Coordination complexes of the bismuth(III) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands

Article abstract of DOI:10.1039/b305711a

The chloro-aryl bismuth thiolate Bi(SC₆Cl₅)₃ has been prepared from the reaction between BiPh₃ and the thiol HSC₆ Cl₅ by analogy with the previously described synthesis of the fluoro-aryl species Bi(SC₆F₅)₃. The compound Bi(SC₆Cl₅)₃ is only sparingly soluble but can be isolated as a dmf adduct [Bi(SC₆Cl₅)₃ (dmf)₂] (dmf = N,N-dimethyl-formamide) which adopts a five-coordinate square-based pyramidal geometry in which the two dmf ligands lie in the basal plane with a mutually cis configuration. Treatment of either Bi(SC₆F₅)₃ or Bi(SC₆ Cl₅)₃ with pyridine or 2,2′-bipyridyl ligands affords the coordination complexes fac-[Bi(SC₆ F₅)₃(py)₃] (two crystalline polymorphs), fac-[Bi(SC₆Cl₅)₃(py)₃], fac-[Bi (SC₆F₅)₃(4-pic)₃] (4-pic = 4-picoline), [Bi(SC₆Cl₅)₃(4-pic)₂], [Bi(SC₆F₅)₃(bipy)] (bipy = 2,2′- bipyridyl), [Bi(SC₆Cl₅)₃(bipy)], [Bi₂(SC₆Cl₅)₆(2-pic)₃] (2-pic = 2-picoline) and [Bi(SC₆F₅)₃(4-pic)]. Five- and four-coordinate complexes adopt square-based pyramidal and equatorially vacant, trigonal bipyramidal (disphenoidal) geometries respectively, the former having the two ligands cis to each other in the basal plane. The compound [Bi₂(SC₆Cl₅)₆ (2-pic)₃] contains both five- and four-coordinate mononuclear units. A salt with the formula [4-picH][-(4-pic)₂H][Bi₃ (SC₆F₅) ₁₁] was also isolated in which the anion contains a central bismuth bonded to five thiolate ligands with a square-based pyramidal geometry. Two cis-basal thiolates act as bridging groups to two outer bismuth centres each of which is four-coordinate with the expected disphenoidal geometry in which the bridging thiolate is in an axial position. The structure of the dinuclear arylbismuth thiolate compound [Bi₂ Ph₂(SC₆F₅)₄(4-pic)₂] is also described. Intramolecular conformations and intermolecular associations in all structures are dominated by π-π-interactions.

Full text of DOI:10.1039/b305711a

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Coordination complexes of the bismuth(III) thiolates Bi(SC6F5)3
and Bi(SC6Cl5)3 with pyridine ligands
Kirsty M. Anderson, Christian J. Baylies, A. H. M. Monowar Jahan, Nicholas C. Norman,*
A. Guy Orpen and Jonathan Starbuck
The University of Bristol, School of Chemistry, Bristol, UK BS8 1TS
Received 21st May 2003, Accepted 25th June 2003
First published as an Advance Article on the web 14th July 2003
The chloro-aryl bismuth thiolate Bi(SC6Cl5)3 has been prepared from the reaction between BiPh3 and the thiol
HSC6Cl5 by analogy with the previously described synthesis of the fluoro-aryl species Bi(SC6F5)3. The compound
Bi(SC6Cl5)3 is only sparingly soluble but can be isolated as a dmf adduct [Bi(SC6Cl5)3(dmf )2] (dmf = N,N-dimethyl-
formamide) which adopts a five-coordinate square-based pyramidal geometry in which the two dmf ligands lie in
the basal plane with a mutually cis configuration. Treatment of either Bi(SC6F5)3 or Bi(SC6Cl5)3 with pyridine or
2,2Ј-bipyridyl ligands affords the coordination complexes fac-[Bi(SC6F5)3(py)3] (two crystalline polymorphs),
fac-[Bi(SC6Cl5)3(py)3], fac-[Bi(SC6F5)3(4-pic)3] (4-pic = 4-picoline), [Bi(SC6Cl5)3(4-pic)2], [Bi(SC6F5)3(bipy)] (bipy =
2,2Ј-bipyridyl), [Bi(SC6Cl5)3(bipy)], [Bi2(SC6Cl5)6(2-pic)3] (2-pic = 2-picoline) and [Bi(SC6F5)3(4-pic)]. Five- and four-
coordinate complexes adopt square-based pyramidal and equatorially vacant, trigonal bipyramidal (disphenoidal)
geometries respectively, the former having the two ligands cis to each other in the basal plane. The compound
[Bi2(SC6Cl5)6(2-pic)3] contains both five- and four-coordinate mononuclear units. A salt with the formula [4-picH][-
(4-pic)2H][Bi3(SC6F5)11] was also isolated in which the anion contains a central bismuth bonded to five thiolate
ligands with a square-based pyramidal geometry. Two cis-basal thiolates act as bridging groups to two outer
bismuth centres each of which is four-coordinate with the expected disphenoidal geometry in which the bridging
thiolate is in an axial position. The structure of the dinuclear arylbismuth thiolate compound [Bi2Ph2(SC6F5)4(4-pic)2]
is also described. Intramolecular conformations and intermolecular associations in all structures are dominated by
π–π-interactions.
