Design, synthesis, and photoluminescence properties of one-, two-, and three-dimensional coordination polymers: Anion-assisted argentophillic interactions as building blocks

Article abstract of DOI:10.1021/cg500898c

Five new Ag(I) complexes of the formulae {[Ag₂(L₁)₂(NDS)]3H₂O}_n (1), {[Ag₂(L₂)₂(NDS)]·2H₂O}_n (2), {[Ag₃(L₂)₂(IQS)₂]·(NO₃)·4H₂O·2MeOH}_n (3), {[Ag₂(L₃)₂(NDS)]·4H₂O}_n (4), and {[Ag₂(L₃)₂(IQS)]·(NO₃)·H₂O}_n (5) (L₁ = 2,5-bis-pyridine-3-ylmethylene-cyclopentanone, L₂ = 2,5-bis-pyridine-3-ylmethylene-cyclohexanone, L₃ = 2,5-bis-pyridine-4-ylmethylene-cyclopentanone, NDS = naphthalene disulfonate, and IQS = isoquinoline-5-sulfonate) have been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complexes 1-3 were found to have sulfonate supported Ag...Ag interaction, and the sulfonate ions act as linkers to form higher dimensional networks (ladder, two- and three-dimensional networks). The complexes 4 and 5, which contain 4-pyridyl substitution, do not form such Ag...Ag interactions, indicating a clear tendency of 3-pyridyl derivatives to promote such interactions over 4-pyridyl derivatives. This observation was also evidenced by the analysis of Ag(I) complexes in Cambridge Structural Database. Further, complexes 1-5 were found to exhibit solid-state photoluminescence in the green region at room temperature.

Full text of DOI:10.1021/cg500898c

Article
pubs.acs.org/crystal
Design, Synthesis, and Photoluminescence Properties of One‑, Two‑,
and Three-Dimensional Coordination Polymers: Anion-Assisted
Argentophillic Interactions as Building Blocks
Kaustuv Banerjee, Sandipan Roy, and Kumar Biradha*
Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India
S
* Supporting Information
ABSTRACT: Five new Ag(I) complexes of the formulae
{[Ag2(L1)2(NDS)]3H2O}n (1), {[Ag2(L2)2(NDS)]·2H2O}n (2),
{[Ag3(L2)2(IQS)2]·(NO3)·4H2O·2MeOH}n (3), {[Ag2(L3)2(NDS)]·
4H2O}n (4), and {[Ag2(L3)2(IQS)]·(NO3)·H2O}n (5) (L1 = 2,5-bis-
pyridine-3-ylmethylene-cyclopentanone, L2 = 2,5-bis-pyridine-3-ylmethy-
lene-cyclohexanone, L3 = 2,5-bis-pyridine-4-ylmethylene-cyclopentanone,
NDS = naphthalene disulfonate, and IQS = isoquinoline-5-sulfonate) have
been synthesized and characterized by elemental analysis, IR, powder X-ray
diffraction, and single-crystal X-ray diffraction. Complexes 1−3 were found
to have sulfonate supported Ag···Ag interaction, and the sulfonate ions act
as linkers to form higher dimensional networks (ladder, two- and three-
dimensional networks). The complexes 4 and 5, which contain 4-pyridyl
substitution, do not form such Ag···Ag interactions, indicating a clear
tendency of 3-pyridyl derivatives to promote such interactions over 4-
pyridyl derivatives. This observation was also evidenced by the analysis of Ag(I) complexes in Cambridge Structural Database.
Further, complexes 1−5 were found to exhibit solid-state photoluminescence in the green region at room temperature.
important role in determining the solid state structures as well
as the luminescence properties.10
The CPs of Ag(I) or hydrogen bonded complexes with L1−
L3 and related derivatives have been extensively explored by us
for their photochemical reactivity and guest inclusion abilities
(Scheme 1).11 From the studies of the CPs of Ag(I), it was
INTRODUCTION
■
The design, synthesis, and exploration of the properties of
coordination polymers (CPs) have gained momentum given
their fascinating network topologies and various functional
properties such as luminescence, magnetic, and semiconduc-
tivity, gas sorption and separation, and molecular recogni-
tion.1−6 For the construction of CPs, the ligands containing
pyridyl and/or carboxylate functionalities are of major interest
given their propensity for coordination with various metal
atoms. In contrast, CPs formed via sulfonate linkers are very
limited owing to the weak coordination abilities of sulfonates
with several transition metal salts. However, they coordinate
better with alkali ions, larger alkaline earth ions, and Ag(I) ions,
as these ions do not have any preferable coordination number
or geometries.7 The Ag(I) ions are known to form
argentophilic, Ag(I)···Ag(I), interactions with/without the
help of anion templation. Such metallophilic interactions are
known to be formed by heavy coinage transition metals
containing nd10 configuration with a stability order of Au···Au >
Ag···Ag > Cu···Cu.8 We and others have recently shown that
argentophilic interactions act as good templates for promoting
solid state [2 + 2] reactions. These interactions were found to
be often templated by anions such as acetates, nitrates, and to
some extent by sulfonates. Such closed shell argentophilic
interactions were also been utilized for the exploration of
semiconducting and luminescent properties.9 Notably, the
contribution of short Ag···Ag interactions were found to play an
Scheme 1. Bis-Pyridyl Cyclic Ketones and Sulfonate Ligands
Used in This Work
Received: June 19, 2014
Revised: August 18, 2014
Published: August 27, 2014
© 2014 American Chemical Society
5164
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
Table 1. Crystallographic Parameters for the Crystal Structures of 1−5
compound
formula
1
2
3
4
5
C44H34Ag2N4O11S2
1074.63
293(2)
C23H19AgN2O5S
543.34
C56H46Ag3N6O14S2
1490.84
C23H19AgN2O5S
1098.68
C34H28Ag2N6O9S
1032.51
MW
T (K)
system
space group
a (Å)
293(2)
293(2)
293(2)
293(2)
monoclinic
C2/c
triclinic
triclinic
triclinic
triclinic
̅
̅
P1
P1
P1
P1
̅
̅
̅
̅
24.0884(16)
10.7929(8)
16.1990(11)
90.00
7.5490(15)
11.126(2)
13.287(3)
103.367(6)
105.626(6)
93.767(6)
1035.8(4)
1
7.4241(7)
14.8914(14)
14.959(2)
114.498(4)
99.310(4)
100.904(3)
1423.3(3)
1
8.496(3)
11.529(4)
12.340(4)
102.401(10)
101.842(9)
106.290(9)
1086.7(6)
1
11.0439(10)
13.4634(11)
16.3020(14)
66.454(2)
73.330(2)
67.759(2)
2030.3(3)
2
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
vol (Å3)
Z
90.677(2)
90.00
4211.2(5)
4
D
calc (mg/m3)
1.6950
1.7420
1.6506
1.7420
1.6299
R1 (I > 2σ(I))
wR2 (on F2, all data)
0.0387
0.0390
0.0672
0.0787
0.0454
0.1139
0.0585
0.1249
0.1593
0.0696
evident that the solid state [2 + 2] reactivity and the geometry
of the products obtained depend on the presence of anions.
These one-dimensional CPs of nitrate, perchlorate, and triflate
salts of Ag(I) indicated that Ag···Ag interactions template such
reactions to give double or single [2 + 2] reactions with variable
product geometries. In particular, the triflate structure was
found to have Ag···Ag interactions that are templated by triflate
ions (I, Scheme 1). These studies inspired us to link such one-
dimensional CPs with linkers containing sulfonates two
produce two-dimensional (2D) networks with alignment of
double bonds of L1, L2, and L3 for topochemical reactions. Such
structures create an opportunity to produce crystalline
coordination polymers of organic polymers, a new class of
materials, which were explored by us and others very recently.
Two sulfonate containing molecules were selected as linkers,
namely, isoquinoline-5-sulfonic acid (IQSA) and naphthalene
disulfonic acid (NDSA). To date, only four complexes of Ag(I)
with naphthalene disulfonate (NDS) and pyridine containing
ligands have been reported; among these only two have Ag···Ag
interactions12a,b supported by sulfonates,12 whereas no Ag(I)
complex containing isoquinoline-5-sulfonate (IQS) has been
reported to date.
In this paper, we describe our studies on the synthesis, crystal
structures, and interesting photoluminscent properties of five
new Ag(I) CPs of L1, L2, and L3 with NDS and IQS as linkers.
In some of these CPs, as anticipated the Ag···Ag interactions
were indeed templated by sulfonates, which are further linked
to form 2D networks. More importantly, the CPs with short
Ag···Ag contacts display significant differences in photo-
luminescence properties with respect to the CPs without
such argentophillic interactions.
obtained for CPs of 1−5. In the case of NDS as a linker,
single crystals were obtained for all three ligands, whereas in the
case of IQS, single crystals were obtained only with L2 and L3.
The crystal structure analysis reveals that four of the five
complexes (2−5) exhibit triclinic, P1 space group, and one
̅
complex exhibits monoclinic, C2/c space group. The crystal
structures of complexes 1−3 were found to have Ag···Ag
interactions templated by sulfonate ions, while 4 and 5 does not
exhibit such interactions. The overall network geometries were
found to be different in all the structures, although they have
similarities in terms of coordination geometry around Ag(I)
and ligand coordination to Ag(I). For example, all the
complexes contain one-dimensional -ML- chains via coordina-
tion of ligand to Ag(I) ions in near linear geometry. The
pertinent crystallographic information for all the complexes 1−
5 is given in Table 1.
{[Ag2(L1)2(NDS)]·3H2O}n, 1
{[Ag2(L2)2(NDS)]·2H2O}n, 2
{[Ag3(L2)2(IQS)2]·(NO3)·4H2O·2MeOH}n, 3
{[Ag2(L3)2(NDS)]·4H2O}n, 4
{[Ag2(L3)2(IQS)]·(NO3)·H2O}n, 5
Ag···Ag Interactions As Building Blocks for 1D → 2D
and 2D → 3D CPs. The complex 1 crystallized in the C2/c
space group, and the asymmetric unit is constituted by one unit
each of Ag(I) and L1, half of NDS and 11/2 units of
noncoordinated water molecules. The Ag(I) exhibits distorted
T-shape geometry with the coordination of two L1 units and
one anion. With respect to the coordination of the ligand, it
forms 1D zigzag -ML- chains (N−Ag−N: 142.32(12)°) which
are further interconnected to three-dimensional network via
NDS and Ag···Ag (3.1086(7) Å) interactions. The ligands and
anions separate the Ag(I) ions by 15.629 and 11.687 Å,
respectively. The interconnection of -ML- chains by NDS leads
to 2D layers containing herringbone geometry with (6,3)
topology (Figure 1a,b)14 in which each cyclic unit is generated
by Ag6(L1)4(NDS)2. Two of these networks interpenetrate in
parallel mode which are further interconnected with such
neighbors to form a three-dimensional network via Ag···Ag
interactions (Figure 1c). Only one of the O atoms of the
sulfonate ion was found to bridge via argentophillic interaction,
one of the Ag(I) bonds strongly (Ag−O: 2.363(3) Å), while
with the other form weak interactions (3.872(3) Å).
