One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

Accepted Manuscript One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties Dursun Karaağaç, Güneş Süheyla Kürkçüoğlu, Mustafa Şenyel, Onur Şahin PII:

S0022-2860(16)30612-3

DOI:

10.1016/j.molstruc.2016.06.036

Reference:

MOLSTR 22655

To appear in:

Journal of Molecular Structure

Received Date: 18 March 2016 Revised Date:

11 June 2016

Accepted Date: 13 June 2016

Please cite this article as: D. Karaağaç, G.S. Kürkçüoğlu, M. Şenyel, O. Şahin, One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.06.036. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT

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Graphical Abstract:

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ACCEPTED MANUSCRIPT 1

One dimensional coordination polymers: Synthesis, crystal

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structures and spectroscopic properties

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Dursun Karaağaça, Güneş Süheyla Kürkçüoğlub,*, Mustafa Şenyelc and Onur Şahind

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a

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b

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26480 Eskişehir, Turkey

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c

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Turkey

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Eskişehir Osmangazi University, Faculty of Arts and Sciences, Department of Physics, TR-

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Anadolu University, Faculty of Sciences, Department of Physics, TR-26470 Eskişehir,

Sinop University, Scientific and Technological Research Application and Research Center,

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Ulubatlı Hasan Anatolian High School, TR-16320 Bursa, Turkey

TR-57000 Sinop, Turkey

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Abstract Two

new

one

dimensional

(1D)

cyanide

complexes,

namely

[M(4-

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aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)),

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have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy,

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single crystal X-ray diffraction, thermal and elemental analyses techniques. The

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crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize

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in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four

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cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter

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ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry,

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the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate

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ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar

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each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D

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supramolecular network. Vibration assignments of all the observed bands are given and the

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spectral features also supported to the crystal structures of the complexes.

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ACCEPTED MANUSCRIPT Keywords: Tetracyanoplatinate(II) complex, Copper(II) complex, Zinc(II) complex, 4-(2-

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aminoethyl)pyridine complex, Vibrational spectra, Crystal structure.

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E-mail: [email protected] (G.S. Kürkçüoğlu).

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1. Introduction

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Cyanide metal complexes have attracted great interest because of a variety of desired features,

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depending on the used metal centers and auxiliary ligands. Therefore, these complexes show

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high structural variability due to binding to metal atom with different coordination numbers of

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the cyanide ligand. This structural variability was explored previously in the syntheses of

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various types of cyanometallates [1, 2]. Cyanometallates have useful building blocks for

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various dimensional coordination polymeric networks such as the dicyanides in linear

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geometry [M(CN)2]− (M = Cu, Ag, Au), the tetracyanides in square planar geometry

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[M(CN)4]2− (M = Ni, Pd, Pt) and the hexacyanides in octahedral geometry [M(CN)6]3− (M =

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Ti, V, Cr, Mn, Fe, Co) [3]. To the best of our knowledge, there are a few reports related with

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the tetracyanoplatinate(II) complexes [4-8]. In the literature, structural properties of cyanide

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metal complexes synthesized using these building blocks are usually examined such as

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[Cu(hydeten)2Pt(CN)4]

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{[Cu(tmen)][Pt(CN)4]n

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CN)2(CN)2]n (hepH = 2-pyridineethanol) [11] and Cd(H2O)2(µ-ampy)Pt(µ-CN)2(CN)2]n

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(ampy = 4-aminomethylpyridine) [12].

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(tmen

=

N-(2-hydroxyethyl-ethylenediamine)

tetramethylethylenediamine)

[10],

[9],

[Zn(hepH)2Pt(µ-

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These building blocks of cyanometallates have useful functional properties, and they

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can act as clathrate hosts [13] and single molecular magnets [14], and may also exhibit

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electrical conductivity [1]. Cyanide metal supramolecular structures can occur by non-

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covalent interactions, such as electrostatic interactions, hydrogen bond interactions, π-π, C-

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H···M, C-H···π, M···π interactions. Hydrogen bond interactions may plays a crucial role in

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packaging and stabilizing of the molecular cluster and may also play an important role as a

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ACCEPTED MANUSCRIPT 51

possible exchange path for the magnetic interactions [15-17]. On the other hand, hydrogen

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bond interactions are effective in forming to supramolecular structures of the metalloligands

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[18]. We report here the synthesis, elemental analyses, spectral (FT-IR and Raman)

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properties and thermal analyses of two new one dimensional (1D) cyanide complexes, [Cu(4-

