Bi6(SeO3)3O5Br2: A new bismuth oxo-selenite bromide

Article abstract of DOI:10.1016/j.jssc.2012.06.020

A new bismuth oxo-selenite bromide Bi₆(SeO₃) ₃O₅Br₂ was synthesized and structurally characterized. The crystal structure belongs to the triclinic system (space group P1, Z=2, a=7.1253(7) A, b=10.972(1) A, c=12.117(1) A, α=67.765(7)°, β=82.188(8)°, γ=78.445(7)°) and is unrelated to those of other known oxo-selenite halides. It can be considered as an open framework composed of BiO_x or BiO_yBr_z polyhedrons forming channels running along [1 0 0] direction which contain the selenium atoms in pyramidal shape oxygen coordination (SeO₃E). The spectroscopic properties and thermal stability were studied. The new compound is stable up to 400 °C.

Full text of DOI:10.1016/j.jssc.2012.06.020

Journal of Solid State Chemistry 196 (2012) 232–237
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Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Bi6(SeO3)3O5Br2: A new bismuth oxo-selenite bromide
Peter S. Berdonosov a,n, Andrei V. Olenev b, Maria A. Kirsanova a, Julia B. Lebed c, Valery A. Dolgikh a
a Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia
b SineTheta Ltd., MSU Building 1-77, 119991 Moscow, Russia
c Institute for nuclear research RAS, 142190, Troitsk, Moscow region, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
A new bismuth oxo-selenite bromide Bi6(SeO3)3O5Br2 was synthesized and structurally characterized.
Received 29 March 2012
Received in revised form
15 June 2012
˚
¯
The crystal structure belongs to the triclinic system (space group P1, Z¼2, a¼7.1253(7) A,
˚
˚
b¼10.972(1) A, c¼12.117(1) A,
a¼67.765(7)1, b¼82.188(8)1, g¼78.445(7)1) and is unrelated to those
of other known oxo-selenite halides. It can be considered as an open framework composed of BiOx or
BiOyBrz polyhedrons forming channels running along [1 0 0] direction which contain the selenium
atoms in pyramidal shape oxygen coordination (SeO3E). The spectroscopic properties and thermal
stability were studied. The new compound is stable up to 400 1C.
Accepted 17 June 2012
Available online 23 June 2012
Keywords:
Bismuth
& 2012 Elsevier Inc. All rights reserved.
Lone-pair elements
Selenite
Bromide
Open-framework
Crystal structure
1. Introduction
from those of MSeO3Cl (M¼Ln) while all Cu3M(SeO3)2O2X (X¼Cl,
Br, I) compounds (M¼Bi; M¼all Ln in case of X¼Cl) adopt the
The family of complex selenite halides attracts growing atten-
tion in the last decades due to the specifics of their crystal
chemistry governed by stereochemical effect of Se(IV) lone
electron pair [1–4]. These pairs are considered to be similar in
size to oxygen anions [5] and do not participate in the chemical
bonding, usually segregating in the channels or in inter-layer
gaps. The presence of the halogen ions alongside with a lone-pair
element enhances the probability of formation of open-frame-
work or layered structures [6–8]. Not only the polyhedrons with
asymmetric coordination, but also the lone-pair atoms them-
selves may be the reason for noncentrosymmetric structures
which lead to new potential piezoelectric and non-linear optic
materials.
same francisite structure [2,14]. However, the bismuth selenite-
halides are relatively scarce. Besides BiSeO3Cl, only two selenite-
bromides are hitherto known: BiSeO3Br and Bi10.67(SeO3)12Br8,
the former observed upon investigation of the BiOBr–SeO2 system
[15], and the latter synthesized by chemical transport reaction
from BiOBr to SeO2 in a temperature gradient [3].
For a long time, our group had performed a systematical
search and study of selenite halogenides in order to establish
the correlation between their chemical composition and crystal
structures. In the present work, we report on the synthesis, crystal
structure, thermal and spectroscopic properties of a yet new
bismuth oxo-selenite bromide, Bi6(SeO3)3O5Br2.