Interestingly, within the 3D network the naphthyl unit is
RESULTS AND DISCUSSION
■
The ligands L1, L2, and L3 were synthesized by following
previously reported procedures by us.13 The complexation
reactions were carried out by mixing the DMF and MeOH
solution of ligand with an aqueous solution of corresponding
sodium salt of sulfonic acid. The addition of MeOH solution of
AgNO3 to the above mixture resulted in the precipitates which
were dissolved by the addition of concentrated aq. NH3
solution, and the resultant clear solution was kept undisturbed
for crystallization. By following this procedure, single crystals
suitable for single crystal X-ray diffraction analyses were
5165
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
Figure 2. Illustrations for the crystal structure of 2: (a) ladderlike
network generated via linking 1D zigzag -ML- chains by NDS, (b)
argentophilic interaction templated by sulfonates of NDS, (c) 2D
layers generated by the interconnection of ladders via Ag···Ag
interactions.
sulfonate ions for three-dimensional packing. Further, the layers
also linked via other C−H···O hydrogen bonds between CO,
sulfonate and aromatic C−H groups.
In a similar fashion, the ligands L1 and L2 are reacted with
Ag(I) by considering IQS as an anionic linker in the place of
NDS. However, single crystals suitable for X-ray diffraction
studies were obtained only in the case of L2 in the form of
complex 3. In this structure, the asymmetric unit was found to
be constituted by two Ag(I) ions one with full occupancy and
the other with half occupancy, one each of L2, IQS, and MeOH
and two water molecules. Interestingly, two of the IQS moieties
are inter connected by Ag(I) ion (Ag1, sits on inversion center
and exhibits linear coordination geometry) to form a
disulfonate like linker. The second Ag(I) ion (Ag2), similar
to complexes 1 and 2, exhibits a distorted T-shape geometry
and coordinates to two L2 units and O atom of IQS (N−Ag−
N: 163.0(3)° and N−Ag−O: 107.7(3)° and 88.9(19)°). Similar
to complex 2, linking of 1D chains of -ML- by Ag(IQS)2 leads
to formation of a ladderlike structure (Figure 3a) with Ag···Ag
separation of 17.3 Å between the chains, which is much higher
than that of complex 2 (13 Å). These ladders are further
interconnected to 2D layer via Ag···Ag (3.135(1) Å)
interactions that are supported by sulfonate ions (Ag−O:
2.571(6) Å; Ag···O: 3.390(6) Å) (Figure 3b). The layers are
highly corrugated and pack via Ag···π-naphthyl (Ag···C:
3.287(8) Å) and other weak interactions (Figure 3c). Two of
the water molecules form dimer (O···O: 2.810(3)), which are
further hydrogen bonded to the sulfonate O atom (O···O:
2.781(16)).
NDS and NO3 Ions As Linkers of -ML- Chains To Form
1D → 2D and 1D → Ladder CPs. The reaction of L3, which
contains 4-pyridyl substitution, and Ag(I) with both the
sulfonate linkers NDS and IQS resulted in the single crystals
of complexes 4 and 5 respectively. Unlike the complexes of 1−
3, 4 and 5 do not exhibit Ag···Ag interactions. The asymmetric
unit of complex 4 contains one unit of L3, half unit of NDS, two
half units of Ag(I) ion, and two water molecules. Both the
Ag(I) ions coordinate to two units of L3 (N−Ag−N: 180°) to
generate a wavy 1D chain. In addition, the 1D chains are
interconnected through the bridging of one of the Ag(I) ion by
Figure 1. Illustrations for the crystal structure of 1: (a) Doubly
interpenetrated herringbone layers with (6,3) topology generated via
connecting 1D (-ML-) chains via NDS; depiction of (b) 2D layers and
(c) 3D-network, via Ag···Ag interactions, by reducing ligands to node
connections and metals to nodes. The boxed part in (c) is nothing but
the side view of the doubly interpenetrated layers.
sandwiched by aliphatic CH2 groups of L1, and the pyridyl
groups interact with each other via π···π interactions and with
Ag(I) ions via Ag···π interactions. Further, the water molecules
form a hydrogen bonded trimer with an O···O···O angle of
120.2(4)° and O···O distance of 2.945(7) Å, the terminal water
molecules further bonded to sulfonates (O···O 2.850(6) Å) and
CO of L1 (O···O 2.943(6) Å).
In 2, the asymmetric unit is constituted by one each of L2,
Ag(I) and uncoordinated water and NDS with half occupancy.
The Ag(I) ion exhibits distorted T-shape geometry with N−
Ag−N of 162.32(12)° and N−Ag−O of 85.89(12)° and
110.21(12)°. The zigzag -ML- 1D chains are interconnected to
the ladder network by NDS (Figure 2a), unlike in 1 that forms
herringbone layer. Such ladders are interconnected to form
corrugated 2D layers via Ag···Ag (3.0759(9) Å) interactions
(Figure 2b) which are found to be bridged by sulfonate ion
(Figure 2c), one of O atom coordinates to Ag(I) strongly (Ag−
O 2.655(3) Å) as the other forms weak interaction (Ag···O
3.065(3) Å). The water molecules lie in between the 2D layers
and form −C-H···Ow (C···O, C−H···O: 3.310(5) Å, 150.37°)
with Sp2 C−H of L2 and Ow-H···O (O···O: 2.804(5) Å) with
5166
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
Figure 4. Illustrations for the crystal structure of 4: (a) (4,4) layer of
rectangular grids generated via linking 1D (-ML-) wavy chains by
NDS, note that the sulfonates are very weakly coordinated (Ag···O:
2.954 Å); depiction of packing of the layers (shown with different
colors): (b) top view (ab plane); side views; (c) along the a-axis, (d)
along the b-axis. Notice the interdigitation of the layers.
Figure 3. Illustrations for the crystal structure of 3: (a) ladderlike
structures generated via linking 1D (-ML-) chains by Ag(IQS)2, (b)
extended 2D layer generated via argentophilic interaction, (c) Ag···π
interaction between adjacent 2D layers.
