Syntheses, structures and characterization of heterobimetallic compounds [Et4N]2[(MS4)Ag8(SBu t)8](M = W, Mo) and {[Et4N][WOS 3Ag2(S2COEt)]}n

Article abstract of DOI:10.1016/j.poly.2004.12.011

Three new M/Ag/S heterobimetallic compounds [Et₄N] ₂[(MS₄)Ag₈(SBu^t)₈] (1a, M = W; 1b, M = Mo) and {[Et₄N][WOS₃Ag₂(S ₂COEt)]}_n (2) have been prepared from the reactions of [MO_nS_4-n]^2- (M = W, Mo; n = 0-1) with AgSBu^t or AgS₂COEt. Single crystal structural studies show that the compound 1a contains a [WS₄]^2- dianion encapsulated in a neutral octanuclear (AgSBu^t)₈ cage via weak Ag?S(WS₄) interactions. In compound 2, butterfly WOS ₃Ag₂ fragments are connected via bidentate bridging [S₂COEt]^- ligands to give a chain polymeric anion. These compounds are fully characterized by IR, UV-vis and microanalyses. Compound 2 is the first W/Ag/S polymer with bidentate thiolato linkages.

Full text of DOI:10.1016/j.poly.2004.12.011

Polyhedron 24 (2005) 481–485
www.elsevier.com/locate/poly
Syntheses, structures and characterization of
heterobimetallic compounds [Et N] [(MS )Ag (SBu ) ]
t
4
2
4
8
8
(
M = W, Mo) and {[Et N][WOS Ag (S COEt)]}
2
4
3
2
n
Jian-Rong Li , Zhi-Hua Li , Shao-Wu Du a,*, Xin-Tao Wu a
a,b
a
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, PR China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, PR China
Received 23 November 2004; accepted 3 December 2004
Available online 1 February 2005
Abstract
t
Three new M/Ag/S heterobimetallic compounds [Et N] [(MS )Ag (SBu ) ] (1a, M = W; 1b, M = Mo) and {[Et N][WOS Ag -
4
2
4
8
8
4
3
2
2ꢀ
t
(M = W, Mo; n = 0–1) with AgSBu or AgS COEt. Single
( (2) have been prepared from the reactions of [MO
crystal structural studies show that the compound 1a contains a [WS
S
2
COEt)]}
n
n
S
4ꢀn
]
2
2
ꢀ
t
4
]
dianion encapsulated in a neutral octanuclear (AgSBu )
8
cage via weak Agꢁ ꢁ ꢁS(WS ) interactions. In compound 2, butterfly WOS Ag fragments are connected via bidentate bridging
4
3
2
ꢀ
[S COEt] ligands to give a chain polymeric anion. These compounds are fully characterized by IR, UV–vis and microanalyses.
2
Compound 2 is the first W/Ag/S polymer with bidentate thiolato linkages.
Ó 2005 Elsevier Ltd. All rights reserved.
Keywords: Tetrathiotungstate; Tetrathiomolybdate; Silver (I) compounds; W/Ag/S polymer; Crystal structure; Monocyclic silver alkanethiolates
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1
. Introduction
AgX ðX ¼ NO ; Cl ; Br ; I ; CN ; SCN Þ to react
3
2
ꢀ
with [W(Mo)O S
n
]
(n = 0–2), often using transition
4ꢀn
The syntheses and characterization of compounds
containing thioanions of molybdenum (VI) or tungsten
metal complexes, rare earth metal complexes or alkali
metal complexes as cations. These reactions resulted in
the formation of a large number of W(Mo)/Ag/S com-
pounds, such as a zigzag chain with unequal steps:
[W Ag S Æ 2Ca(DMSO) ] [12], a loose helical chain:
[W Ag S Æ Nd(DMSO) ] [13], a single-stranded helical
chain: [W Ag S Æ La(DMAC)(H O) Æ (DMAC) ] [14],
a hanging ladder-like polymer chain: [W Ag S Æ Ca
(DEAC) ] [15] and an one-dimensional linear chain:
[WS Ag Æ Li(DMF) ] [16]. However, reactions employ-
2
ꢀ
(
VI), such as [W(Mo)OnS
]
(n = 0–2), have been
4ꢀn
widely studied due to their relevance to biological sys-
tems, interesting physicochemical properties and versa-
tile structural types [1–8]. In particular, the study of
compounds containing these multidentate chelating
ligands with Ag(I) has continued to attract attention be-
cause of their high tendency to form Ag–S bonds [9–16].
