Coordination networks with flexible ligands based on silver(I) salts: Complexes of 1,3-bis(phenylthio)propane with silver(I) salts of PF 6-, CF3COO-, CF3CF 2COO-, CF3CF2CF2COO -, p-TsO-, and CF3SO3-

Article abstract of DOI:10.1021/ic050617n

The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L³, and silver(I) salts of PF ₆^- (1), CF₃COO^- (2), CF ₃CF₂COO^- (3), CF₃CF ₂CF₂COO^- (4), p-TsO^- (5, 6), and CF₃SO₃^- (7-9) are reported. Only 1 and other isostructural complexes with weakly coordinating anions such as ClO₄^- and SbF₆^- are of the host-guest type. In all the other complexes, the anions and the acetone molecules, when present, are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5 adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5 is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four different ligands. The PF₆^- anions and acetone molecules, sandwiched between silver-ligand cationic sheets, are held through van der Waals interactions. In each of the three perfluorocarboxylates (2-4), two silver atoms are joined by the anions in a diatomic bridging mode. The Ag...Ag distances are sufficiently short to indicate weak metal...metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination polymer is generated. In the case of the sulfonate anions (p-TsO^- and CF₃SO₃^-), the crystallization solvent influences the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room temperature - 450°C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures, reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver.

Full text of DOI:10.1021/ic050617n

Inorg. Chem. 2005, 44, 7833
−7845
Coordination Networks with Flexible Ligands Based on Silver(I) Salts:
-
Complexes of 1,3-Bis(phenylthio)propane with Silver(I) Salts of PF ,
6
-
-
-
-
-
CF COO , CF CF COO , CF CF CF COO , p-TsO , and CF SO
3
3
2
3
2
2
3
3
Mohamed Osman Awaleh, Antonella Badia, and Fran c¸ ois Brisse*
D e´ partement de chimie, UniVersit e´ de Montr e´ al, C.P. 6128, Succursale Centre-Ville,
Qu e´ bec, Canada H3C 3J7
Received April 21, 2005
3
The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L , and
-
3 3 2 3 2 2 3 3
(1), CF CF CF CF SO
COO- (2), CF COO- (3), CF COO- (4), p-TsO- (5, 6), and CF
-
silver(I) salts of PF
6
-
(7−
9) are reported. Only 1 and other “isostructural” complexes with weakly coordinating anions such as ClO
4
and
-
SbF
6
are of the host−guest type. In all the other complexes, the anions and the acetone molecules, when present,
are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5
adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5
is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four
-
different ligands. The PF
6
anions and acetone molecules, sandwiched between silver
−ligand cationic sheets, are
held through van der Waals interactions. In each of the three perfluorocarboxylates (2−4), two silver atoms are
joined by the anions in a diatomic bridging mode. The Ag‚‚‚Ag distances are sufficiently short to indicate weak
metal‚‚‚metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating
a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination
polymer is generated. In the case of the sulfonate anions (p-TsO- and CF -), the crystallization solvent influences
SO
3 3
the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver
atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized
from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room
temperature−450 °C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures,
reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind
the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver.
Introduction
coordination polymer materials are to some extent dependent
on their network topology. Thus, it is of interest to understand
and control the subtle factors that influence the formation
of these supramolecular networks. Moreover, the strategy
consisting of varying the coordination site and/or the size
and shape of the ligand is usually employed in crystal
engineering to synthesize new coordination polymers. The
In the last two decades, there has been considerable activity
in the design and synthesis of solid frameworks. The self-
assembly of metal-organic coordination polymers has at-
tracted a great deal of attention because of their potential
applications as functional materials.2 The properties of
1
3
*
To whom correspondence should be addressed. E-mail: francois.brisse@
metal centers are linked with rigid bridging ligands or less
umontreal.ca. Fax: (+)-(514) 343-7586.
4
frequently by flexible building blocks. However, for a given
(
1) (a) Hagrman, P. J.; Hagrman, D.; Zubieta, J. Angew. Chem., Int. Ed.
999, 38, 2638. (b) Khlobystov, A. N.; Blake, A. J.; Champness, N.
1
R.; Lemenovskii, D. A.; Majouga, A. G.; Zyk, N. V.; Schr o¨ der, M.
Coord. Chem. ReV. 2001, 222, 155. (c) Batten, S. R.; Robson, R.
Angew. Chem., Int. Ed. 1998, 37, 1461. (d) Swiegers, G. F.; Malefetse,
T. J. Chem. ReV. 2000, 100, 3483.
(3) (a) Blake, A. J.; Champness, N. R.; Hubberstey, P.; Li, W. S.;
Withersby, M. A.; Schr o¨ der, M. Coord. Chem. ReV. 1999, 183, 117.
(b) Sharma, C. V. K.; Broker, G. A.; Huddleston, J. G.; Baldwin, J.
W.; Metzger, R. M.; Rogers, R. D. J. Am. Chem. So. 1999, 121, 1137.
(c) Abrahams, B. F.; Batten, S. R.; Hoskins, B. F.; Robson, R. Inorg.
Chem. 2003, 42, 2654. (d) Abrahams, B. F.; Jackson, P. A.; Robson,
R. Angew. Chem., Int. Ed. 1998, 37, 2656.
(
2) (a) Stumpf, H. O.; Ouahab, L.; Pei, Y.; Grandjean, D.; Kahn, O.
Science 1993, 261, 447. (b) Yaghi, O. M.; Li, G.; Li, H. Nature 1995,
378, 703.
1
0.1021/ic050617n CCC: $30.25
© 2005 American Chemical Society
Inorganic Chemistry, Vol. 44, No. 22, 2005 7833
Published on Web 09/30/2005

Awaleh et al.
ligand, the structure of the resulting coordination polymer
is difficult to predict because of factors affecting the
reported in parts per million, were referenced to tetramethylsilane
1
13
1
as an internal standard for H and C{ H} spectra, while the
chemical shifts for 19F were referenced to C H CF (-63.9 ppm).
5
6
framework formation, such as the solvent, the counteranion,
6
5
3
7
The weight loss experiments were carried out on a TG Instrument
and the metal-to-ligand ratio. The ability of the sulfur atom,
as a soft base, to coordinate to the silver atom, a soft acid,
has been exploited in this study. We have previously attemp-
ted to analyze the effects of the counteranions and the length
of the spacer on the topology of the coordination polymer
on the basis of the mutual attraction between the soft silver
atom and the soft sulfur atom.4 We have reported earlier
2
min
950 TGA HR V5.3C thermal analyzer at a scan rate of 10 °C
-
1
.
3
Syntheses. The ligand 1,3-bis(phenylthio)propane, L , was
synthesized by following a literature method.11 Yield: 82%. Anal.
Found: C, 69.36; H, 6.35. Calcd for C15
H
16
S
2
: C, 69.18; H, 6.19.
CH
S-), 7.151-7.364 (m, 10H,
, 100.56 MHz): 34.21 (SCC),
31.80 (SCC), 136.67, 129.37, 129.16, 126.19 (C H ).
1
H NMR (acetone-d
6
, 300 MHz): δ 2.021 (qt, 2H, -SCH
CH CH
-). C{ H} NMR (acetone-d
2
2
-
b,7
CH
2
S-), 3.082 (t, 4H, -SCH
2
2
2
on the structures of several silver(I) complexes with the bis-
13
1
C H
6 5
6
8
(
phenylthio)methane ligand. In an effort to rationalize further
6
5
3
the structural effect of the ligand spacer and the counteranion,
we have now synthesized and characterized a number of
complexes, all based on the 1,3-bis(phenylthio)propane lig-
2 4 6 2 3 3 2 ∞
{[Ag L ](PF ) (CH COCH ) } (1). To a solution of AgPF6
(290 mg, 1.15 mmol) in acetone (10 mL) was added a solution of
3
L (0.25 mL, 1.08 mmol) in diethyl ether (5 mL) and heated at 50
3
°C for 30 min. Evaporation of the solvent in the dark and at room
temperature produced single crystals suitable for X-ray analysis.
and, L , but with different classes of anions: weakly coor-
-
dinating ones such as PF
6
-
(1); perfluorocarboxylates
-
-
Yield: 70% based on AgPF
for C66 : C, 47.65; H, 4.60. H NMR (DMSO-d
00 MHz): δ 2.104 (qt, 2H, -S(CH )(CH )-), 3.312 (t, 4H,
)-), 7.341-7.523 (m, 10H, C -). F{ H} NMR
, 376.31 MHz): -71.851 and -74.293, (d, F-P). IR
6
. Anal. Found: C, 47.83; H, 4.33. Calcd
CF
3
COO (2), CF
3
CF
2
COO (3), CF
3 2 2
CF CF COO (4); sul-
1
H76Ag
F
2 12
O S
2 8
P
2
6
,
-
-
fonates p-TsO (5, 6), CF
3
SO
3
(7-9). The crystal structures
3
-
2
2
of 1, 3, and 7 incorporate a molecule of solvent, either as a
guest or as a coordinating molecule. The ease of release of
these molecules is examined by thermogravimetric analysis.
