Isolation, structure and spectroscopic characterization of silver complexes of the zwitterionic thiolate Tab: [Ag(Tab)2] (PF6), {[Ag3(Tab)4](PF6) 3·2DMF}n, and [Ag14 (μ6-S)(Tab)12(PPh3)8] (PF6)12(Tab=4-(trimethylammonio)benzenethiolate)

Article abstract of DOI:10.1016/j.jorganchem.2004.01.016

Reactions of Ag(PPh₃)₂Cl with equimolar TabHPF₆ (TabH=4-(trimethylammonio)benzenethiol) under the presence of Et₃N in CH₃OH/CH₂ Cl₂ afforded a mononuclear complex [Ag(tab)₂] (PF₆) (1). Treatment of 1 with excess Na₂S in CH₃CN/DMF gave rise to a unusual one-dimensional polymer {[Ag₃(tab)₄](PF₆)₃ · 2DMF}_n (2) as a major product and a netradecanuclear cage-like cluster [Ag₁₄(μ₆-S) (Tab)₁₂(PPh₃)₈](PF₆) ₁₂ (3) as a minor product. Compounds 1 and 2 were characterized by elemental analysis, IR, UV-Vis, and X-ray analysis. The Ag atom of the [Ag(Tab)₂]⁺ cation of 1 adopts a linear AgS₂ coordination geometry. Compound 2 has an one-dimensional chain structure in which the repeating [Ag₆ (Tab)₈]⁶⁺ units are interconnected by four Ag-S bonds with [PF₆]^- anions and DMF solvated molecules located between the polymeric chains. The structure of the [Ag₁₄(μ₆-S)(tab)₁₂(PPh₃) ₈]¹²⁺ dodecation of 3 consists of a μ₆-sulfur atom encapsulated by an Ag₁₄ S₁₂ cage. The luminescence properties of 1 and 2 in solution and in the solid state at room temperature are also reported.

Full text of DOI:10.1016/j.jorganchem.2004.01.016

Journal of Organometallic Chemistry 689 (2004) 1071–1077
www.elsevier.com/locate/jorganchem
Isolation, structure and spectroscopic characterization of
silver complexes of the zwitterionic thiolate Tab: [Ag(Tab)2](PF6),
{[Ag3(Tab)4](PF6)3 ꢀ 2DMF}n, and [Ag14(l6-S)(Tab)12(PPh3)8]
(PF6)12(Tab ¼ 4-(trimethylammonio)benzenethiolate)
a
a
a
b
Jin-Xiang Chen , Qing-Feng Xu , Yong Zhang , Zhong-Ning Chen ,
a,b,
*
Jian-Ping Lang
a
Key laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and Chemical Engineering,
Suzhou University, 1 Shizi Street, Suzhou 215006, Jiangsu, China
State Key Laboratory of Structural Chemistry of FJIRSM, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China
b
Received 11 October 2003; accepted 9 January 2004
Abstract
Reactions of Ag(PPh3)2Cl with equimolar TabHPF6 (TabH ¼ 4-(trimethylammonio)benzenethiol) under the presence of Et3N in
CH3OH/CH2Cl2 afforded a mononuclear complex [Ag(tab)2](PF6) (1). Treatment of 1 with excess Na2S in CH3CN/DMF gave rise
to a unusual one-dimensional polymer {[Ag3(tab)4](PF6)3 ꢀ 2DMF}n (2) as a major product and a netradecanuclear cage-like cluster
[Ag14(l6-S)(Tab)12(PPh3)8](PF6)12 (3) as a minor product. Compounds 1 and 2 were characterized by elemental analysis, IR, UV–
Vis, and X-ray analysis. The Ag atom of the [Ag(Tab)2]þ cation of 1 adopts a linear AgS2 coordination geometry. Compound 2 has
an one-dimensional chain structure in which the repeating [Ag6(Tab)8]6þ units are interconnected by four Ag–S bonds with [PF6]ꢁ
anions and DMF solvated molecules located between the polymeric chains. The structure of the [Ag14(l6-S)(tab)12(PPh3)8]12þ
dodecation of 3 consists of a l6-sulfur atom encapsulated by an Ag14S12 cage. The luminescence properties of 1 and 2 in solution and
in the solid state at room temperature are also reported.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Zwitterionic thiolate; Silver cluster; Sulfide cluster; Crystal structures
1. Introduction
For example, treatment of [NEt4][AgCl2] with 2-merca-
ptoethylamine hydrogen chloride in DMF gave rise to an
1D chain polymer [{Ag8(l4-SC2H4NH3)6Cl2}Cl2]n. In
the case of TabHPF6 (TabH ¼ 4-(trimethylammo-
nio)benzenethiol) [17], there are several papers which re-
ported the utilization of this ligand [18] and only one
compound [(PPh3)Au(Tab)](PF6) was structurally de-
termined [19]. Actually the chemistry of this zwitterionic
thiolate with other transition metals is virtually unknown.
In this regard, we carried out the reaction of TabHPF6
with Ag(PPh3)2Cl and successfully isolated three novel
Ag/Tab complexes: [Ag(tab)2](PF6) (1), {[Ag3(tab)4]
(PF6)3 ꢀ 2DMF}n(2), and [Ag14(l6-S)(tab)12(PPh3)8]
(PF6)12 (3) (minor product). Compounds 1 and 2 exhib-
ited the luminescence properties both in solution and in
Over the past decades, there has been considerable
interest in the coordination chemistry of silver complexes
of organic thiolates due to their structure diversity [1–6]
and potential application as precursors for materials [7–
10], antimicrobial drugs [11], and models for the active site
of metallothioneins [12,13]. However, the chemistry of
silver complexes of the zwitterionic organic thiolates is
less explored and as a matter of fact, only several com-
pounds have been structurally determined so far [14–16].
* Corresponding author. Tel.: +86-512-65213506; fax: +86-512-
65224783.
E-mail address: jplang@suda.edu.cn (J.-P. Lang).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.01.016

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J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
the solid state at room temperature. Herein we report the
synthesis and structural and spectroscopic characteriza-
tion of 1–3.
[21]. As shown in Table 1, the Ag–S bond lengths,
ꢀ
ranging from 2.379(3) to 2.391(2) A, are comparable to
those observed in two-coordinated silver complexes such
ꢀ
as [Ag(SC(Me)Et2)] (2.371 A) [22] and [AgL](ClO4)
ꢀ
(2.398 A) (L ¼ cyclo(
L-methionyl-L-methionyl)) [23].
2. Results and discussion
There is no evident silver–silver interaction in the solid
state probably owing to the steric hindrance of the bulky
Tab moieties, which prevent the approach of two
neighboring silver atoms.
2.1. Preparation and crystal structure of [Ag(tab)2](PF6)
(1)
Treatment of a suspension of TabHPF6 in CH3OH
with slightly excess Et3N afforded a colorless solution,
to which a solution of equimolar Ag(PPh3)2Cl in
CH2Cl2 was added. The resulting mixture was refluxed
to give rise to a white precipitate. After filtration, the
filtrate was cooled down to 5 ꢁC to form colorless
crystals of a known product [Ag(PPh3)4]PF6 [20] in
93.1% yield, which was confirmed by elemental analysis,
2.2. Preparation and crystal structures of {[Ag3
(tab)4](PF6)3 ꢀ 2DMF}n (2) and [Ag14(l6-S)(Tab)12
(PPh3)8](PF6)12 (3)
The purpose that we run the reactions of 1 with Na2S is
based on the following considerations. One is that S2ꢁ is a
versatile bridging ligand to combine metal ions or com-
plexes into relatively larger clusters. The other is that, as
described above in this paper, the coordination of the Ag
atom of 1 is un-saturated (two-coordinated) and may
1
IR, H NMR, and X-ray analysis. The resulting solid
was re-crystallized in CH3CN to produce colorless
plates of [Ag(tab)2](PF6) (1) in 87.0% yield (Scheme 1).
