Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 816

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Vibrational spectra, powder X-ray diffractions and physical properties

of cyanide complexes with 1-ethylimidazole
Gnes Sheyla Krkoglu a,, Fulya etinkaya Kiraz b, Elvan Sayn c
a

Eskisehir Osmangazi University, Faculty of Arts and Sciences, Department of Physics, TR-26480 Eskisehir, Turkey
_
Turkey
Atasehir Adgzel Vocational School, Department of Optician, TR-34779 Istanbul,
c
Eskisehir Osmangazi University, Graduate School of Natural and Applied Sciences, Physics, TR-26480 Eskisehir, Turkey
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 New three cyanide complexes with 1-

New cyanide-bridged heteronuclear polymeric complexes M(II)/Ni(II) (M = Fe, Mn and Co) with 1ethylimidazole were synthesized and characterized. The structures of these complexes were elucidated
using vibrational spectra and powder X-ray diffraction patterns with the peak assignment to provide a
better understanding of the structures.

ethylimidazole were synthesized.

 The complexes were characterized by
FT-IR, Raman and PXRD techniques.
 The complexes exhibit weak
semiconductive behavior.

a r t i c l e

i n f o

Article history:
Received 5 November 2014
Accepted 11 April 2015
Available online 17 April 2015
Keywords:
Cyanide-bridged complex
Heteronuclear complex
Tetracyanonickelate(II) complex
1-Ethylimidazole complex
FT-IR and Raman spectra
Powder XRD

a b s t r a c t
The heteronuclear tetracyanonickelate(II) complexes of the type [M(etim)Ni(CN)4]n (hereafter, abbreviated as MNietim, M = Mn(II), Fe(II) or Co(II); etim = 1-ethylimidazole, C5H8N2) were prepared in powder form and characterized by FT-IR and Raman spectroscopy, powder X-ray diffraction (PXRD), thermal
(TG; DTG and DTA), and elemental analysis techniques. The structures of these complexes were elucidated using vibrational spectra and powder X-ray diffraction patterns with the peak assignment to provide a better understanding of the structures. It is shown that the spectra are consistent with a proposed
crystal structure for these compounds derived from powder X-ray diffraction measurements. Vibrational
spectra of the complexes were presented and discussed with respect to the internal modes of both the
etim and the cyanide ligands. The C, H and N analyses were carried out for all the complexes. Thermal
behaviors of these complexes were followed using TG, DTG and DTA curves in the temperature range
30700 C in the static air atmosphere. The FT-IR, Raman spectra, thermal and powder X-ray analyses
revealed no signicant differences between the single crystal and powder forms. Additionally, electrical
and magnetic properties of the complexes were investigated. The FT-IR and Raman spectroscopy, PXRD,
thermal and elemental analyses results propose that these complexes are similar in structure to the
Hofmann-type complexes.
2015 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +90 222 2393750; fax: +90 222 2393578.
E-mail address: gkurkcuo@ogu.edu.tr (G.S. Krkoglu).
http://dx.doi.org/10.1016/j.saa.2015.04.019
1386-1425/ 2015 Elsevier B.V. All rights reserved.