The rare-earth (REE) complex selenite halides are probably the
most numerous and well-studies part of the family under discus-
sion. The most common compositions are M3O2(SeO3)2Cl (M¼Tb,
Dy, Er), M4O3(SeO3)2Cl2 (M¼Er, Yb), Tb5O4(SeO3)2Cl3 and Gd5O4(-
SeO3)2Br3, M9O8(SeO3)4Cl3 (M¼Pr, Nd, Sm, Gd), M9O8(SeO3)4Br3
(M¼La, Pr) [4,9,10], and Nd7O5(SeO3)4Cl3 [11]. The simplest
composition MSeO3Cl is described for M¼Sm–Lu [12]. Com-
pounds with similar compositions have also been observed for
trivalent bismuth but their structures may be different. For
instance, the structures of both BiSeO3Cl polymorphs [1,13] differ
2. Experimental
2.1. Synthesis
Our original attempts were aimed at the preparation of
Bi8(SeO3)4O8X3 (X¼Cl, Br) by analogy to similar compounds of
early rare-earths [4,9]. Chemically pure Bi2O3, BiOX (X¼Cl, Br)
were used as starting materials as received. SeO2 was obtained by
dehydratation of pure selenous acid under vacuum at 70–80 1C
followed by sublimation of product in a flow of dry air/NO2
mixture. The mixtures of starting materials (ꢀ0.5 g total weight)
were weighted in an argon-filled glovebox in the desired ratios,
vacuum-sealed in quartz tubes, preheated at 300 1C for 24 h and
n Corresponding author. Fax: þ7 495 939 0998.
E-mail address: berdonosov@inorg.chem.msu.ru (P.S. Berdonosov).
0022-4596/$ - see front matter & 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jssc.2012.06.020

P.S. Berdonosov et al. / Journal of Solid State Chemistry 196 (2012) 232–237
233
then annealed at 475 1C for 60 h. Small crystals were found in the
2.3. Thermal and IR characterization
sample aimed at Bi9(SeO3)4O8Br3 composition. Powder X-ray
diffraction (XRD) analysis was performed on STOE STADI/P
The thermal behavior of Bi6(SeO3)3O5Br2 was studied using a
NETZSCH STA 409 PC instrument in air and argon atmosphere.
The samples (ca. 10 mg) were heated from room temperature to
1000 1C with a rate of 10 1C/min. The results are presented in the
supplement (Figs. S1 and S2).
The thermal decomposition process of Bi6(SeO3)3O5Br2 is not
sensitive to atmosphere, so oxidation processes may be ruled out.
Bi6(SeO3)3O5Br2 is stable up to 400 1C There are at least two
plateaus in the 400–900 1C range with loss of about 4% and 19–
20% sample mass.
The IR transmission spectrum collected on a PerkinElmer FT-IR
spectrometer Spectrum One in 450–4000 cmꢁ1 range is given in
supplement Fig. S3. The examined sample of Bi6(SeO3)3O5Br2 was
pressed into thick pellet in KBr matrix (Aldrich, for FTIR analysis)
with sample content about 0.2–0.5 mass%. In the range 1700–
4000 cmꢁ1 the sample is transparent. The range 450–1800 cmꢁ1
is presented in the supplement (Fig. S3 in supplement).
instrument (CuK radiation, transmission geometry, linear PSD
a
1
detector). The XRD patterns of chloride and bromide samples
were different from each other. In the former, only BiOCl could be
identified; all other lines belong to yet unknown compound(s).
Further attempts identify them were not successful. In the
bromide sample, only Bi2O3 could be identified; the unidentified
reflexions in the Cl and Br samples are not similar to each other or
those for known rare-earth compounds [4,9]. A small crystal
taken from the ‘Bi9(SeO3)4O8Br3’ sample was selected for struc-
ture investigation which revealed a different composition of the
novel compound, Bi6(SeO3)3O5Br2. The composition was con-
firmed by a successful synthesis from a mixture of 2BiOBr,
2Bi2O3, and 3SeO2 at 475 1C for 60 h. The observed XRD pattern
agreed well with that simulated from single crystal data. All
attempts to prepare analogous chloride at different synthesis
temperatures and annealing times were unsuccessful.