Neutral thiolates of bismuth() are known from a number of
studies but relatively few compounds are well characterised and
structural data remain scarce. Compounds of the general form-
ula Bi(SR)3 are known for R = Ph,1 C6F5 (1),2,3 4-MeC6H4,3b 2,6-
Me2C6H3,3b 3,5-Me2C6H3,3b 2-CO2MeC6H4,1b 4-FC6H4,4 2,4,6-
But3C6H2,5 Et,6 benzyl,6,7 CH2CH2OH6 and But 8 although only
etries was observed for the species [BiX3(L)3] and [BiArX2(L)2]
(X = halide, Ar = aryl) respectively.†
Results
Compound 1 was prepared, with typical isolated yields of 70%,
from BiPh3 and three equivalents of the thiol HSC6F5 accord-
ing to eqn. (1)
13a and Bi(S-2,4,6-But3C6H2)3 have been characterised by
5
X-ray crystallography. Other examples of bismuth() thiolate
compounds include the ionic species [AsPh4][Bi(SC6F5)4]2a and
[Na2(thf )4][Bi(SC6F5)5]3a (thf = tetrahydrofuran), the latter
having been characterised crystallographically,3a and a range
of Lewis base adducts of 1 comprising [Bi(SC6F5)3(SPPh3)],
BiPh3 ϩ 3 HSC6F5
Bi(SC6F5)3 (1) ϩ 3PhH
(1)
as described in ref. 3b. The structure of orange crystalline 1 was
reported in ref. 3a, and comprises loosely bound centro-
symmetric dimers with a long Bi ؒ ؒ ؒ S contact trans to one of
the primary Bi–S bonds, but on a number of occasions during
the present study, both dark and light orange crystalline forms
of 1 were observed. Mass spectra and microanalytical data for
both apparent modifications were consistent with the formula
of 1, i.e. Bi(SC6F5)3, and the possibility that the two forms
might represent different polymorphs was discounted by unit
cell measurements performed on bulk powders and single
crystals of each; the unit cell reported for 1 in ref. 3a was found
in all cases.
[K(18-crown-6)][Bi(SC6F5)3(NCS)],
[Bi(SC6F5)3(hmpa)2] (hmpa
[Bi(SC6F5)3(OPPh3)2],
hexamethylphosphoramide),
=
[Bi(SC6F5)3(dmpu)2] (dmpu = N,N Ј-dimethylpropylene urea)
and [Bi(SC F ) {S᎐C(NHMe) } ] all of which were structurally
᎐
6
5
3
2 3
characterised.9 More recently, a range of dithiolate derivatives
has been prepared including the structurally characterised
compounds Bi2(SCH2CH2S)3 and Bi2(SCH2CH2SCH2CH2S)3
which exhibit both intra- and inter-molecular Bi ؒ ؒ ؒ S
interactions,10 as well as a range of tris-thiolate compounds
exhibiting intramolecular O- or N-coordination. Structurally
characterised examples of the latter types include Bi(SC6H4-2-
CO2Me)3, Bi(SCH2CH2NH2)3 and Bi(SCH2CO2Me)3.11 Recent
studies have also highlighted important applications of bismuth
thiolates, for example in the chemical vapour deposition of
Bi2S3 7 and in medicine.12
Herein we describe the preparation and structures of a range
of pyridine adducts of 1 and of Bi(SC6Cl5)3 (2). These studies
were prompted by our previous work both on the coordination
chemistry of 19 and on the coordination of pyridine ligands to
bismuth halides and arylbismuth halides.13 Thus, in the former
case, adducts of the form [Bi(SC6F5)3(L)2] and [Bi(SC6F5)3(L)3]
were found to have cis and fac ligand geometries respectively
whereas a preference for mer and trans pyridine ligand geom-
† Five- and six-coordinate compounds adopt square-based pyramidal
and octahedral geometries respectively as described in refs. 9 and 13
and refs. therein. In the former case the ligands lie in the basal plane.
D a l t o n T r a n s . , 2 0 0 3 , 3 2 7 0 – 3 2 7 7
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
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The perchloro-aryl derivative Bi(SC6Cl5)3 (2) was prepared in
an analogous fashion according to eqn. (2)
BiPh3 ϩ 3 HSC6Cl5
Bi(SC6Cl5)3 (2) ϩ 3PhH (2)
and was obtained as an orange powder in similar isolated yields
(91%). Compound 2, however, is much less soluble than 1 and
dissolves only in strongly coordinating solvents. Pyridine
adducts are described below but a useful solvent in which to
conduct reactions of 2 is dmf (N,N-dimethylformamide). From
a dmf solution of 2, crystals of the adduct [Bi(SC6Cl5)3(dmf )2]
(3) were obtained. A view of the molecular structure of 3 is
shown in Fig. 1 and reveals a five-coordinate square-based
pyramidal geometry in which the two dmf ligands lie in the
basal plane with a mutually cis configuration. Compound 3 is
thus similar to bis-ligand derivatives of 1 such as [Bi(SC6F5)3-
(OPPh3)2], [Bi(SC6F5)3(hmpa)2] and [Bi(SC6F5)3(dmpu)2].9 The
apical thiolate has the shortest Bi–S bond as expected from
previous studies.9 Intra- and inter-molecular solid-state
interactions for this and all other structures are described and
discussed below.
Fig. 2 A view of the molecular structure of 4a. Selected bond
distances (Å) and angles (Њ) include Bi(1)–S(1) 2.6244(13), Bi(1)–S(2)
2.6388(13), Bi(1)–S(3) 2.6398(14), Bi(1)–N(1) 2.837(4), Bi(1)–N(2)
2.778(4), Bi(1)–N(3) 2.753(4); S(1)–Bi(1)–N(1) 177.9(1), S(2)–Bi(1)–
N(2) 172.20(9), S(3)–Bi(1)–N(3) 171.47(10).