A common synthetic strategy for the preparation of
W(Mo)/Ag/S compounds is to employ neutral species
4
4
16
6 n
3
3
12
8 n
3
3
12
2
3
4 n
4
6 16
6
n
4
4 n
ing AgSR or AgS COEt as a silver source to react with
2
thiomolybdates or thiotungstates have not been
reported.
Recently we have reported several W(Mo)/Cu/S hete-
robimetallic clusters prepared from the reactions be-
*
Corresponding author. Tel./fax: +86 591 83709470.
E-mail address: swdu@ms.fjirsm.ac.cn (S.-W. Du).
2
ꢀ
t
(n = 0–1) and CuSBu or
tween [W(Mo)OnS
]
4ꢀn
0
277-5387/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.12.011

482
J.-R. Li et al. / Polyhedron 24 (2005) 481–485
Cudtp (dtp = diethyldithiophosphate), such as [Et N] -
4
[Et N] [MoS ] (0.24 g, 0.5 mmol) was used instead of
4 2 4
2
t
ꢀ1
[
[
[
{MOS } Cu (l-S-Bu ) ] (double butterfly), [Et N]-
[Et N] [WS ]. IR (KBr pellet, cm ): m(Mo–S) 458 (s).
4 2 4
3
2
4
2
4
t
ꢀ3
ꢀ1
ꢀ1
{MOS } Cu (l-S-Bu ) ] (double incomplete cubane),
UV–vis (MeCN) kmax/nm (10 emax/M cm ):
243(23.6), 324(22.4), 486(12.4). Anal. Calc. for 1b: C,
27.97; H, 5.48; N, 1.36. Found: C, 27.70; H, 5.28; N,
1.51%.
3
2
6
3
t
t
Bu N][{MOS } Cu (l-S-Bu ) (l -S-Bu )] (triple incom-
4
3 3
9
3
3
plete cubane) [17], [Bu N] [{MoOS } Cu (dtp) ]
4
2
3 4
12
6
(
(
closed double cubane) and [Et N][{WS Cu }(dtp) ]
4 4 4 3
1-D polymer) [18]. To expand our studies to the
W(Mo)/Ag/S system, we have investigated the reactions
2.5. Synthesis of {[Et N][WOS Ag (S COEt)]} (2)
n
4
3
2
2
2
ꢀ
(n = 0–1) with AgSBu and AgS -
2
t
of [W(Mo)OnS
]
4ꢀn
COEt. Herein we report three new compounds prepared
t
from these reactions, namely, [Et N] [(MS )Ag (SBu ) ]
A solution of [Et N] [WOS ] (0.28 g, 0.5 mmol) and
4 2 3
AgS COEt (0.23 g, 1.0 mmol) in 6 mL of DMF was stir-
2
4
2
4
8
8
(
COEt)] (2).
1a, M = W; 1b, M = Mo) and [Et N][WOS Ag (S -
4
red for 1 h. A small amount of black precipitate was re-
moved by filtration and the filtrate was slowly
evaporated in an i-PrOH atmosphere to give yellow
3
2
2
n
ꢀ
1
crystals of 2 (yield 23%). IR (KBr pellet, cm ): m(W–
2
. Experimental
S ) 455 (m), 435 (s), 417 (m), m(W–O) 921 (vs). UV–
br
ꢀ
3
ꢀ1
ꢀ1
vis (MeCN) kmax/nm (10 emax/M cm ): 309(8.1),
353(sh)(4.1), 408(sh)(2.6). Anal. Calc. for compound 2:
C, 17.30; H, 3.28; N, 1.83. Found: C, 17.32; H, 3.09;
N, 1.96%.
2
.1. General procedures
All experiments were carried out in air. Starting
materials [Et N] [WS ], [Et N] [MoS ] and [Et N] -
4
2
4
4
2
4
4
2
[
Complex AgSBu was synthesized by adding AgNO
WOS ] were prepared by published procedures [19].
t
2.6. X-ray crystallography
3
3
t
to HSBu in ethanol. Complex AgS COEt was synthe-
Intensity data for the two compounds were collected
at 293(2) K on a Rigaku Mercury CCD area-detector
diffractometer with a graphite monochromator utilizing
2
sized by the reaction of AgNO with potassium ethylx-
3
anthate in aqueous solution. Other chemicals were
obtained from commercial sources and used without
further purification.
˚
Mo Ka radiation (k = 0.71073 A). The structures were
solved by direct methods using SHELXS-97 [20]. Aniso-
tropic displacement parameters were refined for all
non-hydrogen atoms. The organic hydrogen atoms were
2
.2. Physical measurements
˚
generated geometrically (C–H, 0.96 A). The crystallo-
graphic data are summarized in Table 1.
Infrared spectra were recorded on a Nicolet Magna
50 FT-IR spectrophotometer as KBr pellets in the
7
ꢀ
1
range 4000–400 cm . Electronic spectra were recorded
on a Lambda 35 spectrophotometer in MeCN solution
between 600 and 200 nm. Elemental analyses were per-
formed in the Elemental Analysis Laboratories at our
institute.
Table 1
Crystallographic data for compounds 1a and 2
1a
2
Empirical formula
Formula weight
Crystal system
Space group
8 2 11 25 2 2 5
C48H112Ag N S12W C H Ag NO S W
2148.93
monoclinic
C2/c
763.21
monoclinic
P2 /n
t
.3. Synthesis of [Et N] [(WS )Ag (SBu ) ] (1a)
2
4
2
4
8
8
1
˚
a (A)
39.29(5)
14.83(3)
27.66(3)
106.434(6)
15,460(4)
8
11.467(3)
11.820(3)
16.564(4)
106.613(1)
2151.4(9)
4
t
Complex AgSBu (0.20 g, 1.0 mmol) was added to a
DMF solution (5 mL) of [Et N] [WS ] (0.29 g,
0
3
˚
b (A)
c ( A˚ )
4
2
4
.5 mmol). After stirring at room temperature for
0 min, the resulting orange–red solution was filtered.
The filtrate was allowed to slowly evaporate in an
i-PrOH atmosphere to afford 1a as red crystals. Yield:
4% (based on AgSBu ). IR (KBr pellet, cm ): m(W–S)
45 (s). UV–vis (MeCN) kmax/nm (10 emax/M cm ):
91(37.3), 407(16.2). Anal. Calc. for 1a: C, 26.83; H, 5.25;
b (°)
˚
3
V (A )
Z
F(0 0 0)
8448
1.846
3.815
1448
2.356
ꢀ3
)
q
calc (g cm
t
ꢀ1
ꢀ
1
5
4
2
l (mm
h range (°)
Data collected
)
7.624
3.07–27.48
16181
ꢀ
3
ꢀ1
ꢀ1
2.02–22.50
31919
9950 (0.0430)
Unique data (Rint
)
4905 (0.0232)
4741
199
N, 1.30. Found: C, 26.70; H, 5.02; N, 1.39%.
Observed data [I > 2r (I)] 9209
Number of parameters
2
640
1.164
t
.4. Synthesis of [Et N] [(MoS )Ag (SBu ) ] (1b)
2
Goodness-of-fit on F
R
1.058
0.0210, 0.0526
4
2
4
8
8
a,b
1
, wR
2
[I > 2r (I)]
0.0721, 0.1722
P
P
a
Dark crystals of 1b were obtained in a 50% yield
t
based on AgSBu ) by a similar way as for 1a except
R ¼ kF j ꢀ j F k= j F j.
1
o
c
o
P
P
b
2
2
2
2
2 0:5
(
wR2 ¼ ½ wðF o ꢀ F c Þ = wðF o Þ ꢂ
.

