Silver coordination polymers based on p-cyanophenylsilanes as ligands

Article abstract of DOI:10.1002/cplu.201402026

Differently substituted p-cyanophenylsilanes, Me_4-nSi(C ₆H₄CN)_n, (n=2, 3, 4), PhSi(C₆H ₄CN)₃, cycHexSi(C₆H₄CN)₃ (cycHex=cyclohexyl), and MePhSi(C₆H₄CN)₂, were prepared and fully characterized. Their coordination behavior was studied by utilizing silver salts of the type AgX (X=O₃SCF₃ ^-, CO₂CF₃^-), which led to coordination polymers. One-dimensional chains were observed for the bidentate p-cyanophenylsilane ligands, whereas two- and three-dimensional networks, including macrometalacycles, were found for the tridentate ligand. Treatment of AgO₂CCF₃ with the tetradentate ligand Si(C ₆H₄CN)₄ led to the formation of a diamond-like three-dimensional network with two interpenetrating nets linked by bridging Ag₂(CF₃CO₂)₂ dimers. X-ray structures show a wide range of close Ag'''Ag distances in the polymers, which are dependent on the ligand and the anion utilized.

Full text of DOI:10.1002/cplu.201402026

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FULL PAPERS
DOI: 10.1002/cplu.201402026
Silver Coordination Polymers Based on p-Cyanophenylsilanes
as Ligands
Bianca Blankschein,[a] Axel Schulz,*[a, b] Alexander Villinger,[a] and Ronald Wustrack[a]
Dedicated to Professor Ingo-Peter Lorenz on the occasion of his 70th birthday
Differently substituted p-cyanophenylsilanes, Me4ꢀnSi(C6H4CN)n,
(n=2, 3, 4), PhSi(C6H4CN)3, cycHexSi(C6H4CN)3 (cycHex=cyclo-
hexyl), and MePhSi(C6H4CN)2, were prepared and fully charac-
terized. Their coordination behavior was studied by utilizing
cycles, were found for the tridentate ligand. Treatment of
AgO2CCF3 with the tetradentate ligand Si(C6H4CN)4 led to the
formation of a diamond-like three-dimensional network with
two interpenetrating nets linked by bridging Ag2(CF3CO2)2
dimers. X-ray structures show a wide range of close Ag···Ag dis-
tances in the polymers, which are dependent on the ligand
and the anion utilized.
ꢀ
silver salts of the type AgX (X=O3SCF3ꢀ, CO2CF3 ), which led
to coordination polymers. One-dimensional chains were ob-
served for the bidentate p-cyanophenylsilane ligands, whereas
two- and three-dimensional networks, including macrometala-
Introduction
In recent years, there has been increasing interest in metal-
containing coordination polymers. Their topological diversity
makes them interesting for versatile applications.[1–9] In most
cases, the resulting topology is unpredictable and can be influ-
enced by many factors. Besides the ligand and metal center,
the coordination behavior of the anion,[10–13] solvent mole-
cules,[14,15] or the ratio[16] of metal salt and ligand can also
change the topology of the network.
polymers generated from Si(C6H4CN)4 and AgOTf (OTf=
O3SCF3) as well as AgPF6.[30] Herein, we describe in detail the in-
fluence and structural diversity of silver coordination com-
ꢀ
ꢀ
pounds dependent upon the anion (O3SCF3 and CO2CF3 ) and
differently substituted neutral p-cyanophenylsilanes. For this,
we started with the preparation of Me(4ꢀn)Si(p-C6H4CN)n (n=1–
3) and their silver salts. To study the influence of the methyl
group on the structure, we also prepared Ph(4ꢀn)Si(p-C6H4CN)n
(n=2, 3), cycHexSi(p-C6H4CN)3 (cycHex=cyclohexyl), and their
silver salts.
This study presents a series of different p-cyanophenylsilanes
as ligands and their application and function in network forma-
tion. For the last five years, we have been dealing with novel
CN-based anions (e.g., [Al(OꢀC6H4ꢀCN)4]ꢀ) and their application
as weak coordinating anions for the generation of ionic liq- Results and Discussion
uids.[17–20] We were intrigued by the idea to use neutral p-cya-
Synthesis of ligands
nophenylsilanes, which are formally isolobal to [Al(OꢀC6H4ꢀ
CN)4]ꢀ (Alꢀ substituted by Si). The use of silicon-based cyano
compounds is interesting because they are robust and the
starting materials are available in large quantity at low cost. In
comparison to the analogous carbon compounds, the larger
SiꢀC distance relative to the CꢀC distance makes these ligands
structurally more flexible.[21] In recent years, many examples of
silicon-based ligands have been published;[22–29] however, to
the best of our knowledge, only two examples of coordination
polymers with p-cyanophenylsilanes and silver centers have
been reported. In 1997, Tilley and Liu described coordination
Generally, there are two different synthetic routes to p-cyano-
phenylsilanes of the type R(4ꢀn)Si(p-C6H4CN)n (R=Me, Ph; n=1–
4). 1) As shown by van Walree et al.,[31] Me3Si(p-C6H4CN) and
Me2Si(C6H4CN)2 were prepared from lithiated 1,4-dibromoben-
zene (BrC6H4Br) and the corresponding chlorosilane, R3SiCl,
leading to the formation of bromophenylsilane, R3SiꢀC6H4Br,
which gave the desired cyano compound, R3SiꢀC6H4CN, after
the addition of CuCN. 2) Tilley and Liu obtained Si(C6H4CN)4 di-
rectly from BrC6H4CN after lithiation and addition of SiCl4
(Scheme 1).[30] We preferred the second approach because the
method by van Walree did not seem to be applicable for
higher substituted cyanosilanes. A major challenge of the ap-
proach by Tilley and Liu arises from lithiation of the cyano
group, which competes with the desired lithium–halogen ex-
change at the phenyl ring; this was intensively studied by
Parham and Jones in the 1970s.[32] In contrast to Tilley and Liu,
we therefore decided to dramatically decrease the reaction
time and kept the reaction mixture always below ꢀ808C. This
protocol prevents nBuLi from reacting with the CN triple bond.