2.2. Crystal structure determination
3. Results
A suitable single crystal was mounted on an IPDS II (STOE)
goniometer head. The X-ray data were collected at room tempera-
ture and indexed based on a triclinic unit cell parameters with
According to the crystal structure determination, the title oxo-
selenite bromide of bismuth possesses composition that has not
been known among oxo-selenite halides of REEs. The compound
is stable in air up to 400 1C and decomposes at higher tempera-
tures. The first plateau on the TG curve in 400–900 1C range is in
good agreement with the loss of first molecule of SeO2 (which
should correspond to the mass loss of 6%). The loss of three SeO2
molecules corresponds to 17.7% loss. Therefore, the second
plateau at 800 1C corresponds to a mixture of bismuth oxide or
oxybromides. The small disagreement with suggested model of
decomposition and observed values of mass loss may be caused
by a complex decomposition mechanism wherein several pro-
cesses may run simultaneously.
˚
˚
˚
a¼7.1253(7) A, b¼10.972(1) A, c¼12.117(1) A,
a¼67.765(7)1,
b
¼82.188(8)1, and g¼78.445(7)1. The intensities of reflections
were integrated using the X-area STOE software. Numerical
absorption correction was performed with the programs X-red
and X-shape implemented in X-Area package. The structure was
¯
solved in the centrosymmetric space group P1 (No 2) by Direct
methods (SHELXS 97) [16] and refined by full matrix least squares
against F2 (SHELXL 97) [16]. The final anisotropic refinement led to
R1¼0.066, and wR2¼0.160 and composition Bi6(SeO3)3O5Br2. The
data collection and structure refinement parameters are listed in
Table 1.
Further details of the crystal structure determination may be
obtained from Fachinformationszentrum Karlsruhe, 76344
Eggenstein–Leopoldshafen, Germany, on quoting the depository
number CSD-423997.
Bi6(SeO3)3O5Br2 crystallizes in the centrosymmetric space
¯
group P1 (Table 1). There are six bismuth, two bromine, three
selenium and 14 oxygen atoms per one unit cell (Fig. 1).
The bismuth atoms reside in irregular coordination polyhe-
drons comprised of oxygen and bromine atoms, or oxygen atoms
only (Table 2). The bond valence sum (BVS) calculations [17,18]
using constants from [19] lead to Bi(1)O6, Bi(2)O7, Bi(3)O8,
Bi(4)O8Br, Bi(5)O5Br2 and Bi(6)O6Br six-to-nine-vertex polyhe-
drons (Table 2). The BVS for Bi(5) atom somewhat exceeds 3 if
two bromide ions are included in consideration. However, the
difference in bond lengths for Bi(5)–Br(1) and Bi(5)–Br(2) is
negligible (Table 24). Hence, we suggest both bromide ions
should be considered in the Bi(5) environment. A general feature
of all Bi polyhedrons is their asymmetry, which manifests the
Table 1
Crystal data and structure refinement for Bi6(SeO3)3O5Br2.
¯
Space group
P1 (N 2)
Cell parameters
7.1253(7)
10.972(1)
12.117(2)
˚
A, A
˚
B, A
effect of the stereochemically active lone E-pair of the Bi3þ
.
˚
c, A
a
b
, deg.
, deg.
67.765(7)
82.188(8)
78.445(7)
858.2(1)
All three selenium atoms exhibit pyramidal oxygen coordina-
tion usual for selenite groups with lone electron pair. The Se–O
g
, deg.
˚
distances in the SeO3 E groups vary from 1.66 to 1.72 A. The BVS
3
˚
V, A
value equals 4.09 for Se1, taking into account O11, O10 and O6,
4.31 for Se2 with O12, O13 and O14, and 4.20 for Se3 with O1, O8
and O9.
Z
2
Density (calc.), g cmꢁ3
7.263
0.71073
˚
Radiation, l, A
m
Data collection range, deg.
