Solvation effect on the construction of coordination polymers containing a flexible four-pyridyl ligand. Synthesis and crystal structures of silver(I) complexes

Article abstract of DOI:10.1016/j.molstruc.2011.04.031

Construction of AgX (X^- = ClO4- and BF4-) with highly flexible N,N,N′,N′-tetrakis(ethylisonicotinoyl)ethylendiamine (L) has been scrutinized for the weak argentophilic, Ag anion, and Ag·solvent interactions. All such complexes afford coordination polymers consisting of 2:1 (Ag(I):L). [Ag₂(L)(CH₃CN)₂](X)₂ (X^- = ClO4- and BF4-) and [Ag₂(L)(H₂O)](BF ₄)₂ are double-stranded 1D, whereas [Ag ₂(ClO₄)₂(L)(Me₂CO)₂] yields a 2D network structure. The molecular construction has been affected by anions, solvents, and the crystallization method. The natures of anion- and solvent-coordination, including the argentophilic interaction play important roles in the formation of skeletal structures. For [Ag₂(L)(CH ₃CN)₂](ClO₄)₂, weakly coordinated solvate acetonitrile reversibly associates and dissociates in the solid state.

Full text of DOI:10.1016/j.molstruc.2011.04.031

Journal of Molecular Structure 996 (2011) 115–119
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Solvation effect on the construction of coordination polymers containing a
flexible four-pyridyl ligand. Synthesis and crystal structures of silver(I) complexes
Sojung Lee a, Kyung Hwan Park a, Jungmin Ahn a, Young-A Lee b, Ok-Sang Jung a,
⇑
a Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Pusan 609-735, Republic of Korea
b Department of Chemistry, Chonbuk National University, Jeonju 561-756, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Construction of AgX (Xꢀ = ClO4ꢀ and BF4ꢀ) with highly flexible N,N,N0,N0-tetrakis(ethylisonicotinoyl)ethyl-
endiamine (L) has been scrutinized for the weak argentophilic, Ag anion, and Agꢁsolvent interactions. All
such complexes afford coordination polymers consisting of 2:1 (Ag(I):L). [Ag2(L)(CH3CN)2](X)2 (Xꢀ = ClO4ꢀ
Article history:
Received 21 March 2011
Received in revised form 20 April 2011
Accepted 20 April 2011
and BFꢀ) and [Ag2(L)(H2O)](BF4)2 are double-stranded 1D, whereas [Ag2(ClO4)2(L)(Me2CO)2] yields a 2D
4
Available online 27 April 2011
network structure. The molecular construction has been affected by anions, solvents, and the crystalliza-
tion method. The natures of anion- and solvent-coordination, including the argentophilic interaction play
important roles in the formation of skeletal structures. For [Ag2(L)(CH3CN)2](ClO4)2, weakly coordinated
solvate acetonitrile reversibly associates and dissociates in the solid state.
Keywords:
Anion effects
Argentophilic interaction
Nitrogen multidentate
Silver(I) complexes
Solvent effects
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
AgX (Xꢀ = ClO4ꢀ and BFꢀ4 ) with new N,N,N0,N0-tetrakis(ethylisonicot-
inoyl)ethylendiamine (L) were carried out. To date, Ag(I) ion has
Molecular design and construction of metal coordination mate-
rials with specific motifs is a fruitful field, given coordination poly-
mers’ various potential applications such as molecular separation,
toxic materials adsorption, molecular containers, gas adsorption,
ion exchangers, molecular recognition, catalysts, and luminescent
sensors [1–9]. Thus, various kinds of coordination polymers, (coor-
dinations of metal ions with multidentate ligands) have been
constructed [10–19]. The geometry and flexibility of multidentate
N-donor ligands play key roles in the development of tailor-made
coordination polymers. In particular, rigid pyridyl ligands have
known to be very effective for the synthesis of desirable skeletal
coordination polymers [20–24]. These rigid organic ligands, in-
deed, have been applied for easy manipulation of the shape and
symmetry of coordination assemblies. The corresponding flexible
multipyridyl ligands, however, have not seen comparably exten-
sive research attention. Effective utilization of such ligands at var-
iable conformation levels is an exciting challenge, as they produce
plenty of coordination chemistries [25,26]. Flexible multipyridyl li-
gands offer additionally to nonrigid conformations, various bridg-
ing abilities, and intraligand angles. Construction of coordination
polymers containing flexible ligands is, accordingly, very sensitive
to various factors. In the present study, in order to scrutinize the
solvation and anion effects on the construction of coordination
polymers containing a flexible multipyridyl ligand, reactions of
been employed as various directional units in linear, T-shaped,
and tetrahedral geometries [27]. The main strategy employed in
the present study entailed both the use of flexible multidentate li-
gands and solvent-coordination ligands.