G.S. Krkoglu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 816

Introduction
The coordination chemistry of cyanide bridged metal complexes
attracts interest because of their magnetic behavior, extraordinary
electronic states and photochemical properties [13]. The cyanide
ion may coordinate either through the C atom, as a monodentate
ligand, or through the C and N atoms as a bridging ligand, forming
polymeric complexes with one-, two- or three-dimensional networks. There is still much to be explored in the structures of
Hofmann-type and its analogous that are built by the CN-bindings
among square planar or tetrahedral tetracyanometallate(II) units
and octahedral metal(II) units combined with auxiliary ligands [4].
Hofmann-type complexes are determined by the general formula
[ML2M0 (CN)4] (M(II) = Mn, Fe, Co, Ni, Cu, Zn or Cd; M0 (II) = Ni, Pd
or Pt; L = unidentate ligand). The structures of these complexes consist of two-dimensional polymeric layers formed from [ML2]2+
cations and [M0 (CN)4]2 anions. The M0 atom is coordinated to four
C atoms of the CN groups forming a square-planar geometry. The
M(II) ion is octahedrally surrounded by six N atoms, four from
the CN units and the other two are from two ligand molecules.
The ligand molecules are located above and below the layers. The
ligands and the layers as blocking units provide voids of varying
shapes and dimensions, in which guest molecules may be conned
[4]. Similar to this structure, several metal tetracyanonickelate(II)
complexes with regard to Hofmann-type host have been improved
by using N-donor ligands [512].
Metal complexes containing imidazole-based ligands are subject of intensive researches due to their rich coordination chemistry and a number of installed potential application areas [1315].
Recently, we have synthesized heteronuclear polymeric complexes with cyanide and 1-ethylimidazole ligands [1618]. In our
previous work [17], we reported that the FT-IR, Raman spectra, thermal property and crystal structure results of tetracyanonickelate(II)
complexes with 1-ethylimidazole (etim). As a part of an ongoing
research project dealing with the coordination chemistry of cyanide
and 1-ethylimidazole ligands, herein we report the results of our
study on the preparation, vibrational spectra, powder X-ray diffractions and thermal properties of three new heteronuclear
tetracyanonickelate(II) complexes, namely, [Mn(etim)Ni(CN)4]n,
{[Fe(etim)Ni(CN)4]2H2O}n and [Co(etim)Ni(CN)4]n. In addition to
the structural analysis of the complexes were also measured electrical conductivity and magnetic susceptibility.
Experimental
Materials

water (10 mL) with potassium cyanide (4 mmol, KCN = 0.260 g) in

water (10 mL) solution. M[Ni(CN)4]H2O was prepared by mixing
together the water solution of 1 mmol (0.258 g) K2[Ni(CN)4]H2O.
To this K2[Ni(CN)4]H2O solution, 1 mmol metal(II) chloride
(MnCl2 = 0.126 g, FeCl24H2O = 0.199 g or CoCl2 = 0.130 g) dissolved
in water (10 mL) were added with continuous stirring approximately
for 4 h at 50 C in a temperature-controlled bath. The compounds
were ltered and washed with water and dried in open air. To this
1 mmol of M[Ni(CN)4]H2O (M = 0.236 g for Mn(II), 0.236 g for Fe(II)
and 0.240 g for Co(II)) water solution, 4 mmol (0.385 g) of etim dissolved in ethyl alcohol (10 mL) was added a few drops to resulting
solution with continuous stirring approximately for 5 h at 60 C in a
temperature-controlled bath and then ltered, washed with water,
ethanol, and ether, respectively, and dried at room temperature.
Physical measurements
The complexes obtained were performed elemental analyses.
Elemental analyses were carried out on LECO, CHNS-932 analyzer
for C, H and N at the Middle East Technical University Central
Laboratory. Elemental analyses are in good agreement with the calculated values which are given in Table 1. FT-IR and Raman spectra
of the complexes were recorded in the region of 4000250 cm1
via Perkin-Elmer FT-IR 100 spectrometer at a resolution of
4 cm1 and Bruker Senterra Dispersive Raman Microscope using
the 785 nm line of a 3B diode laser, respectively. Perkin Elmer
Diamond TG/DTA thermal analyzer was used to record simultaneous TG, DTG and DTA curves in the static air atmosphere at a heating rate of 10 K min1 in the temperature range of 30700 C using
platinum crucibles. The XRD patterns of the powder products were
obtained on a Rigaku Rint 2200 diffractometer using Cu-Ka radiation. The samples were loaded in a 0.3 mm glass capillary, which
were rotated during the data collection. Electrical conductivity
with four-probe technique was measured using Keithley 2601 A
System Sourcemeter four terminal conductometer. The two opposite surfaces of the pellet were coated, under pressure, with a mixture of the material and iodine powder in the weight ratio 3:1.
Contacts were glued to the complexes with a graphite paste using
1020 lm diameter platinum wire. Applied current was 1020 lA.
Magnetic susceptibility was measured using Sherwood Scientic
Magnetic susceptibility balance (MSB) MX I Model. The MSB
Mark I or Evans magnetic balance is designed as a reverse traditional Gouy magnetic balance.

