Synthesis and properties of bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-) salts, [Q][Bi(dmit)2]. Crystal structure of [AsPh4][Bi(dmit)2]·1/2DMSO: Comparison of the solid state structures of [Q][Bi(dmit)2] and [Q][Sb(dmit)2]

Article abstract of DOI:10.1016/S0277-5387(00)00643-4

Ionic complexes, [Q][Bi(dmit)₂] (5:Q= NEt₄, NBu₄, 1.4-Me₂-pyridinium and AsPh₄), have been obtained from BiBr₃ and [Q]₂[Zn(dmit)₂] [H₂-dmit=4.5-dimercapto-1.3-dithiole-2-thione]. As established by the crystal structure determination of [(5:Q=AsPh₄)·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: Bi₂S₂ 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:Q=AsPh₄)·1/2DMSO] and those reported previously for (5:Q=NEt₄), [(5:Q=NEt₄)·1/2Et₂O] and [(5:Q=NBu₄) as well as those for [Q][Sb(dmit)₂] (4).

Full text of DOI:10.1016/S0277-5387(00)00643-4

www.elsevier.nl/locate/poly
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 [AsPh4][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 Antoˆnio 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 Qu´ımica Inorgaˆnica, Instituto de Qu´ımica, Uni6ersidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro,
RJ, Brazil
b Department of Chemistry, Uni6ersity of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, Scotland, UK
c Departamento de Qu´ımica Orgaˆnica, Instituto de Qu´ımica, Uni6ersidade Federal Fluminense, 24020-150 Nitero´i, RJ, Brazil
Received 9 August 2000; accepted 23 October 2000
Abstract
Ionic complexes, [Q][Bi(dmit)2] (5:QꢀNEt4, NBu4, 1,4-Me2-pyridinium and AsPh4), have been obtained from BiBr3 and
[Q]2[Zn(dmit)2] [H2–dmitꢀ4,5-dimercapto-1,3-dithiole-2-thione]. As established by the crystal structure determination of
[(5:QꢀAsPh4)·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: Bi2S2 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:QꢀAsPh4)·1/2DMSO] and those reported previously for (5:QꢀNEt4), [(5:QꢀNEt4)·1/2Et2O] and [(5:QꢀNBu4) 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
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
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 [NMe4]0.5[M(dmit)2] (M=
* Corresponding author. Tel.: +44-1224-272-907; fax: +44-1224-
272-921.
,
two sulfur atoms [3.70 A] [14] in 1 and 3. In general, the
E-mail address: r.a.howie@abdn.ac.uk (R.A. Howie).
packing of the anions is strongly dependent on [Q]+.
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

416
N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421
In contrast to 1–3, metal–S inter-anion bonds occur
in solid [Q][Sb(dmit)2] (4:QꢀNEt4, 1,4-dimethylpyri-
dinium or PPh4): these Sb–S inter-anion bonds involve
thione S atoms [15,16]. Both the anion packing and the
coordination number of the metal are strongly depen-
dent on the cation: in (4:QꢀNEt4) the anions are ar-
ranged in a polymeric two-dimensional network with
six-coordinate Sb, in (4:Qꢀ1,4-dimethylpyridinium) the
anions are arranged in dimeric units with five-coordi-
nate Sb [15], while in (4:QꢀPPh4) the anions are ar-
ranged in centrosymmetric pairs of chains with
six-coordinate Sb [16]. Recently we reported that the
structure of [NBu4][Bi(dmit)2] (5:QꢀNBu4) was
analogous to that of (4:QꢀPPh4) [17]. Also recently,
Fig. 1. Atom numbering scheme and arrangement of anions in
[(5:QꢀAsPh4)·1/2DMSO]. Probability ellipsoids are drawn at 50%:
symmetry operations i: −x+1, −y, −z+1; ii: −x, −y, −z+1.