2. Experimental
2.1. Materials and measurements
AgX (Xꢀ = ClO4ꢀ and BFꢀ4 ), N,N,N0,N0-tetrakis(2-hydroxyethyl)eth-
ylendiamine, isonicotinoyl chloride hydrochloride, and triethyl-
amine were purchased from Aldrich, and used without further
purification. Elemental microanalyses (C, H, N) were performed
on crystalline samples by the Pusan Center, KBSI, using a Vario-
EL III. Thermal analyses were carried out under a dinitrogen atmo-
sphere at a scan rate of 10 °C/min using a Labsys TGA-DSC 1600.
Infrared spectra were obtained on a Nicolet 380 FTIR spectropho-
tometer with samples prepared as KBr pellets and Nujol mulls.
1H (300 MHz) and 13C (75 MHz) NMR spectra were recorded on a
Varian Mercury Plus 300.
2.2. Preparation of N,N,N0,N0-tetrakis(ethylisonicotinoyl)
ethylendiamine (L)
Triethylamine (6.97 mL, 50 mmol) in chloroform (50 mL) was
added to a mixture of N,N,N0,N0-tetrakis(2-hydroxylethyl)ethylen-
diamine (1.18 g, 5 mmol) and isonicotinoyl chloride (4.68 g,
⇑
Corresponding author. Tel.: +82 51 510 2591; fax: +82 51 516 7421.
E-mail address: oksjung@pusan.ac.kr (O.-S. Jung).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.04.031

116
S. Lee et al. / Journal of Molecular Structure 996 (2011) 115–119
25 mmol) in chloroform (100 mL). The reaction mixture was stir-
red and refluxed for 6 h, and then was cooled. Water (150 mL)
was added to the cooled solution. The chloroform layer was
washed successively with 0.5 N NaCl solution and cold water.
The chloroform solution was dried using MgSO4, and the solvent
was removed under a reduced pressure. Excess diethyl ether was
added into the chloroform solution, and left at 5 °C affording white
solids in a 90% yield. Anal. Calcd for C17H18N3O4: C, 62.19; H, 5.53;
N, 12.80. Found: C, 61.90; H, 5.45; N, 12.60. IR (KBr, cmꢀ1):
3032(w), 2962(w), 2827(m), 1728(s), 1294(s), 1142(s), 754(s),
700(s), 679(m). 1H NMR (CDCl3, SiMe4, d): 8.73 (d, J = 4.8 Hz, 8H,
Py), 7.76 (d, J = 4.8 Hz, 8H, Py), 4.40 (t, J = 5.7 Hz, 8H, AOCH2A),
2.96 (t, J = 5.7 Hz, 8H, ANCH2A), 2.76 (s, 4H, ANCH2 A). 13C NMR
(CDCl3, SiMe4, d): 165.0, 150.7, 137.2, 122.8, 63.6, 53.8, 53.5.