J.-R. Li et al. / Polyhedron 24 (2005) 481–485
483
3
. Results and discussion
3.3. Description of the crystal structure of
t
[
Et N] [(WS )Ag (SBu ) ] (1a)
4 2 4 8 8
3
.1. Synthesis
The complex of compound 1a consists of an octanu-
2ꢀ
t
The polymeric complex AgSBu was not soluble in
t
clear monocyclic [Ag(SBu )] ring, a [WS ] anion and
8
4
+
two [Et N] cations. A view of the anion of compound
DMF but it dissolved rapidly in the presence of the tet-
rathiotungstate anion to form a cyclic octanuclear Ag
4
1a is shown in Fig. 1 and selected bond lengths and an-
gles are summarized in Table 2. In the structure of the
anion, eight Ag atoms construct a distorted cage with
t
compound 1a. The ratio of AgSBu to [Et N] [WS ]
did not change the nature of the product. However,
4
2
4
t
the reaction with 2 equiv. of AgSBu gave a better yield
several Ag planes, e.g. atoms Ag2, Ag5, Ag6, Ag9 al-
4
˚
most lie in a plane (mean deviation: 0.1668 A) while
t
of 1a. The reaction between [Et N] [MoS ] and AgSBu
4
2
4
˚
the rest are also coplanar (mean deviation: 0.1191 A).
by the same method afforded [Et N] [(MoS )Ag -
4
2
4
8
t
SBu ) ] (1b), a Mo analogue of 1a. The structure of
(
It is noted that this distorted cage structure is different
from those reported for the octanuclear monocyclic
AgSR ring compounds. For example, the octanuclear
8
1
b was confirmed by IR, microanalyses and the X-ray
diffraction study. The X-ray crystal data was not good
enough and only a raw structure could be obtained.
1
2ꢀ
cluster [Ag8 (mba)10] (H2 mba = 2-mercaptobenzoic
acid) is composed of two butterfly type Ag S cones
2
The reactions between [W(Mo)S4] or [W(Mo)OS3]
ꢀ
2ꢀ
4
4
and AgS COEt often gave rise to a large amount of
2
[28] and the complexes (Ag SCMeEt ) (PPh ) [29,30],
8 2 8 3 2
Ag S precipitation or insoluble solids. However, a poly-
2
[AgSCH(SiMe)2]8 [31] and {[Ag(SC H -o-SiMe )] }
6 4 3 4 2
meric W/Ag/S cluster 2 was successfully isolated from
[32] all show bis-cyclic structures. In the Ag ring, adja-
8
2
the reaction between [Et N] [WOS ] and AgS COEt
ꢀ
cent Ag atoms are connected through one bridging –
t
SBu ligand. The distance between an Ag atom and
4
2
3
2
in moderate yield under appropriate conditions.
t
the bridging –SBu ranges from 2.380(5) to 2.453(5) A,
˚
which is similar to the corresponding values in [Ag
1
8
2ꢀ
3
.2. Infrared and UV–vis spectra
(mba) ]
1
[28], (Ag SCMeEt ) (PPh ) [29,30],
8 2 8 3 2
0
[
[32]. There are weak secondary metal–metal interactions
AgSCH(SiMe)2]8 [31] and {[Ag(SC H -o-SiMe )] }
6 4 3 4 2
ꢀ
1
The 400–520 cm region of the IR spectra of hetero-
2
ꢀ
thiometallic cluster compounds containing [W(Mo)S4]
between the adjacent Ag atoms (Ag3ꢁ ꢁ ꢁAg4: 3.022(6);
˚
moieties has proven to be valuable in studying their
structural characteristics [1,21–23]. It has been observed
that the m(M–S) frequency decreases on increasing the
number of coordinated hetero-metal atoms (M = W,
Mo) [22–24]. The spectra of compounds 1a and 1b exhi-
bit a single strong band at 445 and 458 cm , which may
be contributed to the m(W = S) and m(Mo = S) stretching
vibrations, respectively. Comparing these values with
Ag5ꢁ ꢁ ꢁAg6: 3.184(4) A), which are intermediate between
˚
the Ag–Ag separation found in metallic silver (2.88 A)
[33] and twice the van der Waals radii for silver
˚
(3.44 A) [34,35], and also are comparable to those found
2ꢀ
in other related compounds [28–32]. A [WS4] fragment
ꢀ
1
C20
C23
C18
C24
C21
ꢀ
1
C26
the corresponding values for [Et N] [WS ] (458 cm )
ꢀ
and [Et N] [MoS ] (470 cm ) reveals some red shift to
4
2
4
C17
1
C19
C22
Ag7
S11
4
2
4
Ag8
C27
C31
low frequencies, indicating weakening of the M = S
bonds as a result of interactions with Ag atoms. The
spectra of compound 2 exhibits a very strong band at
C25
S9
C14
S10
S4
Ag6
Ag9
C28
C29
ꢀ
1
9
21 cm , which is ascribed to the m(W = O) vibrations,
1
and the bands at 455, 435 and 417 cm were due to the
ꢀ
W1
C16
C11
C13 S8
S1
C32
C30
vibrations of m(W-l -S) and m(W-l -S), respectively [25].
