The preparation and structural characterisation of thiolato anions of bismuth(III)

Article abstract of DOI:10.1016/j.ica.2004.03.025

The preparation and structures of the bismuth thiolato anions [Bi ₂(SC₆F₅)₆(μ-SC₆F ₅)]^- and [Bi₂(SC₆F₅) ₆(μ-SC₆F₅

Full text of DOI:10.1016/j.ica.2004.03.025

Inorganica Chimica Acta 358 (2005) 1358–1364
www.elsevier.com/locate/ica
The preparation and structural characterisation of
thiolato anions of bismuth(III) q
*
Jonathan P.H. Charmant, A.H.M. Monowar Jahan, Nicholas C. Norman , A. Guy Orpen
School of Chemistry, The University of Bristol, Bristol BS8 1TS, UK
Received 1 March 2004; accepted 13 March 2004
Available online 11 September 2004
Dedicated to F.G.A. Stone in recognition of his contributions to inorganic chemistry
Abstract
The preparation and structures of the bismuth thiolato anions [Bi2(SC6F5)6(l-SC6F5)]ꢀ and [Bi2(SC6F5)6(l-SC6F5)2]2ꢀ and
the halothiolato anions [Bi2(SC6F5)6(l-Br)]ꢀ, [Bi2(SC6F5)6(l-Cl)2]2ꢀ and [Bi3(SC6F5)9(l-Br)2]2ꢀ are described. All compounds
have been isolated from reactions between Bi(SC6F5)3 and ammonium or phosphonium halides. The basic structural units in the
dinuclear species are of two types namely [Bi2(SR)6(l-X)]ꢀ and [Bi2(SR)6(l-X)2]2ꢀ, where X ¼ thiolate or halide. In the former
case the single bridging groups occupy an axial site within the disphenoidal (equatorially vacant, trigonal bipyramidal) geometry
around the bismuth centres whereas in the latter the two bridging groups occupy cis basal sites in square based pyramidal
bismuth environments. The trinuclear anion [Bi3(SC6F5)9(l-Br)2]2ꢀ has features in common with the basic [Bi2(SC6F5)6(l-Br)]ꢀ
unit.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Bismuth(III); Thiolato anions; Halothiolato anions; X-ray crystallography
1. Introduction
nuclear di-anion which also contains bridging thiolates
[5]. As part of a more systematic study of the reactivity
of the Lewis acidic thiolate Bi(SC6F5)3 towards anionic
donor ligands, we have examined its reactions with
sources of halide ion and describe herein the synthesis
and structural characterisation of both homoleptic
thiolato anions of bismuth and species which contain
halide ions.
Neutral thiolates of bismuth(III), Bi(SR)3, are known
from a number of studies together with a range of co-
ordination complexes with neutral two-electron donor
ligands, L, of the form [Bi(SR)3(L)1–3] particularly in the
case where R ¼ C6F5 [1–5]. Thiolato anions result when
L is an anionic donor and examples include the species
[AsPh4][Bi(SC6F5)4] [1a], [Na2(thf)4][Bi(SC6F5)5] [2]
(thf ¼ tetrahydrofuran) and [K(18-crown-6)][Bi(SC6F5)3
(NCS)] [4] the latter two having been characterised
crystallographically. More recently, we reported the
structure of the compound [4-picH][(4-pic)2H]
[Bi3(SC6F5)11] (4-pic ¼ 4-picoline) incorporating a tri-
2. Results and discussion
The compounds isolated from reactions between
Bi(SC6F5)3 (1) and sources of halide anions are sum-
marised in Eqs. (1)–(4). Compounds 2–6 were all char-
acterised by X-ray crystallography, the results of which
are described below. Selected bond distance and angle
data for all anionic complexes are given in Table 1 and
crystallographic data are presented in Table 2. Whilst
compounds 4–6 contain both thiolate and halide groups
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.ica.2004.03.025.
* Corresponding author. Tel.: +44-117-928-7577; fax: +44-117-929-
0509.