2.3. Preparation of [Ag2(ClO4)2(L)(Me2CO)2](1)
An acetone solution (6 mL) of L (13 mg, 0.02 mmol) was slowly
diffused into an aqueous solution (6 mL) of AgClO4 (8 mg,
0.04 mmol). Colorless crystals of 1 suitable for crystallographic
characterization formed at the interface, and were obtained in a
72% yield in 2 days. Anal. Calcd for C20H24N3O9ClAg: C, 40.46; H,
4.07; N, 7.08. Found: C, 40.20; H, 3.98; N, 7.12. IR (KBr, cmꢀ1):
3060(w), 2964(w), 2829(w), 1732(s), 1288(s), 1122(s), 1088(s,
m(ClO4)), 758(w), 704(w), 623(w).
Scheme 1. Synthetic process and skeletal structures.
2.4. Preparation of [Ag2(L)(H2O)2](BF4)2 (2)
Diethyl ether was diffused into an acetonitrile solution (15 mL)
of the white solids. Colorless crystals of 3 suitable for crystallo-
graphic characterization formed at the interface, and were ob-
tained in a 74% yield in 1 day. Anal. Calcd for C19H21N4O8ClAg: C,
39.57; H, 3.67; N, 9.71. Found: C, 40.10; H, 3.62; N, 9.50. IR (KBr,
cmꢀ1): 3056(w), 2964(w), 2831(w), 1728(s), 1286(s), 1122(s),
A tetrahydrofuran solution (6 mL) of L (7 mg, 0.01 mmol) was
slowly diffused into a mixed acetone (4.5 mL) and water (1.5 mL)
solution of AgBF4 (4 mg, 0.02 mmol). Colorless crystals of 2 suitable
for crystallographic characterization formed at the interface, and
were obtained in a 63% yield in 5 days. Anal. Calcd for C17H20N3O5B-
F4Ag: C, 37.74; H, 3.73; N, 7.77. Found: C, 37.60; H, 3.73; N, 7.65. IR
(KBr, cmꢀ1): 3032(w), 2962(w), 2827(w), 1726(s), 1294(s), 1142(s),
1095(s, m(ClO4)), 758(m), 706(m), 679(w), 627(m).
1122(s), 1084(s), 1061(s), 1036(s, m(BF4)), 754(w), 700(w), 679(w).
2.6. Preparation of [Ag2(L)(CH3CN)2](BF4)2 (4)
2.5. Preparation of [Ag2(L)(CH3CN)2](ClO4)2 (3)
An acetone solution (10 mL) of AgBF4 (195 mg, 1.0 mmol) was
added to
a tetrahydrofuran solution (10 mL) of L (328 mg,
An aqueous solution (10 mL) of AgClO4 (207 mg, 1.0 mmol) was
added to an acetone solution (10 mL) of L (328 mg, 0.5 mmol). The
reaction mixture was stirred for 15 min, after which precipitated
powder was filtered and washed with acetone several times.
0.5 mmol). The reaction mixture was stirred for 15 min, after
which precipitated powder was filtered and washed with acetone
several times. Diethyl ether was diffused into an acetonitrile solu-
tion (15 mL) of the white solids. Colorless crystals of 4 suitable for
Table 1
Crystallographic data.
1
2
3
4
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C
40H48N6O18Cl2Ag2
C17H20N3O5BF4Ag
541.04
170(2)
Monoclinic
C2/c
30.105(3)
11.251(1)
13.672(1)
91.907(6)
4628.4(7)
8
C19H21N4O8ClAg
576.72
170(2)
Monoclinic
C2/c
30.9303(4)
10.9638(2)
13.6514(2)
91.1250(1)
4628.48(1)
8
C19H21N4O4BF4Ag
564.08
296(2)
Monoclinic
C2/c
30.5018(4)
10.9900(2)
13.6994(2)
92.0820(1)
4589.21(1)
8
1187.48
296(2)
Monoclinic
P21/c
30.678(3)
10.4667(1)
15.0729(2)
96.983(7)
4804.0(8)
4
b (Å)
c (Å)
b (°)
V (Å3)
Z
dcalc (gcmꢀ3
)
1.642
1.005
1.553
0.934
1.655
1.038
1.633
0.944
l
(mmꢀ1
)
Completeness
99.3% (h = 28.24°)
11790/0/613
1.042
0.0562
0.1903
99.2% (h = 20.36°)
2255/0/280
2.194
0.0909
0.1839
99.8% (h = 28.27°)
5727/0/298
1.061
0.0415
0.1236
99.8% (h = 28.23°)
5667/0/298
0.787
0.0569
0.2187
Data/restraints/parameters
Goodness-of-fit on F2
R1 [I > 2
r
(I)]a
wR2 (all data)b
P
P
a
R1
=
||Fo| ꢀ |Fc||/ |Fo|.
