Square planar Ni(ii) complexes of acetone: N 4-phenyl-thiosemicarbazone and in situ generated benzoyl thiosemicarbazide ligands: Synthesis, spectral and structural characterizations, thermal behaviour and electrochemical studies

Article abstract of DOI:10.1039/c7nj01030c

Two novel square planar complexes [Ni(Hapt)₂] (1) and [Ni(btsc)] (2) have been synthesized from acetone N⁴-phenyl-thiosemicarbazone (Hapt) and benzoyl-3-thiosemicarbazide (Hbtsc) by the reaction of nickel(ii) salt. The ligand and complexes have been characterized by various physicochemical methods. Complexes 1 and 2 crystallize in the monoclinic and orthorhombic systems with space group C2/c and Pbcn, respectively. In complexes 1 and 2 the nickel centre is coordinated through the nitrogen and sulphur atoms forming a square planar geometry. Complexes 1 and 2 are stabilized via various types of intermolecular interactions. The course of the thermal degradations of complexes 1 and 2 has been investigated by TGA which indicated that a metal sulphide/oxide is formed as the final residue. Cyclic voltammetric studies show that complex 1 exhibits a reversible Ni(ii)/Ni(iii) redox process at 0.525 V (E_1/2 value at 20 mV s^-1) while complex 2 shows reversible redox behavior with an E_1/2 value of 0.43 V. Furthermore, efficient electrocatalytic properties of complexes 1 and 2 toward the oxidation of hydrazine and methanol are demonstrated after immobilizing the complexes into Nafion films. The electrocatalytic properties may find applications in industry, in methanol sensing and in methanol fuel cells.

Full text of DOI:10.1039/c7nj01030c

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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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ARTICLE
4
Square planar Ni(II) complexes of acetone N -phenyl-
thiosemicarbazone
and
in
situ
generated
benzoyl
Received 00th January 20xx,
Accepted 00th January 20xx
thiosemicarbazide ligand: Synthesis, spectral and structural
characterizations, thermal behaviour and electrochemical
studies
DOI: 10.1039/x0xx00000x
www.rsc.org/
a
a
a
a
a
Santosh Paswan , M.K. Bharty *, Pooja Bharati , Piyush Kumar Sonkar , Vellaichamy Ganesan , R. J.
b
Butcher
4
2
Two novel square planar complexes [Ni(Hapt) ] (1) and [Ni(btsc)] (2) have been synthesized from acetone N ꢀphenylꢀ
thiosemicarbazone (Hapt) and benzoylꢀ3ꢀthiosemicarbazide (Hbtsc) by the reaction of nickel (II) salt. The ligand and
complexes have been characterized by various physicochemical methods. Complexes 1 and 2 crystallize in monoclinic and
orthorhombhic system with space group C2/c and P b c n, respectively. In complexes 1 and 2 nickel centre is coordinated
through the nitrogen and sulphur atoms forming a square planar geometry. Complexes 1 and 2 are stabilized via various
types of intermolecular interactions. The course of the thermal degradations of complexes 1 and 2 have been investigated by
TGA which indicate that metal sulphide/oxide is formed as the final residue. Cyclic voltammetric studies show that complex
ꢀ1
1
exhibits reversible Ni(II)/Ni(III) redox process at 0.525 V (E1/2 value at 20 mVs ) while complex 2 shows reversible redox
behavior with an E1/2 value of 0.43 V. Further, efficient electrocatalytic properties of the complexes 1 and 2 toward the
oxidation of hydrazine and methanol are demonstrated after immobilizing the complexes into Nafion films. The
electrocatalytic properties may find applications in industries, methanol sensing and in methanol fuel cells.
complexes, have been studied because of their complexing
1
. Introduction
The coordination chemistry of nitrogen sulphur ligands is an properties [17], biological activity [18, 19] and analytical
important and developing area of research in recent years because of applications [20, 21]. The coordination chemistry of
their structural features and biological activity. Apart from these thiosemicarbazide/ substituted thiosemicarbazide complexes has
above features the complexes possess semiconducting behaviour, received much attention owing to their significant biological and
molecular magnetism and electrocatalytic properties [1ꢀ7]. There has medicinal properties which are dependent upon the chemical nature
been extensive growth in the field of synthetic, structural and of the moiety attached to the C=S carbon atom [22ꢀ24].
biological chemistry of this class of metal complexes. They find Thiosemicarbazones are one of the most studied ligands not only
applications as fungicides, pesticides and show remarkable because of their flexibility to bind metal ions in various modes but
antineoplastic activity against a variety of tumours [8ꢀ10] which has also because of the wide range of applications that they possess [25,
generated interest in this class of complexes. Among various types 26]. Thiosemicarbazones exhibit thioneꢀthiol tautomerism in
of
thiosemicarbazide,NꢀacylꢀN'ꢀthioaroylhydrazides,
thiosemicarbozones, simple as well as and
nitrogen
sulphur
ligands
such
as
thiohydrazide, solution owing to the presence of –NH–C=S moiety. Depending on
the reaction conditions and basicity of the medium or the metal ions,
N
S
substituted these ligands coꢀordinate to a metal ion through the azomethine
dithiocarbazates,1,3,4ꢀoxadiazole/thiadiazoleꢀ2ꢀthiones/triazoles and nitrogen either in the neutral thione form or in the anionic thiolate
tetrazoleꢀ2ꢀthiols, have attracted considerable attention because of form as bidentate ligands forming five membered chelate rings [27,
their biological activities [11ꢀ16]. Thiosemicarbazides and their 28]. The ligand can also bind to the metal ion via the hydrazinic
carbazones with different substituents, as well as their metal nitrogen and the thiolate sulphur as monoanionic bidentate N,S
donor forming a four membered chelate ring [29]. Lobana et al. [30]
have reported the nickel complexes of 2ꢀacetylfuranꢀNꢀsubstituted
thiosemicarbazones
and
2ꢀacetylthiopheneꢀN
substituted
thiosemicarbazone. They have also reported the nickel complexes
with salicylaldehyde based thiosemicarbazones which might display
catalytic/biological properties in view of the versatility of the
thiosemicarbazone bonding modes in the complexes [31]. The
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capability of thiosemicarbazones to coordinate to metal ions is due to
the delocalization of electron density over the chelate ring.
Consequently, thiosemicarbazones can coordinate to metal ions as
monodentate ligands through the thiocarbonyl sulphur or as
bidentate through the thiocarbonyl sulphur and one of the hydrazinic
nitrogen atoms, leading to the formation of either a five or a four
membered chelate rings [32, 33]. Moreover, the electrocatalytic
properties and analytical applications of such Ni(II) complexes are
not intensively explored. Accordingly, in view of the possible
electroanalytical applications, interesting bonding modes, and
various other properties exhibited by this type of Ni(II) complexes,
NH
N
O
CH
3
3
3
H C
S
1.NH
2
ꢀNH2.
2. PhNCS
H
2
O
NH NH
S
H3C
N
CH
3
CH3
CH
N
Ni(OAc)
2 2
.4H O
Ni
MeOH
H
3
C
S
N
H
3
C
N
HN
2
Scheme 1 Synthesis of ligand and complex [Ni(Hapt) ] (1)
HC
CH
O
H
N
S
N
N
NH
2
Ni(OAC)
2
.4H
2
O
N
N
N
H
en, MeOH, CHCl
Ni
3
S
2
H N
NH
2
S
Scheme 2 Synthesis of complex [Ni(btsc)] (2)
we have synthesized and studied the crystal structures, thermal 2.1. IR spectra
4
behaviour and electrochemical properties, of square planar nickel(II) The IR spectrum of the ligand acetone N ꢀphenylꢀ
4
thiosemicarbazone (Hapt) shows absorptions due to the
complexes of acetone N ꢀphenyl thiosemicarbazone (Hapt) and in
situ generated benzoylꢀ3ꢀthiosemicarbazide (Hbtsc) ligand
stretching modes of NH (3236, 3166); C=N (1596); NꢀN (1069)
ꢀ
1
2
and C=S (921) cm . The IR spectrum of complex [Ni(Hapt) ]
2
. Results and discussion
(
1) shows two new bands for ν(NiꢀN) and ν(NiꢀS) at 502 and
Complexes
1and 2 were synthesized by simple and very
ꢀ1
4
05 cm , respectively. In addition, the band due to ν(NH)
convenient method in methanol solution at room temperature
and have been characterised by various physicochemical
disappeared. These results suggest the bonding of Ni(II) with
thiol sulphur and hydrazine nitrogen [34]. The ν(C=S) band
techniques. For the structural studies, the crystals of
1 and 2
ꢀ1
shows a negative shift of 149 cm with respect to the free
ligand indicating the ligand converted in to the thiol form
during complexation and the thiol sulphur involves in bonding
through metal ion. Further, the ν(N=N) band shows a positive
were grown at room temperature using simple slow solvent
evaporation technique. A methanol solution of ligand acetone
4
N ꢀphenylꢀthiosemicarbazone
(Hapt)
O to form a brown precipitate yielding complex
). Complex was synthesized by the reaction of
benzoylꢀ3ꢀthiosemicarbazide with methanolic solution of
Ni(OAc) ·4H O to form a brown precipitate. The precipitate
reacts
with
Ni(OAc)
2 2
·4H
ꢀ1
shift of 7 cm with respect to the ligand suggesting the
involvement of hydrazine nitrogen in bonding. It also suggests
[Ni(Hapt) ] (
1
2
2
that in complex
1 the ligand exists in thiol form. The bonding
2
2
through nitrogen and sulphur in complex
by Xꢀray data.
1 is further supported
was dissolved in methanol followed by the addition of acidic
solution (dilute HCl) of ethylenediamine (2 mL, 2:1 molar
ratio) and heated for 30 minutes. Scheme 1 and 2 depict the
IR spectrum of the complex [Ni(btsc)
] (2) shows
absorptions due to the stretching modes of NH (3288, 3168); Cꢀ
formation of the complexes
1 and 2. The complexes are air
ꢀ1
N (1595); NꢀN (1080) and C=S (906) cm . Absence of ν(C=O)
band in complex together and appearance of two new bands
for ν(NiꢀN) and ν(NiꢀS) at 519 and 456 cm respectively,
suggests bonding of Ni(II) with hydrazine nitrogen and thiol
sulphur after loss of one molecule of benzoic acid.
stable, nonꢀhygroscopic crystalline solids, which are soluble in
common organic solvents and can be kept at room temperature
over a prolonged period without any sign of decomposition.
2
ꢀ1
The compounds
1 and 2 melt at 280 and 223 ºC, respectively.
O
HO
2.
O
O
S
H
N
O
NH
2
∆
2. H
N
HCl
en
H
N
+
2
O
N
NH
2
H
H O
2
H
O
S
2
N
H
N
S
NH
3
H
3
N
2
H N
NH
2
S
N
H
NH
2
2NH
3
HO
ꢀ2
O
O
O
N
N
O
N
N
HN
S
N
N
NH
S
O
Ni
H
2
N
NH
2
H
H
S
S
N
NH
2
H
2
N
N
ꢀ2H2
NH
2
H
2
N
2
H N
NH
2
1
,3 sigmatropic shift
S
S
2
.
2
H
2
2
eꢀ + 2H+
N
N
N
N
H
2
N
NH
2
SH
HS
Scheme 3: Proposed mechanism for the formation of ligand and its complex [Ni(btsc)] (2)
2
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shows the major weight loss (Cald; 41.35 %, Obs 41.95; %)
which could be due to loss of –C=NꢀN=(CHꢀCH)=NꢀN=Cꢀ
moiety of the ligand. The final decomposition in the region
2
The
.2. NMR Spectral studies
1
4
H
NMR spectrum of
acetone
N ꢀphenylꢀ
6
00ꢀ700 ºC shows the loss of NiS as the final residue [39].
thiosemicarbazone (Hapt) shows two signals at 9.26 and 2.17
ppm for hydrazine and methyl protons, respectively. The
TGA analysis with 20 and 30 ºC per minute heating rates is
shown in the supplementary Figs.S1 and S2.
1
3
phenyl protons appear in the range of δ 7.57ꢀ6.99 ppm. The
NMR spectrum of Hapt shows three signals at δ 200.16, 149.50
and 25.00 ppm due to the C=S, CꢀN and CH carbons,
C
The above physicochemical characteristics suggest the
successful synthesis of the targeted ligands and metal
complexes. Electronic spectra imply the square planar geometry
of the complexes.
3
respectively. The phenyl ring carbons appear in the range of δ
1
1
17.43ꢀ130.16 ppm. The H NMR spectrum of the complex
2
[Ni(Hapt) ] (1) shows signals at δ 2.07 ppm for methyl protons
and δ 7.25ꢀ7.37 ppm for aromatic protons. The signals for NH
protons appeared at 8.08 and 9.26 ppm. Three signals are
observed at δ 175.07, 154.63 and 24.20 ppm due to the C=S,
1
3
C=N and CH
of complex
3
carbons, respectively in the C NMR spectrum
1
. The phenyl ring carbons appear in the range of δ
1
1
24.15ꢀ126.77 ppm. The H NMR spectrum of the complex
[Ni(btsc)] (
2
) shows three signals at δ 2.01, 7.35, and 8.01 ppm
and NH protons, respectively. In the complex
C NMR shows two signals at δ 178.08 and 31.12 ppm due
to the C=S and CH carbons, respectively.
.3. Electronic spectra
The complexes [Ni(Hapt)
nature suggesting the presence of Ni(II) in low spin squareꢀplanar
due to CH, NH
2
1
3
2
o
ꢀ1
Fig.1. TGA curves showing the degradation of complex 1 at 10 C min in
nitrogen atmosphere.
2
2
] (1) and [Ni(btsc)] (2) are diamagnetic in
ꢀ
1
geometry. Two high energy bands at 28515, 29410 cm for
1
and
may be assigned to charge transfer/intraꢀ
ligand transitions in squareꢀplanar geometry of Ni(II)[35,36].
.4. Thermal studies
ꢀ
1
2
7745, 28411 cm for 2
2
The thermal stability of the complexes was studied by heating the
sample at a controlled rate of 10, 20 and 30 ºC per minute under
nitrogen atmosphere. Complex
absence of lattice water as well as coordinated water [37].
Thermogram (Fig. 1) of complex shows that the complex starts
1 is stable up to 200ºC, indicating the
1
o
decomposing above 190 ºC and exhibits three distinct Fig. 2 TGA curves showing the thermal degradation of complex 2, at 10 C
ꢀ1
min in nitrogen atmosphere
decompositions in the region ranges 200ꢀ250, 350ꢀ450 and 600ꢀ750
ºC associated with release of the ligand molecule in different 2.5. Electrochemical behaviour
composition and complete decomposition with the formation of NiS
2
.5.1 Electrochemical behaviour of [Ni(Hapt)
2
] (1) and
[
38]. The first major weight loss (Cald; 64.11 %, Obs 64.14; %)
[
Ni(btsc)](2)
could be due to loss of two Ph(NH)NCS units of two ligand
molecule. The second decomposition between 350 to 450 ºC shows
the weight loss (Cald; 23.77 %, Obs; 22.86 %) is due to loss of two
Electrochemical characteristics of complexes
1 and 2 are analyzed
using cyclic voltammetry (CV) technique (Fig. 3). The complexes
were immobilized in Nafion (Nf) film separately. The immobilized
complexes show clear anodic and cathodic peaks in 0.1 M NaOH.
The metal complex immobilized Nf coated glassy carbon (GC)
(
3 2
CH ) C=N moieties of two ligand molecule. The final product (>
o
6
50 C) could be a residue of nickel, most probably nickel oxide.
Thermogravimetric curve (Fig. 2) of complex exhibits
electrodes are represented as GC/Nf/1 or GC/Nf/2.. GC/Nf/1 show
2
the anodic and cathodic peaks (E and E ) at 0.47 and 0.39 V
pa
pc
three distinct decompositions in the region 200ꢀ250, 250ꢀ400,
and 550ꢀ700 ºC. The first minor weight loss (Cald; 12.03 %,
ꢀ1
respectively, at 20 mVs scan rate. While GC/Nf/
2
shows the Epa
and Epc at 0.56 and 0.49 V respectively, at 20 mVs . The magnitude
of separation between the anodic and cathodic peak potentials, ꢁE
for GC/Nf/ (69 mV) and GC/Nf/ (70 mV) indicates that both
ꢀ1
2
Obs 12.24; %) could be due to loss of two NH units of the
p
ligand. The second decomposition between 250 to 600 ºC
1
2
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systems are close to the one electron transfer process [40,41]. The whereas at GC/Nf/
New Journal of Chemistry
2
, methanol is electrocatalytically oxidized at
oxidation and reduction peaks observed in both electrodes 0.58 V. The peak currents of methanol oxidation (at 0.58 V) on
II
III
III
II
correspond to Ni /Ni and Ni /Ni electrochemical process [42,43]. GC/Nf/
The ratio of peak currents (Ipa/Ipc) at GC/Nf/ and GC/Nf/ is found respectively. The oxidation current of GC/Nf/
to be 1.2 and 1.1, respectively. The Ipa/Ipc ratio indicates that both high with low onset potential in comparison to GC/Nf/
complexes exhibit the redox signals close to the reversible process indicating the better electrocatalytic performance of GC/Nf/ for
40ꢀ44]. On increasing the scan rate, both Ipa and Ipc increases. A plot methanol oxidation. Therefore these metal complexes can be
of the scan rate (ν) versus Ipa or Ipc is linear (inset of Fig. 3A and potentially used in direct methanol fuel cells and in methanol
1
and GC/Nf/
2
electrodes are 0.21 and 0.05 mA,
1
2
1
is four times
2
1
[
3
B), which concludes that the redox process at GC/Nf/
1
and sensors [45ꢀ47].
GC/Nf/ are surface confined process [40].
2
(
a)
Fig.4 CV responses at three different electrodes, GC/Nf (a, b), GC/Nf/1 (c, d)
and GC/Nf/2 (e, f) in absence (a, c, e) and presence (b, d, f) of 1.0 M
ꢀ1
methanol with the scan rate of 20 mVs in 0.1 M NaOH.
2
.5.3 Mechanism for methanol oxidation
Electrocatalytic oxidation of methanol at the GC/Nf/
electrodes may be represented as shown in equations 1ꢀ3.
1
and GC/Nf/2
II
III
Electrochemical oxidation of Ni L produces Ni L as shown in
III
equation 1. The electrogenerated Ni L reacts with methanol as
shown in equations
2 and 3, oxidizing the methanol to
III
II
formaldehyde. During this oxidation, Ni L is reduced back to Ni L
which forms a cycle. This process is clearly supported by the large
increase in the oxidation current with a significant decrease in the
(
b)
reduction current (during the reverse scan) at both GC/Nf/
1 and
Fig. 3 CV responses at GC/Nf/1 (A) and GC/Nf/2 (B) at different scan rates
ꢀ1
GC/Nf/ electrodes in presence of methanol. The adsorption of
2
from 10 to 500 mVs in 0.1M NaOH. Inset of A and B represents the plot
between scan rates and respective peak currents (anodic and cathodic).
III
methanol to Ni L is a fast step and the rate determining step
corresponds to the formation of formaldehyde from the methanol
2
.5.2 Electrochemical oxidation of methanol
The electrocatalytic activity of the two metal complexes is
examined with GC/Nf/ and GC/Nf/ electrodes for the
III
adsorbed Ni L [48ꢀ50]. Besides the main product, it produces water
representing the one electron transfer process [48ꢀ50].
1
2
electrochemical oxidation of methanol. The GC/Nf electrode is
also evaluated under the same conditions for a blank/control.
NiII
NiIII
+
eꢀ
(1)
L
L
Fig. 4 shows the CV response of GC/Nf/
1 and GC/Nf/2
H
electrodes for methanol oxidation in 0.1 M NaOH. GC/Nf does
not show any characteristic peaks in the potential window. On
the addition of 1.0 M methanol a negligible increase in anodic
current is observed at GC/Nf as shown in Fig. 4. In the absence
NiIII
CH
ꢀOH
NiIII
L
(2)
L
+
3
O
CH
3
H
H
NiIII
+
2OH
ꢀ
NiII
L
+
2H O
+
eꢀ (3)
O
L
C
O
+
2
of methanol, GC/Nf/1 and GC/Nf/2 electrodes exhibit similar
CH
3
H
behavior as mentioned in the previous section. However, in
presence of 1.0 M methanol a large increase in the anodic
2
.5.4. Electrocatalytic oxidation of hydrazine
current and considerable decrease in the cathodic current are Further we used the prepared metal complexes for the
observed indicating the efficient electrocatalytic behavior. At electrocatalytic oxidation of hydrazine. Fig. 5 shows the CV
GC/Nf/1, methanol is electrocatalytically oxidized at 0.46 V response of bare (GC/Nf) and metal complex modified (GC/Nf/
1 and
4
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GC/Nf/
NP lee wa s eJ od uo r nn oa tl aod fj uC s ht em ma ri sg it nr sy
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ARTICLE
2
) electrodes in absence (curves a, c, and e) and presence of Fig.5. CV responses of GC/Nf (a,b), GC/Nf/1 (c,d) and GC/Nf/2 (e,f) in
hydrazine (curves b, d, and f). At bare electrode no significant absence (a, e, c) and presence (b, f, d) of 1.0 mM of HZ in 0.1M NaOH
solution (Scan rate 20 mV/s).
change in current was observed in presence 1.0 mM of hydrazine,
The following tentative mechanism can be produced for the
whereas at metal complex modified electrodes tremendous
oxidation of hydrazine.
increment in anodic current was observed with remarkable decrease
in cathodic current. It was found that the anodic current observed in
NiIIL
NiIII
+
eꢀ
(1)
(2)
L
case of GC/Nf/
GC/Nf/ , concluding that former one have high catalytic activity for
hydrazine oxidation. Therefore, complexes and can be used for
1 was almost two times higher as compared to
2
H
1
2
NiIII
NH
NH
NiIII
L
+
2
2
NH
L
the determination of hydrazine [51,52]. In industries also they can be
used as catalyst for the production of nitrogen from hydrazine [53].
NH
+
2
GC/Nf,
GC/Nf/2,
GC/Nf/1,
GC/Nf + 1mM HZ
GC/Nf/2 + 1mM HZ
GC/Nf/1 + 1 mM HZ
H
d
ꢀ
NiIIL
4H O
+ 3eꢀ
NiIIIL +
4OH
N2
2
(3)
NH
+
NH2
10 µA
c
f
2
.6 Crystal structure description
The crystal structures of complexes
1
and 2 were obtained by
single crystal Xꢀray diffraction data. The ORTEP diagrams of
complexes and with atom numbering schemes are shown in
Figs. and . The details of the data collection, structure
solution and refinement are listed in Table . Selected bond
lengths and angles are included in Tables and
e
1
2
b
a
6
7
1
0
.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
2
3.
Potential / V
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New Journal of Chemistry
Table 1. Crystallographic data, structure solution and refinement for the complexes 1 and 2.
Parameters
Empirical formula
Formula weight
Crystal system
Space group
T ( K)
1
2
C
20
H
24
N
6
NiS
2
C
4
H
6
N
6 2
Ni S
471.28
260.98
Monoclinic
C2/c
Orthorhombic
Pbcn
173(2)
296(2)
0.71073
8.109(4)
14.882(6)
7.304(4)
90.009
881.3(7)
4
λ, Mo Kα (Å)
a (Å)
0.71073
23.403(2)
7.6265(5)
12.2279(9)
96.569(7)
2168.1(3)
4
b (Å)
c (Å)
β (°)
3
V, (Å )
Z
3
ρ
calcd (g/cm )
1.444
1.967
ꢀ1
ꢂ (mm )
F(000)
1.106
2.633
984
528
3
Crystal size(mm )
θ range for data collections(°)
Index ranges
0.35 x 0.25 x0.15
3.22 to 29.15
0.30x0.28x0.250.
2.73ꢀ31.07
ꢀ11≤ h ≤10,
ꢀ21≤ k ≤20,
ꢀ10≤ l ≤4
ꢀ30<=h<=28,
ꢀ9<=k<=9,
ꢀ16<=l<=16
No. of reflections collected
No. of independent reflections(Rint
No. of data/restrains/parameters
8292
8833
)
2563
7684
2563/0/138
1.083
1282/0/64
1.117
2
Goodnessꢀofꢀfit on F
a
b
2
R
1
, wR
2
[(I>2σ(I)]
0.0633,0.1522
0.0635, 0.1254
0.0435, 0.0753
0.0802, 0.0864
a
b
R
1
, wR
(all data)
ꢀ3
Largest difference in peak /hole (e.Å )
0.778, ꢀ0.904
0.654, ꢀ0.343
a
b
2
2
2
2 2 1/2
R
1
= Σ||
F
o
| – |F
c||Σ|F
o
|,
2 o c o
R = [Σw (|F | – |F |) /Σw|F | ]
the two phenyl rings to be 77.71° indicating that both rings are
tilted towards each other. In the complex, Ni(II) ion has a
distorted square planar coordination with bond angles [N(1)ꢀNiꢀ
S(1) = 85.99(9), N(1)ꢀNiꢀN(1) = 103.55(18) and S(1)ꢀNiꢀS(1) =
90.49°]. Both five membered chelate rings are essentially
planar. The average bond lengths of N2ꢀN1 = 1.412(4), N2ꢀC7
2
.6.1 Crystal structure description of [Ni(Hapt)
2
] (1)
] (
Fig. shows ORTEP diagram of [Ni(Hapt)
6
2
1) with the
atomic numbering scheme. The nickel(II) is coordinated in an
N2S manner by two thiosemicarbazide ligand moieties
2
utilizing thioamide sulphur and nitrogen atoms, forming two
five membered chelate rings. The sulphur and nitrogen donor
atoms are in a cis arrangement. The deprotonated ligand
coordinates bidentately to Ni(II) ion through sulphur and
nitrogen. It leads to lengthening of the C7–S1 bond (1.773Å)
and shortening of the C7ꢀN2 bond (1.29Å) and these results are
in agreement with those found for other similar nickel(II)
complexes [54ꢀ56]. It displays an almost square planar
=
1.282(5), C7ꢀS1 = 1.768(4) Å, suggest considerable
delocalization of charge in the chelate ring [57]. Ni(II) and
Zn(II) complexes of a closely related naphthyl derivative of
thiosemicarbazone have been reported where the bond lengths
and bond angles around metal centre are comparable to those in
the present complex [58]. In the solid state complex is
stabilized via intermolecular CꢀH···N interactions between CH
hydrogen of phenyl group and thioamide nitrogen of the ligand
i
nickel(II) ion coordinated by two nitrogen atoms N1 and N1
i
and two thione sulphur atoms S1 and S1 . The molecular
(
Supplementary Fig. S3). In addition, there is also a weak
structure of [Ni(Hapt) ] (1) shows the dihedral angle between
2
6
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intermolecular NꢀH···C interactions between NH hydrogen of nitrogens and two thione sulphur atoms of the ligand moiety.
i
thioamide and CH hydrogen of phenyl group (supplementary The coordination bond distances Ni–N1, Ni–N1 , Ni–S1 and
i
Fig. S3).
Ni–S1 are 1.859(2), 1.859(2), 2.159(11), 2.159(10) Å,
respectively. The coordination bond lengths and angles of the
complex agree with those reported earlier for similar Ni(II)
thiosemicarbazide complexes [54ꢀ56]. The bond distances
i
between the metal chelate ring is C1–N1, C1–C1 , NiꢀN1 and
are 1.310(4), 1.460(7) and 1.859(2) Å which are intermediate
between single and double bonds. In the solid state, the
structure is stabilized by intermolecular NꢀH···S interactions
occurring between the thione sulphur and NH
ligand molecules forming supramolecular architecture
supplementary Fig. S4).
2
hydrogen of
a
Fig.6 ORTEP diagram of [Ni(Hapt)
2
] (1)
(
Table 2. Bond length and bond angles for [Ni(Hapt) ] (1)
2
Table 3. Bond length and bond angles for [Ni(btsc)] (2)
Bond length (Å)
Bond angles (°)
i
NiꢀN(1)
1.945(3)
N(1)ꢀNiꢀN(1 )
N(1)ꢀNiꢀS(1)
103.5(18)
160.2(10)
Bond length (Å)
Bond angles (°)
NiꢀS(1)
2.148(12)
i
Ni(1)ꢀ N(1)
1.859(2)
N(1)ꢀ Ni(1)ꢀ N(1)
84.5(15)
S(1)ꢀC(7)
1.768(4)
S(1)ꢀNiꢀS(1)
C(8)ꢀN(1)ꢀNi
90.49(6)
127.3(3)
i
Ni(1)ꢀ S(1)
S(1) –C(2)
N(1)ꢀ C(1)
N(1)ꢀ N(2)
C(2)ꢀ N(2)
C(2)ꢀ N(3)
2.159(11)
N(1)ꢀNi(1) ꢀS(1)
N(1)ꢀNi(1) ꢀS(1)
171.3(8)
86.8(8)
N(1)ꢀC(8) 1.292(5)
1.761(3)
1.310(4)
1.373(3)
1.328(4)
1.331(4)
1.460(7)
N(1)ꢀN(2) 1.412(4)
N(2)ꢀC(7) 1.282(5)
N(3)ꢀC(7) 1.373(5)
N(3)ꢀC(1) 1.425(5)
N(2)ꢀN(1)ꢀNi
N(3)ꢀC(7)ꢀS(1)
N(2)ꢀC(7)ꢀS(1)
117.8(2)
113.8(3)
124.3(3)
i
S(1)ꢀ Ni(1)ꢀ S(1)
C(2) ꢀS(1) ꢀNi(1)
C(1)ꢀ N(1)ꢀ N(2)
C(1)ꢀN(1) ꢀNi(1)
N(2)ꢀ N(1)ꢀ Ni(1)
N(2)ꢀC(2) ꢀN(3)
N(2)ꢀ C(2)ꢀ S(1)
N(3)ꢀ C(2)ꢀ S(1)
101.7(6)
94.9(12)
120.9(3)
114.4(2)
124.7(19)
118.3(3)
123.3(2)
118.4(3)
2
.6.2 Crystal structure description of [Ni(btsc)] (2)
i
C(1)ꢀ C1 (10)
The crystal structure of complex
2
is depicted in Fig.
