PHYSICAL REVIEW 8 VOLUME 43, NUMBER 16 1 JUNE 1991

Crystal structure of and low-temperature phase transitions in isostructural

RbSm(SO4)2 4Hzo and NH4Sm(SO4)2. 4H20

S. Jasty
Department of Physics and Molecular Science Program, Southern Illinois University at Carbondale,
Carbondale, Illinois 62901-4401

P. D. Robinson
Department of Geology, Southern Illinois University at Carbondale, Carbondale, Illinois 62901-4401

V. M. Malhotra
Department of Physics and Molecular Science Program, Southern IllinoisUniversity at Carbondale,
Carbondale, Illinois 62901-4401
(Received 6 August 1990; revised manuscript received 26 December 1990)
The crystal structure of RbSm(SO4), .4H20 was determined at 296 K using the x-ray-
crystallographic-diffraction technique. The unit cell is monoclinic with P2l/c space group. The
structure can be envisioned as consisting of the following constituents: a nine-coordinated Sm po-
lyhedron, two crystallographically independent sulfate tetrahedra, an interlayer water, and a caged
Rb cation. Both inequivalent sulfates bridge the nine-coordinated Sm polyhedra, forming
crisscrossing networks of chains along the [100j and [001] directions, which result in rippled layers
in the structure parallel to the (010) plane. It is argued that the monovalent cation Rb is caged by
11 sulfate oxygens and 2 water molecules, and the Rb+ ion rattles in a cavitylike geometry. The
crystal structure of RbSm(SO4)2-4H~O has been compared with the published structure of the
NH4Sm(SO4)2 4H20 lattice, and the two structures are isostructural in the conventional sense.
However, from our proposed hydrogen-bonding scheme for water molecules and from a compara-
tive analysis of the two structures, it is suggested that there are significant differences in the mono-
valent cation coordination in the two lattices. Also, the hydrogen-bond strengths, which are crucial
to the cohesion of the lattice, show significant difFerences in these two isostructural lattices. In-
frared and thermal dehydration probing further support our contention that there are three distinct
types of water in lanthanide double sulfates. From the specific-heat measurements at 100 & T(303
K, it is shown that the RbSm(SO4)2. 4820 lattice undergoes a single A. transition at 232+1 K, unlike
NH4Sm(SO4)2 4H20, which has two structural transitions in the above temperature range. The A,
anomaly reflects logarithmic dependence near the transition temperature, thus suggesting the transi-
tion is order-disorder in origin.

I. INTRODUCTION structural materials NH4L(SO4)2 4H2 O(L =La, Ce, Pr,

Structural phase transitions have been investigated ex-
tensively in a wide variety of materials, both experimen-
tally and theoretically. ' The major scientific thrust has
been directed toward understanding the universality of
behavior at critical regions. Some progress has been
made in the study of structural phase transitions in three
dimensions through computer simulations on idealized
systems such as hard-sphere models. ' However, the ex-
act conditions under which a real material will undergo a
structural phase transition still remain an open question.
In order to predict the mechanism that will drive a
structural phase transition, a complete knowledge of the
microscopic force constants is required. In the absence
of such detailed information, substantial headway can be
made by studying a sequence of isostructural materials,
which contain members displaying phase transitions.
Perovskites' have been extensively investigated due to
their simple structure. Recently, another series of iso-
Nd, Sm, Eu, Gd, Tb, and Dy), which show a unique trend
in phase-transition behavior, has been reported. Unlike
other isostructural lanthanide series, the phase-transition
temperatures in this series show no straightforward
correlation either with the unit-cell parameters or with
the host lanthanide ion's ionic radius.
For several ammonium compounds in which phase
transitions occur, the ammonium ion has been found to
be responsible for driving the transition. It has been
observed that the ammonium ion forms a number of com-
pounds which are isostructural with the corresponding
alkali salts, especially rubidium, since NH4+ and Rb+
have similar, effective ionic radii. ' '"
Hence, it would be
interesting to study the effect of the replacement of the
monovalent cation, ammonium by rubidium, on the crys-
tal structure of NH4L(SO4)2 4HzO (ALSTH) and, conse-
quently, compare the phase-transition behaviors of the
ammonium and rubidium compounds. Since the crystal
structure of ammonium samarium sulfate tetrahydrate

43 13 215 1991 The American Physical Society

13 216 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA 43

(ASmSTH) has been reported by Eriksson et al. , ' the
corresponding rubidium compound, i.e. , rubidium
samarium sulfate tetrahydrate (RSmSTH), was chosen for
this study.
In the present paper, we investigate the crystal struc-
ture of RSmSTH by x-ray diffraction and report the re-
sults of the specific-heat measursement on RSmSTH.
Since the hydrogen-atom positions could not be obtained
from the x-ray-diffraction data, a hydrogen-bonding
scheme for the water molecules in RSmSTH and
ASmSTH is proposed based on geometrical considera-
tions derived from crystallographic data. The water's vi-
brational spectra have been used to test the validity of the
proposed hydrogen-bonding model. Thermal data, in
terms of the dehydration behavior of RSmSTH, have also
MITHRIL, together with an automatic procedure DIR-
DIF, for phase extension and refinement of the
difference structure factors. Neutral atom scattering fac-
tors were taken from Cromer and Waber. ' Anomalous
dispersion effects were included in the calculation of F
(=F, ). ' The values for the scattering factors Df' and
Df" required for the treatment of the anomalous disper-
sion were those of Cromer. ' The full-matrix least-
squares refinement was based on F, and the function min-
imized was
The weights w were taken as 4F, /[o (F, )'], where iF,
l
i

been applied to the same end. It will be demonstrated and iF, are the observed and calculated structure factor
i

that a single A, -type phase transition occurs in RSmSTH, amplitudes, respectively.

quite unlike the two successive phase transitions reported A full-matrix least-squares refinement was performed
for ASmSTH. Further, it will be shown that the with 146 variables, and the final unweighted and weight-
significant differences between the hydrogen-bonding net- ed A factors were calculated from
works in the RSmSTH and ASmSTH lattices indicate
that the waters of hydration play a key role in driving the
structural phase transition in RSmSTH. =0.033,
II. EXPERIMENTAL TECHNIQUES
A. X-ray di8'raction measurements
=0.051 .
Single crystals of RSmSTH were grown by isothermal ta;F, l

