One-dimensional coordination polymers with 4-(2-aminoethyl)pyridine: Synthesis, crystal structures and spectroscopic properties

Article abstract of DOI:10.1016/j.poly.2016.10.046

Two new one-dimensional polymeric metal complexes, namely [Zn(NH₃)(μ-4aepy)Ni(μ-CN)(CN)₃]_n(1) and [Cu(H₂O)(μ-4aepy)Pd(μ-CN)(CN)₃]_n(2) [4aepy?=?4-(2-aminoethyl)pyridine], were synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The complexes crystallize in the monoclinic system, P2₁/n space group. The asymmetric units of 1 and 2 contain two M(II) ions [M?=?Zn(II) and Ni(II) in 1 and Cu(II) and Pd(II) in 2], four cyanide ligands, one 4aepy ligand and one coordinated ligand (ammine in 1 and aqua in 2) in a distorted tetragonal coordination geometry. The crystal structures of the complexes revealed that three cyanide groups are terminal whereas one different cyanide group behaves as bridging ligand. The most important features of the complexes are the presence of obvious M?π [M(II)?=?Ni(II) or Pd(II)] interactions. The spectral and thermal analysis results also support the crystal structures of the complexes.

Full text of DOI:10.1016/j.poly.2016.10.046

Accepted Manuscript
One-dimensional coordination polymers with 4-(2-aminoethyl)pyridine: Syn-
thesis, crystal structures and spectroscopic properties
Dursun Karaağaç, Güneş Süheyla Kürkç üoğlu, Mustafa Şenyel, Onur Şahin,
Tuncer Hökelek
PII:
S0277-5387(16)30543-5
DOI:
http://dx.doi.org/10.1016/j.poly.2016.10.046
POLY 12299
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
24 August 2016
17 October 2016
19 October 2016
Please cite this article as: D. Karaağaç, G. Süheyla Kürkç üoğlu, M. Şenyel, O. Şahin, T. Hökelek, One-dimensional
coordination polymers with 4-(2-aminoethyl)pyridine: Synthesis, crystal structures and spectroscopic properties,
Polyhedron (2016), doi: http://dx.doi.org/10.1016/j.poly.2016.10.046
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1
One-dimensional coordination polymers with 4-(2-aminoethyl)pyridine:
Synthesis, crystal structures and spectroscopic properties
a
b
c
d
Dursun Karaağaç , Güneş Süheyla Kürkçüoğlu *, Mustafa Şenyel , Onur Şahin and
e
Tuncer Hökelek
a
Ulubatlı Hasan Anatolian High School, 16320 Bursa, Turkey
b
Eskişehir Osmangazi University, Faculty of Arts and Sciences, Department of Physics,
2
6480 Eskişehir, Turkey
c
Anadolu University, Faculty of Sciences, Department of Physics, 26470 Eskişehir, Turkey
d
Sinop University, Scientific and Technological Research Application and Research Center,
5
7000 Sinop, Turkey
e
Hacettepe University, Faculty of Engineering, Department of Physics, TR-06800 Beytepe,
Ankara, Turkey
Abstract
Two new one-dimensional polymeric metal complexes, namely [Zn(NH
3
)(µ-4aepy)Ni(µ-
4-(2-
CN)(CN) (1) and [Cu(H O)(µ-4aepy)Pd(µ-CN)(CN) (2) [4aepy
3
]
n
2
3
]
n
=
aminoethyl)pyridine], were synthesized and characterised by vibrational (FT-IR and Raman)
spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The
1
complexes crystallize in the monoclinic system, P2 /n space group. The asymmetric units of 1
and 2 contain two M(II) ions [M = Zn(II) and Ni(II) in 1 and Cu(II) and Pd(II) in 2], four
cyanide ligands, one 4aepy ligand and one coordinated ligand (ammine in 1 and aqua in 2) in
a distorted tetragonal coordination geometry. The crystal structures of the complexes revealed
that three cyanide groups are terminal whereas one different cyanide group behaves as
bridging ligand. The most important features of the complexes are the presence of obvious
M⋯π [M(II) = Ni(II) or Pd(II)] interactions. The spectral and thermal analysis results also
support the crystal structures of the complexes.

2
Keywords: cyanide complex, 1D complex, 4-(2-aminoethyl)pyridine complex, crystal
structure, vibrational spectra, M⋯π interaction.
E-mail: gkurkcuo@ogu.edu.tr (G.S. Kürkçüoğlu).
1
. Introduction
Coordination polymers combined of polymeric metal cyanide complexes are attracting
considerable interest in recent decades due to their ability to construct infinite one, two and
three-dimensional structures that may possess interesting catalytic, electrical, spectroscopic,
magnetic properties, defined pores and biological properties [1]. The use of anionic transition
metal cyanide building blocks in coordination chemistry dates back to the discovery of
Prussian blue in the 18th century by Diesbach. The structures of polymeric metal cyanide
complexes occur from transition metal cyanide building blocks. These building blocks can
-
exhibit a variety of different geometries, exemplified by linear [Ag(CN)
2
] , trigonal
2
-
2-
2-
4-
[
Cu(CN)
3
] , tetrahedral [Cd(CN)
4
] , square planar [Ni(CN)
4
] , octahedral [Fe(CN)
6
] and
even seven or eight coordinated ones, all of which may act as anionic building blocks to
build multidimensional structures [2,3]. In metal cyanide complexes, both the carbon and the
nitrogen ends of the cyanide ligand can act as Lewis bases and coordinate to transition metal
cations. In this case, cyanide can behave as either a terminal or a bridging ligand. One, two,
2
-
three or four cyanide groups in the [M(CN) ] [M(II) = Ni(II), Pd(II) or Pt(II)] anion can
4
behave as a bridging ligand. Metal cyanide complexes that exhibit the terminal character of
three cyanide groups and the bridging character of one cyanide group are scarce in the
literature [2,4].
Organic ligands are molecules with more than one functional group that are able to
coordinate to metal centers and thereby allow the possibility of the formation of larger
architectures. 2-Aminoethylpyridine can behave as a chelating or bridging ligand [5-7]. In the
literature, copper and zinc complexes with 2-aminomethylpyridine (ampy) or 2-