Sheng et al. [18] published the structures of
[NEt4][Bi(dmit)2] (5:QꢀNEt4) and [NEt4][Bi(dmit)2]·1/
2Et2O [(5:QꢀNEt4)·1/2Et2O], both of which contain
six-coordinate Bi. While there are structural differences
between (5:QꢀNEt4) and [(5:QꢀNEt4)·1/2Et2O], both
contain Bi–thiolato–S inter-anion bonds and thus are
markedly different from the other Group 15 com-
pounds. As all four compounds 5, so far studied, have
exhibited structural differences, we have carried out the
structural analysis of a further compound, namely
(5:QꢀAsPh4)·1/2DMSO. In this publication, we report a
general synthesis of [Q][Bi(dmit)2] (5), as well as the
crystal structure of [(5:QꢀAsPh4)·1/2DMSO].
Table 1
Selected IR spectral data for 1, 4 and 5
Compound
wCꢀC
wCꢀS
wC–S Ref.
(5:QꢀNEt4)
1434
1428
1409
1435
1416
1415
1411
1437, 1417
1433
1053, 1019
1054, 1021
1029
1054, 1033
1056
1053
1058
1056
1047, 1026
1049, 1026
873 This study
879 This study
886 This study
890 This study
887 This study
876 This study
886 This study
889 This study
880 [15]
(5:QꢀC7H10N)
(5:QꢀNBu4)
(5:QꢀAsPh4)
(1:QꢀNEt4)
(1:QꢀC7H10N)
(1:QꢀNBu4)
(1:QꢀAsPh4)
(4:QꢀNEt4)
(4:QꢀC7H10N)
1431
880 [15]
2. Results and discussion
Table 2
,
Selected bond lengths (A) and bond angles (°) for [(5:QꢀAsPh4)·1/
The air-stable [Q][Bi(dmit)2] compounds, [5:QꢀNEt4,
NBu4, 1,4-Me2-pyridinium (C7H10N) and AsPh4], were
synthesized directly from BiBr3 and [Q]2[Zn(dmit)2] (1).
The compound, (5:QꢀNEt4), has been obtained previ-
ously from Na2(dmit) and BiI3 [18]: however, a higher
yield was obtained by use of the [Zn(dmit)2]2− precur-
sor. As also found for 1 and 4 [15], the CꢀC, CꢀS and
C–S absorptions in 5 occur in the regions 1435–1409,
1054–1033 and 881–889cm−1, respectively, see Table
1. All the salts, 5, are dark red–brown in colour with
umax, in the visible region, between 450 and 457 nm.
The AsPh4 salt used in the structure determination
was obtained as a solvated material on crystallisation
from DMSO solution.
2DMSO a
Bond lengths
Bi–S(1)
Bi–S(6)
Bi–S(2)
2.6680(13)
2.6777(13)
2.8143(13)
Bi–S(7)
2.8370(13)
3.0391(13)
3.1643(14)
Bi–S(2)c1
Bi–S(7)c2
Bond angles
S(1)–Bi–S(6)
S(1)–Bi–S(7)
S(6)–Bi–S(7)
S(1)–Bi–S(2)
S(6)–Bi–S(2)
S(2)–Bi–S(7)
S(1)–Bi–S(2)i
S(6)–Bi–S(2)i
S(2)–Bi–S(2)i
S(7)–Bi–S(2)i
C(5)–S(7)–Biii
Bi–S(7)–Biii
88.83(4)
82.87(4)
76.45(4)
77.25(4)
86.04(4)
153.71(4)
74.37(4)
162.00(4)
96.29(3)
94.71(4)
98.49(18)
77.77(3)
S(1)–Bi–S(7)ii
S(6)–Bi–S(7)ii
S(2)–Bi–S(7)ii
S(7)–Bi–S(7)ii
S(2)i–Bi–(7)ii
C(1)–S(1)–Bi
C(2)–S(2)–Bi
C(4)–S(6)–Bi
C(5)–S(7)–Bi
Bi–S(2)–Bii
155.88(4)
69.90(4)
89.65(3)
102.23(3)
127.83(3)
99.34(17)
96.73(18)
97.43(17)
95.08(18)
83.71(3)
2.1. Crystal structure of [(5:QꢀAsPh4)·1/2.DMSO]
C(2)–S(2)–Bii
100.04(17)
Selected bond angles and lengths for [(5:QꢀAsPh4)·1/
2 DMSO] are listed in Table 2. The atom arrangement
a Symmetry operations i: −x+1, −y, −z+1; ii: −x, −y, −z+1.