evaporation at room temperature from an aqueous solu-

tion of RbzSO4 and Sm2(SO4)3 8HzO mixed in a 4:1 ratio
under conditions described by Jasty and Malhotra.
clear prismatic crystal of RbSm(SO~)2 4HzO, having ap-
proximate dimensions 0.24 X 0.21 X 0. 13 mm, was
mounted on a Rigaku diffractometer with graphite mono-
chromated Mo Ke radiation. The cell constants and an
orientation matrix for data collection were obtained from
a least-squares refinement, using the setting angles of 23
carefully centered reflections in the
49. 55' & 20 &49.95 . The intensity data were collected at
296 K, using the co-20 technique at a speed of 4.0'/min in
co. The weak rejections [I (10. 0o. (I)] were rescanned
(maximum of two rescans) and the counts were accumu-
lated to ensure good counting statistics. Stationary back-
ground counts were recorded on each side of the
reflection. Of the 2143 reflections collected, 1966 were
unique. The intensities of three representative reflections,
which were measured after every 150 reflections,
remained constant throughout data collection, indicating
crystal stability. The data were corrected for Lorentz
and polarization effects. The calculations were per-
formed using the TEXSAN (Ref. 13) crystallographic
software package of Molecular Structure Corporation.
B. Solution and refinement of the structure
The analysis of the RSmSTH crystal structure was
based on 1547 observed unique reflections with intensities
I & 3.00o(I). Since the space group of the crystal was
determined to be centrosymmetric, the structure was
solved by an integrated direct method computer program
The goodness-of-fit indicator
A
was 1.62, where X, was the number of observations and
N, was the number of variables.
range C. Hydrogen-atom positions
We attempted to locate the hydrogen atoms from the
final-difference Fourier map. However, the maximum
and minimum peak densities, corresponding to
(1.05X10 ) e/nm and ( —1.66X10 ) e/nm, respective-
ly, were found within 0. 11 nm of the samarium atom.
This is not surprising since the residual peaks of electron
density, corresponding to hydrogen-atom positions, are
generally obscured' in the presence of heavy atoms like
Sm and Rb. Consequently, the density profiles could not
be used to determine the hydrogen-atom positions. In-
stead, we adopted the following procedure. Based on the
positions of the nonhydrogen atoms and the known
hydrogen-bonding geometries, initial, approximate posi-
tions of the hydrogen atoms were calculated. Then, a
full-matrix least-squares refinement of the 146 variable
nonhydrogen parameters was performed with hydrogen
atoms included in the atoms' list. Successive recalcula-
tion of hydrogen-atom positions and least-squares
refinement was carried out until the maximum shift in the
refinement parameters was negligible.
To determine the approximate positions of the hydro-
gen atoms, the following criteria were applied first to
43 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE.
decide if a particular O(W)-O(S) or O(W)-O(W') contact
[where O(W) and O(W') denote water oxygens and O(S)
denotes a sulfate oxygen] corresponds to a hydrogen
bond.
(1) Distance criterion. The O(W)-0 distance should be
less than 0.31 nm. This follows from a simplified average
description of molecular packing in terms of the Van der
baal's contact radii.
(2) Angle criterion. (a) The hydrogen atoms of a water
molecule are expected to orient away from the electron-
acceptor neighbors X. For the present structure, X could
be Sm, Rb, or an 0-H group. Therefore, the
X —O(W) —O(acceptor) angle should be larger than 75 .
This also precludes the possibility of a hydrogen bond
along an edge of a coordination polyhedron about a cat-
ion. (b) The angle subtended by the two hydrogen-bond
acceptors at the oxygen of a single water molecule should
not deviate by more than 35' from the tetrahedral angle.
Only eight of the O(W)-0 contacts satisfied the above
criteria simultaneously, which corresponds exactly to the
number of hydrogen atoms available. Thus, the position-
al parameters for the hydrogen atoms could be calculated
unambiguously by making the following assumptions: (1)
The O(W)-H distance was assumed to be equal to 0.97
A. (2) The H-O(W)-H angle was assumed to be 107.2',
which corresponds to an average angle of crystalline hy-
drates that has oxygen atoms as acceptors of the hydro-
gen bonds donated by the water molecules. (3) The plane
of the water molecule was assumed to coincide with the
plane defined by O(W) and the two hydrogen-bond accep-
tors since the acceptors tend to be located close to the
water plane.
An isotropic temperature factor, equal to 1.2 times the
isotropic temperature factor of the water oxygen O(W), '
was assigned for each hydrogen atom. The positional
and thermal parameters of the hydrogen atoms were held
fixed. A full-matrix least-squares refinement, based on
the 146 variable parameters given above, was performed.
The positional and thermal parameters of the hydrogen
atoms were recalculated and reassigned using the updat-
ed parameters of the nonhydrogen atoms. A final full-
matrix least-squares refinement converged after one cycle
with a largest-parameter shift of 0.003 times its e.s.d.
TABLE I. Crystal data and statistical summary for RbSm(SO4)z. 4H20.
a =0.6565(2) nm Formula weight: 500.04
b =1.8913(6) nm Space group: Monoclinic P2, /c
c =0. 8728{1) nm Radiation: MO Ko. , A,
P = 96. 26(2)' T =296 K
V=1.0772(5) nm pea)
= 3.083 kg/m'
@=102.7 cm
Transmission coefficient:
0.56—1.00
' Refinement excluding hydrogen atoms.
Refinement including hydrogen atoms.
.. 13 217
The weighted R factor dropped by 0. 1%%uo from the value
obtained before the inclusion of hydrogen atoms, yielding
a final R =0.050 and an unweighted R factor equal to
0.032. The goodness of fit indicator improved by l~o,
with a final value equal to 1.60. The statistics for both
models, without and with the inclusion of hydrogen
atoms, i.e., models I and II, respectively, are summarized
in Table I. The Hamilton signific'ance test was ap-
plied to the weighted R factors to determine if the de-
crease in R, due to the inclusion of hydrogen atoms, is
significant. The computed R factor ratio,
R„(I)/R (II)=1.020. From Table I, the dimension of
the test is (178 —146) =32, and the degrees of freedom
are ( 1547 —178 ) = 1369. Interpolation in Hamilton's
tables for +=0.01 indicates a ratio of about 1.019.
Since the computed R factor ratio was slightly greater
than this value, we conclude that the decrease is
significant at 1% level.
D. Specific-heat measurements
The specific-heat data at 100& T &303 K were ob-
tained by the Differential Scanning Calorimetry (DSC)
technique using a Perkin-Elmer DSC7 system. The
calorimeter was interfaced to a Perkin-Elmer 7700 com-
puter through a thermal controller for data collection
and analysis. Details of the temperature and enthalpy
calibration and the experimental run conditions in the
subambient temperature region have been given else-
where. By comparing the C values of the A1203 discs,
obtained on our instrument, with those published by Gin-
nings and Furukawa, the accuracy of the specific-heat
capacity at 130 & T & 303 K is estimated to be better than
2%.
The dehydration behavior of RSmSTH was also deter-
mined using the Perkin-Elmer DSC7 system. Fine crys-
tals of RSmSTH were selectively picked and crimped in
nonvolatile Al pans. Holes were punched in the lids of
the pans to lower the mechanical barrier to the dehydra-
tion process. High-purity N2 was used as the purge gas.
The heating runs were made at a scan rate of 5 K/min.
Model I' Model IIb
No. of reAections 1547 1547
used in refinement
No. of parameters 146 178
(fixed+ variable) (146+0) (146+32)
=0.07107 nm R 0.033 0.032
R 0.051 0.050
Goodness of fit indicator 1.62 1.61
13 218 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA 43

TABLE II. Positional and equivalent isotropic thermal parameters for the non-H atoms and their
e.s.d. 's.
Beq =(81T /3)( U|1+ U2p+ U33+2U(pcosp+2U)3cosP+2U23coscx) .

