Synthesis and characteristics of N-(glyoxyldioxime)-N′-(2- hydroxybenzylidene)-1,4-diaminonaphthalene and its metal complexes

Article abstract of DOI:10.1134/S1070363208050186

A new vic-dioxime, N-(glyoxyldioxime)-N′-(2-hydroxybenzylidene)-1,4- diaminonaphthalene, was synthesized proceeding from naphthalene. Its complexes of nickel, copper and cobalt were prepared. The vicdioxime and its complexes were charecterized by FT-IR, UV, ¹H NMR, mass spectrometry, elemental analysis, DTA/TG analysis techniques and conductometric measurements.

Full text of DOI:10.1134/S1070363208050186

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 5, pp. 939–945. © Pleiades Publishing, Ltd., 2008.
Published in Russian in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 797–802.
Synthesis and Characteristics of N-(Glyoxyldioxime)-N'-(2-
hydroxybenzylidene)-1,4-diaminonaphthalene
and Its Metal Complexes1
Muharrem Kayaa, Cengiz Yenikayaa, İbrahim Demirb, and Orhan Murat Kalfac
aDumlupınar University, Faculty of Science and Arts, Department of Chemistry,
Kütahya, 43100 Turkey
e-mail: mhrkaya@yahoo.com; yenikaya@dumlupinar.edu.tr
bNigde Universty, Faculty of Science and Arts, Department of Chemistry,
Nigde, 51100 Turkey
e-mail: idemir@nigde.edu.tr
c Gazi University, Faculty of Science and Arts, Department of Chemistry,
Teknikokullar, Ankara, 06500 Turke,
e-mail: omkc@yahoo.com
Received November 1, 2007
Abstract—A new vic-dioxime, N-(glyoxyldioxime)-N'-(2-hydroxybenzylidene)-1,4-diaminonaphthalene, was
synthesized proceeding from naphthalene. Its complexes of nickel, copper and cobalt were prepared. The vic-
dioxime and its complexes were charecterized by FT–IR, UV, 1H NMR, mass spectrometry, elemental analysis,
DTA/TG analysis techniques and conductometric measurements.
DOI: 10.1134/S1070363208050186
Vicinal dioximes and their complexes constitute an
important class of compounds having versatile reac-
tivities. The exceptional stability and unique electronic
properties of the vic-dioximes complexes can be attri-
buted to their planar structure which is stabilized by
hydrogen bonds [1]. These compounds were tested as
liquid crystal, gas sensors, and inhibitors for chemical
warfare agents [2–4]. Numerous oximes and Schiff
bases and their metal complexes have been inves-
tigated [5, 6]. The exceptional stability and unique
electronic properties of these complexes can be
attributed to their planar structure [7]. Acyclic ligands
containing nitrogen, oxygen and sulphur donor atoms
in their structures can act as effective chelating agents
for transition and nontransition metal ions [8]. In this
study, amphi-choloroglyoxime, anti-choloroglyoxime,
4-nitro-1-naphthylamine and FeO(OH) were prepared
by published procedures [9–14]. A new vic-dioxime,
N-(glyoxyldioxime)-N'-(2-hydroxybenzylidene)-1,4-
diaminonaphthalene H2L (III) was synthesized using
naphthalene as starting metarial, and its Ni(II), Co(II),
and Cu(II) complexes were prepared.
In order to understand the structure of the new
1
oxime and free Schiff base ligands, H NMR spectra
were employed. The assignments of the chemical shifts
in the 1H NMR spectra are listed in Table 1.
The singlet (2H) observed at 12 ppm was assigned
to the =NOH proton of H2L. The singlet (1H) observed
at 8.9 ppm was assigned to the protons of CH and to
the proton of the aldoxime group. The multiplet (10H)
observed at 8.4–6.7 ppm corresponded to the aromatic
ring protons of the H2L. Futhermore, the singlets at
15.1 and 3.8 ppm were attributed to the protons of
phenolic OH and NH groups in the ligand H2L,
respectively.
The assigment of the most charecteristic IR bands
is given in Table 2.
The vibrations of the sterically hindered oxime
groups of the free Schiff base ligand [H2L] are
observed at 3400–3500 cm–1 [15, 16]. When the
spectra of the complexes are compared with those of
the uncomplexed imine oxime ligand the ν(C=N) band
1 The text was submitted by authors in English.
939