Fig. 3 A view of the molecular structure of 4b. Selected bond
distances (Å) and angles (Њ) include Bi(1)–S(1) 2.5916(9), Bi(1)–S(2)
2.6447(10), Bi(1)–S(3) 2.6424(8), Bi(1)–N(1) 3.055(3), Bi(1)–N(2)
2.710(3), Bi(1)–N(3) 2.748(3); S(1)–Bi(1)–N(1) 154.4(7), S(2)–Bi(1)–
N(2) 168.18(6), S(3)–Bi(1)–N(3) 172.17(7).
Fig. 1 A view of the molecular structure of 3. Selected bond distances
(Å) include Bi(1)–S(1) 2.661(2), Bi(1)–S(2) 2.634(2), Bi(1)–S(3)
2.581(2), Bi(1)–O(1) 2.577(5), Bi(1)–O(2) 2.664(6).
Treatment of 1 with an excess of pyridine (py) afforded a
yellow crystalline tris-pyridine adduct [Bi(SC6F5)3(py)3] (4)
which was obtained as two polymorphs. One polymorph (4a)
was obtained from a reaction between 1 and pyridine in CH2Cl2
in the presence of BiPh3 with the aim of preparing a pyridine
adduct of an arylbismuth thiolate (see later). The second
polymorph (4b) was prepared similarly but in the absence of
BiPh3. A small quantity of orange crystals was also obtained in
the latter reaction although these could not be obtained in a
pure form and have not been identified (see later). The molec-
ular structure of 4 in 4a is shown in Fig. 2 and reveals an
octahedral geometry with a fac-configuration [cf. fac-[Bi(S-
(see caption to Fig. 2). The structure of 4b is shown in Fig. 3
and reveals a broadly similar fac-octahedral structure also with
one pyridine more loosely bound than the other two, the most
notable difference being that the S–Bi–N angle involving the
more loosely bound pyridine is distinctly non-linear [154.4(7)Њ].
Other bond distances and angles are given in the caption to Fig.
3 and differences in the conformations of the pyridine ligands
and thiolate groups are discussed below.
A tris-pyridine adduct fac-[Bi(SC6Cl5)3(py)3] (5) was isolated
from the reaction between 2 and an excess of pyridine, the
structure of which is shown in Fig. 4. The structure is similar to
that of 4b in having one pyridine much more loosely bound
[3.982(9) vs. 2.795(8) and 2.728(9) Å] with a non-linear S–Bi–N
arrangement [144.8(2) vs. 165.8(2) and 166.28(19)Њ]. In con-
trast, the reaction between 1 and 4-picoline (4-pic) afforded the
adduct fac-[Bi(SC6F5)3(4-pic)3] (6) (Fig. 5) in which the three
picoline ligands are all bonded to the bismuth centre with
similar Bi–N distances and near linear S–Bi–N angles.
C F ) {S᎐C(NHMe) } ]9]. One of the pyridine ligands is sig-
᎐
6
5
3
2 3
nificantly further from the bismuth centre than the other two
[Bi(1)–N(1) 2.837(4) vs. Bi(1)–N(2) 2.778(4) and Bi(1)–N(3)
2.753(4) Å] although all trans N–Bi–S angles are close to 180Њ
[S(1)–Bi(1)–N(1) 177.9(1), S(2)–Bi(1)–N(2) 172.20(9), S(3)–
Bi(1)–N(3) 171.47(10)Њ]. The longer Bi–N(1) distance is
reflected in the trans thiolate having the shorter Bi–S distance
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Fig. 4 A view of the molecular structure of 5. Selected bond distances
(Å) and angles (Њ) include Bi(1)–S(1) 2.577(3), Bi(1)–S(2) 2.639(3),
Bi(1)–S(3) 2.659(3), Bi(1)–N(1) 3.982(9), Bi(1)–N(2) 2.795(8), Bi(1)–
N(3) 2.728(9); S(1)–Bi(1)–N(1) 144.8(2), S(2)–Bi(1)–N(2) 165.8(2),
S(3)–Bi(1)–N(3) 166.28(19).
Fig. 6 A view of the molecular structure of 7. Selected bond distances
(Å) and angles (Њ) include Bi(1)–S(1) 2.619(2), Bi(1)–S(2) 2.654(3),
Bi(1)–S(3) 2.580(3), Bi(1)–N(1) 2.827(8), Bi(1)–N(2) 2.660(8); S(1)–
Bi(1)–N(1) 167.9(2), S(2)–Bi(1)–N(2) 162.03(18).
Fig. 5 A view of the molecular structure of 6. Selected bond distances
(Å) and angles (Њ) include Bi(1)–S(1) 2.639(1), Bi(1)–S(2) 2.6395(9),
Bi(1)–S(3) 2.6599(9), Bi(1)–N(1) 2.757(3), Bi(1)–N(2) 2.788(3), Bi(1)–
N(3) 2.773(3); S(1)–Bi(1)–N(1) 176.01(7), S(2)–Bi(1)–N(2) 168.96(6),
S(3)–Bi(1)–N(3) 174.00(6).
Fig. 7 A view of the molecular structure of 8. Selected bond distances
(Å) include Bi(1)–S(1) 2.670(2), Bi(1)–S(2) 2.678(2), Bi(1)–S(3)
2.559(2), Bi(1)–N(1) 2.607(6), Bi(1)–N(2) 2.572(7).
isomorphous, the molecular structures are similar (Figs. 7 and 8
respectively) having the bipy ligand in the basal plane of
the square-based pyramidal geometry as expected for this
stoichiometry.