N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421
417
and numbering scheme in the anion is shown in Fig. 1.
The [AsPh4] cation has a near tetrahedral geometry: its
structure is not further discussed here. The cations do
not interact with the anions: however, as in other
compounds 5, there are inter-anion interactions in
[(5:QꢀAsPh4)·1/2DMSO]: each Bi atom forms four
strong intra-anion Bi–S bonds to the dithiolato S
atoms, and 2 inter-anion and weaker bonds to sulfur
atoms of adjacent anions. Each dmit unit is asymmetri-
cally bound to Bi, with bite angles of 76.46(4) and
77.25(4)°, see Table 2. Each dmit ligand is essentially
planar, with the Bi atom out of the dmit planes by
S angles being 153.71(4) [S(2)–Bi–S(7)], 155.88(4)
[S(1)–B1–S(7)ii] and 162.00(4)° [S(6)–Bi–S(2)i], [sym-
metry operations i: −x+1, −y, −z+1; ii: −x, −y,
−z+1]; however, the inclusion of a stereochemically
active lone pair on Bi provides a more acceptable
stereochemical designation. Inclusion of the lone pair in
an equatorial site, between the inter-anion bonds to
S(2)i and S(7)ii, [S(2)i–Bi–S(7)ii=127.84(3)°], produces
a distorted pentagonal bipyramidal array about Bi,
with the axial sites occupied by S(2) and S(7). The
distortion from an ideal trans angle of 180° is ac-
counted for, partially at least, by the small chelate bite
angles of 76.45(4) and 77.25(4)°. The sum of the angles
subtended by the equatorial S atoms [S(1), S(6), S(2)i
and S(7)ii] at Bi is 360.94°.
,
1.2585(19) and 1.488(2) A.
The two Bi–S inter-anion bonds involve thiolato
atoms of two adjacent U-shaped anions, thereby form-
ing chains, Fig. 1. The spine of the chains, with Bi2S2
rings, can be considered to be a line of bismuth atoms
with the Bi···Bi distances along the chain alternating in
The anion-anion interactions in [(5:QꢀAsPh4)·1/
2DMSO] are analogous to those in [(5:QꢀNEt4)·Et2O]
[17]
and
[AsPh4][bis(1,2-dicyanoethene-1,2-dithio-
,
length between 3.7760(3) and 3.9092(3) A. There are no
S···S contacts between the chains at distances less than
lato)bismuthate], [AsPh4][Bi(S2C2(CN)2] (6), reported
by Hunter and Weakley [19]: comparative geometric
data for the three species are provided in Table 3. The
structure of (4:QꢀNEt4) [15] was also considered to
show some involvement of a stereochemically active
,
the sum of the van der Waals radii, 3.70 A [14], for two
S atoms. The six Bi–S bonds form a very distorted
octahedral array about Bi, with the three largest S–Bi–
Table 3
Selected geometric parameters for distorted pentagonal bipyramidal 4–6

418
N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421

N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421
419
lone pair, but the effect of the lone pair is very much
less pronounced than in any of [(5:QꢀAsPh4)·1/
2DMSO], [(5:QꢀNEt4)·1/2Et2O] [18] or 6 [19].
The solvate molecules of DMSO, 0.5 molecules per
molecule of (5:QꢀAsPh4), are highly disordered over
centrosymmetrically related pairs of sites in spaces left
by the cations and anions.
thiolato S can not be a prime cause of the asymmetry,
as stated in reference [18]. The chelate bite angles and
Bi–S primary bond lengths in 5 vary significantly from
73.6(4) in (5:QꢀNEt4) to 82.06(3)° in (5:QꢀNBu4), see
Table 3.