Atom ~eq (10

Sm(1) 0. 153 06(6) 0. 124 48(3) 0.782 48(5) 1.01(2)
Rb(1) 0.649 6(2) 0.220 89(7) 0. 114 3(1) 3. 10(5)
S{1) 0. 126 0(4) 0.278 6(1) 0.905 5(2) 1.46(9)
S{2) 0.695 6(3) 0.076 1{1) 0.773 5(3) 1.7(1)
O(1) 0.087(1) 0. 157 6(4) 0.314 4(8) 2.4(3)
O(2) 0. 144(1) 0.296 9(4) 0.070 2(8) 2.9(3)
O(3) 0.958(1) 0.273 2(4) 0.372 5(7) 1.7(3)
O(4) 0.314(1) 0.257 4(4) 0.369 9(7) 1.9(3)
O(5) 0.516(1) 0.379 5(4) 0.285(1) 2.7(3)
O(6) 0.639(1) 0.003 0(5) 0.746(1) 4. 1(4)
O(7) 0.806(1) 0.393 8(5) 0. 149 3{8) 2.6(3)
O(8) 0.845(1) 0.417 4(4) 0.413 8(8) 2.3(3)
O(W(1) ) 0. 187(1) 0.443 7(4) 0.039 3(8) 3.0(3)
O(W(2)) 0.259(1) 0. 113 8(4) 0.059 8(8) 2. 5(3)
O(W(3) ) 0.635{1) 0. 105 8(5) 0.344(1) 4. 1(4)
O(W(4) ) 0.807(1) 0.000 4(4) 0. 168 1(8) 2.7(3)

E. FTIR measurements tween 0.2372 and 0.2556 nm, which is about the same
range observed in ASmSTH. ' The average Sm-sulfate
The infrared vibrational spectra of the RSmSTH and oxygen distance (0.247 nm) is approximately the same as
ASmSTH crystals were recorded at 296 K with the help the average distance from Sm to the water oxygen (0.246
of an IBM IR-32 Fourier transform infrared (FTIR) spec- nm). Based on the data presented in Table IV and that
trometer equipped with an IBM 9001 computer. The listed in Ref. 12, it is reasonable to argue that, on replac-
fiuorolube mull technique was employed. The sample ing the NH4+ ion with Rb+, the geometry around the
mull was sandwiched between polished KBr discs. Fifty lanthanide ion remains unaltered.
interferograms acquired at a resolution of 4 cm ' were The framework of the RSmSTH structure consists of
signal averaged to obtain the final spectrum for each sam- chains of Sm coordination polyhedra, linked in a parallel
ple. manner to the c axis by S(1)04 groups and to the a axis by
S(2)04 groups, as shown in Fig. 1. Due to the c glide
III. RESULTS AND DISCUSSION plane being perpendicular to the b axis, the adjacent Sm
polyhedra parallel to the c axis are displaced along the
A. Structure description: RbSm(SO4)2-4HzO [010] direction by about +0. 25b, with alternating signs.
This results in continuous zigzag chains of Sm
The unit-cell parameters for RSmSTH, along with polyhedra-S(1)O~ tetrahedra parallel to the c axis. On the
structural refinement parameters, are reproduced in other hand, adjacent Sm polyhedra along the a axis are a
Table I. The positional parameters of the final structural distance "a" apart so that the continuous chains of Sm
model for the nonhydrogen and hydrogen atoms in polyhedra-S(2)04 tetrahedra, parallel to the a axis are
RSmSTH are listed in Tables II and III, respectively. linear. Thus, the crisscrossing network of chains along
The isotropic Debye-Wailer temperature factors for the the [100] and [001] directions forms rippled layers in the
nonhydrogen atoms B,„are also given in Table II. The
atom numbering system used for this investigation is
identical to that reported by Eriksson et al. ' for
NH~Sm(SO4)z. 4HzO in order to facilitate a comparison TABLE III. Calculated positional parameters for the H atoms.
between the structural data of RSmSTH and ASmSTH. Atom
The RSmSTH structure may be envisioned as consist-
ing of the following components: a Sm polyhedron, two H(11) 0. 1356 0.4019 —0.0168
crystallographically independent sulfate tetrahedra, an H{12) 0.2533 0.4729 —0.0319
interlayer water molecule, and a caged Rb cation. The H(21) 0. 1893 0. 1388 0. 1359
Sm ion is coordinated to nine oxygens of which six belong H(22) 0.3086 0.0696 0. 1063
to the two independent sulfates and three to the waters of H(31) 0.6883 0. 1023 0.4521
hydration W(1), W(2), and W(4). The bond lengths and H(32) 0.5419 0.0665 0.3217
angles for the Sm polyhedron are given in Table IV. In H(41) 0.8259 0.0257 0.0740
this coordination sphere, the Sm-O distances vary be- H(42) 0.7479 0.0334 0.2359
 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE. . . 13 219

TABLE IV. Coordination around samarium.

Bond distances (nm)
Sm(1) 0(2) 0.2372{7) Sm{1) O(3) 0.2496(6)
Sm(1) 0(5) 0.2383(7) Srn(1) O(W(1)) 0.25 14(7)
Sm(1) 0(W(4)) 0.2411(7) Srn(1) O{4) 0.2551(7)
Sm(1) O(W(2) ) 0.2453(7) Sm(1) 0(8) 0.2556{7)
Sm(1) O(7) 0.2465(7)
Bond angles (deg)
(2) Sm(1) O{5) 88.2{3) O(W(4) ) Sm(l) O(W(1)) 68.3{2)
0(2) Sm(1) 0(W(4)) 138.4(2) 0(W(4) ) Sm(1) O(4) 140.5(2)
0(2) Sm(1) 0(W(2)) 143.4(3) 0(W{4)) Sm{1) 0(8) 72.0(3)
0(2) Sm(1) 0(7) 77. 1(3) 0(W{2)) Sm(1) 0(7) 127.0(2)
0(2) Sm(1) 0(3) 77.8(2) O(W(2)) Sm{1) O(3) 81.6(2)
O(2) Sm(1) 0(W(l)) 70. 1(3) 0(W(2)) Sm(1) 0(W(1)) 138.5(2)
0(2) Sm(1) 0(4) 70. 1(2) O(W(2) ) Sm{1) 0(4) 73.3{2)
0(2) Sm(1) O(8) 126.2(3) 0(W(2) ) Sm(1) O(8) 71.6(2)
0(5) Sm(1) O(W(4) ) 83.0(3) 0(7) Sm(1) 0(3) 77. 1(2)
0(5) Sm(1) 0(W(2) ) 79. 1(3) O(7) Sm(1) O(W(1) ) 72. 1(3)
0(5) Sm(1) O(7) 150.7(3) 0(7) Sm(1) 0(4) 126.4(2)
0(5) Sm(1) 0(3) 124.7(2) 0{7) Sm(1) 0(8) 55.5(2)
0(5) Sm(1) 0(W(1) ) 79.2(3) 0(3) Sm{1) O(W(1)) 39.4(2)
0(5) Sm(1) 0(4) 69. 1(2) 0(3) Sm(1) O(4) 55.7(2)
0(5) Sm(1) 0(8) 145.5(3) 0(3) Sm(1) 0(8) 68.9(2)
0(W(4)) Sm(1) 0(W(2)) 74.3(2) 0(W(1) ) Sm(1) O(4) 129.0(2)
0(W(4) ) Sm(1) O{7) 91.3(3) 0(W(1)) Sm(1) 0(8) 111.5(3)
0(W(4) ) Sm(1) O(3) 138.8(2) 0(4) Sm(1) O(8) 117.3(2)

structure, parallel to the (010) plane. The regions be- "

tween the layers contain the water molecule W(3) and the
monovalent cation Rb. As will be discussed later, the
layers are held together by hydrogen bonds. The intera-
tomic distances and angles of the two crystallographically
independent sulfate groups are given in Table V. As can
be seen from this table, the S(2)04 sulfate is relatively
more distorted than the S(1)04 sulfate.
For the monovalent cation Rb, the atoms comprising
its coordination sphere of radius 0.38 nm are listed in
Table VI. Rb has four close contacts ((0.
31 nm) in the
RSmSTH structure similar to the coordination reported
for the ammonium ion in ASmSTH. However, the coor-
dination number listed for the rubidium ion in various
oxides and halides ranges from 6 to 14. In more com-
plex Rb structures, such as the alums, the Rb ion is at
least octahedrally coordinated. This is not surprising
considering the large size of the ion. Even though the ru-
bidium and ammonium ions have similar effective ra-
dii, ' '"a lower coordination number generally has been
observed for the NH4+ ion in ammonium salts' because
of its tendency to form four, more or less, straight
N— 0
H — hydrogen bonds. For a Rb+ ion, to our
knowledge, the coordination number has never been less
than 6. Therefore, we believe, based on the data listed in
Table VI, that it has 13 nearest neighbors. This large
number of nearest neighbors for the monovalent cation in
RSmSTH appears to be the consequence of the rippled

TABLE V. Tetrahedral coordination around sulfur.

S(1)04 S(2)0
Bond distances (nm)
S(1) 0(1) 0. 1453(8) S(2) O(6) 0. 1446(9)
S(1) 0(4) 0. 1470(7) S(2) 0(5) 0. 1459(7)
S(1) 0(2) 0. 1471(7) S(2) Q(7) 0. 1482(7)
S(1) 0{3) 0. 1481(7) S(2) 0(8) 0. 1489(7)
Bond angles (deg)
0(1) S(1) 0(4) 111.7(4) 0(6) S(2) O(5) 111.5(5)
0(1) S(1) 0(2) 109.3{4) 0(6) S(2) 0(7) 112.7(5)
0(1) S(1) 0(3) 111.1(4) O(6) S(2) 0(8) 110.3(5)
0(4) S(1) O(2) 109.6(4) O(5) S(2) O(7) 107.2(5)
0(4) S(1) 0(3) 106.1(4) 0(5) S(2) O(8) 111.1(5)
0(2) S(1) 0(3) 108.9(4) 0(7) S(2) 0(8) 103.8(4)
13 220 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA 43

TABLE VI. Bond distances (nm) for Rb and N (recalculated based on atomic positions given in
Table II of Ref. 12 with standard deviations from Table VI of Ref. 12).
Rb(1) O(4) 0.2925(6) N(1) O(4) 0.2890(15)
Rb(1) O(W(3)) 0.2969(9) N(1) O(W(3)) 0.2951(17)
Rb(1) O(3) 0.3025(7) N(1) O(3) 0.2986(16)
Rb(1) O(3) 0.3080(6) N(1) O(3) 0.3004'
Rb(1) O(W(2)) 0.3261(8)
Rb(1) O(4) 0.3375(7)
Rb(1) O(1) 0.3413(7)
Rb(1) O(7) 0.3432(7)
Rb(1) O(8) 0.3471(8)
Rb(1) O(5) 0.3472(8)
Rb(1) O(5) 0.3505(8)
Rb(1) O(2) 0.3599(9)
Rb(1) O(2) 0.3607(9)
'Not given in Ref. 12.

layer framework formed by the samarium-sulfate chains Figure 2 shows the 13 nearest neighbors connected by
in the structure, discussed above. With the interlayer wa- bonds to the caged rubidium ion. A comparison of the
ter oxygen O(W(3)), acting as a cap, a cavity is formed first four nearest-neighbor interatomic distances M-0 be-
within which the Rb ion is caged. tween RSmSTH (M =Rb) and ASmSTH (M =NH4),
given in Table VI, indicates that the corresponding dis-
tances are consistently longer in the rubidium structure
than in the ammonium analog. It is worthwhile to point
out that Khan and Baur' have determined that the
effective ionic radius is larger for the ammonium ion than
for the rubidium ion. Since the N —H . hydrogen
0
bond is expected to be weaker than the Rb-0 covalent
bond, the opposite trend in interatomic M-0 distances d
would be expected, i.e. , d(Rb-0)(d(N-0). In addition,
the Rb-0 distances for the fifth and higher nearest neigh-
bors, given in Table VI, are longer than the sum of the
largest effective ionic radii for rubidium (0. 183 nm) and
O(3)- oxygen (0. 142 nm). " This observation suggests fairly
S{1
0{

p{SI 0{@

FIG. 1. Drawing shows the structure of RbSm(SO&)2. 4H20

at 296 K. The a axis is horizontal, the b axis is vertical, and the
c axis points into the paper. W(1), W(2), and W(4) are the oxy-
gens of water which are coordinated to the trivalent Sm ion.
W(3) represents the oxygen atom of the interlayer water. The
two inequivalent sulfates, forming bridges between the Sm po- FICx. 2. The drawing displays the coordination of the rubidi-
lyhedra, are shown by S(1) and S(2). um ion in RbSm(SO4)2. 4H20.
43 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE. .. 13 221

weak bonding between the monovalent cation and its

nearest neighbors. Hence, the model, wherein the mono-
valent cation Rb is envisaged as rattling in a cage bound
by 11 sulfate oxygens and two water oxygens, seems to be
valid. The substantially large thermal factor obtained for
Rb (0.0031 nm ), see Table II, further supports this con-
tention. Due to the odd number of nearest neighbors
(vertices), the cage bounding the rubidium ion does not
appear to have any regular polyhedral geometry.

B. Hydrogen-bonding scheme

The interatomic distances for the hydrogen bond in-

volving water molecules are reproduced in Table VII. As
pointed out earlier, the layers parallel to the (010) plane
are held together primarily by hydrogen bonds. A fur-
ther illustration of the role played by the hydrogen-
bonding network in the cohesion of the structure, both
across and within the (010) layers, is shown in Fig. 3. Of
the eight hydrogen bonds donated by the four waters of
hydration, the majority, in this case six, are involved in
linking the layers. This is in agreement with the observed
peculiarity of the W . 0 hydrogen bonds in crystalline
hydrates to link layers corresponding to cleavage sur-
faces. Only two of the eight hydrogen bonds
O(W(1))~O(1) and O(W2))~O(1) provide in-chain
coupling in addition to the bridging S(1)O(4) sulfate. This
contributes to the stability of the zigzag chains parallel to
the c axis. Of the six hydrogen bonds involved in linking
the layers, two belong to the interlayer water molecule
W(3) which has its hydrogen-bond acceptors O(7) and
O(6) in opposite layers (see Fig. 3). Thus, the interlayer
water molecule W(3) acts as a true bridge across the lay-
ers. Additional cross-layer linking is provided by the
four hydrogen bonds [O(W( 1 ) ) ~O(6), O(W(2) ) ~O(6),
FIG. 3. The proposed hydrogen-bonding scheme for water
molecules in the RbSm(SO4)2. 4H20 structure is presented. The
horizontal dotted lines in the figure signify various layers. The
dashed lines symbolize hydrogen bonds with arrows pointing to-
ward acceptors. Similar bonding is also valid for isostructural
NH4Sm(SO4), .4H20. The bond distances for
RbSm(SO4)2. 4H20 and NH4Sm(SO&)2 4H20 are reproduced in
Table VII.
O(W(4))~O(8), and O(W(4))~O(W(3))] denoted by
the water molecules W(1), W(2), and W(4) whose oxygens
are part of the Sm coordination polyhedron. The range
of hydrogen-bond lengths donated by the water molecules
is 0.034 nm and spans from 0.273 to 0.307 nm, as given in
Table VII. This fairly small spread in hydrogen-bond
lengths is typical of hydrated systems in which hydro-
gen bonds play an important role in the cohesion of the
structure.

