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Zeitschrift für Kristallographie - Crystalline Materials

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Volume 230, Issue 3


One-dimensional cyanide- and fumarate-bridged heteronuclear complex, poly[μ-fumaratotetraaminedizinc(II)di-μ-cyanodicyanonickel(II) dihydrate]

Elvan Sayın
  • The Institute of Science, Department of Physics, Eskişehir Osmangazi University, TR-26480 Eskişehir, Turkey
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Güneş Süheyla Kürkçüoğlu
  • Corresponding author
  • Faculty of Arts and Sciences, Department of Physics, Eskişehir Osmangazi University, TR-26480 Eskişehir, Turkey
  • Email
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Okan Zafer Yeşilel
  • Faculty of Arts and Sciences, Department of Chemistry, Eskişehir Osmangazi University, TR-26480 Eskişehir, Turkey
  • Other articles by this author:
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/ Tuncer Hökelek
  • Faculty of Engineering, Department of Physics, Hacettepe University, TR-06800, Beytepe Ankara, Turkey
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  • De Gruyter OnlineGoogle Scholar
Published Online: 2015-02-10 | DOI: https://doi.org/10.1515/zkri-2014-1818


Cyanide- and fumarate-bridged bimetallic complex, poly[μ-fumaratotetraaminedizinc(II)di-μ-cyanodicyanonickel(II) dihydrate], {[Zn2(μ-fum)(NH3)4Ni(μ-CN)2(CN)2]·2H2O}n (1) (H2fum = Fumaric acid) was synthesized and structurally characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction and elemental and thermal analyses techniques. The structure of the complex consists of a one-dimensional polymeric chain, in which the Zn(II) and Ni(II) ions are linked by CN groups. The Ni(II) ion is four coordinated with four cyanide-carbon atoms in a square planar arrangement and the Zn(II) ions are four coordinated with one cyanide nitrogen atom, two amine nitrogen atoms and one fumarate oxygen atom, in a distorted tetrahedral arrangement. In the complex, the adjacent chains are connected by strong O–H···O, O–H···N, N–H···O and N–H···N hydrogen bonding interactions to form a three dimensional network.

This article offers supplementary material which is provided at the end of the article.

Keywords: cyanide complex; fumarate complex; heteronuclear complex; one-dimensional complex; vibrational spectra


The studies related to the self-assembly of organic and inorganic molecules in the solid state have become an influential research action because of their physical and chemical specifications as well as to their applications in the field of material science, coordination chemistry and the crystal engineering [1–6]. In recent years, designs and constructions of the cyanide complexes have attracted great interest by reason of the linked functions of the cyanide ligand and their potential applications [7, 8]. Generally, the network structures of the cyanide complexes can be designed by checking the size, shape, and charges of the combination of multiply organic linkers and/or inorganic metal connecting (0-D, 1-D chains, 2-D grids and 3-D networks) [9–12].

Fumaric acid, which is known as (E)-butenedioic acid, is among the organic complexes commonly available in nature, and is an important intermediate in biosyntheses of the organic acids, and is known to already compose complexes with other organic molecules [13, 14]. Fumaric acid is good binding molecule that can generate multiple network structures by coordinating either as monodentate or as multidentate ligand [15]. It has been found that almost in all the cases the fumarate acts as a bridging ligand from its carboxylate groups between metal centers. The fumaric acid ligands display two types of coordination modes, bis(bidentate) chelating and bis(monodentate) bridging [16]. In previous studies, some complexes of fumarate with Ag(I) and Cu(II) ions were described in several papers [15, 16]; however, to the best of our knowledge, neither crystallographic nor spectroscopic data have been reported so far that would explicitly allow the structural analyses of Zn(II) fumarate complex of tetracyanonickelate(II) anions.

We report herein the crystal structure of the coordination polymer, poly[μ-fumaratotetraaminedizinc(II)di-μ-cyanodicyanonickel(II) dihydrate], {[Zn2(μ-fum)(NH3)4Ni(μ-CN)2(CN)2]·2H2O}n. We have characterized its structure with vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, elemental and thermal analyses techniques.


Material and instrumentation

Zinc(II) chloride (ZnCl2-96%, Merck), nickel(II) chloride hexahydrate (NiCl2·6H2O- 97%, Riedel-de Haen), potassium cyanide (KCN-96%, Sigma-Aldrich), ammonium hydroxide solution 26% and fumaric acid (C4H4O4-99%, Fluka) were purchased from commercial sources and used without further purification. The formula as well as the constitution of the molecule has been identified by elemental analysis, FT-IR and Raman spectroscopies, thermal analysis and single crystal X-ray diffraction. Elemental analysis (C, H and N) was carried out by using a CHNS-932 (LECO) Elemental Analyzer at Middle East Technical University Central Laboratory in Ankara, Turkey. FT-IR spectrum of the complex was carried out at room temperature by Perkin-Elmer FT-IR 100 spectrometer in the region of 4000 to 250 cm–1. Resolution was set up to 4 cm–1, signal/noise ratio was established by 16 scans with Attenuated Total Reflectance at Eskişehir Osmangazi University, Physics Department in Eskişehir, Turkey, and Raman spectrum of the complex has been recorded in the region of 4000 to 250 cm–1 via Bruker Senterra Dispersive Raman Microscope using the 785 nm line of a 3B diode laser at Anadolu University, Physics Department in Eskişehir, Turkey. The TG and DTG measurements were carried out using Perkin-Elmer Diamond TG/DTA Thermal analysis instrument in the static air atmosphere with heating rate 10 K min–1 in the temperature range of 30–700 °C using platinum crucibles at Eskişehir Osmangazi University, Chemistry Department in Eskişehir, Turkey.

Synthesis of the complex

K2[Ni(CN)4] was prepared by mixing stoichiometric amounts of nickel(II) chloride with potassium cyanide in water solution. K2[Ni(CN)4]·H2O (0.259 g, 1 mmol) to which was added ZnCl2 (0.136 g, 1 mmol) became slurry of Zn[Ni(CN)4]·H2O. The mixture was refluxed with stirring for 3 h at 50 °C in a temperature-controlled bath, and then cooled to room temperature. The complex 1 was disolved of [ZnNi(CN)4]·H2O (2 mmol, 0.492 g) in water (20 mL). To this solution, fumaric acid (2 mmol, 0.116) dissolved in water (10 mL) was added with continuous stirring. After a few minutes, ammonium hydroxide solution was added a few drops to this solution with continuous stirring approximately for 4 h at 55 °C in a temperature-controlled bath. The solution obtained was filtered and kept for crystallization at room temperature. Suitable crystals for X-ray measurements were formed by slow evaporation after a week. The freshly prepared complex was analyzed for C, H and N: Yield: 0.316 g, 30.91% based on ZnCl2. Anal. Found (Calc.) (%) for C8H18N8NiO6Zn2 (1) (MW = 511.75 g/mol): C, 19.17 (18.78); H, 3.34 (3.55); N, 21.93 (21.90).

X-ray data collection and structure refinement

Crystallographic data were recorded on a Bruker Kappa APEXII CCD area-detector diffractometer using Mo Kα radiation (λ = 0.71073 Å) at T = 100 K. Absorption correction by multi-scan [17] was applied. Structure was solved by direct methods [18] and refined by full-matrix least squares against F2 using all data [18]. All non-H atoms were refined anisotropically. H atoms were located in difference syntheses and refined isotropically. The location of the highest difference Fourier peak was 0.78 Å away from N4 atom. To prepare material for publication ORTEP-3 for Windows [19] and MERCURY 3.0 [20] were used.

Results and discussion

Description of crystal structure

Crystal data and structure refinement parameters for the complex are presented in Table 1. Selected bond lengths and angles for complex 1 are collected in Table 2, and the hydrogen bonding geometry for complex 1 is given in Table 3. The molecular structure of the title complex, along with the atom-numbering scheme is depicted in Figure 1. The asymmetric unit contains half of the fumarate ligand, two amine ligands and one half of the [Ni(CN)4]2– anion coordinated to Zn(II) ion, and one uncoordinated water molecule. The nickel atom is located on an inversion centre and surrounded by four C≡N groups, the Ni–C and C≡N bond distances and C–Ni–C bond angles are [1.8739(16) Å and 1.8618(16) Å] and [1.150(2) Å and 1.147(2) Å] and [90.12(7)° and 89.88(7)°], respectively. The C atoms around the Ni atom form a slightly distorted square-planar arrangement. The Zn–O and average Zn–N bond lengths are [1.9906(10) Å] and [1.9971(13) Å], while the O–Zn–N and N–Zn–N bond angles are in the ranges of [99.30(5)°–108.22(5)°] and [107.95(6)°–117.10(6)°], respectively. The Zn(II) ion has a slightly distorted tetrahedral coordination sphere. On the other hand, intramolecular [O–H···O and O–H···N] and intermolecular [N–H···O and N–H···N] hydrogen bonds (Table 3) are also observed. As can be seen from Figure 1, the intramolecular O–Hwater···O and O–Hwater···N hydrogen bonds (Table 3) link the water molecule to fumarate and [Ni(CN)4]2- anions, respectively. The Zn(II) ions are linked by fumarate ligands and tetracyanonickelate(II) anions exhibiting one-dimensional polymeric chains along the diagonal of (1 0 2) (Figure 2).

Tab. 1

Crystallographic data and structure refinement parameters for complex 1.

Tab. 2

The selected bond lengths (Å) and angles (°) for complex 1.

Tab. 3

Hydrogen-bond geometry (Å, °) for complex 1.

The monomer unit of 1 with some O–H···N and O–H···O interactions. Symmetry codes: (i) 2–x, 1–y, 2–z, (ii) –x, 1–y, 1–z.
Fig. 1

The monomer unit of 1 with some O–H···N and O–H···O interactions. Symmetry codes: (i) 2–x, 1–y, 2–z, (ii) –x, 1–y, 1–z.

The polymeric chain extended along the diagonal of (1 0 2) in 1.
Fig. 2

The polymeric chain extended along the diagonal of (1 0 2) in 1.

The adjacent 1D polymeric chains are further connected to each other by N4–H42···O3, O3–H3B···N1 and O3–H3A···O1 hydrogen bonds (Table 3) to form a two-dimensional network oriented parallel to (–2 0 1) (Figure 3). In the crystal structure, intermolecular N–H···O and N–H···N hydrogen bonds (Table 3) seem to be effective in the stabilization of the structure by linking the molecules into a three-dimensional network (Figure 4).

Two-dimensional substructure of 1, oriented parallel to (–2 0 1).
Fig. 3

Two-dimensional substructure of 1, oriented parallel to (–2 0 1).

Packing diagram of 1.
Fig. 4

Packing diagram of 1.

Vibrational spectroscopy

The FT-IR and Raman spectra of the complex 1 comprise bands confirming the presence of all characteristic functional groups in the prepared complex. The FT-IR and Raman spectra of the complex are given in Figures S1a and S1b, respectively. As can be seen from Figures S1a and S1b, the presence of functional group frequencies belonging to the fumaric acid and amine are confirmed in the FT-IR and Raman spectra of the complex 1. The assignments and wavenumbers of the vibrational bands of fumaric acid and amine observed in the spectra of the complex are listed in Tables S1 and S2, together with the wavenumbers of free fumaric acid and amine on which the assignments are based [21, 22]. The shifts are observed to be in high or low frequency regions, when the vibration wavenumbers of free fumaric acid and the complex were compared in Table S1. In complex 1, the symmetric and the asymmetric ν(NH3) stretching vibrations have downward shifts, when compared with the free ammonia molecule (Table S2). The vibration bands of free fumaric acid and amine can also been observed in the spectra of the complex confirming the presence and coordination of fumaric acid and amine ligands.

For cyanide complexes, the absorption bands due to ν(C≡N) stretching vibrations are very characteristic in the FT-IR and Raman spectra. The assigned wavenumbers for [Ni(CN)4]2– group in the complex are given in Table 4, together with the vibrational wavenumbers of [Ni(CN)4]2– [23]. The FT-IR spectrum of the mononuclear compound K2[Ni(CN)4]·H2O showed a band at 2120 cm–1 for ν(C≡N) stretching vibrations. Generally, if the M–C≡N group of [M(CN)4]2- anion forms M–C≡N–M′-type bridge, the ν(C≡N) band shifts to even higher frequency [24] and a single ν(C≡N) band can be splitted into two bands due to the presence of the terminal and bridging cyano groups in the complex [25]. According to this, two different ν(CN) pointed to the existence of both bridging and terminal cyanide groups in 1 (2161 cm–1 for C2≡N2, 2117 cm–1 for C1≡N1). The terminal cyanide frequencies ν(CN)t in cyanide-bridged complexes are generally observed at lower frequencies than those of the bridging cyanides ν(CN)b [26–29]. The Raman spectrum of the K2[Ni(CN)4]·H2O showed two bands at 2160 cm–1 and 2137 cm–1, which can be assigned to the CN stretching, whereas the two strong absorptions are observed at 2190 cm–1 and 2142 cm–1 for complex 1. As described in crystal data for complex 1, C1≡N1 and C2≡N2 bond lengths are 1.149(2) and 1.147(2) Å, respectively. Therefore, the crystal and spectroscopic data for the complex support each other.

Tab. 4

The wavenumbers of the [Ni(CN)4]2– vibrations in the complex 1 (cm–1).

Thermal analysis

Thermal behavior of the complex was studied by TG, DTG and DTA in the temperature range of 30–700 °C in the static air atmosphere. The TG, DTG and DTA curves of complex 1 are shown in Figure S2. The {[Zn2(μ-fum)(NH3)4Ni(μ-CN)2(CN)2]·2H2O}n (1) complex is thermally stable up to 106 °C and it shows a two stage mass loss. The first stage between 106 and 238 °C corresponds to the endothermic elimination of the four amine ligands and two water molecules with a mass loss of 16.97% (calcd. 20.35%). The last stage is related with a strong exothermic peak removal of four cyano ligands and one fumarate ligand show up in the DTG curve (DTGmax = 407 °C) between 238 and 457 °C with a mass loss of 39.30% (calcd. 42.62%). The final decomposition product was identified as ZnO + NiO (Found: % 43.30, Calcd.: %46.40) by FT-IR spectroscopy.


In this study, we have synthesized the complex {[Zn2(μ-fum)(NH3)4Ni(μ-CN)2(CN)2]·2H2O}n (1) and its crystal structure has been determined by single crystal X-ray diffraction, FT-IR and Raman spectroscopies, elemental and thermal analyses. Crystal structure of complex 1 is one dimensional and based on coordinated Zn(II) ions linked by amine, bridging tetracyanonickelate(II) and bridging fumarate. The complex 1 is first sample containing both cyanide and fumarate ligands.


The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer.

Supplementary data

CCDC 982867 contains the supplementary crystallographic data for this paper. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033; e-mail: ).


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Supplemental Material

The online version of this article (DOI: 10.1515/zkri-2014-1818) offers supplementary material, available to authorized users.

About the article

Corresponding author: Güneş Süheyla Kürkçüoğlu, Faculty of Arts and Sciences, Department of Physics, Eskişehir Osmangazi University, TR-26480 Eskişehir, Turkey, Tel.: +90 222 2393750; Fax: +90 222 2393578, E-mail:

Received: 2014-11-10

Accepted: 2014-12-16

Published Online: 2015-02-10

Published in Print: 2015-03-01

Citation Information: Zeitschrift für Kristallographie - Crystalline Materials, Volume 230, Issue 3, Pages 193–198, ISSN (Online) 2196-7105, ISSN (Print) 2194-4946, DOI: https://doi.org/10.1515/zkri-2014-1818.

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