7. The
molecular structure of the complex
2
is planar in which each
atom lie in the same plane except the ethylendiamine
hydrogens. Complex adopts a squareꢀplanar geometry around
the Ni(II) ion in which the metal centre is bonded through two
The reversible redox behaviour of the Ni(II) complexes makes them
as potential catalysts in the electrochemical applications. Methanol
and hydrazine are electroꢀcatalytically oxidized by the Ni(II)
complexes immobilized in the Nafion films. This property may be
exploited in industries, in methanol sensing and in methanol fuel
cells. The thermal degradation of the metal complexes, as analysed
by TGA method, shows evidence for the formation of their
respective metal sulphides/oxides as the final thermally stable
chemical entities.
4
. Experimental
4
.1 Materials and methods
Fig.7. ORTEP diagram of [Ni(btsc)] (2) at 30% ellipsoids probability level.
Commercial reagents were used without further purification.
Ethyl acetate, methanol, and thiosemicarbazide (SD Fine
Chemicals), Nafion (5%) and phenyl isothiocyanate (Sigmaꢀ
Hydrogen atoms are omitted for clarity
3
. Conclusions
In this paper we report on the synthesis, structural investigations, and Aldrich), benzoyl chloride (Rankem), and NaOH (Qualigens)
4
physicochemical properties of Ni(II) complexes with acetone N ꢀ were used as received. All experiments were carried out at
phenylꢀthiosemicarbazone (Hapt) and in situ generated benzoylꢀ3ꢀ room temperature. The solvents were dried and distilled before
thiosemicarbazide (Hbtsc) ligand. The solid state structures of Ni(II)
complexes revealed intermolecular NꢀH···S & CꢀH···N interactions.
use following the standard procedure. Carbon, hydrogen and
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ARTICLE
New Journal of Chemistry
nitrogen contents were estimated on a CHN Model CEꢀ440 57.00, H = 5.85, N = 20.95, S = 15.91 (%) Anal. Calcd for
Analyser and on an Elementar Vario EL III Carlo Erba 1108.
C
10
H
13
N
3
S (207.00) C = 57.97, H = 6.28, N = 20.28, S = 15.45
1
13
1
H and C NMR spectra were recorded in DMSOꢀ
d
6
on a %. IR (ν cmꢀ , KBr): ν(NH) 3302,3166 ν(C=N) 1596; ν(NꢀN)
1
JEOL AL300 FTꢀNMR spectrometer using TMS as internal 1069s; ν(C=S) 973. H NMR (CDCl ); δ ppm): 9.26 (NH),
3
1
3
reference. Electronic spectra were recorded on a SHIMADZU 7.57ꢀ6.99 (m, 5H, phenyl ring), 2.17 (s, CH
700 UVꢀVis spectrophotometer. Infrared spectra were (DMSOꢀd ; δ ppm): 200.16 (C=S), 155.50 (C=N), 117.43ꢀ
recorded in the 4000ꢀ400 cm region as KBr pellets on a 130.16 (phenyl ring carbons), 25.00 (CH carbon).
Varian Excalibur 3100 FTꢀIR spectrophotometer. 4.5 Synthesis of [Ni(Hapt) ] (1)
Thermogravimetric analysis (TGꢀDTA) of complexes
were done using a Perkin ElmerꢀSTA 6000 thermal analyzer, thiosemicarbazone (Hapt) (0.207 g, 1 mmol) in MeOHꢀCH
3
). C NMR
1
6
ꢀ1
3
2
4
1
and
2
A solution of freshly prepared ligand acetone N ꢀphenylꢀ
CN
(3:1, 10 mL) was added to a MeOH solution (10 mL) of
Ni(OAc) ·4H O (0.125 g, 0.5 mmol). This mixture was stirred
3
o
ꢀ1
TA Instruments with heating rate of 10º, 20 and 30º
.2 Cyclic Voltammetry
C min .
4
2
2
Electrochemical studies were performed on a CH Instruments for 3 h at room temperature. The resulting brown precipitate
potentiostat/galvanostat (CHI 660C, USA). A three electrode, was filtered off and washed thoroughly with methanol. A
one compartment cell with glassy carbon (GC) electrode as the methanolꢀchloroform solution (10 mL) was added to the
working electrode, platinum wire as the counter electrode and methanol suspension of the above compound. The resulting
saturated calomel electrode (SCE) as the reference electrode clear solution was cooled to room temperature, filtered off and
were used. All electrochemical studies were carried out at room kept for crystallization. Single crystals of the complex suitable
temperature under nitrogen atmosphere. To immobilize the for Xꢀray analyses were obtained by slow evaporation of the
complexes on the electrode surface, 10.0 µL of Nafion (Nf) above methanolic solution over a period of 30 days. Yield:
solution (0.1%) was drop casted on the glassy carbon (GC) 45%; m.p.280 ºC. Anal. Found: C = 50.15.82, H = 4.50, N =
electrode and kept for 2 h at room temperature condition for 17.50, S = 13.77 %. Anal. Calcd for C H N NiS (471.28) C
2
0
24
6
2
1
drying (represented as GC/Nf). Further, this GC/Nf electrode = 50.92, H = 5.09, N = 17.82, S = 13.58 %. IR (ν cmꢀ , KBr):
was immersed in acidified aqueous solution of complex (5.0 ν(NH) 3371, ν(C=N) 1598; ν(NꢀN) 1076s; ν(CꢀS) 824, ν(NiꢀN)
mM) for 1 h and rinsed with distilled water. This electrode is 502; ν(NiꢀS) 405. UVꢀvis(λmax, DMSO, cm ) 28515 and 29410.