Reflections collected
Independent reflections
Parameters refined
, mmꢁ1
72.466
The Bi(4)O8Br polyhedrons are connected via O(6)–O(6) and
O(3)–O(3) edges in zigzag chains propagating along [1 0 0] direc-
tion (Fig. S4 in supplement). The seven-vertex Bi(2)O7 and
Bi(5)O5Br2 polyhedrons are connected to zigzag Bi(4)O8Br chains
by shared O(10)–O(3) and O(3)–O(11) edges or O(3)–O(8)–Br
plane and O(3)–O(6) and O(6)–O(9) edges, respectively. The
Bi(1)O6 and Bi(3)O8 polyhedrons are linked together into
Bi(4)O8Br, Bi(2)O7 and Bi(5)O5Br2 columns in layers (Fig. S5 in
supplement).
1.82 to 29.22
9796
4587 [R(int)¼0.1426]
227
R1, wR2 (F044
R1, wR2 (all data)
sF0)
0.0669, 0.1606
0.1141, 0.1926
4.614 and ꢁ4.371
3
˚
Largest diff. peak and hole, e/A
G–O–f. on F2
0.972
ICSD number
423997

234
P.S. Berdonosov et al. / Journal of Solid State Chemistry 196 (2012) 232–237
Se2
Se1
Se1
Se2
Se3
Se3
O
Se2
Se
Br
Bi
Se1
b
Se1
c
a
Se2
Fig. 1. The view on unite cell of Bi6(SeO3)3O5Br2.
Table 2
of the oxygen atoms are bound only to Bi atoms which permits to
consider the new compound Bi6(SeO3)3O5Br2 as a member of oxo-
selenite halide family.
´
Bond lengths [A] for Bi6(SeO3)3O5Br2.
Bond
Length
Bond
Length
In general, the crystal structure of Bi6(SeO3)3O5Br2 may be
described as a 3D framework composed of bismuth-oxygen-
bromine polyhedrons additionally decorated by SeO23ꢁ groups
situated close to framework voids.
Besides the new compound, there are two known composi-
tions of bismuth selenite halogenides, BiSeO3X (X¼Cl, Br)
[1,13,15] and Bi8(SeO3)9Br6 [3]. The list of related REE compounds
longer. The known compositions of Bi and/or REE selenite halides
are schematically represented in Fig. 3 [1,3,4,9–13,15,20–23]. As
yet, Bi6(SeO3)3O5Br2 has no analogues among REEs derivatives
and can be considered as a new structure type.
The MSeO3X family is the most numerous among those given
in Fig. 3. The chloride family consists of the bismuth compound
[1,13] and analogs formed by almost all REEs [12]. Other compo-
sitions (Fig. 3) include only several or even one REE compounds.
The compositions M4(SeO3)2O3Cl2 (M¼Er, Yb [4,9]),
M9(SeO3)4O8X3 (M¼Pr, Nd, Sm, Gd, X¼Cl; M¼La, Pr, X¼Br
[4,9]) and Nd7(SeO3)4O5Cl3 [11] are situated quite close to the
Bi6(SeO3)3O5Br2 composition in the M2O3–MCl3–SeO2 ‘triangle’
(Fig. 3). We can now compare the structure of Bi6(SeO3)3O5Br2
with some others. The cell constants for related compounds are
presented in Table 3.