NDS (Ag···O: 2.883(7) Å) to form a (4,4)-layer containing
rectangular grids (Figure 4a), while the second Ag(I) weakly
bonds to two H2O molecules (Ag···OH2: 2.992(8) Å). In effect,
both silver ions exhibit a square planar coordination geometry.
The corrugated layers pack on each other along the c-axis with
shortest interlayer separation 4.15 Å due to the interdigitation
(Figure 4b,c). Notably, among other weak interactions Ag···
OC (3.897 Å) interactions found to contribute for packing of
the layers.15 The water molecules also form a hydrogen-bonded
dimer (O···O: 2.829(13) Å), which further linked NDS ions via
O−H···O hydrogen bonds (O···O: 2.743(10) and 2.823(11)
Å).
excitation wavelength of 325 nm. All three ligands L1, L2, and
L3 were found to exhibit almost the same broad bands between
560 and 585 nm (Figure 6a) with λmax values of 579, 560, and
587 nm, respectively. Interestingly, as depicted in Figure 6b,
solids of 1−5 also exhibit photoluminescence with emission
maxima at 561, 571, 580, 548, and 554 nm, respectively.
Compared to the λmax values of their respective ligands, the
complexes 1, 4, and 5 are blue-shifted, while those 2 and 3
exhibit a red shift. These results indicate that the emissions of
all complexes mainly originate from ligand-based luminescence,
corresponding shifts originate from ligand-to-metal charge
transfer (LMCT) transition, and the presence of ligand
supported short Ag···Ag and Ag···π interactions. We note
here that recently a similar observation was made for
cuprophillic interactions in the CPs of Cu(I) complexes.18
CSD Analysis on the Propensity of Ag···Ag Inter-
actions for 3-Pyridyl and 4-Pyridyl-Containing Com-
plexes. From the above observations, it is clear that 3-pyridyl
containing ligands have a higher tendency to form Ag···Ag
interactions that are supported by sulfonates. The Cambridge
Structural Database (CSD)19 analysis was carried out to
examine this observation further. It reveals that in general the
4-pyridyl and 3-pyridyl containing Ag(I) complex have almost
same propensity to form Ag···Ag interactions. In particular, 252
out of 1056 Ag(I) complexes (24%) containing 4-pyridyl were
found to exhibit such interactions,20 whereas in the case of 3-
pyridyl, 140 out of 540 complexes (26%) were found to exhibit
such interactions. When only organic sulfonate containing
In the case of 5, the asymmetric unit contains two each of
−
Ag(I) and L3 and one each of IQS, NO3 ion, and one
noncoordinated water molecule. Both the Ag(I) ions
coordinate to two L3 units to form wavy -ML- chains which
are interconnected further by μ2 bridging of nitrate ion (Ag···O:
2.918 and 3.123 Å) such that there is a formation of twisted
double chain (Figure 5a).16 Interestingly, the IQS unit does not
involve in the bridging; however it was found to bind weakly to
one of the Ag(I) atom (Ag···O: 2.897 Å). The interdigitation of
these twisted 1D chains via plethora of weak interactions
generates the 3D packing (Figure 5b,c).
Photoluminescence of L1, L2 L3, and Complexes 1−5.
Luminescent CPs are of great interest due to their diverse
applications in chemical sensors, electroluminescent displays,
and photochemistry.17 Therefore, the photoluminescence
properties of the crystalline solids of 1−5 and the free ligands
(L1, L2, L3) were investigated at room temperature using an
5167
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
containing ligands have more of a tendency to form Ag···Ag
interactions than the 4-pyridyl containing ligands in the
presence of organic sulfonates. We note here that all the five
complexes contain water molecules, and they were found to
prefer to form hydrogen bonds over coordination to Ag(I).
Moreover, all of these complexes exhibit solid-state photo-
luminescence in the green region at room temperature, which
suggests that they may be good candidates for optical materials.
EXPERIMENTAL SECTION
■
FTIR spectra were recorded with a PerkinElmer instrument, Spectrum
Rx, serial no. 73713. 1H NMR (200 MHz) spectra were recorded on a
BRUKER-AC 200 MHz spectrometer. Powder XRD data were
recorded with a PHILIPS Holland PW-171 defractometer. The diffuse
reflectance spectra (DRS) of the inclusion crystals were recorded with
a Cary model 5000 UV−visible-NIR spectrophotometer. Elemental
analyses were carried out with a PerkinElmer Series II 2400, and
melting points were taken using a Fisher Scientific melting point
apparatus cat. No. 12-144-1.
Synthesis of 2,6-Di(3-pyridylmethylidene)cyclohexanone L1.
A mixture of 3-pyridinecarbaldehyde (1.071 g, 0.01 mol) and
cyclohexanone (0.0981 g, 0.005 mol) in 20 mL of water was stirred
and cooled to 5 °C, 1 mL of 20% sodium hydroxide solution was
added, and vigorous stirring was continued for 5 h at 25 °C. The
solution was neutralized with diluted hydrochloric acid, and the yellow
colored solid was collected by filtration. Recrystallization from ethanol
gave 2.10 g (72.0%) yellow crystals. mp = 139 °C. IR (cm−1): 1670
Figure 5. Illustrations for the crystal structure of 5: (a) wavy (-ML-)
chains interconnected via μ-2 bridging by NO3 ions, (b)
interdigitation between three adjacent twisted double chains via
Ag···OC interaction, (c) side view of interdigitated twisted double
chains.
−
1
(CC) 1610 (CO), H NMR (CDCl3, δ, ppm): 1.83 (2H, m, 4
−CH2), 2.92 (4H, m, 3- and 5-CH2), 7.33 (2H, dd, 5′-Py), 7.74 (4H,
m, 4′-H Py and −CH), 8.55 (2H, d, and 6′-H Py), 8.70 (2H, s, 2′-H
Py).
Synthesis of 2,6-Di(3-pyridylmethylidene)cyclopentanone
L2. L2 was prepared using a similar procedure as described for L1
except that cyclopentanone (0.0981 g, 0.005 mol) was used instead of
cyclohexanone. mp = 216 °C.IR (cm−1): 1670 (CC) 1610 (CO),
1H NMR (CDCl3, δ, ppm): 3.16 (4H, s, -CH2), 7.33 (2H, dd,), 7.57
(2H, s, CH), 7.87 (4H, d), 8.59 (2H, d,), 8.85 (2H, s br).
Synthesis of 2,6-di(4-Pyridylmethylidene)cyclopentanone
L3. L3 was prepared in a similar procedure as described for L1 except
that cyclopentanone (0.0981 g, 0.005 mol) was taken instead of
cyclohexanone and 4-pyridinecarbaldehyde (1.071 g, 0.01 mol) was
taken instead of 3-pyridinecarbaldehyde. mp = 239 °C.IR (cm−1):
1
1670 (CC) 1630 (CO), H NMR (CDCl3, δ, ppm): 3.16(4H, s,
-CH2), 7.42 (4H, d,), 7.49 (2H, s, CH), 8.70 (4H, d).
Figure 6. Solid-state photoluminescence (PL) spectra of (a) for
ligands L1−L3 and (b) complexes 1−5.
Synthesis of Coordination Polymers of 1−5. Preparation of 1.
A 2 mL aqueous solution of Na2NDSA (0.017 g, 0.05 mmol) was
added to a hot 5 mL MeOH and DMF (1:1 v/v) solution of L1 (0.013
g, 0.05 mmol). To this solution, the addition of 3 mL MeOH solution
of AgNO3 (0.0169 g, 0.1 mmol) resulted in a yellow-colored
precipitate, which was dissolved by the gradual addition of conc.
aqueous NH3 solution. Deep yellow-colored crystals were obtained
after 2 days and dried in the air to give 0.012 g of 1. Yield: 64.23%
based on L1, Elemental analysis: (%) Calc. for C44H34Ag2N4O11S2: C,
49.20; H, 3.20; N, 5.20. Found C,48.69; H,3.15; N,5.02. IR (cm−1):
3569.24(s), 3447.94(s), 1684.08(s), 1654.11(s), 1627.83(s),
1601.70(s), 1584.60(s), 1562.34(s), 1499.91(s), 1477.21(s),
1449.75(s), 1413.90(s), 1333.73(s), 1293.91(s), 1265.84(s),
1239.19(s), 1205.66(s), 1161.72(s), 1044.54(s), 988.83(s),
954.15(s), 785.93(s), 769.40(s), 690.29(m), 614.63(s), 572.64(s),
530.14(s), 467.77(m).
Preparation of 2. The compound of 2 was prepared in a similar
procedure as described for 1 except L2 was taken in the place of only
L1. The dark yellow crystals were obtained and dried in the air to give
0.0098 g. Yield: 55.65% based on L2, Elemental analysis: (%) Calc. for
C23H19AgN2O5S: C, 50.80; H, 3.50; N, 5.20. Found C, 50.69; H,3.45;
N,5.12. IR (cm−1):. 3568.64(s), 3449.20(m), 1607.90(s), 1581.86(s),
1474.53(s), 1276.98(s), 1205.90(s), 1164.35(s), 1143.13(s),
1045.47(s), 1022.06(s), 785.96(s), 769.70(s), 709.15(s), 615.99(s),
540.31(s).
Ag(I) complexes were considered, it was found that the
propensities for the formation of Ag···Ag interactions are 40%
and 23% for complexes containing 3-pyridyl (32 out of 88) and
4-pyridyl (34 out of 150) respectively. These statistics clearly
support our observations.
CONCLUSIONS
■
Five examples for a new series of Ag(I) CPs were synthesized
and characterized using ligands such as L1, L2, and L3 and
aromatic sulfonate linkers such as NDS and IQS. In the case of
1, 2, and 3, 1D wavy (-ML-) chains are linked via sulfonates to
form 1D → 2D and 1D chains → 1D-ladderlike networks,
which are further linked to 2D → 3D and ladder → 2D layers
via Ag···Ag interactions. In all three complexes, the
argentophillic interactions were found to be supported by
sulfonate ions, whereas complexes 4 and 5 do not contain such
Ag···Ag interactions, and only in 4 NDS weakly coordinates
with Ag(I) to form a 2D-layer containing rectangular grids. In
5, NO3 ion bridges 1D chains to a ladderlike network. Further,
our studies and CSD analysis reveal that the 3-pyridyl
5168
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
Preparation of 3. It was prepared in a similar procedure as
described for 1 except instead of Na2NDSA, isoquinoline-5-sulfonic
acid (0.0105 g, 0.05 mmol) was taken. The pale yellow-colored crystals
were obtained and dried in the air to give 0.011 g. Yield: 60.23% based
on L1, Elemental analysis: (%) Calc. for C56H46Ag3N6O14S2: C, 47.50;
H, 3.30; N, 5.90. Found C, 47.39; H, 3.05; N, 5.82. IR (cm−1):
3568.73(s), 3448.59(m), 2943.00(s), 1611.67(s), 1592.52(s),
1578.06(s), 1413.70(s), 1324.32(s), 1276.23(s), 1205.79(s),
1171.38(s), 1146.12(s), 1044.20(s), 995.11(s), 971.95(s), 939.90(s),
816.82(s), 785.90(s), 769.45(s), 614.91(s), 573.00(m), 536.17(s).