TABLE VII. Effect of cation on the hydrogen-bond geometries in isostructural RbSm(SO4)2 4H20
and NH4Sm(SO4)2 4H20.
RbSm(SO4)2 4H20 NH4Sm( SO4) 2-4HqO'
Donor Acceptor Distances (nm)

O(W(1) ) O(1) 0.277(1) 0.2761(14)

O(W(1) ) O(6) 0.307(1) 0.3049
O(W(2) ) O(1) 0.273(1) 0.2710(14)
O(W(2) ) O(6) 0.282(1) 0.2884(16)
O(W(3)) O(7) 0.278(1) 0.2781(15)
O(W(3)) O(6) 0.279(1) 0.287(16)
O(W(4) ) O(8) 0.274(1) 0.2704(13)
O(W(4)) O(W(3) ) 0.283(1) 0.2777(15)
Angles (deg)

O(1) —0( W( 1)—O(6) 75.9(3) 78

O(1) —O(W(2) —O(6) 80.9(3) 82
O(7) —0( W( 3 ) —0( 6) 117.1(4) 113
O(8) —O(W(4) —O(W(3) ) 96.8(3) 99
' Standard deviations taken from Table VI of Ref. 12.
Data for NH4Sm(SO4)2 4H20 has been calculated based on atomic positions given in Table II of Ref.
12. Hence, the standard deviations are not given.
13 222 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA 43

0
In RSmSTH, there are two O(W) — distances longer scheme. However, there are consequential differences in
than, but close to, the upper limit (0.31 nm) of hydrogen- the hydrogen-bond strength in these two isostructural lat-
bond lengths in the scheme discussed above. These dis- tices. The differences are best manifested by comparing
tances, corresponding to [O(W(1) ), O(5)] =0. 312 nm the corresponding distances listed in Table VII, and will
and [O(W(3)), O(1)]=0.316 nm, raise the possibility of be discussed along with the vibrational results in the next
bifurcated hydrogen bonds for W(1) and W(3). Based on section. The hydrogen-bond strength difFerences can
the hydrogen-bonding scheme illustrated in Fig. 3 and have a substantial effect on the thermodynamic stability
Table VII, the O(W) — O(acceptor) bond lengths and the of these two isostructural lattices since hydrogen bonding
O(acceptor, ) —O(W) —O(acceptor2) angles fall within the is crucial to their cohesion.
acceptable limits for hydrogen-bond geometry. Conse-
quently, O(W(1)) —O(5) and O(W(3)) —O(1) really can- C. Vibrational results
not be considered as true hydrogen bonds. Instead, it is
preferable to say that they correspond to very weak con- It is well known that the vibrational spectrum provides
tacts such as assigned in the MgHPO4 3H20 lattice.
~ critical information about the structure of water and
The hydrogen-bond acceptors are all sulfate oxygens water's hydrogen-bonding behavior. We believe the wa-
except for O(W(3)), shown in Fig. 3. Three oxygens of ter, and consequently the hydrogen bonding, play an im-
the S(2)04 group O(6), O(7), and O(8) participate in hy- portant role in triggering the structural phase transitions
drogen bonding, while only one of the S(1)04 oxygens in MLSTH systems. Therefore, we studied the FTIR
O(1) is involved. The coordination around the atoms spectra of RSmSTH and ASmSTH in the frequency range
of 3800—1550 cm ', where water's stretching and bend-
O(6), O(7), and O(8) of S(2)O~ is different. Around O(6)
ing modes are located. Figure 4 reproduces the observed
the coordination is approximately tetragonal, while
vibrational spectra of MSmSTH. In the water's stretch-
around O(7) and O(8) it is approximately trigonal. Con-
ing region for ASrnSTH, five overlapping bands were ob-
sequently, the distribution of S-O bond lengths about the
served at 3527 (shoulder), 3320 (severely overlapped
mean value is expected to be broader for S(2)04 than for
shoulder), 3270 (sharp but weak band), 3063 (sharp shoul-
S(1)04. This is precisely what was observed by compar- der), and 2857 cm . Three distinct vibrations at 1682,
ing the standard deviations in the S-0 bond lengths to the
1636, and 1433 cm ' were observed for ASmSTH in the
mean values for the S(1)04 and S(2)04 groups, as dis-
bending region of water. Based on published results on
cussed earlier. The standard deviation of the S-0 bond ammonium halides, 1433-, 2857-, 3063-, and 3270-cm
length from its mean value rejects the distortion of the
SO4 "tetrahedron.
" We therefore conclude that the
bands for ASmSTH can be assigned to the triply degen-
erate bending mode (v4), first overtone (2v~), symmetric
different role played by the two inequivalent SO4 stretch (v& ), and asymmetric stretch (v3), respectively, of
"tetrahedra" in the hydrogen-bonding network is one the ammonium ion. According to the crystal structure,
reason for the increased linear distortion for the S(2)04 the ammonium ion occupies C& site symmetry. Under
tetrahedron as compared to the S(1)04 tetrahedron. The such a low symmetry, the crystalline-field effects are ex-
other reason is the difference in the nature of the bridging pected to lift the degeneracy of the v4 mode. As can be
performed by the two sulfates. seen from Fig. 4, no three distinct vibrations are observed
The interatomic distances and angles around the water
rnolecules in the isostructural ASmSTH were recalculat-
ed based on the positional and thermal parameters given
in Table II of Ref. 12. A careful scrutiny of these results
revealed that the hydrogen-bonding scheme for ASmSTH
is identical to that given in Fig. 3 for RSmSTH. We have
also listed the computed hydrogen-bond lengths for iso-
structural ASmSTH in Table VII. Based on the data
presented in Table VII and the foresaid discussion, it is
suggested that the isostructural MSmSTH (M =NH4 or
Rb) lattices have three distinct types of water, i.e., W(1), A
distorted geometry; W(2) and W(4); and W(3), layer
geometry.
From the comparative analysis of the crystal structure
of RbSm(SO4)2 4H20 and NH~Sm(SO4)2 4H20, it is ar-
gued that these two systems are isostructural in the con-
ventional sense. However, there are significant
l l I I

differences in the coordination around the monovalent 3500 3000 2500 2000 1 500
cation and the hydrogen-bonding behavior. The am-
WAVE NL) M HER (crn )
monium ion in ASmSTH has four close contacts to which
hydrogen atoms of the ammonium ion are hydrogen
bonded, while the Rb cation in RSmSTH is held in a FICi. 4. The observed infrared spectra of isostructural
cagelike structure. The water molecules in RSrnSTH and MStn(SO4)z. 4HzO [M =NH4 (a) and Rb (b)] crystals show the
ASmSTH participate in an identical hydrogen-bonding similarities and dissimilarities between the two lattices.
43 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE.
at around 1433 cm '. We speculated from our specific-
heat measurements that ammonium ions rotate in the
ALSTH (L =Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) lat-
tice at T &200 K. If such is the case, the rotational
motion of NH&+ ions at 296 K will effectively modulate
the crystalline-electric-field effects. This will result in a
narrowed, single-vibrational bending mode, as observed
in the present case. Thus, we believe that ammonium
ions rotate in ASmSTH at 296 K. This observation is
further supported by the absence of the combination
band v4+v6, which appears at around 1800 cm ' if the
ammonium ions do not rotate in the lattice. No such
band was observed for ASmSTH at 296 K.
Water molecules in the RSmSTH and ASmSTH lat-
tices occupy C, site symmetry. According to our
hydrogen-bonding scheme, there are three distinct water
molecules in the lattice, i.e. , group I, W(1); group II, W(2)
and W(4); and group III, W(3). The hydrogen-bond dis-
tances for water, listed in Table VII, predict a complex
vibrational spectrum in the water's stretching and bend-
ing regions due to the range of distribution of distances.
The well-resolved shoulder at 3553 cm ' for RSmSTH
and 3527 cm ' for ASmSTH occurs at an unusually high
water-stretching frequency for crystalline hydrates.
This unusually high frequency suggests that the band ob-
served at ) 3500 cm ' originates from a water molecule
which is very weakly hydrogen bonded. ' The water mol-
ecule (W(1)) participates in a very weak hydrogen bond
since the bond length O(W(1)) —H(12) . . O(6)=0. 307
nm lies close to the upper limit for a bond of this type.
The other hydrogen bond for W(1),
O(W(1) —H(ll) O(1)=0.277 nm is of intermediate
strength, thus resulting in asymmetric hydrogen bonding
for W(1). The asymmetric force field for water (W(1))
should break down the coupling between the symmetric
(v, ) and antisymmetric (v3) stretch oscillations for W(l)
in RSmSTH and ASmSTH, producing two separate
bands. Thus, we assign the shoulders at 3553 (RSmSTH)
and 3527 cm ' (ASmSTH) to the O(W(1)) —H(12)
oscillator. The hydrogen-bond distance
O(W(l)) —H(12) . O(6) for ASmSTH is smaller than
the corresponding distance for RSmSTH. Therefore, the
observed lower frequency for the O(W(1)) —H(12) oscil-
lator in ASmSTH is consistent with our hydrogen-
bonding scheme since, the stronger the hydrogen bond,
the lower the stretching frequency of the 0-H vibra-
tion. The other hydrogen-bond distances for various
waters in RSmSTH and ASmSTH are centered at around
0.278 nm (see Table VII). This fact should result in oscil-
lators other than O(W(1) —H(12) producing a broad, sin-
gle overlapping band at around 3320 cm '. Figure 4
rejects this. However, there is striking difference in
these intermediate-strength hydrogen bonds between
RSmSTH and ASmSTH as revealed by the bar graph in
Fig. 5. In RSmSTH, the bond distances are closely
clustered about the mean (0.278 nm) with a standard de-
viation of +0.004 nm, while, in ASmSTH, the distribu-
tion about the mean is broader with a deviation of
+0.007 nm. This implies that waters' hydrogen bonding
plays a more dominant role in the cohesion of the
RSmSTH structure than of the ASmSTH structure. As
.. 13 223
RbSrn(SO4) 2 4H20
I h II
ih
ii
ih I hii
ihlhi
NH4Srn(SO4)2 4H20
I
0.250 0.275 0.300 0.325
HYDROGEN BOND LENGTH (nrn)
FIG. 5. This bar graph shows the distribution of hydrogen-
bond lengths in RbSm(SO4)2 4H20 and NH4Sm(SO4)2 4H20.
suggested earlier, the above-discussed differences could
significantly alter the thermodynamic behavior of the two
lattices.
bending region of water (see Fig. 4), both
In the
RSmSTH and ASmSTH show two distinct vibrations at
1636 and 1682 cm '. Eriksson et al. ' for ASmSTH and
Malhotra et QI. for ACeSTH also observed a similar
doublet in the bending region, and they assigned the
lower-frequency oscillator to the bending mode of water
due to W(1), W(2), and W(4), and the higher-frequency
oscillator to the bending mode of W(3). According to our
hydrogen-bonding scheme, we expected to observe three
distinct bending oscillators. We attempted to curve
resolve the bending region using the procedure outlined
in Ref. 31. Only two bands could be fitted to the ob-
served spectrum. The hydrogen-bonding effects on wa-
ter, though, are manifested in the bending region, but
they are not as sensitive as in the stretching region. Also,
it has been argued by Falk that the bending frequency is
strongly inlluenced by the cation charge (to which water
is coordinated), i.e. , the higher the cation charge, the
lower the frequency of the bending oscillator. Since the
water molecules W(1), W(2), and W(4) are coordinated to
the trivalent Sm ion and these water molecules are also
participating in hydrogen bonding, the observed bending
mode frequency will be dictated by the complex combina-
tion of the two foresaid effects.
D. Thermal behavior at 303 & T & 473 K
Although the infrared results, presented above, are not
inconsistent with our proposed hydrogen-bonding
scheme for MSmSTH, they do not provide conclusive
evidence in support of the scheme. Consequently, we un-
dertook thermal (DSC) measurements on RSmSTH at
303 & T &473 K to see if three distinct activation ener-
gies could be observed during the process of dehydration.
Figure 5 shows the observed dehydration behavior of
RSmSTH at 303 & T &473 K. The measured weight loss
at the end of the DSC run was found to be equal (within
13 224 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA
the limits of experimental error) to the calculated weight
fraction for the four waters of hydration per formula unit
in the RSmSTH sample before the run. This indicates
that dehydration was completed on heating to the fairly
low temperature of 473 K, not 1323 K as reported by
Erametsa and Niinisto. Figure 5 displays two major en-
dothermic peaks in the DSC curve, a complex asym-
metric, overlapped peak at 407 K and a low enthalpy
peak at 432 K. It should be noted that, after dehydration
has occurred, the water molecules released from the lat-
tice can still be trapped in the pores of the anhydrous
powder crimped in the perforated DSC sample pan. Ad-
ditional energy must be supplied for the water molecules
to overcome the mechanical barrier due to the product
layer ' in order to be completely removed from the sys-
tem. A distribution of barrier heights as a function of
particle size, packing density, and other geometrical pa-
rameters is expected. It was suspected that the broad,
low enthalpy peak at 432 K was due to the release of such
mechanically trapped water molecules rather than anoth-
er stage of the dehydration reaction. To ascertain the
origin of the endothermic peak at 432 K, the DSC run
was terminated at 420 K and the FTIR spectrum of the
powder retrieved from the DSC pan was recorded. A sin-
' was observed in the
gle, low-intensity band at 1626 cm
H-0-H bending region of the ir spectrum instead of the
doublet shown in Fig. 4. This band can be assigned to