Bi(1)–O(7)
Bi(1)–O(5)
Bi(1)–O(5)
Bi(1)–O(2)
Bi(1)–O(1)
Bi(1)–O(9)
Bi(1)–O(10)
Bi(1)–O(4)
Bi(2)–O(4)
Bi(2)–O(2)
Bi(2)–O(7)
Bi(2)–O(12)
Bi(2)–O(11)
Bi(2)–O(10)
Bi(2)–O(3)
Bi(3)–O(5)
Bi(3)–O(4)
Bi(3)–O(4)
Bi(3)–O(2)
Bi(3)–O(1)
Bi(3)–O(14)
Bi(3)–O(12)
Bi(3)–O(8)
Bi(4)–O(3)
Bi(4)–O(3)
Bi(4)–O(6)
Bi(4)–O(10)
2.15(2)
2.17(2)
2.29(2)
2.36(2)
2.67(2)
2.83(2)
3.02(3)
3.15(2)
2.19(2)
2.21(2)
2.213(16)
2.66(2)
2.70(2)
2.74(2)
2.80(2)
2.18(2)
2.204(19)
2.26(2)
2.56(2)
2.81(2)
2.83(3)
3.00(2)
3.06(3)
2.21(2)
2.25(2)
2.47(2)
2.52(2)
Bi(4)–O(11)
Bi(4)–O(6)
Bi(4)–O(8)
Bi(4)–O(9)
Bi(4)–Br(2)
Bi(5)–O(2)
Bi(5)–O(3)
Bi(5)–O(8)
Bi(5)–O(9)
Bi(5)–O(6)
Bi(5)–Br(1)
Bi(5)–Br(2)
Bi(6)–O(7)
Bi(6)–O(13)
Bi(6)–O(14)
Bi(6)–O(1)
Bi(6)–O(12)
Bi(6)–O(5)
Bi(6)–Br(2)
Se(1)–O(11)
Se(1)–O(10)
Se(1)–O(6)
Se(2)–O(13)
Se(2)–O(14)
Se(2)–O(12)
Se(3)–O(8)
Se(3)–O(9)
Se(3)–O(1)
2.61(2)
2.90(2)
2.95(2)
2.99(2)
3.011(3)
2.173(17)
2.23(2)
2.42(2)
2.44(2)
2.48(2)
3.211(4)
3.218(3)
2.142(16)
2.26(2)
2.35(3)
2.49(2)
2.50(2)
2.92(3)
3.210(3)
1.66(2)
1.71(2)
1.72(2)
1.67(2)
1.67(3)
1.69(2)
1.66(2)
1.68(2)
1.72(2)
Similarly to Bi6(SeO3)3O5Br2, the compositionally closest com-
¯
pounds crystallize in triclinic system (space group P1) and have
similar cell constants (Table 3). The common structural feature for
these compounds is the pure-oxygen and mixed oxygen–halogen
environment of REEs ions, as also observed for Bi6(SeO3)3O5Br2.
The most comon environment among these structures is a
distorted cube or a square antiprism with different ratio of
oxygen and halogen vertexes. In addition, seven-and nine-vertex
polyhedrons may exist in the structures. In Table 4 we compare
similar polyhedrons in bismuth and REE compounds. The REE
polyhedrons are generally less distorted compared to the bismuth
ones. This trend may be illustrated by the differences between the
longest and shortest M–O distances, by their ratio, or by the
Bi(6)O6Br polyhedrons share common O(7)–O(12) edges with
Bi(2)O7 and O(1) vertex with Bi(1)O6 from one layer and
Br(2) vertex with another Bi(6)O6Br from the other layer forming
an open-framework structure (Fig. 2).
In the bismuth-oxygen framework, there are channels running
along [1 0 0] direction of the structure. In the corners of the
channels, the selenium atoms are situated. All of them are bonded
to oxygen atoms from the Bi polyhedrons (Fig. 2). The lone
electron pairs of Se(IV) are thus located inside the channels. Some

P.S. Berdonosov et al. / Journal of Solid State Chemistry 196 (2012) 232–237
235
Fig. 2. Polyhedron representation of Bi6(SeO3)3O5Br2 crystal structure.
MХ
MOX
M (SeO )OX
MSe O X
MSeO X
M (SeO ) O X
M (SeO ) O Cl
M O X
M (SeO ) O X
MSe O X
Bi (SeO ) Br
Nd (SeO ) O Cl
Bi (SeO ) O Br
M (SeO ) O Cl
SeO
M O
M SeO
M (SeO )
Fig. 3. The known compositions of Bi or REE selenite halides. M¼Bi or REE. X¼Cl, Br.
difference between the mean and the shortest distance in the
MO8 polyhedron (Table 4).
The bromine atoms reside in the space between Bi–Se–O
layers. The Br(1) atoms are connected with Bi atoms from one
The MOx and MOyHalz polyhedrons are linked in frameworks
in individual manner in case of different Bi or REE compounds.