Results and discussion

All materials such as manganese(II) chloride (MnCl2, 96%),

iron(II) chloride tetrahydrate (FeCl24H2O, 99%), cobalt(II) chloride
(CoCl2, 99%), potassium cyanide (KCN, 96%) and 1-ethylimidazole
(C5H8N2, 95%) were purchased from commercial sources and used
without further purication.
Syntheses of the complexes
K2[Ni(CN)4]H2O was prepared by mixing stoichiometric amounts
nickel(II) chloride hexahydrate (1 mmol, NiCl26H2O = 0.238 g) in

Vibrational spectroscopy
1-Ethylimidazole vibrations
The FT-IR and Raman spectra of the complexes are shown in
Figs. 13, respectively. Additionally, the assignments of the
wavenumbers of the etim molecule observed in the FT-IR and
Raman spectra of the complexes are given in Table 2, together
with the wavenumbers for etim and complex [Ni(etim)4Ni(lCN)2(CN)2]n [17]. As shown from Table 2, considerable shifts to

Table 1
Elemental analyses of the complexes.
Complex

Mwt. (g/mol)

Elemental analyses
C%

[Mn(C5H8N2)Ni(CN)4]n
{[Fe(C5H8N2)Ni(CN)4]2H2O}n
[Co(C5H8N2)Ni(CN)4]n

313.83
350.77
317.83

Color
H%

N%

Calc.

Found

Calc.

Found

Calc.

Found

35.74
31.34
35.28

34.44
30.82
34.01

2.92
3.45
2.83

2.57
3.45
2.54

25.83
22.19
25.55

26.78
23.96
26.44

White
Orange
Pink

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Fig. 1. The FT-IR (a) and Raman (b) spectra of MnNietim complex.

higher or lower wavenumber occur in the presence of numerous

absorption bands in the spectra of all complexes.
The absorption bands are observed in the region from
3588 cm1 to 3446 cm1 due to the symmetric and asymmetric
m(OH) stretching vibrations of the water molecules [17].
Moreover, the presence of water molecules manifests itself at

about 1650 cm1 and 1620 cm1 due to d(OH) deformation vibrations [19]. In FT-IR spectra of FeNietim, the absorption band at
3489 cm1 may be attributed to the asymmetric and symmetric
m(OH) stretching mode of water molecules. Furthermore, d(OH)
deformation vibrations belonging to OH bending modes was
observed at 1639 cm1. The shift to lower frequencies of these

G.S. Krkoglu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 816

11

Fig. 2. The FT-IR (a) and Raman (b) spectra of FeNietim complex.

stretching modes and the shift to higher frequencies of the bending

modes may be connected to the hydrogen bonding in the complex.
These bands were not observed MnNietim and CoNietim
complexes.
As evident from Table 2, in the FT-IR and Raman spectra of the
complexes, the observed bands at 3152 and 3122 cm1 for MnNi
etim, at 3154 and 3122 cm1 for FeNietim, at 3157 and
3122 cm1 for CoNietim can be assigned to the characteristic
imidazole ring CH symmetric and antisymmetric stretching
modes, respectively. The absorption bands of the m(CH3) and
m(CH2) groups in the complexes are observed in the frequency
range of 30022887 cm1, and signicantly shifted to lower
or higher frequencies compared to the free ligand. The

17001200 cm1 frequency range is mainly characteristic for

antisymmetric and symmetric, C@C and C@N, stretching vibrations
of the imidazole ring as well as various CH bond deformations.
When the aromatic ring nitrogen involves in the complex formation, the certain ring modes, particularly the modes in the region
of 16001400 cm1 increase in value both due to the coupling with
MN(ligand) bond vibrations and due to the alterations of the ring
force. The CH bond deformation vibrational modes of the etim can
be observed in the 14601400 cm1 region of the spectra, the
1200900 cm1 region is dominated by the CC stretches, CH
deformation vibrations as well as by the ring vibrations. The spectral features and assignments of the other vibrations are included
in Table 2.