In this study, supramolecular isomerism was observed for
1
9
1
S(CH
2
6 5
H
(
DMSO-d
6
-1
(KBr, cm ): 1637 m, 1583 m, 1479 s, 1438 s, 1303 m, 1146 m,
1086 m, 1025 m, 843 vs, 737 s, 690 s, 560 s, 501 m. Attempts to
-
-
complexes 5, 6 (with p-TsO ), and 7-9 (with CF
SO
3 3
).
obtain complexes with different stoichiometries failed. The various
intended ligand:silver salt ratios investigated (1:1, 1:2, 1:3, 2:1)
always give crystals identical with 1.
The isomerism of supramolecular networks, which has been
noted in similar systems, is influenced by several factors,
9
10
3
such as the metal-to-ligand ratio or the guest molecule.
[Ag
2
L (CF
3
CO
)
2 2
]
∞
(2). A solution of AgCF
3
CO
2
(217.2 mg,
3
0
.98 mmol) in acetone (10 mL) was stirred with a solution of L
The isomerism reported herein occurred as a consequence
of the solvent used for recrystallization.
(0.20 mL, 0.87 mmol) in diethyl ether (10 mL) at 50 °C for 70
min. The resulting solution was kept for 3 days in the dark at room
temperature to obtain single crystals suitable for X-ray analysis.
Experimental Section
Yield: 70% based on AgCF
Calcd for C19 : C, 32.50; H, 2.30. H NMR (acetone-
, 300 MHz): δ 2.097 (qt, 2H, -S(CH )(CH )-), 3.282 (t, 4H,
S(CH )-), 7.281-7.553 (m, 10H, C
acetone-d
3 2
CO . Anal. Found: C, 32.68; H, 2.18.
Materials and General Methods. Except for the ligand, all the
reagents required for the syntheses were commercially available
and employed without further purification. The elemental analyses
were performed by the Laboratoire d’analyse e´ l e´ mentaire (Univer-
sit e´ de Montr e´ al). The IR spectra (KBr pellets) were recorded on
1
2 6 4 2
H16Ag F O S
d
-
(
6
2
2
19
1
2
6
H
5
-). F{ H} NMR
-1
6
, 376.31 MHz): -74.148 (s, F-C). IR (KBr, cm ):
1
7
685 vs, 1583 m, 1479 s, 1436 s, 1208 s, 1025 m, 838 s, 804 s,
24 s, 689 m.
-1
1
a Perkin-Elmer 1750 FTIR spectrometer (4000-450 cm ). H (400
and 300 MHz), 13C{ H} (100.56 MHz), and F (376.31 MHz)
solution NMR spectra were recorded at 25 °C, either on a Bruker
ARX400, AMX300, or AV300 spectrometer. Chemical shifts,
1
19
3
[Ag
2
L (CF
3
CF
2
CO
2
)
2
(CH
3
COCH
3
)]
∞
(3). A 10 mL volume of
CF CO . The
mixture was stirred with a solution of L (0.20 mL, 0.87 mmol) at
0 °C for 140 min. The resulting solution was layered on diethyl
acetone was added to 360 mg (1.33 mmol) of AgCF
3
2
2
3
6
(
(
(
4) (a) Goodgame, D. M. L.; Grachvogel, D. A.; Hussain, I.; White, A. J.
P.; Williams, D. J. Inorg. Chem. 1999, 38, 2057. (b) Bu, X. H.; Chen,
W.; Lu, S. L.; Zhang, R. H.; Liao, D. Z.; Bu, W. M.; Shionoya, M.;
Brisse, F.; Ribas, J. Angew. Chem., Int. Ed. 2001, 40, 3201.
5) (a) Withersby, M. A.; Blake, A. J.; Champness, N. R.; Cooke, P. A.;
Hubberstey, P.; Li, W. S.; Schr o¨ der, M. Inorg. Chem. 1999, 38, 2259.
ether and then stored at room temperature in the dark. Several days
later, relatively large colorless crystals appeared. Yield: 35% based
on AgCF
3 2 2
CF CO . One such crystal was cut into a platelet and
mounted for X-ray analysis. Anal. Found: C, 33.84; H, 2.61. Calcd
1
(
b) Blake, A. J.; Champness, N. R.; Cooke, P. A.; Nicolson, J. E. B.;
for C24
3
H
22Ag
2
F
10
O
5
S
2
: C, 33.51; H, 2.58. H NMR (DMSO-d
00 MHz): 2.053 (qt, 2H, -S(CH )(CH )-), 3.194 (t, 4H,
)-), 7.236-7.449 (m, 10H, C
, 376.31 MHz): -84.064 (CF ) and -119.248 (CF
6
,
Wilson, C. J. Chem. Soc., Dalton Trans. 2000, 3811.
2
2
6) For example: (a) Withersby, M. A.; Blake, A. J.; Champness, N. R.;
Hubberstey, P.; Li, W. S.; Schr o¨ der, M. Angew. Chem., Int. Ed. 1997,
1
9
1
-
S(CH
2
6
H
5
-). F{ H} NMR
CF ).
3
6, 2327. (b) Noro, S.; Kitaura, R.; Kondo, M.; Kitagawa, S.; Ishii,
T.; Matsuzaka, H.; Yamashita, M. J. Am. Chem. Soc. 2002, 124, 2568.
c) Chatterton, N. P.; Goodgame, D. M. L.; Grachvogel, D. A.;
Hussain, I.; White, A. J. P.; Williams, D. J. Inorg. Chem. 2001, 40,
12.
(DMSO-d
6
3
3
2
-
1
IR (KBr, cm ): 1679 vs, 1481 m, 1438 m, 1329 m, 1210 m, 1159
(
s, 1030 s, 817 m, 734 m, 690 m.
3
3
[AgL (CF
CF CF CO )]
3 2 2 2 ∞
(4). A solution of AgCF
3
CF
2
CF
2
CO
2
(
(
(
7) Bu, X. H.; Chen, W.; Hou, W. F.; Du, M.; Zhang, R. H.; Brisse, F.
(252 mg, 0.785 mmol) in acetone (10 mL) was stirred with a
solution of L (0.25 mL, 1.08 mmol) in diethyl ether (5 mL) at 60
Inorg. Chem. 2002, 41, 3477.
8) Awaleh, M. O.; Badia, A.; Brisse, F. Submitted for publication in
Cryst. Growth Des.
3
°
C. The mixture was refluxed for 70 min and layered on hexane at
9) Oh, M.; Carpenter, G. B.; Sweigart, D. A. Angew. Chem., Int. Ed.
room temperature and left in the dark. After 3 days, single crystals
suitable for X-ray analysis were obtained. Yield: 35% based on
2002, 41, 3650.
(
10) (a) Moulton, B.; Zaworotko, M. J. Chem. ReV. 2001, 101, 1629. (b)
Gudbjartson, H.; Biradha, K.; Poirer, K. M.; Zaworotko, M. J. J. Am.
Chem. Soc. 1999, 121, 2599. (c) Kasai, K.; Aoyagi, M.; Fujita, M. J.
Am. Chem. Soc. 2000, 122, 2140.
(11) Hartley, F. R.; Murray, S. G.; Levason, W.; Soutter, H. E.; McAuliffe,
C. A. Inorg. Chim. Acta 1979, 35, 265.
7834 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
1
AgCF
3
CF
2
CF
2
CO
: C, 39.26; H, 2.77. H NMR (acetone-d
)(CH )-), 3.208 (t, 4H, -S(CH
-). 19F{ H} NMR (acetone-d
), -116.658 (CF CF CF ), -127.852
2
. Anal. Found: C, 39.44; H, 2.34. Calcd for
Ag
2 6 6 4 6
F O S : C, 26.37; H, 2.08. H NMR (acetone-d , 300 MHz):
1
C
19
H16AgF
7
O
2
S
2
6
, 300
)-
2.347 (qt, 2H, -S(CH )(CH )-), 3.356 (t, 4H, -S(CH )-), 7.312-
7.548 (m, 10H, C H -). F{ H} NMR (acetone-d , 376.31 MHz):
2
2
2
19
1
MHz): δ 2.046 (qt, 2H, -S(CH
, 7.223-7.466 (m, 10H, C
76.31 MHz): -81.986 (CF
CF CF CF ).
AgL (p-TsO)]
2
2
2
6
5
6
1
-1
)
3
6
H
5
6
,
-78.868 (s, F-C). IR (KBr, cm ): 3434 m, 1623 m, 1257 vs,
172 s, 1030 s, 742 m, 687 m, 636 s, 521 m.
[Ag ](ClO (CH COCH (10) and {[Ag
L3
CH COCH (11). Other complexes related to 1 were synthe-
3
3
2
2
1
(
3
2
3
2
{
2
4
)
4 2
3
3
) }
2 ∞
L3
](SbF ) -
2 4 6 2
[
∞
(5). A solution of Ag(p-TsO) (302.9 mg, 1.08
(
3
1
3 2 ∞
) }
3
mmol) in acetone (5 mL) was stirred with a solution of L (0.20
mL, 0.87 mmol) in diethyl ether (5 mL) at 60 °C for 150 min.
