Author:
Bowmaker Graham A.,Hannaway Frances M. M.,Junk Peter C.,Lee Aaron M.,Skelton Brian W.,White Allan H.
Abstract
Room-temperature single-crystal X-ray studies are recorded for a number of
adducts of BiX3 and
N,N′-bidentate ligand (2,2′-bipyridine (bpy)
or 1,10-phenanthroline (phen)), devoid of coordinated solvent.
BiBr3/bpy/MeCN (1 : 1 : 1) is triclinic
P-1, a
12·129(2), b 9·955(4),
c 7·748(1) Å, α 73·14(2),
β 77·34(1), γ 69·79(2)°, Z
= 2; conventional R on
|F| was 0·036 for
No 2252 independent
‘observed’ (I >
3σ(I)) reflections. The phen analogue is
isomorphous, a 11·586(3), b
10·839(6), c 7·769(10) Å, α
73·70(7), β 76·67(7), γ 70·34(4)°,
Z = 2, R 0·042 for
No 800.
BiI3/bpy (1 : 1) is triclinic,
P-1, a
11·742(4), b 9·261(1),
c 8·261(3) Å, α 86·46(2),
β 71·48(3), γ 67·25(2)°, Z
= 2, R 0·043 for
No 1164. All complexes are
centrosymmetric binuclear
[(N,N′-bidentate)X2Bi(µ-X)2BiX2(N,N′-bidentate)]
with six-coordinate pseudo-octahedral bismuth(III). Attempts to produce a
chloride analogue have resulted, in the case of
N,N′-bidentate = bpy, in a novel adduct of
BiCl3/bpy 1 : 1·5 stoichiometry, monoclinic,
P21/c,
a 9·377(8), b
17·699(5), c 21·58(1) Å, β
107·82(6)°, Z = 8,
R 0·055 for
No 1804. The complex is
[(bpy)2Cl2Bi(µ-Cl)BiCl3(bpy)],
containing seven- and six-coordinate bismuth. Bands in the far-infrared
spectra due to the v(BiX) vibrations in
[(bpy)2Cl2Bi(µ-Cl)BiCl3(bpy)]
and
[(bpy)I2Bi(µ-I2)BiI2(bpy)]
are assigned and discussed in relation to the structures of the complexes.