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Fig. 3. The FT-IR (a) and Raman (b) spectra of CoNietim complex.

Ni(CN)4 group vibrations

The most important aspects of the FT-IR and Raman spectra of
the complexes, involve the characteristic vibrations of m(CN). In
the spectra of the complexes, the dominant feature is represented
by strong and sharp well identiable absorption bands, due to the
m(CN) stretching vibrations [20]. The [Ni(CN)4]2 anion possesses
ideally D4h symmetry and, thus, will have 16 fundamental vibrations (2A1g, 1A2g, 2B1g, 2B2g, 1Eg, 2A2u, 2B2u, and 4Eu) [21]. Of these,
A2u and Eu are infrared active, while A1g, B1g, B2g, and Eg are Raman
active. The A2g and B2u vibrations are inactive. No B2g modes were
observed. The m(CN) vibrations are the most important absorption bands for the complexes. The vibrational wavenumbers of

[Ni(CN)4]2 group for the K2[Ni(CN)4]H2O and all complexes are

presented in Table 3, together with vibrational assignments of
[Ni(CN)4]2 [22].
The characteristic bands in the FT-IR and Raman spectra of
metal complexes containing cyanide are sharp and strong between
2000 and 2200 cm1 resulting from m(CN). The m(CN) modes are
observed at 2151 cm1 for MnNietim, 2155 cm1 FeNietim,
and 2158 cm1 CoNietim in the FT-IR spectra. Seven Raman
active modes are expected in the same region, but only two of
these, the m(CN) modes (2176 and 2122 cm1 for MnNietim,
2177 and 2135 cm1 for FeNietim and, 2182 and 2138 cm1
for CoNietim) are observed in the complexes on which Raman

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13

Table 2
The vibration wavenumbers of etim in the complexes (cm1).
Assignments [29]

etim (liquid)

ms(CH) of CH@CH
mas(CH) of CH@CH
mas(CH3), mas(CH2)
ms(CH3), ms(CH2)
ms(CH2)
m(C@C) m(C@N)
m(R), combination

3134 sh
3107 m
2981 s
2940 m
2889 w
1676 w
1596 w
1510 vs
1465 m
1448 m
1394 m
1385 m
1355 m
1287 m
1250 w
1228 vs
1194 sh
1110 s
1078 vs
1034 m
958 m
908 s
875 sh
819 s
742 s
667 vs
624 m
515 vw

das(CH2)scis
das(CH3)scis
m(R), combination
d(CH), m(R)

m(R), d(CH2)twist
Combination

q(CH3), q(CH2), m(R) combination

d(R)

c(CH)
c(CH), m(CC)

m(CH2N), m(CCH2)
d(CH)
d(CH2), m(CC)

NiNietim [17]

MnNietim

FeNietim

CoNietim

FT-IR

Raman

FT-IR

Raman

FT-IR

Raman

FT-IR

Raman

3140 sh
3129 m
2971 m
2943 m
2903 w
1681 sh
1591 m
1524 s
1468 m
1449 m

1377 m
1359 m
1290 m
1252 m
1235 s

1109 s
1090 s
1036 m
955 m

852 m
829 s
742 s
658 m
620 m

3155 m
3135 m
2974 m
2948 m
2929 w

1530 m
1460 w
1419 w

1356 m
1294 w

1245 w

1105 m

1048 m
967 m

864 vw

770 vw
663 w

3152 m
3122 m
2989 m
2942 m
2891 w
1682 w
1596 w
1512 s
1470 m
1458 m
1397 m
1377 m