This solution was filtered and layered on petroleum ether at room
temperature. After 2 days in the dark, the mixture yielded single
crystals suitable for X-ray analysis. These crystals were then stored
in a freezer to avoid their eventual decomposition. Yield: 65% based
2
-
-
sized using weakly coordinating anions: ClO
4 6
(10); SbF (11).
Their syntheses follow the procedure detailed for 1. These will not
be fully described as the acetone molecules were too disordered to
be precisely located by X-ray analysis.
Caution! Although we met no problems in handling perchlorate
salts, great care should be taken due to their potentially explosive
nature.
on Ag(C
AgO
.963 (qt, 2H, -S(CH
t, 4H, -S(CH )-), 7.304-7.403 (m, 10H, C
m, 4H, CH
7
H
O
7 3
S). Anal. Found: C, 48.55; H, 4.15. Calcd for C22
H
23
-
1
3
S
3
: C, 48.98; H, 4.30. H NMR (acetone-d
6
, 400 MHz): δ
SO ), 3.175
-), 7.762-7.791
). IR (KBr, cm ): 1583 m, 1480 m, 1438 m,
1
(
(
)(CH )-), 2.424 (s, 3H, CH C H
2 2 3 6 4
3
Crystal Structure Determinations. X-ray diffracted intensities
were measured on a Bruker AXS Platform diffractometer equipped
with a SMART 2K CCD area detector using monochromatic Cu
KR (λ ) 1.541 78 Å) radiation. The X-ray intensity data were
processed with the program SAINT. An empirical absorption
correction, based on multiple measurements of equivalent reflec-
tions, was applied using the program SADABS. The space group
was confirmed by the XPREP15 routine in the program SHELXTL.16
The structures were solved by direct methods and refined by full-
2
6 5
H
-
1
3
C
6
H
4
SO
3
1189 vs, 1131 m, 1044 m, 1014 m, 816 m, 737 s, 690 s, 565 m.
3
[AgL (p-TsO)]
∞
(6). The synthesis of this complex is identical
13
with that of 5, except that 6 was recrystallized from diethyl ether
at room temperature. The mixture was kept in the dark for 2 days
to obtain single crystals suitable for X-ray analysis. Yield: 65%
based on Ag(p-TsO). Anal. Found: C, 48.56; H, 4.15. Calcd for
14
C
22
H
23AgO
S
3 3
: C, 48.98; H, 4.30. 1H NMR (acetone-d
MHz): δ 2.045 (qt, 2H, -S(CH )(CH )-), 2.403 (s, 3H, CH
SO ), 3.202 (t, 4H, -S(CH )-), 7.189-7.464 (m, 10H, C
.761-8.012 (m, 4H, CH
m, 1480 m, 1438 m, 1384 s, 1190 vs, 1131 m, 1044 m, 1015 m,
6
, 400
2
2
3 6 4
C H -
3
3
2
6
H
5
-),
(12) {[Ag2L 4](ClO4)2(CH3COCH3)2}∞ (10): C66H76Ag2O10Cl2S8; fw 1572.47.
-1
This was synthesized using the same conditions as 1 with AgClO4‚H2O
178 mg, 0.79 mmol) and L (0.35 mL, 1.52 mmol). Yield: 65% based
7
3 6 4 3
C H SO ). IR (KBr, cm ): 3439 m, 1583
3
(
on AgClO4‚H2O. A TGA curve indicated a two-step decomposition
(Figure S9). First, two acetone molecules were released between 95
and 110 °C (expt/theor ) 7.19/7.38%). In a second step occurring
between 180 and 310 °C, the ligands were eliminated (expt/theor )
8.56/66.24%). The residue consisted of AgClO4. This result is
coherent with the analytical results. Anal. Found: C, 49.94; H, 4.53.
815 m, 738 s, 690 s, 565 m.
3
[Ag
2
L (CF
SO ) (CH COCH )]
3 3 2 3 3 ∞
(7). A solution of AgCF
SO
3 3
(
617.9 mg, 2.4 mmol) in acetone (5 mL) was stirred with a solution
6
3
of L (0.20 mL, 0.87 mmol) in diethyl ether (5 mL) at 60 °C for
0 min. The resulting mixture was layered on petroleum ether and
1
Calcd for C66H76Ag2O10Cl2S8: C, 50.41; H, 4.87. H NMR (DMSO-
9
d6, 400 MHz): δ 1.813 (qt, 2H, -S(CH2)(CH2)-), 3.064 (t, 4H,
kept at room temperature in the dark. After 4 days, single crystals
suitable for X-ray analysis were obtained. Yield: 40% based on
-1
-
S(CH2)-), 7.272-7.694 (m, 10H, C6H5-). IR (KBr, cm ): 3447
m, 3057 w, 2916 w, 1634 s, 1583 m, 1479 s, 1438 s, 1297 w, 1137
s, 1073 vs, 1025 m, 934 w, 737 s, 689 s, 474 w. Crystal data:
monoclinic, P21/c; a ) 26.3970(1), b ) 12.8558(2), c ) 20.9301(3)
AgCF
Ag
3
SO
3
. Anal. Found: C, 28.29; H, 2.27. Calcd for C20
H
22
-
1
2
F
6
O
7
S
4
: C, 28.86; H, 2.66. H NMR (DMSO-d
6
, 300 MHz):
)-),
, 376.31
3
-1
Å; â ) 94.47(1)°; V ) 3540.54(8) Å ; Z ) 4; µ(Cu KR) ) 7.15 mm
;
δ 2.115 (qt, 2H, -S(CH
2
)(CH
2
)-), 3.343 (t, 4H, -S(CH
2
Nref 6997, Npar 398; R1 (I > 2σ(I)) ) 0.0597, wR2 ) 0.1550, R1
(all data) ) 0.0808, wR2 ) 0.1674, S ) 0.947. The perchlorate anions,
the acetone molecules, and half of the ligands are disordered. All
attempts to form complexes with different stoichiometries failed. The
starting ligand:silver perchlorate ratios (1:1, 1:2, 1:3, 1:4, 2:1, 2:3;
2:5) always produced crystals with the same unit-cell dimensions as
-). 19F{ H} NMR (DMSO-d
1
7
.362-7.574 (m, 10H, C
6
H
5
6
MHz): -79.015 (s, F-C). IR (KBr, cm 1): 1480 m, 1438 m, 1258
-
vs, 1178 s, 1033 s, 737 s, 690 s, 642 s, 580 m, 519 m.
3
[Ag
2
L (CF
3
SO
3
)
]
2 ∞
(8). To a solution of AgCF
3
SO
3
(274.7 mg,
3
3
10. {[Ag2L 4](SbF6)2(CH3COCH3)2}∞ (11): C66H76Ag2F12O2S8Sb2; fw
1845.07. This was synthesized using the same conditions as 1 with
AgSbF6 (164 mg, 0.48 mmol) and L (0.35 mL, 1.52 mmol). Yield:
74% based on AgSbF . Anal. Found: C, 42.88; H, 3.89. Calcd for
1.07 mmol) in acetone (5 mL) was added a solution of L (0.20
)
mL, 0.87 mmol) in diethyl ether (5 mL). The mixture was stirred
at 50 °C for 40 min and then layered on diethyl ether and left to
stand in the dark at room temperature. Crystals suitable for an X-ray
study appeared after 3 weeks. Yield: 38% based on AgCF
Anal. Found: C, 26.78; H, 2.15. Calcd for C17
3
6
1
C66H76Ag2F12O2S8Sb2: C, 42.96; H, 4.15. H NMR (DMSO-d6, 400
MHz): δ 1.845 (qt, 2H, -S(CH2)(CH2)-), 3.073 (t, 4H, -S(CH2)-
3 3
SO .
-
1
)
, 7.281-7.598 (m, 10H, C6H5-). IR (KBr, cm ): 3435 w, 3057 m,
H
16Ag
2
F
6
O
6
S
4
: C,
2
918 m, 1583 s, 1480 s, 1438 s, 1334 w, 1301 w, 1257 w, 1158 w,
1
26.37; H, 2.08. H NMR (acetone-d
6
, 300 MHz): 2.255 (qt, 2H,
)-), 7.206-7.415 (m, 10H,
, 376.31 MHz): -79.210 (s,
1089 m, 1069 w, 1024 s, 737 vs, 691 vs, 664 vs, 491 m. Crystal data:
monoclinic, P21/c; a ) 27.1584(2), b ) 13.0497(2), c ) 20.5848(3)
-
S(CH
2
)(CH
2
1
)-), 3.186 (t, 4H, -S(CH
2
3
Å; â ) 97.79(1)°; V ) 3614.10(9) Å ; Z ) 4; µ(Cu KR) ) 12.87
C
6
H
5
-). 19F{ H} NMR (acetone-d
6
-1
mm ; Nref 7095, Npar 434; R1 (I >2σ(I)) ) 0.0528, wR2 ) 0.1454,
-
1
F-C). IR (KBr, cm ): 1630 m, 1481 m, 1438 m, 1385 s, 1260
vs, 1178 m, 1089 m, 1034 s, 739 m, 691 m, 645 m.
R1 (all data) ) 0.0695, wR2 ) 0.1529, S ) 1.045. The fluorine atoms
have a slight oscillating disorder while the acetones are much more
disordered. The silver atoms and the ligands form cationic sheets of
3
[Ag
2
L (CF
3
SO
3
)
]
2 ∞
(9). To generate different structures the
3
composition Ag2L 4. The noncoordinating anions and the guest
molar ratio of silver salt to ligand was modified. To a solution of
AgCF SO (614 mg, 2.4 mmol) in acetone (5 mL) was added a
solution of L (0.30 mL, 1.3 mmol) in diethyl ether (5 mL). The
mixture was stirred at 60 °C for 160 min and then layered on hexane
and left to stand in the dark at room temperature. Crystals suitable
for an X-ray study appeared after 3 weeks. Yield: 81% based on
molecules occupy the voids between parallel sheets. The TGA curve
shown in Figure S10 reveals the same decomposition pattern noted
for 1 and 10. The acetone molecules leave first, at a temperature
between 75 and 90 °C (expt/theor ) 6.59/6.29%), followed by the
loss of the ligands, between 160 and 310 °C (expt/theor ) 60.41/
56.45%), which leaves a residue of AgSbF6.
3
3
3
(
13) SAINT, Release 6.06, Integration Software for Single-Crystal Data;
Bruker AXS Inc.: Madison, WI, 1999.
14) Sheldrick, G. M. SADABS Bruker Area Detector Absorption Correc-
tions; Bruker AXS Inc.: Madison, WI, 1996.
3 3
AgCF SO . These crystals had a morphology clearly different from
(
those of 8. Anal. Found: C, 26.06; H, 1.91. Calcd for C17
16
H -
Inorganic Chemistry, Vol. 44, No. 22, 2005 7835

Awaleh et al.
Table 1. Crystal Data and X-ray Data Collection Parameters
param
formula
1
2
3
4
5
C66H76Ag2F12O2S8P2
1663.51
0.35 × 0.25 × 0.15
monoclinic
P21/c
26.7293(3)
13.0101(1)
20.9805(2)
90
C19H16Ag2F6O4S2
702.18
0.31 × 0.12 × 0.03
monoclinic
P21/c
26.1193(2)
11.2175(1)
7.3670(1)
90
91.709(1)
90
C24H22Ag2F10O5S2
860.28
0.23 × 0.12 × 0.03
monoclinic
C2/c
25.5907(3)
8.4233 (1)
29.4683 (3)
90
107.886(1)
90
C19H16AgF7O2S2
581.31
0.43 × 0.11 × 0.04
Monoclinic
C2/c
17.1456(2)
8.3145(1)
30.1588(3)
90
105.543(1)
90
C22H23AgO3S3
mol wt
539.45
0.23 × 0.13 × 0.10
monoclinic
P21/n
15.0658(2)
8.8692(1)
16.2685(2)
90
93.760(1)
90
2169.14(5)
4
cryst size (mm)
cryst system
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
95.253(1)
90
γ (deg)
3
V (Å )
7265.34(12)
4
2236.59(4)
4
6045.13(12)
8
4142.12(8)
8
Z
D(calcd) (g cm-3)
F(000)
1.521
3392
2.085
1368
1.890
3376
1.864
2304
1.652
1096
temp (K)
220(2)
7.514
72.98
0.0622
0.1746
0.0727
0.1830
1.072
220(2)
16.501
72.91
0.0446
0.1099
0.0495
0.1129
1.007
220(2)
12.574
72.94
0.0527
0.1357
0.0545
0.1378
1.053
100(2)
10.420
72.89
0.0367
0.0878
0.0426
0.0902
0.998
220(2)
10.329
72.90
0.0452
0.1264
0.0511
0.1309
1.055
-
1
µ (mm
)
θmax (deg)
a
R1
Rw
b
2
R [F > 2σ(F2)]
2
wR(F )
S
param
6
7
8
9
formula
mol wt
C22H23AgO3S3
539.45
C20H22Ag2F6O7S4
832.36
C8.5H8AgF3O3S2
387.14
C17H16Ag2F6O6S4
774.28
cryst size (mm)
cryst system
space group
a (Å)
b (Å)
c (Å)
0.26 × 0.24 × 0.17
monoclinic
P21/c
14.6787(3)
9.8460(2)
15.7897(4)
90
99.383(2)
90
2251.50(9)
4
0.30 × 0.07 × 0.05
monoclinic
P21/n
8.4179(2)
24.1660(4)
13.9928(2)
90
93.960(1)
90
2839.72(9)
4
0.17 × 0.05 × 0.02
monoclinic
C2/c
28.9764(10)
4.8104(2)
20.3261(7)
90
119.012(1)
90
2477.70(16)
8
0.21 × 0.12 × 0.09
monoclinic
P21/n
8.1416(1)
23.6395(2)
12.3921(1)
90
90.757(1)
90
2384.82(4)
4
R (deg)
â (deg)
γ (deg)
3
V (Å )
Z
D(calcd) (g cm-3)
F(000)
1.591
1096
1.947
1640
2.076
1512
2.157
1512
temp (K)
220(2)
9.952
72.85
0.0461
0.1157
0.0624
0.1226
0.975
220(2)
14.538
72.77
0.0561
0.1366
0.0669
0.1433
0.975
220(2)
16.569
55.03
0.0367
0.0727
0.0608
0.0778
0.898
100(2)
17.214
72.75
0.0476
0.0727
0.1292
0.1507
1.097
-
1
µ (mm
)
θmax (deg)
a
R1
Rw
b
2
2
R [F > 2σ(F )]
2
wR(F )
c
S
a
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(Fo2 - Fc ) /∑w(Fo ) ] . c S ) [∑w(Fo2 - Fc ) /(m - n)]1/2, where m is the number of observations and n the
b
2 2
2 2 1/2
2 2
number of parameters.
matrix least-squares and difference Fourier techniques.17 All non-
hydrogen atoms were refined anisotropically, while the hydrogen
atoms were introduced at calculated positions using a riding model
sites in the proportions of 39, 15, 27, and 19%. The C-F distances
17
in both anions were constrained to be equal (SADI ). The thermal
parameters of all disordered atoms were constrained such that the
corresponding atoms of the major and the minor entities kept the
and refined isotropically. The thermal parameters of the fluorine
-
17
atoms of the PF
6
counteranions in complex 1 were slighty higher
same values (EADP ). Because of the correlation between the
than those of the other atoms in the structure, indicating a slight
disorder for this group. Because the acetone molecules were also
disordered, their carbon atoms were refined isotropically. The
occupancy factors of the two disordered pentafluoropropionate
anions in complex 3 were refined. One anion is split over two sites,
with occupancies of 61 and 39%, while the other occupies four
temperature factor and the occupancy factor, the former was refined
isotropically. Finally, the occupancy factor was fixed and the model
was refined anisotropically with the ISOR17 constraints imposed
on the fluorine atoms. The data collection for 8 was limited to θ )
55°, since the crystal did not diffract at higher angles. The solvent
molecules in 10 and 11, present in a very disordered state, prevented
us from establishing their exact position within the structures.
However, the main constituents of the structures were found without
ambiguity. Crystal data, data collection, and structure refinement
parameters are listed in Table 1.
(15) XPREP Release 5.10, X-ray Data Preparation and Reciprocal Space
Exploration Program; Bruker AXS Inc.: Madison, WI, 1997.
(16) SHELXTL Release 5.10, The Complete Software Package for Single-
Crystal Structure Determination; Brucker AXS Inc.: Madison, WI,
1
997.
Results and Discussion
(
17) (a) Sheldrick, G. M. SHELXS97, Program for the Solution of Crystal
Structures; University of G o¨ ttingen: G o¨ ttingen, Germany, 1997. (b)
Sheldrick, G. M. SHELXL97, Program for the Refinement of Crystal
Structures; University of G o¨ ttingen: G o¨ ttingen, Germany, 1997.
Crystal Structures. {[Ag
Complex 1 forms a two-dimensional coordination network,
L3
](PF ) (CH COCH ) } (1).
2 4 6 2 3 3 2 ∞
7836 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
Figure 1. (a) Cationic sheet of 1 parallel to (001). (The anions, the acetone, and the H atoms are omitted for clarity.) (b) Packing of 1 shown as a projection
of the cationic sheets onto the ac-plane.
in which each crystallographically independent Ag(I) is
linked in a tetrahedral manner to a sulfur atom of four
different L ligands. The other sulfur atom of each ligand is
bound to a neighboring Ag(I) ion thus forming a cationic
sheet parallel to the (001)-plane (Figure 1a). The Ag-S
distances, 2.538(1)-2.598(1) Å, fall within the normal range
of silver(I)-thiol complexes. The silver atoms adopt a
pounds, 1, 10, and 11, may be considered as being isostruc-
+
tural. Related structures, [Ag (PhSCH
2
CH
2
CH
2
SPh)
2
] with
-
the BF
SePh)
4
anion and water and [Ag (PhSeCH
2
CH
2
2
CH -
]+ with BF
-
and CH
Cl
2
8,19
4
2
2
, were reported by Black et
1
al.
pounds are in fact “isostructural” with 1, 10, and 11, although
the guest is now water (Figure S1d) or CH Cl . Common to
The authors indicate a 3D-network, but their com-
2
2
distorted tetrahedral environment (S-Ag(1)-S ) 104.4(1)-
all these structures is the fact that the anions have a slight
oscillating disorder and the guest is, in most cases, very
disordered. This is a typical occurrence in host-guest (inter-
calation) compounds. In contrast, it is worth pointing out
that the structures observed when the shorter bis(phenylthio)-
methane ligand is combined with the same anions, a 1D-
coordination polymer is observed instead of the layered
-
1
16.5(1)°; S-Ag(2)-S ) 99.0(1)-128.6(1)°). The PF
6
anions and the acetone molecules are inserted between the
layers. The distance between sheets is half the c-dimension
of the unit cell (10.49 Å). The sheets are stacked parallel to
the ab-plane. The repeating unit in 1 is a 24-membered
3
macrometallocycle Ag
4
L
4
. The S‚‚‚S distances of the ligands
8
-
-
are different and have values of 5.525(1), 5.510(1), 5.027-
structure. Furthermore, XY
4
anions, as well as CF
3
COO
-
(1), and 5.535(1) Å, respectively. This complex forms a
and CF
3
SO
3
, are coordinated to the Ag(I) ions. To study
noninterpenetrating framework and the phenyl groups are
located on both sides of the layers in a manner comparable
to the 1,4-bis(phenylthio)butane ligand. In the packing of
the effect of the anion upon the network structure, complexes
with more strongly coordinating counteranions, such as
trifluoroacetate and trifluoromethanesulfonate were studied.
7
20
the structural units, the aromatic rings are concentrated in a
3
[Ag
2
L (CF
3
COO)
2
]
∞
(2). Two silver atoms are joined in
-
plane at c/2 that also includes the PF
6
anions and the acetone
a bridging mode by two trifluoroacetate groups, thus giving
molecules (Figure 1b). Weakly coordinating counterions such
as tetrafluoroborate18 and hexafluorophosphate are situated
between the cationic sheets, instead of being coordinated to
the metal. However, since 1 also accommodates acetone
molecules between the layers, a thermogravimetric investiga-
tion was undertaken to establish how strongly the acetone
21a
rise to a (AgOOCCF
)
3 2
dimer (Chart 1). These dimers are
-S bridge, so as
linked together by the ligands, through a µ
2
to form a chain parallel to the b-axis (Figure S2). Since each
sulfur is bound to two silver ions, the chains are intercon-
nected and form a 2D-coordination network (Figure 2a). Each
Ag(I) ion is linked to two sulfur atoms from two distinct
ligands (Ag-S: 2.478(1) and 2.697(1) Å) and to two oxygen
atoms from two distinct trifluoroacetate groups (Ag-O:
molecules are held within the structure (see below).
3
3 2 ∞ 2 4
) } (10) and {[A ]-
gL3
{
[Ag
SbF
comparable unit cell dimensions, space groups, and stoichi-
2
L
4
](ClO
4
)
2
(CH
3
COCH
(
)
6 2
(CH
3
COCH
3 2 ∞
) } (11). Complexes 1, 10, and 11 have
2
.268(3) and 2.348(3) Å). There is a further weak bond
between the silver atoms of the dimer (Ag‚‚‚Ag: 3.2459(5)
Å). Thus, the coordination around the silver atom is a
distorted triangular bipyramid (S-Ag-S ) 155.6(1);
1
2
3
2 4
ometries. The structure consists of Ag L layers (silver(I)
and ligands) between which are inserted the anions and the
guest molecules. These cationic sheets are practically identi-
cal with 1 (Figure S1a-d). Furthermore, as we report above
(
(
(
19) Black, J. R.; Champness, N. R.; Levason, W.; Reid, G. J. Chem. Soc.,
-
Dalton Trans. 1995, 3439.
20) Jung, O. S.; Kim, Y. J.; Lee, Y. A.; Park, K. M.; Lee, S. S. Inorg.
Chem. 2003, 42, 844.
21) (a) Griffin, R. G.; Ellett, J. D., Jr.; Mehring, M.; Bullitt, J. G.; Waugh,
J. S. J. Chem. Phys. 1972, 57, 2147. (b) Blakeslee, A. E.; Hoard, J. L.
J. Am. Chem. Soc. 1956, 78, 3029.
for the PF
6
anion, the acetone molecules present in 10 and
1
1 are in a very disordered state. Hence, the three com-
(
18) Black, J. R.; Champness, N. R.; Levason, W.; Reid, G. J. Chem. Soc.,
Chem. Commun. 1995, 1277.
Inorganic Chemistry, Vol. 44, No. 22, 2005 7837

Awaleh et al.
Chart 1
torted square-based pyramid (S-Ag(1)-Ag(1) ) 150.6(1)°;
O-Ag(1)-O ) 103.6(1), 123.7(2), and 123.8(2)°). On the
other hand, the other silver, Ag(2), is coordinated to the
oxygen of the acetone molecule (Ag(2)-O: 2.333(4) Å), to
two other oxygen atoms, each from a different pentafluoro-
propionate (Ag(2)-O: 2.354(4), 2.408(4) Å), and to a sulfur
atom also bound to Ag(1) (Ag(2)-S: 2.488(1) Å). This
second silver atom, Ag(2), has the environment of a distorted
tetrahedron (S-Ag(2)-O ) 125.8(1), 115.8(1)°; O-Ag(2)-O
)
110.4(2), 78.6(2)°). Two adjacent Ag(2) atoms are coupled
in a monatomic bridging mode by two pentafluoropropi-
onates, thus forming a (Ag OOCCF CF dimer (Chart 1).
2
2
3 2
)
However, the long Ag(2)‚‚‚Ag(2) distance, 3.6854(8) Å,
signals the absence of any interaction between the Ag(2)
2
3
ions. There are two distinct repeat units in this complex:
unit A (Figure 3a); unit B (Figure 3b, Figure S4). In unit A,
two pentafluoropropionate groups bring adjacent silver atoms
together in a dibridging mode. Two of these are linked into
3
a 14-membered-ring, the Ag
4
L
2
repeat unit A, by two ligand
molecules. The A units share Ag‚‚‚Ag edges and, in doing
so, give rise to a ribbon. The B units, whose pairs of
neighboring silver atoms are tied in a monatomic bridging
mode by pentafluoropropionate groups, consist of 20-
membered-rings. They, in turn, share edges yielding another
ribbon. Neighboring A and B ribbons share their ligand edges
resulting in a 2D-sheet (Figure 3c). The neutral sheets are
stacked parallel to the (100)-plane (Figure 3d). The S‚‚‚S
O-Ag-O ) 110.2(2), 112.1(1), and 133.0(1)°). The
Ag‚‚‚Ag interaction is somewhat longer than that observed
distances in all the ligands of complex 3 are 5.621(3) Å long.
3
[
AgL (CF
3
CF
2
CF
2
CO
2
)]
∞
(4). Here, two adjacent silver
2
2
in trifluoroacetate-bridged silver-silver systems (3.16 Å )
atoms are brought together in a diatomic bridging mode by
two heptafluorobutyrate anions (Chart 1) resulting in Ag (O
CCF CF CF dimers, which are connected by two ligands
8
or from our own results but significantly shorter than the
2
2
-
23
sum of the van der Waals radii (3.40 Å ). The S‚‚‚S distance
2
2
3 2
)
for all the ligands is 4.938(1) Å. The repeat unit of this
to generate a double chain parallel to the b-axis (Figure 4a,b).
The packing of the chains, projected end on onto the ac-
plane, is of the distorted hexagonal-type (Figure 4c). Each
silver atom is linked to two oxygen atoms (Ag-O: 2.330-
3
complex is formed by two rings, an 11-membered, Ag
and a seven-membered, Ag
4
L S
2
,
3
2
L , metallomacrocycle sharing
a side (Figure 2a). These rings constitute a puckered 2D-
3
2 3 2 ∞
network of [Ag L (CF COO) ] , sheets parallel to the (100)-
(
2) and 2.417(2) Å), from different heptafluorobutyrate
groups, to two sulfur atoms from distinct ligands (Ag-S:
.5027(8) and 2.5913(8) Å) and to another silver atom
3.1594(4) Å). Hence, the silver atom has a 5-fold coordina-
tion (O-Ag-O ) 119.4(1)°; O-Ag-S ) 110.2(1), 117.1-
plane and separated by a/2 (Figure 2b). In addition, the
topology of this complex is that of a wire netting, where the
repeat unit is a chairlike six-membered ring reminiscent of
that adopted by some elements such as arsenic, antimony,
2
(
2
4,25
and bismuth
(Figure S3).
3 ∞
CF CO (CH COCH )] (3). In this complex,
(
1)°; S-Ag-Ag ) 149.5(1)°). The short silver-silver
3
22,27
[
Ag
2
L (CF
3
2
2
)
2
3
distance indicates again a weak metal-metal interaction.
which incorporates an acetone molecule, there are two kinds
of silver atoms. On one hand, Ag(1) atoms are coordinated
to two sulfurs from two distinct ligands (Ag-S: 2.500(1)
and 2.625(1) Å) and to two oxygens from two different
pentafluoropropionates (Ag-O: 2.345(4) and 2.359(4) Å).
In addition, two neighboring Ag(1) atoms are connected in
a diatomic bridging mode by two pentafluoropropionates to
form an Ag (O CCF CF ) dimer (Chart 1). These silver
2 2 2 3 2
atoms are weakly bound, as the Ag(1)‚‚‚Ag(1) distance is
only 3.0502(7) Å. The coordination of Ag(1) is that of a dis-
The repeat unit of complex 4 is a 14-membered metallo-
3
macrocycle, Ag
of complex 3. However, contrary to 3, complex 4 forms a
D-coordination polymer. It seems that the increased length
4 2
L , which is identical with that of unit A
1
and bulk of the counteranion prevent the formation of B units
as in complex 3. It is worth noting that the fluorocarbon
chain length of the counteranion modifies the supramolecular
-
-
networks.Indeed,complexes2(CF
3
CO
2
)and3(CF
CF
3
CF
CF
2
CO
2
)
form 2D-networks, whereas complex 4 (CF
3
2
2
CO
2
-)
is a 1D-coordination polymer. This fact shows the influence
of the size of the counteranion upon the supramolecular
architecture. The S‚‚‚S distances in all ligands of complexes
3 and 4 are respectively 5.621(3) and 5.537(1) Å. These
(
(
22) Bosch, E.; Barnes, C. L. Inorg. Chem. 2002, 41, 2543.
23) Porterfield, W. W. Inorganic Chemistry: A Unified Approach,
Addison-Wesley: Reading, MA, 1994; pp 168, 180.
(
(
24) Brandys, M.-C.; Puddephatt, R. J. J. Am. Chem. Soc. 2002, 124, 3946.
25) Wells, A. F. Structural Inorganic Chemistry; Oxford University
Press: Oxford, U.K., 1975.
(26) Ara, I.; El Bahij, F.; Lachkar, M. Acta Crystallogr. 2003, C59, m265.
(27) Wang, Q. M.; Mak, T. C. W. J. Am. Chem. Soc. 2001, 123, 7594.
7838 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
Figure 2. (a) Repeat unit of 2 showing the 7-and 11-membered metallomacrocycles associated in a sheetlike structure. (The phenyl and the trifluoroacetate
groups, as well as the H atoms, are omitted for clarity.) (b) Sheets, perpendicular to the a-axis, shown edge-on in this packing of 2. Note the “in-phase”
disposition of consecutive layers.
Figure 3. (a). A repeat unit of complex 3. (Phenyl group and H atoms are omitted for clarity.) (b) View of the B repeat unit. (c) Association of the A and
B units into ribbons, which in turn combine into the 2D-network of 3. (d) Packing of complex 3. The layers are shown edge-on.
distances are significantly longer than that in complex 2,
.938(1) Å. This difference may be explained by the fact
that the heptafluorobutyrate and the pentafluoropropionate
anions are more flexible than the trifluoroacetate, thus
allowing complexes 3 and 4 to be less strained than complex
averaged C-O distances remain fairly constant (1.228, 1.216,
and 1.236 Å in 2-4, respectively). However, the average
Ag‚‚‚O distance increases from 2.290 for 2, to 2.351
for3,and2.374Åfor4.Thisobservationseemstopointtoacorrelation
between average Ag-O distance and the increasing electron-
withdrawing power related to the number of fluorine atoms
in the anions, increasing from acetate to butyrate. Here again,
when the shorter bis(phenylthio)methane ligand is used with
perfluorocarboxylate anions, no 2D-networks are reported
4
2. This fact reveals that the structure of coordination networks
based on flexible ligands depends not only on their degree
7
of flexibility but also on the size of the counteranion, when
the latter is part of the network. The carboxylate planes in
each dimer form a dihedral angle of about 120°, and the
8
but double-stranded 1D-chains are noted.
Inorganic Chemistry, Vol. 44, No. 22, 2005 7839

Awaleh et al.
Figure 4. (a) View of the repeat unit of 4 and (b) their association into a 1D-chain extending parallel to the b-axis. (The phenyl and heptafluorobutyrate
groups and the H atoms are omitted for clarity.) (c) Packing projection of complex 4, showing the chains perpendicular to the ac-plane.
3
Figure 5. (a) Repeat unit of 5 showing the eight-membered Ag2O4S2. (b) 20-membered Ag4L 2O4S2 metallomacrocycles as part of a 1D-chain extending
in the b-direction. (The phenyl groups and the H atoms are omitted for clarity.) (c) Packing of the chains of 5 seen along the chain axis.
3
[
AgL (p-TsO)]
∞
(5). In this complex, two silver atoms
O-Ag-S ) 131.5(1), 103.5(1), and 88.2(2)°. The S‚‚‚S
separation in every ligand is 5.548(1) Å indicative of a fully
extended conformation. The Ag‚‚‚Ag distance, which is
3.7503(5) Å, excludes any metal-metal interaction (Chart
1). The projection of the structure onto the ac-plane reveals
that each double chain is surrounded by four others in a
and two p-tosylate groups form a dimer in a bridging mode
through two of the latter’s oxygen atoms. The dimers are
interconnected by the ligand molecules, giving rise to a
double chain extending parallel to the b-axis (Figure 5a-c).
Hence, the structure of this complex may be described as a
ladderlike 1D-coordination polymer. The repeat unit of this
double chain may be seen as the combination of a 20-
membered, Ag
metallomacrocycles. The silver(I) ion adopts a distorted
tetrahedral coordination: the Ag-S distances are 2.496(1)
and 2.578(1) Å, while the Ag-O distances are 2.472(4) and
23
centered-type of packing (Figure 5c).
3
[AgL (p-TsO)]
∞
(6). Complex 6 was obtained in the same
3
4
L
2
O
4 2
S , and an eight-membered, Ag
2
O
4
S
2
,
manner as 5, except that the recrystallization solvent was
diethyl ether instead of the petroleum ether used for 5. As a
consequence, a totally different structure is observed. The
3
repeat unit of 6 consists of a 28-membered, Ag
6
L
4
, metal-
2.348(4) Å. The bond angles are O-Ag-O ) 109.2(2)° and
lomacrocycle. Taking part in that large ring are four four-
7840 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
3
Figure 6. (a) Atomic numbering and the repeat unit of 6 showing the 4-membered Ag2O2 and the 28-membered Ag6L 4 metallomacrocycles. (The phenyl
groups and the H atoms are omitted for clarity.). (b) View of the 2D-polymer coordination of 6 parallel to the (100)-plane. (c) Double-layer sheet of complex
6
shown edge on.
membered, Ag
2
O
2
, diamond-shaped rings (Figure 6a). In this
The other silver atom, Ag(2), is coordinated to two sulfur
atoms from two distinct ligands (Ag(2)-S: 2.602(1) and
2.631(1) Å), to two oxygen atoms from two distinct trifluoro-
methanesulfonates (Ag(2)-O: 2.518(5) and 2.393(4) Å), and
to the oxygen atom of an acetone molecule (Ag(2)-O:
2.486(4) Å). Thus, Ag(2) adopts a distorted triangular bipy-
ramid coordination (O-Ag(2)-O ) 170.6(2)°; O-Ag(2)-S
diamond-shaped ring, two silver atoms are bridged by two
oxygen atoms, each from a different p-tosylate anion (Chart
1). The distorted tetrahedral coordination of silver is com-
pleted with two S atoms from different ligands. The larger
rings share edges and form puckered layers parallel to the
bc-plane (Figure 6b). The projection of the layers onto the
ab-plane clearly shows the disposition of the aromatic rings
on either side of the layer (Figure 6c). The silver atom has
a distorted tetrahedral coordination. Each silver is bound to
two sulfur atoms (Ag-S: 2.461(1) and 2.468(1) Å) from
different ligands and to two oxygen atoms from distinct
p-tosylate groups (Ag-O: 2.400(3) and 2.491(3) Å). The
bond angles (deg) are as follows: O-Ag-O ) 74.9(1);
S-Ag-S ) 150.3(1); O-Ag-S 113.8(1) and 92.9(1). The
S‚‚‚S separation for all ligands is 4.954(3) Å, establishing
the existence of gauche torsion angles in the aliphatic
)
128.1(1), 106.3(1), and 124.8(1)°). Since the S‚‚‚S
separation in all of the ligands is 5.609 (2) Å, these are in
the all-trans conformation.
3
[Ag
2
L (CF
3
SO
3
)
2
]
∞
(8). Complex 8 was synthesized with
a ligand-to-silver salt ratio different from that used for 7.
The recrystallization solvent was diethyl ether as opposed
to petroleum ether in the case of 7. In the structure of 8, the
asymmetric unit contains only half the above composition.
Hence, the central carbon of the ligand is on a crystal-
lographic 2-fold axis. Each silver atom is linked to three
oxygen atoms from three different trifluoromethanesulfonates
sequence of the ligand in this form of the complex.
3
[Ag
2
L (CF
3
SO
) (CH COCH )]
3 2 3 3 ∞
(7). Here adjacent silver
(
Ag-O: 2.415(4), 2.459(4), and 2.481(4) Å) to build a chain
along the b-axis formed by the alternation of two adjacent
Ag and Ag rings (Figure 8a). In turn, these chains
ions are linked by the triflate anion and by the S of a ligand in
a µ -S bridging mode (Chart 1). Adjacent silver ions are link-
2
2
O
2
2 4 2
O S
ed by the trifluoromethanesulfonate into a chain parallel to
the [202]-direction, and every second silver atom is linked to
an acetone molecule (Figure S5). These chainlike structures
are then interconnected by ligand molecules, thus yielding
a 2D-network whose repeat unit is a 16-membered metallo-
are linked through the ligands along the c-axis so as to
generate a 2D-coordination network (Ag-S: 2.445(2) Å)
(Figure 8b). The silver atom adopts a distorted tetrahedral
coordination where the bond angles range from 77.4(1) to
141.0(1)°. The S‚‚‚S separation for all of the ligands is 5.418-
3
3
macrocycle, Ag
CH COCH )]
c). It is worth noting that there are two distinct silver atoms
Figure S6a). On one hand, Ag(1) has the environment of a
4
L
S
2 2
(Figure 7a,b). The [Ag
2 3 3 2
L (CF SO ) -
(
3) Å. The repeat unit of this complex is a 21-membered
metallomacrocycle. The complex forms layers parallel to the
100)-plane spaced at a/2 intervals. The complex adopts a
(
3
3
∞
sheets are parallel to the (010)-plane (Figure
7
(
(
zigzag-like 2D-coordination polymer (Figure 8c).
distorted tetrahedron (Ag(1)-S ) 2.516(1) and 2.590(1) Å;
Ag(1)-O ) 2.356(4) and 2.463(5) Å; S-Ag(1)-S )
Both the monatomic bridge and the double-bridge modes
are observed in this compound obtained from diethyl ether.
124.6(1)°; O-Ag(1)-S ) 131.4(1), 103.9(1), and 83.1(1)°).
Inorganic Chemistry, Vol. 44, No. 22, 2005 7841

Awaleh et al.
Figure 7. (a) Atomic numbering and structure showing the two distinct environments of the silver atoms in complex 7. (b) View of the 2D-sheet parallel
to the (010)-plane. (The phenyl groups and the H atoms are omitted for clarity.) (c) Packing of 7 illustrating the “in-phase” relative disposition of the sheets.
The anions are omitted for clarity.
When petroleum ether is used, only the double-bridged mode
the complexes do not associate in 2D-networks but form 1D-
coordination polymers.
is noted (complex 7) (Chart 1).
3
[Ag
2
L (CF
3
SO
3
)
2
]
∞
(9). Although it does not contain
Supramolecular Isomerism of the Networks. As noted
in the above crystal structure reports, the choice of recrys-
tallization solvent for complexes with the sulfonate anions
influences the coordination of the silver and consequently
the resulting network. Two complexes were obtained with
the p-tosylate anion (5 and 6). Complex 5, characterized by
the presence of a double-bridge coordination, was recrystal-
lized in petroleum ether, while diethyl ether was used for 6
which is characterized by a monatomic bridge coordination.
Three distinct complexes were synthesized with the
trifluoromethanesulfonate anion (7-9).
acetone, this third complex, with the trifluoromethane-
sulfonate anion, bears a very strong topological relationship
with 7 (Figure S7). The two silver atoms, although crystal-
lographically distinct, have the same kind of environment.
Ag(1) and Ag(2) are connected, in a dibridging mode, by
3 3
the oxygen atoms from two CF SO anions (Figure 9a, Chart
1). Each silver is, in turn, bound to another one through a
µ
2
-S bridge (Figure 9a, Figure S6b). Thus, a metallomacro-
3
4 2 2
cycle of composition Ag L S is obtained. This metallo-
macrocycle is identical with that observed for 7, although
the anions are connected to the silver ions in different ways.
Nethertheless, there is also an acetone molecule bound to
one of the silver ions of 7. The projection of the 2D-network
on the bc-plane is shown in Figure 9b. The backbone
undulations from one layer to the next are “out-of-phase”,
while they are “in-phase” for 7 (Figure 7c, Figure S8). The
S1‚‚‚S2 distance of 5.538(2) Å indicates that the ligands are
in a fully extended conformation. The two Ag(1) and Ag(2)
The situation described above is also observed these
complexes with the trifluomethanesulfonate anion. Thus,
complex 7, obtained from a petroleum ether solution and
complex 9, from a hexane solution, both give rise to a
double-bridge mode, while the diethyl ether solution yielded
complex 8, which has a monoatomic bridge mode (as well
as a double-bridge mode) (Chart 1). It is concluded that, in
the case of anions containing the sulfonate group, supramo-
lecular isomerism is solvent driven: the diethyl ether solvent
promotes the formation of a monatomic-bridge mode whereas
the petroleum ether (a nonpolar solvent) favors a double-
bridge mode. This is confirmed by the fact that when
2
ions, forming a dimer with a triflate and a µ -S bridge do
not interact since they are separated by 4.8535(5) Å.
Interestingly, the bis(phenylthio)methane silver(I) complexes
with the triflate anion are also polymorphic due to the
influence of the solvent. Contrary to what is reported here,
3
3
2 3 3
recrystallizing [AgL (p-TsO)] or [Ag L (CF SO )] from
7842 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
interaction between the metal atoms comparable to that
2
7
reported by Wang and Mak. Although the larger number
of fluorine atoms seems to affect the average Ag-O
distances, it does not reinforce or weaken the Ag‚‚‚Ag
interactions. Interestingly, complexes with the p-tosylate and
the trifluoromethanesulfonate anion, which both form bridged
dimers, do not have metal-metal interactions as the
Ag‚‚‚Ag distances are 3.750(1) and 3.745(1) Å, respectively.
Infrared Spectroscopy. The peaks observed at 1685 and
-
1
1
410 cm in the IR spectrum of complex 2 are assigned to
the characteristic antisymmetric and symmetric stretching
bands of the carboxylate group, respectively. Furthermore,
-
1
the difference of 275 cm [νas(CO
2
s 2
) - ν (CO )] obviously
28
points to the occurrence of the dibridging mode, in
agreement with the established crystal structure (see Table
3
). This observation also applies to 3 and 4. Although the
crystal structure of 3 reveals the presence of dimers with
either the diatomic or the monatomic bridging modes, only
the former is identified from its FTIR spectrum. The IR
spectra of complexes 5 and 6 are similar. Thus, the different
coordinations of the silver atom in monatomic (5) and
diatomic (6) bridging modes cannot be established by means
of IR data. The unambiguous assignment of the vibration
-
modes of the CF
3
SO
3
anion in complexes 7-9 is quite
and SO vibrations in
the stretching-mode region between 1000 and 1300 cm .
difficult because of the mixing of CF
3
3
-
1 29
3
4
Figure 8. (a) 1D-chain of complex 8 is made up of two adjacent rings:
the square Ag2O2; the puckered Ag2O4S2. (b) The 2D-sheet structure of 8
obtained with the ligand linking the chains. The sheet is parallel to (100).
The phenyl and triflate groups and the H atoms are omitted for clarity. (c)
Packing diagram, showing the sheets parallel to the bc-plane. The chains
However, according to Lawrance, the silver atom in silver
trifluoromethanesulfonate is coordinated to the anion, which
has absorption bands at 1270 and 1043 cm . These have
-
1
0,31
been assigned to the ν[SO
3
3 1
(E)] and ν[SO (A
)] vibrations.3
(a) are parallel to the b-axis.
The two bands observed here for complexes 7-9, listed in
Table 3, are consistent with the triflate being coordinated to
3
2
the silver atom. In complex 1, the peaks at 843 and 560
-
1
cm are assigned respectively to the ν
3
(T1u) and ν
The peaks observed in 10
at 1137 and 1073 cm are assigned respectively to ν (E)
anion. The IR spectrum
4
(T1u)
-
33-35
vibrations of the PF
6
anion.
-
1
4
-
36
and ν
1 1 4
(A ) vibrations of the ClO
-
1
of complex 11 shows a band at 664 cm that is assigned to
(T1u) vibration of the SbF
-
34,37
ν
3
6
anion.
Thermogravimetric Investigation. Three complexes in-
corporate acetone molecules in their structures. However,
the crystallographic results reveal two types of associations.
-
In 1, acetone and PF
6
are inserted between the layers, while
in 3 and 7 acetone is part of the network through its
Figure 9. (a) Repeat unit of 9 is very similar to that of 7. (b) Side view
of the 2D-network. Notice the “out-of-phase” disposition of consecutive
planes as compared to the “in-phase” disposition in of Figure 7c. The anions
and the H atoms have been omitted for clarity.
(
28) Szlyk, E.; Szymanska, I.; Surdykowski, A.; Glowiak, T.; Wojtczak,
A.; Golinski, A. J. Chem. Soc., Dalton Trans. 2003, 3404 and
references therein.
pentane or hexane (nonpolar solvents), one gets crystals
whose unit-cell dimensions are identical with those of 5 or
(29) Johnston, D. H.; Shriver, D. F. Inorg. Chem. 1993, 32, 1045.