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aepy)2(H2O)2][Pt(CN)4] (1) and [Zn(4-aepy)2(H2O)2][Pt(CN)4] (2) (4-aepy = 4-(2-

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aminoethyl)pyridine). The crystal structures of the complexes have been determined by X-ray

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single crystal diffraction. The spectral data are structurally consistent with those of obtained

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from single crystal X-ray studies. According to the obtained results, in complexes 1 and 2, 1D

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coordination polymer occurs with a combination of metalloligands and adjacent 1D

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coordination polymers are connected by O–H···N hydrogen bonds. The crystal packing of the

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complexes are stabilized through the hydrogen bonds and Pt⋯π interactions, resulting in a 3D

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framework.

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2. Experimental

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2.1. Material and Instrumentation

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Copper(II) chloride dihydrate (CuCl2·2H2O, 99%), zinc(II) chloride (ZnCl2, 96%), platinum(II)

chloride

(PtCl2,

99%),

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aminoethyl)pyridine (C7H10N2, 96%) were purchased from commercial sources and used

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without further purification. The FT-IR spectra of the complexes were recorded as KBr pellets

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in the range of 4000-400 cm-1 (2 cm-1 resolution) on a Perkin Elmer 100 FT-IR spectrometer,

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which was calibrated using polystyrene and CO2 bands. The Raman spectra of the complexes

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were recorded in the range of 4000-100 cm-1 on a Bruker Senterra Dispersive Raman

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instrument using 785 nm laser excitation. A Perkin Elmer Diamond TG/DTA thermal

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analyzer was used to record simultaneous TG, DTG and DTA curves in a static air

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atmosphere at a heating rate of 10 K min-1 in the temperature range of 30-800 ºC using

potassium

cyanide

(KCN,

96%)

and

4-(2-

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ACCEPTED MANUSCRIPT platinum crucibles. Elemental analyses were carried out on a LECO, CHNS-932 analyzer for

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C, H and N at the Middle East Technical University Central Laboratory.

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2.2. Crystallographic data collection and refinement

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Suitable crystals of 1 and 2 were selected for data collection which was performed on a

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Bruker APEX-II diffractometer equipped with a graphite-monochromatic Mo-Kα radiation.

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The structures were solved by direct methods using SHELXS-97 [19] and refined by full-

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matrix least-squares methods on F2 using SHELXL-97 [19] from within the WINGX [20]

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suite of software. All non-hydrogen atoms were refined with anisotropic parameters. The H

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atoms of C atoms were located from different maps and then treated as riding atoms with C-H

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distances of 0.93-0.97 Å. All other H atoms were located in a difference map refined subject

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to a DFIX restraint. In 1 and 2, the large s.u. values and displacement parameters of some

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aqua oxygen atoms (O1 in 1 and O2 in 2) in the molecule are caused by disorder. This

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disorder was modelled as two different orientations, seen in Figs. 3 and 4, with occupancy

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factors of 0.5 and 0.5, respectively. In the course of structural check for complex 1, we found

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that some atoms met NPD problem. In order to avoid this, a restraint comment of ISOR was

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used to refine the some atoms. In the absence of significant anomalous dispersion effects 1018

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in 1 and 1001 in 2 Friedel pairs were merged before the refinement and the assignment of

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absolute configuration is arbitrary. Molecular diagrams were created using MERCURY [21].

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Supramolecular analyses were made and the diagrams were prepared with the aid of

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PLATON [22].

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2.3. Synthesis of the complexes

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2.3.1. M[Pt(CN)4]·H2O (M = Cu(II) or Zn(II))

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To water solution of PtCl2 (0.265 g, 1 mmol) was added a solution of KCN (0.260 g, 4 mmol)

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in water (10 mL) and colorless K2[Pt(CN)4]·3H2O was crystallized. K2[Pt(CN)4]·3H2O (0.431

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g, 1 mmol) to which was added metal chloride solutions (CuCl2·2H2O = 0.170 g or ZnCl2 =

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ACCEPTED MANUSCRIPT 0.136 g, 1 mmol) became M[Pt(CN)4]·H2O. The colors of Cu[Pt(CN)4]·H2O and

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Zn[Pt(CN)4]·H2O are blue and yellow, respectively.

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2.3.2. [M(4-aepy)2(H2O)2][Pt(CN)4], (M = Cu(II) or Zn(II))

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A mixture of Cu[Pt(CN)4]·H2O (0.380 g, 1 mmol) in water (10 mL) and 4-aepy (0.244 g, 2

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mmol) in ethanol (10 mL) was stirred at 55 °C for 4 h in a temperature-controlled bath. The

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obtained solution was filtered and kept for crystallization at room temperature. Blue [Cu(4-

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aepy)2(H2O)2][Pt(CN)4] (1) block-shaped single crystals were obtained by slow evaporation

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after one week. The complex was analyzed for C, H, and N with the following results: [Cu(4-

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aepy)2(H2O)2][Pt(CN)4] (1): Anal. Calcd. for C18H24N8O2CuPt (Mw = 643.06 g/mol) : C,

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33.26 (33.62); H, 3.76 (3.76); N, 17.34 (17.43). Complex 2 was obtained in a similar method

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to 1, but Cu(II) was replaced by Zn (II) (0.382 g). Yellow crystals of 2 were obtained. [Zn(4-

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aepy)2(H2O)2][Pt(CN)4] (2), Anal. Calcd. for C18H24N8O2ZnPt (2) (Mw = 644.90 g/mol) : C,

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33.11 (33.52); H, 3.72 (3.75); N, 18.58 (19.51). Elemental analyses of the complexes are in

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good agreement with the calculated values.

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3. Results and Discussion

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3.1. Vibrational Spectra

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3.1.1. Ligand vibrations

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The FT-IR and Raman spectra of the complexes are given in Figs. 1 and 2,

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respectively. The spectra of the complexes are found to be very similar. The FT-IR spectra of

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the complexes contain more absorption bands originating from ν(OH) and δ(OH) vibrations.

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The most important vibration bands of the aqua ligand are asymmetric and symmetric ν(OH)

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stretching vibration bands and δ(OH2) deformation vibration band. In the FT-IR spectra of the

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complexes, the ν (OH) stretching vibration bands of aqua ligand are observed at 3359 cm-1 for

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1 and 3340 cm-1 for 2, and δ(OH2) deformation vibration bands are identified at 1632 cm-1 for

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1 and 1665 cm-1 for 2. These bands are not observed in the Raman spectra.

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ACCEPTED MANUSCRIPT The vibrational wavenumbers confirming the presence of the 4-aepy molecule in the

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complexes are listed in Table 1. Individual bands in Table 1 are assigned according to [23]

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and [24]. Since there is no the theoretical and experimental vibration assignments so far in the

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literature of 4-aepy molecule, the vibration assignments of 2-aminomethylpyridine [23] and 2-

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aminoethylpyridine [24] molecules for vibration assignments of 4-aepy molecule are used.

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The vibration bands at 3362, 3292 and 3181 cm-1 correspond to the ν(NH) stretching vibration

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of free 4-aepy. This band in FT-IR and Raman spectra of the complexes shifts to the low

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frequency region according to the free 4-aepy. The δ(NH) deformation vibration of the NH2

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group identified at 1605 cm-1 in the free ligand and observed upward shifts according to the

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free ligand in the complexes. These observations expressly show coordination of the amine

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group of 4-aepy to the M(II) ion. The ν(CH) stretching vibration and δ(CH2) deformation

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vibrations occur in the 3072-2993 cm-1 and the 1500-1133 cm-1 ranges as weak bands,

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respectively. The frequencies of the ν(CH) in the infrared spectrum of free 4-aepy at 2993,

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3031 and 3072 cm-1 shifted to a low or high frequency regions in the complexes. The w(CH)

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wagging (1418 cm-1), δ(CH) deformation (1070 cm-1) and γ(CH) deformation (771 cm-1)

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vibrations also observed upward frequency shifts in the spectra of the complexes. The strong

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and medium band identified in the 1300-517 cm-1 range are assigned to the νring, δring, γring and

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the ring breathing vibrations of free 4-aepy. As a result, certain pyridine ring vibrations,

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especially the νring vibration (1221 cm-1) and the ring breathing vibration (807 cm-1) found to

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increase in value upon coordination. Analogous shifts on coordination are observed in

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pyridine [25], 3-aminopyridine [26], 4-aminopyridine [27] and 4-aminomethylpyridine [7].

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According to the spectroscopic results, both the ring nitrogen and the amino nitrogen are

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involved in formation of complexes.

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3.1.2. [Pt(CN)4] 2- group vibrations

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ACCEPTED MANUSCRIPT The vibrational wavenumbers of the [Pt(CN)4]2- group for the complexes are given in

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Table 2, together with the vibration wavenumbers of [Pt(CN)4]2- and K2[Pt(CN)4]·3H2O [28,

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29] for comparison. The ν(CN) stretching vibration of ionic cyanides as NaCN and KCN is

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observed in 2080 cm-1 [30]. This peak shifted to 2136 cm-1 in K2[Pt(CN)4]·3H2O as a result of

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coordination to Pt(II) metal. In the Raman spectra, the cyanide stretching vibration

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wavenumbers are observed at 2173 and 2153 cm-1 for K2[Pt(CN)4]·3H2O. The ν(CN)

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stretching vibration band in the vibration spectra of the complexes is found between 2000 and

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2200 cm-1 [31, 32]. The cyanide groups can be found in bridged or terminal positions in the

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cyanide metal complexes. In this case, the ν(CN) stretching vibration band produces two

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bands as a result of the existence of bridged and terminal cyanide groups in the structures.

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According to the literature, the bridging cyanide vibration wavenumbers in cyanide-bridged

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complexes are generally observed at higher vibration wavenumbers [6, 11]. Two bands are

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seen at 2128 cm-1 and 2134 cm-1 for 1 and 2127 cm-1 and 2140 cm-1 for 2 in the FT-IR spectra

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of the complexes. The ν(CN) stretching vibration wavenumbers in the complexes are found to

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be more close to that of the [Pt(CN)4]2-. Therefore, cyanide groups in the complexes show

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terminal character. In the literature, similar observations have been made for some cyanide

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complexes [2, 33]. The presence of two ν(CN) stretching vibration wavenumbers also

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indicates deviation from the ideal D4h geometry. A1g and B1g modes in the Raman spectra of

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the complexes are observed at 2173 cm-1 for 1 and 2156 and 2179 cm-1 for 2. According to

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these spectral data, A1g and B1g modes of 1 and 2 shifted to a higher frequency range around

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5-11 cm-1 when compared with that of the [Pt(CN)4]2- (Table 2). These spectral data are in

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agreement with the crystallographic data presented. According to this, C8≡N5 and C9≡N6

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bond lengths are found as 1.135 Å and 1.156 Å in 1, C8≡N3 and C9≡N4 bond lengths are

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found as 1.143 Å and 1.151 Å in 2, respectively. In the FT-IR spectra of 1 and 2, ν(PtC)

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stretching and δ(PtCN) bending vibration wavenumbers are observed at 529 and 414 cm-1 for

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1 and 411 cm-1 for 2, respectively (Table 2). These bands shift to a higher frequency value in

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the FT-IR spectra of the complexes. The ν(PtC) stretching vibration wavenumbers in the

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Raman spectra of the complexes are identified at 484 cm-1 for 1 and 480 cm-1 for 2.

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3.2. Structural analyses Details of data collection and crystal structure determinations are given in Table 3.

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Selected bond lengths and angles for 1-2 are collected in Table 4, and the hydrogen bond

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parameters for complexes 1-2 is given in Table 5. The X-ray single crystal study shows that

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complexes 1-2 have 1D coordination polymer. The molecular structures of the complexes 1-2,

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with the atom numbering schemes, are shown in Figs. 3 and 4. The asymmetric units of the

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complexes 1-2 contain one Pt(II) ion, one M(II) ion [M(II) = Zn(II) in 1 and Cu(II) in 2], two

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cyanide ligands, one 4-aepy ligand and two half aqua ligands. Each Pt(II) ion is located on a

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centre of symmetry and is coordinated by four carbon atoms from four different cyanide

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ligands, thus showing a square-planar coordination geometry. Each M(II) ion [M(II) = Zn(II)

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in 1 and Cu(II) in 2] is located on a centre of symmetry and is coordinated by four nitrogen

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atoms from four different 4-aepy ligands and two oxygen atoms from aqua ligands. The

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geometry around the M(II) ion [M(II) = Zn(II) in 1 and Cu(II) in 2] is that of a distorted

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octahedron. The M(II) ions [M(II) = Zn(II) in 1 and Cu(II) in 2] are bridged by 4-aepy ligands

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to

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metalloligands produces 1D coordination polymer, with the M···M separation is 8.398 Å in 1

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and 8.254 Å in 2 (Fig. 5a). Adjacent 1D coordination polymers are further joined by O–H···N

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hydrogen bonds (Fig. 5b). In 1 and 2, the hydrogen bonds and Pt⋯π interactions link the

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molecules to form a 3D supramolecular architecture and provide the crystal packing (Fig. 5c).

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The presence of the intermolecular Pt⋯π interactions between Pt and pyridine rings of the 4-

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aepy ligands is the most striking feature of the complexes (Fig. 6).

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3.3. Thermal Analyses

[M2(C7H10N2)2]

metalloligand.

The

combination

of

[M2(C7H10N2)2]

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ACCEPTED MANUSCRIPT Thermal behaviors of the complexes are performed by TG, DTG and DTA methods in

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the temperature range of 30-800 °C in the static air atmosphere. Thermal decomposition

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curves of the complexes are given in Figs. 7 and 8, respectively. Thermal decomposition of

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complexes 1 and 2 proceeds in three and five degradation steps, respectively (Figs. 7 and 8).

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The complexes are thermally stable up to 37 for 1 and 84 ºC for 2. 1 exhibits three distinct

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decomposition stages. In the first stage, two aqua ligands of the complex are released in the

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temperature range 37-95 ºC (Found (Calcd.) % = 5.99 (5.60)). The second stage between 95

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and 436 ºC are related to the release of the two 4-aepy ligands (DTAmax = 181 ºC, found 36.88

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%, calcd. 37.99 %). In the following stage, the strong exothermic peak in the temperature

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range 436-456 ºC (DTAmax = 452 ºC) is associated with the burning of the cyanide ligands.

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The final solid products of thermal decompositions were identified by FT-IR spectroscopy as

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CuO+Pt (Found (Calcd.) (%) = 42.06 (42.70)).

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Thermal decomposition of 2 begins at 85 °C and shows five distinguishable

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degradation at the temperatures of 107 °C, 149 °C, 205 °C, 272 °C and 506 °C stages. In the

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first stage, 2 loses to two aqua ligands between 85 and 122 °C (found 5.87 %, calcd. 5.58 %).

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Then, three endothermic decomposition steps at 149 °C, 205 °C and 272 °C follow the second

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step as shown in Fig. 8 and two 4-aepy ligands are released in the temperature range 122-456

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ºC (Found (Calcd.) (%) = 37.44 (37.88). The final stage at 456-535 °C (DTAmax = 502 ºC) is

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associated with the burning of the cyanide ligands. The final solid products of thermal

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decompositions were identified by FT-IR spectroscopy as ZnO+Pt (Found (Calcd.) (%) =

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42.47 (42.87)). According to the thermal analyses results, complex 2 is thermally more stable

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than complex 1. Such decompositions were observed for other cyanide complexes [34-37].

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4. Conclusion

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Two new one dimensional (1D) cyanide complexes, [Cu(4-aepy)2(H2O)2][Pt(CN)4]

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(1), and [Zn(4-aepy)2(H2O)2][Pt(CN)4] (2), are synthesized and characterized. The structures

10

ACCEPTED MANUSCRIPT of the complexes are determined by vibration (FT-IR and Raman) spectroscopy, X-ray single

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crystal diffraction, thermal and elemental analysis techniques. In the crystal structures of 1

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and 2, the coordination environment of the Cu(II) or Zn(II) ions described as distorted

228

octahedral geometry, whereas around the Pt(II) center have square planar geometry.

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According to the crystallographic data, the crystal packing of 1 and 2 are a composite of

230

intermolecular hydrogen bonding and Pt⋯π interactions. Vibration assignments are given for

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all the observed bands and the spectral features support the structures of cyanide complexes.

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FT-IR and Raman spectral analyses indicate that complexes 1 and 2 are isostructural. The

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results obtained from vibrational data are compared with the X-ray data and the results are

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shown supporting each other.

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Supplementary material

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Crystallographic data for the structural analysis have been deposited with the

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Cambridge Crystallographic Data Centre, CCDC No. 1455090 for 1 and 1455091 for 2.

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Copies of this information may be obtained free of charge from the Director, CCDC, 12

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Union

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[email protected] or www: http://www.ccdc.cam.ac.uk).

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Acknowledgements

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The authors acknowledge Scientific and Technological Research Application and Research

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Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.

CB2

1EZ,

UK

(fax:

+44-1223-336033;

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Cambridge

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Road,

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e-mail:

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ACCEPTED MANUSCRIPT References

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AC C

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245

12

ACCEPTED MANUSCRIPT [16] V.B. Medaković, M.K. Milčić, G.A. Bogdanović, S.D. Zarić, J. Inorg. Biochem. 98

270

(2004) 1867.

