Black plate (657,1)

Chapter 22 . Group 5: niobium and tantalum 657

Fig. 22.6 Representations of the structures of (a) the ½Nb6 I8 3þ unit found in Nb6 I11 and (b) the ½M6 X12 nþ (n ¼ 2 or 3)
unit found in compounds of type M6 X14 and M6 X15 for M ¼ Nb or Ta, X ¼ halide. The cluster units are connected into
(c) a 3-dimensional network or (d) a 2-dimensional sheet by bridging halides (see text).

solids with polymeric structures; fluoride analogues have not
been fully established.
Nb
Nb Nb
= Cl
(22.12)
A range of halides with M3 or M6 frameworks exist, but
all have lattice structures with the metal cluster units
connected by bridging halides. The structure of Nb3 Cl8 is
represented in 22.12, but of the nine outer Cl atoms
shown, six are shared between two adjacent units, and
three between three (see worked example 22.1). Alterna-
tively, the structure can be considered in terms of an hcp
array of Cl atoms with three-quarters of the octahedral
holes occupied by Nb atoms such that they form Nb3 trian-
gles. Reduction of Nb3 I8 (structurally analogous to Nb3 Cl8 )
with Nb in a sealed tube at 1200 K yields Nb6 I11 . The
formula can be written as ½Nb6 I8 I6=2 indicating that
½Nb6 I8 3þ units are connected by iodides shared between
two clusters. (The ionic formulation is purely a formalism.)
The ½Nb6 I8 3þ cluster consists of an octahedral Nb6 -core,
each face of which is iodo-capped (Figure 22.6a). The clusters
are connected into a network by bridges (Figure 22.6c). Two
other families of halides are M6 X14 (e.g. Nb6 Cl14 , Ta6 Cl14 ,
Ta6 I14 ) and M6 X15 (e.g. Nb6 F15 , Ta6 Cl15 , Ta6 Br15 ). Their
formulae can be written as ½M6 X12 X4=2 or ½M6 X12 X6=2
showing that they contain cluster units ½M6 X12 2þ and
½M6 X12 3þ respectively (Figure 22.6b). The clusters are
connected into either a three-dimensional network (M6 X15 ,
Figure 22.6c) or two-dimensional sheet (M6 X14 , Figure
22.6d).
Magnetic data show that the subhalides exhibit metal–
metal bonding. The magnetic moment of Nb3 Cl8 is 1.86 B
per Nb3 -unit (298 K) indicating one unpaired electron. This
can be rationalized as follows: