Synthesis and characterization of some metal complexes of isonitroso-2-acetylnaphthalene derivative

Article abstract of DOI:10.1134/S1070363216080235

Nickel(II), copper(II), and zinc(II) complexes with the Schiff base obtained from isonitroso-2-acetylnaphthalene and 1,2-phenylenediamine were synthesized. The compounds were characterized by elemental analyses, FT-IR, UV-Vis, and ¹H and ¹

Full text of DOI:10.1134/S1070363216080235

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 8, pp. 1917–1921. © Pleiades Publishing, Ltd., 2016.
Synthesis and Characterization of Some Metal Complexes
1
of Isonitroso-2-acetylnaphthalene Derivative
S. Y. Uçan, M. Uçan*, and İ. Demir
Department of Chemistry, Faculty of Arts and Sciences, Niğde University, 51200 Niğde, Turkey
*
e-mail: selma.y.ucan@gmail.com
Received September 30, 2015
Abstract—Nickel(II), copper(II), and zinc(II) complexes with the Schiff base obtained from isonitroso-2-
acetylnaphthalene and 1,2-phenylenediamine were synthesized. The compounds were characterized by
1
13
elemental analyses, FT-IR, UV-Vis, and H and C NMR spectra, conductance measurements, magnetic
susceptibility measurements, and thermal analysis. The results suggest tetradentate coordination of the
symmetrical Schiff base ligand through the two oxime oxygen atoms and two azomethine nitrogen atoms. The
molar conductance data showed that the synthesized complexes are non-electrolytes.
Keywords: isonitroso-2-acetylnaphthalene, Schiff bases, metal chelates
DOI: 10.1134/S1070363216080235
–
1
Synthesis of imine oximes and their complexes is
one of the challenging areas in the field of the oxime
coordination chemistry. Imine oximes have been
extensively studied because of their biological and
structural importance which lies mainly in their
specific and selective reactions with metal ions [1–7].
On the other hand, metal complexes of Schiff bases
derived from aromatic carbonyl compounds are of
great interest in inorganic chemistry. Schiff bases of
diamines and their complexes have a variety of applica-
tions, including biological, clinical, and analytical
due to C–Harom stretching, and 990–980 cm due to
N–O stretching [10−13]. The spectrum also contained
characteristic C=N stretching band in the region 1645–
–
1
1620 cm , which shifted to lower frequencies in the
–
1
spectra of complexes 1–3 (1625–1585 cm ). Metal
complexes 1–3 displayed in the IR spectra new bands
–
1
in the regions 470–420 and 520–470 cm due to
formation of M–O and M–N bonds, respectively [3, 8, 19].
1
The H NMR spectrum of the ligand showed a
broad singlet at δ 9.20−9.00 ppm from the oxime OH
protons [2–4] and a singlet at δ 8.75–8.72 ppm due to
the N=CH protons [13–17]. Aromatic protons re-
sonated as multiplet signals in the regions δ 8.50−
.59 ppm. Unlike free ligand L, the spectra of metal
complexes 1–3 lacked OH proton signal, and the
[8–10]. In recent years, many Schiff bases and their
metal complexes have been synthesized and reported
to exhibit biological activity [11–18]. In this paper, we
report the synthesis and spectral characterization of
Ni(II), Cu(II), and Zn(II) complexes of the Schiff base
derived from isonitroso-2-acetylnaphthlene [2-hydroxy-
imino-1-naphthalen-2-yl)ethanone] and 1,2-phenylene-
diamine (Scheme 1).
7
N=CH signal was observed in a slightly stronger field
13
(
δ 8.68 ppm for Zn complex 1). In the C NMR
spectrum of the ligand, the signals at δ 189.79 and
71.26 ppm were assigned to the azomethine and
C
1
The analytical and physical data of Schiff base
ligand L and its complexes 1–3 are given in Table 1.
The complexes are soluble in DMF and DMSO and are
insoluble in ethanol, acetone, and chloroform. The
elemental analyses of the Schiff base and its
complexes are consistent with those calculated from
their empirical formulas.
oxime carbon atoms respectively [5, 14]. All signals in
the region δ 150.84−125.10 ppm corresponded to
C
aromatic carbons.
The molar conductances of complexes 1–3 were
measured at 25°C in DMF solutions with a concentra-
–3
tion of 10 M. Taking into account the obtained values
–1
2
–1
(
10.3–18.4 W cm mol ; Table 1), the complexes
The IR spectrum of the ligand showed bands at
265–3260 cm due O–H stretching, 3090–3085 cm
may be regarded as non-electrolytes.
–
1
–1
3
The magnetic moment of copper(II) complex 2 is
1
The text was submitted by the authors in English.
1.81 B.M. suggesting its square planar geometry [11].
1
917

1
918
UÇAN et al.
Scheme 1.
H
NOH
NH2
H
NOHHON
H
O
Me n-BuONO, EtONa
O
NH2
N
N
L
N O
O N
H
H
M
N
N
M(OAc) ·nH O
2
2
1
–3
1
, M = Ni, n = 4; 2, M = Cu, n = 1; 3, M = Zn, n = 2.
3
3
The magnetic moment of complex 1 was estimated at
.01 B.M., which is typical of tetrahedral Ni(II)
complexes (2.9–3.9 B.M.) [4, 5]. Zinc(II) complex 3 is
diamagnetic, as expected for d metal ion in a
tetrahedral geometry [20].
T (F)→ A (F) transition presumably arising from a
1 2
3
tetrahedral geometry [15]. The spectrum of zinc(II)
complex 3 showed an absorption band at λ 418–
423 nm due to ligand-to-metal charge transfer, which
is consistent with its tetrahedral structure. No d–d
1
0
1
0
transition is expected for d Zn(II) complexes [12].
The electronic spectra of complexes 1–3 were
–
3
recorded from 10 M solutions in DMF at room
temperature. The free ligand displayed two absorption
bands with their maxima at λ 257−269 and 329−346 nm.
These bands were attributed to π→π* transitions, the
first involving the aromatic ring, and the second, the
imino group. In the spectra of complexes 1–3, the
second absorption band was shifted to longer
wavelengths as a result of coordination. The electronic
spectrum of Cu(II) complex 2 showed absorption
bands in the λ ranges 500–553 and 650–709 nm
Thermogravimetric analysis data for complexes 1–3
are given in Table 2. The results showed a good
agreement with their elemental analyses (Table 1).
Weight losses for each chelate were calculated within
the corresponding temperature ranges (Fig. 1).
Thermal behavior of the complexes was studied using
thermogravimetric analysis from ambient temperature
to 900°C in a nitrogen atmosphere. Nickel(II) complex
1 decomposed in two steps. The first step was
observed in the range 30–450°C with a weight loss of
36.50%, which was assigned to partial elimination of a
C H N fragment. The second step was found in the
2
2
2
2
assignable, respectively, to B → E and B → A
1g
g
1g
1g
transitions of a square planar structure [17]. Nickel(II)
complex 1 was characterized by an absorption band at
λ 660–690 nm which may be attributed to the
1
3
8
2
temperature range 450–900°C with a weight loss of
49.31%, which was assigned to removal of C H N O.
1
7
12
2
Table 1. Yields, melting points, elemental analyses, and molar conductances of Schiff base ligand L and complexes 1–3
Found, %
H
Calculated, %
H N
Comp. Yield,
m
L ,
mp, °C
Formula
M
–1
–1
2
no.
%
W mol cm
C
N
C
L
1
2
3
86
80
87
76
143
198
129
164
76.48 4.42 11.79
68.22 3.63 10.43
67.63 3.60 10.40
67.38 3.51 10.35
C
30
C
30
C
30
C
30
H
H
H
H
22
20
N
N
4
4
O
2
76.58 4.71 11.91
68.35 3.82 10.63
67.72 3.79 10.53
470.53
527.20
532.06
533.90
–
NiO
2
15.8
18.4
10.3
4 2
20CuN O
20
4 2
N O Zn 67.49 3.78 10.49
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