Crystals of a bis-ligand adduct of 2, namely [Bi(SC6Cl5)3-
(4-pic)2] (7) were obtained from a solution of 2 in dmf and
4-picoline. The structure is shown in Fig. 6 and reveals a square-
based pyramidal geometry with cis-basal ligands leading
to a structure analogous to 3 and bis-ligand adducts of 1,9
although the Bi–N distances are markedly different [2.660(8) vs.
2.827(8) Å].
Crystals of the compound [Bi2(SC6Cl5)6(2-pic)3] (10) (2-pic =
2-picoline) were isolated from the reaction between 2 and
2-picoline. The structure is shown in Fig. 9 and reveals two
distinct molecular units present in the asymmetric unit. One of
these comprises the species [Bi(SC6Cl5)3(2-pic)] in which a single
2-pic ligand is bonded trans to one thiolate group [Bi(2)–N(4)
2.789(11) Å] giving an overall disphenoidal coordination
around the bismuth. In the other species, two 2-picoline ligands
are weakly associated with the bismuth centre [Bi(1)–N(1),
Both 1 and 2 form adducts with 2,2Ј-bipyridyl (bipy) namely
[Bi(SC6F5)3(bipy)] (8) and [Bi(SC6Cl5)3(bipy)] (9). Although not
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Fig. 10 A view of the molecular structure of 11. Selected bond
Fig. 8 A view of the molecular structure of 9. Selected bond distances
(Å) include Bi(1)–S(1) 2.618(4), Bi(1)–S(2) 2.698(4), Bi(1)–S(3)
2.572(4), Bi(1)–N(1) 2.730(8), Bi(1)–N(2) 2.697(8).
distances (Å) and angles (Њ) include Bi(1)–S(1) 2.627(3), Bi(1)–S(2)
2.553(4), Bi(1)–S(3) 2.562(4), Bi(1)–N(1) 2.706(8); S(1)–Bi(1)–N(1)
165.2(2).
crystalline 4 although these were not formed in sufficient
quantity or with satisfactory crystallinity to be identified. In
the formation of yellow crystalline 11, an orange crystalline
product was also formed which in this case was identified by
X-ray crystallography. The product, 12, is a salt with the form-
ula [4-picH][(4-pic)2H][Bi3(SC6F5)11]. A view of the trinuclear
anion [Bi3(SC6F5)11]2Ϫ is shown in Fig. 11. A central bismuth is
bonded to five thiolate ligands with a square-based pyramidal
geometry similar to that found in the species [Na2(thf )4]-
[Bi(SC6F5)5].3a Two cis-basal thiolates act as bridging groups to
two outer bismuth centres each of which is four-coordinate
with the expected equatorially vacant, trigonal bipyramidal
geometry in which the bridging thiolate is in an axial position.
The Bi–S distances show the expected trends; terminal are
shortest and bridging are longest. The cations comprise an
isolated protonated 4-picoline, [4-picH]ϩ, and a hydrogen
bonded picoline–picolinium ion [(4-pic)2H]ϩ. It is likely that
12 and the orange material formed in preparations of 4 are due
to hydrolysis from adventitious water since more strictly
anhydrous conditions afford less or no orange material.
Fig. 9 A view of the molecular structure of 10. Selected bond
distances (Å) and angles (Њ) include Bi(1)–S(1) 2.625(3), Bi(1)–S(2)
2.592(3), Bi(1)–S(3) 2.621(4), Bi(2)–S(4) 2.618(3), Bi(2)–S(5) 2.570(3),
Bi(2)–S(6) 2.579(3), Bi(1)–N(1) 2.932(11), Bi(1)–N(3) 2.828(11), Bi(2)–
N(4) 2.789(11); S(1)–Bi(1)–N(1) 150.3(3), S(3)–Bi(1)–N(3) 147.1(3),
S(4)–Bi(2)–N(4) 159.0(3).
2.932(11); Bi(1)–N(3) 2.828(11) Å] each approximately trans to
a thiolate.
A mono-ligand complex [Bi(SC6F5)3(4-pic)] (11), similar to
one of the species in 10, was isolated from a reaction between 1
and less than three equivalents of 4-picoline (with an excess of
4-pic, compound 6 was obtained, see above). The structure is
shown in Fig. 10 which reveals a disphenoidal geometry with
one 4-picoline ligand bound trans to one thiolate [Bi(1)–N(1)
2.706(8) Å]; this thiolate has the longest Bi–S bond [Bi(1)–S(1)
2.627(3) Å]. There are no short intermolecular contacts to the
bismuth centre.
Fig. 11 A view of the molecular structure of the anion [Bi3(SC6F5)11]2Ϫ
in 12. Selected bond distances (Å) include Bi(1)–S(1) 2.576(3), Bi(1)–
S(2) 2.640(4), Bi(1)–S(3) 2.575(3), Bi(1)–S(4) 2.973(3), Bi(2)–S(4)
2.896(3), Bi(2)–S(5) 2.733(3), Bi(2)–S(6) 2.542(3), Bi(2)–S(7) 2.728(3),
Bi(2)–S(8) 2.980(3), Bi(3)–S(8) 2.996(3), Bi(3)–S(9) 2.578(3), Bi(3)–
S(10) 2.642(3), Bi(3)–S(11) 2.553(4).
As a final point relating to synthesis, we were also interested
in making pyridine adducts of arylbismuth thiolates for
comparison with the pyridine adducts of arylbismuth halides
described in ref. 13 in which trans pyridine configurations were
observed (the only previous report of an arylbismuth thiolate
As mentioned above for 4, in some cases small quantities of
orange crystals were sometimes formed in addition to yellow
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of which we are aware describes the compound BiPh2(SPh)14).