1288 vw
1258 w
1240 s
1136 w
1121 s
1087 s
1038 m
968 w

850 w
832 s
747 s
660 s
616 m
526 vw

3159 m
3133 m
3002 m
2953 m
2898 w
1687 vw
1545 w

1470 m
1423 w

1355 m

1258 w

1136 w

1100 m
1054 w

862 vw

757 vw
667 m

3154 m
3122 m
2989 m
2943 m
2890 w
1683 w
1597 m
1513 s
1470 m
1459 m
1398 m
1376 m
1354 w
1289 w
1257 w
1241 s
1137 sh
1122 s
1088 s
1037 m
968 w

850 w
833 s
747 s
661 s
617 m

3161 m
3138 w
2999 m
2950 m
2887 w
1697 vw
1543 vw
1513 vw
1475 w
1427 w
1395 vw

1355 w
1297 vw

1248 vw
1137 vw

1103 w
1050 w
970 w
911 vw
863 vw

756 vw
669 w
628 vw
530 vw

3157 m
3122 m
2989 m
2942 m
2892 w
1684 w
1596 m
1514 s
1471 m
1459 m
1398 m
1375 m
1359 m
1288 vw
1257 w
1242 s
1137 sh
1121 s
1088 s
1037 m
969 w

850 w
834 s
747 s
661 s
617 m
525 vw

3160 m
3132 m
2984 m
2952 m
2894 w
1697 vw
1542 m

1469 w
1423 w

1358 w
1299 vw
1267 vw

1137 w

1100 m
1053 w
983 w
914 vw
864 vw

754 vw
665 w
622 w

Abbreviations used: m stretching, d deformation, c wagging, t twisting, r rocking, s strong, m medium, w weak, sh shoulder, v very.

Table 3
The wavenumbers of the [Ni(CN)4]2 and metalligand vibrations in the complexes (cm1).
Assignments [22]

K2[Ni(CN)4]H2O

NiNietim [17]

MnNietim

FeNietim

CoNietim

A1g, m(CN)
B1g, m(CN)
Eu, m(CN)
Eu, m(13CN)
Eu, m(NiC)
A2u,p(NiCN)
Eu, d(NiCN)
A1g, m(NiC)
Eg, p(NiCN)
B2g, d(CNiC)

(2160)vs
(2137)m
2122 vs
2084 w
540 w
443 w
417 s
(374)
(298)
(109)

(2179)vs
(2142)w
2155 vs, 2120 s
2079 w
541 w
449 w
425 s
(376) w
(344) w

(2176)vs
(2122)w
2151 vs
2111 w
543 w
453 vw
427 s
(378) w
(349) w

(2177)vs
(2135)w
2155 vs
2114 w

455 vw
431 s
(376) w
(342) vw

(2182)vs
(2138)w
2158 vs
2116 w
544 vw
457 vw
432 s
(376) vw
(343) w

Metalligand vibrations [30]

A2u,m(MN)(etim)
Eu, m(MN)(CN)4
A1g/Eg, m(MN)(etim)
A2u, d(NMN)(etim)
Eu, d(NMN)(CN)4

369 w
289 w
(261) w

367 w
281 w
(259) w

368 vw
278 w
(260) vw

362 w
285 vw
(250) vw

Abbreviations used: s strong, m medium, w weak, sh shoulder, br broad, v very. The symbols m, d, and p refer to valence, in-plane and out-of-plane vibrations,
respectively.

experiments were made. m(CN) and d(NiCN) are both strong sharp
bands in the FT-IR spectra of the complexes. m(CN) is shifted
upwards by about 30 cm1 compared to the same frequency in
the K2Ni(CN)4 complex. d(Ni-CN) is shifted upwards much less.
These frequencies of both bands are dependent on the metal. The
m(NiC) stretching vibration is observed as a broad, weak band
around 540 cm1 and this vibration shows a small metal dependence. The out-of-plane p(NiCN) mode is only observed weakly
in the complexes. As can be seen from Table 3, m(CN) frequencies
are metal dependent and increase in the order Mn < Fe < Co. In
tetracyanonickelate(II) complexes, mechanical coupling between
the m(CN) stretching mode and m(NiC) modes is well known
[23]. Therefore, the metal dependence of the m(CN) wavenumbers

reects the strength of the metal anion bond, MN(NC) [23].