SYNTHESIS AND CHARACTERIZATION OF SOME METAL COMPLEXES
1919
(
a)
DTA, mV
(b)
DTA, mV
Temperature, °C
Temperature, °C
(
c)
Temperature, °C
Fig. 1. Thermal analysis of complexes (a) 1, (b) 2, and (c) 3.
The final weight of the residue corresponds to nickel
oxide. Copper(II) complex 2 decomposed in two steps.
The first step was observed in the range 30–450°C
with a weight loss of 36.59%, which was assigned to
partial elimination of a C H N fragment. The second
step found in the range 550–900°C with a weight loss
of 37.47% was assigned to removal of C H N O mole-
cule. The weight of the residue corresponded to ZnO.
10
8
4
Scanning electron microscopy analysis of the
ligand and transition metal complexes 1–3 showed that
the original morphology of Schiff base ligand L
disappeared and that aggregates of amorphous pieces
of irregular size appeared (Fig. 2).
13
10
2
step corresponded to removal of C H N O molecule
1
7
10
2
with a weight loss of 48.46%. The residue was
identified as CuO. Zinc(II) complex 3 decomposed in
two steps. The first step in the temperature range 30–
5
50°C with a weight loss of 47.19% was assigned to
In summary, Ni(II), Cu(II), and Zn(II) complexes
of the Schiff base derived from isonitroso-2-acetyl-
removal of the naphthalene rings (C H ). The second
2
0
12
Table 2. Thermal analysis of the complex compounds
Weight loss, %
Inorganic residue (MO), %
Comp.
no.
Temperature
range, °C
Formula
Lost fragment
found
calculated
found
14.19
14.95
15.34
calculated
1
2
3
C
C
C
30
30
30
H
H
H
20
N
4
NiO
2
30–450
36.50
49.31
36.46
49.37
C
C
13
H
H
8
N
2
4
4
5
50–900
17
12
N
2
O
O
14.17
20CuN
4
O
2
30–450
50–900
36.59
48.46
36.51
48.58
C
C
13
H
H
10
10
N
N
2
2
17
14.94
20
N
4
O
2
Zn
30–550
50–900
47.19
37.47
47.26
37.50
C
C
20
H
H
12
8
10
N
4
O
15.24
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

1
920
UÇAN et al.
(b)
(
a)
1
μm
1 μm
(
c)
(d)
1
μm
1 μm
Fig. 2. Scanning electron micrographs of (a) ligand L and complexes (b) 1 (c) 2, and (d) 3.
naphthlene and 1,2-phenylenediamine have been syn-
thesized in good yields and characterized by spectral
data, molar conductance and magnetic moment
measurements, and thermogravometric analysis. The
results suggest a square–planar geometry of the Cu(II)
complex and tetrahedral geometry of the Ni(II) and
Zn(II) complexes.
spectra were recorded in KBr using a Pye-Unicam SP
1025 instrument. The electronic spectra were measured
on a Shimadzu 160 UV-Vis spectrophotometer in the
wavelength range 200–600 nm. The molar conducti-
vities were measured in DMF with a WTW LF 330
conductivity meter. Thermal gravimetric analysis was
carried out on a Shimadzu TGA-50 instrument.
EXPERIMENTAL
(
2E,2′E)-2,2′-(1,2-Phenylenediazanylylidene)bis
All reagents were of analytical grade and were used
without further purification. Isonitroso-2-acetylnaphtha-
lene was prepared according to our previous procedure
[(naphthalen-2-yl)acetaldehyde] dioxime (L). A
solution of 1.081 g (10 mmol) of 1,2-phenylenedi-
amine in 10 mL of methanol was added to a solution of
3.984 g (20 mmol) of isonitroso-2-acetylnaphthalene
in 20 mL of methanol. The mixture was stirred for 3 h
and left overnight at 25°C. The precipitate was filtered
off, washed with cold ethanol, recrystallized from
methylene chloride, and dried under reduced pressure.
[
19, 20]. Benzene-1,2-diamine, Ni(OAc) · 4H O,
2 2
Cu(OAc) ·H O, and Zn(OAc) ·2H O were purchased
2
2
2
2
from Merck and Sigma–Aldrich. All solvents were
obtained from Merck. The elemental analyses (C, H
and N) were determined using a Carlo Erba 1106
analyzer. The magnetic susceptibilities of the
complexes in the solid state were determined using a
Gouy balance at room temperature using copper
–
1
Its purity was checked by TLC. IR spectrum, ν, cm :
1
3265 (O–H), 1640–1620 (C=N), 990 (N–O). H NMR
spectrum (DMSO-d ), δ, ppm: 9.00 s (2H, NOH), 8.72
6
1
13
13
sulfate as calibrant. The H and C NMR spectra of
were recorded on a Varian T 200–A spectrometer in
s (2H, CH=N), 8.17–7.59 m (18H, Harom). C NMR
spectrum (DMSO–d ), δ , ppm: 189.79 (C=NOH),
6
C
CDCl using TMS as internal standard. The FT IR
171.26–171.16 (CH=N), 150.84–125.10 (Carom).
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