An X-ray analysis revealed that 1 crystallizes in the
monoclinic space group C2=c and the asymmetric unit
consists of two one-half of the crystallographiꢁcally in-
dependent [Ag(Tab)2]þ dications and one PF6 anion.
Because the two [Ag(Tab)2]þ cations are structurally
very similar, only one of them is presented in Fig. 1. In
[Ag(Tab)2]þ cation, the Ag atom is coordinated by two
S atoms of the two Tab moieties, forming a linear AgS2
coordination geometry with two C6H4NMe3 groups
oriented at opposite directions. Such a structure closely
resembles those of the anions of the gold-thiolate com-
plexes [n-Bu4N][Au(SC6H4R)2] (R ¼ o-Me, o-Cl, m-Cl)
further complete its coordination by binding to S2ꢁ
.
Therefore, treatment of the solution of 1 with Na2S in
CH3CN/DMF immediately threw out some insoluble
black precipitate. After centrifugation, diffusion of Et2O
into the colorless solution gave rise to long colorless col-
umn crystals of {[Ag3(tab)4](PF6)3 ꢀ 2DMF}n(2) in 75%
yield, coupled with several colorless plates of [Ag14
(l6-S)(tab)12(PPh3)8](PF6)12 ꢀ 12CH3CN (3 ꢀ 12CH3CN)
(Scheme 2). The black solids were confirmed to be Ag2S
by X-ray fluorescence analysis. Although the formation
of 2 was reproducible, its yield understandably decreased
when the amount of Na2S added was increased. If very
excess Na2S were used, almost no 2 could be isolated from
the solution. Intriguingly, reactions of 1 with Na2S did
not form the sulfur-bridged clusters as we expected. In-
stead, the linear structure of 1 was broken and the re-
maining silver atoms and Tab moieties were re-arranged
into the structure of 2. However, the detailed formation
mechanism of 2 is unknown currently. The formation of 3
was occasional and may be ascribed to the existence of
very small amount of contaminated PPh3 in the bulky
sample of 1. It should be noted that only compound 2 was
isolated from the above reaction if pure sample of 1, which
was thoroughly washed by CH2Cl2, was used. Both 2 and
3 were finally confirmed by X-ray crystallography.
CH OH
3
2 Tab + 2 HNEt PF
2 TabHPF + 2 NEt
3
6
6
3
+ 2 Ag(PPh) Cl
2
CH Cl
2
2
[Ag(PPh ) ](PF ) + [Ag(Tab) ](PF ) + 2 HNEt Cl
3 4
6
2
6
3
(1)
Scheme 1.
Compound 2 crystallizes in the monoclinic space group
P21=c and the asymmetric unit of 2 contains one-half of
ꢁ
[Ag6(Tab)8]6þ hexacation, three PF6 anions, and two
DMF solvated molecules. The repeating [Ag6(Tab)8]6þ
units are held together by four Ag–S bonds to form an
interesting 1D chain structure along the a-axis. Fig. 2
shows the packing diagram of 2 in a unit cell. Except for
the electrostatic forces betweꢁen the cationic polymeric
chains and the associated PF6 anions, there are no evi-
dent interactions between the DMF solvent molecules
Fig. 1. Perspective view of the [Ag(Tab)2]þ cation of 1 with 50%
thermal ellipsoids. Hydrogen atoms are omitted for clarity.
ꢁ
and the cationic polymeric chains or the associated PF6

J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
1073
Table 1
ꢀ
Selected bond distances (A) and angles (ꢁ) for 1, 2 and 3
1
Ag(1)–S(1)
2.391(2)
Ag(2)–S(2)
2.379(3)
C(1)–S(1)–Ag(1)
S(1)–Ag(1)–S(10)
105.2(3)
180
C(10)–S(2)–Ag(2)
S(2)–Ag(2)–S(20)
105.8(4)
180
2
Ag(1)–S(1)
Ag(1)–S(4)
Ag(2)–S(2)
Ag(3)–S(4)
Ag(3)–S(20)
Ag(1)ꢀ ꢀ ꢀAg(3)
2.483(4)
2.538(4)
2.514(4)
2.481(4)
2.577(4)
3.560(2)
Ag(1)–S(2)
Ag(2)–S(3)
Ag(2)–S(100)
Ag(3)–S(3)
2.592(4)
2.561(3)
2.524(4)
2.488(4)
3.207(2)
3.896(2)
Ag(2)ꢀ ꢀ ꢀAg(3)
Ag(3)ꢀ ꢀ ꢀAg(30)
S(1)–Ag(1)–S(2)
S(2)–Ag(1)–S(4)
S(2)–Ag(2)–S(100)
S(3)–Ag(3)–S(4)
S(4)–Ag(3)–S(20)
Ag(2)–S(2)–Ag(30)
Ag(3)–S(3)–Ag(2)
Ag(1)–S(1)–Ag(200)
115.61(12)
105.06(11)
132.45(12)
120.45(13)
122.79(12)
115.67(13)
78.86(10)
99.5(1)
S(1)–Ag(1)–S(4)
S(2)–Ag(2)–S(3)
S(3)–Ag(2)–S(100)
S(3)–Ag(3)–S(20)
Ag(1)–S(2)–Ag(2)
Ag(1)–S(2)–Ag(30)
Ag(1)–S(4)–Ag(3)
125.53(13)
116.81(12)
107.24(12)
114.93(12)
108.82(12)
115.79(13)
90.33(12)
3
Ag(1)–S(1)
Ag(1)–S(1b)
Ag(2)–S(1)
Ag(1)–P(1)
2.6625(12)
2.663(5)
2.423(5)
2.475(3)
Ag(1)–S(1a)
Ag(2)–S(2)
Ag(2)–S(1g)
2.663(4)
2.937(2)
2.423(5)
S(1)–Ag(1)–P(1)
S(1)–Ag(1)–S(1b)
P(1)–Ag(1)–S(1b)
S(1)–Ag(2)–S(2)
S(2)–Ag(2)–S(1g)
119.00(12)
98.48(12)
119.00(9)
94.96(11)
94.96(11)
S(1)–Ag(1)–S(1a)
P(1)–Ag(1)–S(1a)
S(1a)–Ag(1)–S(1b)
S(1)–Ag(2)–S(1g)
Ag(1)–S(1)–Ag(2)
98.48(9)
119.00(11)
98.5(1)
170.1(2)
92.94(11)
Na S
2
Ag S + NaPF + Tab
[Ag(Tab) ](PF )
2
6
2
6
CH CN/DMF
3
+
(1)
.
{[Ag (Tab) ](PF ) 2DMF}
n
3
4
6 3
(2)
Scheme 2.
anions. Fig. 3 presents the perspective view of a part of the
polymeric cationic chain of 2. Each [Ag6(Tab)8]6þ has a
saddle-shaped Ag6S6 core structure with a crystallo-
graphic symmetry center on the midpoint of Ag(3) and
Ag(30). The core structure consists of two eight-membered
Ag4S4 boat-like rings (Ag(1)S(2)Ag(30)S(30)Ag(20)
S(20)Ag(3)S(4) and Ag(2)S(3)Ag(3)S(20)Ag(10)S(40)Ag(30)
S(2)), which share the same boat-bottom plane (Ag(3)
S(20)Ag(30)S(2)). In the Ag6S6 core, either Ag(1) or Ag(10)
atom is coordinated by a l3-Sand two l-Satoms, showing
a pyramidalized Y-shape coordination geometry. Such a
coordination is uncommon in the Ag(I) complexes [24].
ꢀ
The Ag(1) atom is displaced 0.55 A from the trigonal
plane of S(1), S(2), and S(4). On the other hand, the Ag(2)
and Ag(3) atoms show typical trigonal planar geometry.
As shown in Table 1, the average Ag–S bond length of
Fig. 2. Cell packing diagrams of 2 looking down the a-axis. Hydrogen
atoms are omitted for clarity.

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J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
Fig. 3. Perspective view of a part of the polymeric cationic chain in 2 with 50% thermal ellipsoids. The C6H4NMe3 groups are omitted for clarity.
ꢀ
2.529 A is not unusual as compared with the struc-
tures containing three-coordinated Ag(I) such as
than those of the corresponding ones in [Ag14(l6-S)
(SPh)12(PPh3)8].
ꢀ
A)
[PPh4]2[Ag4(SCH2C6H4CH2S)3]
(2.505
ꢀ
and
[PPh4]3[Ag9(SCH2CH2S)6] (2.579 A) [25,26]. The
ꢀ
2.3. Spectral aspects of 1 and 2
Agꢀ ꢀ ꢀAg contacts range from 3.207(2) to 3.896(2) A,
which fall into two categories. The Ag(2)ꢀ ꢀ ꢀAg(3) contact
Solids 1 and 2 are relatively stable towards oxygen
and moisture. They are soluble in CH3CN, DMSO, and
DMF but insoluble in benzene, CH2Cl2, and CHCl3.
The elemental analysis of 1 and 2 were consistent with
their chemical formula. In the IR spectra of 1 and 2,
characteristic bands due toꢁvibrations of Ph (1485, 1126
and 1006 cmꢁ1) and PF6 (837 and 559 cmꢁ1) were
observed. The 1H NMR spectrum of 1 and 2 in
(CD3)2SO at room temperature showed a multiplet for
Ph groups at 7.43–7.48 ppm and a single peak related to
NMe3 protons at 3.34 ppm.
As shown in Fig. 5, complexe 1 or 2 in MeCN shows
a strong absorption at 293 nm (1) or 296 nm (2) and a
long absorption tail to ca. 400 nm. Since the absorption
spectrum of the corresponding free ligand Tab (prepared
from reaction of TabHPF6 with excess Et3N in MeCN)
in MeOH has a broad absorption band at 283 nm, the
peaks at 293 nm (1) and 296 nm (2) observed in the
spectra of 1 and 2 in MeCN are red-shifted, and are
ꢀ
of 3.207(2) A is shorter than the sum of the van der Waals
ꢀ
radii of two Ag atoms (3.44 A), and may suggest they
are related by so-called agentophilicity [27]. The
Ag(2)ꢀ ꢀ ꢀAg(3) and Ag(3)ꢀ ꢀ ꢀAg(3a) separations, 3.560(2)
ꢀ
and 3.896(2) A, may be assumed to be non-bonding and
may be involved in very weak interactions.
ꢁ
Compound 3 crystallizes in the cubic space group Im3
and the asymmetric unit of 3 contains 24th of [Agꢁ14(l6-
S)(tab)12(PPh3)8]12þ dodecation, one-half of PF6 an-
ion, and one-half of MeCN solvated molecule. As
shown in Fig. 4, the cluster framework of the dodeca-
cation has an Ag14S12 cage that is composed of Ag8
cube, Ag6 octahedron, and an S12 icosahedron centred
around a l6-sulfur atoms. The structure of the Ag14S12
cage closely resembles that of neutral phenyl thiolate
analogue [Ag14(l6-S)(SPh)12(PPh3)8] [28]. Each Ag atom
in Ag8 cube of 3 adopts a distorted tetrahedral geometry
while that in Ag6 octahedron has a trigonal geometry.
As presented in Table 1, the average Ag(octa)–l6-S,
Ag(octa)–S, Ag(cube)–S, and Ag–P bond lengths, 2.936,
ꢀ
1.0
2.426, 2.6625(12), and 2.475(3) A, are somewhat longer
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
-0.1
2
Tab
200
250
300
350
400
450
Wavelength [nm]
Fig. 4. Perspective view of the [Ag14(l6-S)(tab)12(PPh3)8]12þ dodeca-
cation of 3 with 50% thermal ellipsoids. The C6H4NMe3 and phenyl
groups are omitted for clarity.
Fig. 5. Absorption spectra of 1 (solid line) and 2 (short dashed line) in
MeCN along with the free Tab ligand (short dotted line) in MeOH
with a 1 mm optical length.