[a] B. Blankschein, Prof. Dr. A. Schulz, Dr. A. Villinger, Dr. R. Wustrack
Universitꢀt Rostock, Institut fꢁr Chemie
Albert-Einstein-Strasse 3a, 18059 Rostock (Germany)
[b] Prof. Dr. A. Schulz
Leibniz-Institut fꢁr Katalyse e.V. an der Universitꢀt Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
E-mail: axel.schulz@uni-rostock.de
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cplu.201402026.
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Reaction of AgX (X=CF3SO3, CF3CO2) with p-cyanophenylsi-
lanes
Synthesis of [Ag{Me2Si(C6H4CN)2}]X (X=CF3SO3 (6), CF3CO2 (7))
The silver triflate and trifluoroacetate salts of the Me2Si-
(C6H4CN)2 ligand are easily obtained in the reaction of AgX in
CH2Cl2 (suspension) with Me2Si(C6H4CN)2 within 1 h in good
yields (yields: 70 (6), 64% (7)).
Scheme 1. General synthesis of p-cyanophenylsilanes of the type R(4ꢀn)Si(p-
C6H4CN)n (R=Me, Ph, etc.; n=1-4).
Synthesis of [Ag{RSi(C6H4CN)3}]CF3SO3 (R=Me (8), Ph (10), and
cycHex (12)) and reaction of AgCF3CO2 with RSi(C6H4CN)3
(R=Me (11), Ph (13))
Because the product, R(4ꢀn)Si(p-C6H4CN)n, is water stable, further
reactions and the formation of side products at elevated tem-
peratures was avoided by adding water to decompose remain-
ing or excess nBuLi. In addition to the decomposition of excess
nBuLi, lithium chloride, which is also formed in the reaction,
can easily be separated (Scheme 1).
All three triply substituted triflate silver coordination polymers
were obtained within 1 h from a stirred solution of silver tri-
flate in benzene (10 mL) after the addition of RSi(C6H4CN)3 dis-
solved in benzene. The concentration of these solutions often
gave viscous colorless oils, from which 8, 10, and 12 crystal-
lized in moderate yields (30–40%). Interestingly, although for
the reaction of AgCF3CO2 with PhSi(C6H4CN)3 a salt of the type
[Ag{PhSi(C6H4CN)3}]CF3CO2 (11) was observed (yield 48%), the
analogous reaction with MeSi(C6H4CN)3 led to the formation of
[(Ag{MeSi(C6H4CN)3})2][Ag4(CF3CO2)6] (13), which exhibited
a silver-containing complex anion (Scheme 2). This reaction
was then optimized, with respect to the stoichiometry, which
gave finally 13 in good yields (51%).
By this modified synthetic route, all p-cyanophenylsilanes of
the type Me4ꢀnSi(p-C6H4CN)n (n=1, 2, and 4) and novel RSi-
(C6H4CN)3 (R=Ph, Me, cycHex) were obtained in moderate to
good yields (between 10 and 65%). All ligands were fully char-
1
acterized by means of elemental analysis; H NMR, 13C NMR,
29Si NMR, IR, and Raman spectroscopy; and X-ray structure elu-
cidation. These data are summarized in Table 1. All prepared p-
Table 1. Experimental data for p-cyanophenylsilanes 1–4.[a]
Reaction of AgX with Si-
(C6H4CN)4 (X=CF3SO3, CF3CO2)
Yield [%]
M.p. [8C]
d13C (CN) [ppm]
d29Si [ppm]
n˜IRCN [cmꢀ1
]
n˜RamanCN [cmꢀ1
]
In 1997, Tilley and Liu reported
on the synthesis of [(Ag2{Si-
(C6H4CN)4})2][CF3SO3]2·2benzene
(14·2benzene), which was af-
Me2SiY2 (1)
MeSiY3 (2)
PhSiY3 (3)
cycHexSiY3 (4)
SiY4 (5)
53
10
26
52
65
101
119
192
183
270
118.9
118.7
118.7
118.7
118.5
ꢀ5.96
ꢀ9.35
2224 (m)
2228 (s)
2229 (m)
2227 (m)
2228 (s)
2226(10)
2230(10)
2230(10)
2229(10)
2231(10)
ꢀ14.17
ꢀ10.23
ꢀ14.09
forded from
a
solution of
[a] Y=ꢀC6H4CN.
AgCF3SO3 in benzene layered
with Si(C6H4CN)4 dissolved in
CH2Cl2.[30] A similar approach was
used for silver trifluoroacetate. However, crystalline material
was only obtained if the mixture of AgCF3CO2 Si(C6H4CN)4 in
benzene was boiled under reflux for 30 min followed by slow
cyanophenylsilanes (species 1–5, Table 1) are neither air nor
moisture sensitive, can be prepared in bulk, and are almost in-
definitely stable when stored in a sealed tube. They are ther-
mally stable up to over 3008C and melt between 101 (1) and
2708C (5).
The NMR spectroscopy data illustrate very similar 13C chemi-
cal shifts between d=118.5 and 118.9 ppm, whereas 29Si NMR
spectroscopy can be used to distinguish between alkyl and
phenyl substitution, as well as displaying different degrees
of substitution. According to the observed IR and Raman
data, the stretching mode of the CN groups was detected in
the typical region between n˜2224 and 2231 cmꢀ1[17–20] and
could not be utilized to distinguish between species 1–5 in
Table 1.
Scheme 2. Generation of silver coordination polymers in the reaction of AgX
with several p-cyanophenylsilanes.
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cooling to room temperature (yield 42%. X-ray studies of
ered species were selected in Fomblin YR-1800 (Alfa Aesar) at
ambient temperature. All samples were cooled to 173 K during
the measurements.
these colorless crystals revealed the presence of 13.
Properties and spectroscopic characterization
p-Cyanophenylsilanes
All silver coordination polymers described herein are air stable,
but slowly decompose in water. The IR and Raman data of all
considered species in Table 2 show sharp bands in the expect-
ed region n˜2236–2254 cmꢀ1, which can be assigned to the nCN
Apart from species 4·benzene, all other considered p-cyano-
phenylsilanes (Figure 1) crystallized free from benzene and
CH2Cl2. (Crystallization of pure 4 from thf leads to the forma-
tion of 4·thf.) Although in all
structures the molecules are
Table 2. Wavenumbers [cmꢀ1] of n˜CN in the coordination polymers, along with AgꢀN, AgꢀO, and Ag···Ag distan-
well-separated from each other,
there are numerous very weak
ces [ꢁ].
