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Polyhedron 20 (2001) 415 – 421
Synthesis and properties of
bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-) salts,
[Q][Bi(dmit)
2
]. Crystal structure of [AsPh
4
][Bi(dmit)
2
]·1/2DMSO:
comparison of the solid state structures of [Q][Bi(dmit)
2
] and
[Q][Sb(dmit)
2
]
Nadia Maria Comerlato
a
, Luiz Anto ˆ nio Sodre ´ Costa
a
, R. Alan Howie
b,
*,
Robson Pacheco Pereira
a
, Ana Maria Rocco
a
, Alexandre Carneiro Silvino
a
,
James L. Wardell
a,1
, Solange M.S.V. Wardell
c
a
Departamento de Quı ´mica Inorga ˆnica, Instituto de Quı ´mica, Uniersidade Federal do Rio de Janeiro, CP 68563, 21945 -970 Rio de Janeiro,
RJ, Brazil
b
Department of Chemistry, Uniersity of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, Scotland, UK
c
Departamento de Quı ´mica Orga ˆnica, Instituto de Quı ´mica, Uniersidade Federal Fluminense, 24020 -150 Nitero ´i, RJ, Brazil
Received 9 August 2000; accepted 23 October 2000
Abstract
Ionic complexes, [Q][Bi(dmit)
2
](5:QNEt
4
, NBu
4
, 1,4-Me
2
-pyridinium and AsPh
4
), have been obtained from BiBr
3
and
[Q]
2
[Zn(dmit)
2
] [H
2
–dmit4,5-dimercapto-1,3-dithiole-2-thione]. As established by the crystal structure determination of
[(5:QAsPh
4
)·1/2DMSO], the cations have near tetrahedral geometries and are well separated from the anions. The anions,
containing chelating dmit ligands, are linked into chains via Bi – thiolato – S inter-anion bonds: Bi
2
S
2
rings are formed within the
chains, with Bi···Bi distances alternating between 3.7760(3) and 3.9092(3) A . The bismuth atoms are six-coordinate, arising from
two inter-anion Bi–S [Bi–S =3.0391(13) and 3.1643(14) A ] and four intra-anion Bi – S bonds [between 2.6680(13) and 2.8370(13)
A ], with stereochemistries, including the equatorial-sited stereochemically active lone pair, of distorted pentagonal bipyramids.
There are no S···S contacts between the anions less than the sum of the van der Waals radii. Comparisons are made between the
structure of [(5:QAsPh
4
)·1/2DMSO] and those reported previously for (5:QNEt
4
), [(5:QNEt
4
)·1/2Et
2
O] and [(5:QNBu
4
) as
well as those for [Q][Sb(dmit)
2
](4). © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Bismuth; Dmit; 1,3-Dithiole-2-thione-4,5-dithiolates; Crystal structures
1. Introduction
Metal-dmit complexes have attracted considerable
attention in the recent past. Much of the interest has
centred on transition metal compounds due, in the large
part, to the conducting and super-conducting properties
[1–5] of such compounds as [NMe
4
]
0.5
[M(dmit)
2
] (M =
Ni [6]; M =Pd [7]. With main group compounds, the
dominant concern has been the anion structures and
packing arrangements. In complexes, [Q]
2
[Zn(dmit)
2
(1)
[8–10], [Q]
2
[Sn(dmit)
3
], (2), [11,12] and [Q][Sb(dmit)
3
]
(3), [13] (Q =onium cation), the metal atoms are solely
bonded to the dithiolate sulfur atoms within the [M(d-
mit)
n
]
m-
anions, and thus have distorted tetrahedral
[Zn] or octahedral geometries [Sn or Sb]. There are,
however, sulfur – sulfur intra-anion contacts, at dis-
tances less then the sum of the van der Waals radii for
two sulfur atoms [3.70 A ] [14] in 1 and 3. In general, the
packing of the anions is strongly dependent on [Q]
+
.
* Corresponding author. Tel.: +44-1224-272-907; fax: +44-1224-
272-921.
E-mail address: r.a.howie@abdn.ac.uk (R.A. Howie).
1
On leave from the University of Aberdeen.
0277-5387/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII:S0277-5387(00)00643-4