However, we were not able to isolate arylbismuth thiolates of
the form BiAr(SC6F5)2 or BiAr2(SC6F5) from reactions between
1 and BiPh3. Moreover, reactions between 1 and BiPh3 in the
presence of pyridine ligands afforded ligand adducts of 1 as
was the case in the synthesis of 4a. On one occasion, however,
a reaction between 1 and 4-picoline afforded a small quantity
of crystals identified by X-ray crystallography as [Bi2Ph2-
(SC6F5)4(4-pic)2] (13) indicating that some aryl containing
compound was present as an impurity in that particular sample
of 1. Although we have not been able to reproduce the prepar-
ation of 13, the structure is included here. Compound 13 (Fig.
12) is dimeric with an edge-shared, bis-square-based pyramidal
structure in which the phenyl groups are in apical sites and syn
with respect to the two basal planes. Two thiolates bridge
asymmetrically, the longer Bi–S bonds trans to terminal thiol-
ates (one on each bismuth centre) and the shorter bonds trans
to the two 4-picoline ligands.
It is also informative to look at the inter-ligand interactions
both in terms of intramolecular conformations and inter-
molecular associations. In both cases, these interactions are
dominated by π-stacking between aryl and/or pyridine rings.
If we look first at intramolecular interactions, then for the
tris-ligand complexes 4–6, it is clear that for complexes 4a and 6
(Figs. 2 and 5) the aryl ring of each thiolate lies parallel to a cis
pyridine ring as shown schematically in A. This results in a
propeller arrangement of both thiolate and pyridine groups
and approximate molecular C3 symmetry. In contrast, only two
such parallel intramolecular thiolate–pyridine interactions are
present in 4b and 5 (Figs. 3 and 4). For these two species, one
arylthiolate is rotated away as shown in B although the three
pyrdine ligands retain the propeller orientation seen in A. Inter-
ring separations between thiolate (C6F5) and pyridine rings
(ring centroid to ring centroid) range from 3.493 to 3.775 Å for
4a and from 3.596 to 3.641 Å in 6.
The bis-ligand complexes 3, 8 and 9 (Figs. 1, 7 and 8) all have
very similar conformations. Thus, the two thiolates trans to the
two ligands have parallel aryl rings whilst the third, apical
thiolate ring lies over the dmf or bipy ligands. This is shown
schematically for 8/9 in C. Thiolate ring to thiolate ring
separations here range from 3.699 Å in 9 to 3.938 Å in 8
although we note that the distance between the C6F5 groups in
8 is significantly greater than that between the corresponding
C6Cl5 groups in 9. In complex 7 the arrangement is different in
that the thiolates adopt the propeller conformation seen in 4a
and 6 with each of the two 4-picoline ligands parallel to one
thiolate aryl ring as shown in D. Arrangement D can be derived
from A simply by removing one pyridine ligand. Intramolecular
π–π-interactions between adjacent thiolate aryl rings and
between pyridine and thiolate aryl rings are also present in the
structures of 10 and 12 as is evident from Figs. 9 and 11. In
the former case (Fig. 9) pyridine to thiolate distances range
from 3.492 to 3.671 Å, an intramolecular thiolate to thiolate
separation is present (between C6Cl5 groups) at 3.793 Å and an
additonal intermolecular π–π-interaction is evident between the
thiolates S(1) and S(5) [3.946 Å].
Fig. 12 A view of the molecular structure of 13. Selected bond
distances (Å) and angles (Њ) include Bi(1)–S(1) 2.827(3), Bi(1)–S(2)
2.627(3), Bi(1)–S(4) 3.148(3), Bi(2)–S(1) 3.139(3), Bi(2)–S(3) 2.627(3),
Bi(2)–S(4) 2.817(3), Bi(1)–N(1) 2.568(10), Bi(2)–N(2) 2.582(9), Bi(1)–
C(1) 2.238(10), Bi(2)–C(25) 2.240(11); S(2)–Bi(1)–S(4) 171.6(3), S(1)–
Bi(2)–S(3) 170.7(3).
Discussion
Looking first at the structures described above which contain
two or three pyridine ligands bonded to a bismuth centre, it is
evident that in no cases do pyridine ligands occupy trans sites.
Thus octahedral complexes have fac configurations and in five-
coordinate structures the pyridine ligands are cis rather than
trans to each other in the square-basal plane. This observation
is in line with the previously characterised complexes of 19
although in contrast to the situation found for pyridine com-
plexes of arylbismuth halides where trans pyridines are the
norm.13 There is little to add to the discussion on this matter
given in ref. 13 except to reiterate that general predictions of the
preferences for fac vs. mer or cis vs. trans configurations cannot
yet be made with any confidence.
Intermolecular associations involving π–π-interactions
between C6F5 or C6Cl5 rings is also a dominant feature in all of
the structures reported here and two representative examples
D a l t o n T r a n s . , 2 0 0 3 , 3 2 7 0 – 3 2 7 7
3274

View Article Online
Preparations
Bi(SC6Cl5)3 (2). HSC6Cl5 (1.92 g, 6.800 mmol) was added to a
solution of BiPh3 (1.00 g, 2.270 mmol) in toluene (40 cm3) and
the resulting reaction mixture was then refluxed for 96 h during
which time it turned from colourless to orange. After this time,
the solvent was removed by vacuum at room temperature and
the residue was washed with hexane and dried by vacuum
affording 2 as an orange powder (2.66 g, 91%). C18BiCl15S3
requires C, 20.55. Found C, 22.10%.