Preparation of 4. The complex 4 was prepared in a similar
procedure as described for 1 except instead of L1, L3 (0.013 g, 0.05
mmol) was taken. The deep yellow-colored crystals were obtained and
dried in the air to give 0.0105 g. Yield: 62.12% based on L3, Elemental
analysis: (%) Calc. for C22H17AgN2O6S: C, 48.50; H, 3.10; N, 5.10.
Found C,48.39; H,3.02; N,5.01. IR (cm−1): 3569.08(s), 3448.78(m),
1696.11(s), 1630.93(s), 1608.75(s), 1595.48(s), 1418.12(s),
1327.24(s), 1291.32(s), 1205.87(s), 1174.37(s), 1161.83(s),
1044.22(s), 999.48(s), 927.23(s), 813.08(s), 785.95(s), 769.29(s),
614.22(s), 572.49(s), 532.55(s), 523.23(m).
Preparation of 5. The compound of 5 was prepared in a similar
procedure as described for 3 except L3 (0.013 g, 0.05 mmol) was used
in place of only L1. Pale yellow-colored crystals were obtained and
dried in the air to give 0.011 g. Yield: 63.75% based on L3, calc. for
C34H28Ag2N6O9S: C, 41.00; H, 2.80; N, 8.40. Found C, 40.29; H, 2.22;
N, 7.51. IR (cm−1): 3421.31(s), 2367.99(m), 2341.56(s), 1696.16(s),
1607.70(s), 1595.86(s), 1418.48(s), 1348.28(s), 1326.72(s),
1291.39(s), 1251.51(s), 1218.52(s), 1170.08(s), 1075.73(s),
1055.23(s), 999.59(s), 983.31(s), 927.49(s), 839.53(s), 813.98(s),
749.16(s), 708.84(s), 629.90(s), 574.56(s), 533.74(s), 523.23(s).
Crystal Structure Determination. All the single crystal data were
collected on a Bruker-APEX-II CCD X-ray diffractometer that uses
graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at room
temperature (293 K) by the hemisphere method. The structures were
solved by direct methods and refined by least-squares methods on F2
using SHELX-97.21 Non-hydrogen atoms were refined anisotropically,
and hydrogen atoms were fixed at calculated positions and refined
using a riding model. The H atoms attached to the O atom or N atoms
are located wherever possible and refined using the riding model. The
nitrate ion in 3 could not be located. In the case of 5, IQS was found
to be highly disordered, and NO3 and H2O were found to have high
thermal motions. Therefore, they were removed in the final refinement
and Platon squeeze option was used.22
O. M.; Li, H. J. Am. Chem. Soc. 1995, 117, 10401−10402. (d) Fujita,
M.; Ogura, D.; Miyazawa, M.; Oka, H.; Yamaguchi, K.; Ogura, K.
Nature 1995, 378, 469−471. (e) Power, K. N.; Hennigar, T. L.;
Zaworotko, M. J. Chem. Commun. 1998, 595−596. (f) Losier, P.;
Zaworotko, M. J. Angew. Chem., Int. Ed. 1996, 35, 2779−2782.
(2) (a) Sharma, C. V. K.; Broker, G. A.; Huddleston, J. G.; Baldwin, J.
W.; Metzger, R. M.; Rogers, R. D. J. Am. Chem. Soc. 1999, 121, 1137−
1144. (b) Heintz, R. A.; Zhao, H.; Ouyang, X.; Grandinetti, G.;
Cowen, J.; Dunbar, K. R. Inorg. Chem. 1999, 38, 144−156. (c) Mayr,
A.; Guo, J. Inorg. Chem. 1999, 38, 921−928.
(3) (a) Ye, Q.; Wang, X. S.; Zhao, H.; Xiong, R. G. Chem. Soc. Rev.
2005, 34, 208−225. (b) Fang, Q. R.; Zhu, G. S.; Xue, M.; Zhang, Q.
L.; Sun, J. Y.; Guo, X. D.; Qiu, S. L.; Xu, S. T.; Wang, P.; Wang, D. J.;
Wei, Y. Chem.Eur. J. 2006, 12, 3754−3758. (c) Luo, T. T.; Tsai, H.
L.; Yang, S. L.; Liu, Y. H.; Yadav, R. D.; Su, C. C.; Ueng, C. H.; Lin, L.
G.; Lu, K. L. Angew. Chem., Int. Ed. 2005, 44, 6063−6067. (d) Biradha,
K.; Sarkar, M.; Rajput, L. Chem. Commun. 2006, 4169−4179.
(4) (a) Zhang, X. M.; Hao, Z. M.; Zhang, W. X.; Chen, X. M. Angew.
Chem., Int. Ed. 2007, 46, 3456−3459. (b) Horike, S.; Dinca,
Tamaki, K.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 5854−5855.
(5) (a) Kato, R.; Kobayashi, H.; Kobayashi, A. J. Am. Chem. Soc.
̆
M.;
1989, 111, 5224−5232. (b) Sinzger, K.; Hunig, S.; Jopp, M.; Bauer, D.;
̈
Bietsch, W.; von Schutz, J. U.; Wolf, H. C.; Kremer, R. K.; Metzenthin,
̈
T.; Bau, R.; Khan, S. I.; Lindaum, A.; Lengauer, C. L.; Tillmanns, E. J.
Am. Chem. Soc. 1993, 115, 7696−7705. (c) Dybtsev, D. N.; Chun, H.;
Yoon, S. H.; Kim, D.; Kim, K. J. Am. Chem. Soc. 2004, 126, 32−33.
(6) (a) Zheng, S. L.; Zhang, J. P.; Wong, W. T.; Chen, X. M. J. Am.
Chem. Soc. 2003, 125, 6882−6883. (b) Seward, C.; Jia, W. L.; Wang, R.
Y.; Enright, G. D.; Wang, S. Angew. Chem., Int. Ed. 2004, 43, 2933−
2936. (c) Dong, Y. B.; Jin, G. X.; Smith, M. D.; Huang, R. Q.; Tang,
B.; Loye, H. C. zur Inorg. Chem. 2002, 41, 4909−4914.
(7) (a) Busse, M.; Andrews, P. C.; Junk, P. C. Eur. J. Inorg. Chem.
2012, 1061−1071. (b) Li, F. F.; Ma, J. F.; Song, S. Y.; Yang, J. Cryst.
Growth Des. 2006, 6, 209−215. (c) Li, F. F.; Ma, J. F.; Song, S. Y.;
Yang, J.; Liu, Y. Y.; Su, Z. M. Inorg. Chem. 2005, 44, 9374−9383.
(d) Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem. Soc. Rev.
2009, 38, 1430−1449. (e) Hoffart, D. J.; Dalrymple, S. A.; Shimizu, G.
K. H. Inorg. Chem. 2005, 44, 8868−8875. (f) Cote, A. P.; Shimizu, G.
̂ ́
K. H. Inorg. Chem. 2004, 43, 6663−6673. (g) Hoffart, D.; Dalrymple,
S. A.; Shimizu, G. K. H. Inorg. Chem. 2005, 44, 8868−8875.
(8) (a) Phillips, V.; Willard, K. J.; Golen, J. A.; Moore, C. J.;
Rheingold, A. L.; Doerrer, L. H. Inorg. Chem. 2010, 49, 9265−9274.
(b) Chen, W.; Liu, F.; Xu, D.; Matsumoto, K.; Kishi, S.; Kato, M. Inorg.
Chem. 2006, 45, 5552−5560. (c) Ray, L.; Shaikh, M. M.; Ghosh, P.
ASSOCIATED CONTENT
* Supporting Information
■
Inorg. Chem. 2008, 47, 230−240. (d) Kriechbaum, M.; Holbling, J.;
̈
S
Stammler, H. G.; List, M.; Berger, R. J. F.; Monkowius, U.
1H NMR spectra for L1, L2, and L3, IR spectra of the complexes
1−5, TGA thermograms for the complexes 1−5, calculated and
experimental PXRD patterns for the complexes 1−5, DRS for
the complexes 1−5. This material is available free of charge via
the Internet at http://pubs.acs.org.
Organometallics 2013, 32, 2876−2884. (e) Pyykko, P.; Mendizabal,
̈
F. Inorg. Chem. 1998, 37, 3018−3025. (f) Mukherjee, G.; Biradha, K.
Cryst. Growth Des. 2013, 13, 4100−4109.
(9) (a) Rana, A.; Jana, S. K.; Pal, T.; Puschmann, H.; Zangrando, E.;
Dalai, S. J.Solid. State. Chem. 2014, 216, 49−55. (b) Xi, L.; Guo, G. C.;
Fu, M. L.; Liu, X. H.; Wang, M. S.; Huang, J. S. Inorg. Chem. 2006, 45,
3979−3985.
AUTHOR INFORMATION
Corresponding Author
*Fax: +91-3222-282252. Tel: +91-3222-283346. E-mail:
kbiradha@chem.iitkgp.ernet.in.
■
(10) (a) Hamel, A.; Mitzel, N. W.; Schmidbaur, H. J. Am. Chem. Soc.
2001, 123, 5106−5107. (b) Katz, M. J.; Sakai, K.; Leznoff, D. B. Chem.
Soc. Rev. 2008, 37, 1884−1895. (c) Zhou, Y. B.; Chen, W. Z.; Wang,
D. Q. Dalton Trans. 2008, 1444−1453. (d) Catalano, V. J.; Malwitz,
M. A. Inorg. Chem. 2003, 42, 5483−5485.
Notes
(11) (a) Santra, R.; Garai, M.; Mondal, D.; Biradha, K. Chem.Eur. J.
2013, 19, 489−493. (b) Sonoda, Y. Molecules 2011, 16, 119−148.
(c) Kole, G. K.; Tan, G. K.; Vittal, J. J. Org. Lett. 2010, 12, 128−131.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
̀
(d) Frontera, A.; Quinonero, D.; Costa, A.; Ballester, P.; Deya, P. M.
̃
We gratefully acknowledge the DST for the financial support
and DST-FIST for the single-crystal X-ray facility. K.B. thanks
CSIR for a research fellowship.
New J. Chem. 2007, 31, 556−560. (e) Singh, A. S.; Sun, S. S.
Chem.Commun. 2013, 49, 10070−10072. (f) Kim, E.; Lee, H.; Noh, T.
H.; Jung, O. S. Cryst. Growth Des. 2014, 14, 1888−1894. (g) Katagiri,
K.; Ikeda, T.; Tominaga, M.; Masu, H.; Azumaya, I. Cryst. Growth Des.
2010, 10, 2291−2297. (h) Han, L. L.; Zhang, X. Y.; Chen, J. S.; Li, Z.
H.; Sun, D. F.; Wang, X. P.; Sun, D. Cryst. Growth Des. 2014, 14,
2230−2239. (i) Santra, R.; Banerjee, K.; Biradha, K. Chem. Commun.
REFERENCES
■
(1) (a) Zaworotko, M. J.; Moulton, B. Chem. Rev. 2001, 101, 2619.
(b) Yaghi, O. M.; Li, G.; Li, H. Nature 1995, 378, 703−706. (c) Yaghi,
5169
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170

Crystal Growth & Design
Article
2011, 47, 10740−10742. (j) Santra, R.; Ghosh, N.; Biradha, K. New J.
Chem. 2008, 32, 1673−1676.