E-mail address: n.c.norman@bristol.ac.uk (N.C. Norman).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.03.025

Table 1
ꢀ
Selected bond distance (A) and angle (°) data for complexes 2–6
Compounds
2
3
4
5
6
Bond distance
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–S(7)
Bi(1)–S(6)
Bi(2)–S(4)
Bi(2)–S(5)
Bi(2)–S(6)
Bi(2)–S(7)
2.586(5)
2.549(4)
2.655(5)
3.114(4)
3.482
Bi(1)–S(1)
Bi(1)–S(3)
Bi(1)–S(5)
Bi(1)–S(6)
Bi(1)–S(8)
Bi(2)–S(1)
Bi(2)–S(2)
Bi(2)–S(3)
Bi(2)–S(4)
Bi(2)–S(7)
3.154
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–Br(1)
Bi(1)–S(5)
Bi(2)–S(4)
Bi(2)–S(5)
Bi(2)–S(6)
Bi(2)–Br(1)
Bi(2)–Br(2)
Bi(2)–S(11)
Bi(3)–S(7)
Bi(3)–S(8)
Bi(3)–S(9)
Bi(3)–Br(2)
Bi(3)–S(1)
Bi(3)–S(8)
Bi(3)–Br(1)
Bi(4)–S(10)
Bi(4)–S(11)
Bi(4)–S(12)
Bi(4)–Br(2)
Bi(4)–S(8)
2.621(4)
2.569(4)
2.634(4)
3.0040(18)
3.426
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–Cl(1)
Bi(1)–Cl(1a)
2.6708(17)
2.567(2)
Bi(1)–S(1)
Bi(1)–S(2)
Bi(1)–S(3)
Bi(1)–Br(1)
Bi(2)–S(2)
Bi(2)–S(4)
Bi(2)–S(5)
Bi(2)–S(6)
Bi(2)–Br(1)
Bi(2)–Br(2)
Bi(3)–S(6)
Bi(3)–S(7)
Bi(3)–S(8)
Bi(3)–S(9)
Bi(3)–Br(2)
2.6716(17)
2.5907(16)
2.6012(18)
3.0956(7)
3.482
2.901(3)
2.626(3)
2.701(3)
2.566(3)
2.961(3)
2.583(3)
3.160
2.6800(18)
2.9190(19)
2.9229(19)
2.598(4)
2.643(4)
2.615(4)
3.052(3)
2.604(4)
2.641(4)
2.617(4)
3.1443(19)
3.533
2.6244(17)
2.6601(16)
2.5852(16)
3.1280(7)
3.2400(7)
3.455
2.627(3)
2.678(3)
3.301
2.620(4)
2.651(4)
2.595(4)
3.1830(18)
3.197
2.6019(19)
2.6111(17)
2.5830(16)
3.1890(7)
2.646
3.596
2.636(4)
2.610(4)
2.561(4)
3.0163(18)
3.461
Bond angle
S(3)–Bi(1)–S(7)
S(5)–Bi(2)–S(7)
Bi(1)–S(7)–Bi(2)
S(6)–Bi(1)–S(1)
157.05(13)
162.68(12)
95.92(10)
144.61
S(1)–Bi(1)–S(5)
S(3)–Bi(1)–S(6)
S(1)–Bi(2)–S(7)
S(3)–Bi(2)–S(4)
Bi(1)–S(1)–Bi(2)
Bi(1)–S(3)–Bi(2)
168.03
166.18(8)
169.58(8)
168.64
88.88
Br(1)–Bi(1)–S(3)
Br(1)–Bi(2)–S(6)
Br(2)–Bi(3)–S(7)
170.20(11)
169.39(10)
169.41(10)
S(1)–Bi(1)–Cl(1a)
S(3)–Bi(1)–Cl(1)
Bi(1)–Cl(1)–Bi(1a)
177.29(5)
165.42(6)
90.54(5)
S(1)–Bi(1)–Br(1) 179.21(4)
Bi(1)–Br(1)–Bi(2) 88.525(18)
Br(1)–Bi(2)–S(5)
Br(2)–Bi(2)–S(4)
171.09(4)
155.09(4)
Br(2)–Bi(4)–S(10) 169.42(11)
Bi(1)–Br(1)–Bi(2) 93.78(5)
Bi(3)–Br(2)–Bi(4) 90.50(5)
Bi(2)–Br(2)–Bi(3) 88.633(16)
S(8)–Bi(3)–Br(2) 160.21(5)
89.84
S(5)–Bi(1)–S(1)
S(5)–Bi(1)–S(2)
S(11)–Bi(2)–S(5)
Br(2)–Bi(2)–S(4)
S(1)–Bi(3)–S(8)
Br(1)–Bi(3)–S(9)
S(8)–Bi(4)–S(11)
S(8)–Bi(4)–S(12)
146.80
103.56
172.50
141.69
165.54
141.51
146.33
105.55

Table 2
Crystallographic data for compounds 2–6
[PPh4][Bi2(SC6F5)6(l-SC6F5)] [NEt4]2[Bi2(SC6F5)6(l-SC6F5)2] [PPh3CH2CO2CH3][Bi2(SC6F5)6
[PPh3CH2Ph]2[Bi2(SC6F5)6(l-Cl)2] [PPh4]2[Bi3(SC6F5)9(l-Br)2]