The secondary bonds to the thione S atoms in
,
(5:QꢀNBu4) [3.4628(13) and 3.2548(11) A], are longer
than those to thiolato–S atoms in (5:QꢀNEt4),
[(5:QꢀNEt4)·1/2Et2O] and (5:QꢀAsPh4)·1/2DMSO], the
2.2. Comparison of the anion arrangements in 4 and 5
,
range being 3.0391(14) to 3.1643(14) A, see Table 3.
,
The Bi centres in all four Bi compounds,
[(5:QꢀAsPh4)·1/2DMSO], (5:QꢀNBu4), (5:QꢀNEt4) and
[(5:QꢀNEt4)·1/2Et2O], are six coordinate and, including
the lone pairs, with pseudo pentagonal bipyramidal
geometries. The lone pair on each bismuth in the chains
is directed away from that on a neighbouring bismuth.
Despite the gross similiarities about Bi in these com-
pounds, and the formation of chains of anions and
Bi2S2 rings, appreciable differences are exhibited in the
anion arrangements. The three distinct anionic arrange-
ments, found, so far, are:
1. Single chains formed by inter-anion Bi–thiolato–S
bonds, with a thiolato S atom of each dmit ligand
involved in the inter-anion bonding, Figs. 1 and
2(a). This arrangement is found in the two solvates,
[(5:QꢀAsPh4)·1/2DMSO] and [(5:QꢀNEt4)·1/2Et2O]:
the only difference being the weak S···S interactions,
between the chains, detected in the latter.
2. Single chains also formed by inter-anion Bi–thio-
lato–S bonds, but here there are different roles for
the dmit ligands. One dmit type acts primarily as a
chelate to one Bi centre-, with an additional, but
weaker, interaction to a second Bi, while the other
type of dmit group primarily bridges two Bi centres,
with a weaker contact to one of these Bi atoms, see
Fig. 2(b). This arrangement is found in (5:QꢀNEt4).
3. Centrosymmetric pairs of anion chains formed by
inter-anion Bi–thione–S bonds, see Fig. 2(c). There
are two types of chelating dmit ligands per anion:
one is not involved in any inter-anion bonding,
while in the other, the thione S acts as a m3-bridging
atom to Bi atoms in different chains within the
chain pair. The Bi2S2 rings are formed between the
chain pairs. The short separations between the par-
allel dmits in the two strands of the centrosymmetric
chain pairs allows for p–p interactions. This ar-
rangement is present in (5:QꢀNBu4), as well as in
(4:QꢀPPh4).
The longer Bi–thione–S bond, [3.4628(13) A], in
(5:QꢀNBu4) is between the chain pairs: the equivalent
,
value in (4:QꢀPPh4) is 3.54(1) A. The minimum allowed
,
perpendicular separation, ca. 3.5 A, of parallel dmits
places a lower limit on these M–thione–S bond lengths
(M=Sb or Bi): both the M–thione–S bond lengths in
,
,
(5:QꢀNBu4) [3.4628(13) A] and (4:QꢀPPh4) [3.54(1) A]
appear close to this limit. The shorter Bi–thione–S
,
bond in (5:QꢀNBu4) [3.2548(11) A], within a single
chain, is still outside the range established for Bi–thio-
lato–S secondary bonds. This indicates that the M–
thione–S secondary bonding (M=Sb or Bi) leads to
weaker associations, which may be required for steric
reasons. The bulkier the cation in 5, the greater will be
the restrictions to the closeness of approach of the
anions: hence, bulkier (5:QꢀNBu4), rather than smaller
(5:QꢀNEt4), will prefer Bi–thione–S secondary bond-
ing. All compounds, 4, possesses Sb–thione–S sec-
ondary bonding: the larger bite angles of Sb–dmit
chelates and generally shorter Sb–S bonds, compared
to the situation in Bi–dmit chelates, result in a more
hindered approach to approach to the Sb centre and
consequently there is a greater preference for M–
thione–S secondary bonding in 4 compared with 5.