(
(
30) Lawrance, G. A. Chem. ReV. 1986, 86, 17 and references therein.
31) Batchelor, R. J.; Ruddick, J. N. R.; Sams, J. R.; Aubke, F. Inorg.
Chem. 1977, 16, 1414 and references therein.
7, respectively.
Metal-Metal Bonds. The complexes synthesized with
(32) Zhong, J. C.; Munakata, M.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga,
Y.; Konaka, H. Inorg. Chem. 2001, 40, 3191.
33) Matsumoto, K.; Hagiwara, R.; Ito, Y.; Tamada, O. Solid State. Sci.
trifluoroacetate, pentafluoropropionate, and heptafluorobu-
tyrate present short silver-silver contacts. The observed
distances, listed in Table 2, are compared with others reported
(
(
(
2002, 4, 1465.
34) Reger, D. L.; Semeniuc, R. F.; Rassolov, V.; Smith, M. D. Inorg.
Chem. 2004, 43, 537.
35) Jung, O. S.; Kim, Y. J.; Lee, Y. A.; Chae, H. K.; Jang, H. G.; Hong,
J. Inorg. Chem. 2001, 40, 2105.
8
in an earlier work. All these distances are shorter than the
sum of the van der Waals radii of two silver atoms (3.40
(
(
36) Rosenthal, M. R. J. Chem. Educ. 1973, 50, 331 and references therein.
37) Chen, Y. D.; Zhang, L. Y.; Shi, L. X.; Chen, Z. N. Inorg. Chem.
2004, 43, 7493.
23
Å ) and slightly longer than 2.89 Å, which is twice the
metallic radius of silver.23 There is therefore a weak
Inorganic Chemistry, Vol. 44, No. 22, 2005 7843

Awaleh et al.
Table 2. Comparison of the Short Ag‚‚‚Ag Contacts (Å) Observed with the Corresponding Values Reported for Bis(phenylthio)methane Complexes8
anion
CF3COO-
complex L1 a
Ag‚‚‚Ag contacts
complex L3 b
Ag‚‚‚Ag contacts
2
3
4
5
8
9
3.2459(5)
3.0502(7)
3.1594(4)
3.7503(5)
3.745(1)
4.854(1)
-
CF3CF2COO
-
CF3CF2CF2COO
6
5
7
3.1593(3)
-
p-TsO
-
CF3SO3
4.711(2), 5.524(1)
-OOCCF2CF2COO-
2.9836(5)
3
.0168(5)
L ) 1,3-bis(phenylthio)propane.
Table 3. Comparison of FTIR Frequencies (cm-1) of COO Vibrations and SO3 Vibrations
a
1
8
b
3
L ) bis(phenylthio)methane.
complex
νas(CO2)
νs(CO2)
νas(CO2) - νs(CO2)
3
[
[
[
[
[
[
Ag2L (CF3COO)2] (2)
1685
1679
1681
1670
1672
1670
1410
1411
1411
1407
1406
1396
275
268
270
263
266
274
3
Ag2L (CF3CF2COO)2(CH3COCH3)] (3)
3
AgL (CF3CF2CF2COO)] (4)
3
a
Ag2L (CF3COO)2(dppm)]
3
a
Ag2L (CF3CF2COO)2(dppm)]
3
a
Ag2L (CF3CF2CF2COO)2(dppm)]
complex
νas(SO3)
νs(SO3)
7
8
9
1258
1260
1257
1257
1033
1034
1030
1035
2
b
Ag2(L )(CF3SO3)2
a
Reference 28. b Reference 32.
coordination to silver atoms. A different thermal behavior
is therefore expected. Another question is whether the
6 2 3 3 2
(PF ) (CH COCH ) ] (expt/theor ) 7.12/6.98%). The second
step, which occurs between 150 and 280 °C, corresponds to
3
acetone molecule in 1 is necessary for the stability of the
the loss of the ligand L , (expt/theor ) 66.32/62.62%). The
3
structure. The thermograms of {[Ag
2
L
4
](PF (CH
6
)
2
3
-
remaining white residue is AgPF . Hence, very soon after
6
3
3
COCH ) ]}
3 2 ∞
(1) and [Ag L (CF CF CO )
2 3 2 2 2
3
(CH COCH )] (3)
3 ∞
the loss of acetone, the [Ag
2
L
4
]
∞
layer structure starts to
are shown in Figure 10a,b, respectively. The TGA curve of
complex 1 exhibits a two-step degradation. The first step,
which occurs in the interval of 85-100 °C, corresponds to
disintegrate with the loss of the four ligand molecules. Not
-
- 12
surprisingly, all three complexes, 1 (PF
6
), 10 (ClO
4
), and
-
12
1
1 (SbF ), in which the anions and the acetone molecules
6
64 8 2
the departure of 2 mol of acetone/mol of [C60H S Ag
are sandwiched between the layers, have the same thermal
decomposition pattern (Figures S9, S10). The residues are
4 6
AgClO and AgSbF for 10 and 11, respectively.
In the case of 3 and 7, the acetone molecules are more
strongly held, through coordination bonds to the silver atoms.
However, the decomposition of the complexes, which start
at about 180 °C, is a one-step process completed at 300 and
3
20 °C for 3 (Figure 10b) and 7, respectively (Figure S11).
The weight loss corresponds to the departure of the acetone
molecules, the ligands, and the anions (expt/theor ) 76.62/
74.92% for 3, expt/theor ) 74.30/74.08% for 7). The collapse
of the network is total, as the remaining black residue is
silver. In a study on chemical vapor deposition of silver
3
8
films, it was reported for example that the silver(I)
heptafluorocarboxylate complex decomposes between 250
and 380 °C and the residue consists of metallic silver. The
decomposition of complex 3, which incorporates the pen-
tafluoropropionate anion, ends at a lower temperature, 300
°
C. Thus, complex 3 could be used as a material for the
vapor deposition of silver film because of its low-temperature
decomposition. This suggestion could be confirmed by a
volatility study.
Figure 10. TGA curves recorded at a heating rate of 10 °C min-1. (a)
Two-step decomposition of 1 is shown. The acetone is lost first, followed
by the loss of the ligand. (b) Acetone, the ligand, and the anion of 3 are
eliminated in a single step between 180 and 300 °C.
(38) Edwards, D. N.; Harker, R. M.; Mahon, M. F.; Molloy, K. C. Inorg.
Chim. Acta 2002, 328, 134.
7844 Inorganic Chemistry, Vol. 44, No. 22, 2005

Complexes of 1,3-Bis(phenylthio)propane with Ag(I)
Conclusions
Complexes 7-9 all adopt a 2D-structure, those of 7 and 9
being almost identical. The type of silver environment in
the polymorphs is associated with the polarity of the
recrystallization solvent.
We have synthesized and characterized nine different
coordination networks involving Ag(I) and 1,3-bis(phenylthi-
o)propane. The type of anion and, in some cases, the
recrystallization solvent is responsible for the remarkable
diversity in the structures observed. However, some common
features emerge:
(4) Here all, but 4 and 5, complexes with 1,3-bis-
(phenylthio)methane form a 2D-network. However, the
structures generated with the shorter bis(phenylthio)methane
ligand were all of the 1D-coordination polymer class, and
no 2D-networks were formed. Furthermore, it was found that
(
1) With weakly coordinating, nearly spherical anions
-
-
(
4 6
XY and XY ), comparable cationic layer structures are
-
formed between Ag(I) and the ligand. The anions and acetone
molecules held between the sheets, through van der Waals
interactions with the layers.
the XY4 anions were coordinated to the silver(I) ions.
Clearly, the length of the ligand affects the outcome.
Acknowledgment. Financial support from the Natural
Sciences and Engineering Research Council of Canada (F.B.)
and a graduate scholarship from the Program Canadien de
Bourse de la Francophonie (M.O.A.) are gratefully acknowl-
edged. The authors also thank Dr. M. Simard and F.
B e´ langer-Gari e´ py for the X-ray data collections and H. Dinel
for elemental analyses.
(
2) All perfluorocarboxylates form dimeric units with
moderately short metal-metal distances indicating weak
Ag‚‚‚Ag interactions. These units, in turn, form 2D-
coordination networks, except for 4, which forms a 1D-
coordination polymer.
(
3) Solvent-driven supramolecular isomerism is observed
-
-
3 3
with the sulfonate anions (p-TsO and CF SO ). Four of
the five complexes adopt a 2D-structure of neutral sheets in
which the anions are coordinated to the metal centers. As
for the polymorphic p-tosylates, 6 adopts a 2D-layer struc-
ture, while the other, 5, forms a linear coordination polymer.
All three triflates, 7-9, have the same metal-to-ligand ratio
Supporting Information Available: Tables of bond distances
and angles involving the silver atoms, Figures S1-S11, and X-ray
crystallographic information files (CIF) for compounds 1-9. This
materialisavailablefreeofchargeviatheInternetathttp://pubs.acs.org.
(2:1), although 7 includes an extra acetone molecule.
IC050617N
Inorganic Chemistry, Vol. 44, No. 22, 2005 7845