3
aminoethylpyridine (aepy) are known for their mainly chelating manner of coordination and
the bridging mode of bonding to central atoms is rather rare [6-8]. Cationic Cu(II) and Zn(II)
ions generally adopt a coordination number of six or four. Two discrete geometry types are
available for four coordination. These geometries are tetrahedral and square planar. Square
planar and tetrahedral structures of Cu(II) and Zn(II) ions have been studied in the literature
[
9-12]. According to our knowledge, no metal cyanide complexes formed from tetrahedral
2
-
4
cationic copper(II) or zinc(II) central ions and square-planar [M(CN) ] anions, where M(II)
=
Ni(II), Pd(II) or Pt(II), have been reported in the literature.
A few metal complexes were obtained using 3-aminomethylpyridine [13], 4-
aminomethylpyridine [14] and 4-(2-aminoethyl)pyridine [5] ligands in previous studies. We
have recently reported the tetracyanonickelate(II) or tetracyanopalladate(II) complexes with
3
-aminomethylpyridine [15], 4-aminomethylpyridine [16, 17] and 4-(2-aminoethyl)pyridine
18, 19]. As a continuation of these works, we describe here the syntheses, spectral, thermal
and structural properties and the elemental analyses of cyanide bridged coordination polymers
1D) with the 4aepy ligand, [Zn(NH )(µ-4aepy)Ni(µ-CN)(CN) (1) and [Cu(H O)(µ-
aepy)Pd(µ-CN)(CN) (2). The 4aepy ligand was used to obtained
copper(II)/palladium(II) cyanide complex, formulated as [Cu(4aepy) (H O) ][Pd(CN)
which was summarized in the work of [5]. According to this study, the crystal structure of this
[
(
3
3
]
n
2
4
3
]
n
a
2
2
2
4
n
] ,
2
-
4
complex consists of a Cu(II) ion, two aqua ligands, one 4aepy ligand and [Pd(CN) ] counter
anions, and thus it is structurally different from 2.
2
2
. Experimental
.1. Materials
All materials, copper(II) chloride dihydrate (CuCl
2
·2H
2
O, 99%), zinc(II) chloride (ZnCl
2
,
,
9
6%), nickel(II) chloride hexahydrate (NiCl ·6H O, 97%), palladium(II) chloride (PdCl
2
2
2

4
9
9%), potassium cyanide (KCN, 96%), and 4-(2-aminoethyl)pyridine (C
7
H
10
N
2
, 96%), were
used as received from commercial sources.
2
.2. Syntheses of the complexes
.2.1. M[M′(CN) ]·H O [M(II) = Cu or Zn, M′(II) = Ni or Pd]
·6H O (0.238 g, 1 mmol) or PdCl
was added a solution of KCN (0.260 g, 4 mmol) in water (10 mL), and yellow
[Ni(CN) ]·H O or white K [Pd(CN) ]·H O was crystallized. A metal(II) chloride solution
CuCl ·2H O = 0.170 g or ZnCl = 0.136 g, 1 mmol) was added to the synthesized
[Ni(CN) ]·H O (0.259 g, 1 mmol) or K [Pd(CN) ]·H O (0.306 g, 1 mmol), giving
]·H
]·H
2
4
2
To a water solution (10 mL) of NiCl
2
2
2
(0.177 g, 1 mmol)
K
2
4
2
2
4
2
(
2
2
2
K
2
4
2
2
4
2
M[M′(CN)
M[M′(CN)
4
4
2
O [M = Cu(II) or Zn(II), M′ = Ni(II) or Pd(II)], respectively. The
O [M(II) = Cu(II) or Zn(II), M′(II) = Ni(II) or Pd(II)] complexes were
2
investigated and analyzed by elemental and spectral analysis. The Zn[Ni(CN)
Cu[Pd(CN) ]·H O complexes were analyzed for C, H and N content with the following
results: Anal. Found (Calcd.) (%) for C
H, 1.01 (0.82); N, 22.70 (22.76); for C
4 2
]·H O and
4
2
4
H
2
N
4
ONiZn (M
w
= 246.17 g/mol) : C, 19.65 (19.52);
= 292.05 g/mol) : C, 16.68 (16.45);
4
H
2
N
4
OPdCu (M
w
H, 0.78 (0.69); N, 19.23 (19.18). The experimental elemental analysis values were shown to
be consistent with the calculated values. Furthermore, the obtained analysis results were
supported by the literature data [20]. The colors of Zn[Ni(CN)
were yellow and blue, respectively.
4 2 4 2
]·H O and Cu[Pd(CN) ]·H O
FT-IR studies of zinctetracyanonickelate and coppertetracyanopalladate were carried
-
1
out. For the zinctetracyanonickelate complex, a sharp band in the range 2121-2194 cm was
obtained, which is characteristic of C≡N stretching. Another band obtained in the range 459-
-
1
-1
6
69 cm is characteristic of M-C stretching. A band in the range 558-762 cm is
-1
characteristic of M-N stretching. A broad band in the range 3414-3440 cm was observed due

