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SHORT COMMUNICATION
DOI: 10.1002/zaac.200900226
Constitutional Isomerism of BiW6Cl15: (BiCl)[W6Cl14] and (BiCl2)[W6Cl13]
Markus Ströbele[a] and H.ꢀJürgen Meyer*[a]
Keywords: Bismuth; Tungsten; Cluster compounds; Isomerism; Structure elucidation
Abstract. The compound (BiCl)[W6Cl14] was previously characterized 1234.4(2) pm, c = 1538.9(2) pm, and β = 118.76(1) °). The structure
i
a
a–a –
as a product of the reduction of tungsten hexachloride with elemental of (BiCl2)[W6Cl13] contains chains of [(W6Cl8 )Cl4 Cl2/2
]
clusters
bismuth. Another modification of BiW6Cl15 is now presented as bridged by chlorine atoms. The (BiCl2)+ counterion exhibits two short
(BiCl2)[W6Cl13], based on the results of an Xꢀray single crystal strucꢀ Bi–Cl distances of 244.1(4) and 245.9(3) pm, respectively.
ture determination (space group P21/c, a = 1354.3(2) pm, b =
Xꢀray Diffraction
Introduction
Single crystal Xꢀray diffraction data of (BiCl2)[W6Cl13] were collected
on an IPDS diffractometer (STOE, Darmstadt) using monochromatized
MoꢀKα radiation. Cell refinements and the data reduction were carried
out using the STOE IPDS software. An absorption correction was apꢀ
plied using the programs XꢀShape/XꢀRed [3]. The structures were reꢀ
fined by fullꢀmatrix leastꢀsquares procedures using SHELXꢀ97 [4].
Crystallographic data and structure refinement results are summarized
in Table 1, atom positions are presented in Table 2, and a comparison
of bond lengths is provided in Table 3.
The reduction of WCl6 with bismuth metal can be used for
the synthesis of metalꢀrich tungsten chlorides [1,2]. The raw
product obtained from this reaction has brought up
(BiCl)[W6Cl14] after the coproduced BiCl3 was sublimed off.
The crystal structure of (BiCl)[W6Cl14] was already deterꢀ
mined by Xꢀray diffraction a short while ago [2]. However, the
Xꢀray powder pattern of the raw product revealed the presence
of several unknown Xꢀray reflections, evidenced after subtractꢀ
ing the pattern of the known (BiCl)[W6Cl14].
This raw product, containing (BiCl)[W6Cl14] and other minor
phases, is used in course of the W6Cl12 synthesis. Dissolution
of the raw product into concentrated HCl yields the cluster
acid (H3O)2[W6Cl14]·7H2O besides other compounds [2], and
its pyrolysis yields deep yellow W6Cl12.
This entire synthesis was reproduced by us several times in
order to collect larger quantities of W6Cl12. After finishing up
the first reaction step and subliming off the BiCl3, bright red
crystals of an unknown phase appeared besides those of
(BiCl)[W6Cl14]. The new structure was characterized as
(BiCl2)[W6Cl13] by singleꢀcrystal Xꢀray diffraction.
Further details on the crystal structure investigation may be obtained
from the Fachinformationszentrum Karlsruhe, 76344 EggensteinꢀLeoꢀ
Table 1. Crystal data and results on the structure refinement of
(BiCl2)[W6Cl13].
Compound
(BiCl2)[W6Cl13]
Formula weight /g·mol–1
1843.83
Crystal system
monoclinic
P21/c
Space group
Unit cell dimensions /pm
a = 1354.3(2)
b = 1234.4(2)
c = 1538.9(2)
β = 118.76(1)
2.2554(5)
4
Monoclinic angle /°
Volume /nm3
Experimental Section
Z
Crystal size /mm
0.26 × 0.28 × 0.16
All reactions were performed under the same reaction conditions as
described very recently, using the same sources and purities of materiꢀ
als [2]. Bright red crystals, which later turned out to represent a new
modification of BiW6Cl15, were selected from the raw product for Xꢀ
ray single crystal structure analysis.
Temperature /K
293(2)
λ (MoꢀKα) /pm
71.073
Calc. density /g·mol–3
Absorption coefficient /mm–1
F(000)
5.430
40.006
3128
Θ range for data collection /°
Index ranges
2.24 to 24.99
–16 ≤ h ≤ 16, –14 ≤ k ≤ 14, –18 ≤ l ≤ 18
17067
Reflections collected
Independent reflections
Refinement method
Data / parameters
Goodnessꢀofꢀfit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
Extinction coefficient
Largest diff. peak and hole /e·Å–3
* Prof. Dr. H.ꢀJ. Meyer
3818 [R(int) = 0.0769]
Fullꢀmatrix leastꢀsquares on F2
3818 / 200
Fax: +49ꢀ7071ꢀ29ꢀ5702
EꢀMail: juergen.meyer@uniꢀtuebingen.de
[a] Abteilung für Festkörperchemie und Theoretische Anorganische
Chemie
1.000
R1 = 0.0334, wR2 = 0.0762
R1 = 0.0394, wR2 = 0.0785
0.00108(3)
Institut für Anorganische Chemie
Ob dem Himmelreich 7
Universität Tübingen
2.061 and –1.808
72074 Tübingen, Germany
Z. Anorg. Allg. Chem. 2009, 635, 1517–1519
© 2009 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim
1517