Coupled to this will be the effect of the bulk of the
cation, on both the aggregation and coordination num-
ber of Sb.
3. Experimental
NMR spectra were run on a Bruker 300 MHz instru-
ment, IR spectra on a Nicolet Magna 760 FTIR instru-
ment and UV–Vis spectra on a Varian-Cary 1E
UV–Vis instrument. Melting points were measured on
a Melt-TempII instrument. Elemental analyses were
performed with a Perkin Elmer 2400 apparatus. The
compounds, (1:[Q]2[Zn(dmit)2]) [QꢀNEt4, 1,4-Me2-pyri-
dinium (C7H10N), NBu4 or AsPh4] were prepared ac-
cording to a published procedure [11].
The chelating ligands are asymmetrically bound in all
cases, with distinct ranges for the shorter [2.5872(14)–
,
,
2.677(13) A] and the longer [2.7299(11)–2.87(1) A]
Bi–S bonds of each chelate. The longer Bi–S bond to
each chelating ligand results mainly from the proximity
of the lone pair on the metal. As the ligand asymmetry
is met in (5:QꢀNBu4) and in 4, in which none of the
thiolato S atoms are involved in bridging, bridging by a
3.1. Preparations of 5
3.1.1. Preparation of (5:QꢀNEt4)
A solution of BiBr3 (0.313 g, 0.697 mmol) in acetone
(30 ml) was added slowly to a solution of (1:QꢀNEt4)

420
N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421
Table 4
(aryl-C’s), 135.5 (CꢀC), 213.7 (CꢀS). IR (KBr): 1428
cm−1 (C=C), 1054, 1021 (CꢀS) and 879 (C–S).
UV–Vis (CH3CN): 241, 299, 358, 450 nm.
Crystal data and structure refinement for [(5:QꢀAsPh4)·1/2DMSO]
Empirical formula
Formula weight
T (K)
Wavelength (A)
Crystal system
Space group
C31H23As Bi O0.5S10.5
1024.02
150(2)
0.71073
triclinic
3.1.3. Preparation of (5:QꢀNBu4)
,
This was prepared analogously to compound
(5:QꢀNEt4), from BiBr3 (0.697 mmol) and (1:QꢀNBu4)
(0.697 mmol), and was recrystallized from dimethyl
sulfoxide as a dark brown crystalline solid; m.p. 191–
192°C. 1H NMR (300 MHz, acetone-d6): l 0.98 (t, 12H,
CH3), 1.41 (sext., 8H, CH2), 1.81 (quint., 8H, CH2),
3.43 (t, 8H, H2C–N). 13C NMR (75.4 MHz, DMSO-d6)
l 13.5 (CH3), 19.2 (CH2), 23.0 (CH2), 57.0 (CH2), 135.6
(CꢀC), 214.0 (CꢀS). IR (KBr) 1409 (CꢀC), 1029, 991
(CꢀS), 886 (C–S). UV–Vis (CH3CN): 227, 366, 300,
456 nm.
(
P1
Unit cell dimension
,
a (A)
7.54720(10)
14.4797(5)
17.6663(5)
72.3992(13)
89.3480(18)
82.3798(17)
1823.12(8)
2
1.865
6.362
994
red–brown
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
Dcalc (mg m−3
)
Absorption coefficient (mm−1
F(000)
)
3.1.4. Preparation of (5:QꢀAsPh4)
Crystal colour
This was prepared analogously to compound
(5:QꢀNEt4), from BiBr3 (0.697 mmol) and (1:QꢀAsPh4)
(0.697 mmol), and was recrystallized from DMSO to
give a dark red crystalline solid; m.p. 193–195°C. Anal.
Calc. for C54H40As2S10Bi: C, 36.58; H, 1.75. Found: C,
36.20; H, 2.03%.