(12) (a) Chen, C. H.; Cai, J.; Feng, X. L.; Chen, X. M. Polyhedron
2002, 21, 689−695. (b) Wu, D. L.; Liu, L.; Luo, G. G. Acta Crystallogr.
Sect. C: Cryst. Struct. Commun. 2011, 67, m311. (c) Fang, X. Q.; Deng,
Z. P.; Huo, L. H.; Wan, W.; Zhu, Z. B.; Zhao, H.; Gao, S. Inorg. Chem.
2011, 50, 12562−12574. (d) Deng, Z. P.; Huo, L. H.; Li, M. S.; Zhang,
L. W.; Zhu, Z. B.; Zhao, H.; Gao, S. Cryst. Growth Des. 2011, 11,
3090−3100. (e) Awaleh, M. O.; Badia, A.; Brisse, F. Cryst. Growth Des.
2006, 6, 2674−2685. (f) Lian, Z. X.; Cai, J.; Chen, C. H.; Luo, H. B.
CrystEngComm 2007, 9, 319−327.
(13) Vatsadze, S. Z.; Manaenkova, M. A.; Sviridenkova, N. V.; Zyk,
N. V.; Krut’ko, D. P.; Churakov, A. V.; Antipin, M. Yu.; Howard, J.;
Lang, H. Russ. Chem. B 2006, 55, 1184−1194.
(14) (a) Banfi, S.; Carlucci, L.; Caruso, E.; Ciani, G.; Proserpio, D. M.
Cryst. Growth Des. 2004, 4, 29−32. (b) Go, Y. B.; Wang, X.; Jacobson,
A. J. Inorg. Chem. 2007, 46, 6594−6600. (c) Gotthardt, J. M.; White,
K. F.; Abrahams, B. F.; Ritchie, C.; Boskovic, C. Cryst. Growth Des.
2012, 12, 4425−4430. (d) Ni, J.; Wei, K. J.; Liu, Y.; Huang, X. C.; Li,
D. Cryst. Growth Des. 2010, 10, 3964−3976. (e) Stork, J. R.; Thoi, V.
S.; Cohen, S. M. Inorg. Chem. 2007, 46, 11213−11223.
(15) (a) Nasser, N.; Puddephatt, R. J. Cryst. Growth Des. 2012, 12,
4275−4282. (b) Zeng, J. P.; Zhang, S. M.; Zhang, Y. Q.; Tao, Z.; Zhu,
Q. J.; Xue, S. F.; Wei, G. Cryst. Growth Des. 2010, 10, 3964−3976.
(16) (a) Santra, R.; Biradha, K. Cryst. Growth Des. 2010, 10, 3315−
3320. (b) Zhang, G.; Yang, G.; Chen, Q.; Ma, J. S. Cryst. Growth Des.
2005, 5, 661−666. (c) Hu, B.; Tao, T.; Bin, Z. Y.; Peng, Y. X.; Ma, B.
B.; Huang, W. Cryst. Growth Des. 2014, 14, 300−309. (d) Huang, Z.;
Du, M.; Song, H. B.; Bu, X. H. Cryst. Growth Des. 2004, 4, 71−78.
(e) Zhang, Q. L.; Zhu, B. X.; Zhang, Y. Q.; Tao, Z.; Clegg, J. K.;
Lindoy, L. F.; Wei, G. Cryst. Growth Des. 2011, 11, 5688−5695.
(f) Cheng, P. S.; Marivel, S.; Zang, S. Q.; Gao, G. G.; Mak, T. C. W.
Cryst. Growth Des. 2012, 12, 4519−4529.
(17) (a) Yam, V. W. W.; Lo, K. K. W. Chem. Soc. Rev. 1999, 28, 323−
334. (b) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T.
Chem. Soc. Rev. 2009, 38, 1330−1352. (c) Wu, C. D.; Ngo, H. L.; Lin,
W. Chem. Commun. 2004, 1588−1589. (d) Chan, S. C.; Chan, M. C.
W.; Wang, Y.; Che, C. M.; Cheung, K. K.; Zhu, N. Chem.Eur. J.
2001, 7, 4180−4190. (e) Che, C. M.; Tse, M. C.; Chan, M. C. W.;
Cheung, K. K.; Phillips, D. L.; Leung, K. H. J. Am. Chem. Soc. 2000,
122, 2464−2468.
(18) (a) Mukherjee, G.; Biradha, K. CrystEngComm 2014, 16, 4701−
05. (b) Zhang, Y.; Wu, T.; Liu, R.; Dou, T.; Bu, X.; Feng, P. Cryst.
Growth Des. 2010, 10, 4519−4529. (c) Hou, L.; Shi, W. J.; Wang, Y.
Y.; Wang, H. H.; Cui, L.; Chen, P. X.; Shi, Q. Z. Inorg. Chem. 2011, 50,
261−270. (d) Wu, T.; Li, M.; Li, D.; Huang, X. C. Cryst. Growth Des.
2008, 8, 568−574. (e) Knorr, M.; Guyon, F.; Khatyr, A.; Strohmann,
C.; Allain, M.; Aly, S. M.; Lapprand, A.; Fortin, D.; Harvey, P. D. Inorg.
Chem. 2012, 51, 9917−9934.
(19) Allen, F. H. Acta Crystallogr. 2002, B58, 380−388.
(20) The Ag···Ag contact was considered only when the distance
between the two Ag(I) atoms is within the sum of van der Waals radii
+ 0.2 Å.
(21) Sheldrick, G. M. SHELX-97, Program for the Solution and
Refinement of Crystal Structures; University of Gottingen: Germany,
̈
1997.
(22) Spek, A. L. PLATON A Multi Purpose Crystallographic Tool;
Utrecht University: Utrecht, The Netherlands, 2002.
5170
dx.doi.org/10.1021/cg500898c | Cryst. Growth Des. 2014, 14, 5164−5170