However, all these structures contain channels, as in the case of
Bi6(SeO3)3O5Br2 which home the selenium atoms coordinated by
three oxygen atoms with pyramidal shape [SeO3E]. The Se–O
layer. Br(2) are C-connected with Bi atoms from two different
layers and complete the formation of the open framework
(Fig. 4d).
Description of the crystal structure, given in terms of OM4
tetrahedrons, shows common features between Bi6(SeO3)3O5Br2
and related REE derivatives, described in [4,9]. However, the
framework in each case is individual.
The synthesis of new bismuth containing selenite bromide
confirmed the purpose of this work to find new open framework
structures among selenite halides. The crystal structure of
Bi6(SeO3)3O5Br2 is related to those of REEs selenite halides, but
it has, as yet, no complete analogues among them and demon-
strate a unique structural type.
˚
distances vary in a narrow range of 1.65–1.75 A.
The crystal structures of complex REE selenite halides may be
represented in terms of oxygen polyhedrons–tetrahedrons OM4
[4,9]. In Bi6(SeO3)3O5Br2 the OBi4 polyhedrons are formed by
O(2)–O(5) atoms and all Bi atoms. These tetrahedrons share edges
with each other to form 2D nets. The key elements of these nets
are junctions between O(2)Bi4, O(5)Bi4 and O(4)Bi4 tetrahedrons
(Fig. 4.). The groups of six tetrahedrons (Fig. 4b) are ‘‘stitched’’ by
pairs of O(3)Bi4 tetrahedrons (Fig. 4c) connected by common
Bi(4)–Bi(4) edges.
Acknowledgments
The selenium atoms are situated between the OBi4 nets. All
these are bonded to oxygen atoms not contributing to the into
OBi4 nets, to form SeO3 pyramids (Fig. 4d). At the same time, the
oxygen atoms of SeO3 pyramids are bridged by Bi atoms.
This work was supported by RFBR grants 12-03-00665-a and
11-03-00776-a. Drs T.B. Shatalova and I.V. Kolesnik are gratefully

236
P.S. Berdonosov et al. / Journal of Solid State Chemistry 196 (2012) 232–237
Fig. 4. The 2D net formed by OBi4 tetrahedrons in the structure of Bi6(SeO3)3O5Br2: (a) edge connected O(5)Bi4 group, (b) the junction of O(2)Bi4, O(5)Bi4 and O(4)Bi4
tetrahedrons (c) final net, and (d) OBi4 presentation of the Bi6(SeO3)3O5Br2 crystal structure.
Table 3
Crystallographic data for known selenate(IV) halides of REEs and Bi expect MSeO3X composition.
Composition
Space group
Z
a, 1
g, 1
Reference
˚
˚
˚
b, 1
a, A
b, A
c, A
Bi10.666(SeO3)12Br8
Bi6(SeO3)3O5Br2
Tb3(SeO3)2O2Cl
Dy3(SeO3)2O2Cl
Y3(SeO3)2O2Cl
B bab
¯
P1
4
2
4
4
4
4
4
4
2
2
2
1
1
1
1
1
1
15.884(5)
7.1253(7)
5.3516(4))
5.3381(2)
5.4824(4)
14.9823(6)
8.6164(2)
8.5387(6)
6.9446(4)
12.4370(10)
12.2913(4)
7.1172(3)
7.0035(4)
7.0012(1)
6.9630(2)
6.8870(1)
6.8017(5)
15.884(5)
10.972(1)
15.3051(9)
15.2104(7)
14.5792(9)
11.0203(5)
11.7056(3)
11.4592(8)