weakly hydrogen-bonded surface water. ' The FTIR
spectrum of the RSmSTH sample, after being heated to
473 K, was also recorded. An extremely weak band at
exactly the same frequency 1626 cm ' was again ob-
served in the H-0-H bending region. Therefore, it is ar-
gued that the type of water present in the sample after
heating to 420 K is identical to the traces of the type of
water present in the anhydrous sample. This implies that
there are no waters of hydration present in the sample
DJ 4—
C)
CL
QJ
C3
2—
350 400 450
TEMPERATURE (K)
FIG. 6. Differential Scanning Calorimetry (DSC) thermo-
gram depicts the dehydration and desorption of water from
RbSm(SO&)&-4H&O. The broad peak in the curve at 432 K
represents the desorption of mechanically held water, while the
three overlapped peaks are associated with the dehydration pro-
cess.
43
0.8
~ 0. 6
CL
0.4—
I
I I I
150 200 250 300
TEMPERATURE (K)
FIG. 7. This graph reproduces the observed specific heat for
isostructural (a) NH4Sm(SO4)~. 4H20 and (b) RbSm(SO4) 2 4H20
crystals at 100 & T & 305 K.
after heating to 420 K, confirming our suspicion that the
endothermic peak at 432 K in Fig. 6 is due to the release
of mechanically trapped water. Hence, from Fig. 6, it
can be seen that the dehydration of RSmSTH occurs over
the temperature range 355& T &420 K, although com-
plete removal of the water molecules from the system re-
quires higher temperatures. A similar, two-step mecha-
nism for the dehydroxylation of clay minerals was sug-
gested by Malhotra and Ogloza.
For DSC data, the peak in the dehydration curve
occurs at a temperature at which there is maximum wa-
ter loss. The peak temperature can be used as a reference
temperature to calculate the activation energy for the
dehydration of the water. As seen from Fig. 6, three
peaks were observed in the dehydration
overlapping
curve for RSmSTH at approximately 400, 407, and 410
K. The presence of three peaks indicates that there are
three types of water with three different activation energy
barriers. This observation is consistent with the
classification of the four waters of hydration into three
groups, based on the crystallographic data and the pro-
posed hydrogen-bonding scheme. The dehydration
enthalpy required for the liberation of the four waters of
hydration from the RSmSTH structure was determined
to be 99 kJ/mol. This value compares favorably with the
range of activation energies 46—170 kJ/mol, reported for
other crystalline hydrates.
E. Phase transitions and speci6c heat
Jasty and Malhotra, from their specific-heat measure-
ments on ASmSTH, showed that this system undergoes
two structural phase transitions at 110& T &300 K. In
addition, they argued from the observed specific heat of
ASmSTH that NH&+ ions initiate rotation at around 200
K in this lattice. In view of the overall similarity of the
crystal structure of ASmSTH and RSmSTH lattices, but
yet having discernable differences in the hydrogen-
bonding strengths and in the coordination of monovalent
cations, it was felt it would be interesting to determine
43 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE. . .
how the replacement of the NH4+ ions by the Rb ions
affects the phase-transition behavior in the MSmSTH lat-
tice. Consequently, the specific heat (C ) of RSmSTH
was recorded at 100& T &310 K and is reproduced in
Fig. 7. Also depicted in Fig. 7, for the sake of compar-
ison, is the observed specific heat of ASmSTH. Unlike
the two anomalies observed for ASmSTH, a single anom-
aly was observed in the specific-heat curve of RSmSTH at
100 & T & 303 K. The shape of the anomaly with its long,
low-temperature tail indicates that the transition occur-
ring in the RSmSTH lattice is partly gradual, but it is
completed isothermally at 232 K. This results in a k-
shaped anomaly in the specific heat which has been asso-
ciated with order-disorder transition, magnetic transi-
tion, onset of molecular rotation, and/or ordering of axis
orientation of molecular rotation.
The total entropy (AS) for the observed second-order
transition for RSmSTH was determined from
(3)
To determine AS from Eq. (3), a graph representing
C /T for each T at 180 & T & 250 K was generated, and
the total entropy was simply calculated by determining
the area under the curve between the given limits. The
total entropy AS associated with the second-order transi-
tion for RSmSTH was determined to be 0.0096 J/g K. It
is worth mentioning here that the observed anomaly for
RSmSTH is not as sharp or energetically intense as typi-
cal A, transitions observed ' in NH&cl or (NH&)2SO&.
However, the transition in RSmSTH is almost ten times
more intense than the two transitions observed in
ASmSTH.
As can be seen from Fig. 7, the specific heat of
RSmSTH above the transition has a temperature depen-
dence which is different from the one observed below the
transition temperature ( To =232+1 K). The observed C
(in J/g K) at T & 215 K & To can be described by
C~ =(0.221+8. 664X10 T+1.QZQX1Q
~T2
—2. 357X10 T ), 110& T &210 K, (4)
while the C~ (in )
J/g K) at T 245 K) To is represented
by
C =(0.267+1.618X10 T), 245&T &303 K.
On extrapolating Eq. (4) to 245 K, the computed C„does
not join Eq. (5) but lies 0.036 J/g K above it. Similar be-
havior in C for ferroelectric gadolinium molybdate has
been reported by Cheung and Ullman. They suggested
this behavior may be due to differences in anharmonicity
between the T & To and T & To phases.
As described earlier, the observed A, transition for
RSmSTH indicates that the second-order transition is ei-
ther an order-disorder effect or is the onset of molecular
rotation in the lattice. We exclude the possibility that the
transition in RSmSTH is a magnetic transition, especially
because the observed phase transitions in isostructural
ASmSTH are structural in nature. Also, the distances
13 225
between the nearest paramagnetic Sm + ions are larger
than 0.6 nm (calculated from Table II). If it is argued
that the A, shape implies the onset of molecular rotation
in the RSmSTH lattice, then the possible candidates are
sulfate ions and/or water molecules. The Rb+ ions are
held in a distorted cavitylike structure in the lattice and,
therefore, will rattle rather than rotate. Since both
S(1)Oz and S(2)O& ions in the RSmSTH lattice are in-
volved in bridging the samarium polyhedra, it is difficult
to see how the lattice will remain stable if the sulfate ions
rotate. However, it is possible that the water molecule
dipoles initiate Auctuations in the RSmSTH lattice at 210
K& T & To, similar to those reported for alums. The
specific-heat measurements alone cannot distinguish be-
tween an order-disorder transition and the transition in-
duced as a consequence of fluctuations of water dipoles.
For order-disorder transition, a logarithmic diver-
gence ' ' in C is expected near the transition tem-
perature, i.e. ,
C = 2+8 In(e), (6)
where e= (T/To) —l~. Using the procedure outlined in
Refs. 39 and 43, we attempted to fit our specific-heat data
near the transition temperature, i.e. , 215 K & T & To and
)
240 K) T To. The logarithmic divergence of specific
heat for RSmSTH at 215 K & T & To can be described by
T —1
C = 0. 550 —0. 403 ln (J/g K),
232
0. 006 & e'& 0. 095, (7)
and at 240 K & T & T, as
T —1
Cp
= 0. 535 —0. 035 ln (J/g K),
0. 003 & e &0.033 . (8)
The regression coe%cients for Eqs. (7) and (8) were 0.994
and 0.959, respectively. Owens, from his EPR measure-
ments on KCr(SO~)z 12H20 alum, showed that the
linewidth of Cr + ions diverges as the transition tempera-
ture of 157 K is approached. It is interesting to note the
divergence in linewidth can be explained by a logarithmic