271

[17] M.J. Calhorda, Chem. Commun. (2000) 801.

272

[18] S.-i. Noro, S. Kitagawa, T. Wada, Inorg. Chim. Acta 358 (2005) 423.

273

[19] G. M. Sheldrick, Acta Cryst. A64 (2008) 112.

274

[20] L. J. Farrugia, J. Apply. Cryst. 32 (1999) 837.

275

[21] Mercury, version 3.0; CCDC, available online via ccdc.cam.ac.uk/products/mercury.

276

[22] A. L. Spek, PLATON-a multipurpose crystallographic tool. Utrecht University, Utrecht

277

(2005).

278

[23] M.L. Niven, G.C. Percy, Trans. Metal Chem. 3 (1978) 267.

279

[24] D. Rastogi, K. Sharma, J. Inorg. Nucl. Chem. 36 (1974) 2219.

280

[25] S. Akyüz, A. Dempster, R. Morehouse, S. Suzuki, J. Mol. Struct. 17 (1973) 105.

281

[26] S. Akyüz, J. Mol. Struct. 449 (1998) 23.

282

[27] S. Akyüz, J. Mol. Struct. 482 (1999) 171.

283

[28] G.J. Kubas, L.H. Jones, Inorg. Chem. 13 (1974) 2816.

284

[29] D. Sweeny, I. Nakagawa, S.I. Mizushima, J. Quagliano, J. Am. Chem. Soc. 78 (1956)

285

889.

286

[30] S. Akyüz, Vib. Spectrosc. 22 (2000) 49.

287

[31] A.G. Sharpe, The chemistry of cyano complexes of the transition metals, Academic Press

288

London 1976.

289

[32] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds,

290

Part B: Applications in Coordination, Organometallic, and Bioinorganic Chemistry, 5th ed.,

291

Wiley, New York, 1997.

292

[33] D. Karaağaç, G.S. Kürkçüoğlu, O.Z. Yeşilel, T. Hökelek, Y. Süzen, Syntheses, Inorg.

293

Chim. Acta 406 (2013) 73.

AC C

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269

13

ACCEPTED MANUSCRIPT [34] V.T. Yilmaz, E. Senel, C. Kazak, J. Inorg. Organometal. Polym. Mater. 18 (2008) 407.

295

[35] A. Karadağ, İ. Önal, A. Şenocak, İ. Uçar, A. Bulut, O. Büyükgüngör, Polyhedron 27

296

(2008) 223.

297

[36] I. Potočňák, M. Vavra, E. Čižmár, K. Tibenská, A. Orendáčová, D. Steinborn, C.

298

Wagner, M. Dušek, K. Fejfarová, H. Schmidt, J. Solid State Chem. 179 (2006) 1965-1976.

299

[37] S.C. Manna, J. Ribas, E. Zangrando, N.R. Chaudhuri, Polyhedron 26 (2007) 3189.

RI PT

294

AC C

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M AN U

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300

14

ACCEPTED MANUSCRIPT Figure Captions

302

Fig. 1. The FT-IR spectra of 4-aepy and the complexes.

303

Fig. 2. The Raman spectra of the complexes.

304

Fig. 3. The molecular structure of 1 showing the atom numbering scheme [(i) x, y, z+1; (ii) -

305

x+2, y, -z+1; (iii) -x+2, y, -z+2; (iv) -x+1, y, -z+1; (v) x, y, z-1].

306

Fig. 4. The molecular structure of 2 showing the atom numbering scheme [(i) x, y, z+1; (ii) -

307

x+1, y, -z; (iii) -x+1, y, -z+1; (iv) -x, y, -z; (v) x, y, z-1].

308

Fig. 5. (a) An infinite 1D layer, (b) the O-H⋅⋅⋅N hydrogen bonds and (c) 3D network in 1-2.

309

Fig. 6. Pt⋯π interactions in 1.

310

Fig. 7. The TG, DTG and DTA curves of 1.

311

Fig. 8. The TG, DTG and DTA curves of 2.