Such frequency shifts have been observed for other Hofmann-type
clathrates [512] and Hofmann-type complexes [23,30].
Metal-ligand vibrations
The FT-IR spectra of the complexes showed a group of new
bands with different intensities which characteristics for m(MN).
The m(MN) stretching and d(NMN) bending bands in the far infrared region enable the information about the structure of the
metalligand. m(MN) stretching vibrations of 16 imidazole complexes of Ni(II), Cu(II), Zn(II), and Co(II) were observed in the
325210 cm1 region [21]. The m(MN) stretching bands were
observed at 367 and 281 cm1 for MnNietim, at 368 and

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Fig. 4. The powder X-ray diffraction patterns of the complexes (a) MnNi-etim; (b) FeNietim; (c) CoNietim; (d) NiNietim.

Powder X-ray diffraction

Single crystal X-ray diffraction method could not be used, due
to poor single crystal quality. Thats why, powder X-ray diffraction
and energy minimization methods were used to predict three
dimensional molecular geometries of the complexes. The powder
diffraction patterns of the four compounds are shown in Fig. 4.
As a result of energy minimization studies three main atomic
planes were obtained. The diffractogram of complexes exhibits
intense peaks.
In previous study [17], NiNietim complex was obtained as a
single crystal (Fig. 5). NiNietim complex obtained as single crystal was also examined by PXRD in this study, and the structure of
NiNietim complex was compared with other complexes.

Magnetic properties

Fig. 5. The molecular structure of complex NiNietim complex [17].

278 cm1 for FeNietim, at 362 and 285 cm1 for CoNietim, at
369 and 289 cm1 for NiNietim in the FT-IR spectra. The same
bands were found at 261 cm1 for NiNietim, at 259 cm1 for
MnNietim, at 260 cm1 for FeNietim, at 250 cm1 for Co
Nietim in the Raman spectra. d(NMN) bending bands were not
observed for spectra taken up to 250 cm1.

The magnetic susceptibility of the complexes was determined

by Evans Method. The complexes exhibit paramagnetic behavior.
Since the Ni(II) atom in the [Ni(CN)4] unit remains in diamagnetic
state, these results are conclusive evidence on the high spin state
for the four metals (Mn, Fe, Co, Ni). In Table 4, the values for the
effective magnetic moment (leff) at room temperature, calculated
from the magnetic susceptibility are summarized.
MnNietim complex exhibits a magnetic moment value of
5.57 BM, which corresponds to ve of unpaired electrons per
Mn(II) ion. This value is considerably lower than the spin-only
value of 5.92 BM, expected for high-spin Mn(II). The magnetic
value of CoNietim complex at room temperature is 4.12 BM,
which is higher than the calculated spin-only value of 3.87.

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15

Table 4
Magnetic susceptibilities at room temperature of the complexes.
Complex

Experimental values

Expected value [31]

(spin + orbital)

Expected value [31]

(spin only)

Unpaired electrons

[Mn(C5H8N2)Ni(CN)4]n
{[Fe(C5H8N2)Ni(CN)4]2H2O}n
[Co(C5H8N2)Ni(CN)4]n
[Ni(C5H8N2)4Ni(CN)4]n

5.57
4.68
4.12
3.04

5.90
5.15.5
4.15.2
2.84.0

5.92
4.90
3.87
2.83

5
4
3
2

e
e
e
e

However, it agrees with the values observed for octahedral Co(II)