(l-Br)](C6H12)0.50 (CH2Cl2)0.16
2
3
4
5
6
Formula
C
66H20Bi2F35PS7
C68H48Bi2F40N2OS8
2343.52
monoclinic
C117:17H47:33Bi4Br2Cl0:33F60O4P2S12 C86H44Bi2Cl2F30P2S6
4112.96
triclinic
C102H40Bi3Br2F45P2S9
3257.58
monoclinic
Molecular weight
Crystal system
Space group
2151.17
triclinic
2390.37
monoclinic
ꢁ
ꢁ
P1
P21=c
P1
P21=n
P21=c
ꢀ
a (A)
15.056(23)
15.536(45)
15.553(26)
73.96(25)
88.49(16)
82.12(13)
3463.0(6)
2
27.1737(11)
13.7689(6)
22.4789(9)
13.6346(14)
16.8210(15)
30.319(3)
75.770(9)
82.126(7)
89.489(8)
6674.5(12)
2
14.7522(6)
13.2545(5)
22.4229(10)
27.7454(6)
13.5241(3)
30.1460(7)
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
107.010(9)
104.350(1)
108.86(2)
3
ꢀ
V (A )
8042.6(6)
4
1.935
4247.6(3)
2
1.869
10704.4(4)
4
2.021
Z
Dc (g cmꢀ3
)
2.063
5.447
2.018
6.202
71078
l (Mo Ka)/mmꢀ1
Data collected
4.715
51816
4.498
21873
5.998
69701
36516
14294 (0.1396)
Unique data (Rint
)
14164 (0.1080)
0.0502, 0.1182
0.1559, 0.1394
30106 (0.0880)
0.0321, 0.1106
0.1031, 0.756
9748 (0.0603)
0.0483, 0.0963
0.1037, 0.1372
24470 (0.0518)
0.0331, 0.0861
0.0694, 0.1190
Final R1, wR2 [I > 2rðIÞ] 0.0534, 0.1116
(All data) 0.1787, 0.1810

J.P.H. Charmant et al. / Inorganica Chimica Acta 358 (2005) 1358–1364
1361
as anticipated, compounds 2 and 3 are bismuthate an-
ions containing only thiolate groups. Redistribution
reactions wherein ligands or groups are exchanged be-
tween bismuth centres in solution are not unexpected,
however, and have been well documented for aryl bis-
muth halides in particular see references 6 and 7 and
references therein. A considerable range and type of
anionic species is therefore possible and factors such as
the solvent, the counter-cation, concentration of the
reactants in solution and crystallisation processes are
likely to have an impact on which particular species are
isolated in a manner which is hard to predict. Reactions
between 1 and other ammonium and phosphonium ha-
lides were carried out although no crystalline materials
were isolated
unique thiolate bridges the two bismuth centres fairly
symmetrically but with Bi–S bonds [3.052(3) and
ꢀ
3.114(4) A] significantly longer than any of the terminal
Bi–S bonds (Table 1). For the terminal Bi–S distances,
equatorial bonds are slightly shorter than axial bonds as
expected. The conformations about the S(7)–Bi(1) and
S(7)–Bi(2) bonds are noteworthy in that the conforma-
tion about the latter bond places S(6) in close proximity
ꢀ
to Bi(1) [Bi(1)–S(6) 3.482 A] such that S(6) lies ap-
proximately trans to S(1) [S(6)–Bi(1)–S(1) 144.61°] with
Bi(1) therefore approaching a five-coordinate geometry.
The presence of this semi-bridging thiolate could be
viewed as a snapshot along a reaction pathway for thi-
olate exchange between bismuth centres, the importance
of which is highlighted above in relation to the nature of
the products isolated in this study. Additional semi-
bridging interactions are also seen in some of the
structures described below.
Compound 3 comprises the dinuclear di-anion
[Bi2(SC6F5)6(l-SC6F5)2]2ꢀ (Fig. 2) with two [NEt4]þ
cations and two molecules of thf (tetrahydrofuran) of
crystallisation per formula unit. In 3, two thiolates
bridge the one bismuth centres albeit more asymmetri-
cally than in 2 [S(1)–Bi(1) 3.154, S(1)–Bi(2) 2.961(3);
BiðSC6F5Þ ð1Þ þ ½PPh4ꢁBr
3
! ½PPh4ꢁ½Bi2ðSC6F5Þ ðl-SC6F5Þꢁ ð2Þ
þ ½PPh4ꢁ ½Bi3ðSC6F5Þ6ðl-BrÞ ꢁ ð6Þ
ð1Þ
ð2Þ
ð3Þ
ð4Þ
2
9
2
BiðSC6F5Þ ð1Þ þ ½NEt4ꢁBr
3
! ½NEt4ꢁ ½Bi2ðSC6F5Þ ðl-SC6F5Þ ꢁ ð3Þ
2
6
2
BiðSC6F5Þ ð1Þ þ ½PPh3CH2CO2CH3ꢁBr
3
ꢀ
S(3)–Bi(1) 2.901(3), S(3)–Bi(2) 3.160 A]. Each bismuth
! ½PPh3CH2CO2CH3ꢁ½Bi2ðSC6F5Þ ðl-BrÞꢁ ð4Þ
6
centre is five-coordinate with a square-based pyramidal
geometry in which the bridging thiolates occupy basal
sites. All Bi–S distances follow expected trends; the
apical bonds are the shortest whilst the Bi–S bonds to
the bridging thiolates are longer than the terminal Bi–S
bonds in the basal plane. Moreover, the shortest ter-
minal Bi–S bonds are trans to the longer bridging bonds.
Both apical thiolates lie on the same side of the Bi2S6
plane, i.e. a syn rather than an anti arrangement.
BiðSC6F5Þ ð1Þ þ ½PPh3CH2PhꢁCl
3
! ½PPh3CH2Phꢁ ½Bi2ðSC6F5Þ ðl-ClÞ ꢁ ð5Þ
2
6
2
Compound 2 comprises the [PPh4]þ cation and the
dinuclear mono-anion [Bi2(SC6F5)6(l-SC6F5)]ꢀ. The
anion is shown in Fig. 1 which reveals two bismuth
centres bridged by a single thiolate group. Each bismuth
centre is four-coordinate with the expected equatorially
vacant, trigonal bipyramidal or disphenoidal geometry
in which the bridging thiolate occupies an axial site. The
Compound 4 is a salt containing the phosphonium
cation [PPh3CH2CO2CH3]þ and the mono anion
Fig. 1. A view of the dinuclear mono-anion [Bi2(SC6F5)6(l-SC6F5)]ꢀ
in the structure of 2.
Fig. 2. A view of the dinuclear di-anion [Bi2(SC6F5)6(l-SC6F5)2]2ꢀ in
the structure of 3.

1362
J.P.H. Charmant et al. / Inorganica Chimica Acta 358 (2005) 1358–1364
[Bi2(SC6F5)6(l-Br)]ꢀ with two of each per asymmetric
unit. Each [Bi2(SC6F5)6(l-Br)]ꢀ anion is superficially
similar to the anion in 2 in which the bridging thiolate in
2 is replaced by a bridging bromide in 4. Geometrically
and conformationally, both anions in 4 are similar to
each other and to the anion in 2 including the close
contact between one bismuth centre and a terminal (or
semi-bridging) thiolate sulfur on the other [Bi(1)–S(5)
and triphenylbenzyl phosphonium cations [PPh3CH2ꢀ
Ph]þ. The [Bi2(SC6F5)6(l-Cl)2]2ꢀ di-anion resembles the
di-anion in 3 with the exception that the chlorines in 5
bridge much more symmetrically [Bi(1)–Cl(1) 2.9190
ꢀ
(19), Bi(1)–Cl(1a) 2.9229(19) A] than the thiolates in 3
(see above) and that the apical thiolates in 5 adopt an
anti disposition with respect to the adjoined square-
basal planes rather than the syn arrangement found
in 3.
ꢀ
3.426; Bi(4)–S(8) 3.461 Aꢁ. Unlike in 2, however, the two
anions in 4 are weakly associated into an approximately
centrosymmetric dimer through additional long Biꢂ ꢂ ꢂBr
and Biꢂ ꢂ ꢂS contacts as is evident from Fig. 3; distances
and angles associated with these longer interactions are
given in Table 1.
Compound 6 incorporates the trinuclear di-anion
[Bi3(SC6F5)9(l-Br)2]2ꢀ (Fig. 5) with associated [PPh4]þ
cations. The structure of the anion [Bi3(SC6F5)9(l-
Br)2]2ꢀ comprises a central bismuth tristhiolate unit
linked to two other bismuth centres by single bridging
bromides. The geometry around the central bismuth is
square-based pyramidal with the two bromides in
mutually cis basal sites. Each terminal bismuth centre
is four-coordinate with a disphenoidal geometry in
which the bromines occupy axial sites. Bi–S bond
lengths in 6 follow the expected trends described
above (Table 1) and the bromines bridge fairly sym-
metrically. The Bi(1), Br(1), Bi(2) unit and the Bi(2),
Br(2), Bi(3) unit each resemble the basic structure seen
in the [Bi2(SC6F5)6(l-Br)]ꢀ anion in 4 notably in
terms of the conformations about the Bi(1)–Br(1) and
Bi(3)–Br(2) bonds which place S(2) close to Bi(2)
Compound 5 contains the crystallographically cen-
trosymmetric di-anion [Bi2(SC6F5)6(l-Cl)2]2ꢀ (Fig. 4)
ꢀ
ꢀ
[3.482 A] and S(6) close to Bi(3) [3.455 A]. The
presence of these two semi-bridging thiolates results in
Bi(2) and Bi(3) approaching six- and five-coordina-
tion, respectively, as is clear from Fig. 5. The structure
of the anion in 6 is closely related to the trinuclear di-
anion found in the structure of [4-picH][(4-
pic)2H][Bi3(SC6F5)11]5 in which the bridging groups
are thiolates although conformationally the two
structures are rather different and the [Bi3(SC6F5)11]2ꢀ
anion lacks the semi-bridging thiolates seen in 6.
Fig. 3. A view of the dimeric arrangement of [Bi2(SC6F5)6(l-Br)]ꢀ
anions in the structure of 4.
Fig. 4. A view of the crystallographically centrosymmetric dinuclear di-
anion [Bi2(SC6F5)6(l-Cl)2]2ꢀ in the structure of 5.
Fig. 5. A view of the trinuclear di-anion [Bi3(SC6F5)9(l-Br)2]2ꢀ in the
structure of 6.

J.P.H. Charmant et al. / Inorganica Chimica Acta 358 (2005) 1358–1364
1363
3.5
3.4
3.3
3.2
3.1
3.0
2.9
2.8
2.7
2.6
2.5
2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5
B–S/ Å
Fig. 6. A plot of trans related S–Bi–S distances for bismuth thiolates
and thiolato anions.
3. Experimental
3.1. 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 sol-
vents 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].
Whilst all the structures reported here are different,
a number of general structural features are apparent.
The basic units are of two types namely [Bi2(SR)6(l-
X)]ꢀ (this can be taken to include the anion in 6, see
2ꢀ
discussion above) and [Bi2(SR)6(l-X)2]
, where
X ¼ thiolate or halide. In the former case the single
bridging groups occupy an axial site within the dis-
phenoidal geometry around the bismuth centres
whereas in the latter the two bridging groups occupy
cis basal sites in the square based pyramid (apical
groups can adopt both syn and anti arrangements).
Semi-bridging thiolates are also encountered in the
structures of the type [Bi2(SR)6(l-X)]ꢀ. A further
point to note is that in the structures of 4–6 which
contain both thiolate and halide groups, it is the ha-
lides which bridge rather than the thiolates. A similar
situation is found in the alkoxide anion [Bi2(O-2,6-
Me2C6H3)6(l-Cl)2]2ꢀ which is closely related to the
structure of the anion in 5, although in the neutral
3.2. Preparations
3.2.1. [PPh4][Bi2(SC6F5)6(l-SC6F5)] (2) and
[PPh4]2[Bi3(SC6F5)9(l-Br)2] (6)
A solution of 1 (0.11 g, 0.136 mmol) in CH2Cl2 (3
cm3) was added to solid [PPh4]Br (0.057 g, 0.136 mmol)
affording a clear orange solution. After stirring for 5
min, the solvent volume was reduced by vacuum and
hexane (3 cm3) was added as an overlayer. Solvent dif-
fusion at )30 °C over a period of several days afforded
orange crystals of 2 (0.075 g, 45%) and a small crop of
yellow crystals of 6. Difficulties in separating crystals of
2 and 6 prevented satisfactory analytical data from be-
ing obtained.
species
[Bi2Cl4(thf)2(l2-O-2,6-Me2C6H3)2]
and
[Bi2Cl4ꢀ (thf)2(l2-O-2,4,6-Me3C6H2)2], it is the alk-
oxides which bridge in preference to the halides [8].
Finally, we note that if a graph is plotted of all the
trans related S–Bi–S pairs of distances in the structures
reported herein, as well as previously reported struc-
tures (Fig. 6), the expected correlation in both dis-
tances is observed as discussed in ref. 9, and references
therein.
3.2.2. [NEt4]2[Bi2(SC6F5)6(l-SC6F5)2] ꢂ 2thf (3)
A filtered solution of [NEt4]Br (0.05 g, 0.237 mmol) in
thf (2 cm3) was added to a solution of 1 (0.10 g, 0.124
mmol) in thf (3 cm3). After stirring, hexane (3 cm3) was
added an overlayer. Solvent diffusion at )30 °C over a
period of days afforded orange crystals of 3 (0.072 g,
48%). Satisfactory analytical data were not obtained due
to facile solvent loss from the crystals.

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J.P.H. Charmant et al. / Inorganica Chimica Acta 358 (2005) 1358–1364
3.2.3. [PPh3CH2CO2CH3][Bi2(SC6F5)6(l-Br)] (4)
Compound (0.06 g, 0.074 mmol) and
tropic parameters and refined without positional
constraints for all structures. In addition to the bismuth
containing species, the solid state structure of 4 has a
unit cell containing one hexane molecule and two,
symmetry related, sites partially occupied by a dichlo-
romethane molecule.
1
[PPh3CH2CO2CH3]Br (0.025 g, 0.074 mmol) were dis-
solved in CH2Cl2 (3 cm3) and hexane (3 cm3) was added
an overlayer. Solvent diffusion over a period of days )30
°C afforded orange crystals of 4 (0.043 g, 51%). Anal.
Calc. for C57H20Bi2BrF30O2PS6: C, 33.75; H, 1.00.
Found: C, 34.00; H, 1.40%.
References
3.2.4. [PPh3CH2Ph]2[Bi2(SC6F5)6(l-Cl)2] (5)
[1] (a) M. Muller, R.J.H. Clark, R.S. Nyholm, Transition Met.Chem.
3 (1978) 369;
Compound
1
(0.10 g, 0.124 mmol) and
[PPh3CH2Ph]Cl (0.048 g, 0.124 mmol) were dissolved in
CH2Cl2 (3 cm3) and hexane was added as an overlayer.
Solvent diffusion over a period of days at )30 °C af-
forded orange crystals of 5 (0.083 g, 73%). Anal. Calc.
for C86H44Bi2Cl2F30P2S6: C, 43.20; H, 1.85; Cl, 2.95.
Found: C, 43.15; H, 1.80; Cl, 2.70%.
(b) M.E. Peach, Can. J. Chem. 46 (1968) 2699.
[2] L.J. Farrugia, F.J. Lawlor, N.C. Norman, Polyhedron 14 (1995)
311.
[3] W. Clegg, M.R.J. Elsegood, L.J. Farrugia, F.J. Lawlor, N.C.
Norman, A.J. Scott, J. Chem. Soc., Dalton Trans. (1995) 2129.
[4] L.J. Farrugia, F.J. Lawlor, N.C. Norman, J. Chem. Soc., Dalton
Trans. (1995) 1163.
[5] K.M. Anderson, C.J. Baylies, A.H.M.M. Jahan, N.C. Norman,
A.G. Orpen, J. Starbuck, Dalton Trans. (2003) 3270.
[6] See, for example: W. Clegg, R.J. Errington, G.A. Fisher, R.J.
Flynn, N.C. Norman, J. Chem. Soc., Dalton Trans. (1993) 637.
[7] R.J. Errington, G.A. Fisher, N.C. Norman, A.G. Orpen, S.E.
Stratford, Z. Anorg. Allg. Chem. 620 (1994) 457, and references
therein.
3.3. X-ray crystallography
All crystals were mounted under argon on glass fibres
using paraffin oil. Data were collected on a Bruker AXS
(formally Siemens) SMART [10,11] area detector dif-
fractometer using graphite monochromated Mo Ka ra-
diation, at )100 °C. Intensities were integrated from
several series of exposures covering 0.3° in x.
[8] P. Hodge, S.C. James, N.C. Norman, A.G. Orpen, J. Chem. Soc.,
Dalton Trans. (1998) 4049.
[9] J. Starbuck, N.C. Norman, A.G. Orpen, New J. Chem. 23 (1999)
969.
Structures were solved and refined by standard
methods using SHELXTL software [12]. In each case
hydrogen atom were constrained to idealized geometries
and assigned isotropic displacement parameters 1.2
times the Uiso the attached carbon.
Absorption corrections were applied using SADABS
[13] and extinction coefficients were refined where ap-
propriate. Non-hydrogen atoms were assigned aniso-
[10] SMART diffractometer control software, Bruker Analytical X-ray
Instruments Inc., Madison, WI, 1998.
[11] SAINT integration software, Siemens Analytical X-ray Instru-
ments Inc., Madison, WI, 1994.
[12] SHELXTL program system version 5.1, Bruker Analytical X-ray
Instruments Inc., Madison, WI, 1998.
[13] G.M. Sheldrick, SADABS: a program for absorption correction
€
with the Siemens SMART system, University of Gottingen,
Germany, 1996.