[Bi(SC6Cl5)3(dmf)2] (3). Compound 2 (0.105 g, 0.100 mmol)
was dissolved in dmf (4 cm3) affording an orange solution. Slow
solvent evaporation over a period of days afforded yellow
block-like crystals of 3 (0.084 g, 80%). C24H14BiCl15O2N2S3
requires C, 24.05; H, 1.20; N, 2.35; S, 8.00. Found C, 24.05; H,
0.60; N, 2.50; S, 6.24%.
[Bi(SC6F5)3(py)3] (4a). Compound 1 (0.190 g, 0.240 mmol)
and BiPh3 (0.064 g, 0.14 mmol) were dissolved in CH2Cl2 (6
cm3) and pyridine (0.30 cm3) added resulting in a darkening of
the orange colour. Hexane (5 cm3) was added as an overlayer
and solvent diffusion over a period of days at Ϫ30 ЊC afforded
yellow crystals of 4a (0.124 g, 65%). C33H15BiF15N3S3 requires
C, 38.00; H, 1.50; N, 4.05. Found C, 37.30; H, 1.15; N, 3.60%.
Fig. 13 A view of the packing of molecules of 4a in the crystal.
[Bi(SC6F5)3(py)3] (4b). Compound 1 (0.130 g, 0.161 mmol)
was dissolved in CH2Cl2 (3 cm3) and pyridine (0.20 cm3) added
resulting in a darkening of the orange colour. Hexane (4 cm3)
was added as an overlayer and solvent diffusion over a period
of days at Ϫ30 ЊC afforded yellow crystals of 4b (0.08 g, 25%).
C33H15BiF15N3S3 requires C, 38.00; H, 1.50; N, 4.05. Found C,
38.25; H, 1.20; N, 3.40%. A small quantity of orange crystals
were also obtained although these could not be isolated in a
pure form and have not been identified.
[Bi(SC6Cl5)3(py)3] (5). Compound 2 (0.028 g, 0.027 mmol)
was dissolved in dmf (2 cm3) to which pyridine (0.02 cm3) was
then added after which Et2O (4 cm3) was added as an overlayer.
Solvent diffusion over a period of days at room temperature
afforded orange crystals of 5 (0.017 g, 50%). C33H15BiCl15N3S3
requires C, 30.70; H, 1.20; N, 3.25. Found C, 30.45; H, 1.00; N,
3.05%.
[Bi(SC6F5)3(4-pic)3] (6). Compound 1 (0.407 g, 0.500 mmol)
was dissolved in CH2Cl2 (3 cm3) and 4-picoline (0.141 cm3,
1.5 mmol) added resulting in a darkening of the orange colour.
Hexane (4 cm3) was added as an overlayer and solvent diffusion
over a period of days at Ϫ30 ЊC afforded yellow crystals of
6 (0.091 g, 47%). C36H21BiF15N3S3 requires C, 39.85; H, 1.95; N,
3.85; S, 8.85. Found C, 39.50; H, 1.70; N, 3.75; S, 8.60%.
Fig. 14 A view of the packing of molecules of 11 in the crystal.
are shown in Figs. 13 and 14 which illustrate the molecular
packing in the crystals of 4a and 11. Intermolecular thiolate to
thiolate ring separations are 3.878 and 4.567 Å respectively.
π-Stacking of the type seen here has been observed in many
situations and we note the recent work of Marder described in
refs. 15 and refs. therein.
[Bi(SC6Cl5)3(4-pic)2] (7). Compound 2 (0.052 g, 0.050 mmol)
was dissolved in dmf (2 cm3) to which 4-picoline (0.01 cm3) was
added after which Et2O (5 cm3) was added as an overlayer.
Solvent diffusion over a period of days at Ϫ30 ЊC afforded a
mixture of yellow 7 (0.05 g, 75%) and a small crop of orange
crystals. C30H14BiCl15N2S3 requires C, 29.05; H, 1.15; N, 2.25; S,
7.75; Cl, 42.90. Found C, 30.40; H, 0.60; N, 2.35; S, 8.00; Cl,
42.80%.
Experimental
General considerations
All reactions were carried out under an atmosphere of dry
dinitrogen or argon using standard Schlenk or dry-box
techniques and oven-dried glassware. Dry solvents were
obtained from an Anhydrous Engineering Solvent System or
were dried over molecular sieves, and were degassed prior
to use. Compound 1 was prepared by the literature method.3
BiPh3, pyridine and substituted pyridines were procured
commercially and were dried over molecular sieves. 2,2Ј-
Bipyridyl was dried prior to use by the Dean–Stark method.
Yields are isolated yields of crystalline material.
[Bi(SC6F5)3(bipy)] (8). Compound 1 (0.180 g, 0.223 mmol)
and 2,2Ј-bipyridyl (0.140 g, 0.890 mmol) were dissolved in thf
(3 cm3) and hexane (3 cm3) was added as an overlayer. Solvent
diffusion over a period of days at Ϫ30 ЊC afforded orange crys-
tals of 8 (0.044 g, 14%). C28H8BiF15N2S3 requires C, 34.95; H,
0.85; N, 2.90. Found C, 34.95; H, 0.70; N, 2.85%.