5
to interstitial water molecules present in the lattice of the metal cyanogen complex for the Zn
tetracyanonickelate. No new peaks appeared for Zn[Ni(CN)
20].
.2.2. [Zn(NH
A mixture of Zn[Ni(CN)
4 2 4 2
]·H O and Cu[Pd(CN) ]·H O
[
2
3
)(µ-4aepy)Ni(µ-CN)(CN)
3 n 2 3 n
] and [Cu(H O)(µ-4aepy)Pd(µ-CN)(CN) ]
4
]·H O (0.246 g, 1 mmol) in water (10 mL) and 4aepy (0.244 g, 2
2
mmol) in ethanol (10 mL) were stirred at 50 °C for 4 h in a temperature-controlled bath and
ammonia (5 mL) was also added to the solution during mixing. The obtained solution was
filtered and kept for crystallization at room temperature. Yellow [Zn(NH
CN)(CN) (1) block-shaped single crystals were obtained by slow evaporation after one
week. [Zn(NH )(µ-4aepy)Ni(µ-CN)(CN) (1), Anal. Found (Calcd.) (%) for C11 NiZn
= 367.35 g/mol): C, 35.41 (35.96); H, 3.74 (3.57); N, 26.07 (26.69).
was obtained in a similar method to 1, but the Zn(II) and Ni(II) ions were replaced
3
)(µ-4aepy)Ni(µ-
3 n
]
3
3
]
n
13 7
H N
(
M
w
2
by Cu(II) and Pd(II) ions (0.292 g), respectively. Blue crystals of 2 were obtained. The
complex was analyzed for C, H, and N with the following results: Anal. Found (Calcd.) (%)
for C11
H
12
N
6
OCuPd (M
.3. Physical measurements
Elemental analyses (C, H and N) were carried out by standard methods using a CHNS-932
LECO) analyzer at the Middle East Technical University Central Laboratory in Ankara,
Turkey. The FT-IR spectra of 4aepy and the complexes were recorded as KBr pellets in the
w
= 414.22 g/mol): C, 31.21 (31.90); H, 3.02 (2.92); N, 19.55 (20.29).
2
(
-1
-1
range 4000-400 cm (2 cm resolution) on a Perkin Elmer 100 FT-IR spectrometer, which
was calibrated using polystyrene and CO bands. Raman spectra of the complexes were
recorded from 4000 to 250 cm on a Bruker Senterra Dispersive Raman Microscope using the
85 nm line of a 3B diode laser. The TG, DTA and DTG measurements were carried out
using a Perkin-Elmer Diamond TG/DTA Thermal Analysis instrument under static air at a
2
-1
7

6
-1
heating rate of 10 K min from 30 to 800 °C using platinum crucibles.
.4. Crystallographic analyses
Suitable crystals of the complexes were selected for data collection which was performed on a
Bruker APEX-II QUAZAR diffractometer equipped with graphite-monochromatic Mo-K
2
α
radiation. The structures were solved by direct methods using SHELXS-97 [21] and refined
2
by full-matrix least-squares methods on F using SHELXL-97 [21] from within the WINGX
[
22] suite of software. All non-hydrogen atoms were refined with anisotropic parameters. The
H atoms attached to C atoms were located from different maps and then treated as riding
atoms with C-H distances of 0.93-0.97 Å. All other H atoms were located in a difference map
and were refined freely. Molecular diagrams were created using MERCURY [23].
Supramolecular analyses were made and the diagrams were prepared with the aid of
PLATON [24].
3
3
. Results and discussion
.1. Vibrational spectra
The FT-IR and Raman spectra of the complexes are illustrated in Figs. S1 and S2,
respectively. The spectra of the complexes are seen to be very similar to each other, indicating
that they have analogous structures. The absorption bands observed in the region from 3600 to
-1
3
300 cm are due to symmetric and asymmetric ν(X-H) (X = N or O) stretching vibrations of
the coordinated ammine or aqua ligands. The most important vibrational bands of the ammine
ligand are ν(NH) stretching and δ(NH) deformation vibrational bands. Asymmetric and
symmetric ν(NH) stretching and δ(NH) deformation vibrational bands are found in the
-
1
regions 3400-3000 and 1650-1550 cm , respectively [25]. According to the spectral data of 1,
-
1
the asymmetric stretching band of the ammine ligand is observed at 3345 cm , whereas
symmetric ν(NH) stretching and δ(NH) deformation bands are not observed due to the overlap

7
of ν(NH) stretching and δ(NH) deformation bands of the 4aepy ligand, respectively. However,
the FT-IR spectrum of 2 contains more absorption bands originating from ν(OH) and δ(OH)
vibrations. The most important vibration bands of the aqua ligand are the asymmetric and
symmetric ν(OH) stretching and δ(OH) deformation bands. In the FT-IR spectrum of 2, the
-1
ν(OH) stretching band of the aqua ligand is observed as a broad band at 3420 cm and the
-
1
δ(OH) deformation band is identified at 1659 cm .
3
.1.1. The ligand (4aepy) vibrations
The 4aepy molecule has two nitrogen atoms, which can donate electrons. Therefore, it is
expected that the binding take place between the two nitrogen atoms of the 4aepy ligand
and the transition metal ions. When the 4aepy ligand is coordinated to transition metal ions,
important changes in the vibrational bands of 4aepy are observed. To the best of our
knowledge, no complete vibrational assignments have been reported for 4aepy. The
assignments and the wavenumbers of the vibrational bands of the 4aepy ligand observed in
the spectra of the complexes are given in Table S1, together with the wavenumbers for the
free 4aepy molecule in the liquid phase. The assignments of the vibrational data of free
4
aepy in the liquid phase have been reported to be in accord with 2-aminomethylpyridine
26] and 2-aminoethylpyridine [27]. Considering the present spectral data, it is not possible
to give an account of the conformation of the 4aepy ligand in the complexes. The most
significant spectral data for 4aepy are as follows: ν(NH ), ν(CH), δ(NH ), ν(C=C)+ν(C=N),
w(CH) νring and ring breathing. The asymmetric and symmetric ν(NH ) stretching vibration
bands of free 4aepy are found at 3362 and 3292 cm , respectively. The ν(NH ) stretching
[
2
2
2
-
1
2
vibrational bands of the complexes are lower than those of free 4aepy. There are the two
reasons of this shift and one is the effect of coordination. Upon coordination, the N-H bond
is weakened and the ν(NH ) stretching frequencies are lowered. The other reason is the
2

8
effect of hydrogen bonding. The formation of N-H⋅⋅⋅N and N-H⋅⋅⋅O type hydrogen bonding
in the complexes leads to the weakening of the N-H bond, whereas the effects of
coordination and hydrogen bonding increase the δ(NH) deformation vibrational frequencies
2 2
of the NH group [28]. The δ(NH) deformation vibration frequency of the NH group was
−1
identified at 1605 cm for free 4aepy, and was observed as upward shifts for the 4aepy
ligand in the complexes. The ν(CH) stretching vibration bands are assigned to 3072, 3031
-1
and 2993 cm for free 4aepy. ν(C=C)+ν(C=N), νring, ring breathing and γring bands are
-1
assigned tot 1558, 1221, 807 and 517 cm for free 4aepy, respectively. According to the
presented spectral data, the vibrational frequencies of the complexes shifted to lower or
higher frequencies compared to the free ligand. These shifts show that the 4aepy molecule
is connected directly to the transition metal atoms through the nitrogen atom of the pyridine
ring. All of these frequency shifts are sensitive to the coordination of the 4aepy ligand
directly to the transition metal atoms. Similar shifts were observed in studies of pyridine
and its derivatives [18,19,29,30].
2
-
3
.1.2. [M(CN)
4
] [M(II) = Ni(II) or Pd(II)] group vibrations
In FT-IR and Raman spectra of the complexes, the vibrational wavenumbers of the
2
-
[
M(CN)
4
] [M(II) = Ni(II) or Pd(II)] groups for the complexes are given in Table S2, together
with the vibration wavenumbers of K
2
Ni(CN) ·H O [31] and K Pd(CN) ·H O [32]. One of the
4
2
2
4
2
most dominant features of cyanide is its ability to act as either a terminal or a bridging ligand.
When cyanide acts as a bridging ligand between metal atoms, the ν(CN) stretching vibrations
-
in the metal cyanide complexes are generally higher than the value for the free CN ion [33].
In the FT-IR spectra of the complexes, sharp and strong vibrational modes are clearly seen at
-
1
-1
2
173 cm for 1 and 2190 and 2177 cm for 2. The vibrational modes [ν(CN), E
u
] for the
-
1
complexes have shifted to a higher frequency range by around 51-68 cm . Bridging cyanide

9
frequencies in metal cyanide complexes are generally found at higher frequencies due to
kinematic coupling, which is a mechanical constraint upon the bridging cyanide ligand
confined to the second metal [34]. In the FT-IR spectra of the complexes, two vibration bands
-1
-1
seen at 2122 and 2126 cm for 1 and 2141 and 2144 cm for 2 are observed to be more close
2
-
to that of the [M(CN) ] anon. The splitting of the ν(CN) stretching vibration modes is
4
interpreted to be the result of the existence of bridged and terminal cyanide groups in the
structures of the complexes. In addition, A1g and B1g modes in the Raman spectra of the
-1
-1
complexes are assigned at 2185 and 2137 cm for 1 and 2206 and 2166 cm for 2. According
to these spectral values, the A1g and B1g modes are shifted to a higher frequency range by 1-37
-1
2-
4
cm in the complexes. As a result, only one of the CN groups of the [M(CN) ] [M(II) =
Ni(II) or Pd(II)] anion is identified as having bridging character. When the FT-IR and Raman
spectral data of the complexes are compared with the crystallographic data, the results are
observed to be consistent with each other. According to this, the C1≡N1, C2≡N2, C3≡N3 and
C4≡N4 bond lengths are 1.152, 1.146, 1.148 and 1.147 Å in 1, and the C8≡N3, C9≡N4,
C10≡N5 and C11≡N6 bond lengths are 1.131, 1.142, 1.137 and 1.148 Å in 2, respectively.
3
.2. Crystallographic analyses
Details of the data collection and crystal structure determinations are given in Table 1.
Selected bond lengths and angles for 1 and 2 are collected in Table 2, and the hydrogen bond
parameters for 1 and 2 are given in Table 3. The molecular structures of the heterometallic
complexes 1 and 2, with the atom numbering schemes, are shown in Figs. 1 and 2. The
asymmetric units of the heterometallic complexes 1 and 2 contain two M(II) ions [M(II) =
Zn(II) and Ni(II) in 1 and Cu(II) and Pd(II) in 2], four cyanide ligands, one 4aepy ligand and
one coordinated ligand (ammine ligand in 1 and aqua ligand in 2). Each M(II) ion [M(II) =
Ni(II) in 1 and Pd(II) in 2] is coordinated by four carbon atoms from four different cyanide