H
aryl···NꢀC and Haryl···Cphenyl,alkyl in-
6
7
8
13
10
11
12
14
teractions in the range between
2.4 and 3.0 ꢁ. The silicon atom
in all p-cyanophenylsilanes is tet-
rahedrally coordinated with
bonding angles around the sili-
con atoms of 105.2–111.48 (2),
106.2–112.78 (3), 104.7–112.68
(4), and 106.4–111.88 (5); these
values display a significant devi-
ation from an ideal tetrahedral
environment. The SiꢀC distances
all lie in the expected range
1.859(1)–1.886(1) (2), 1.869(2)–
1.884(2) (3), 1.877(1)–1.880(1) (4),
and 1.874(1)–1.878(1) ꢁ (5); this
indicates typical SꢀC single
bonds (cf. Srcov(SiꢀC)=1.91 ꢁ).[34]
The average CN distances
n˜IR
n˜Raman
Dn˜IR
Dn˜Raman
AgꢀN
2254
2254
30
28
2.207(3)
2.241(3)
2236
2243
12
17
2.361(3)
2.397(3)
2249
2262
21
32
2.226(4)
2.268(4)
2.288(4)
2250
2253
22
23
2.194(2)
2.238(2)
2.292(2)
2.637(2)
2.185(5)
2.235(2)
2.317(2)
2.232(4)
2.324(2)
2250 2248, 2231[b] 2249
2252 2229[b]
2254, 2235
2259, 2243
26, 7
28, 12
2.272(5)
2.233(4)
2254
22
25
2.210(2)
2.237(2)
2.311(2)
[a]
21
22
19, 2[b]
1[b]
2.279(6)
2.291(5)
[a]
[c]
–
[c]
AgꢀO
2.472(2)
2.837(7)
2.84(1)
2.277(2)
2.300(8)
2.595(8)
–
2.293(6)
2.354(8)
2.388(9)
2.284(3)
2.207(4)
2.219 (4)
2.392(3)
2.366(3)
[c]
Ag···Ag
4.3892(4)
3.0657(6) 14.047(3) 2.9708(3)
–
3.173(1)
14.5496(3) 3.3039(4)
2.9512(7)
3.0826(3)
3.1033(3)
3.1091(4)
3.5024(7)
[a] Compared with the naked ligand molecule, see Table 1. [b] Uncoordinated CN group. [c] Poor data set.
stretching frequencies. As previously shown, the coordination
of Lewis acids, such as B(C6F5)3, or cationic metal centers to
a NCꢀR species causes a significant band shift to higher wave-
numbers.[33] Hence, both IR and Raman spectroscopy are par-
ticularly well suited to distinguish between metal–CN-coordi-
nated p-cyanophenylsilanes and the naked p-cyanophenylsi-
lane molecule with shifts between n˜7 and 32 cmꢀ1 to higher
wavenumbers in the silver coordination polymers. Uncoordi-
nated CN groups, such as those in compound 11, are also
easily spotted. The shift to higher wavenumbers upon metal
coordination correlates nicely with a slightly smaller CꢀN dis-
tance (Table 2).
amount to 1.145(2) (2), 1.144(2) (3), 1.144(2) (4), and 1.143(2)
(5, cf. Srcov(CꢁN)=1.14 ꢁ).[34]
Coordination polymers with the bidentate ligand Me2Si(p-
C6H4CN)2
1
1
{[Ag{Me2Si(p-C6H4CN)2}]O3SCF3·CH2Cl2} (6·CH2Cl2) crystallizes
in the orthorhombic space group Pnma with eight formula
units per cell. Each Ag+ ion is surrounded by two neutral
Me2Si(p-C6H4CN)2 ligands, which coordinate to Ag+ through
one nitrogen atom of the CN group (Ag1ꢀN1 2.241(3) and
Ag1ꢀN2 2.207(3) ꢁ (cf. rcov(AgꢀN)=1.99 ꢁ)), and two triflate
ions, which each coordinate through one oxygen atom (Ag1ꢀ
O4 2.472(2) ꢁ) and two oxygen atoms (AgꢀO2 2.84(1), Ag1ꢀO3
2.827(7) ꢁ). Only weak van der Waals interactions can be ex-
pected along the Ag···O5 (3.222(3) ꢁ) units. Although the N2-
Ag1-N1 angle is rather large at 127.6(1)8, all other angles
around the Ag+ ion are smaller than 1008 (e.g., O3-Ag1-O4
73.1(2)8, O2-Ag1-O3 51.3(2)8). It should be noted that one tri-
flate anion (around S1) is disordered over two positions. Be-
cause one oxygen atom (O1, O3) of both triflate anions act as
bridging ligand atoms, the formation of Ag2(OTf)2L2 (L=
Me2Si(p-C6H4CN)2) dimers as the smallest building block is ob-
served (Figures 2 and 3). As depicted in Figure 3, the remaining
CN group of the Me2Si(p-C6H4CN)2 ligand connects this dimer
X-ray crystallography
To further evaluate the influence of the counterions on the
structure of the complexes, the more strongly coordinating
anion CF3CO2ꢀ (TFA) was used in the reaction with p-cyanophe-
nylsilanes for comparison with structures with weakly coordi-
ꢀ
nating CF3SO3 (OTf) anions. The structures of all utilized p-cya-
nophenylsilanes, RSi(p-C6H4CN)3 (with R=Ph, Me, cycHex) and
Si(p-C6H4CN)4, as well as silver salts 6–8 and 10–14, deter-
mined. Tables S1–S6 present the X-ray crystallographic data;
selected molecular parameters are listed in Tables S7–S18 in
the Supporting Information. X-ray quality crystals of all consid-
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tate ligands.[35–37] One CH2Cl2 sol-
vent molecule per [Ag{Me2Si(p-
C6H4CN)2}]O3SCF3 unit is found
between these chains.
1
1
{[Ag{Me2Si(p-
C6H4CN)2}]O2CCF3·0.5CH2Cl2}
(7·0.5CH2Cl2) also crystallizes in
the orthorhombic space group
Pnma with eight formula units
per cell, but with half of a CH2Cl2
molecule per formula unit. Simi-
lar to 6·CH2Cl2, the TFA anion
and Me2Si(C6H4CN)2 act as biden-
tate ligands. Although the che-
lating TFA anions are responsible
for the formation of a Ag2(TFA)2
dimer (Figure 4), the Me2Si-
(C6H4CN)2 ligand links these
silver dimers to double-stranded
chains, leading to a 1D coordina-
tion polymer, as shown in
Figure 5. It is worth noting that
the TFA anion is capable of ex-
hibiting different coordination
modes, as shown in Scheme 3.[38]
The Ag+ ions sit in a strongly
distorted tetrahedral environ-
ment with local C2v symmetry,
rather large O1-Ag1-O2 angles
(154.2(2)8), and much shorter
N1-Ag1-N2 angles (104.5(1)8),
contrary to the situation found
for 6·CH2Cl2 (see above); this dis-
plays the high flexibility of the
Me2Si(C6H4CN)2 ligand. Relative
to 6·CH2Cl2 the AgꢀN bond
lengths are considerably longer
(7·0.5CH2Cl2: Ag1ꢀN1 2.397(3),
Figure 1. ORTEP drawing of the molecular structure of MeSi(C6H4CN)3 (top left, 2), PhSi(C6H4CN)3 (top right, 3),
cycHexSi(C6H4CN)3 (bottom left), and Si(C6H4CN)4 (bottom right) in the crystal. Thermal ellipsoids with 50% proba-
bility at 173 K. Selected bond lengths [ꢁ]: 2: Si1ꢀC1 1.859(1), Si1ꢀC9 1.880(1), Si1ꢀC2 1.881(1), Si1ꢀC16 1.886(1),
N1ꢀC8 1.144(2), N2ꢀC15 1.143(2), N3ꢀC22 1.149(2); 3: Si1ꢀC1 1.869(2), Si1ꢀC14 1.876(2), Si1ꢀC7 1.881(2), Si1ꢀC21
1.884(2), N1ꢀC13 1.142(2), N2ꢀC20 1.147(3), N3ꢀC27 1.143(2); 4·benzene (benzene not shown for clarity): Si1ꢀC14
1.877(1), Si1ꢀC1 1.877(2), Si1ꢀC21 1.879(1), Si1ꢀC7 1.880(1), N1ꢀC13 1.141(2), N2ꢀC20 1.143(2), N3ꢀC27 1.144(2);
5: Si1ꢀC1 1.878(2), Si1ꢀC8 1.871(2), Si1ꢀC15 1.876(2), Si1ꢀC22 1.874(2), N1ꢀC7 1.143(2), N2ꢀC14 1.147(3), N3ꢀC21
1.140(2), N4ꢀC28 1.142(2).[56]
Figure 2. Ball-and-stick representation of the Ag+ ion environment in
Figure 3. Ball-and-stick representation of a section of the double strand in
6·CH2Cl2 (view along c-axis). Solvent molecules, which are located in the
voids, are omitted.
6·CH2Cl2 (symmetry code: ’: x, 0.5ꢀy, z; ’’: 1+x, y, z). Disorder around S1 not
shown. Hydrogen atoms are omitted for clarity.
to a chain in the unit cell. Hence, compound 6·CH2Cl2 might
be regarded as a 1D coordination polymer, which was de-
scribed before in a number of structural reports utilizing biden-
Ag1ꢀN2 2.361(3) ꢁ vs. Ag1ꢀN1 2.241(3), and Ag1ꢀN2
2.207(3) ꢁ in 6·CH2Cl2), whereas the AgꢀO distances are signifi-
cantly shorter in 7·0.5CH2Cl2 (7·0.5CH2Cl2: Ag1ꢀO1 2.300(8),
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Figure 4. Ball-and-stick representation of the Ag2(TFA)2Y2 dimer in
7·0.5CH2Cl2 (symmetry codes: ’: x,1.5ꢀy,z; ’’: 1+x,y,z; ’’’: 1+x,1.5y,z). Disorder
around C18 and C20 is not shown. Hydrogen atoms are omitted for clarity.
Scheme 3. Different coordination modes of the TFA anion.
OTfꢀ ion and the Ag+ ions. Otherwise, the Me2Si(C6H4CN)2
ligand coordinates stronger to Ag+ in 6·CH2Cl2.
Coordination polymers with the tridentate ligand RSi(p-
C6H4CN)3 (R=Me, Ph, cycHex)
3
1
{[Ag{MeSi(p-C6H4CN)3}]O3SCF3·2benzene} (8·2benzene) crys-
tallizes in the monoclinic space group P21/n with four formula
units per cell. Voids are filled with benzene molecules (two per
formula unit). As shown in Figure 6 (top left), the (distorted)
tetrahedral coordination of each Ag+ ion consists of three ni-
trogen atoms from three distinct MeSi(p-C6H4CN)3 ligand mole-
cules and one oxygen atom from the triflate group. Whereas
all nitrogen atoms of the MeSi(p-C6H4CN)3 ligand are involved
in binding Ag+ ions, leading to a 3D network, the triflate
anion acts as monodentate ligand and two oxygen atoms
remain uncoordinated. Because each CN group of MeSi(p-
C6H4CN)3 always links one Ag+ ion and the MeSi(p-C6H4CN)3
ligand acts as a bridging ligand, the formation of a macrocycle
(repeat unit) can be observed. The repeat unit of the 3D coor-
dination polymer is a 70-membered Ag5L5 macrocycle (L=
MeSi(C6H4CN)3; Figure 6, top left). Cross-linking between the
macrocycles, which leads to the formation of a 3D network
(Figure 6, bottom), is achieved by one cyano group per
MeSi(p-C6H4CN)3 ligand. In this macrometalacycle, the length of
the sides are about 29.7 (transannular Ag···Si distance) and
16.7 ꢁ (transannular Ag···Ag distance). A closer look at the 3D
Figure 5. Ball-and-stick representation of a section of the double strand
(top) and view of the cell along the c axis in 7·CH2Cl2 (bottom). Solvent mol-
ecules, which are located in the voids, are omitted for clarity as well as all
hydrogen atoms.