complexes with a signicant rst-order orbital contribution to only
a spin magnetic moment. FeNietim complex exhibits magnetic
moment value of 4.68 BM, which correspond to four unpaired electron of the Fe(II) ion, respectively. This value is close to the spinonly value of 4.90. NiNietim complex exhibit magnetic moment
values of 3.04 BM which both correspond to paramagnetic
with two unpaired electrons. Compare the experimental values
with the theoretical values of complexes we can say that
they have paramagnetic properties [24]. The complexes have a
similar measurement to the previously reported 5.04 BM in
Co(EtIm)2[Ni(CN)4] and 2.97 BM in Ni(EtIm)2[Ni(CN)4] (EtIm = 2ethylimidazole) [25], 4.59 BM in Fe(Im)2[Ni(CN)4], 5.18 BM
Co(Im)2[Ni(CN)4] and 3.24 BM Co(Im)2[Ni(CN)4] (Im = Imidazole)
[26].
Electrical measurements
All products produced by the reaction with the solution of
iodine MNietim complexes exhibited a higher value of the electrical conductivity over the whole range of frequencies used (10
105 Hz, at 25 C). The conductivity of compounds was measured
by the standard four-point probe method in the dc plane. The conductivities at room temperature were found to be
2.596  108 X1 cm1 for MnNietim, 2.047  108 X1 cm1
for FeNietim, 1.137  107 X1 cm1 for CoNietim and
1.923  109 X1 cm1 for NiNietim. The conductivity values
of the complexes are a like each other and rather high in spite of
the measurements on the powder compressed pellets. The electrical conduction properties of several examples of these types of
complexes have been studied [27,28] and they have been found
to behave as semiconductors with the conductivity in the direction
of the metal atom chain ranging from 107 to 1010 X1 cm1 at
room temperature. The complexes show very weak semiconductor.
Thermal analyses of the complexes
Thermal behaviors of the complexes were studied by TG, DTG
and DTA curves in the temperature range 30700 C in the static
air atmosphere. Thermal decomposition curves of the complexes
are presented in the labels of Fig. 6.
The complexes are thermally stable up to 118 C for MnNi
etim, 138 C for FeNietim and 137 C for CoNietim and the
complexes show two stage mass loss (Fig. 6). The MnNietim
and CoNietim complexes followed usual decomposition mechanism in which neutral ligand (etim) is released rst stage. The Fe
Nietim complex followed usual decomposition mechanism in
which two water molecules and etim ligand are released rst
stage. In the second stage, cyanide ligands in the complexes are
decomposed. The stage between 118 and 407 C for MnNietim,
138 and 385 C for FeNietim and 137 and 413 C for CoNi
etim corresponds to the exothermic peak on the DTA curve
(DTAmax = 401 C in MnNietim, 365 C in FeNietim and
395 C in CoNietim). This peak is associated with the decomposition and burning of the cyanide ligands. The nal decomposition
products are found to be the corresponding metal oxides. The

Fig. 6. TG, DTG and DTA curves of (a) MnNietim, (b) FeNietim and (c) CoNi
etim.

thermal decomposition products were identied as MnO and NiO

with a mass loss of 43.20% (calcd. 46.40%) for MnNietim, as
FeO and NiO with a mass loss of 43.20% (calcd. 47.07%) in

16

G.S. Krkoglu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 816

FeNietim and as CoO and NiO with a mass loss of 44.52% (calcd.
47.07%) in CoNietim.

[10]

Conclusion
The present paper is a part of our investigations on the structures and physical properties of heterometallic cyanide complexes
with 1-ethylimidazole. We have synthesized and characterized the
three new heterometallic cyanide complexes [Mn(etim)Ni(CN)4]n,
{[Fe(etim)Ni(CN)4]2H2O}n and [Co(etim)Ni(CN)4]n. On the basis
of the vibrational (FT-IR and Raman) spectroscopic results, we propose that in the case of the complexes the etim molecule are coordinated to M(II) (M = Mn, Fe and Co) ions of the adjacent layers of
[M-Ni(CN)4]n. For a given series of isomorphous complexes, the
effects of metal ligand bond formation on the ligand vibrational
modes are examined. The complexes showed a moderate conductivity of 108 X1 cm1 at room temperature. These results suggest
that cyanide complexes with stronger donor ability may give new
complexes having electrically and magnetically intriguing
properties.
Acknowledgement
This paper is dedicated to Prof. Dr. Ziya KANTARCI, who died on
January, 2012.

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