abbreviated as GC/Nf/ . Same procedure was followed for the 4.6 Synthesis of benzoyl-3-thiosemicarbazide (Hbtsc)
preparation of GC/Nf/ also. These two electrodes, GC/Nf/ Benzoylꢀ3ꢀthiosemicarbazde (Hbtsc) was prepared by the literature
and GC/Nf/ were used for electrochemical oxidation of method as described earlier [63]. Yield: 60%; m.p.178 ºC. Anal.
methanol and hydrazine. Found: C = 49.30, H = 4.45, N = 21.30, S = 16.55 %. Anal. Calcd
.3 X-ray crystallography
XꢀRay diffraction measurements of complexes
1
ꢀ1
1
2
1
2
4
for C
8
H
9
N
3
OS (195.24), C =49.17, H = 4.60, N = 21.51, S = 16.39
1
1
and
2
were %. IR (ν cmꢀ , KBr): ν(NH) 3261, 3156, ν(CꢀN) 1544; ν(NꢀN)
1
performed on a Oxford Gemini diffractometer/Bruker threeꢀ 1067s; ν(C=S) 999. H NMR (DMSOꢀd
6
; δ ppm): 10.43 (2H, NH),
1
3
circle diffractometer equipped with a CrysAlis CCD software 9.30(NH ), 7.43ꢀ7.86 (m, 5H, phenyl ring). C NMR (DMSOꢀd ; δ
2
6
package (for
monoꢀchromated Mo Kα (λ= 0.71073 Å) radiation source at carbons).
73 (for )/296 K (for ). Multiꢀscan absorption correction was 4.7 Synthesis of [Ni(btsc)](2)
applied to the Xꢀray data collection for both the complexes. The A solution of freshly prepared ligand, benzoyl 3 thiosemicarbazide
1) /SMART 6000 detector (for 2) using a graphite ppm): 182.96 (C=S), 167.40 (C=N), 127.90ꢀ132.98 (phenyl ring
1
1
2
structures were refined by direct methods (SHELXLꢀ97/2016) (Hbtsc) was dissolved in MeOHꢀCH
3
CN solution (3:1, 10 mL) in
·4H O was added dropwise.
2
and refined against all data by full matrix leastꢀsquares on F
which methanolic solution of Ni(OAc)
2
2
using anisotropic displacement parameters for all nonꢀhydrogen Green precipitate was obtained in which two drops of ethyleneꢀ
atoms. All hydrogen atoms were included in the refinement at diamine was added in slightly acidic (dil. HCl) condition. It was kept
geometrically ideal position and refined with a riding model for crystallization and blue color needle shaped crystals were
[59,60]. The MERCURY package and ORTEPꢀ3 for Windows obtained after two weeks. Yield: 45%; m.p.223 ºC. Anal. Found: C
program were used for generating molecular graphics [61,62].
= 17.95, H = 3.05, N = 32.30, S = 23.40 %. Anal. Calcd for
4
4
.4 Synthesis of acetone N -phenyl-thiosemicarbazone (Hapt)
C
4
H
6
N
6
NiS
2
(260.98), C =18.39, H = 2.29, N = 32.18, S = 24.52 %.
4
1
Acetone N ꢀphenylꢀthiosemicarbazone (Hapt) was prepared by IR (ν cmꢀ , KBr): ν(NH) 3288, 3168, ν(CꢀN) 1595; ν(NꢀN) 1080s;
ꢀ
1
adding hydrazine hydrate and phenyl isothiocyanate to a ν(C=S) 906, ν(NiꢀN) 519, ν(NiꢀS) 456. UVꢀvis(λmax, DMSO, cm )
refluxing mixture containing excess acetone in ethanol (50 27745 and 28411.
mL). The mixture was further heated and stirred for about 1 h
5
. Acknowledgement
and then left at room temperature in the open air to yield white
crystalline solid. Yield: 60 %; m.p. 167 ºC. Anal. Found: C = Research Board, India for the award of young scientist project
Dr. M. K. Bharty is thankful to the Science and Engineering
8
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(
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0 T. S. Lobana,P. Kumari,R. Sharma,A. Castineiras,R.J.
Dr. U.P. Azad, Department of Chemistry, Banaras Hindu
University for their useful suggestions.
3
Butcher,T. Akitsu, Y. Aritake, Dalton Trans., 2011,40, 3219–
6
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