9.4453(5)
5.4991(4)
5.4617(4)
9.1956(4)
9.0609(6)
9.0163(2)
8.9680(3)
8.8879(2)
8.8286(7)
18.305(5)
12.117(2)
10.8272(7)
10.7656(4)
11.0283(7)
5.4795(3)
12.0842(3)
11.9546(9)
15.6792(9)
10.0529(9)
9.7879(7)
9.9658(5)
9.8591(7)
9.6688(2)
9.6387(4)
9.5909(2)
9.6018(8)
[3]
67.765(7)
82.188(8)
78.445(7)
This study
[4,9,10]
[4,9]
[20]
[4,9]
[9]
P nma
P nma
P nma
C 2/c
¯
P1
¯
P1
Er3(SeO3)2O2Cl
Er4(SeO3)2O3Cl2
Yb4(SeO3)2O3Cl2
Nd7(SeO3)4O5Cl3
Gd5(SeO3)2O4Br3
Tb5(SeO3)2O4Cl3
La9(SeO3)4O8Br3
Pr9(SeO3)4O8Br3
Pr9(SeO3)4O8Cl3
Nd9(SeO3)4O8Cl3
Sm9(SeO3)4O8Cl3
Gd9(SeO3)4O8Cl3
105.515(2)
77.833(1)
78.113(7)
81.649(3)
91.869(3)
90.485(6)
94.938(2)
95.076(3)
94.979(1)
95.176(2)
95.419(1)
95.539(6)
67.666(1)
68.132(7)
87.821(3)
85.270(1)
85.748(7)
84.852(3)
[4,9]
[11]
[9]
¯
P1
C 2 m
C 2 m
¯
P1
[9,10]
[9]
99.658(2)
99.623(3)
99.787(1)
99.528(2)
98.647(1)
97.241(6)
95.840(2)
95.874(3)
95.901(1)
95.893(2)
96.031(1)
96.265(6)
¯
P1
[9]
¯
P 1
[9]
¯
P 1
[9]
¯
P 1
[9]
¯
P 1
[4,9]
Table 4
Comparison of some characteristics of the [MO8] polihedrons (M¼Bi, Ln) for Bi6(SeO3)3O5Br2 and related compounds.
Compound
Yb4(SeO3)2O3Cl2
Gd9(SeO3)4O8Cl3
Nd7(SeO3)4O5Cl3
Bi6(SeO3)3O5Br2
Reference
[4,9]
[4,9]
[11]
This study
Bi(3)O8
2.15
Polyhedron
Yb(1)O8
2.19
Yb(2)O8
2.20
Yb(3)O8
2.23
Gd(1)O8
2.03
Gd(2)O8
2.08
Nd(3)O8
2.04
Nd(4)O8
n
sh
2.03
2.48
0.45
˚
, A
L
L
nn
2.53
0.34
2.59
0.39
2.98
0.75
2.34
0.31
2.48
0.40
2.46
0.42
3.15
1.00
˚
, A
l
˚
Ll–Lsh, A
Ll/Lsh
Lavnnn–Lsh, A
1.15
0.14
1.17
0.16
1.34
0.20
1.15
0.18
1.19
0.16
1.20
0.26
1.22
0.27
1.46
0.43
˚
n
—Lsh shortest M–O distance in polyhedron.
nn
—Ll longest M–O distance in polyhedron.
P
8
1 Li
¼
nnn
i
—Lav average M–O distance in polyhedron Lav
¼
.
8

P.S. Berdonosov et al. / Journal of Solid State Chemistry 196 (2012) 232–237
237
acknowledged for help with thermal properties investigation and
IR data collection. We also want to thank Dr D.O. Charkin for his
valuable discussions of our work.
[8] B. Sto¨ger, M. Weil, K.A. Silich, A.V. Olenev, P.S. Berdonosov, V.A. Dolgikh, Z.
Anorg. Allg. Chem. 637 (2011) 1322–1329.
[9] J. Wontcheu, Oxoselenates(IV) of the Trivalent Rare-Earth Elements and Some
Derivatives PhD Thesis University of Stuttgart 2004 p. 212 /http://elib.
uni-stuttgart.de/opus/volltexte/2004/1846/S.
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[12] C.H. Lipp, Th. Schleid, Z. Naturforsch. 63b (2008) 229–236.
[13] S.A. Ibragimov, P.S. Berdonosov, V.A. Dolgikh, D.Q. Huong, H Oppermann,
Inorg. Mater. 38 (2002) 1291–1296.
[14] P.S. Berdonosov, V.A Dolgikh, Russ. J. Inorg. Chem. 53 (2008) 1353–1358.
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Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.jssc.2012.06.020.
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