10
ligands, showing a square planar coordination geometry. Each M(II) ion [M(II) = Zn(II) in 1
and Cu(II) in 2] is coordinated by two nitrogen atoms from two different 4aepy ligands, one
nitrogen atom from a cyanide ligand and a coordinated ligand (ammine ligand in 1 and aqua
ligand in 2). The geometry around the M(II) ion [M(II) = Zn(II) in 1 and Cu(II) in 2] is a
distorted tetrahedral coordination. The M(II) ions [M(II) = Zn(II) in 1 and Cu(II) in 2] are
bridged by 4aepy ligands to generate a 1D coordination polymer, with an M···M separation of
9
.555 Å in 1 and 9.554 Å in 2. Adjacent 1D coordination polymers are further joined by N-
H···N hydrogen bonds in 1 and O-H···N hydrogen bonds in 2 (Fig. 3). Non-covalent
interactions are very important in biological structures, supramolecular chemistry and
molecular recognition. An experimental study on the complexes has revealed the great
importance of the non-covalent M⋯π interactions betweenthe M(II) ion [Ni(II) or Pd(II)] and
the 4aepy ligand. In addition, there are also interactions between the M(II) ion [Ni(II) or
i
i
Pd(II)] and the centroids of the pyridine rings [Ni1⋯C5 , 3.253 Å, Ni1⋯C6 , 3.310 Å,
i
i
Ni1⋯C7 , 3.948 Å and Ni1⋯Cg, 3.634 Å for 1 (i : 2.5-x,-1/2+y,1/2-z), Pd1⋯C1 , 3.453 Å,
i
i
Pd1⋯C2 , 3.197 Å, Pd1⋯C3 , 3.719 Å and Pd1⋯Cg, 3.657 Å for 2 (i : 1.5-x,-1/2+y,1/2-z)]
Fig. 4). The M⋯π interactions play an important role in the formation of the crystal
(
structures of 1 and 2. To the best of our knowledge, this manner of arrangements is rarely
available so far [17,35]. In 1 and 2, the intermolecular N-H···N (in 1) and O-H···N (in 2)
hydrogen bonds and M⋯π interactions link the molecules to form a 3D supramolecular
architecture and provide the crystal packing. Therefore, these weak M⋯π interactions play a
major role in constructing the 3D network.
3
.3. Thermal analyses of the complexes
The thermal behaviors of the complexes were examined by TG, DTG and DTA methods in
the temperature range 30-800 °C in a static air atmosphere. Thermal decomposition curves of

11
1
and 2 are shown in Figs. S3 and S4, respectively. The thermal decompositions of the
complexes proceed in three stages. 1 is stable up to 197 °C and then begins to decompose.
The first stage corresponds to the endothermic decomposition of the ammine ligand between
1
97 and 217 °C [Found (Calcd.) (%): 4.59 (4.63)]. In the second stage, the decomposition of 1
proceeds with two maxima at 239 and 288 °C and loses the 4aepy ligand in the temperature
range 217-383 °C [Found (Calcd.) (%): 30.11 (33.25)]. The last stage, in the range 383-491
°C (DTAmax = 466 °C), corresponds to the exothermic decomposition of the four cyanide
ligands. The final decomposition products were found by FT-IR spectroscopy to be ZnO and
NiO [Found (Calcd.) (%): 42.14 (42.48)]. Complex 2 is thermally stable up to 36 °C. In the
first stage, 2 loses one aqua ligand in the temperature range 35-141 °C [Found (Calcd.) (%):
3
.15 (4.35)]. The second stage shows two endothermic decomposition steps at 174 and 233
C, one 4aepy ligand is released in the temperature range 141-379 ºC [Found (Calcd.) (%):
7.06 (29.49]. The next stage for 2 is related to the exothermic removal of -CN groups in the
°
2
temperature range 379-414 °C (DTAmax = 403 °C). The final solid products of the thermal
decomposition were identified by FT-IR spectroscopy as CuO and PdO [Found (Calcd.) (%):
4
7.15 (48.75)].
4
. Conclusion
In this study, two new one dimensional (1D) metal cyanide complexes, [Zn(NH
3
)(µ-
4
aepy)Ni(µ-CN)(CN) (1) and [Cu(H O)(µ-4aepy)Pd(µ-CN)(CN) (2) [4aepy = 4-(2-
3
]
n
2
3 n
]
aminoethyl)pyridine], were prepared and investigated using spectroscopic, thermal and
diffraction techniques. The Ni(II) or Pd(II) centers are four coordinate with four cyanide-
carbon atoms in a square-planar arrangement. The Cu(II) or Zn(II) ions are coordinated by
two nitrogen atoms from two different 4aepy ligands, one nitrogen atom from a cyanide
ligand and a coordinated ligand (ammine in 1 and aqua in 2). The structures of the complexes

