Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Bismuth (ChemPur, 99.9999%) was treated with streaming H
20 °C, BiBr (Alfa-Aesar), AlBr and AlCl were sublimed three- silica ampoules.
times before being used. [BMIm]Cl (98%, Sigma–Aldrich) and
BMIm]Br (99%, ABCR) were both dried under vacuum at 100 °C.
LiBr, NaBr KBr, CsBr, NH Br (lab stock), iron (99.95%, ABCR) and
2
at Ϯ2 and Ϯ0.2 K/min were employed on samples sealed in evacuated
2
3
3
3
[
Supporting Information (see footnote on the first page of this article):
Additional graphical representations of the crystal structure, tables of
atomic parameters and interatomic distances, results of geometry opti-
mization.
4
indium powder (99.999%, Sigma Aldrich) were used without further
purification. Homogenization by ball mill (Pulveristte 23, Fritsch) has
been performed for 25 minutes under argon atmosphere in a glovebox.
0
3
.5 mmol CsBr, 1 mmol bismuth, and 0.5 mmol BiBr were sealed
Keywords: Bromine; Bismuth; Cluster compounds; Phase
diagrams; Polycations
under vacuum in a Duran glass ampoule (10 cm). The ampoule was
heated in the center of a tube furnace (80 cm) and cooled by removing
it from the furnace. After 10 d of annealing at 270 °C or alternatively
at 300 °C, the reaction remained incomplete showing the starting mate-
rials besides some Cs
20 °C a multiphase product was obtained. According to powder X-
ray diffraction (PXRD), the product mainly consisted of Cs Bi Br and
small fractions of polycrystalline Bi Br and BiOBr (oxygen from
traces of water in CsBr). The amount of Bi Br was below the detec-
3 2 9 6 7
Bi Br and Bi Br . In contrast, after 18 h at
References
4
3
2
9
[
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6
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[
[
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1
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[
3
[
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crystal shape was optimized
using sets of symmetrically equivalent
[
[
52]
reflections and then utilized for a numerical absorption correction.
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[
52,53]
The structure was solved with direct methods.
Structure refine-
included anisotropic displacement parameters for all
The occupancy of the atom Bi8 refined to approximately
0% and was then fixed to this value. Graphical representations of
2
ment against F
o
atoms.[
53,54]
[
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5
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parameters and selected interatomic distances are listed in Tables S1
and S2 of the Supporting Information.
[
[
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6
28, 2179.
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Further details of the crystal structure investigations may be obtained
from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-
[
2
Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail: [20] M. Knies, M. Kaiser, A. Isaeva, U. Müller, T. Doert, M. Ruck,
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for de-
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Data in Brief for Bi
5
Br
4
: a = 1800.0(2) pm, b = 1476.1(1) pm, c =
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6
3
9
7
1
4
24.5(2) pm, V = 2456.4(6)·10 pm , Pmmn (no. 59), Z = 8; ρcalc
=
–3
–1
.38 g·cm ; μ(Mo-K
826 unique; –19 Յ h Յ 19, –16 Յ k Յ 16, –10 Յ l Յ 9, 2θmax
6.1°; 100 parameters; Rint = 0.134, R = 0.083, R = 0.045 for 1239
Ͼ 4σ(F ), R = 0.087 for all F , wR = 0.073, Goof = 1.05; residual
electron density 3.1 to –3.5 e /(10 pm ).
α
) = 84.4 mm ; 13572 reflections measured,
[
24] A. N. Kuznetsov, A. V. ShevelЈkov, S. I. Troyanov, B. A. Popov-
kin, Russ. J. Inorg. Chem. 1996, 41, 920.
=
σ
1
[
25] A. N. Kuznetsov, A. V. ShevelЈkov, B. A. Popovkin, Russ. J. Co-
ord. Chem. 1998, 24, 861.
F
o
o
1
o
2
3
–
6
[
[
26] M. Ruck, V. Dubenskyy, Z. Anorg. Allg. Chem. 2003, 629, 375.
27] A. N. Kuznetsov, P. I. Naumenko, B. A. Popovkin, L. Kloo, Russ.
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Quantum Chemical Calculations: DFT-based calculations were per-
formed with the quantum mechanical package FHI-aims.
utility program cif2cell
[
56]
With the
[28] S. Hampel, P. Schmidt, M. Ruck, Z. Anorg. Allg. Chem. 2005,
631, 272.
[
57]
the input coordinates were generated based
on the ordered variant obtained from X-ray diffraction shown in Fig- [29] B. Wahl, M. Ruck, Z. Anorg. Allg. Chem. 2008, 634, 2873.
[
[
30] B. Wahl, M. Ruck, Z. Anorg. Allg. Chem. 2010, 636, 337.
31] A. Gerisch, M. Ruck, Z. Kristallogr. 2011, 226, 613.
ure 1. Using the numerical atom-centered basis sets of light level, the
zora scalar relativistic correction, and a mesh of (4ϫ4ϫ8) k-points,
[
58]
[32] M. F. Groh, U. Müller, A. Isaeva, M. Ruck, Z. Anorg. Allg. Chem.
017, 643, 1482.
33] M. Ruck, V. Dubenskyy, T. Söhnel, Angew. Chem. 2003, 115,
086; Angew. Chem. Int. Ed. 2003, 42, 2978.
34] M. Ruck, V. Dubenskyy, T. Söhnel, Z. Anorg. Allg. Chem. 2004,
30, 2458.
the geometry optimization was performed with the PBE functional,
2
relaxing the individual atomic coordinates while keeping the lattice
parameters fixed. The atomic coordinates of the optimized structure
are gathered in Table S4 (Supporting Information).
[
[
[
3
6
Thermal Analysis: Differential scanning calorimetry was carried out
on a SETARAM Labsys ATD-DSC using a k-probe (Ni–Cr/Ni–Al;
35] B. Wahl, L. Kloo, M. Ruck, Angew. Chem. 2008, 120, 3996; An-
gew. Chem. Int. Ed. 2008, 47, 3932.
2 3
Tmax = 800 °C) and Al O as a reference. Heating and cooling rates of [36] B. Wahl, M. Ruck, Z. Anorg. Allg. Chem. 2008, 634, 2267.
Z. Anorg. Allg. Chem. 2019, 1–8
www.zaac.wiley-vch.de
6
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim