Synthesis and characterisation of N-coordinated pentafluorophenyl gold(I) thiazole-derived complexes and an unusual self-assembly to form a tetrameric gold(I) complex

Article abstract of DOI:10.1039/b303625a

Treatment of [Au(C₆F₅)(SC₄H₈)] (1) (SC₄H₈ = tetrahydrothiophene or tht) with HC=NC(CH₃)=C(H)S, CH₃SC=NC(CH₃)=C(H)S, (I) or piperidine yields the neutral mononuclear imine complexes [Au(C₆F₅)-{N=C(H)SC(H)=CCH₃}] (2) and [Au(C₆F₅){N=C(SCH₃)SC(H)=CCH₃}] (3), or the amine complex [Au(C₆F₅){N(H)CH₂(CH₂)₃CH ₂}] (4). The reaction of 1 with S=CN(H)C(CH₃)=C(H)S, (II) affords the thione complex [Au(C₆F₅){S=CN(H)C(CH₃)=C(H)S}] (5), which, in CH₂Cl₂ via spontaneous intermolecular deprotonation of the thione ligand, self-assembles to an unique tetramer of Au(I), [Au{S=CNC(CH₃)=C(H)S}]₄ (6) containing a folded rectangle of Au-atoms with aurophlilic interactions [av. Au ... Au distance, 3.02(4) A and av. Au-Au-Au angle, 87(2)°]. N-coordination of the imine complexes has been confirmed by ¹⁵N NMR and the crystal structure determination of 2 which exhibits the expected linear N-coordination and intermolecular Au ... Au [3.345(1) A] contacts. The crystal structure of 5 shows thione S-coordination of II to the central Au atom.

Full text of DOI:10.1039/b303625a

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Synthesis and characterisation of N-coordinated pentafluorophenyl
gold(I) thiazole-derived complexes and an unusual self-assembly to
form a tetrameric gold(I) complex†
Stephanie Cronje,*a Helgard G. Raubenheimer,a Hendrik S. C. Spies,a Catharine Esterhuysen,b
Hubert Schmidbaur,b Annette Schierb and Gert J. Krugerc
a Department of Chemistry, University of Stellenbosch, Private Bag X1, Matieland 7602,
Stellenbosch, South Africa. E-mail: scron@sun.ac.za; Fax: ϩ27 21 808 3849;
Tel: ϩ27 21 808 2180
b Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4,
D-85747 Garching, Germany
c Department of Chemistry and Biochemistry, Rand Afrikaans University, PO Box 524,
Auckland Park 2006, Johannesburg, South Africa
Received 1st April 2003, Accepted 2nd June 2003
First published as an Advance Article on the web 20th June 2003
Treatment of [Au(C F )(SC H )] (1) (SC H = tetrahydrothiophene or tht) with HC᎐NC(CH )᎐C(H)S,
᎐
᎐
3
6
5
4
8
4
8
CH SC᎐NC(CH )᎐C(H)S, (I) or piperidine yields the neutral mononuclear imine complexes [Au(C F )-
᎐
᎐
3
3
6
5
{N᎐C(H)SC(H)᎐CCH }] (2) and [Au(C F ){N᎐C(SCH )SC(H)᎐CCH }] (3), or the amine complex
᎐
᎐
᎐
᎐
3
6
5
3
3
[Au(C F ){N(H)CH (CH ) CH }] (4). The reaction of 1 with S᎐CN(H)C(CH )᎐C(H)S, (II) affords the thione
᎐
᎐
3
6
5
2
2
3
2
complex [Au(C F ){S᎐CN(H)C(CH )᎐C(H)S}] (5), which, in CH Cl via spontaneous intermolecular deprotonation
᎐
᎐
6
5
3
2
2
of the thione ligand, self-assembles to an unique tetramer of Au(), [Au{S᎐CNC(CH )᎐C(H)S}] (6) containing
᎐
᎐
3
4
a folded rectangle of Au-atoms with aurophlilic interactions [av. Au ؒ ؒ ؒ Au distance, 3.02(4) Å and av. Au–Au–Au
angle, 87(2)Њ]. N-coordination of the imine complexes has been confirmed by 15N NMR and the crystal structure
determination of 2 which exhibits the expected linear N-coordination and intermolecular Au ؒ ؒ ؒ Au [3.345(1) Å]
contacts. The crystal structure of 5 shows thione S-coordination of II to the central Au atom.
ised in recent years. The crystal structures of gold() amine and
Introduction
imine complexes show extensive aurophilic and coulombic
interactions as well as interhalogen contacts and hydrogen
bonding which also stabilise these compounds.17–20
Medical interest in gold compounds that are used to treat
rheumatoid arthritis and display anticancer, antiviral and
antimicrobial activity, can be sustained with improved under-
standing of the molecular and biochemical mechanism of
their pharmacological action.1,2 The coordination of gold() to
ligands from biological systems (purines, pyrimidines, vitamins,
coenzymes and anitbiotics) or even ligands analogous to those
found in biological systems, can provide important information
in this regard. Of biological interest are nitrogen donor ligands
(e.g. amines and five-membered heterocycles), thioethers,
thiolates, thiols and thiones.2
Although many gold complexes containing five-membered
heterocycles like imidazole,3–6 pyrazole,6–8 oxazole8,9 and
thiazole8 have been described, only a few containing neutral
imidazole,10,11 oxazole,11 triazole12 and azaphosphole13 ligands
have been reported. This investigation of the coordination
of a group of ligands derived from the vitamin B1 analogue,14
4-methylthiazole, now reveals that the soft metal centre Au()
prefers imine coordination when provided with a choice
between the borderline (hard/soft) imine and soft endo-
and exocyclic thioether ligands. This result supports the
Neutral thione-coordinated gold() complexes have pre-
viously been prepared by coordination of the ligand to
AuCl30,31 and AuCN32 or by the substitution of tht in AuX(tht)
(X = Cl or C6F5).33 Cationic thione-coordinated gold() com-
plexes, obtained by the substitution of tht in [Au(PPh3)(tht)]ϩ,33
reduction of HAuCl4 with excess thione ligand12,34,35 or treat-
ment of Au(PPh3)Cl with thione (1 : 1) (helped along by
AgPF6 36 or by refluxing in methanol37) are also known.
Instances in which simple syntheses of linear two-coordinate
gold() compounds were attempted have surprisingly resulted in
the isolation of dimers, tetramers, oligomers and polymers of
gold compounds.38–41 This phenomenon, promoted by gold()
atoms with a closed-shell electronic configuration, and showing
a strong tendency to form aggregates through aurophilic
interaction, has projected gold compounds into the realm
of supramolecular chemistry. The slow deprotonation of
[Au(SCNHCH2CH2NH)2Cl] has produced a tetrameric gold
complex with N and S donor atoms.38 Two neutral tetrameric
complexes {(iPr3P)2Au4[S2C6H4]2} and {(iPr3P)2Au4[S2C6H3-
Me]2} were prepared by treating the corresponding phenyl-1,2-
dithiol with [(iPr3PAu)3O]BF4.41 The crystal structures of these
compounds show a rhombus formed by four Au atoms with
Au ؒ ؒ ؒ Au contacts of ca. 3.11 Å.
structures [Au{N᎐C(C᎐CHCH᎐CHS)OCH C(CH ) } ]ϩ and
᎐
᎐
᎐
2
3 2 2
C F Au[N᎐C(C᎐CHCH᎐CHS)OCH C(CH ) ] proposed in
᎐
᎐
᎐
6
5
2
3 2
previous work.9 The generalization sometimes made that
gold() prefers S-donor to N-donor ligands15–17 should thus be
treated with caution as demonstrated by the many Au()
imine17–25 and amine16,17,26–29 complexes, prepared mostly from
Au() thioether complexes,16–18,20–22,24–27 isolated and character-
By using 4-methylthiazole, its derivatives CH3-
SC᎐NC(CH )᎐C(H)S (I) and S᎐CN(H)C(CH )᎐C(H)S (II),
᎐
᎐
᎐
᎐
3
3
and an amine, we prepared the linear N- and S-coordinated
gold() complexes, [Au(C F ){N᎐C(H)SC(H)᎐CCH }] (2),
᎐
᎐
6
5
3
[Au(C F ){N᎐C(SCH )SC(H)᎐CCH }
(3),
and
[Au(C6F5)-
᎐
᎐
6
5
3
3
† Electronic supplementary information (ESI) available: Characteris-
ation data for 1. See http://www.rsc.org/suppdata/dt/b3/b303625a/
{N(H)CH2(CH2)3CH2}]
(4)
[Au(C6F5)-
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
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
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a signal at 11.75 ppm for the N–H proton and only the CH3-
signal in the region where S–H protons (2–4 ppm)46,47 are
expected indicating that the thione tautomer predominates
in solution. The 13C NMR chemical shifts of the NCS and
SCC(CH3)N carbons at 191.2 and 139.3 ppm are similar to
values observed for the thiazole rings of carbene compounds.48
A weak S–H vibration at (2500 cmϪ1)42,46 was observed in the
infrared spectrum recorded (KBr pellet) along with the N–H
vibration (3000 cmϪ1). This is not quite unexpected as strong
hydrogen bonding between the S and N–H of adjacent
molecules of the thiones was observed in the crystal structures
of 1,3-thiazoline-2-thione, 4-(3-nitrophenyl)thiazole-2(3H )-
thione and benzothiazole-2-thione.49
{S᎐CN(H)C(CH )᎐C(H)S}] (5) as well as an unusual tetrameric
᎐
᎐
3
gold compound, [Au{S᎐CNC(CH )᎐C(H)S}] (6).
᎐
᎐
3
4
Results and discussion
Synthetic aspects
The thioether, I, was previously prepared by the addition of
MeI to the corresponding thione42 in a basic medium followed
by distillation to purify the product. The new preparation via
deprotonation of 4-methylthiazole followed by reaction with
MeSSMe produces the thioether in very high yield (70%) after
a simple filtration to purify it. The product is a colourless liquid
The 1H and 13C NMR spectra of 2, 3 and 5 provide no clues
as to the identity of the coordinated heteroatom. The signals
in contrast to the crystalline thioethers CH SC᎐NC H S-o43
᎐
3
6
4
and CH SC᎐NC(H)᎐C(C H OH)S.44 A convenient simplific-
1
in the H NMR spectra are shifted not more than 0.7 ppm
᎐
᎐
3
6
4
ation of a cyclization reaction (reaction of bromoacetone with
dithiocarbamate followed by a dehydration45) achieved by
reacting 4-methylthiazolyl-2-lithium with S8 and quenching
with H2O, yielded 43% of the thione II after crystallisation.
Both ligands are soluble in polar and nonpolar organic
solvents.
The treatment of equimolar amounts of the starting
material, 1, with 4-methylthiazole, I, piperidine or II (Scheme 1)
readily effects substitution of the tht (SC4H8, tetrahydro-
thiophene) ligand to produce colourless N-coordinated 2, 3, 4
and light yellow thione-coordinated 5 in very high yields. The
reaction mixtures were filtered through MgSO4 to remove solids
and evaporated to complete dryness. The products are soluble
in CH2Cl2, acetone and THF.
downfield from their positions in the spectra of the free ligand.
In the 13C NMR most signals are also shifted downfield, but not
more than 4.5 ppm from those in the free ligand. The exception
is the signal for the NCS-carbon which is shifted downfield in
the thiazole compound, 2 (11.1 ppm), and in the thioether
compound, 3 (6.5 ppm), but upfield in the the thione, 5 (4.5
ppm).
The signals in the 1H NMR spectrum of the amine complex,
4, are shifted not more than 0.5 ppm from the signals of the free
ligand and equatorial and axial protons can be distinguished
for the β- and γ-CH2 groups. The 13C NMR signals are shifted
upfield and downfield (4 ppm) from those in the free ligand.
The N–H signal for the piperidine is observed at 2.08 ppm
for the free ligand but appears at 5.17 ppm when the ligand is
coordinated. While the N–H signal of II appeared at 11.75 ppm
as mentioned before, it was observed at 8.94 and 5.27 ppm in
5 for different concentrations.47 The 19F NMR spectra display
the normal pattern observed for C6F5-groups in gold()
complexes.18,50
The endocyclic thioether S is unlikely to be the site of
coordination as 14N NMR data suggests that the lone pair of
the sulfur is delocalized into the conjugated ring.51 For 2 this
only leaves imine coordination to gold, which was confirmed by
a crystal structure determination, and for 5 thione or amine
coordination.
To determine the site of coordination in 3 we resorted to 15
N
NMR spectra as no suitable crystals for a crystal structure
determination could be grown and at least two coordination
sites, the imine N-atom and exocyclic thioether S-atom were
available. The low natural abundance and severe sensitivity of
the 15N nucleus makes direct NMR measurement difficult but
very useful.52 The use of labelled ligands though successful,53
has been limited to C15NϪ ligands. 15N chemical shifts
have been reported for 2,3-dihydro-1H-imidazol-2-ylidene-gold
complexes.54
An upfield shift of 59.2 ppm was observed for the 15N-atoms
in the thiazole gold complex 2 compared to the signal for the
free thiazole upon coordination. A similar result was obtained
for the thioether gold complex 3 (upfield shift 57.7 ppm) thus
confirming imine coordination above endocyclic and exocyclic
thioether coordination. The signal for the 15N-atoms in the
thione gold complex 5 showed a small downfield shift (∆δ = 6.7
ppm) when compared to the 15N-atoms of the amine N-atom in
the free thione ligand. However, the amine complex, 4, (also
characterised by other means) exhibits a small downfield (∆δ =
4.5 ppm) shift compared to the free ligand in contrast to the
changes in the imine complexes. This could be because π-back
bonding possibilities in 4 are non-existent. π-Back bonding in 5
is possible and thus a conclusive result as to the coordination
site of the thione could only be achieved by determining the
crystal structure of the compound.
Scheme 1
Complex 4 is stable at room temperature under inert
atmosphere but is more air- and moisture-sensitive than the
imine complexes 2 and 3. These compounds are isolable and
characterisable eventhough their “instability” was predicted on
many occasions.16,18 The formation of 6 is described below.
Characterisation
Efforts to crystallise the thione gold complex were com-
plicated by unexpected proton transfer from the amine group
on the thione to the C6F5-ligand yielding C6F5H and 6 (15 mg,
No unexpected features were observed in the mass, IR, 1H and
13C NMR spectra of I. The 1H NMR of II in d6-acetone shows
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
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CD2Cl2, 20 days). The formation of insoluble 6 was slow
enough to give crystals suitable for a structure determination.
Crystals of 5 were finally obtained within 7 days by dissolving
some microcrystalline material in a minimum of CH2Cl2 and
layering with pentane. The X-ray crystal structure determin-
ation confirmed thione coordination.
ϩ
No homoleptic rearrangement to yield AuL2
and
(C6F5)2AuϪ occurred in 2, 3, 4 and 5 as only one set of peaks
is observed in the NMR spectra of each compound.
Homoleptic rearrangements have previously been observed for
C F Au[CNHCH᎐CHN(CH )] (accompanied by proton
᎐
6
5
3
migration) and C6F5Au[CCHCHN(CH3)S]55 but not for
C6F5Au(NC5H4CH3-3)18 and C F Au[CN(CH )C(CH )᎐CHS].9
᎐
6
5
3
3
Pseudopotential ab initio calculations on the molecular
and ionic dimers of the type [(H3P)AuCl]2 and
{[(H3P)2Au]ϩ[AuCl2]Ϫ} have shown that the compounds are
closely comparable in energy.56 The same is probably true
for C6F5AuL compounds and ClAuL compounds of which
many species viz. [AuL2]ϩ[LAuCl][AuCl2]Ϫ,16 [AuL2]ϩ-
[AuCl2]Ϫ,24,18,20,25 and [L2Au]ϩClϪ 16 have been crystallised.
Most examples were prepared with a huge excess of ligand
although the rearrangement was also observed when equimolar
amounts were used.57 The occurrance of homoleptic
rearrangements are unpredictable.
The molecular ions of all the new products were observed in
the mass spectra (electron impact is the preferred method as
FAB samples are dissolved creating an opportunity for
homoleptic rearrangement18) indicating that these compounds
were all neutral monomers.
Fig. 3 Molecular structure of 6 showing only one of the two
molecules per asymmetric unit and the numbering scheme. Ellipsoids
are shown at the 50% probability level.
bonded to a C6F5-group and to the imine N-atom of a thiazole
ligand in 2 [N(1)–Au–C(5) 174.0(4)Њ] or the thione S-atom of
a thiazole-thione ligand in 5 [S(1)–Au–C(5) 178.7(4)Њ].
The ligands in these compounds are almost co-planar [angle
between the plane of the thiazole ring and the plane of the C6F5
ring = 10.0(2)Њ for 2 and 5.5(4)Њ for 5].
In 6 the ligands are coordinated to two different Au atoms,
one through the thione S-atom and the other through the amide
N-atom. Although the N(1)–Au–S(1) angle [169(3)Њ] in 6 is
slightly smaller than similar angles in 2 and 5, as a result of
the distortion due to the aurophilic interactions [3.02(4) Å]
of the four Au-atoms in the 16-membered ring of 6, the
coordination of the Au-atoms is still approximately linear. The
same distortion of the linear geometry of the Au-atoms was
Molecular structure
The molecular structures of 2, 5 and 6 are shown in Figs. 1–3
and selected bond lengths and angles in Table 1. The
approximately linear two-coordinate Au atoms in 2 and 5 are
observed for the tetramer [AuSCNHCH2CH2N]4 in which the
ligands, contrary to the situation in 6, are arranged homo-
leptically around each Au-atom.38
The ligands in 6, forming loops connecting the Au atoms
together, with two ligands above the four-membered Au ring
and two below it, remain planar (maximum deviations from
planarity for each ligand: 0.019(12), 0.032(13) 0.027(7),
0.012(10), 0.030(7), 0.024(7), 0.009(7), 0.010(10)Å). The four-
membered ring is folded (deviations from planarity in the
four-membered Au rings: 0.3731(3) Au11, Ϫ0.3625(3) Au12,
0.3599(3) Au13, Ϫ0.3705(3) Au14, Ϫ0.3210 (3) Au21, 0.3293(4)
Au22, Ϫ0.3310(4) Au23, 0.3227(3) Au24). This contrasts with
most previously published complexes containing similar
four-membered Au rings where the gold atoms form a planar
rhombus, although smaller distortions do occur in some
examples.26,41,58 The rings are no longer co-planar with each
other as they were in 2 and 5, although the thiazole rings lying
opposite each other are almost parallel [angles between the
planes of the two thiazole ligands above the four-membered Au
ring in the two molecules = 8.1(7), 4.9(7)Њ; angles between the
planes of the two thiazole rings lying below the four-membered
Au ring = 2.3(1)Њ, 4.4(1)]. The planes of the thiazole rings of
adjoining ligands, i.e. where the ligands are coordinated to a
common Au atom, are perpendicular to each other [angles
between 87.1(4) and 90.0(4)Њ]. Furthermore, the plane of each
ligand is twisted by about 20Њ with respect to the bond between
the two Au atoms it is coordinated to (Au–Au–N–S torsion
angles = Ϫ17.8(3), 19.6(3), Ϫ19.3(3), 18.6(3), Ϫ17.2(3), 18.5(3),
Ϫ14.6(3), 17.1(3)Њ). In literature examples containing compar-
able tetrameric complexes the bidentate ligands twist out of the
plane much less, with equivalent torsion angles no greater than
8.8Њ.58,38,59,60 Closer investigation shows that the reason for the
twisting is the formation of weak face-to-face arene–arene
interactions between the thiazole rings of opposing ligands
(distances between centroids of pairs of thiazole rings: 3.654,
3.569, 3.572, 3.618 Å).