12
consist of one dimensional coordination polymers containing the M(II) ions [M(II) = Zn(II) in
and Cu(II) in 2] bridged by 4aepy ligands. The crystal packing arrangements of 1 and 2 are
1
a composite of intermolecular hydrogen bonding and Ni or Pd⋯π interactions. The vibrational
data of the complexes is compared to the results obtained from X-ray data and the results are
shown to support each other.
Supplementary material
Crystallographic data for the structural analysis have been deposited with the Cambridge
Crystallographic Data Centre, CCDC No. 1473852 for 1 and 1473853 for 2. Copies of this
information may be obtained free of charge from the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
Acknowledgments
This paper is dedicated to Prof. Dr. Ziya KANTARCI, who died in January, 2012. The
authors would like to thank the editor for considering the manuscript for review and the
esteemed reviewers for reviewing and giving valuable suggestions for modifications of the
paper. This work was supported by the Research Fund of Eskişehir Osmangazi University.
Project number: 201519047.
References
[
1] L. Ouyang, The use of tetracyanozincate(II) in the preparation of supramolecular
coordination polymers, Department of Chemistry - Simon Fraser University, 2007.
2] J. Cernak, M. Orendac, I. Potocnak, J. Chomic, A. Orendacova, J. Skorsepa, A. Feher,
Coord. Chem. Rev. 224 (2002) 51.
[
[
[
[
3] Z. Kartal, Braz. J. Phys. 42 (2012) 6.
4] H. Kurihara, S.-I. Nishikiori, T. Iwamoto, Acta Crystallogr., Sect. C 53 (1997) 1409.
5] J. Kuchár, M. Miklošová, J. Černák, L.R. Falvello, J. Mol. Struct. 1072 (2014) 94.

13
[
[
[
6] M. Puchoňová, M. Mazúr, D. Valigura, Acta Chim. Slov. 7 (2014) 94.
7] S. Hamamcı, V.T. Yılmaz, W.T. Harrison, Z. Naturforsch. B 60 (2005) 978.
8] G.S. Kürkçüoglu, O.Z. Yesilel, İ. Kavlak, O. Büyükgüngör, J. Mol. Struct. 920 (2009)
20.
2
[
[
[
9] H. Wang, M.-X. Li, M. Shao, X. He, Polyhedron 26 (2007) 5171.
10] A.M. Chippindale, S.M. Cheyne, S.J. Hibble, Angew. Chem. Int. Ed. 44 (2005) 7942.
11] S.K. Dey, B. Bag, D.K. Dey, V. Gramlich, Y. Li, S. Mitra, Z. Naturforsch. B 58 (2003)
1
009.
12] R. Giménez, A.B. Manrique, S. Uriel, J. Barberá, J.L. Serrano, Chem. Commun. (2004)
064.
[
2
[
[
[
(
[
(
[
13] R.P. Feazell, C.E. Carson, K.K. Klausmeyer, Inorg. Chem. 45 (2006) 2635.
14] R.P. Feazell, C.E. Carson, K.K. Klausmeyer, Inorg. Chem. 45 (2006) 935.
15] D. Karaağaç, G.S. Kürkçüoğlu, O.Z. Yeşilel, T. Hökelek, H. Dal, Z. Kristallogr. 227
2012) 639.
16] D. Karaağaç, G. Kürkçüoğlu, T. Hökelek, O. Yeşilel, Y. Süzen, Z. Kristallogr. 228
2013) 100.
17] D. Karaağaç, G.S. Kürkçüoğlu, O.Z. Yeşilel, T. Hökelek, Spectrochim. Acta Mol.
Biomol. Spectrosc. 121 (2014) 196.
[
[
18] D. Karaağaç, G.S. Kürkçüoğlu, M. Şenyel, O. Şahin, J. Mol. Struct. 1123 (2016) 327.
19] D. Karaağaç, G.S. Kürkçüoğlu, M. Şenyel, Tuncer Hökelek, J. Mol. Struct. 1130 (2017)
8
0.
[
[
[
20] P. Kumar, Intern. J. Inform. & Futuristic Research (I.J.I.F.R.) 2 (2014) 346.
21] G.M. Sheldrick, Acta Cryst. A64 (2008) 112.
22] L.J. Farrugia, J. Appl. Cryst. 32 (1999) 837.

14
[
23] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J.v.d. Streek, Mercury: visualization and analysis of crystal structures, J. Appl.
Crystallogr. 39 (2006) 453.
[
24] A.L. Spek, PLATON-a Multipurpose Crystallographic Tool, Utrecht University, Utrecht,
005.
25] N. Kazuo, Infrared and Raman spectra of inorganic and coordination compounds, New
York: John Wiley and Sons, 1 (1986) 978-226.
2
[
[
[
[
26] M.L. Niven, G.C. Percy, Transition Met. Chem. 3 (1978) 267.
27] D. Rastogi, K. Sharma, J. Inorg. Nucl. Chem. 36 (1974) 2219.
28] K. Nakamoto, Infrared and Raman spectra of inorganic and coordination compounds,
Wiley Online Library, 1986.
[
[
[
[
[
29] S. Akyüz, A. Dempster, R. Morehouse, S. Suzuki, J. Mol. Struct. 17 (1973) 105.
30] D. Karaağaç, G.S. Kürkçüoğlu, O.Z. Yeşilel, M. Taş, Polyhedron 62 (2013) 286.
31] R. McCullough, L. Jones, G. Crosby, Spectrochim. Acta 16 (1960) 929.
32] L.H. Jones, Inorganic vibrational spectroscopy, Dekker New York, 1971.
33] D. Ghoshal, T.K. Maji, G. Rosair, G. Mostafa, Acta Crystallogr., Sect. C: Cryst. Struct.
Commun. 60 (2004) 212.
34] J. Ribas, A. Escuer, M. Monfort, R. Vicente, R. Cortés, L. Lezama, T. Rojo, Coord.
Chem. Rev. 193 (1999) 1027.
35] K. Gör, G.S. Kürkçüoğlu, O.Z. Yeşilel, O. Büyükgüngör, J. Mol. Struct. 1060 (2014)
66.
[
[
1