SYNTHESIS AND CHARACTERIZATION OF SOME METAL COMPLEXES
Metal complexes 1–3 (general procedure). A
00958970802345831.
1921
solution of 1 mmol of the corresponding transition
metal acetate [0.248 g of Ni(OAc) ·4H O, 0.199 g of
7. Uçan, S.Y., Uçan, M., and Mercimek, B., Synth. React.
Inorg. Met.-Org. Nano-Met. Chem., 2005, vol. 35, no. 5,
p. 417. doi 10.1081/SIM-200059233.
2
2
Cu(OAc) ·H O, or 0.219 g of Zn(OAc) ·2H O] in
2
2
2
2
8
9
. Raman, N., Jeyamurugan, R., Subbulakshmi, M.,
Boominathan, R., and Yuvarajan, C. R., Chem Pap.,
2
0 mL of ethanol was added to a solution of 1 mmol
(
0.470 g) of Schiff base L in 30 mL of ethanol. The
2
0
010, vol. 64, no. 3, p. 318. doi 10.2478/s11696-010-
003-0.
mixture was stirred for 2 h at 60°C. After cooling, the
precipitate was filtered off, washed with cold ethanol,
and dried under vacuum over CaCl2.
. El-Sherif, A.A. and Eldebss, T.M.A., Spectrochim.
Acta, Part A, 2011, vol. 79, no. 5, p. 1803. doi
10.1016/j.saa.2011.05.062.
–
1
Nickel complex 1. IR spectrum, ν, cm : 1625–
1
1
600 (C=N), 920 (N–O), 480 (M–N), 430 (M–O).
10. Taha, Z.A., Ajlouni, A.M., Al-Hassan, K.A., Hijazi, A.K.,
and Faiq, A.B., Spectrochim. Acta, Part A, 2011,
vol. 81, no. 1, p. 317. DOI:10.1016/j.saa.2011.06.018.
–
1
Copper complex 2. IR spectrum, ν, cm : 1620–
590 (C=N), 925 (N–O), 520 (M–N), 470 (M–O).
1
1. Singh, K., Barwa, M.S., and Tyagi, P., Eur. J. Med.
Chem., 2006, vol. 41, no. 1, p. 147. doi 10.1016/
j.ejmech.2005.06.006.
–
1
Zinc complex 3. IR spectrum, ν, cm : 1610–1585
1
(
C=N), 915 (N–O), 490 (M–N), 440 (M–O). H NMR
spectrum (DMSO–d ), δ, ppm: 8.68 s (2H, CH=N),
12. Al-Ne’aimi, M.M., and Al-Khuder, M.M., Spectrochim.
Acta, Part A, 2013, vol. 105, p. 365. doi 10.1016/
j.saa.2012.10.046.
6
8
.09–7.29 m (18H, Harom).
ACKNOWLEDGMENTS
The authors thank the Research Foundation of the
1
3. Eltayeb, M.A.Z. and Sulfab, Y., Polyhedron, 2007,
vol. 26 no.1, p. 1. doi 10.1016/j.poly.2006.04.019.
1
4. Keypour, H., Rahpeyma, N., Arzhangi, P., Rezaeivala, M.,
Elerman, Y., Buyukgungor, O., and Valencia, L.,
Polyhedron, 2010, vol. 29, p. 1144. doi 10.1016/
j.poly.2009.12.005.
Nigde University (BAP) for financial support of this
work (P.N. FEB 2007–05).
1
1
1
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