Silver(I)-organic networks constructed with flexible silver-ethynide supramolecular synthon o-, m-, p-Cl-C6H5OCH 2C≡C?Agn (n = 4, 5)

Article abstract of DOI:10.1016/j.jorganchem.2011.05.002

A series of five silver coordination polymers [(AgL1)·(AgCF ₃COO)₅·(H₂O)₃] (1), [(AgL1)₂·(AgCF₃COO)₁₁·(H ₂O)₆] (2), [(AgL2)·(AgCF₃COO) ₃

Full text of DOI:10.1016/j.jorganchem.2011.05.002

Journal of Organometallic Chemistry 696 (2011) 2820e2828
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Silver(I)-organic networks constructed with flexible silver-ethynide
supramolecular synthon o-, m-, p-CleC6H5OCH2C^CIAgn (n ¼ 4, 5)
,
a
a,b,
**
Bo Li a, Shuang-Quan Zang a , Can Ji , Thomas C.W. Mak
*
a Department of Chemistry, Zhengzhou University, Zhengzhou 450001, PR China
b Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of five silver coordination polymers [(AgL1)$(AgCF3COO)5$(H2O)3] (1), [(AgL1)2$(AgCF3COO)11
$
Received 24 March 2011
Received in revised form
3 May 2011
(H2O)6] (2), [(AgL2)$(AgCF3COO)3$(H2O)] (3), [(AgL3)$(AgCF3COO)4$(CH3CN)2] (4), and [(AgL3)$
(AgCF3COO)7$(CH3CN)2$(H2O)2] (5) have been constructed from threeflexible anionic ligands HL1, HL2, and
HL3 (HL1 ¼ 1-chloro-2-(prop-2-ynyloxy)benzene, HL2 ¼ 1-chloro-3-(prop-2-ynyloxy)benzene, HL3 ¼ 1-
Accepted 3 May 2011
chloro-4-(prop-2-ynyloxy)benzene). In these compounds, the invariable appearance of the m4- and m5
-
ligation modes of the ethynide moiety affirms the general utility of the flexible silver-ethynide supramo-
lecular synthon o-, m-, p-ClꢀC6H5OCH2C^CIAgn (n ¼ 4, 5) in coordination network assembly. Among
them, Ag/Cl interaction plays a vital role in assembling the supramolecular structures in complexes 1ꢀ3.
Ó 2011 Elsevier B.V. All rights reserved.
Keywords:
Silver-organic coordination polymer
Ag/Cl interaction
Supramolecular synthon
1. Introduction
2.804(6) Å in cyclo-[{Pt(C6Cl5)2(m-OH)(m-Ag)}4], 3.287(2) Å in
2AgL2$5AgCF3COO$2CH3CN$H2O, (L2 ¼ 3,4-dichlorophenylethy-
nide), and 3.280(3) Å in AgL5$4AgCF3COO$2CH3CN (L5 ¼ 2-
chlorophenylethynide)) [26,28,40].
The design of new supramolecular synthons with multi-center
binding sites for constructing new kinds of non-classical coordina-
tion/organometallic supramolecular architectures is receiving
increasing attention [1e13]. Indeed, common weak intermolecular
Followingourinvestigationofthecoordinationchemistryofsilver
ethynediide (Ag2C2) [41e43], we have conducted systematic studies
on various complexes containing silver(I) 1,3-butadiynediide (Ag2C4)
[44]. Furthermore, utilizing new metaleligand supramolecular syn-
thonsof the type ReC^CIAgn (R ¼ aryl oralkyl; n ¼ 4, 5) [45,46] and
Agn3C^CꢀReC^CIAgn (R ¼ o-, m-, p-C6H4; n ¼ 4, 5) [47], we have
obtained a series of metal-organic networks stabilized by argento-
interactions such as hydrogen bonding [14e17] and
p/p [18e21]
have been employed as available cohesive forces in the consolida-
tion of such supramolecular architectures. However, several other
unconventional intermolecular interactions metal/halogen
[22e28] argentophilic [29e37] remain largely unexplored. Though
supramolecular structures held by the Ag/Iꢀaryl interaction (Ag/I
distance ranges from 2.719 to 3.357 Å) have been known for over
a decade [23,38,39], the significance of analogous interactions
involving the lighter halogens has been called into question until
recent times, when examples are reported for both the Ag/Brꢀaryl
(Ag/Br 3.179(5), 3.726(6) Å in {[Ag2(bppy)3][Ag(bppy)2][Ag(bp-
py)]2PW11Co(bppy)O39}$2H2O, where bppy represents 5-(4-
philic andsilver-ethynide (s, p and mixed s, p) interactions. Recently,
we have explored the employment of several ligands with an ethy-
nide ethynyl group attached to a phenyl, biphenyl, or naphthyl
skeleton via a flexible eCH2eOe link for the construction of MOFs
consolidated by both silver(I)eethynide and silver(I)earomatic
interactions [48e50]. By utilizing new metaleligand supramolecular
synthons of the type p-XꢀC6H5OCH2C^CIAgn (X ¼ I, Br; n ¼ 4, 5)
[51], we have obtained a series of metal-organic networks, which
provides unequivocal evidence for the existence of the Ag/Brꢀaryl,
Ag/Iꢀaryl interactions. The change of substituent group of the
phenyl ring may leads to a modification of the resulting coordination
networks. As a continuation of our research, in this work, we
systematically investigate the effect of the supramolecular synthon
o-, m-, p-ClꢀC6H5OCH2C^CIAgn (n ¼ 4, 5) to see whether non-
covalent Ag/Clꢀaryl interaction could be an effective and reliable
tool in the context of metal-organic network assembly.
bromophenyl)-2-(4-pyridinyl)pyridine, and 3.186(6) Å in Ag(Br4
-
C6(OH)O)(Ph3P)2) [25,26] and Ag/Clꢀaryl interactions (3.184(5) Å
in Ag(Cl4C6(OH)O)(Ph3P)2, 2.721(5), 2.739(5), 2.740(5), 2.770(5),
* Corresponding author. Tel.: þ86 0371 67780136; fax: þ86 371 6778 0136.
** Corresponding author. Department of Chemistry and Center of Novel Functional
Molecules, The Chinese University of Hong Kong, Shatin, New Territories,
Hong Kong SAR, PR China. Tel.: þ86 852 2609 6279; fax: þ86 852 2603 5057.
E-mail addresses: zangsqzg@zzu.edu.cn (S.-Q. Zang), tcwmak@cuhk.edu.hk
(T.C.W. Mak).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.05.002

B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
2821
Fig. 1. Coordination mode of L1 in 1. All hydrogen atoms and CF3 groups are omitted for
clarity. Selected bond lengths [Å]: C1^C21.213(2), Ag1ꢀC12.240(11), Ag2ꢀC12.212(12),
Ag2ꢀC2 3.064(14), Ag3ꢀC1 2.293(13), Ag3ꢀC2 2.995(13), Ag4ꢀC1 2.419(12), Ag4ꢀC2
2.536(14), Ag5ꢀC1 2.914(14), Ag6#2ꢀCl1 3.204(8), Ag1/Ag2 2.793(14), Ag1/Ag3
2.896(2), Ag1/Ag4 2.934(14), Ag1/Ag5 3.140(2), Ag2/Ag3 3.069(2), Ag3/Ag4
3.088(2), Ag5/Ag6 2.951(2). Symmetry codes: #11 ꢀ x, 1 ꢀ y, 1 ꢀ z; #2 ꢀ x, 1 ꢀ y, ꢀz.
Scheme 1. Structural formulas used as ligands in forming new silver(I)-ethynide
complexes.
Hereinwe report the syntheses and structural characterization of
five silver (I) complexes of three new ligands, which bearing
terminal ethynide moieties attached via pendent arms to the ortho-,
meta- and para-position of a chlorobenzene skeleton, respectively:
[(AgL1)$(AgCF3COO)5$(H2O)3] (1), [(AgL1)2$(AgCF3COO)11$(H2O)6]
(2), [(AgL2)$(AgCF3COO)3$(H2O)] (3), [(AgL3)$(AgCF3COO)4$
(CH3CN)2] (4), and [(AgL3)$(AgCF3COO)7$(CH3CN)2$(H2O)2] (5),
where HL1 ¼1-chloro-2-(prop-2-ynyloxy)benzene, HL2 ¼1-chloro-
yielding organic ligands and polymeric starting materials were
carried out under a nitrogen atmosphere.
Caution! Silver ethynide complexes are potentially explosive
and should be handled in small amounts with extreme care.
2.1.1. Synthesis of 1-chloro-2-(prop-2-ynyloxy)benzene (HL1)
HL1 was synthesized according to the literature method [52].
Propargyl bromide (1.4 mL, 12.5 mmol) and K2CO3 (1.73 g,
12.5 mmol) were added to a solution of 2-chlorophenol (1.67 g,
10 mmol) in acetone (30 mL). The solution was heated under reflux
for 24 h under nitrogen atmosphere. The precipitate was filtered off
and the filtrate was evaporated to dryness to yield the crude
product as a yellow oil. It was purified by chromatography on silica
gel to afford pale yellow oil. Yield: 73%. 1H NMR (300 MHz, CDCl3):
3-(prop-2-ynyloxy)benzene, and HL3
ynyloxy)benzene) (Scheme 1).