15
Figure Captions
Fig. 1. The molecular structure of 1 showing the atom numbering scheme [(i) x, y-1, z; (ii) x,
y+1, z].
Fig. 2. The molecular structure of 2 showing the atom numbering scheme [(i) x, y-1, z; (ii) x,
y+1, z].
Fig. 3. The N-H⋅⋅⋅N (a) and O-H⋅⋅⋅N (b) hydrogen bonds in 1 and 2.
Fig. 4. Pd⋯π interactions in 2.

16
Table 1. Crystal data and structure refinement parameters for 1 and 2.
Crystal data
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
1
2
C
11
H
13
N
7
NiZn
C
11
H
12
N
6
OCuPd
367.36
Monoclinic
P2 /n
414.21
Monoclinic
P2 /n
1
1
7.2791(2)
9.5548(3)
20.9035(5)
92.328(2)
1452.65(7)
4
7.2865(4)
9.5540(6)
20.9054(12)
92.343(4)
1454.12(15)
4
b (Å)
c (Å)
β (º)
3
V (Å )
Z
-
3
D
c
(g cm )
1.680
1.892
θ range (º)
2.3-27.5
11367
2.3-26.4
10818
Measured refls.
Independent refls.
3343
2697
R
int
0.040
0.124
S
1.06
1.27
R1/wR2
0.029/0.063
0.48/-0.35
0.128/0.354
4.76/-2.93
-
3
∆ρmax/∆ρmin (e Å )

17
Table 2. Selected bond distances and angles for 1 and 2 (Å, º).
Complex 1
i
Zn1-N2
Zn1-N7
Ni1-C3
1.973(2)
1.998(2)
1.868(2)
Zn1-N5
Ni1-C1
Ni1-C4
2.026(2)
1.877(3)
1.867(2)
Zn1-N6
Ni1-C2
2.013(2)
1.854(2)
i
N2-Zn1-N5
105.89(8)
N2-Zn1-N6
N7-Zn1-N5
103.87(8)
106.18(8)
N2-Zn1-N7
N7-Zn1-N6
116.04(9)
111.81(9)
i
i
N6 -Zn1-N5 113.13(8)
Complex 2
Cu1-N3
1.972(1)
2.010(1)
1.849(1)
Cu1-O1
C8-Pd1
C11-Pd1
2.008(1)
1.879(1)
1.855(2)
Cu1-N1
C9-Pd1
2.027(1)
1.885(2)
i
Cu1-N2
C10-Pd1
i
i
N3-Cu1-O1
N3-Cu1-N1
115.9(5)
107.2(5)
N3-Cu1-N2
O1-Cu1-N1
103.6(5)
106.4(5)
O1-Cu1-N2
110.6(5)
i
N2 -Cu1-N1 113.2(5)
Symmetry codes: (i) x, y-1, z for 1; (i) x, y-1, z for 2.

18
Table 3. Hydrogen-bond parameters for 1 and 2 (Å, º).
D-H· · ·A
Complex 1
D-H
H···A
D···A
D-H···A
iii
iv
iii
v
N6-H61···N4
N6-H62···N3
N7-H72···N4
N7-H73···N1
0.81(2)
0.82(3)
0.84(3)
0.87(4)
0.93
2.40(3)
2.22(3)
2.42(3)
2.17(4)
2.60
3.095(3)
2.972(3)
3.115(3)
3.030(3)
3.453(3)
3.440(3)
145
152
141
170
153
149
i
C6-H6···N3
iii
C9-H9···N4
Complex 2
0.93
2.61
iii
iv
O1-H1B···N5
C4-H4···N6
N2-H2A···N6
0.83(2)
0.93
0.90
2.49(12) 3.129(19)
135 (15)
153
154
ii
2.58
2.17
3.435(17)
3.007(16)
Symmetry codes: (i) x, y+1, z; (iii) x-1/2, -y+1/2, z-1/2; (iv) -x+3/2, y+1/2, -z+1/2; (v) -x+5/2, y-1/2, -z+1/2 for
; (ii) x, y+1, z; (iii) x-1/2, -y+3/2, z-1/2; (iv) -x+3/2, y+3/2, -z+1/2 for 2.
1