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301

15

ACCEPTED MANUSCRIPT Table 1. The vibration wavenumbers of 4-aepy in the complexes (cm-1) Assignmentsa

4-aepy

1

2

FT-IR

Raman

FT-IR

Raman

νas(NH2)

3362 vs

3306 m

3319 vw

3319 m

3267 vw

νs(NH2)

3292 vs

3244 m

3248 w

3265 w

3249 vw

ν(NH2)

3181 vw

3141 vw

3179 vw

3149 w

3155 vw

ν(CH)

3072 w

3085 vw

3092 m

3083 vw

3088 vw

ν(CH)

3031 w

3002 vw

3056 w

3003 vw

3010 vw

ν(CH)

RI PT

(liquid)

2973 vw

3009 vw

2978 vw

2964 vw

ν(C-CH2-NH2)

2940 w

2951 vw

2941 vw

2936 vw

2938 vw

ν(C-CH2-NH2)

b

2868 w

2862 vw

2868 vw

2866 vw

2873 vw

1663 sh

1638 sh

1666 vw

1666 w

1672 vw

1605 vs

1620 s

1630 w

1617 s

1558 s

1587 m

1595 vw

1585 s

1498 w

1503 w

1512 vw

1504 vw

1461 vw

1463 w

1442 w

w(CH)

δ(NH2) ν(C=C)+ν(C=N)

b

δ(CH2) δ (CH2)

1627 m

1592 w

1516 w

M AN U

ν(C=N)

SC

2993 vw b

1464 vw

1477 vw

1443 vw

1462 vw

1439 vw

1450 vw

1418 vs

1429 m

1429 vw

1425 s

1432 vw

t(CH)

1386 w

1377 m

1387 vw

1375 m

1377 w

νring+ δ(CH)

1360 w

1363 vw

1366 vw

1368 vw

1350 vw

t(NH2)

1320 w

1344 vw

-

1324 vw

1334 w

νring

1221 s

1224 s

1224 m

1226 s

1222 s

1133 w

1137 m

1138 vw

1162 m

1170 w

ν(C=N)+ν(C=N)

νring+ δ(CH) δ(CH)

b

TE D

1474 vw

b

1070 m

1096 w

1081 vw

1092 w

1082 w

Ring breathing

b

1029 w

1038 w

1032 m

1041 m

1052 m

Ring breathing

b

1000 m

1002 m

978 vw

998 s

1025 vs

896 w

934 w

942 w

930 w

939 m

842 w

873 vw

873 vw

819 m

877 m

807 m

825 s

843 vw

811 m

822 w

t(CH2)

EP

δring

b

Ring breathing γ(CH)

b

771 w

790 w

795 w

786 w

795 m

597 w

595 w

609 vw

729 w

668 w

585 w

-

681 vw

588 w

606 w

517 m

509 w

525 vw

512 vw

518 vw

496 w

496 vw

512 vw

498 w

503 vw

AC C

r(NH2) r(NH2) γring

b

γ(CC)

b

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. [23].

b

Taken from Ref. [24].

16

ACCEPTED MANUSCRIPT Table 2. The vibrational wavenumbers of the [Pt(CN)4]2- group in the complexes (cm-1). Assignments [28, 29]

[Pt(CN)4]2- [28]

K2[Pt(CN)4]·3H2O [28]

K2[Pt(CN)4]·3H2O

1

2

A1g, ν(CN)

(2168)

(2165)

(2173) vs

(2173) vs

(2179) s

B1g, ν(CN)

(2148)

(2145)

(2153) m

-

(2156) m

Eu, ν(CN)

2133

2134

2136 vs

2134 m, 2128 s

2140 vs, 2127 vs

ν( CN)

2087

2087

2085 w

2090 vw

2093 vw

Eu, ν(PtC)

506

506

504 m

529 vw

-

A2u, π(PtCN)

-

468

428 vw

A1g, ν(PtC)

(469)

(467) w

(477) w

Eu, δ(PtCN)

407

407

407 s

473 vw

420 w

(484) vw

(480) w

414 m

411 w

RI PT

13

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.

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*Raman spectra are given in parenthesis

17

ACCEPTED MANUSCRIPT Table 3. Crystal data and structure refinement parameters for complexes 1-2. Crystal data

1

2

C18H24N8O2PtZn

C18H24N8O2PtCu

Formula weight

644.91

643.08

Crystal system

Monoclinic

Monoclinic

Space group

C2

C2

a (Å)

11.932 (5)

11.700 (5)

b (Å)

11.668 (4)

11.884 (4)

c (Å)

8.398 (5)

8.254 (5)

β (º)

111.569 (5)

110.183 (4)

V (Å3)

1087.3 (9)

1077.2 (9)

2 -3

SC

Z

RI PT

Empirical formula

2

Dc (g cm )

1.970

θ range (º)

2.5-27.5

Measured refls.