Ag1ꢀO2 2.77(2) ꢁ vs. Ag1ꢀO4 2.472(2), AgꢀO2 2.84(1), Ag1ꢀO3
2.827(7) ꢁ in 6·CH2Cl2), which indicates stronger bonding be-
tween the TFA anion and the Ag+ centers compared with the
network revealed
a
highly interpenetrated structure for
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Figure 6. Ball-and-stick representation of one macrocycle (repeat unit) in 8·2benzene (top left), space-filling representation of four-fold interpenetration (top
right) and one 3D network (without interpenetrating networks; bottom) built from the repeat unit via CN coordination. Solvent molecules, which are located
in the voids, are omitted for clarity as well as all hydrogen atoms.
8·2benzene, which does not possess large free channels or
pores.[39–42] It consists of four independent infinite frameworks,
each with the same topology as that discussed before
(Figure 6, top right). Ni et al. described such a fourfold inter-
penetrated structure with four symmetry-equivalent frame-
works for AgX (X=BF4, ClO4, CF3SO3) with tris(4-cyanophenyl)a-
mine (TCPA).[43]
anions (as well as solvent molecules) that are fixed in the cavi-
ties of the host networks for 13·3.5benzene (Figure 8). A simi-
lar situation was reported by Ni et al. for AgO2CCF3 with the tri-
dentate ligand TCPA.[43]
Although the anion is different from that of 8·2benzene, the
coordination mode by the bridging MeSi(p-C6H4CN)3 ligand is
the same as that observed in 13·3.5benzene; however, one ni-
trogen atom of MeSi(p-C6H4CN)3 acts a m2-bridge, leading to
the formation of a four-membered Ag2N2 ring in a centrosym-
metric Ag2N6 dimer (Figure 7 left, Ag-N-Ag 77.86(6)8). For this
reason, two types of AgꢀN bond lengths are detected: three
short distances ranging from 2.194(2) to 2.292(2) ꢁ and one
significantly longer distance of 2.637(2) ꢁ (cf. rcov(AgꢀN)=
1.99 ꢁ), which is considerably shorter than the sum of covalent
radii (rvdW(Ag···N)=3.27 ꢁ).[44] Therefore, coordination around
Ag1 might be considered as a distorted trigonal arrangement
(N-Ag-N 113.69(8), 121.42(9), and 123.44(8)8) or as a distorted
tetrahedral (N-Ag-N 87.00(8), 92.70(8), and 102.14(6)8) in
a [3+1] coordination mode. In addition, as depicted in
Figure 6, transannular Ag···Ag interactions must be considered
as well as Ag···Ag interactions between the silver centers of
the cationic framework and the silver centers of the cluster
anion; a very intriguing unprecedented structural feature,
which is of interest with respect to the question of the dimen-
sionality of the network (see above). The Ag···Ag distances be-
The AgꢀN bond lengths range from 2.226(4) to 2.288(4) ꢁ,
which is slightly shorter than that observed in 7·0.5CH2Cl2, but
in the range found in 6·CH2Cl2. The AgꢀO bond amounts to
2.595(8) ꢁ, which is in accordance with those found for
6·CH2Cl2 and 7·0.5CH2Cl2. The Ag···Ag distances are all larger
than 11.79(9) ꢁ; thus no metallophilic interactions are found
(see above).
2
1
{[Ag{MeSi(p-C6H4CN)3}]2[Ag4(O2CCF3)6]·3.5benzene}
(13·3.5benzene), which precipitates from
a solution of
AgO2CCF3 and MeSi(p-C6H4CN)3, in contrast to 8·2benzene,
¯
crystallizes in the triclinic space group P1 with two formula
units per unit cell. Single-crystal analysis revealed three inde-
pendent silver(I) centers (Scheme S10 in the Supporting Infor-
mation): Ag1 is exclusively bound by nitrogen atoms, whereas
Ag2 and Ag3 are exclusively linked by oxygen atoms of the
carboxy group (Figure 7). Hence, in contrast to the triflate spe-
ꢀ
cies 8·2benzene, CF3CO2 causes
a 2D cationic network
2
(
{[Ag{MeSi(p-C6H4CN)3}]22+) with large guest [Ag4(CF3CO2)6]2ꢀ
1
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radii of two silver atoms (3.42 ꢁ[44]) and are comparable to
those found in other structurally characterized AgCF3CO2 com-
plexes.[45,46]
Starting from the distorted trigonal AgN3 unit (Figure 7, left),
each MeSi(p-C6H4CN)3 ligand links three Ag1 atoms to generate
an infinite honeycomb network.[47,48] The 3 Ag1 ions and 3
MeSi(p-C6H4CN)3 ligands (each MeSi(p-C6H4CN)3, using two of
the three arms, connects two silver atoms in each macrocyclic
unit) form a 48-membered (Ag3L3) macrocyclic ring. In this
macrometalacycle, the lengths of the sides are almost equiva-
lent (9.2–9.5 ꢁ), and the intermetallic separations of Ag···Ag are
about 15.7 ꢁ, which are slightly shorter than those of 8·2ben-
zene. As shown in Figure 8, two of these honeycomb-like,
simple-sheet nets are linked into a 2D double layer through in-
terpolymer AgꢀN coordinative interactions (Ag1ꢀN1’ and
Ag1’ꢀN1) if dimer coordination (see Figure 7, left) is taken into
account. The view along the b axis (Figure 8, right) displays
these double layers, which are additionally linked by Ag···Ag
(d10–d10 closed shell) interactions with the cluster anions lead-
1
1
ing to infinite
[AgI+] chains along [100]. Interestingly, to
enable such Agcation···Agcluster–anion interactions, the tetrameric
[Ag4(CF3CO2)6]2ꢀ cluster ion must adopt a highly distorted
structure (especially around Ag2), as illustrated in Figure 7. Evi-
dently, this severe deformation results from strong interactions
of the guest cluster anions to the cationic host networks,
which is a rare example of the host cationic networks contain-
ing guest cluster anions.[43] In [Ag3(TCPA)(CF3CO2)3]n nCH2Cl2),
no such Agcation···Agclusterꢀanion interactions are found. The tetra-
meric cluster anion is also much less distorted (see the Sup-
porting Information) and composed of four silver(I) ions and
six trifluoroacetate anions, in which the four Ag+ ions are
bridged by carboxylate groups alternately above and below
Figure 7. Ball-and-stick representation of the coordination sphere around
Ag1+ in the cationic framework (top; only the N atoms of the MeSi(p-
C6H4CN)3 ligands are shown) and the molecular cluster anion [Ag4-
(O2CCF3)6]2ꢀ·(bottom) in 13·3.5benzene. Dashed lines represent Ag(d10)···Ag-
(d10) van der Waals interactions. Symmetry codes: left, ’: ꢀx, 1ꢀy, 1ꢀz; ’’: x,
1+y, z; ’’’: x, y, 1+z; ’’’’: ꢀx, ꢀy, 1ꢀz; ’’’’’: ꢀx, 1ꢀy, ꢀz; right, ’: 1ꢀx, 1ꢀy,
1ꢀz.
tween 3.0826(3) (“interionic”) and 3.1091(4) ꢁ (transannular)
are significantly shorter than the sum of the van der Waals
2
1
2+
Figure 8. View of the cationic 2D network in {[Ag{MeSi(p-C6H4CN)3}]2 along the a axis (left). Cluster anion [Ag4(O2CCF3)6]2ꢀ, hydrogen atoms and solvent
molecules are omitted for clarity. Right: View long the b axis, the four Ag centers (light blue) of the cluster anion are included to demonstrate the interaction
of the cluster anion with the cationic framework, leading to infinite Ag···Ag chains (dotted red line).
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the Ag4-plane (Scheme 3, species G). In this discrete tetranu-
clear silver cluster anion (Figure 7, right), each Ag+ ion is a dis-
torted triangle coordinated by three oxygen atom from the
ꢀ
three CF3CO2 anions with AgꢀO distances ranging from
2.185(5) to 2.324(2) ꢁ (cf. 2.201(5) to 2.345(5) ꢁ in [Ag3(TCPA)-
(CF3CO2)3]n nCH2Cl2).[43] In each Ag4O12 moiety, the four Ag+
ions are linked by six m2-CF3CO2 anions. The Ag···Ag distances
ꢀ
range from 2.9708(3) to 3.033(3) ꢁ (cf. 2.956–3.072 ꢁ in [Ag3-
(TCPA)(CF3CO2)3]n·nCH2Cl2), which are significantly shorter than
the sum of the van der Waals radii of two silver atoms (see
above). Notably, there are numerous weak CarylꢀH···Fanion and
CarylꢀH···Oanion van der Waals interactions that fix the benzene
molecules in the cavities. Additionally, such stabilizing interac-
tions are also found between the cationic framework and the
cluster anions.
In the next series of experiments, we studied the influence
of the noncoordinating substituent attached to the silicon
atom. For this reason, PhSi(p-C6H4CN)3 and cycHexSi(p-C6H4CN)3
were prepared. With the PhSi-
Figure 9. View of the cationic 2D network in 10+. Hydrogen atoms and sol-
vent molecules are omitted for clarity.
(C6H4CN)3 linker, we were able to
synthesize the OTf and TFA silver
salts. Because the data set of the
single-crystal X-ray study of
2
1
{[Ag{PhSi(p-C6H4CN)3}]-
[O3SCF3]·benzene} (10·benzene)
was poor, we have only dis-
cussed the topology, but not the
distances and angles, in detail.
Compound 10·benzene crystalli-
zes in the triclinic space group
Pꢀ1 with two formula units per
cell. Voids are filled with ben-
zene molecules (one per formula
unit). As shown in Figure 9, the
(distorted) tetrahedral coordina-
tion of each Ag+ ion consists of
three nitrogen atoms from three
distinct PhSi(p-C6H4CN)3 ligand
molecules and one oxygen atom
from the triflate group; a situa-
tion that is similar to 8·2ben-
zene. Although all nitrogen
atoms of the MeSi(p-C6H4CN)3
2
Figure 10. Left: View of a section of a double layer in {[Ag{PhSi(p-C6H4CN)3}[O3SCF3]. Right: Two double layers.
1
Hydrogen atoms and solvent molecules are omitted for clarity.
ligand are involved in the binding of Ag+ ions, leading to a 2D
network, the triflate anion acts as monodentate ligand and
two oxygen atoms remain uncoordinated. Starting from the
distorted trigonal AgN3 unit (Figure 9), each PhSi(p-C6H4CN)3
ligand links three silver atoms to generate an infinite honey-
comb cationic network. Thus, in contrast to the interpenetrat-
ed 3D network in 8·2benzene, in which a methyl group is re-
placed with a phenyl group (as in 10·benzene), only a 2D net-
work is formed (Figure 10 versus Figure 6). The honeycomb-
like macrometalacycles are composed of 6 SiꢀCNꢀC6H4ꢀAg
moieties in contrast to 5 in 8·2benzene, which leads to a 48-
membered heterocycle. In addition, each infinite honeycomb
network forms a double layer with a second one, with weakly
interacting triflate and phenyl groups, as illustrated in
Figure 10 (left). Between such double layers, no significant in-
teractions were observed (Figure 10, right).
3
1
{[Ag{PhSi(C6H4CN)3}]O2CCF3 (11) crystallizes in the tetrago-
nal space group P43212 with eight formula units per unit cell.
In contrast to 10·benzene, treatment of AgTFA with PhSi(p-
C6H4CN)3 led to a compact 3D network without solvent mole-
cules because no voids formed. The most prominent structural
feature is the formation of Ag2(O2CCF3)2L2 (L=PhSi(p-C6H4CN)3)
dimers. Adjacent silver atoms are joined in a bridging fashion
by two TFA groups; thus giving rise to Ag2(O2CCF3)2L2 dimers,
which are identical to those found in the structure of the TFA
silver salt[49] (Figure 11 and Scheme 3, species D). Both silver
atoms have a distorted tetrahedral coordination, are surround-
ed by two oxygen atoms of two distinct [O2CCF3]ꢀ ions (AgꢀO
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mation of a 2D network (Figure 13), is achieved by one cyano
group per cycHexSi(p-C6H4CN)3 ligand. The triflate counterion
only acts as a monodentate ligand. In this macrometalacycle,
the length of the sides are about 15.3 (transannular Ag···Si dis-
tance) and 15.1 ꢁ (transannular Ag···Ag distance), that is, the
size of the window is smaller than those in 8·2benzene (29.7/
16.7 ꢁ) and 10·benzene (19.0/15.6 ꢁ). Nevertheless, the struc-
ture resembles that of 10·benzene, although no double layers
are formed (Figure 10) owing to the absence of directing weak
F···HꢀCaryl interactions. Hence, as depicted in Figure 13 (right),
two independent interpenetrating networks are observed.
Coordination around the silver centers is distorted tetrahe-
dral with three CN groups of three different ligands (AgꢀN
2.10(2)–37(2) ꢁ) and an oxygen atom of a triflate counteranion
(AgꢀO1 2.388(9) ꢁ; cf. AgꢀO2 4.19(1) and AgꢀO2 3.71(1) ꢁ).
The bond angles around silver are in the range of 87.0(3)–
126.2(2) (O-Ag-N) and 106.34(8)–122.27(8)8 (N-Ag-N).
Figure 11. Ag2(O2CCF3)2L2 (L=PhSi(p-C6H4CN)3) dimer in 11. Symmetry
codes: ’: x, ꢀy, z; ’’: ꢀ0.5+x, 0.5ꢀy, ꢀ0.25+z; ’’’: ꢀ0.5+x, 0.5ꢀy, 0.25ꢀz.
2.354(8), 2.293(6) ꢁ), and are linked to two nitrogen atoms
from different PhSi(C6H4CN)3 linkers (AgꢀN 2.279(6), 2.291(5) ꢁ).
The Ag···Ag’ contact distance is 3.173(1) ꢁ, which is shorter
than the sum of the van der Waals radii. Interestingly, although
11 forms a dense 3D network, only two of the CN groups of
the linker connect silver dimers, whereas the third remains un-
coordinated (Figure 12).
Coordination polymers with the tetradentate ligand Si(p-
C6H4CN)4
As early as 1997, Tilley and Liu reported on the structures of
silver coordination polymers with the tetradentate ligand Si(p-
ꢀ
ꢀ [30]
C6H4CN)4 and the counterions CF3SO3 and PF6
.
Si(p-C6H4CN)4 crystallized with AgCF3SO3 from ben-
zene and dichloromethane to give [Ag2Si(p-C6H4CN)4]-
[CF3SO3]2·2benzene (15·2benzene). The extended
solid structure is composed of interpenetrating
double layers which are three-connected through
trigonal planar silver and tetrahedral silver centers.[30]
Because our studies on coordination polymers with
RSi(C6H4CN)3 and R2Si(C6H4CN)2 revealed large differ-
ences between AgCF3SO3- and AgCF3CO2-based coor-
dination polymers (see above), it seemed interesting
to treat a solution of AgCF3CO2 in benzene with Si(p-
3
1
C6H4CN)4. Indeed, crystals of isolated
{[Ag4{Si(p-
C6H4CN)4}](O2CCF3)4}·3benzene (14·3benzene) dis-
played, contrary to 15·2benzene reported by Tilley
and Liu,· a diamond-like 3D network (Figure 14).
Compound 14·3benzene crystallizes in the mono-
clinic space group C2/c with four formula units per
cell with three independent silver ions. Two CN
groups of each Si(p-C6H4CN)4 coordinates Ag+ cen-
ters (Ag3) in a monodentate fashion (Figure 15),
whereas the two remaining CN groups bind to Ag1
and Ag2 in a bridging fashion through m2-N1. It is
worthwhile mentioning that the AgꢀN distances of bridging
N1 are significantly different (m2-N1: Ag1ꢀN1 2.272(5) and
Ag2ꢀN1 2.664(9) ꢁ): one is short and in the range of the mon-
odentate AgꢀN distance (Ag3ꢀN2 2.233(4) ꢁ), whereas the
other is considerably longer, but still much shorter than the
sum of the van der Waals radii (cf. SvdW(Ag···N)=3.27 versus
Scov(AgꢀN)=1.99 ꢁ).[34,44] As depicted in Figure 16, the coordi-
nation sphere around the silver ions is different. Whereas Ag1
and Ag3 bind to two nitrogen and two oxygen atoms and
have near-tetrahedral geometry with bond angles between
94.8(3) and 122.4(2)8, the Ag2 ion is almost T-shaped and sur-
Figure 12. Section of the 3D network in 11, which highlights coordination of the Ag2
dimers and the noncoordinating CN groups. Hydrogen atoms are omitted for clarity.
Finally, we used the cycHexSi(p-C6H4CN)3 ligand in the reac-
tion with AgOTF in benzene and obtained a 2D layer structure
2
1
with a honeycomb-like structural motif (Figure 13).
{[Ag-
{cycHexSi(C6H4CN)3}][O3SCF3]·benzene} (12·benzene) crystallizes
in the orthorhombic space group P212121 with four formula
units in the unit cell. The structure of complex 12 is comprised
of (6,3) layers of hexagonal meshes, with alternating three-con-
nected AgI centers and tridentate cycHexSi(C6H4CN)3 ligands
(Figure 13). The layers are highly undulated and composed of
42-membered Ag3L3 macrocycles (L=cycHexSi(p-C6H4CN)3.
Cross-linking between the macrocycles, which leads to the for-
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Figure 13. Left: Front view of a section of a single layer in 12·benzene. Right: View along the a axis of the twofold interpenetrated layers. Hydrogen atoms
are omitted for clarity.
Figure 15. Coordination modes of the Si(C6H4CN)4 ligand. Symmetry codes: ’:
1+x, y, 1+z; ’’: 0.5ꢀx, ꢀ0.5+y, 1.5ꢀz; ’’’: 0.5+x, ꢀ0.5+y, z; ’’’’: 0.5+x,
ꢀ0.5+y, 1+z; ’’’’’:1ꢀx, y, 1.5ꢀz.
bisphenoidal geometry around Ag2. Compared with 15·2ben-
zene, the triflate anion plays an integral part in deciding the
structure around the silver ions, as illustrated in Figure 16. The
TFA ion adopts different coordination modes (cf. Scheme 3):
1) Ag1 and Ag3 are bridged by one O1 atom of two different
Figure 14. Adamantane motif in 14·3benzene. (Structure reduced to this
TFA ions to form a planar four-membered Ag2O2 dimer (Ag1ꢀ
motif.)