Fig. 1 Molecular structure of 2 showing the numbering scheme and
intermolecular interaction with a neighbouring molecule. Ellipsoids are
shown at the 50% probability level.
Fig. 2 Molecular structure of 5 showing the numbering scheme and
intermolecular interaction with a neighbouring molecule. Ellipsoids are
shown at the 50% probability level.
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
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The Au–C(5) distances in 2 and 5 are similar and correspond
to the separations in [Au(C F ){CN(CH )C(CH )᎐CHS}]
᎐
3
6
5
3
[1.993(10) Å]61 and [Au(C F )(Ph C᎐NN᎐CPPh )] [1.992(6)
᎐
᎐
6
5
2
2
Å].62 The observed Au–N(1) distances in 2 and 6 are
comparable to Au–N distances in gold() amine {[Au-
{NH(CH2)4CH2}Cl],
Au–N
2.068(18)
Å26},
imine
{[Au(NC5H4CH3-3)(C6F5)], Au–N 2.066(5) Å,18 [Au(mmb)-
(PPh3)],
benzimidazole,
mmb
=
1-methyl-2-(methylthiomethyl)-1H-
2.080(6) and
Å19
Au–N
[Au{C᎐C[C᎐CN(CH ) CH O]SCH᎐CH}] , Au–N 2.065(8) Å9}
᎐
᎐
᎐
3
2
2
2
and amide {[Au(L)(PPh3)], HL = pyrazole, Au–N 2.024(7) Å,
HL = imidazole, Au–N 2.027(4) Å63} complexes. The Au–S(1)
distances in 5 and 6 are the same as the Au–S distances in
gold() thione {[AuCl(S᎐CSCH CH S)], Au–S 2.258(4) Å,31
᎐
2
2
[Au(HL)2]ClO4, HL = C5H5NS, Au–S 2.388(3) and 2.282(3)
Å33} and thiolate {[Au(2-Spym-4-NH2)(PEt3)], Au–S 2.291(3)
Å, [Au(2-Spym-4-NH2)(PPh3)], Au–S 2.308(1) Å, 2-Spym-
4-NH2
=
4-amino-2-pyrimidinethiol64}compounds. The
S(1)–C(1) distances in 5 and 6 are also similar to C᎐S distances
᎐
in similar complexes {[AuCl(S᎐CSCH CH S)], C(1)–S(1)
᎐
2
2
1.687(12) Å,31 [Au(HL)2]ClO4, HL = C5H5NS, C(1)–S(1)
1.719(11) and 1.727(11) Å33}. The Au–S(1)–C(1) angle in
6 [av. 108.3(1)Њ] is slightly enlarged [102.5(5)Њ in 5] as a
result of the rectangular aurophilic interactions. A reduction
in the same angle [92.3(4) and 92.6(4)Њ] is observed in
38
[AuSCNHCH2CH2N]4 as a result of rhombic Au ؒ ؒ ؒ Au
contacts. The bond lengths and angles in the C6F5-group
and thiazole units do not differ significantly from
those reported for [Au(C F )CN(CH )C(CH )᎐CHS],61
᎐
6
5
3
3
[CuCl{CN(CH )C(CH )᎐CHS}]65 and [Fe(η5-C5H5)(CO)2-
᎐
3
3
{CNHC(CH )᎐CHS}]CF SO ؒ0.5H O.66
᎐
3
3
3
2
The Au-atoms in 2 are involved in aurophilic interactions
[Au ؒ ؒ ؒ Au 3.345(1) Å] across the inversion centre at the centre
of the unit cell. The dihedral angle N–Au–Au–N is Ϫ180.0(4)Њ
thus placing the C6F5-unit of one molecule across the thiazole
unit of a neighbour. No aurophilic interactions are observed in
the crystal structure of 5 but hydrogen bonding and arene–
arene interactions seem to dominate lattice organisation. The
molecules in the crystal are arranged in sheets with the C6F5-
unit of one molecule across from the thiazole unit in the neigh-
bouring molecule as a result of the N–H ؒ ؒ ؒ F(1)Ј [3.203(15) Å]
and N–H ؒ ؒ ؒ F(2)Ј [3.310(17) Å] interactions. These inter-
actions lead one to speculate that the formation of the H-bond
in 5 may play a role in the deprotonation that results in the
formation of 6. In the above mentioned sheets the molecules are
arranged to form “dimers” with the molecules in the neighbour-
ing sheets. These “dimers” associate via intermolecular
Au ؒ ؒ ؒ S(1) contacts and are related by a crystallographic
centre of inversion. The atoms Au, S(1), AuЈ and S(1)Ј form a
parallelogram with the Au ؒ ؒ ؒ S(1)Ј edges 3.529(4) Å and an
Au ؒ ؒ ؒ AuЈ diagonal of 4.177(1) Å. This general pattern also
occurs in [2,6-(CH3)2C6H3NCAuSCN] [Au ؒ ؒ ؒ S(1)Ј 3.459(2)
and Au ؒ ؒ ؒ Au 3.983(1) Å] and [2,3,6-(CH3)3C6H2NCAuSCN]
[Au ؒ ؒ ؒ S(1)Ј 3.938(2), 3.719(2) and Au ؒ ؒ ؒ Au 3.397(1),
5.125(1) Å].40
Substitution reactions
Piperidine substituted the 4-methyl-2-methylsulfanylthiazole
ligand in 3 and tht in 1 in diethyl ether solution at 32 ЊC. The
addition of the imine, 4-methylthiazole, to a solution of 4 or
a solution of 5 did not yield any substitution products. The
addition of the thione to a solution of 2 in diethyl ether,
however, yielded 5.
As a result of these reactions and the preferred coordination
sites observed for 5 and 2, a new series in order of increasing
preference for the coordination of ligands to the soft Auϩ centre
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
2862

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can be proposed: tht < 4-methylthiazole and 4-methyl-2-
methylsulfanylthiazole < piperidine < 4-methyl-3H-thiazole-
2-thione. According to SHAB principles the series should
be: piperidine < 4-methylthiazole and 4-methyl-2-methyl-
sulfanylthiazole < tht < 4-methyl-3H-thiazole-2-thione.67
to Ϫ80 ЊC. Colourless crystals isolated at Ϫ80 ЊC melted before
reaching room temperature and the colourless oil obtained was
used without further purification (0.56g, 70%) (Found: C,
41.40; H, 4.79; N, 9.59%; C5H7NS2 requires C, 41.35; H, 4.86;
N, 9.64%); νmax/cmϪ1 3107s, 2981m, 2954m, 2923s, 2858m,
1527s, 1492w, 1437s, 1410s, 1371s, 1310m, 1292s, 1060m, 1037s,
993w, 961s, 637w, 928w, 873w, 845w, 804w, 715m (Nujol); δH
Conclusions
(CD3COCD3) 6.72 [1H, q, JHH = 1.2Hz, CH SC᎐NC(CH )᎐
᎐
᎐
3
3
The thiazolylthione, II, which contains three possible co-
ordination centres viz. thione, amine and endocyclic thioether,
substitutes tht in 1 to yield the thione coordinated compound 5.
Complex 5 converts very slowly in a CH2Cl2 solution by nucleo-
philic attack of C6F5 on the amine hydrogen to the unusual
Au() tetramer 6. The lablile tht ligand in 1 is easily substituted
by 4-methylthiazole (two coordination sites, imine N-atom and
thioether S-atom) to produce an imine complex 2. Since the
tht in 1 is substituted by 3-methylpyridine to form Au(C6F5)-
C(H )S], 2.66 [3H, s, CH SC᎐NC(CH )᎐C(H)S], 2.32 [3H, d,
᎐
᎐
3
3
JHH = 1.2Hz, CH SC᎐NC(CH )᎐C(H)S]; δ (CD3COCD3)
᎐
᎐
3
3
C
165.4 (s, NCS), 153.0 [s, C᎐NC(CH )], 112.6 [s, NC(CH )᎐
᎐
᎐
3
3
CHS], 17.0 (s, SMe), 16.8 [s, NC(CH )᎐CHS]; δ (CD COCD )
᎐
3
N
3
3
Ϫ63.8; m/z 145 (Mϩ), 112 (M Ϫ SH), 99 [HC᎐NC(CH )᎐
᎐
᎐
3
C(H)S], 86 [HC᎐NC(CH )᎐C(H)S Ϫ CH], 71(SCCCH ), 45
᎐
᎐
3
3
(HCS).
Preparation of S᎐CN(H)C(CH )᎐C(H)S II. Methylthiazol-2-
(N-3-methylpyridine),18 H2N(CH2)nNH2 to form Au(C6F5)-
᎐
᎐
3
yllithium was prepared as described above from 4-methyl-
thiazole (0.60 cm3, 6.1 mmol) and 1.6 mol dmϪ3 n-butyllithium
in hexane (3.80 cm3, 6.1 mmol). The mixture was stirred for
15 min at Ϫ80 ЊC before a suspension of S8 (0.192 g, 6.0 mmol)
in 10 ml of THF was added. The mixture was stirred for 2 h at
Ϫ70 ЊC prior to the addition of H2O (0.11 cm3, 6.1 mmol).
Stirring was continued at this temperature for 1 h, before
warming to room temperature. The solvent was removed in
vacuo. The residue was extracted with diethyl ether (2 × 60 cm3)
and the extract was filtered through SiO2 (10 g) and evaporated
to dryness in vacuo. The formed microcrystalline off-white
product (0.35 g, 43%) was washed with three portions (20 cm3)
of hexane to remove unreacted 4-methylthiazole and dried in
vacuo. Alternatively the product can be purified by flash column
chromatography72 on SiO2 (230–400 mesh) with diethyl ether–
hexane (1 : 4) as eluent. The last fraction contained 0.26 g (33%)
of the off-white product, mp 87 ЊC (decomp.) (Found: C, 36.57;
H, 3.88; N, 10.70%, C4H5NS2 requires C, 36.61; H, 3.84; N,
10.67%); νmax/cmϪ1 3200 (sh), 3106m, 3050w, 3019w, 2940m,
2920m, 2878m, 2712m, 1604s, 1466s, 1440sh, 1428s, 1384s,
1320s, 1247s, 1207m, 1146m, 1140m, 1123w, 1075s, 1044sh,
1063s, 988m, 944s, 919w, 838m, 781s, 741s, 679s (KBr);
27
NH2(CH2)nNH2 (n = 2 or 3), Ph C᎐N–N᎐CPh to form
᎐
᎐
2
2
Au(C F )(Ph C᎐NN᎐CPPh )59 or piperidine to form the
᎐
᎐
6
5
2
2
neutral monomeric complex 4 and the imine coordinated
ligand, I, in 3 is also substituted by piperidine, the following
substitution series in order of decreasing preference for ligands
on the C F Au centre (Auϩ soft acid) can be proposed: >C᎐S >
᎐
6
5
R NH (hard base) > >C᎐N– (borderline base) > RSR (soft
᎐
2
base). This series contradicts the expected order, >C᎐S > RSR
᎐
> >C᎐N– > R NH, according to the typical classification of
᎐
2
hard and soft acids and bases.67
The successful preparation and characterisation of 2, 3, 4
and the many other reported examples of Au() imine17–25,68 and
amine17,26–29 complexes as well as the observed substitution
reactions add to the evidence that soft Auϩ centres do form
stable imine and amine complexes.
Experimental
General
Reactions were carried out under argon using standard Schlenk
and vacuum-line techniques. Tetrahydrofuran and diethyl ether
were distilled under N2 from sodium diphenylketyl, CH2Cl2
from CaH2 and hexane from sodium. Butyllithium was pur-
chased from Merck and CH3SSCH3, 4-methylthiazole and
CF3SO3Me from Aldrich. Literature methods were used to
prepare [Au(C6F5)(SC4H8)] (1)69 from HAuCl4.70 Melting points
were determined on a Büchi 535 apparatus in unsealed capillary
tubes. Mass spectra (electron impact) were recorded on a
Finnigan Mat 8200 instrument, the infrared spectra, using KBr
pellets or NaCl disks, on a Perkin-Elmer 841 spectrometer and
NMR spectra on a Varian Gemini 2000, Varian 300 FT or
INOVA 600MHz spectrometer (1H NMR at 200/300/600 MHz
and 13C{1H} NMR at 50/75/151 MHz, δ reported relative to the
solvent resonance converted to TMS). 15N NMR (60.8 MHz,
CH3NO2 external reference) spectra (concentration 450 mg
in 0.75 cm3) were determined on an INOVA 600MHz spectro-
meter. Elemental analyses were carried out by the Department
of Chemistry, University of Cape Town, South Africa. The full
characterisation data of 1 is available electronically (ESI).†
δH (CD COCD ) 11.75 [1H, br s, S᎐CN(H )C(CH )᎐C(H)S],
᎐
᎐
3
3
6.41 [1H, q, JHH3= 1.2 Hz, S᎐CN(H)C(CH )᎐C(H )S], 2.21 [3H,
᎐
᎐
3
d, JHH = 1.2 Hz, S᎐CN(H)C(CH )᎐C(H)S]; δ (CD3COCD3)
᎐
᎐
3
C
191.2 (s, NCS), 139.3 [s, NC(CH )], 108.4 [s, NC(CH )᎐CHS],
᎐
3
3
13.5 [s, NC(CH3)]; δN (CD3COCD3) Ϫ185.3; m/z 131 (Mϩ), 99
(M Ϫ S), 86 (M Ϫ S Ϫ CH), 71 (SCCCH3), 45 (HCS).
Preparation of [Au(C F ){N᎐C(H)SC(H)᎐CCH }] 2. The
᎐
᎐
6
5
3
addition of 4-methylthiazole (0.15 cm3, 1.6 mmol) to a solution
of 1 (0.452 g, 1.6 mmol) in diethyl ether (40 cm3) and stirring for
1.5 h at room temperature produces a clear solution of 2. The
solution was reduced to dryness in vacuo, the residue extracted
with diethyl ether (2 × 30 cm3), the extract was filtered through
anhydrous MgSO4 (18 g) and the filtrate again reduced to
dryness in vacuo. Colourless 2 (0.73g, 99%) was recrystallised by
layering a diethyl ether solution of 2 with hexane. Needle-like
crystals suitable for a crystal structure determination were
obtained, mp 58 ЊC (decomp.) (Found: C, 25.89; H, 1.11; N,
3.00%, C10H5AuF5NS requires C, 25.93; H, 1.09; N, 3.02%);
νmax/cmϪ1 3137m, 1640m, 1612m, 1541s, 1501s, 1460s, 1453s,
1438s, 1420s, 1380m, 1356m, 1311m, 1279w, 1252w, 1227m,
1144m, 1113w, 1070m, 1055s, 1001m, 985s, 948s, 884s, 818s,
799s, 742s, 717w, 704w, 667w (KBr); δH (CD3COCD3) 9.55 [1H,
Preparation of CH SC᎐NC(CH )᎐C(H)S I. Methylthiazol-2-
᎐
᎐
3
3
yllithium71 was prepared by the addition of 4-methylthiazole
(0.50 cm3, 5.5 mmol) to 1.6 mol dmϪ3 n-butyllithium in hexane
(3.10 cm3, 5.0 mmol) in THF (20 cm3) at Ϫ80 ЊC, and was
stirred at Ϫ80 ЊC for 15 min before CH3SSCH3 (0.40 cm3, 5.4
mmol) was added. Stirring was continued at this temperature
for 1 h before warming to room temperature. The solvent was
removed in vacuo. The residue was extracted with diethyl ether
(2 × 60 cm3) and the extract was filtered through n-alumina
(15 g) and evaporated to dryness in vacuo. The clear oil was
diluted with 10 ml of diethyl ether and the mixture was cooled
d, JHH = 2.1 Hz, HC᎐NC(CH )᎐C(H)S)], 7.81 [1H, dq, J
=
=
᎐
᎐
3
HH
1.2 Hz, JHH = 2.1 Hz, HC᎐NC(CH )᎐C(H )S], 2.68 [3H, d, J
᎐
᎐
3
HH
1.2 Hz, HC᎐NC(CH )᎐C(H)S]; δ (CD3COCD3) 160.8 (s,
᎐
᎐
3
C
NCS), 153.2 [s,NC(CH3)], 150.2 (ddm, JCF = 231.4 Hz, JCF
=
23.5 Hz, AuCCFCFCFCFCF), 139.2 (dm, JCF = 244.5 Hz,
AuCCFCFCFCFCF), 137.4 (dm, JCF = 249.3 Hz, AuC-
CFCFCFCFCF), 118.7 (tm, JCF
=
52.7 Hz, AuC-
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
2863

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CFCFCFCFCF), 118.2 [s, NC(CH )᎐CHS], 17.3 [s, NC(CH )];
δF (CD3COCD3) Ϫ112.9 (2F, dd, JFF = 9.3 Hz, JFF = 19.99 Hz,
1559s, 1542w, 1508s, 1459s, 1455s, 1425s, 1391m, 1358m,
1325m, 1278w, 1260w, 1144m, 1114w, 1097m, 1068s, 1056s,
1003m, 951s, 829w, 794s (KBr); δH (CD3COCD3) 6.94 [1H, s,
᎐
3
3
AuCCFCFCFCFCF), Ϫ158.7 (1F, t, JFF 19.9 Hz,
=
AuCCFCFCFCFCF), Ϫ161.7 (2F, dt, JFF = 9.3, JFF = 19.9 Hz,
AuCCFCFCFCFCF); δN (CD3COCD3) Ϫ108.3; δN (4-methyl-
thiazole) (CD3COCD3) Ϫ49.1; m/z 463 (Mϩ), 364 [M Ϫ
S᎐CN(H)C(CH )᎐C(H )S], 5.27 [1H, brs, S᎐CN(H )C(CH )᎐
᎐ ᎐ ᎐ ᎐
3 3
C(H)S] 2.39 [3H, s, S᎐CN(H)C(CH )᎐C(H)S]; δ (CD COCD )
᎐
᎐
3
C
3
3
186.4 (s, NCS), 143.2 [s,NC(CH3)], 149.6 (ddm, JCF = 203.7 Hz,
JCF = 24.6 Hz, AuCCFCFCFCFCF), 139.1 (dm, JCF = 243.8
Hz, AuCCFCFCFCFCF), 137.7 (dm, JCF = 250.2 Hz,
AuCCFCFCFCFCF), 128.6 (tm, JCF = 57.1 Hz, AuC-
HC᎐NC(CH )᎐C(H)S], 334 (C F ), 296 (M Ϫ C F ), 265
᎐
᎐
3
12 10
6
5
[F C C᎐NC(CH )᎐C(H)S], 99 [HC᎐NC(CH )᎐C(H)S], 71
᎐
᎐
᎐
᎐
3
5
6
3
(CH3CCS), 45 (HCS).
CFCFCFCFCF), 112.8 [s, NC(CH )᎐CHS], 13.7 [s, NC(CH )];
᎐
3
3
δF (CD3COCD3) Ϫ112.8 (2F, dd, JFF = 9.3 Hz, JFF = 19.99 Hz,
Preparation of [Au(C F ){N᎐C(SCH )SC(H)᎐CCH }] 3. This
᎐
᎐
6
5
3
3
AuCCFCFCFCFCF), Ϫ159.0 (1F, t, JFF 19.9 Hz,
=
product was prepared in the same way as 2 from 4-methyl-2-
methylsulfanylthiazole I (0.314 g, 2.2 mmol) and 1 (0.979 g, 2.2
mol). Colourless 3 (1.00 g, 91%) was obtained, mp 68 ЊC
(Found: C, 25.90; H, 1.42; N, 2.76%, C11H7AuF5NS requires C,
25.94; H, 1.39; N, 2.75%); νmax/cmϪ1 3128m, 2917m, 1635m,
1609m, 1558s, 1540s, 1501s, 1458s, 1439s, 1394m, 1378m,
1356m, 1299m, 1253m, 1146vw, 1110s, 1056s, 1014w, 949s,
799s, 725m (KBr); δH (CD3COCD3) 7.44 [1H, q, JHH = 1.2 Hz,
AuCCFCFCFCFCF), Ϫ161.4 (2F, m, AuCCFCFCFCFCF);
δN (CD COCD ) Ϫ178.6; m/z 495 (Mϩ), 364 [M Ϫ CH SC᎐
᎐
3
3
3
NC(CH )᎐C(H)S], 328 [AuS᎐CN(H)C(CH )᎐C(H)S], 262
᎐
᎐
᎐
3
3
[{SCN(H)C(CH )᎐C(H)S} ], 246 [{SCN(H)C(CH )᎐C(H)S}
᎐
᎐
3
2
3
2
Ϫ CH ], 230 [S{CNC(CH )᎐C(H)S} ], 215 [S{CNC(CH )᎐
᎐
᎐
3
3
3
2
C(H)S} Ϫ CH ], 168 (C F H), 131 [S᎐CN(H)C(CH )᎐C(H)S],
᎐
᎐
3
2
3
6
5
99 [HC᎐NC(CH )᎐C(H)S], 71 (CH CCS), 45 (HCS).
᎐
᎐
3
3
CH SC᎐NC(CH )᎐C(H )S], 2.83 [3H, s, CH SC᎐NC(CH )᎐
᎐
3
᎐
᎐
᎐
3
3
3
Preparation of [Au{S᎐CNC(CH )᎐C(H)S}] 6. 1H NMR
C(H)S], 2.55 [3H, d, JHH = 1.2 Hz, CH SC᎐NC(CH )᎐C(H)S];
᎐
᎐
3
3
᎐
᎐
3
4
spectra of a solution of 5 (15 mg, 0.03 mmol) in 0.75 cm3 of
CD2Cl2 were recorded over 20 days. Insoluble yellow micro-
crystalline 6 precipitated (9 mg, 23%). Crystals suitable for a
crystal structure determination were obtained from a solution
of 5 in CH2Cl2 layered with hexane after several weeks at 4 ЊC,
mp 128 ЊC (decomp.) (Found: C, 14.78; H, 1.05; N, 4.20%,
C16H16Au4N4S8 requires C, 14.68; H, 1.23; N, 4.28); νmax/cmϪ1
3102w, 3075m, 3012vw, 2986vw, 2968vw, 1548s, 1425m, 1376w,
1355s, 1285s, 1143m, 1078s, 931m, 848m, 754w, 727m, 713s
(KBr).
δC (CD3COCD3) 176.9 (s, NCS), 153.2 [s,NC(CH3)], 151.6
(ddm, JCF = 226.3 Hz, JCF = 23.5 Hz, AuCCFCFCFCFCF),
139.2 (dm, JCF = 244.1 Hz, AuCCFCFCFCFCF), 137.5 (dm,
JCF = 249.3 Hz, AuCCFCFCFCFCF), 119.7 (tm, JCF = 53.1 Hz,
AuCCFCFCFCFCF), 116.1 [s, NC(CH )᎐CHS], 17.8 (SCH ),
᎐
3
3
17.5 [s, NC(CH3)]; δF (CD3COCD3) Ϫ112.9 (2F, dd, JFF = 9.3
Hz, JFF = 19.99 Hz, AuCCFCFCFCFCF), Ϫ158.8 (1F, t, JFF
=
19.9 Hz, AuCCFCFCFCFCF), Ϫ161.7 (2F, m, AuC-
CFCFCFCFCF); δN (CD3COCD3) Ϫ121.6; m/z 509 (Mϩ), 364
[M Ϫ CH SC᎐NC(CH )᎐C(H)S], 334 (C F ), 296 [AuN᎐
᎐
᎐
᎐
3
3
12 10
C(H)SC(H)᎐CCH ], 265 [F C C᎐NC(CH )᎐C(H)S], 145
᎐
᎐
᎐
3
3
5
6
[CH SC᎐NC(CH )᎐C(H)S], 112 [CH C᎐NC(CH )᎐C(H)S], 99
Substitution reactions. All substitution reactions were per-
formed in the same way.
᎐
᎐
᎐
᎐
3
3
3
3
[HC᎐NC(CH )᎐C(H)S], 86 [NC(CH )CHS], 71 (CH CCS), 45
᎐
᎐
3
3
3
(HCS).
(1) A solution of 3 (0.279 g, 0.55 mmol) in diethyl ether
(40 cm3) was treated with piperidine (0.054 cm3, 0.55 mmol).
The reaction mixture was stirred for 2 h at 32 ЊC, filtered to
remove solids and evaporated to dryness in vacuo. The products
and their yields (69.7% of 4, 13.8% of I and 16.5% of 3) were
determined by 1H NMR spectroscopy.
2) Reagents: 4 (0.408 g, 0.91 mmol) and 4-methylthiazole
(0.08 cm3, 0.91 mmol). Products: 1 : 1 4 and 4-methylthiazole.
3) Reagents: 5 (0.322 g, 0.65 mmol) and 4-methylthiazole
(0.06 cm3, 0.65 mmol). Products: 1 : 1 5 and 4-methylthiazole.
4) Reagents: 3 (0.276 g, 0.60 mmol) and II (0.078 g,
0.60 mmol). Products: 1 : 1 5 and 4-methylthiazole.
Preparation of [Au(C6F5){N(H)CH2(CH2)3CH2}] 4. Com-
pound 4 was prepared in the same way as 2 from piperidine
(0.25 cm3, 2.5 mmol) and 1 (1.152 g, 2.5 mmol). Colourless 4
was recrystallised from CH2Cl2 layered with hexane (1.06 g,
92%), mp 115 ЊC (decomp.) (Found: C, 29.38; H, 2.51; N,
3.09%, C11H11AuF5N requires C, 29.41; H, 2.47; N, 3.12%);
νmax/cmϪ1 3216m, 2946s, 2937m, 2928m, 2884m, 1631s, 1603m,
1548w, 1497s, 1451s, 1438s, 1417m, 1368m, 1355m, 1340w,
1310m, 1304w, 1285m, 1252s, 1181s, 1158w, 1105s, 1095m,
1053s, 1035m, 1021vw, 1008w, 950s, 867s, 871m, 802s, 745vw,
715w, 632w, 604w, 667w, 494m (KBr); δH (CD3COCD3) 5.17
[1H, brs, NH ], 3.21 [4H, m, α-CH2], 1.96 [2H, m, β-CHeHa],
1.72 [1H, m, γ-CHeHa], 1.68 [2H, m, β-CHeHa], 1.45 [1H, m,
X-Ray crystal structure determinations
Crystal structure determination of 2. C10H5AuF5NS, M =
463.18, monoclinic, space group P21/a, a = 7.5140(15), b =
21.352(3), c = 8.1590(13) Å, β = 115.528(17)Њ, U = 1181.2(4) Å3,
T =293 K, Z = 4, µ(Mo-Kα) = 12.67 mϪ1, 3443 reflections
measured, 2521 unique (Rint = 0.055) which were used in
all calculations. The final wR(F 2) was 0.043 (all data). The
diffraction data were collected on an Enraf-Nonius CAD-4F
diffractometer with graphite-monochromated Mo-Kα radi-
ation (λ = 0.71073 Å) using ω–2θ scans (Enraf-Nonius CAD-4
software73). Emperical absorption corrections were performed
using psi scans.74 The structure of 2 was solved by the heavy
atom method. All non-H atoms were eventually refined with
anisotropic displacement parameters. The positions of some
of the H atoms could be found from difference maps. Their
positions were therefore calculated in ideal positions. In the
final cycles of refinement the H atoms were included with equal
and constant isotropic displacement parameters and no
positional parameters were refined. For structure solution
and refinement the XTAL 3.474 computing system was used.
Figures were generated utilizing Ortep3 for Windows;75
displacement ellipsoids are at the 50% probability level.
γ-CHeHa]; δC (CD3COCD3) 149.9 (ddm, JCF = 227.7 Hz, JCF
23.7 Hz, AuCCFCFCFCFCF), 138.9 (dm, JCF = 230.8 Hz,
AuCCFCFCFCFCF), 137.3 (dm, JCF = 225.1 Hz, AuC-
=
CFCFCFCFCF), 120.0 (tm, JCF
=
55.0 Hz, AuC-
CFCFCFCFCF), 52.3 [s, α-CH2], 27.0 [s, β-CH2], 24.2 [s,
γ-CH2]; δF (CD3COCD3) Ϫ116.1 (2F, m, AuCCFCFCFCFCF),
Ϫ161.8 (1F, t, JFF = 19.9 Hz, AuCCFCFCFCFCF), Ϫ164.2 (2F,
m, AuCCFCFCFCFCF); δN (CD3COCD3) Ϫ338.3; δN (piper-
idine) (CD3COCD3) Ϫ342.5; m/z 449 (Mϩ), 364 [M Ϫ
HNCH2(CH2)3CH2], 334 (C12F10), 296 (C10H5F9), 265 (C9H5F8),
168 (C6F5), 99 (C3H5F3), 85 [HNCH2(CH2)3CH2], 84
[NCH2(CH2)3CH2], 56 [(CH2)4], 28 (C2H6).
Preparation of [Au(C F ){S᎐CN(H)C(CH )᎐C(H)S}] 5.
᎐
᎐
3
6
5
Compound 5 was prepared in the same way as 2 from 4-methyl-
3H-thiazole-2-thione (0.259 g, 2.0 mmol) and 1 (0.867 g, 1.9
mmol). Light yellow 5 was recrystallised from CH2Cl2 layered
with hexane (0.93 g, 97%), mp 90 ЊC (decomp.) (Found: C,
24.28; H, 1.05; N, 2.79%, C10H5AuF5NS2 requires C, 24.25; H,
1.02; N, 2.83); νmax/cmϪ1 3368s, (N–H) 3085m, 1640m, 1597s,
D a l t o n T r a n s . , 2 0 0 3 , 2 8 5 9 – 2 8 6 6
2864

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15 J. Vicente, M-T. Chicote and C. Rubio, Chem. Ber., 1996, 129, 327;
Crystal structure determination of 5. C10H5AuF5NS2, M =
495.24, monoclinic, space group P21/a, a = 7.4858(5), b =
12.2944(9), c = 13.5153(10) Å, β = 92.933(2)Њ, U = 1242.23(15)
Å3, T = 293(2) K, Z = 4, µ(Mo-Kα) = 12.223 mϪ1, 3901 reflec-
tions measured, 1846 unique (Rint = 0.0814) which were used in
all calculations. The final wR(F 2) was 0.1854 (all data). The
diffraction data were collected on a Nonius Kappa CCD
diffractometer with graphite monochromated Mo-Kα radiation
(λ = 0.71073 Å) using ꢀ and ω scans to fill the Ewald sphere
(Nonius COLLECT76). Data reduction was performed using
DENZO.77 Empirical absorption corrections were performed
using SCALEPACK.77 The initial structure solution was found
using direct methods, while the rest of the atomic positions
were found from difference Fourier maps. All non-hydrogen
atoms were refined anisotropically by full-matrix least squares
methods. The hydrogen atoms were fixed in calculated
positions. All calculations were performed using SHELX-9778
within the WINGX package.79 Figures were generated utilizing
Ortep3 for Windows;75 displacement ellipsoids are at the 50%
probability level.
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Crystal structure determination of 6. C32H32Au8N8S16, M =
1308.67, triclinic, space group P1, a = 11.6203(2), b =
¯
14.5242(2), c = 16.0147(2) Å, α = 88.2480(10), β = 89.3080(10),
γ = 81.5490(10)Њ, U = 2672.21(7) Å3, T = 173(2) K, Z = 2, µ(Mo-
Kα) = 22.532 mϪ1, 15382 reflections measured, 7405 unique
(Rint = 0.0526) which were used in all calculations. The final
wR(F 2) was 0.1419 (all data). Other details are the same as for
the structural determination of 5. A small amount of disorder
was observed, and could not be correctly modelled.
CCDC reference numbers 207317–207319.
See http://www.rsc.org/suppdata/dt/b3/b303625a/ for crystal-
lographic data in CIF or other electronic format.
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Acknowledgements
We thank the Volkswagen Stiftung and National Research
Foundation, South Africa for financial support and AngloGold
for the generous loan of gold.
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