Inorganica Chimica Acta 331 (2002) 48 – 51
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Cyano-bridged cluster-metal coordination compound:
synthesis and crystal structure of
[Cu(NH
3
)
3
][Cu(NH
3
)
4
][Cu(NH
3
)
5
][W
4
Te
4
(CN)
12
]·5H
2
O
Vladimir P. Fedin
a,
*, Irina V. Kalinina
a
, Andrey Gerasimenko
b
,
Alexander V. Virovets
a
a
Institute of Inorganic Chemistry of the Russian Academy of Sciences, pr. Larentjea 3, Noosibirsk 630090, Russia
b
Institute of Chemistry of the Far -Eastern Diision of the Russian Academy of Sciences, pr. 100 -letya Vladiostoka 159,
Vladiostok 690022, Russia
Received 25 May 2001; accepted 27 September 2001
Dedicated to A.G. Sykes in recognition of his many, diverse and creative contributions to Inorganic Chemistry
Abstract
Dark-brown single crystals of the title compound 1 were obtained in high yield by layering a CuCl
2
solution in 25% aqueous
ammonia on a glycerol solution of K
6
[W
4
Te
4
(CN)
12
]·5H
2
O. The complex 1 was characterized by single crystal X-ray diffraction
analysis and IR spectroscopy. The X-ray structure of 1 reveals a polymeric chain cyano-bridged cluster-metal coordination
compound. The [W
4
Te
4
(CN)
12
]
6 -
cluster anions are linked one to another by Cu
2 +
cations through coordination by nitrogen
atoms of the CN groups. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Crystal structure; Copper complexes; Telluride complexes; Cyano-bridged complexes; Cubane-type complexes
1. Introduction
Homo- and heterometallic cuboidal cluster com-
plexes with bridging chalcogenide ligands are known
for a wide variety of transition metals and they appear
to be one of the most important common basic struc-
tures of transition metal cluster complexes [1]. Ho-
mometallic Mo
4
S
4
cubane-type clusters have been
known for some 20 years [2–6]. They have the general
formula [Mo
4
S
4
L
12
], where L denotes ligating atoms of
either neutral or anionic ligands. Cubane-type molecu-
lar cluster complexes [Mo
4
Se
4
]
4 +/5 +/6 +
have also been
reported by Sykes for the first time [7,8]. In contrast to
molybdenum, reports of W
4
chalcogenide complexes in
the literature are very scarce. The corresponding tel-
lurides were also neglected. In the course of our joint
study with Sykes on the synthesis and reactivities of
solid-state molybdenum and tungsten chalcogenides, we
have recently obtained the first complexes with cubane-
type M
4
Te
4
(M =Mo, W) cluster cores [9,10]. In the
present paper a cubane-type telluride compound
K
6
[W
4
Te
4
(CN)
12
]·5H
2
O was used for the synthesis of a
polymeric chain cyano-bridged cluster-metal coordina-
tion compound [Cu(NH
3
)
3
][Cu(NH
3
)
4
][Cu(NH
3
)
5
]-
[W
4
Te
4
(CN)
12
]·5H
2
O(1) in which the [W
4
Te
4
(CN)
12
]
6 -
cluster anions are linked one to another by Cu
2 +
cations through coordination by nitrogen atoms of the
CN groups.
2. Experimental
2.1. Syntheses
All the manipulations were performed in air.
K
6
[W
4
Te
4
(CN)
12
]·5H
2
O were prepared according to the
procedure published earlier [10]. Elemental analyses
were carried out in the Laboratory of Microanalysis,
* Corresponding author. Tel.: +7-3832-355 253; fax: +7-3832-
344 489.
E-mail address: cluster@che.nsk.su (V.P. Fedin).
0020-1693/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII:S0020-1693(01)00754-X