[Bi(SC6Cl5)3(bipy)] (9). Compound 2 (0.170 g, 0.160 mmol)
and 2,2Ј-bipyridyl (0.025 g, 0.160 mmol) were dissolved in dmf
D a l t o n T r a n s . , 2 0 0 3 , 3 2 7 0 – 3 2 7 7
3275

D
Table 1 Crystallographic data for compounds 3–13
[(4-picH)-
{(4-pic)2H}]
[Bi3(SC6F5)11] [Bi2Ph2(SC6F5)4-
(12)
[Bi(SC6Cl5)3- [Bi(SC6F5)3-
[Bi(SC6F5)3-
(py)3] (4b)
[Bi(SC6Cl5)3- [Bi(SC6F5)3-
(py)3] (5) (4-pic)3] (6)
[Bi(SC6F5)3-
(4-pic)2] (7)
[Bi(SC6F5)3-
(bipy)] (8)
[Bi(SC6Cl5)3- [Bi2(SC6Cl5)6-
(bipy)] (9) (2-pic)3] (10)
[Bi(SC6F5)3-
(4-pic)] (11)
(dmf )2] (3)
(py)3] (4a)
(4-pic)2] (13)
Formula
C24H14BiCl15- C66H30Bi2F30- C33H15BiF15- C33H15BiCl5- C36H21BiF15- C30H14BiCl15- C28H8BiF15-
C28H8BiCl15- C54H21Bi2Cl30- C24H7BiF15-
C84H23Bi3F55- C53H34Bi2F20-
N2O2S3
N6S6
N3S3
N3S3
N3S3
N2S3
N2S3
N2S3
N3S6
NS3
N3S11
N2S4
M
1199.28
Monoclinic
P21/n
2087.28
Monoclinic
P21/n
1043.64
Monoclinic
P21/c
1290.39
Monoclinic
P21/c
1085.72
Monoclinic
P21/n
1239.34
Monoclinic
P21/c
962.52
Monoclinic
P21
1209.27
Monoclonic
P21/n
1192.78
Triclinic
P1
899.47
Orthorhombic
P212121
3097.90
Monoclinic
P21/n
16.25.06
Triclinic
P1
Crystal system
Space group
¯
¯
a/Å
b/Å
c/Å
α/Њ
9.5990(13)
14.627(2)
26.667(4)
8.7632(8)
13.6101(16)
30.018(5)
10.0822(6)
20.558(2)
17.130(2)
17.820(3)
14.940(3)
17.057(3)
9.3018(12)
17.925(2)
23.774(3)
8.7882(7)
10.3833(8)
44.413(4)
9.6388(15)
12.2386(15)
13.241(2)
9.437(3)
14.708(4)
26.464(7)
8.699(3)
20.999(7)
21.750(7)
73.156(6)
79.295(6)
83.486(6)
3729(2)
4
2.125
5.998
32476
13093
(0.1006)
0.0524,
0.0847
(0.1247,
0.1052)
5.4276(5)
19.4615(17)
25.877(2)
15.128(8)
28.483(15)
22.941(9)
13.7168(18)
13.9845(19)
16.666(2)
69.780(2)
81.689(2)
65.438(2)
2728.4(6)
2
1.978
6.702
8065
8065
(0.0000)
0.0456,
0.0891
(0.0848,
0.1003)
β/Њ
97.1799(3)
95.040(15)
97.476(10)
110.423
98.982(2)
94.538(2)
111.083(13)
97.530(6)
99.93(4)
γ/Њ
U/Å3
3715.0(9)
4
2.144
6.025
23718
8509
(0.0844)
0.0466,
0.0889
(0.1051,
0.1044)
3566.3(8)
4
1.994
5.228
22813
8195
(0.0646)
0.0374,
0.0544
(0.0853,
0.0627)
3520.3(6)
4
1.969
5.297
22387
8045
(0.0352)
0.0225,
0.0508
(0.0393,
0.0527)
4255.8(15)
4
2.014
5.265
35722
7495
(0.1845)
0.0536,
0.0848
(0.1443,
0.1098)
3915.3(8)
4
1.842
4.766
25092
8904
(0.0388)
0.0280,
0.0476
(0.0498,
0.0518)
4040.0(5)
4
2.038
5.540
40850
9280
(0.1237)
0.0733,
0.1339
(0.1237,
0.1462)
1457.4(4)
2
2.193
6.386
9460
3641.7(17)
4
2.206
6.143
31075
6413
(0.1425)
0.0654,
0.1529
(0.1276,
0.1820)
2733.4(4)
4
2.186
6.800
14692
4834
(0.0802)
0.0406,
0.0640
(0.0742,
0.0732)
9737(8)
4
2.113
Z
Dc/g cmϪ3
µ(Mo-Kα)/mmϪ1
Data collected
Unique data
5.798
51982
17128
(0.1158)
0.0560,
0.0875
(0.1311,
0.1076)
5281
(Rint
Final R1, wR2
[I>2σ(I )]
)
(0.0434)
0.0354,
0.0577
(0.0540,
0.0604)
(all data)

View Article Online
(5 cm3) and Et2O (5 cm3) was added as an overlayer. Solvent
diffusion over a period of days at room temperature afforded
orange crystals of 9 (0.091 g, 47%). C28H8BiCl15N2S3 requires
C, 27.81; H, 0.65; N, 2.30; S, 7.95; Cl, 43.95. Found C, 27.35; H,
0.50; N, 2.50; S, 8.60; Cl, 39.40%.
References
1 (a) M. E. Peach, J. Inorg. Nucl. Chem., 1979, 41, 1390 and refs.
therein; (b) H. Gilman and H. L. Yale, J. Am. Chem. Soc., 1951, 73,
2880.
2 (a) M. Muller, R. J. H. Clark and R. S. Nyholm, Transition Met.
Chem., 1978, 3, 369; (b) M. E. Peach, Can. J. Chem., 1968, 46,
2699.
3 (a) L. J. Farrugia, F. J. Lawlor and N. C. Norman, Polyhedron, 1995,
14, 311; (b) W. Clegg, M. R. J. Elsegood, L. J. Farrugia, F. J. Lawlor,
N. C. Norman and A. J. Scott, J. Chem. Soc., Dalton Trans., 1995,
2129.
4 S. C. Hergett and M. E. Peach, J. Fluorine Chem., 1988, 38, 367.
5 D. A. Atwood, A. H. Cowley, R. D. Hernandez, R. A. Jones,
L. L. Rand, S. G. Bott and J. L. Atwwod, Inorg. Chem., 1993, 32,
2972.
[Bi2(SC6Cl5)6(2-pic)3] (10). Compound 2 (0.22 g, 0.2 mmol)
was dissolved in dmf (2 cm3) to which 2-picoline (0.02 cm3) was
added after which Et2O (5 cm3) was added as an overlayer.
Solvent diffusion over a period of days at room temperature
afforded orange crystals of 10 (0.081 g, 34%). C54H21Bi2-
Cl30N3S6 requires C, 27.20; H, 0.90; N, 1.75; S, 8.05; Cl, 44.60.
Found C, 26.20; H, 0.60; N, 1.55; S, 8.50; Cl, 44.20%.
6 M. Wieber and U. Baudis, Z. Anorg. Allg. Chem., 1976, 423, 47.
7 P. Boudjouk, M. P. Remington, D. G. Grier, B. R. Jarabek and
G. J. McCarthy, Inorg. Chem., 1998, 37, 3538.
8 A. F. Jansen, O. C. Vaidya and C. J. Willis, J. Inorg. Nucl. Chem.,
1981, 43, 1469.
9 L. J. Farrugia, F. J. Lawlor and N. C. Norman, J. Chem. Soc., Dalton
Trans., 1995, 1163.
10 L. Agocs, N. Burford, T. S. Cameron, J. M. Curtis, J. F. Richardson,
K. N. Robertson and G. B. Yhard, J. Am. Chem. Soc., 1996, 118,
3225; G. G. Briand and N. Burford, Adv. Inorg. Chem., 2000, 50, 285.
11 N. Burford, M. D. Eelman and T. S. Cameron, Chem. Comm., 2002,
1403; G. G. Briand, N. Burford, T. S. Cameron and W. Kwiatkowski,
J. Am. Chem. Soc., 1998, 120, 11374; G. G. Briand, N. Burford and
T. S. Cameron, Chem. Comm., 2000, 13; G. G. Briand, N. Burford,
M. D. Eelman, T. S. Cameron and K. N. Robertson, Inorg. Chem.,
2003, 42, 3136.
[Bi(SC6F5)6(4-pic)] (11). Compound 1 (0.150 g, 0.186 mmol)
and 4-picoline (0.2 cm3) were dissolved in CH2Cl2 (3 cm3) and
hexane (3 cm3) was added as an overlayer. Solvent diffusion
over a period of days at Ϫ30 ЊC afforded yellow crystals of 11
(0.05 g, 15%) and a small crop of orange crystals of 12. C24H7-
BiF15NS3 (11) requires C, 32.05; H, 0.80; N, 1.55; S, 10.70.
Found C, 32.10; H, 0.50; N, 1.25; S, 11.50%.
X-Ray crystallography
All crystals were mounted under argon on glass fibres using
paraffin oil. Data were collected on a Bruker AXS (formally
Siemens) SMART16,17 area detector diffractometer using
graphite monochromated Mo-Kα radiation, at Ϫ100 ЊC. Inten-
sities were integrated from several series of exposures covering
0.3Њ in ω.
12 G. G. Briand and N. Burford, Chem. Rev., 1999, 99, 2601.
13 S. C. James, N. C. Norman and A. G. Orpen, J. Chem. Soc., Dalton
Trans., 1999, 2837.
Structures were solved and refined by standard methods
using SHELXTL software.18 In each case hydrogen atoms were
constrained to idealized geometries and assigned isotropic
displacement parameters 1.2 times the Uiso of the attached
carbon.
14 F. Calderazzo, A. Morvillo, G. Pelizzi, R. Poli and F. Ungari, Inorg.
Chem., 1988, 27, 3730.
15 J. C. Collings, K. P. Roscoe, R. Ll. Thomas, A. S. Batsanov,
L. M. Stimson, J. A. K. Howard and T. B. Marder, New J. Chem.,
2001, 25, 1410; J. C. Collings, K. P. Roscoe, E. G. Robins,
A. S. Batsanov, L. M. Stimson, J. A. K. Howard, S. J. Clark and
T. B. Marder, New J. Chem., 2002, 26, 1740.
16 SMART diffractometer control software, Bruker Analytical X-ray
Instruments Inc., Madison, WI, 1998.
17 SAINT integration software, Siemens Analytical X-ray Instruments
Inc., Madison, WI, 1994.
18 SHELXTL program system version 5.1, Bruker Analytical X-ray
Instruments Inc., Madison, WI, 1998.
19 G. M. Sheldrick, SADABS: A program for absorption correction
with the Siemens SMART system, University of Göttingen,
Germany, 1996.
Absorption corrections were applied using SADABS19 and
extinction coefficients were refined where appropriate. Non-
hydrogen atoms were assigned anisotropic parameters and
refined without positional constraints for all structures.
Crystallographic data for all structures reported herein are
presented in Table 1.
CCDC reference numbers 211633–211644.
See http://www.rsc.org/suppdata/dt/b3/b305711a/ for crystal-
lographic data in CIF or other electronic format.
D a l t o n T r a n s . , 2 0 0 3 , 3 2 7 0 – 3 2 7 7
3277