Crystal size (mm)
q Range for data collection (°)
Index range
0.25×0.20×0.15
2.19–30.51
−105h510, −205k520,
−245l524
40012/10504 [Rint=0.0733]
30.51, 94.3
semi-empirical from
equivalents
0.855 and 0.742
Full-matrix least-squares on
F2
Reflections collected/unique
Completeness to 2q (%)
Absorption correction
1H NMR (DMSO-d6, 300MHz): l 7.7–7.9 (m, aryl-
H’s). 13C NMR (DMSO-d6, 75.5 MHz): l 121.6, 131.5,
134.9 and 135.9 (aryl-C’s), 133.7 (CꢀC), 213.8 (CꢀS). IR
(KBr): 1435 cm−1 (CꢀC), 1054, 1033 (CꢀS), 890 (C–S).
UV–Vis (CH3CN): 457, 295 nm.
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I\2q(I)]
R indices (all data)
10504/0/396
1.057
R1=0.0434, wR2=0.0959
R1=0.0632, wR2=0.1038
3.2. Crystallography
Largest difference peak and hole 2.423 and −2.291
(e A−3
)
Intensity data at 150 K were obtained with an Enraf
Nonius KappaCCD diffractometer. The programs
DENZO [20] and COLLECT [21] were used for data
collection, cell refinement and data reduction. SORTAV
was used to apply absorption correction by the multi-
scan technique [22]. The structure was solved by the
heavy atom method with SHELXS-86 [23] and refined
with SHELXL-97 [24]. All non-H atoms were refined
anisotropically and H atoms were placed in calculated
positions and refined with a riding model. The asym-
metric unit contained one half of a DMSO solvate
molecule: these molecules were highly disordered over
centrosymmetrically related pairs of sites (Table 4).
(0.500 g, 0.697 mmol) in acetone (20 ml). Reaction
occurred immediately as shown by the colour change.
A dark red–brown solid precipitated on addition of
propan-2-ol. Yield: 86%. The crude product was recrys-
tallized from acetone-propan-2-ol; m.p. 160–162°C.
Anal. Calc. for C14H20NS10Bi: C, 22.98; H, 2.73; N.
1.91. Found: C, 22.74; H, 3.17; N. 1.91%.
1H NMR (acetone-d6, 300 MHz): l 1.42 (tt, 12H,
CH3), 3.54 (q, 8H, CH2N). 13C NMR (DMSO-d6, 75.5
MHz): l 8.0 (CH3), 52.0 (CH2N), 135.1 (CꢀC), 213.5
(CꢀS). IR (KBr): 1434 cm−1 (CꢀC), 1054, 1019 (CꢀS),
881 (C–S). UV–Vis (CH3CN): 254, 291, 370, 453 nm.
3.1.2. Preparation of (5:QꢀC7H10N)
4. Supplementary material
This was prepared analogously to compound
(5:QꢀNEt4), from BiBr3 (0.697 mmol) and
(1:QꢀC7H10N) (0.697 mmol), and recrystallized from
acetone as a dark brown solid; m.p. 203°C.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 147211. Copies of this infor-
mation may be obtained from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44-
1233-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
1H NMR (acetone-d6, 300 MHz): l 2.63 (s, 3H, H,
C–CH3), 4.34 (s, 3H, N–CH3), 7.91 (d, 2H, H3), and
8.82 (d, 2H, H2). 13C NMR (DMSO-d6, 75.5 MHz): l
21.3 (CH3–C), 47.1 (CH3–N), 127.93, 144.5 and 158.2

N.M. Comerlato et al. / Polyhedron 20 (2001) 415–421
421
[9] Z.H. Chohan, R.A. Howie, J.L. Wardell, R. Wilkens, S.M.S.V.
Doidge-Harrison, Polyhedron 16 (1997) 2689.
Acknowledgements
[10] H. Wang, D. Zhu, N. Zhu, H. Fu, Wuli Huaxue Xuebao 35
(1986) 378.
[11] F. deAssis, Z.H. Chohan, R.A. Howie, A. Khan, J.N. Low,
G.M. Spencer, J.L. Wardell, S.M.S.V. Wardell, Polyhedron 18
(1999) 3533.