function. If a similar fluctuation of some polar lattice
mode is in effect in RSmSTH near 215 K, and if Aucta-
tions are slow enough with respect to the specific-heat-
measurement time, then a logarithmic divergence in
specific heat is expected.
Usually in isostructural lattices, the replacement of a
monoatomic cation such as Rb+ by a polyatomic cation
such as NH4+ has been known to induce a phase transi-
tion. For example, RbzSO4 does not undergo any
structural phase transitions at T &290 K. On the other
hand, it is well known that (NH&)2SO& exhibits a fer-
roelectric transition at 223 K. It has been argued that
the ammonium ion is critically involved in triggering the
transition. If one extends the foresaid analogy to the
double sulfates, i.e. , RSmSTH and ASmSTH, then it may
appear that the 273-K transition in ASmSTH is triggered
13 226 S. JASTY, P. D. ROBINSON, AND V. M. MALHOTRA
by ammonium ions. This especially seems plausible be-
cause NH4+ ions in ASmSTH initiate rotation at T 200 ) former acts as a strain absorber in the linear samarium-
K. Though the hydrogen-bonding networks in RSmSTH
and ASmSTH are identical, the strength of the dynamic
coupling between the coordinated water molecules and
the interlayer water molecules differs appreciably be-
tween the two lattices. On the other hand, the role of the
sulfate ions in the two structures is identical. Also, the
sulfate ions do not exhibit any disorder similar to the
kind observed in some of the alums. Since the monoa-
tomic rubidium ion is not expected to cause a phase tran-
sition, by the process of elimination it is possible that the
water molecules through hydrogen bonding hold the key
to the mechanism that drives the structural phase transi-
tion in RSmSTH. Temperature-dependent x-ray
diffraction and/or neutron scattering and/or solid-state
NMR measurements are required to shed more light on
the transition mechanism.
IV. SUMMARY AND CONCLUSIONS
Based on a comparative analysis of the room-
temperature crystal structures, infrared spectra, and
temperature-dependent (100(T (303 K) specific heats
of RbL(SO4)2 4H20 and NH4L(SO4)2 4H20 lattices, we
conclude the following: (1) RbSm(SO4)2 4H20 and
NH4Sm(SO4)2 4HzO are isostructural at room tempera-
ture. (2) The coordination geometry around the samari-
um ion remains unaffected by a substitution of the mono-
valent cation, ammonium by rubidium. (3) In the
RbSm(SO4)z 4H20 as well as NH&Sm(SO4)2 4H20 struc-
tures, the two crystallographically inequivalent sulfates
are distorted to different extents from the tetrahedral
symmetry. The distortion of the S(2)O~ tetrahedron is
~J. F. Scott, Rev. Mod. Phys. 46, 83 (1974).
S. Jasty, M. Al-Naghy, and M. de Llano, Phys. Rev. A 35, 1376
(1987).
J. G. Berryman, Phys. Rev. A 27, 1053 (1983).
4M. Rousseau, J. Y. Gesland, J. Julliard, J. Nouet, J. Zarem-
bowitch, and A. Zarembowitch, Phys. Rev. B 12, 1279 (1975).
5S. Jasty and V. M. Malhotra (unpublished).
6N. G. Parsonage and L. A. K. Staveley, Disorder in Crystals
(Clarendon, Oxford, 1978).
7D. R. Taylor, Phys. Rev. B 40, 493 (1989).
SN. E. Schumaker and C. W. Garland, J. Chem. Phys. 53, 392
(1970).
E. O. Schlemper and W. C. Hamilton, J. Chem. Phys. 44, 4498
(1966).
A. A. Khan and W. H. Baur, Acta Crystallogr. B 28, 683
(1972).
R. D. Shannon, Acta Crystallogr. A 32, 751 (1976) ~
~B. Eriksson, L. O. Larsson, L. Niinisto, and U. Skoglund,
Inorg. Chem. 13, 290 (1974).
TEXSAN-TEXRAY Structure Analysis Package, Molecular
Structure Corporation (1985).
' C. J. Gilmore, J. Appl. Cryst. 17, 42 (1984).
P. T. Beurskens, Crystallography Laboratory, Toernooiveld
Report No. 1984/1 (unpublished).
43
greater than that of the S(1)04 tetrahedron because the
sulfate chains parallel to the a axis. (4) Unlike the am-
monium ion which can be hydrogen bonded to four oxy-
gens, the large size of the rubidium ion precludes the pos-
sibility of only four nearest-neighbor oxygen atoms for
the Rb ion. Hence, for RSmSTH, the structural data in-
dicate that the rubidium ion is located in a cavity bound-
ed by 11 sulfate oxygens and 2 water oxygens. (5) The
hydrogen-bonding scheme proposed on the basis of crys-
tallographic data, which suggests three distinct types of
water molecules in lanthanide double sulfates, was criti-
cally evaluated and found to be consistent with our spec-
troscopic and thermal data. (6) From the specific-heat
measurements at 100(T (303 K, the structural phase-
transition behaviors in RbSm(SO4)2. 4HzO and
NH~Sm(SO4)2 4HzO were found to be different.
RbSm(SO4)z 4H20 undergoes a single, A, -type transition
at 232 K, unlike the successive structural transitions ob-
served in NH4L(SO4)2 4H20 at 160 and 273 K. The I,—
shape anomaly can be fitted by a logarithmic function
near the transition temperature. This argues that the
transition in RbSm(SO„)2 4H20 is an order-disorder type.
Based on the significant differences between the
hydrogen-bonding networks in the two isostructural
MSm(SO4)2 4H20 lattices, it is possible that the water
molecules are critically involved in driving the structural
phase transition in RbL(SO~)2 4H20.
V. SUPPLEMENTARY MATERIAL
A listing of the anisotropic temperature factors and
structure factor amplitudes for RbSm(SO4)z 4H20 are
available from the authors.
D. T. Cromer and J. T. Waber, International
Crystallography (Kynoch, Birmingham,
Tables for XRay-
England, 1974), Vol.
IV, Table 2.2A.
J. A. Ibers and W. C. Hamilton, Acta Crystallogr. 17, 781
(1964).
'sD. T. Cromer, International Tables for X Ray Crystallograp-hy
(Kynoch, Birmingham, England, 1974), Vol. IV, Table 2.3. 1.
G. H. Stout and L. H. Jensen, X-Ray Structure Determination
(Macmillan, New York, 1972).
M. Falk and O. Knop, in Water, A Comprehensive Treatise,
edited by F. Pranks (Plenum, New York, 1973), Vol. 2, Chap.
2, p. 55.
~ H. D. Lutz, Struct. Bonding 69, 97 (1988).
W. H. Baur and A. A. Khan, Acta Crystallogr. B 26, 1584
(1970).
G. C. Chiari and G. Ferraris, Acta Crystallogr. B 38, 2331
(1982).
~4W. C. Hamilton, Acta Crystallogr. 18, 502 (1965).
25W. C. Hamilton, Statistics in Physical Science: Estimation,
Hypothesis Testing, and Least Squares (Ronald, New York,
1964).
D. C. Ginnings and G. T. Furukawa, J. Amer. Chem. Soc. 75,
522 (1953).
~7A. C. Larson and D. T. Cromer, Acta Crystallogr. 22, 793
43 CRYSTAL STRUCTURE OF AND LOW-TEMPERATURE PHASE. . .
{1967).
2~G. Ferraris and M. Franchini-Angela, Acta Crystallogr. B 28,
3572 (1972).
H. A. Buckmaster, V. M. Malhotra, and H. D. Hist, Can. J.
Phys. 59, 596 (1981).
G. Brink and M. Falk, Can. J. Chem. 48, 2096 (1970).
V. M. Malhotra, S. Jasty, and R. Mu, Appl. Spectrosc. 43, 638
(1989).
3~V. M. Malhotra, H. A. Buckmaster, and H. D. Bist, Can. J.
Phys. 58, 1667 (1980).
J. Schiffer and D. F. Hornig, J. Chem. Phys. 49, 4150 (1968).
~M. Falk, Spectrochim. Acta 40A, 43 (1984).
50. Erametsa and L. Niniisto, Suom. Kemistil. B 44, 207
(1971).
M. E. Brown, D. D. Dollimore, and A. K. Galway, in Chemi-
cal Kinetics, edited by C. H. Bamford and C. F. H. Tipper (El-
13 227
sevier, Amsterdam, 1980), Vol. 22, p. 115.
V. M. Malhotra and A. A. Ogloza, Phys. Chem. Miner. 16,
386 (1989).
L. L. Sparks, in Materials at I.om Temperatures, edited by R.
P. Reed and A. F. Clark (American Society for Metals, Met-
als Park, Ohio, 1983).
K. M. Cheung and F. G. Ullman, Phys. Rev. B 10, 4760
(1974)~
4"F. J. Owens, in Magnetic Resonance of Phase Transitions, edit
ed by F. J. Owens, C. P. Poole, and H. A. Farach (Academic,
New York, 1979).
" E. Pytte and H. Thomas, Phys. Rev. 175, 610 (1968).
42I. Hatta and A. Ikushima, J. Phys. Chem. Solids 34, 57 (1973).
43H. J. Fecht, Z. Fu, and W. L. Johnson, Phys. Rev. Lett. 65„
1753 (1990).