 ?(I01 Wylor & Franci,
FERROELASTIC PHASE TRANSITIONS IN
TRIETHYLAMMONIUM AND PIPERIDINIUM
CHLOROANTIMONATE(V)
B. BEDNARSKA-BOLEKa, R. J AKUBASa, G. BATORa
and A. PIETRASZKOb
aFaculty of Chemistg, University of Wroclaw, 50-383 Wroclaw,
Poland;
bInstitute of Low Temperature and Structure Research, Polish
Academy of Sciences, 50-950 Wroclaw, Poland
(Received infinal form August 3, 2001)
Abstract. Preliminary x-ray diffraction, IR, Raman and dielectric
studies of (C5HloNH2)SbC16 and [(C2H5)3NH]SbC16 are reported. The
former crystal undergoes three phase transitions: at 294, 310 and
369 K, whereas latter crystal one transition at 336 K. Both salts reveal
ferroelastic domain structure at room temperature. Dynamic of the
organic cations is suggested to contribute to ferroelastic-paraelastic
phase transitions at 369K (piperidinium salt) and 336K
(triethylammonium one).
Kevwords: phase transition; ferroelastic; IR; Raman
INTRODUCTION
In spite of the fact that the chloroantimonates(V) were synthesized
nearly hundred years ago, very little is known about their physical
properties, especially possible phase transitions (PTs) in solid state.
Recently, we have reported that several compounds belonging to
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146/11804] B. BEDNARSKA-BOLEK el a1
RSbC16 family exhibit interesting ferroic (ferroelastic) properties. Up
to now four RSbC16 crystals were discovered: [P(CH,),]SbC16 [I],
[C(NH2)3]SbC16 2 1, (C~H~ONHZ)S~C~~.(C~H~ONH~)C~ 3 1 and
[(CzH5)3NH]SbC16 [4]. The structure of these salts is quite simple. In
the crystal lattice one can distinguish isolated SbC1; anions and
organic cations. In the case of piperidinium salt having more
complicated stoichiometry, RSbClgRCl, the crystal lattice contains
also isolated C1- ions.
This paper is devoted to preliminary x-ray, dielectric, Raman and
IR studies and optical observations for new ferroic crystals:
[(CzH5)3NH]SbC16 (abbreviated as TCA) and (C5HdHZ)SbC16
(PCA).
EXPERIMENTAL
Temperature x-ray results were obtained using the four circle x-ray
diffractometer KM4-CCD (KUMA Diffraction Company). The Raman
spectra of the powdered samples were recorded using a NICOLET
Magna 860 spectrometer with FT Raman Module (Nd:YV04 laser).
The IR spectra were recorded with FT-IR BRUKER IFS-88
spectrometer. The complex electric permittivity E* was measured
using a HP 4285 LCR meter within the frequency range 75 kHz-30
MHz.
RESULTS
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FERROELASTIC PHASE TRANSITIONS I I8051/147
X-ray measurements showed that TCA and PCA crystallize at room
temperature in monoclinic (space group P21/n) and triclinic (Pl)
symmetry, respectively. Crystallographic results will be presented
elsewhere [ 5] . Structure of these compounds consist of isolated SbCli
anions and ordered organic cations. The temperature x-ray studies
revealed that both compounds undergo structural PTs above room
temperature. The sequence of the PTs (on heating) is following (f-
ferro-, p-paraelastic, 1 st-, 2d- order of PT):
TCA: ~ 2 1 / n (0 336R(1) F c222 (PI
+Cmcm(p)
369K(1)
+CC(0
310K( Z d )
PCA: ~2l /m(p?) 2WK(1) 3 Pl (0
The sequence of the PTs in TCA and PCA crystals was confirmed by
DSC and dilatometric measurements.
The temperature dependence of E (on cooling) for TCA and PCA
crystals is shown in Figure 1. It suggests that para-ferroelastic PT
exhibits the features typical for so called rotator phase. Since our x-
ray studies show that cationic sublattice is characterised in the
paraelastic phase by important disorder, mentioned PT should
obviously lead to a drastic fieezing of rotational freedom of dipolar
organic cations. In the ordered, ferroelastic phase of TCA a low
frequency dielectric relaxation process reveals (see Figure 1).
The optical observations under polarizing microscope show that
both TCA and PCA crystals exhibit ferroelastic domain texture at
room temperature and their high temperature PT at 336 and 369 K,
respectively, lead to paraelastic phase. An example of domain texture
seen in the ab plane for the triclinic phase (III) of PCA is shown in
Figure 2.
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148/[ 18061 B. BEDNARSKA-BOLEK et a/
The most interesting changes in the Raman spectra of TCA at
T, = 336 K are observed in the frequency range assigned to the anionic
internal vibrations (400 - 150 cm-'). The temperature evolution of
the spectra in this wavenumber region is shown in Figure 3a, whereas
Figure 3b displays the temperature dependence of positions of some
bands.
1.1
7.2
E;. 6.7
6.2
5.1
240 280 320 360
Temperalure [Kl
FIGURE 1. Temperature dependence of E' for TCA and PCA.
FIGURE 2. Ferroelastic domain structure in the ab plane of PCA at
290 K (phase 111).
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8 s 1
1 9 1
t 9 1
1 9 1
O L L
E L L
9 L l
6 L l
2 8 1
s e I
0 8 2
v v i v v v v v
: x x x x x
O M
O S E
O 6 E O S E O L E O L Z O E Z 0 6 1 O S l o t s c 0 9 S l 0 0 s 1 0 0 8 1 0 2 9 1
8 E S 1
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V 3 d
6 P I l [ L 0 8 [ 1 S N O I I I S N V X I 3 S V H d 3 I I S V 7 3 O N W d
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l50/[ 18081 B. BEDNARSKA-BOLEK el a/
The observed changes in the evolution of the spectra may suggest that
some kind of motion of SbCli ions is released when the crystal
undergoes the structural PT at 336 K.
On the other hand in the case of the PCA crystal the most
spectacular changes are observed for some bands in the internal
vibration frequency region of the piperidinium cations (see Figure 3c
and d). An important temperature changes are visible around the
( N4I I ) PT, whereas the (11141) one is practically inactive in the IR
studies. One can conclude, that change in the dynamic state of
piperidinium cation plays the main role in the mechanism of PTs at
294 and 369 K.
CONCLUSIONS
1. Two new RSbC16 ferroelastic crystals were found:
[(CzH5)3NH] SbCI6 and (C5H 1 oNH2)SbC16.
2. The presented results indicate that dynamics of the cationic
sublattice plays the main role in the mechanism of ferroelastic PTs.
REFERENCES
[ 11 P. Ciqpala, R. Jakubas, G. Bator, A. Pietraszko and B. Kosturek,
J. Phvs.:Condens. Matter, to, 5439 (1998).
[2] R. Jakubas, P. Ciqpala, A. Pietraszko, J . Zaleski and J. Kusz,
J . Phvs. Chem. Solids, 59, 1309 (1998).
[3] B. Bednarska-Bolek, A. Pietraszko, R. Jakubas, G. Bator
and B. Kosturek, J . Phvs.: Condens. Matter, 12,1143 (2000).
[4] B. Bednarska-Bolek, Z. Ciunik, R. Jakubas, G. Bator and
P. Ciqpala, J . Phvs. Chem. Solids, submitted for publication.
[5] A. Pietraszko, B. Bednarska-Bolek, R. J akubas and P. Zielinski,
J . Phys.:Condens. Matter, submitted for publication.
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