P
P
wR2 = ( w(F2o ꢀ Fc2)2/ wFo2)1/2
.
b

S. Lee et al. / Journal of Molecular Structure 996 (2011) 115–119
117
crystallographic characterization formed at the interface, and were
obtained in a 71% yield in 1 day. Anal. Calcd for C19H21N4O4BF4Ag:
C, 41.98; H, 3.82; N, 9.52. Found: C, 41.60; H, 3.80; N, 9.56. IR (KBr,
cmꢀ1): 3056(w), 2964(w), 2835(w), 1728(s), 1286(s), 1126(m),
least-squares techniques (SHELXL 97) [28]. The non-hydrogen
atoms were refined anisotropically, and the hydrogen atoms were
placed in calculated positions and refined only for the isotropic
thermal factors. The crystal parameters and procedural informa-
tion on the data collection and structure refinement are listed
in Table 1.
1034(m, m(BF4)), 758(m), 706(m), 679(m).
2.7. Crystal structure determination
3. Results and discussion
X-ray data were collected with a Bruker SMART automatic dif-
fractometer employing graphite-monochromated Mo Ka radiation
3.1. Synthesis and properties
(k = 0.71073 Å) and incorporating a CCD detector at ambient tem-
perature. Thirty-six frames of two-dimensional diffraction images
were collected and processed to obtain the cell parameters and
orientation matrix. The data were corrected for the Lorentz and
polarization effects. The absorption effects were corrected by
the multi-scan method. The structures were solved by means of
the direct method (SHELXS 97) and refined with full-matrix
The new multi N-donor ligand, N,N,N0,N0-tetrakis(ethylisonicot-
inoyl)ethylendiamine (L), was synthesizedꢀin high yield. Crystalli-
zation via self-assembly of AgX (Xꢀ = ClO4 and BF4ꢀ) with L was
compared with the recrystallization, via slow diffusion, of the
crude product. Self-assembly of AgClO4 with L in a mixture of
acetone and H2O produces 2D coordination polymers consisting
of [Ag2(ClO4)2(L)(Me2CO)2] (1), whereas self-assembly of AgBF4
with L in a mixture of tetrahydrofuran and acetone/H2O affords
double-stranded 1D coordination polymers consisting of [Ag2(L)
(H2O)2](BF4)2 (2). The recrystallization of crude products via diffu-
sion leads to double stranded-1D ꢀcoordination polymers consisting
of [Ag2(L)(CH3CN)2](X)2 (Xꢀ = ClO4 (3) and BFꢀ4 (4)) (Scheme 1). For
all such products, both anions and solvents weakly interact with
the Ag(I) cation. The self-assembly reactions were originally con-
ducted in the 1:1 mol ratio of Ag(I) and L, but all of the complexes
afforded coordination polymers of 2:1 (Ag(I):L) ratio, presumably
owing to the similar coordinating nature of the anions [22]. Thus,
it can be said that the structures of products are strongly depen-
dent on solvent, method, and anions, thanks to the very flexible
L. However, the products were not significantly affected by the
mole ratio. All crystalline products are insoluble in water and com-
mon organic solvents, and are stable for several days even in aque-
ous suspensions. They are air-stable, but slowly turn to gray
powder under light. The crystalline solids are easily dissociated
in dimethyl sulfoxide, and N,N-dimethylformamide. The IR spectra
Fig. 1. Asymmetric units along with thermal ellipsoids at the 50% level (20%
probability for anions) of 1 (a), 2 (b), 3 (c), and 4 (d).
Fig. 2. Infinite structures of 1 (a), 2 (b), 3 (c), and 4 (d). Hydrogen atoms, anions, and
solvated molecules (a, b) are omitted for clarity.

118
S. Lee et al. / Journal of Molecular Structure 996 (2011) 115–119
Table 2
Selected bond lengths (Å) and angles (°).
1
2
3
4
Ag(1)AN(3)
Ag(1)AN(4)
Ag(1)ꢁ ꢁ ꢁO(11)
Ag(1)ꢁ ꢁ ꢁO(19)
Ag(2)AN(5)
2.174(4)
2.161(3)
3.123(5)
2.776(4)
2.165(4)
2.162(4)
2.808(7)
2.886(5)
174.3(1)
144.8(1)
177.5(2)
Ag(1)AN(1)
2.14(2)
2.12(2)
3.142(2)
2.77(2)
3.17(2)
Ag(1)AN(1)
Ag(1)AN(3)
Ag(1)ꢁ ꢁ ꢁAg(1)#1
Ag(1)ꢁ ꢁ ꢁN(4)
Ag(1)ꢁ ꢁ ꢁO(8)
2.159(3)
2.154(3)
3.190(1)
2.622(4)
3.257(5)
Ag(1)AN(1)
Ag(1)AN(2)
Ag(1)ꢁ ꢁ ꢁAg(1)#1
Ag(1)ꢁ ꢁ ꢁN(4)
Ag(1)ꢁ ꢁ ꢁF(1)
2.154(4)
2.164(4)
3.181(1)
2.597(6)
3.275(7)
Ag(1)AN(2)
Ag(1)ꢁ ꢁ ꢁAg(1)#1
Ag(1)ꢁ ꢁ ꢁO(5 W)
Ag(1)ꢁ ꢁ ꢁF(1)
Ag(2)AN(6)
Ag(2)ꢁ ꢁ ꢁO(14)
Ag(2)ꢁ ꢁ ꢁO(18)
N(3)AAg(1)AN(4)
O(11)AAg(1)AO(19)
N(5)AAg(2)AN(6)
N(1)AAg(1)AN(3)
N(1)AAg(1)AN(4)
N(3)AAg(1)AN(4)
Ag(1)#2AAg(1)AN(1)
Ag(1)#2AAg(1)AN(3)
Ag(1)#2AAg(1)AN(4)
171.0(1)
94.3(1)
94.5(1)
102.3(1)
79.9(1)
89.5(1)
N(1)AAg(1)AN(2)
N(1)AAg(1)AN(4)
N(2)AAg(1)AN(4)
Ag(1)#2AAg(1)AN(1)
Ag(1)#2AAg(1)AN(2)
Ag(1)#2AAg(1)AN(4)
170.0(2)
94.9(2)
94.8(2)
79.3(2)
102.9(1)
89.5(2)
N(1)AAg(1)AN(2)
F(1)AAg(1)AO(5W)
172(1)
175.2(4)
Symmetry transformations used to generate equivalent atom: #1 ꢀx + 2, y, ꢀz + 3/2 #2 1 ꢀ x, y, 1/2 ꢀ z.
3.2. Crystal structures
110
100
90
The crystal structure of 1 is shown in Figs. 1 and 2, and its bond
lengths and angles are listed in Table 2. Each L connects four Ag(I)
ions (AgAN = 2.161(3)–2.174(4) Å) via four pyridyl groups to form
2D network coordination polymers. Two Ag(I) ions exist in an
asymmetric unit in the solid state. The 2D formation is attributable
to a favorable combination of the stable conformer of L and the
appropriate NAAgAN angle (N(3)AAg(1)AN(4) = 174.3(1); N(5)A
Ag(2)AN(6) = 177.5(2)). The perchlorate anions are positioned
around the Ag(I) ions (Ag(1)ꢁ ꢁ ꢁO(11) 3.123(5) Å; Ag(2)ꢁ ꢁ ꢁO(14)
= 2.808(7) Å). The lengths between the Ag(I) ions and the solvate
acetone molecules are 2.776(4) Å (Ag(1)ꢁ ꢁ ꢁO(19)) and 2.886(5) Å
(Ag(2)ꢁ ꢁ ꢁO(18)). Thus, both the perchlorate anion and the solvate
acetone molecule weakly interact with each Ag(I) ion. The deviation
from the linear NAAgAN indicates the existence of weak interac-
tions. That is, the two Ag(I) ions have different coordination envi-
ronments. One layer thickness of 2D is about 1 nm (9.489(2) Å),
and the interlayer distance is 5.795(1) Å. The crystal structure of
2 is depicted in Figs. 1 and 2, and the selected bond lengths and an-
gles are listed in Table 2. Its skeleton is a 1D structure consisting of
Ag(I) and L (2:1). Two pyridyl moieties of L connect to an Ag(I) ion
(AgAN = 2.12(2)–2.14(2) Å), inducing a double-stranded 1D struc-
ture. The solvate water molecule is positioned at 2.77(2) Å, which
is much shorter than the van der Waals radii [29]. However, the tet-
rafluoroborate anion does not significantly interact with the Ag(I)
ion (Agꢁ ꢁ ꢁF = 3.17(2) Å), and thus the geometry around the Ag(I)
ion approximates the T-shape arrangement.
(a)
100
50
TGA
DSC
80
(b)
(c)
70
0
60
cm-1
50
2500
2000
-50
-100
40
30
1000
0
200
400
600
800
O
Temperature ( C)
Fig. 3. Overlay of thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) of 3. The inset designates the acetonitrile IR bands of
[Ag2(L)(CH3CN)2](ClO4)2 (3, (a)), [Ag2(L)](ClO4)2 (b, acetonitrile-dissociation),
and [Ag2(L)(CH3CN)2](ClO4)2 (c, acetonitrile-association).
For crystals formed via diffusion, the molecular structures of 3
and 4 are depicted in Figs. 1 and 2, and their selected bond lengths
and angles are listed in Table 2. Their skeleton is a 1D structure
consisting of Ag(I) and L (2: 1). Two pyridyl moieties of L connect
an Ag(I) ion (AgAN = 2.154(3) Å and 2.159(3) Å for 3; 2.154(4) Å
and 2.64(4) Å for 4, forming a double-stranded 1D structure. The
solvate acetonitrile molecule is coordinated to an Ag(I) ion
(Agꢁ ꢁ ꢁN(acetonitrile) = 2.622(4) Å for 3; 2.597(6) Å for 4). The an-
ions do not significantly interact with the Ag(I) ion, and thus act
as simple counteranions (Agꢁ ꢁ ꢁO = 3.257(5); Agꢁ ꢁ ꢁF = 3.275(7) Å)
in contrast to 1. Thus, the geometry around the Ag(I) ion approxi-
mates the T-shape arrangement. In particular, for the 1D structure,
the argentophilic interaction [30,31] exists (3.142(2) Å for 2;
3.190(1) Å for 3; 3.181(1) Å for 4).
Fig. 4. Slight change of ligand conformation depending on the dimensions of
coordination polymers, 2D (top) and 1D (down).
3.3. Thermal analyses
of 3 and 4 in a KBr pellet do not show any acetonitrile peak, but the
spectrum in a Nujol mull does show the acetonitrile band. The ace-
tonitrile moiety easily evaporates during the formation of the KBr
pellet, indicating that the acetonitrile is a very weak coordinating
ligand.
The thermal behaviors of such products are significantly depen-
dent on their solvate molecules. The TGA and DSC of 3 (Fig. 3) show
a two-step decomposition around 164 °C and 210 °C, respectively.
The thermal change at 164 °C can be ascribed to the evaporation of

S. Lee et al. / Journal of Molecular Structure 996 (2011) 115–119
119
solvate acetonitrile (obs. 6.0%; calcd. 7.1%). This evaporation tem-
perature is relatively high compared with that of a known similar
compound [32], which is evidence of stronger interaction between
Ag(I) and acetonitrile. The skeletal 1D structure seems to be re-
tained, but at 210 °C, a drastic change corresponding to skeletal
collapse occurs. Specifically, after evacuation at 170 °C, its IR spec-
trum indicates the absence of acetonitrile. Furthermore, when the
desolvated skeletal species were immersed in acetonitrile at 25 °C,
the acetonitrile peaks reappeared. Such a fact indicates a reversible
association–dissociation of acetonitrile (Eq. (1), see Appendix A for
the XRD patterns). Those of
exhibits systematic structural change. Among various factors, the
anion- and solvent-coordinating natures are two significant factors
in construction of the skeletal structure and its dimensions. This
new coordinating nature of polyatomic anions can be used to
quantitatively predict the dimension of coordination polymers.
Acknowledgments
This work was supported by a National Research Foundation of
Korea (NRF) Grant funded by the Korean Government [MEST]
(2010-0026167).
þCH3CN
210ꢃ
C
(
ꢀCH3CN
½Ag2ðLÞðCH3CNÞ2ꢂðCO4Þ2
+ ½Ag2ðLÞꢂðClO4Þ2
Ag O
ð1Þ
ꢀꢀ!
Appendix A. Supplementary data
2
4 showed a similar thermal pattern. For 1, the acetone molecule
slowly evaporates in the wide temperature range of 80–120 °C in
contrast to 3, and the skeletal structure decomposes within a simi-
lar range. For 2, the water molecules evaporate in the range of 80–
120 °C, and the skeletal structure also decomposes, at around
210 °C (Appendix A).
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.molstruc.2011.04.031.
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A combination of a variety of Ag(I) ion geometries and the flex-
ible tetradentate ligand seems to afford characteristic 1D and 2D
coordination structures. The reactions afford 2:1 (Ag(I):L) coordina-
tion polymers, because the ClOꢀ4 and BFꢀ4 have a very similar coor-
dinating nature [7,22,24]. Furthermore, all of the complexes
indicate that the pyridyl nitrogen of L is a better donor than the eth-
ylenediamine nitrogen of L: all of the Ag(I) ions are coordinated by
the pyridyl nitrogen donors rather than the ethylenediamine moi-
ety. The solvate molecules play a key role in Ag(I) ion geometry.
The basic coordination geometry is delicately dependent on the sol-
vent used. Solvate acetonitrile, water, and acetone molecules act as
a coordinating ligand rather than simple solvent. On the other hand,
formation of each skeleton seems to be dependent on the coordi-
nating nature of the anions. The interaction between Ag(I) and
ClO4 affords the 2D structure whereas the very weak interactions
between Ag(I) and the anions yield the 1D skeletal structures. For
1, the distances of Agꢁ ꢁ ꢁOClOꢀ3 (1) are 2.808(7) Å and 3.123(5) Å
(the sum of the van der Waals radii (3.20 Å) of Ag and O [29]), which
are stronger than the corresponding distances of the three 1D coor-
dination polymers. Thus, the ionic interaction significantly affects
the formation of the skeletal structure and its dimensions. The
argentophilic interaction exists in the 1D structure, whereas it does
not exist in 2D. The argentophilic interaction induces a sinusoidal
1D structure. The weak argentophilic, Agꢁꢁꢁanion, and Agꢁꢁꢁsolvent
interactions compete with each other, and therefore are very inte-
gral to the construction of coordination polymers using the highly
flexible organic spacer ligands. The ligand conformation difference
between the 1D and 2D structures exists in the solid state (Fig. 4).
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4. Conclusions
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Our results demonstrate that the highly flexible multidentate
tetrakispyridine spacer is a fascinating molecular building unit that