8095

7361

Independent refls.

2150

2119

Rint

0.050

0.031

S

1.07

1.15

R1/wR2

0.026/0.066

0.024/0.063

∆ρmax/∆ρmin (eÅ-3)

1.74/-1.61

1.16/-1.34

2.5-27.5

M AN U

TE D EP AC C

1.983

18

ACCEPTED MANUSCRIPT Table 4. Selected bond distances and angles for complexes 1-2 (Å, º) 1.918(17) 2.122(8)

Zn1–O1 Pt1–C8

2.40(2) 1.992(9)

Zn1–N1 Pt1–C9

2.255(6) 1.989(10)

C9–Pt1-C8

90.6(4)

O2–Zn1–O1

169.6(4)

O2–Zn1–N1

94.8(5)

Complex 2 Cu1–O1 Cu1–N2i

2.392(14) 1.985(8)

Cu1–O2 Pt1–C8

2.462(11) 1.994(10)

Cu1–N1 Pt1–C9

2.097(6) 1.989(11)

O2–Cu1–N1

90.17(4)

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C9–Pt1–C8 90.8(5) O2–Cu1–O1 167.5(2) Symmetry codes: (i) x, y, z+1 for 1; (i) x, y, z+1 for 2.

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Complex 1 Zn1–O2 Zn1–N2i

19

ACCEPTED MANUSCRIPT Table 5. Hydrogen-bond parameters for complexes 1-2 (Å, º) D–H· · ·A

D –H

H···A

D···A

D–H···A

0.76

2.22

2.665 (11)

117.8 (3)

Complex 1 O2–H2A···N4vi

0.91

2.39

3.268 (13)

160.7 (5)

vii

0.891 (17)

1.98

2.711 (19)

138.4 (11) 131.8 (5)

O1–H1A···N3

N2–H2B···N1ii Complex 2 C1–H1···O1

0.87

2.33

2.979 (9)

0.93

2.49

3.126 (17)

C5–H5···O2

0.93

2.58

3.18 (2)

0.93

2.39

3.09 (2)

0.83 (3)

2.05 (12)

2.555 (10)

C5–H5···O2

iii

O1–H1A···N4

vi ii

RI PT

N2–H2C···O2

v

126

122

132

119 (11)

AC C

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0.83 2.34 2.834 (11) 119 (1) N2–H2A···N1 Symmetry codes: (ii) −x+2, y, −z+1; (v) x, y, z−1; (vi) x+1/2, y−1/2, z; (vii) −x+3/2, y+1/2, −z+2 for 1; (ii) −x+1, y, −z; (iii) −x+1, y, −z+1; (vi) −x+1/2, y+1/2, −z+1 for 2.

20

M AN U

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ACCEPTED MANUSCRIPT

AC C

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Fig. 1. The FT-IR spectra of 4-aepy and the complexes.

21

M AN U

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ACCEPTED MANUSCRIPT

AC C

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Fig. 2. The Raman spectra of the complexes.

22

M AN U

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ACCEPTED MANUSCRIPT

AC C

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Fig. 3. The molecular structure of 1 showing the atom numbering scheme [(i) x, y, z+1; (ii) x+2, y, -z+1; (iii) –x+2, y, -z+2; (iv) -x+1, y, -z+1; (v) x, y, z-1].

23

SC

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ACCEPTED MANUSCRIPT

M AN U

Fig. 4. The molecular structure of 2 showing the atom numbering scheme [(i) x, y, z+1; (ii) -

AC C

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x+1, y, -z; (iii) -x+1, y, -z+1; (iv) -x, y, -z; (v) x, y, z-1].

24

ACCEPTED MANUSCRIPT

TE D

M AN U

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(a)

AC C

EP

(b)

(c) Fig. 5. (a) An infinite 1D layer, (b) the O–H···N hydrogen bonds and (c) 3D network in 1-2.

25

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

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M AN U

Fig. 6. Pt⋯π interactions in 1.

26

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

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M AN U

Fig. 7. The TG, DTG and DTA curves of 1.

27

SC

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ACCEPTED MANUSCRIPT

AC C

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Fig. 8. The TG, DTG and DTA curves of 2.

ACCEPTED MANUSCRIPT Hightlights ►New heterometallic cyanide complexes were synthesized. ► The complexes were characterized by different analysis techniques ► The Pt(II) ions are coordinated in square planar geometry.

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► Pt⋯π interactions have observed between the Pt(II) ion and pyridine rings.