19
Fig. 1. The molecular structure of 1 showing the atom numbering scheme [(i) x, y-1, z; (ii) x,
y+1, z].

20
Fig. 2. The molecular structure of 2 showing the atom numbering scheme [(i) x, y-1, z; (ii) x,
y+1, z].

21
Fig. 3. The N-H⋅⋅⋅N (a) and O-H⋅⋅⋅N (b) hydrogen bonds in 1 and 2.

22
Fig. 4. Pd⋯π interactions in 2 (i : 1.5-x,-1/2+y,1/2-z)

23
Supporting Information
One-dimensional coordination polymers with 4-(2-aminoethyl)pyridine:
Synthesis, crystal structures and spectroscopic properties
a
b
c
d
Dursun Karaağaç , Güneş Süheyla Kürkçüoğlu *, Mustafa Şenyel , Onur Şahin and
e
Tuncer Hökelek
a
Ulubatlı Hasan Anatolian High School, 16320 Bursa, Turkey
b
Eskişehir Osmangazi University, Faculty of Arts and Sciences, Department of Physics,
2
6480 Eskişehir, Turkey
c
Anadolu University, Faculty of Sciences, Department of Physics, 26470 Eskişehir, Turkey
d
Sinop University, Scientific and Technological Research Application and Research Center,
5
7000 Sinop, Turkey
e
Hacettepe University, Faculty of Engineering, Department of Physics, TR-06800 Beytepe,
Ankara, Turkey

24
-
1
Table S1. The vibration wavenumbers of 4aepy in the complexes (cm ).
a
Assignments
4aepy
liquid)
1
2
(
FT-IR
Raman
FT-IR
Raman
ν
ν
as(NH
2
)
3362 vs
3292 vs
3309 m
3243 m
-
-
-
3295 m
3241 w
3160 w
3291 vw
3253 w
3168 vw
s 2
(NH )
ν(NH
2
)
3181 vw 3151 m
ν(CH)
ν(CH)
ν(CH)
3072 w
3031 w
3099 vw 3080 vw 3066 vw 3092 m
3046 vw
-
-
3045 vw 3053 vw
2981 vw 2966 w
2993 vw 2973 vw
b
b
ν(C-CH
ν(C-CH
ν(C=N)
2
2
-NH
2
)
)
2940 w
2868 w
1663 sh
1605 vs
1558 s
-
2956 vw 2956 vw 2947 vw
-NH
2
2908 vw 2919 vw 2894 vw 2904 vw
1653 sh
1623 s
-
1659 w
1618 s
1658 vw
1627 m
1606 w
δ(NH
ν(C=C)+ν(C=N)
δ(CH
δ (CH
2
)
1632 w
b
1587 w
1569 vw 1598 m
2
)
1498 w
1515 vw 1531 vw 1498 vw 1522 vw
1461 w
1431 vw 1439 vw
2
)
1461 vw 1468 vw 1489 vw 1469 w
b
ν(C=N)+ν(C=N)
w(CH)
1442 w
1418 vs
1386 w
1360 w
1320 w
1221 s
1133 w
1070 m
1029 w
1000 m
896 w
1444 w
1438 w
-
1455 w
1414 vw 1411 vw
-
t(CH)
-
-
1378 m
ν
ring+ δ(CH)
1362 vw 1372 vw 1367 vw 1353 vw
t(NH
2
)
1335 w
1275 m
1138 m
1076 w
1041 s
983 w
1321 vw 1351 vw 1322 w
ν
ν
ring
1232 m
1231 m
1225 s
1181 vs
1078 w
1036 s
983 vw
919 vw
869 w
ring+ δ(CH)
1154 vw 1171 m
b
δ(CH)
1087 w
1047 m
998 vw
898 vw
869 m
1065 w
1028 m
1006 m
935 vw
859 w
829 m
677 w
625 w
-
b
b
Ring breathing
Ring breathing
b
δ
ring
889 vw
836 w
t(CH
2
)
842 w
Ring breathing
807 m
771 w
828 w
837 m
838 m
754 w
b
γ(CH)
785 vw
613 w
802 vw
677 m
r(NH
2
2
)
)
597 w
635 w
r(NH
585 w
566 vw
518 w
566 vw
533 vw
494 vw
606 vw
545 w
b
γ
ring
517 m
496 w
-
b
γ(CC)
501 w
532 w
524 vw
Abbreviations used: ν, stretching; δ, in plane deformation; γ, out of plane deformation; w, wagging; t, twisting; r, rocking; s,
strong; m, medium; w, weak; sh, shoulder; v, very.
a
Taken from Ref. [26].
b
Taken from Ref. [27].

25
2-
Table S2. The vibrational wavenumbers of the [M(CN)
4
] [M(II) = Ni(II) or Pd(II)] group in
-1
the complexes (cm ).
Assignments [31, 32]
2 4
K [Ni(CN) ]·H
2
O
K [Pd(CN)
2
4
2
]·H O
1
2
A
1g, υ(C≡N)
(2160) vs
(2137) m
2122 vs
2084 w
540 w
443 w
-
(2169) vs
(2159) s
2135 vs
2097 w
486 w
-
(2185) vs
(2137) s
(2206) vs
(2166) vs
B1g, ν(C≡N)
E
u
, ν(C≡N)
2173 vs, 2126 vs, 2122 vs
2190 m, 2177 s, 2144 w, 2141 m
1
3
ν( CN)
2085 vw
2076 sh
532 vw
451 vw
(436) w
433 m
E
u
, ν(M-C)
-
A
A
E
2u, π(M-CN)
441 vw
-
1g, ν(M-C)
(436) w
400 m
u
, δ(M-CN)
417 s
419 m
Abbreviations used; s strong, m medium, w weak, v very. The symbols ν, δ, and π refer to valence, in-plane and
out-of-plane vibrations, respectively. *Raman spectra are given in parenthesis.

26
Figure S1. The FT-IR spectra of 4aepy and the complexes.

27
Figure S2. The Raman spectra of the complexes.

28
Figure S3. The TG, DTG and DTA curves of 1.
Figure S4. The TG, DTG and DTA curves of 2.

29
Graphical Abstract: