Synthesis, IR spectrum, thermal analysis, and crystal structure of the cyano-bridged heteronuclear polymeric complex: [Zn(teta)Ni(μ-CN) 2(CN)2]n

Article abstract of DOI:10.1002/zaac.200800337

The heteronuclear polymeric complex, [Zn(teta)Ni(μ-CN) ₂(CN)₂]_n (teta: triethylenetetramine), was synthesized and characterized by elementel analysis, FT-IR spectroscopy, thermal analysis and single crystal X-ray diffracti

Full text of DOI:10.1002/zaac.200800337

ARTICLE
DOI: 10.1002/zaac.200800337
Synthesis, IR Spectrum, Thermal Analysis, and Crystal Structure of the
Cyano-bridged Heteronuclear Polymeric Complex: [Zn(teta)Ni(μ-CN)2(CN)2]n
[a]
[b]
[a]
˙
ˇ
Günes Süheyla Kürkcüoglu,* Okan Zafer Yesilel, Ilkan Kavlak, and
¸
¸
¸
Orhan Büyükgüngör[c]
Keywords: Cyano-bridged complex; Tetracyanonickelate complex; Triethylenetetramine complex
Abstract. The heteronuclear polymeric complex, [Zn(teta)Ni(μ-
by one tetradentate teta ligand and two bridging cyano groups as
CN)2(CN)2]n (teta: triethylenetetramine), was synthesized and a trans position, whereas the NiII ion has square planer coordi-
characterized by elementel analysis, FT-IR spectroscopy, thermal
nation and is coordinated by four cyano ligands. The decompo-
analysis and single crystal XϪray diffraction techniques. The com-
sition reaction takes places in the temperature range 30Ϫ600 °C in
plex crystallizes in the monoclinic system, space group P21/c and the static air atmosphere.
in which the ZnII ion exhibits a distorted octahedral coordination
nickelate(II) complex with a triethylenetetramine ligand as
1 Introduction
blocking ligand [17]. As part of our on going research, in
this study, we describe the synthesis, spectroscopic, thermal
characterization and crystal structure of a heteronuclear
polymeric complex, [Zn(teta)Ni(μ-CN)2(CN)2]n (1).
Lattice inclusion complexes are the result of the supra-
molecular self-assembly of molecules in their crystal lattice
with voids which are occupied by guest species [1]. The cy-
anide anion is able to behave as a bridging ligand at both
ends, with the carbon and the nitrogen atom acting as
Lewis bases between two coordination centers, which are
generally metal cations acting as Lewis acids. The square-
planar Ni(CN)4 moiety may take a number of catenation
modes to build up multidimensional structures [2]. Square
planar [M(CN)4]2Ϫ (M ϭ Ni, Pd, Pt) have been extensively
used as building blocks for the synthesis of extended cyano-
bridged structures [3Ϫ32]. In particular, the Hofmann-type
complexes, [ML2MЈ(CN)4], where M is a divalent transition
2 Experimental Section
2.1 Materials and Instrumentation
Zinc(II) chloride, nickel(II) chloride hexahydrate, triethylenetetra-
mine (teta), potassium cyanide were purchased from commercial
sources and used as received. The infrared spectra were recorded
on a IFS 66 v/S Brukeroptics FT-IR spectrometer using Nujol and
KBr discs in the 4000-4000 cmϪ1 (4 cmϪ1 resolution). Perkin Elmer
Diamond TG/DTA thermal analyzer was used to record simul-
metal and L is a N-donor ligand molecule, have a structure taneous TG, DTG and DTA curves in the static air atmosphere at
a heating rate of 10 KminϪ1 in the temperature range 30Ϫ600 °C
consisting of polymeric two-dimensional networks formed
Ni(CN)42Ϫ anions bridged by ML22ϩ cations [33, 34].In one
using platinum crucibles.
series of these studies [20, 22Ϫ26], the {Zn(L)[Ni(CN)4]}
(L ϭ ammine or diammine) systems have shown a wide 2.2 X-ray Crystallography
range of complexation patterns involving two- or three-di-
Diffraction experiments were carried out at 296 K on a Stoe IPDS
mensional networks, and a wide variety in the shape or en-
vironment of the cavity where mainly aromatic organic
compounds are accomodated.
We have recently reported the [Cd(teta)Ni(μ-CN)2-
(CN)2]·2H2O which is the first example of tetracyano-
diffractometer. The structure was solved by direct methods and re-
fined using the programs SHELXS97 and SHELXL97 [35]. All
non-hydrogen atoms were refined anisotropically by full-matrix le-
ast-squares methods [SHELXL-97]. The hydrogen atoms were
placed in geometrically idealized positions and refined as riding
atoms. Data collection: X-Area, cell refinement: X-Area, data
reduction: X-RED [36]; program(s) used for molecular graphics:
ORTEP-3 for Windows [37]; software used to prepare material for
publication: WinGX [38].
ˇ
* Dr. G. S. Kürkc¸üoglu
E-Mail: gkurkcuo@ogu.edu.tr
[a] Faculty of Arts and Science, Department of Physics
Eskis¸ehir Osmangazi University
2.3 Synthesis
Eskisehir, Turkey
¸
Zn[Ni(CN)4]
[b] Department of Chemistry, Eskis¸ehir Osmangazi University,
Eskis¸ehir, Turkey
A mixture of a solution of NiCl2 ·6H2O (1.19 g, 5 mmol) in water
(20 mL) and a solution of KCN (1.30 g, 20 mmol) in water (20 mL)
[c] Ondokuz Mayıs University, Faculty of Arts and Science,
Department of Physics, Samsun, Turkey
Z. Anorg. Allg. Chem. 2009, 635, 175Ϫ178
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
175

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G. S. Kürkc¸üoglu, O. Z. Yes¸ilel, I. Kavlak, O. Büyükgüngör
ARTICLE
˚
Table 1. The details of crystal and experimental data of 1
Table 3. Hydrogen bond parameters/A, °
Empirical formula
Formula weight
Temperature /K
Wavelength /A
Crystal system
Space group
C10H18N8NiZn
374.40
296
0.71073
monoclinic
P21/c
D-H
d(D-H)
d(H···A)
d(D···A)
<DHA
N1ϪH1D···N8iii
N2ϪH2C···N6iv
N3ϪH3C···N8iii
N4ϪH4C···N6iv
0.70 (4)
0.71 (4)
0.77 (4)
0.74 (5)
2.53 (4)
2.36 (4)
2.52 (4)
2.49 (5)
3.137 (5)
3.023 (4)
3.180 (4)
3.181 (5)
147 (4)
157 (4)
144 (4)
154 (4)
˚
Unit cell dimensions
˚
a, b, c /A
13.2535 (4), 9.1250 (3), 14.5588(4)
120.477 (2)
1517.44 (8)
Symmetry codes: (iii) Ϫxϩ2, Ϫyϩ1, Ϫzϩ1; (iv) Ϫxϩ1, Ϫyϩ1, Ϫzϩ1.
β /°
3
˚
V /A
Z
4
2.82
1.639
1.62-28.15
33171
3148
The ZnII ion adopts a distorted octahedral coordination
and is coordinated by four N atoms [N(1)-N(4)] from tetra-
dentate teta ligand and two N atoms of the cyano groups,
whereas the NiII ion is coordinated by four C atoms
[C(1)-C(4)] of four cyano ligands in a square-plane fashion
(Fig. 1). The crystallographic analyses reveal that the crys-
tal structure of 1 is a one dimensional zigzag chain polymer
(2,2-CT type) along the c axis (Fig. 2). Two of the CN
groups are in trans positions bridge, other two CN groups
are terminal. The bond distances of NiϪC [range of
μ /mmϪ1
Dcalc /Mg mϪ3
θ range /°
Measured reflections
Independent reflections
Absorption correction
Refinement method
Final R indices [I>2σ(I)]
R[F2 > 2σ(F2)]
wR(F2)
integration
FullϪmatrix leastϪsquares on F2
Rint ϭ 0.052
0.032
0.086
1.08
0.48, Ϫ0.72
GoodnessϪofϪfit on F2
Largest difference peak
and hole (eA
Ϫ3
˚
)
˚
1.863(3)-1866(3) A] in the Ni(CN)4 moiety are in accord-
ance with the reported values for similar complexes
˚
Table 2. Selected bond lengths/A and bond angles/° of 1
[22Ϫ24]. The Zn1ϪN1/N2/N3/N4 average bond distance of
˚
C7ϪNi1
C8ϪNi1
C9ϪNi1
C10ϪNi1
N1ϪZn1
1.866 (3)
1.863 (3)
1.864 (3)
1.873 (3)
2.117 (3)
N2ϪZn1
N3ϪZn1
N4ϪZn1
N5ϪZn1
N7ϪZn1i
2.122 (3)
2.103 (2)
2.119 (3)
2.083 (3)
2.088 (2)
2.115(3) A is similar to the corresponding values found in
˚
[Zn(hydeten)2Pd(CN)4]n (2.178(2) and 2.138(2) A) [20],
˚
[Zn(en)2Ni(CN)4]n (2.107(5) and 2.138(5) A) [23], but
shorter that found in the [Zn(hydeten)2Pt(CN)4]n (2.39(1)
˚
and 2.36(1) A) [22], [Cd(hydeten)2Pd(CN)4]n (2.360(3) and
C8ϪNi1ϪC9
C8ϪNi1ϪC7
C9ϪNi1ϪC7
C8ϪNi1ϪC10
C9ϪNi1ϪC10
C7ϪNi1ϪC10
N5ϪZn1ϪN7ii
N5ϪZn1ϪN3
N7iiϪZn1ϪN3
N5ϪZn1ϪN1
N7iiϪZn1ϪN1
90.52 (13)
87.95 (13)
176.98 (13)
177.09 (14)
88.83 (13)
92.83 (14)
92.61 (11)
91.15 (11)
175.20 (11)
90.63 (11)
88.07 (12)
N3ϪZn1ϪN1
N5ϪZn1ϪN4
N7iiϪZn1ϪN4
N3ϪZn1ϪN4
N1ϪZn1ϪN4
N5ϪZn1ϪN2
N7iiϪZn1ϪN2
N3ϪZn1ϪN2
N1ϪZn1ϪN2
N4ϪZn1ϪN2
94.88 (12)
92.20 (13)
94.22 (11)
82.65 (10)
176.27 (13)
169.65 (11)
93.78 (11)
82.93 (11)
81.46 (11)
95.44 (12)
˚
˚
2.398(2) A) [20] and [Cd(en)2Ni(CN)4]n (2.313(5) and
2.345(5) A) [23]. The Zn1ϪN5 and Zn1ϪN7 bond dis-
˚
tances of 2.083(3) and 2.088(2) A are somewhat shorter that
˚
found in the [Zn(hydeten)2Pt(CN)4]n (2.33(1) A), [Cd(hydet-
˚
en)2Pt(CN)4]n (2.38(3) A) [22], [Zn(hydeten)2Pd(CN)4]n
˚
˚
(2.215(2) A), [Cd(hydeten)2Pd(CN)4]n (2.328(2) A) [20].
Symmetry codes: (i) x, Ϫyϩ1/2, zϪ1/2; (ii) x, Ϫyϩ1/2, zϩ1/2.
was added dropwise with stirring at 50 °C to a solution of ZnCl2
(0.681 g, 5 mmol) in water (10 mL). The mixture was refluxed with
stirring for 2 h at 50 °C in a temperature-controlled bath and then
the solution was cooled to room temperature.
[Zn(teta)Ni(μ-CN)2(CN)2]n
A solution of triethylenetetramine (0.73 g, 5 mmol) in ethanol
(10 mL) was added dropwise upon stirring to a solution of
Zn[Ni(CN)4] (1.14 g, 5 mmol) in water (30 mL). The solutions were
refluxed with stirring for 4 h at 60 °C. The reaction mixture was
cooled to room temperature. The violent crystals formed for
[Zn(teta)Ni(μ-CN)2(CN)2] were filtered and washed with 10 mL of
water and acetone and dried in air.
Figure 1. An ORTEP-3 drawing of 1 with the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50 % probability
level
3 Results and Discussion
The Zn1-N5ϵC7 bond angle is 174.8(3)°, resulting in a
one-dimensional zigzag chain being formed, whereas the
3.1 Crystal Structure of 1
The relevant crystal data and experimental conditions Ni1-C7ϵN5 and Ni1-C9ϵN7 bond angles [175.6(3) and
along with the final parameters are summarized in Table 178.1(3)°, respectively] are essentially linear. The crystal
1. The selected bond lengths, angles and hydrogen bond packing was formed by intermolecular hydrogen bonding
parameters are listed Table 2 and Table 3, respectively.
between the one-dimensional zigzag chain. This weak hy-
176
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Z. Anorg. Allg. Chem. 2009, 175Ϫ178

[Zn(teta)Ni(μ-CN)2(CN)2]n
In order to assign the bands attributable to the Ni(CN)4
ion in the spectrum, we refer to the work of McCullough et
al. who presented vibrational data for the salt Na2Ni(CN)4
in the solid state [40]. The assigned wavenumbers of the
Ni(CN)4 units of the complex appear to be much higher
than those for isolated Ni(CN)4 ion. Such frequency shifts
have been observed for Hofmann-type host frameworks
[41Ϫ44] and are attributed to the mechanical coupling of
the internal modes of Ni(CN)4 group are bound to a ZnII
atom in the complexes.
Figure 2. A view of the one-dimensional zigzag chain of 1
drogen bond is observed between N1/N2/N3/N4-H of teta
ligand and N6, N8 atom of cyano groups [N1···N8iii
ϭ
3.3 Thermal Analysis
3.137(5), N2···N6iv ϭ 3.023(4), N3···N8iii ϭ 3.180(4) and
N4···N6iv ϭ 3.181 (5)°, (iii) Ϫxϩ2, Ϫyϩ1, Ϫzϩ1; (iv)
Ϫxϩ1, Ϫyϩ1, Ϫzϩ1] (Fig. 3). The intramolecular Zn···Zni
The [Zn(teta)Ni(μ-CN)2(CN)2] complex is thermally
stable up to 322 °C. Thermal decomposition of the complex
proceeds in three exothermic stages. The first stage between
314 and 420 °C is related to the release of the 0.5 mole teta
˚
distance is 10.087 A, whereas the shortest interchain
Zn···Znii and Zn···Zniii distances are 5.890 and 7.588 A,
˚
ligand (found ϭ 19.09, calcd. ϭ 19.53 %, DTAmax
ϭ
respectively [symmetry codes (i) x, 1/2ϪyϪ1, Ϫ1/2ϩz, (ii)
1Ϫx, 1Ϫy, 1Ϫz, (iii) 1Ϫx, 1/2ϩy, 3/2Ϫz].
351 °C). In the following stages, remaining organic part and
cyano groups decomposes between 363 and 458 °C and to
calculate mass loss value is impossible due to overlapping
decomposition processes (DTAmax ϭ 382 and 445 °C). The
total mass loss of all decomposition process is 59.26 %
(calcd. 58.30 %) suggest that ZnO and NiO is the end prod-
uct at 458 °C.
Supplementary material. Crystallographic data for the structure re-
ported in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre, CCDC no. 682040 for 1. Copy of this
information may be obtained free of charge from the Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: 44-1223-
336-033; e-mail for deposition: deposit@ccdc.cam.ac.uk)
Acknowledgement
This work has been supported by the Research Fund of Eskisehir
¸
Osmangazi University, Project No. 200719025. We thank Prof. Dr.
Mustafa S¸enyel for support during the FT-IR spectra.
Figure 3. The hydrogen-bonding interactions of 1
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G. S. Kürkc¸üoglu, O. Z. Yes¸ilel, I. Kavlak, O. Büyükgüngör
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