S3
S12
2
3
It is apparent that the UV–vis spectra of the clusters
are characterized by the three strong absorptions (m , m ,
m3) which are attributable to the S–W(Mo) charge trans-
fer transitions. By comparison with the electronic spec-
C15 Ag5
1
2
Ag2
S2
C4
C1
Ag3
S6
C9
Ag4
2
ꢀ
tra of [W(Mo)OnS4ꢀn
]
addition of Ag(I) to [W(Mo)OnS
(n = 0–1), one can see that the
2
C12
S7
S5
ꢀ
(n = 0–1) shifts
the spectra of 1a, 1b and 2 to lower energies. For exam-
C5
]
C2
4ꢀn
C8
C3
C10
C6
ple, the m absorptions for 1a is at 407 nm, which shifts
C7
1
2
ꢀ
to lower energies compared to that of [WS4] (398 nm).
This low energy shift was different from that observed
for another related compound, [W Ag S (AsPh ) ],
t
(SBu )
2ꢀ
Fig. 1. Structure of the [(WS
4
)Ag
8
8
]
anion of 1a (20%
probability displacement ellipsoids). The hydrogen atoms are omitted
for clarity and the weak secondary interactions are drawn as broken
lines.
2
4
8
3 4
which exhibited a m absorption at 356 nm [26,27].
1

484
J.-R. Li et al. / Polyhedron 24 (2005) 481–485
Table 2
Selected bond lengths (A), distances (A) and angles (°) for compound
3.4. Description of the crystal structure of
[Et N][WOS Ag (S COEt)]} (2)
˚
˚
{
4
3
2
2
n
1a
Bond lengths
W(1)–S(1)
W(1)–S(2)
W(1)–S(3)
W(1)–S(4)
Ag(2)–S(5)
Ag(2)–S(12)
Ag(3)–S(5)
Ag(3)–S(6)
Ag(4)–S(6)
Ag(4)–S(7)
The structure of the polymeric anion of 2 is depicted
2.204(5)
2.195(5)
2.197(5)
2.202(5)
2.390(5)
2.380(5)
2.446(5)
2.453(5)
2.416(5)
2.416(6)
Ag(5)–S(7)
Ag(5)–S(8)
Ag(6)–S(8)
Ag(6)–S(9)
Ag(7)–S(9)
Ag(7)–S(10)
Ag(8)–S(10)
Ag(8)–S(11)
Ag(9)–S(11)
Ag(9)–S(12)
2.394(6)
2.390(5)
2.414(5)
2.424(5)
2.392(6)
2.392(5)
2.386(5)
2.381(5)
2.390(5)
2.400(5)
in Fig. 2 and the important bond lengths and angles are
listed in Table 3. The cluster skeleton of the repeating
unit consists of a butterfly OWS Ag cluster, in which
3
2
the W atom has basically retained the tetrahedral geom-
2ꢀ
etry of the free [WOS3] anion. Two such butterfly
fragments connected by a pair of ethylxanthato bridges
form a double-butterfly dimer. Atom Ag2 is in an
approximately trigonal planar environment, coordi-
nated with two S atoms of the oxothiotungstate and
one S atom from the bridging ethylxanthato ligand.