¼
1-chloro-4-(prop-2-
2. Experiments
2.1. Reagents
d
¼ 6.71e7.19 (4H, benzene); 4.68 (2H, OCH2); 2.51 (1H, C^CH). IR
(Nujol):
n
¼ 2108 cmꢀ1 (w,
nC^C). Anal. Calc. for C9H7ClO (166.61): C
Commercially available 2-chlorophenol, 3-chlorophenol,
4-chlorophenol, propargyl bromide (80% in toluene) and K2CO3
were used without further purification. Acetone, dichloromethane,
ethyl acetate, n-hexane, acetonitrile and triethylamine were puri-
fied according to standard procedures. All synthetic reactions
64.88; H 4.23. Found: C 64.81; H 4.29%.
1-Chloro-3-(prop-2-ynyloxy)benzene(HL2): HL2 was obtained
by the above procedure except that 3-chlorophenol replaced 2-
chlorophenol. Yield: 67%. 1H NMR (300 MHz, CDCl3):
Table 1
X-ray crystal data and structure refinement for compounds 1e5.
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
19H10Ag6ClF15O14
C40H24Ag13Cl2F33O30
3084.80
Triclinic
C15H8Ag4ClF9O8
954.14
Triclinic
C21H12Ag5ClF12N2O9
1239.13
Triclinic
C27H16Ag8ClF21N2O17
1937.83
Triclinic
1429.94
Triclinic
ꢀ
Pı
ꢀ
Pı
ꢀ
Pı
ꢀ
Pı
ꢀ
Pı
11.284(3)
11.314(3)
15.299(4)
90.267(5)
101.694(6)
113.166(5)
1750.7(8)
2
11.2472(10)
16.8357(16)
20.7545(19)
108.755(2)
97.071(2)
93.784(2)
3669.6(6)
2
9.9198(17)
10.7012(18)
11.3863(19)
82.885(3)
87.013(3)
75.221(3)
1159.4(3)
2
8.9144(18)
14.203(3)
14.384(3)
69.607(4)
76.707(4)
85.448(4)
1661.3(6)
2
11.324(2)
14.435(3)
17.583(3)
66.531(3)
74.435(3)
87.881(4)
2531.8(8)
2
b (Å)
c (Å)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
Z
Dcalc (g cmꢀ3
F(000)
)
2.713
1340
2.792
2892
2.733
896
2.477
1168
2.542
1820
Reflections collected
Independent reflections
R(int)
9518
6135
0.0419
20214
12893
0.0422
6330
4064
0.1003
9494
6132
0.0440
13911
8876
0.0795
Data/restraints/parameters
6135/1572/509
1.064
12893/102/1129
1. 144
4064/58/353
1.085
6132/48/484
1.062
8876/221/745
1.055
GOF on F2
R1[(I > 2
wR2[(I > 2
s
(I)]
(I)]
0.0828
0.2418
0.0489
0.1376
0.0609
0.1748
0.0462
0.1215
0.0622
0.1697
s
R1 (all data)
0.0913
0.0595
0.0646
0.0523
0.0823
wR2 (all data)
0.2506
2.265 and ꢀ1.861
0.1439
2.380 and ꢀ1.554
0.1797
1.953 and ꢀ1.628
0.1258
1.336 and ꢀ1.116
0.1821
2.555 and ꢀ1.509
Max/min (e Åꢀ3
)

2822
B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
Fig. 2. (a) Layer structure of 1 linked by trifluoroacetate groups. (b) Three-dimensional network in 1 linked by p/p stacking interactions. Color scheme for atoms: Ag purple, C gray,
O red, Cl dark green. Terminal CF3 groups and all hydrogen atoms are omitted for clarity. Symmetry codes: #1 1 ꢀ x, 1 ꢀ y, 1 ꢀ z; #2 ꢀ x, 1 ꢀ y, ꢀz; #3 ꢀ x, ꢀy, 1 ꢀ z. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
d
¼ 6.62e7.12 (4H, benzene); 4.68 (2H, OCH2); 2.52 (1H, C^CH). IR
(w, nC^C). Anal. Calc. for C9H7ClO (166.61): C 64.88; H 4.23.
Found: C 64.86; H 4.20%.
(Nujol):
n
¼ 2053 cmꢀ1 (w,
n
C^C). Anal. Calc. for C9H7ClO (166.61): C
64.88; H 4.23. Found: C 64.84; H 4.27%.
[AgL]n (6) : Silver nitrate (0.82 g, 4.80 mmol) was dissolved in
acetonitrile (50 mL). Then HL (0.80 g, 4.80 mmol) and triethylamine
(0.67 mL, 4.80 mmol) were added with vigorous stirring and the
mixture was stirred overnight under a nitrogen atmosphere in dark-
ness. The white precipitate formed was collected by filtration, washed
1-Chloro-4-(prop-2-ynyloxy)benzene(HL3): HL3 was ob-
tained by the same procedure using 4-chlorophenol. Yield: 77%.
1H NMR (300 MHz, CDCl3):
d
¼ 6.71e7.19 (4H, benzene); 4.68
(2H, OCH2); 2.51 (1H, C^CH). IR (Nujol):
n
¼ 2048 cmꢀ1
Fig. 3. Coordination mode of L1 in 2. All hydrogen atoms and CF3 groups are omitted for clarity. Selected bond lengths [Å]: C1^C2 1.220(9), C10^C11 1.206(10), Ag1ꢀC1 2.227(6),
Ag2ꢀC1 2.266(6), Ag3ꢀC1 2.218 (6), Ag3ꢀC2 3.061(7), Ag4ꢀC1 2.826(7), Ag4ꢀC2 2.820(8), Ag5ꢀC1 2.414(7), Ag5ꢀC2 2.569(8), Ag6ꢀC10 2.223 (7), Ag7ꢀC10 2.336(7), Ag7ꢀC11
2.548(8), Ag8ꢀC10 2.985(7), Ag8ꢀC11 2.937(8), Ag9ꢀC10 2.243(6), Ag9ꢀC11 2.985(6), Ag10ꢀC10 2.261(7), Ag13#1ꢀC17 2.846(12), Ag13#1ꢀC18 2.804(11), Ag1/Ag2 2.874(8),
Ag1/Ag3 2.809(7), Ag1/Ag4 3.251(9), Ag1/Ag5 2.905(4), Ag2/Ag3 2.946(9), Ag2/Ag5 3.126 (3), Ag4/Ag11 2.929(10), Ag6/Ag7 2.984(4), Ag6/Ag8 3.152(10), Ag6/Ag9 2.816
(8), Ag6/Ag10 2.847(8), Ag7/Ag10 3.136(3), Ag8/Ag13 2.919(12), Ag9/Ag10 2.912(9), Ag11ꢀCl1 3.295(2). Symmetry code: #1 ꢀ x, 2 ꢀ y, 1 ꢀ z.

B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
2823
Fig. 5. Coordination mode of L2 in 3. All hydrogen atoms and CF3 groups are omitted
for clarity. Selected bond lengths [Å]: C1^C2 1.209(2), Ag1ꢀC1 2.240(5), Ag2ꢀC1
2.386(7), Ag2ꢀC2 2.401(8), Ag3ꢀC1 2.227(6), Ag4ꢀC1 2.285(6), Ag1/Ag2 3.010(9),
Ag1/Ag3 2.826(9), Ag1/Ag4 2.850(9), Ag2/Ag3 3.214(10), Ag3/Ag4 2.939(10),
Ag4#2ꢀCl1 2.880(2). Symmetry codes: #1 1 ꢀ x, 1 ꢀ y, 1 ꢀ z; #2 ꢀ 1 þ x, y, z.
thoroughly with acetonitrile (2 ꢂ 10 mL) and de-ionized water
(3 ꢂ 10 mL), and then stored in wet form at ꢀ10 ꢁC in a refrigerator.
Yield: 85%.
2.1.2. Synthesis of complexes 1ꢀ5
2.1.2.1. [(AgL1)$(AgCF3COO)5$(H2O)3] (1). AgCF3CO2 (0.440 g,
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL water.
Then [AgL1]n (z35 mg) solid was added to the solution. After
stirring for about half an hour, the solution was filtered and the
filtrate stored at ꢀ10 ꢁC in refrigerator. One day later, needle crys-
tals of 1 were deposited in about 55% yield. Anal. Calcd for
C19H10Ag6ClF15O14 (1429.94): C 15.96, H 0.70. Found: C 15.93, H
0.65%. IR (KBr):
n
¼ 2037 cmꢀ1 (w,
nC^C).
2.1.2.2. [(AgL1)2$(AgCF3COO)11$(H2O)6] (2). AgCF3CO2 (0.440 g,
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL water.
Then [AgL]n (z50 mg) solid was added to the solution. After stir-
ring for about half an hour, the solution was filtered and the filtrate
stored at ꢀ10 ꢁC in refrigerator. After several days, needle crystals of
2
were deposited in about 65% yield. Anal. Calcd for
C40H24Ag13Cl2F33O30 (3084.80): C 15.57, H 0.78. Found: C 15.52, H
0.72%. IR (KBr):
n
¼ 2046 cmꢀ1 (w,
n
C^C).
2.1.2.3. (AgL2)$(AgCF3COO)3$(H2O)
(3). AgCF3CO2
(0.440
g,
Fig. 4. (a) Ag5ꢀ(CF3CO2)4ꢀAg5 building unit in mode A and (b) mode B. (c) Two kinds
of silver rods in parallel orientation are bridged by two m3
h1 2 trifluoroacetate groups
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL water.
Then [AgL2]n (z20 mg) solid was added to the solution. After
stirring for about 2 h, the solution was filtered and the filtrate
stored at ꢀ10 ꢁC in refrigerator. After several days, colorless block
crystals of 3 were deposited nearly in about 60% yield. Anal. Calcd
for C15H8Ag4ClF9O8 (954.14): C 18.88, H 0.85. Found: C 18.81, H
-
,h
to generate a two-dimensional metal-organic network. (d) Three-dimensional network
in 2 linked by inversion-related trifluoroacetate groups and argentophilic interaction.
Terminal CF3 groups and all hydrogen atoms are omitted for clarity. Symmetry codes:
#1 ꢀ x, 2 ꢀ y, 1 ꢀ z; #2 1 ꢀ x, 1 ꢀ y, ꢀz; #3 ꢀ x, 1 ꢀ y, 1 ꢀ z; #4 1 ꢀ x, ꢀy, ꢀz; #5
2 ꢀ x, ꢀy, ꢀz. Color scheme for atoms: Ag purple, C gray, O red, Cl dark green. (For
interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
0.79%. IR (KBr):
n
¼ 2019 cmꢀ1 (w,
nC^C).
2.1.2.4. (AgL3)$(AgCF3COO)4$(CH3CN)2 (4). AgCF3CO2 (0.440 g,
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL

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B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
fullmatrix least squares on F2 using the SHELXTL program
ꢀ
package [54]. Most of the CF3 moieties of CF3CO2 groups in
compounds 1ꢀ5 were disordered, and the SADI command was
used to fix them in the refinements. In 2, silver atoms Ag5 and
Ag7 are located in two disordered positions with occupancy
ratios of 0.8:0.2 and 0.9:0.1, respectively. The crystal data and
details of refinement are summarized in Table 1.
3. Results and discussion
3.1. [(AgL1)$(AgCF3COO)5$(H2O)3] (1)
In the crystal structure of 1, the ethynide group (C1^C2) is
capped by a square-pyramidal Ag5 basket in the m5- , , , ,
h1 h1 h2 h2 h2
coordination mode, as shown in Fig. 1. The Ag6 atom is attached to
the Ag5 basket by two trifluoroacetate groups (O8ꢀO9 and
O10ꢀO11) in the m2-O,O0 and m4-O,O,O0,O0 modes, respectively,
with the assistance of argentophilic interaction (Ag5/Ag6
2.951(2) Å). The distances between the silver atoms range from
2.793(1) to 3.140(2) Å. The linkage of two square-pyramidal Ag5
baskets by two pairs of trifluoroacetate groups (O4ꢀO5,
O4#1ꢀO5#1, O6ꢀO7 and O6#1ꢀO7#1) through m3-O,O0,O0 coor-
dination modes to yield a Ag5ꢀ(m3
-
h1
,
h
2-CF3CO2)4ꢀAg5 building
unit. Such units are connected by two pairs of trifluoroacetate
groups (O10ꢀO11 and O10#2ꢀO11#2) via m4-O,O,O0,O0 coordina-
tion mode, as well as
a pair of inversion-related Ag6/Cl1
(3.204(8) Å) interactions to produce an infinite column. As shown
in Fig. 2a, The infinite columns are also interconnected by a pair of
trifluoroacetate groups (O2ꢀO3 and O2#3ꢀO3#3) via m3-O,O0,O0
coordination mode to engender a two-dimensional network.
Finally, association of layers through face-to-face
p/p interac-
tions between adjacent phenyl rings (centroidꢀcentroid distance
3.712(8) Å) result in a three-dimensional supramolecular structure
(Fig. 2b).
Fig. 6. (a) Layer structure of 3 linked by Ag/Cl interactions. (b) 3D coordination
network in 3 linked by
p/p stacking (blue). Terminal CF3 groups and all hydrogen
3.2. [(AgL1)2$(AgCF3COO)11$(H2O)6] (2)
atoms are omitted for clarity. Symmetry code: #3 1 ꢀ x, ꢀy, 1 ꢀ z. Color scheme for
atoms: Ag purple, C gray, O red, Cl dark green. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
The asymmetric unit of 2 contains two anionic L1 ligands
exhibiting different ligation modes A and B, thirteen crystallo-
graphically independent Ag(I) ions, six coordinated water
water and 0.2 mL acetonitrile. Then [AgL3]n (z15 mg) solid was
added to the solution. After stirring for about 3 h, the solution
was filtered and left to stand in the dark at room temperature.
After several days, colorless needle crystals of 4 were deposited
in about 65% yield. Anal. Calcd for C21H12Ag5ClF12N2O9 (1239.13):
C 20.36, H 0.98. Found: C 20.31, H 0.91%. IR (KBr):
(w, C^C).
n
¼ 2021 cmꢀ1
n
2.1.2.5. (AgL3)$(AgCF3COO)7$(CH3CN)2$(H2O)2
(5). AgCF3CO2
(0.440 g, 2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in
1 mL water and 0.2 mL acetonitrile. Then [AgL3]n (z35 mg) solid
was added to the solution. After stirring for about 3 h, the solution
was filtered and left to stand in the dark at room temperature.
After several days, colorless needle crystals of 5 were deposited in
about 55% yield. Anal. Calcd for C27H16Ag8ClF21N2O17 (1937.83): C
16.74, H 0.83. Found: C 16.68, H 0.81%. IR (KBr):
(w, C^C).
n
¼ 2028 cmꢀ1
n
2.2. X-ray crystallographic analysis
Selected crystals were used for data collection on a Bruker
Fig. 7. Coordination mode of L3 in 4. All hydrogen atoms and CF3 groups are omitted
for clarity. Selected bond lengths [Å]: C1^C2 1.214(8), Ag1ꢀC1 2.371(5), Ag2ꢀC1
2.417(5), Ag2ꢀC2 2.782(8), Ag3ꢀC1 2.240(5), Ag4ꢀC1 2.325(5), Ag4ꢀC2 2.993(5),
Ag1/Ag2 2.915(8), Ag1/Ag3 2.819(7), Ag1/Ag4 2.884 (9), Ag2/Ag3 3.056 (9),
Ag3/Ag4 3.203 (9). Symmetry code: #1 ꢀ x, ꢀy, 1 ꢀ z.
SMART APEXeII CCD diffractometer using frames of oscillation
range 0.3ꢁ, with 2ꢁ
<
q
< 28ꢁ. An empirical absorption
correction was applied using the SADABS program [53]. The
structures were solved by the direct method and refined by

B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
2825
molecules, and eleven trifluoroacetate ions. The distance between
silver and chlorine atom is 3.295(2) Å (Ag11/Cl1), indicating the
presence of weak silver/chloro interaction. As shown in Fig. 3, the
ethynide groups (C1^C2) and (C10^C11) acting in mode A and B
Ag12) are hitched to the Ag5 basket in mode A through tri-
fluoroacetate groups (O15ꢀO16 and O17ꢀO18, as well as Ag4/Ag11
interaction (2.929(1) Å) for Ag11; O15ꢀO16 and O19ꢀO20 for Ag12)
in m4-O,O,O0,O0, m2-O,O0, and m4-O,O,O0,O0, m3-O,O0,O0 coordination
modes, respectively. Another peripheral silver atom Ag13 is
attached to the Ag5 basket in mode B through Ag8/Ag13 interac-
tion (2.919(1) Å) and two trifluoroacetate groups (O21ꢀO22 and
are both attached to a square-pyramidal Ag5 basket in the m5
h1 h1 h2 h2 2 mode that is consolidated by bridging trifluoroacetate
groups and the aqua ligands. The peripheral silver atoms (Ag11 and
-
,
, , ,h
Fig. 8. (a) Ag8 aggregates in 4. (b) Layer structure of 4 linked by p/p stacking. Terminal CF3 groups, acetonitrile molecules and all hydrogen atoms are omitted for clarity. Symmetry
codes: #1 ꢀ x, ꢀ y, 1 ꢀ z; #2 1 ꢀ x, ꢀy, 1 ꢀ z. Color scheme for atoms: Ag purple, C gray, O red, Cl dark green. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)

2826
B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
O23ꢀO24) in m2-O,O0 and m4-O,O,O0,O0 coordination modes. Adjacent
Ag5 baskets in mode A are connected together through two pairs of
trifluoroacetate groups (O5ꢀO6, O5#2ꢀO6#2, O7ꢀO8 and
O7#2ꢀO8#2) via m3-O,O0,O0 and m2-O,O0 coordination modes,
respectively, to generate Ag5ꢀ(CF3CO2)4ꢀAg5 building unit, and
such units are further joined together through Cl1/Cl1#4 interac-
tions [55], to produce a type A column (Fig. 4a and c), which is also
consolidated by Ag11/Cl1 (3.295(2) Å) interactions. Similarly, the
linkage of two square-pyramidal Ag5 baskets in mode B by two pairs
of trifluoroacetate groups (O9ꢀO10, O9#3ꢀO10#3, O11ꢀO12 and
O11#3ꢀO12#3) acting in the m3-O,O0,O0, m2-O,O coordination modes,
respectively, yields a Ag5ꢀ(CF3CO2)4ꢀAg5 building unit (Fig. 4b).
Such units are associated through a pair of trifluoroacetate groups
(O23ꢀO24 and O23#1ꢀO24#1) via m4-O,O,O0,O0 coordination mode
into a type B column (Fig. 4b and c).
As found in 2, two phenyl carbon atoms (C17 and C18) coordi-
nate to silver atom Ag13#1 by the m-h
2 mode with bond lengths of
2.846(1) and 2.804(1) Å, respectively, which also reinforced the
type B column. The two kinds of silver columns in parallel orien-
tation are bridged by two m3
-
h1
,
h2 trifluoroacetate groups (O3ꢀO4
and O13ꢀO14) to generate a two-dimensional metal-organic
network, and such layers are also united together by two m3- ,
h1 h2
inversion-related trifluoroacetate groups (O19ꢀO20 and
O19#5ꢀO20#5) with the assistance of argentophilic interaction
(Ag12/Ag12#5, 2.900(1) Å) to give a 3D supramolecular structure
(Fig. 4d).
Fig. 9. (a) Coordination mode of L3 in 5. All hydrogen atoms and CF3 groups are
omitted for clarity. Selected bond lengths [Å]: C1^C2 1.211(12), Ag1ꢀC1 2.218(9),
Ag2ꢀC1 2.343(9), Ag2ꢀC2 2.903(12), Ag3ꢀC1 2.253(8), Ag4ꢀC1 2.426(9), Ag4ꢀC2
2.946(11), Ag5ꢀC1 2.449(8), Ag5ꢀC2 2.399(8), Ag1/Ag2 2.960(11), Ag1/Ag3
2.808(11), Ag1/Ag4 2.934(11), Ag1/Ag5 2.895(10), Ag2/Ag3 2.946(12), Ag3/Ag4
2.864 (11), Ag4/Ag5 3.004(12). Symmetry codes: #1 ꢀ x, 1 ꢀ y, 1 ꢀ z; #2 ꢀ x, 1 ꢀ y, ꢀz.
3.3. [(AgL2)$(AgCF3COO)3$(H2O)] (3)
The asymmetric unit of 3 contains four crystallographically
independent Ag(I) ions, one unique anionic L2 ligand, three tri-
fluoroacetate ions, and one coordinated water molecule. The
ethynide group (C1^C2) is capped by a butterfly-shaped Ag4
O6#2ꢀO7#2 and O8#2ꢀO9#2) via m3-O,O0,O0 and m4-O,O,O0,O0
coordination modes, to form an infinite silver column along the
a axis. Such chains are further united together through face-to-face
basket in the m4- , , ,
h1 h1 h1 h2 coordination mode, as shown in Fig. 5.
p/p interactions (intercentroid distance 3.973(6) Å) between
Linkage of two butterfly-shaped Ag4 baskets by two pairs of tri-
fluoroacetate groups (O4ꢀO5, O4#1ꢀO5#1, O6ꢀO7 and
adjacent phenyl rings to give a 2D supramolecular structure
(Fig. 8b). There is no obvious intermolecular interaction between
layers.
O6#1ꢀO7#1) produces a Ag4ꢀ(m3
-
h1
,
h
2-CF3CO2)4ꢀAg4 building
unit, and such units are connected by two pairs of trifluoroacetate
groups (O2ꢀO3, O2#3ꢀO3#3, O4ꢀO5 and O4#3ꢀO5#3) via m3
-
3.5. [(AgL3)$(AgCF3COO)7$(CH3CN)2$(H2O)2] (5)
O,O0,O0 and m4-O,O,O0,O0 coordination modes, respectively, to
generate an infinite column. It is notable that strong inter-chain
silver/chloro interaction between Ag4#2 and Cl1 (2.880(2) Å)
occurs in the a direction to give rise to a 2D coordination network
parallel to the ab plane (Fig. 6a). Linkage of these 2D coordination
The asymmetric unit of 5 contains eight crystallographically
independent Ag(I) ions, one unique anionic L3 ligand, seven tri-
fluoroacetate ions, two acetonitrile molecules, and two coordinated
water molecules. In the crystal structure of 5, the ethynide group
networks through face-to-face
p
/p
interactions (centroidꢀcent-
(C1^C2) is capped by a square-pyramidal Ag5 basket in the m5
h1 h1 h2 h2 2 coordination mode, as shown in Fig. 9. Three external
silver (I) atoms (Ag6, Ag7 and Ag8) are hitched to the Ag5 basket by
-
roid distance 3.673(5) Å) between adjacent phenyl rings to
construct a 3D supramolecular structure (Fig. 6b).