J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
1075
probably originated from intraligand transitions. Inter-
estingly, compounds 1 and 2 exhibited luminescenece in
solution and in solid state at ambient temperature, re-
spectively. As shown in Fig. 6, excitation of 1 at
kex > 320 nm resulted in an intense emission at 420 nm
in solution, while that of 2 at kex > 310 nm gave rise to a
similar band at 443 nm. On the other hand, excitation of
1 in the solid state at 390 nm resulted in broad emission
bands at 442 and 533 nm while that of 2 at 395 nm gave
a broad emission band centered at 535 nm (Fig. 7).
However, the free ligand Tab is not emissive both in
MeOH and in the solid state at ambient temperature.
As mentioned above, a set of gold/thiolate complexes
[(n-Bu)4N][Au(SC6H4R)] (R ¼ o-Me, o-Cl, m-Cl) have a
similar linear AuS2 structure to that of 1. These com-
plexes were confirmed to possess luminescence in the
solid state derived from metal-to-ligand charge transfer
(MLCT) or a ligand-centered (LC) transition [21,29].
Therefore, the possible origins of emissions of 1 and 2
may be tentatively assumed to be MLCT from silver
(4d) to ligand (pꢂ) or LC transition from S (non-bonding
3p) to benzene ring (pꢂ) of the Tab ligand [21,30,31],
though the metal-centered transition arising from
the silver–silver contacts could not be ruled out for
compound 2.
3. Experimental
3.1. General
TabHPF6 was prepared according to the literature
method [32]. Other reagents were obtained from com-
mercial sources and used as received. All solvents were
predried over activated molecular sieves and refluxed
over the appropriate drying agents under argon. IR
spectra (KBr disc) were recorded on a Nicolet MagNa-
IR 550 spectrophotometer. Elemental analyses for C, H,
and N were performed on an EA1110 CHNS elemental
analyzer. 1H NMR spectra were recorded at ambient
temperature on a Varian UNITYplus-400 spectrometer.
1H NMR chemical shifts were referenced to the
(CD3)2SO signal. UV–Vis spectra were measured on
HITACHI U-2810 spectrophotometer. The photolumi-
nescent spectra were performed by HITACHI F-2500
spectrofluorometer.
7
1 em
6
x
1 e
5
4
3
2
1
0
2 em
2 ex
3.2. Syntheses
250 300 350 400 450 500
Wavelength (nm)
600 650
550
3.2.1. Preparation of 1
To a suspension containing TabHPF6 (66 mg, 0.21
mmol) in CH3OH (5 ml) was added Et3N (0.25 ml). The
resulting colorless solution was then treated with a so-
lution of Ag(PPh3)2Cl (133 mg, 0.20 mmol) in CH2Cl2
(10 ml). The mixture was refluxed on an oil bath for 0.5
h and a white precipitate was formed. After filtration,
the filtrate was cooled down to 5 ꢁC to form colorless
crystals of [Ag(PPh3)4](PF6). Yield: 121 mg (93.1%
based on Ag). Anal. Calc. for C72H60AgF6P5: C, 66.41;
H, 4.61. Found: C, 66.89; H, 4.53%. IR (KBr disc): 1477
(m), 1435 (s), 1091 (m), 837 (s), 744 (m), 694 (s), 555 (m),
509 (s) cmꢁ1. On the other hand, the white solid was re-
dissolved in CH3CN (5 ml) to give a colorless solution.
Diethyl ether (10 ml) was allowed to diffuse into the
CH3CN solution to afford colorless plates of
[Ag(Tab)2](PF6) (1), which were collected by filtration
and washed with CH2Cl2/Et2O (1:4) and dried in vacuo.
Yield: 51.1 mg (87.0% based on Ag). Anal. Calc. for
C18H26AgF6N2PS2: C, 36.80; H, 4.43; N, 4.77. Found:
C, 36.93; H, 4.21; N, 4.56%. IR (KBr disc): 1485 (m),
1126 (w), 1006 (w), 837 (s), 559 (m) cmꢁ1. UV–Vis
(CH3CN, kmax (nm (e Mꢁ1 cmꢁ1))): 293 (8400). 1H
Fig. 6. Excitation and emission spectra of complex 1 (solid line) and 2
(dashed line) in MeCN at ambient temperature.
30
1 ex
2 ex
1 em
20
2 em
10
0
300 350 400 450
550
650 700
800
750
500
600
Wavelength (nm)
Fig. 7. Excitation and emission spectra of complex 1 (solid line) and 2
(dashed line) in the solid state at ambient temperature.

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J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
NMR (400 MHz, (CD3)2SO): d 7.43–7.48 (m, 4H, Ph),
3.34 (s, 9H, NMe3).
preparation. A colorless plate crystal of 1 with dimen-
sions 0.45 · 0.40 · 0.10 mm, a colorless long column
crystal of 2 with dimensions of 0.20 · 0.45 · 0.15 mm,
and a colorless plate of 3 ꢀ 12CH3CN with dimensions of
0.35 · 0.20 · 0.20 mm were mounted at the top of a glass
fiber, and cooled at 193 K in a liquid nitrogen stream.
Diffraction data were collected at x mode with a de-
tector to crystal distance of 45 mm (1), 55 mm (2), and
55 mm (3 ꢀ 12CH3CN), respectively. Indexing was per-
formed from six images each of which was exposed for
15 s (1 and 2) and 20 s (3 ꢀ 12CH3CN). Cell parameters
were refined by using the program CRYSTALCLEAR
(Rigaku and MSc, Ver. 1.3, 2001) on all observed re-
flections between h of 1.5ꢁ and 31.5ꢁ (1), 3ꢁ and 27.5ꢁ (2),
and 1.6ꢁ and 30.5ꢁ (3 ꢀ 12CH3CN). A total of 720 (1, 2
and 3 ꢀ 12CH3CN) oscillation images were collected in
the range 1:77ꢁ < 2h < 62:6ꢁ for 1 and 1:87ꢁ < 2h < 55ꢁ
for 2, and 1:92ꢁ < 2h < 61:5ꢁ for 3 ꢀ 12CH3CN. The
collected data were reduced by using the program
CRYSTALSTRUCTURE (Rigaku and MSC, Ver. 3.16,
2003), and an absorption correction (Multi-Scan) was
applied which resulted in transmission factors ranging
from 0.596 to 0.889 for 1 and from 0.734 to 0.819 for 2,
and 0.759 to 0.795 for 3 ꢀ 12CH3CN. The data were also
corrected for Lorentz and polarization effects.
3.2.2. Preparation of 2 and 3
Addition of Na2S (4 mg, 0.05 mmol) into the solution
of 1 (469 mg, 0.8 mmol) in CH3CN/DMF (10 ml, v/
v ¼ 9:1) gave some insoluble black precipitate. After fil-
tration, Et2O (10 ml) was allowed to diffuse into the fil-
trate. After standing it at ambient temperature for several
days, long colorless column crystals of {[Ag3(Tab)4]
(PF6)3 ꢀ 2DMF}n (2) coupled with several colorless plates
of [Ag14(l6-S)(tab)12(PPh3)8](PF6)12 (3 ꢀ 12CH3CN) were
formed, which were separated mechanically under the
microscope. Yield for 2: 240 mg (75% based on Ag). Anal.
Calc. for C42H66Ag3F18N6O2P3S4: C, 32.03; H, 4.19; N,
5.34. Found: C, 32.19; H, 4.30; N, 5.63%. IR (KBr disc):
1485 (m), 1126 (w), 1006 (w), 837 (s), 559 (m) cmꢁ1. UV–
Vis (CH3CN, kmax (nm (e Mꢁ1 cmꢁ1))): 296 (26 800). 1H
NMR (400 MHz, (CD3)2SO): d 7.43–7.48 (m, 4H, Ph),
3.34 (s, 9H, NMe3). The identity of 3 ꢀ 12CH3CN was
confirmed directly by an X-ray analysis.
3.2.3. X-ray structure determination
All measurements were made on a Rigaku Mercury
CCD X-ray diffractometer (3 kW, sealed tube) by using
ꢀ
graphite monochromated Mo Ka (k ¼ 0:71070 A).
The structures of 1, 2, and 3 ꢀ 12CH3CN were solved
by heavy-atom Patterson methods (1) [33], and direct
methods (2, and 3 ꢀ 12CH3CN) [34], and were refined by
full-matrix least-squares on F [35]. Non-hydrogen atoms
Crystals of 1 suitable to X-ray analysis were obtained
and
3 ꢀ 12CH3CN were obtained directly from the above
from recrystallization in CH3CN while
2
Table 2
Crystallographic data for 1, 2, and 3
Molecular formula
Formula weight
Crystal system
Space group
C
18H26AgF6N2PS2
C42H66Ag3F18N6O2P3S4
1573.81
Monoclinic
P1=c
8.7364(5)
36.575(2)
18.1407(12)
95.073(3)
5773.9(6)
4
C276H312Ag14F72N24P20S13
7843.7
Cubic
587.39
Monoclinic
C2=c
33.23(1)
10.158(4)
14.316(6)
106.736(4)
4627.5(32)
8
ꢁ
Im3
24.9371(10)
ꢀ
a (A)
ꢀ
b (A)
ꢀ
c (A)
b (ꢁ)
V (A )
3
ꢀ
15507.4(11)
2
193
Z
T (K)
193
1.686
193
1.811
Dcalc (g cmꢁ3
)
ꢀ
1.680
k (Mo Ka) (A)
l (cmꢁ1
0.71070
11.76
62.6
0.71070
13.35
55.0
0.71070
11.51
61.5
)
2hmax (ꢁ)
Total reflections
20323
38659
59186
Unique reflections (Rint
)
6737 (0.036)
2330(I > 3:00rðIÞ)
269
12 407 (0.050)
4491(I > 2:00rðIÞ)
414
4140 (0.058)
1296(I > 2:00rðIÞ)
118
Number of observations
Number of parameters
Ra
0.057
0.065
0.061
0.065
0.062
0.071
b
Rw
Goodness-of-fitc
1.068
1.38
1.198
1.38
1.173
1.85
ꢁ3
ꢀ
Dqmax (e Aꢁ3
)
ꢀ
Dqmin (e A
)
)0.81
)0.99
)1.13
P
c GOF ¼
P
a R ¼ jFoj ꢁ jFcj= jFoj:
n
P
2
o
1=2
P
b Rw
¼
wðjFoj ꢁ jFcjÞ = wjFoj2
:
1=2
n
o
P
2
wðjFoj ꢁ jFcjÞ =ðM ꢁ NÞ
, where M is number of reflections and N is number of parameters.

J.-X. Chen et al. / Journal of Organometallic Chemistry 689 (2004) 1071–1077
1077
except for the F atoms in 1, those of PF6ꢁ, DMF, and
C6H4NMe3 groups in 2, and those of PF6ꢁ, CH3CN,
phenyl groups, and C6H4NMe3 groups in 3 ꢀ 12CH3CN,
were refined anisotropically, and hydrogen atoms were
put on the calculated positions and refined in the final
structure factor refinement. Neutral atom scattering
factors were taken from Cromer and Waber [36].
Anomalous dispersion effects were included in Fcalc [37].
All calculations were performed on a Dell workstation
using the CrystalStructure crystallographic software
package (Rigaku and MSC, Ver. 3.16, 2003) (Table 2).
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Crystallographic data for the structural analyses have
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(2), and 213944 (3 ꢀ 12CH3CN). Copies of this infor-
mation may be obtained free of charge from The Di-
rector, CCDC, 12 Union Road, Cambridge CB2 1E2,
UK (fax: +44-1223-336033; deposit@ccdc.cam.ac.uk or
www.ccdc.cam.ac.uk).
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This research was supported by the NNSF of China
(No. 20271036), the NSF of the Education Committee
of Jiangsu Province (No. 02KJB150001), State Key
Laboratory of Structural Chemistry of FJIRSM (No.
030066), Key Laboratory of Organic Synthesis of Ji-
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for the Returned Overseas Chinese Scholars, State Ed-
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