[12] T.L. Sheng, X.T. Wu, P. Lin, Q.M. Wang, W.J. Zhang, L. Chen,
Coord. Chem. 48 (1999) 113.
[13] J.L. Wardell, G.M. Spencer, J.H. Aupers, Polyhedron 15 (1996)
2701.
The authors would like to thank the CNPq (pro-
grams Balca˜o and PIBIC) and CAPES for financial
assistance. We also acknowledge the use of the Na-
tional Data Collection Service of then EPSRC at the
University of Southampton and the expert assistance of
the staff there.
[14] J.E. Huheey, E.A Keiter, R.L. Keiter, Inorganic Chemistry,
Principles of Structure and Reactivity, 4th edn., Harper Collins,
New York, 1993.
References
[15] S.M.S.V. Doidge-Harrison, J.T.S. Irvine, G.M. Spencer, J.L.
Wardell, P. Ganis, G. Valle, Inorg. Chem. 34 (1995) 4581.
[16] P. Ganis, D. Marton, G.M. Spencer, J.L. Wardell, S.M.S.V.
Wardell, Inorg. Chim Acta (2000) in press.
[1] P. Cassoux, L. Valade, H. Kobayashi, R.A. Clark, A.E. Under-
hill, Coord. Chem. Rev. 110 (1991) 115.
[2] P. Cassoux, Coord. Chem. Rev. 186 (1999) 213.
[3] L. Brossard, M. Ribault, M. Bousseau, L. Valade, P. Cassoux,
C. R. Acad Sci. (Paris) Ser. III B143 (1986) 378.
[4] M.R. Bryce, in: M.C. Petty, M.R. Bryce, D. Bloor (Eds.), An
Introduction to Molecular Electronics, Oxford University Press,
New York, 1995, pp. 168–179.
[17] N.M. Comerlato, W.T.A. Harrison, R.A. Howie, A.C. Silvino,
J.L. Wardell, S.M.S.V. Wardell, Inorg. Chem. Commun. 3
(2000) 572.
[18] T. Sheng, X. Wu, P. Lin, W. Zhang, Q. Wang, L. Chen,
Polyhedron 18 (1999) 1054.
[5] P. Cassoux, L. Valade, in: W.D. Bruce, D. O’Hare (Eds.),
Inorganic Materials, Wiley, New York, 1992, pp. 1–58.
[6] (a) A Kobayashi, H. Kim, Y. Sasaki, R. Kato, H. Koyabashi, S.
Moriyama, Y. Nishio, K. Kajita, W. Sasaki, Chem. Lett. (1987)
1819. (b) K. Kajita, Y. Nishio, S. Moriyama, R. Kato, H.
Koyabayshi, W. Sasaki, Solid State Commun. 65 (1988) 361.
[7] A. Kobayashi, H. Kobayashi, A. Miyamoto, R. Koto, R.A.
Clark, A.B. Underhill, Chem. Lett. (1991) 2163.
[19] G. Hunter, T.J.R. Weakley, J. Chem. Soc., Dalton Trans. (1983)
1067.
[20] Z. Otwinowski, W. Minor, in: C.W. Cater, R.M. Sweet (Eds.),
Methods in Enzymology: Macromolecular Crystallography, Part
A, vol. 276, Academic Press, New York, 1997, pp. 307–326.
[21] R. Hooft, COLLECT. Nonius BV, Delft, The Netherlands. 1998.
[22] (a) R.H. Blessing, Acta Crystallogr., Sect. A 51 (1995) 33. (b) J.
Appl. Crystallogr. 30 (1997) 421.
[8] W.T.A. Harrison, R.A. Howie, J.L. Wardell, S.M.S.V. Wardell,
N.M. Comerlato, L.A.S. Costa, A.C. Silvino, A.I. de Oliveira,
R.M. Silva, Polyhedron 19 (2000) 821.
[23] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 476.
[24] G.M. Sheldrick, SHELXL-97. Program for Crystal Structure
Refinement. University of Go¨ttingen, Germany, 1997.
.