,
, , ,h
ꢀ
m3- ,h
h1 2-CF3CO2 groups (O2, O3, O3 and O6, O6, O7 for Ag6; O8,
3.4. [(AgL3)$(AgCF3COO)4$(CH3CN)2] (4)
O9, O9 and O10, O10, O11 for Ag7; O4, O4, O5 and O14, O14, O15,
and the bridging water ligand O1W for Ag8). Two acetonitrile
molecules are attached to peripheral silver atoms Ag7 and Ag8,
respectively. The linkage of two Ag5 baskets by a pair of inversion-
related trifluoroacetate groups (O12ꢀO13 and O12#1ꢀO13#1)
In the crystal structure of 4, the ethynide group (C1^C2) is
enveloped by a square-pyramidal Ag5 basket in the m5- , , , ,
h1 h1 h2 h2 h2
coordination mode, as shown in Fig. 7. With the inversion center
located at the center of the Ag1/Ag1#1 bond, two Ag5 baskets
share an edge to engender a Ag8 aggregate, as shown in Fig. 8a. The
distances between silver atoms range from 2.819(7) to 3.203(9) Å,
implying the presence of significant argentophilic interaction. Two
acetonitrile molecules are attached to the peripheral silver atom
Ag5. The peripheral silver(I) atoms (Ag5 and Ag5#1) are attached
to the Ag8 aggregate both by a pair of trifluoroacetate group
(O4ꢀO5, O8#1ꢀO9#1 and O4#1ꢀO5#1, O8ꢀO9) in the m3-O,O0,O0
and m4-O,O,O0,O0 modes, respectively. Two adjacent Ag8 aggregates
are linked by two pairs of trifluoroacetate groups (O6ꢀO7, O8ꢀO9,
produces a Ag5ꢀ(m3
-
h1
,
h
2-CF3CO2)2ꢀAg5 building unit, and such
units are connected by
a
pair of m3-O,O0,O0 trifluoroacetate
groups (O6ꢀO7 and O6#2ꢀO7#2) and Ag6/Ag6#2 interaction
(2.919(1) Å) to generate an infinite zigzag chain along the c axis
(Fig.10a). The infinite zigzag chains are interconnected by relatively
weak O1W#3ꢀH1WA#3/F15 (H1WA#3ꢀF15 2.631(2) Å)
hydrogen bond to form two-dimensional network (Fig. 10b), and
also further united together through weak C25ꢀH25A/F19#4
(H25AꢀF19#4 2.523(1) Å) [56,57] hydrogen bond to give a 3D
supramolecular architecture (Fig. 10c).

B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
2827
Fig. 10. (a) One-dimensional zigzag chain in complex 5. (b) Layer structure of 5 linked by hydrogen bonds (O1W#3ꢀH1WA#3/F15). (c) Three-dimensional network in complex 5
interconnected by hydrogen bonds (C25ꢀH25A/F19D). Symmetry codes: #3 1 ꢀ x, 1 ꢀ y, 1 ꢀ z; #4 1 þ x, ꢀ1 þ y, z. Color scheme for atoms: Ag purple, C gray, O red, N blue, F light
green, Cl dark green. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
4. Conclusion
In the present series of five silver (I) complexes, the invariable
appearance of the m4- and m5-ligation modes of the ethynide moiety
affirms the general utility of the flexible silver-ethynide supramo-
lecular synthon o-, m-, p-ClꢀC6H5OCH2C^CIAgn (n ¼ 4, 5) in
coordination network assembly (Scheme 2). The Ag/Clꢀaryl
interaction (Ag/Cl, 3.204(8) Å (1), 3.295(2) Å (2) and 2.880(2) Å
(3)) has been introduced into ethynide-silver supramolecular
chemistry, and further provides unequivocal evidence for the weak
interaction of the Ag/Clearyl interaction. Notably, all chlorine
atoms at the para position of the phenyl ring are not observed to
form Ag/Clꢀaryl interaction (Ag/Cl, 6.381(5)
Å (4) and
12.913(3) Å (5)), which is probably due to the relatively far location
to the silver baskets and the affect of the acetonitrile groups. The
interplay of silver ethynide bonding, argentophilicity, and weak
Scheme 2. Coordination modes observed for L1 (in 1 and 2), L2 (in 3), and L3 (in 4 and 5).
intermolecular interactions such as hydrogen bonding,
pep and

2828
B. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2820e2828
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We gratefully acknowledge financial support by the National
Natural Science Foundation of China (No. 20901070), the
China Postdoctoral Science Foundation (Grant 20090460859 and
201003399) and Zhengzhou University (No. 000001307015), and
the Hong Kong Research Grants Council (Ref. No. CUHK 402408).
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