The coordination environment of Ag1 is almost the
same as that of Ag2 except that there is an additional
Bond distances
Ag(2)ꢁ ꢁ ꢁS(2)
Ag(3)ꢁ ꢁ ꢁS(1)
Ag(4)ꢁ ꢁ ꢁS(3)
Ag(5)ꢁ ꢁ ꢁS(2)
Ag(6)ꢁ ꢁ ꢁS(4)
2.899(7)
2.796(5)
2.934(6)
2.847(7)
2.984(7)
Ag(7)–S(3)
Ag(8)–S(1)
Ag(9)–S(4)
Ag(3)–Ag(4)
Ag(5)–Ag(6)
2.929(5)
3.101(5)
2.933(7)
3.022(6)
3.184(4)
˚
weak Agꢁ ꢁ ꢁS interaction [2.7917(9) A] between Ag2
and S of the adjacent OWS Ag butterfly unit. These
3
2
Bond angles
weak Ag–S bonds link the double-butterfly dimers to-
gether to form a polymeric chain structure running
S(2)–W(1)–S(1)
S(2)–W(1)–S(3)
S(2)–W(1)–S(4)
S(3)–W(1)–S(1)
S(3)–W(1)–S(4)
S(4)–W(1)–S(1)
S(12)–Ag(2)–S(5)
S(5)–Ag(3)–S(6)
S(7)–Ag(4)–S(6)
S(8)–Ag(5)–S(7)
S(8)–Ag(6)–S(9)
108.8(2)
108.4(2)
110.9(2)
111.4(2)
109.1(2)
108.3(2)
171.5(2)
145.4(2)
159.8(2)
166.9(2)
157.1(2)
S(10)–Ag(7)–S(9)
S(11)–Ag(8)–S(10)
S(11)–Ag(9)–S(12)
Ag(2)–S(5)–Ag(3)
Ag(4)–S(6)–Ag(3)
Ag(5)–S(7)–Ag(4)
Ag(5)–S(8)–Ag(6)
Ag(7)–S(9)–Ag(6)
Ag(8)–S(10)–Ag(7)
Ag(8)–S(11)–Ag(9)
Ag(2)–S(12)–Ag(9)
165.0(2)
167.3(2)
157.3(2)
93.0(2)
76.7(2)
95.3(2)
83.0(2)
89.9(2)
90.5(2)
93.0(2)
92.3(2)
C3
C2
O2
S4
C1
Ag1
S5
S2
S1
W
Ag2
S3
O1
is encapsulated in the Ag cage. The coordination geom-
8
etry about the W atom is tetrahedral with a slight distor-
tion (angles of S–W–S range from 108.3(2)° to 111.4(2)°).
The average bond length of W–S is 2.200 A, which is
similar with those reported in the compounds
˚
Fig. 2. Structure of the polymeric anion of 2. The hydrogen atoms are
omitted for clarity.
[
H NCH CH NH ][WS ] [36], [H NCH CH CH NH ]-
3 2 2 3 4 3 2 2 2 3
Table 3
[
tween S atoms of the [WS4] fragment and the Ag
˚
atoms ranges from 2.796(5) to 3.101(5) A, revealing
weak interactions [29–31], which are also demonstrated
by the IR spectrum.
Up until now, there have been only a few crystal
structures reported for monocyclic silver alkanethiolates
or areneticthiolates AgSR, largely due to difficulties with
insolubility and poor crystal habit [30]. One important
method around this problem is to react them with small
proportions of ligands that are bulky and structure ter-
minating, in order to get the resulting compounds repre-
senting monocylic structures. For example, the
structures of Ag (SAr) (PPh ) [39], (Ag SCMeEt )
2 8
WS ] [37] and [PPh ][WS (SH)] [38]. The distance be-
2
4
4
3
˚
ꢀ
Selected bond lengths (A) and angles (°) for compound 2
Bond lengths
W–O(1)
W–S(1)
W–S(2)
W–S(3)
W–Ag(1)
W–Ag(2)
1.726(2)
Ag(1)–S(1)
Ag(1)–S(2)
Ag(1)–S(1)
Ag(2)–S(5)
Ag(2)–S(2)
Ag(2)–S(3)
2.5614(9)
2.5719(9)
2.7917(9)
2.4058(9)
2.4884(8)
2.5148(9)
2.2388(8)
2.2751(9)
2.2210(8)
2.9726(6)
2.9116(7)
1
2
Bond angles
O(1)–W–S(1)
O(1)–W–S(2)
O(1)–W–S(3)
S(1)–W–S(2)
108.19(7)
S(2)–Ag(2)–S(3)
2
S(5) –Ag(2)–S(2)
2
S(5) –Ag(2)–S(3)
96.45(3)
136.75(3)
126.69(3)
76.20(2)
99.84(3)
75.38(2)
75.21(3)
82.33(3)
104.91(3)
75.59(3)
123.5(2)
107.11(7)
107.74(7)
113.34(3)
108.09(3)
112.17(3)
94.57(2)
133.02(2)
126.07(3)
97.67(3)
96.43(2)
99.67(3)
W–S(1)–Ag(1)
W–S(1)–Ag(1)
1
S(3)–W–S(1)
S(3)–W–S(2)
W–S(2)–Ag(1)
W–S(2)–Ag(2)
Ag(1)–S(1)–Ag(1)
Ag(2)–S(2)–Ag(1)
W–S(3)–Ag(2)
S(4)–C(1)–S(5)
6
6
3 5
8
t
S(1)–Ag(1)–S(2)
S(4)–Ag(1)–S(1)
S(4)–Ag(1)–S(2)
S(1)–Ag(1)–S(1)
S(2)–Ag(1)–S(1)
S(4)–Ag(1)–S(1)
(
PPh ) , (Ag SBu ) (PPh ) [30] and (AgSPh) (dppm)
3 2 8 14 3 4 7 3
1
[
as structure-terminating ligands. It is interesting and
40] have been determined by employing PPh or dppm
3
1
1
1
2
rare that a [WS ] fragment is encapsulated in a mono-
ꢀ
4
t
cyclic Ag (SBu ) cage via weak Agꢁ ꢁ ꢁS interactions, as
8
8
in compound 1a, and it is the first example with this kind
of structure in the W(Mo)/Ag/S system.
Symmetry transformations used to generate equivalent atoms:
1
ꢀx + 1, ꢀy + 2, ꢀz; ꢀx + 1, ꢀy + 1, ꢀz.
2

J.-R. Li et al. / Polyhedron 24 (2005) 481–485
485
along crystallographic b axis. The W–Ag1 distance
[10] H. Yu, W.J. Zhang, X.T. Wu, T.L. Sheng, Q.M. Wang, P. Lin,
Angew. Chem., Int. Ed. Engl. 37 (1998) 2520.
˚
[
[
2.9726(6) A] is a little longer than that of W–Ag2
[11] S.F. Gheller, T.W. Hambley, J.R. Rodgers, R.T.C. Brownlee,
M.G. OꢀConnor, M.R. Snow, A.G. Wedd, Inorg. Chem. 23
˚
2.9116(7) A], but both of them are in the normal range
for W/Ag/S clusters [41,42]. As observed in the Cu(I)
clusters, the W–S bonds involving triply bonded S (aver-
˚
age value 2.257 A) are slightly longer than that of dou-
(
1984) 2519.
[12] Q. Huang, X.T. Wu, J.X. Lu, Inorg. Chem. 35 (1996) 7445.
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Dalton Trans. (1999) 4303.
˚
bly bonded S [W–S3: 2.210 A]. W/Ag/S clusters
containing butterfly structures are not common, the
only example is WOS Ag (PPh ) [43].
[
[
[
15] L. Chen, H. Yu, L.M. Wu, W.X. Du, X.C. Gao, P. Lin, W.J.
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3
2
3 3
(
2002) 7.
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438.
4
. Supplementary material
Crystallographic data, excluding structure factors,
2
[
[
18] Z.H. Li, S.W. Du, X.T. Wu, Inorg. Chem. 43 (2004) 4776.
19] J.W. McDonald, G.D. Friessen, L.D. Rosenheim, W.E. Newton,
Inorg. Chim. Acta 72 (1983) 205.
have been deposited at the Cambridge Crystallographic
Data center, CCDC reference numbers 253418 for 1a
and 248288 for 2. Copies of this information may be
obtained free of charge from the Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44-
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Ministry of Science and Technology of China
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of China (20333070) for financial support.
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