O1 2.284, Ag3ꢀO1 2.366(3) ꢁ). The remaining oxygen atom of
both TFA ions (O2) binds to Ag2 (Ag2ꢀO2 2.392 ꢁ); thus lead-
rounded by three oxygen atoms (O2-Ag2-O3 89.9(1), O2-Ag2-
O4 106.5(1), O3-Ag-O4 156.3(2)8), and, in addition, one weaker
coordination mode is found with one nitrogen atom (Ag2-m2-
N1 2.664(9) ꢁ). Thus, the coordination sphere seems to be best
described by a [3O+1N+1Ag] mode, leading to a distorted
ing to the formation of an undulated six-membered Ag2CO2N
heterocycle (if the bridging N1 atom is also taken into ac-
count), which is condensed into the dimer. 2) In addition, two
Ag2 ions are bridged by two chelating TFA ions through O3
and O4 (Ag2ꢀO3 2.219(4), Ag2ꢀO4 2.207(4) ꢁ), resulting in the
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Figure 17. Two interpenetrating adamantane moieties of two independent
diamond-like nets linked by Ag2[CF3CO2]2 dimers (only one linkage is shown;
structure reduced to this motif).
Figure 16. The coordination sphere around the different Ag+ centers in
14·3benzene. Phenyl rings are omitted for clarity. Dashed lines between
Ag+ centers (Ag···Ag<3.304 ꢁ) indicate infinite Ag···Ag chains along the
c axis. Symmetry codes: ’: ꢀ0.5+x, 0.5+y, ꢀ1+z; ’’: 0.5ꢀx, 0.5+y, 1.5ꢀz; ’’’:
ꢀx, y, 0.5ꢀz.
Conclusion
We presented a general synthesis for different p-cyanophenyl-
silanes and their application as bi-, tri, and tetradentate ligands
in the coordination chemistry of AgIX (X=OTf, TFA) and the
coordinating behavior of these compounds in silver coordina-
tion polymers. The topology of the network changed with var-
iation of the denticity, with the coordination strength of the
anion, and also with the variation of the nonfunctional part of
the tridentate ligand. Although the OTf anion only weakly
bound to the Ag+ ions, and thus, strengthened the AgꢀN
bonds, the TFA anion mediated the tuning of the structure of
the motifs by utilizing different coordination modes
(Scheme 3). This often led to silver (cluster) anions with close
Ag···Ag distances[43] or even silver chains,[16,38,54] which were
part of 2D and 3D networks, depending on the denticity of the
p-cyanophenylsilane. Clearly, the [AgLn]TFA salts forced the
Ag+ ions to approach each other (in contrast to the OTf ion)
and were therefore excellent examples suitable for the study
of metallophilic attractions with ligands supported in closed-
shell AgI systems.[55] Coordination polymers with Ag···Ag inter-
actions may possess electrical semiconductive properties.[9] The
[AgLn]OTf solid-state structures with the weaker coordinating
OTf ion were mainly influenced by the denticity and nonfunc-
formation of an planar eight-membered Ag2C2O4 heterocycle,
which is also directly associated with two five-membered rings.
Hence, a chain of connected four-, six-, and eight-membered
silver-containing heterocycles is formed along the c axis. As in-
dicated by the dashed lines in Figure 16, the transannular
Ag···Ag distances (five-membered ring: Ag1···Ag2 3.3039(4) ꢁ,
eight-membered ring: Ag2···Ag2’ 2.9512(7) ꢁ) are shorter than
the sum of the van der Waals radii (SvdW(Ag···N)=3.4 ꢁ), which
indicates significant argentophilic interactions[50] along the
c axis. The Ag···Ag distance within the four-membered ring
amounts to 3.5024(7) ꢁ, which is slightly larger; however,
a chain of silver-containing heterocycles is also formed when
the five- and eight-membered rings are exclusively considered.
Furthermore, all of these heterocycles discussed are part of an
adamantoid network, also known as a super-diamondoid struc-
ture.[42] This long-range structure consists of edge-sharing ada-
mantoid units (Figure 14), which are composed of four silicon,
two silver, and four Ag2O2 (dimers) nodes cross-linked by 12 p-
C6H4CN linkers. Additionally, twofold interpenetration is ob-
served (Figure 17). The two “independent” networks interpene-
trate in such a way that each tetrahedral node is found at the
center of an adamantane unit of the other framework, and the
four connections to nearest neighbors project through the
four cyclohexane-like windows of the surrounding adamantane
unit (Figure 17).[51] Strictly speaking, neither networks is inde-
pendent in 14·3benzene because both networks are linked by
Ag2[CF3CO2]2 dimers, as illustrated in Figure 17. Interpenetra-
tion in adamantoid networks is a common feature.[52] A known
tionalized substituent (Me, Ph, cycHex) of the p-cyanophenylsi-
1
1
lane.
{[Ag{Me2Si(C6H4CN)2}]O2CCF3·0.5CH2Cl2} forms double-
3
stranded chains,
forms a 3D network built from 70-membered Ag5L5 macrocy-
{[Ag{MeSi(C6H4CN)3}]·O3SCF3·2benzene}
1
2
1
cles, and {[Ag{PhSi(C6H4CN)3}][O3SCF3]·benzene} and 12·ben-
zene form an infinite honeycomb cationic 2D network. No
close Ag···Ag distances were observed for any of the triflate
silver salts. In the future, it will be interesting to see whether
we can make use of classic weakly coordinating anions, such
exception to this observation is the intriguing example of
as BF4 or larger B(C6F5)4ꢀ, to display nearly exclusive ligand–
3
1
ꢀ
{[Cu(4,4’,4’’,4’’’-tetracyanotetraphenylmethane]·BF4·xC6H5NO2},
which exists as a single adamantoid array with no interpenetra-
tion, reported by Robson and Hoskins.[39a,53]
metal interactions.
Keywords: coordination modes · coordination polymers · salt
effect · silver · X-ray diffraction
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Published online on April 8, 2014
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