940
KAYA et al.
NO2
NO2
CHO
OH
(1) HNO3/H2SO4
+
(2) NH2OH, KOH, MeOH
NH2
N
CH
NOH
NOH
NH2
H2O
N2H4
HN
OH
HON
HON
Cl
H
H
FeO(OH)
I
+
N
N
OH
CH
HC
OH
III
II
is shifted to lower frequency [17, 18]. This indicated
that the imine nitrogen was coordinated to the metal
ion. The absorbtion bands in the region 525–560 cm–1
and 400–420 cm–1 in the spectra of complexes belong
to ν(M–N) [17] and ν(M–O) [18].
complexes are soluble in DMF, DMSO and insoluble
in the other organic solvents. The electronic absorbtion
spectral data of the free ligand and their complexes are
given in Table 4.
In the spectra of the Schiff base ligand bands at
231–267 nm are attributed to the benzene π–π*
transtions [19–21]. The bands at 332–431 nm are
assigned to the imine π–π* transition. Compared to the
free ligand, the imine π–π* transitions of the complexes
were shifted to some extent, because the imine
The analitical data for the ligands and their metal
complexes are listed in Table 3.
The composition of Ni and Co complexes cor-
responds to a general formula [M3(H2L)2]. The Schiff
base ligand is soluble in common organic solvents. All
Table 1. 1H NMR spectra of the Schiff base ligands
Comp.
δ, ppm
no.
Assignment
-CH=N-
8.9 s (1H)
I
8.4 d (1H), 8.2 d (1H), 8.1 d (1H), 8.0 d (1H), 7.7 d (1H), 7.5 d.d (1H), 7.3 d.d (1H), 7.2 d.d (1H),
Aromatic ring (H)
6.7 d (1H)
15.1 br (1H)
Phenolic OH
-CH=N-
8.9 s (1H)
II
8.4 d (1H), 8.2 d (1H), 8.1 d (1H), 8.0 d (1H), 7.7 d (1H), 7.5 d.d (1H), 7.3 d.d (1H), 7.2 d.d (1H),
Aromatic ring (H)
6.7 d (1H)
15.1 br (1H)
Phenolic OH
NH2
4.2 s (2H)
12 s (2H)
III
=NOH
8.9 s (1H)
-CH=N-
8.4 d (1H), 8.2 d (1H), 8.1 d (1H), 8.0 d (1H), 7.7 d (1H), 7.5 d.d (1H), 7.3 d.d (1H), 7.2 d.d (1H),
Aromatic ring (H)
6.7 d (1H)
8.1 s (1H)
15.1 br (1H)
3.8 s (1H)
-CH=N-
Phenolic OH
NH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

SYNTHESIS AND CHARACTERISTICS OF N-(GLYOXYLDIOXIME)-...
Table 2. Infrared spectral data of the free ligands and their complexes
941
Compound
O–H
3360
3350
3400
C=N
1642
1645
1640
1650
N–H
–
C–H (Ar)
3070
C=C
1585
1585
1590
1590
C–N
1155
1150
1150
1165
N–O
985
–
M–N
M–O
–
–
–
–
I
3330
3320
–
3065
II
III
3070
970
950
–
–
Ni3[H2L]2·4H2O
3300–3500
(H2O)
3060
525
400
Co3[H2L]2·10H2O
Cu[H2L]2
3300–3500
(H2O)
1645
1645
–
3065
3060
1585
1585
1160
1150
960
960
560
550
410
420
3350
3290
Table 3. Some analytical data and physical properties of the Schiff base ligands and complexes
Found (calculated), %
Molecular
weigt
mp,
°C
Yield,
%
Compound
Formula
C
H
N
C17H12N2O3
C17H14N2O
292.3
262.3
348.3
1058.9
155
120
61
92
57
77
69.48 (69.86)
77.80 (77.86)
65.18 (65.52)
47.58 (47.64)
4.03 (4.11)
5.44 (5.34)
4.25 (4.60)
3.97 (4.00)
9.93 (9.59)
10.39 (10.69)
15.95 (16.09)
10.54 (10.58)
I
II
C19H16N4O3
160
III
Ni3[H2L]2·4H2O
C42H42N8Ni3O14
230
decomp.
>300
Co3[H2L]2·10H2O
Cu[H2L]2
C42H54Co3N8O20
C38H30CuN8O6
1167.7
758.2
71
55
43.14 (43.20)
60.07 (60.19)
4.62 (4.66)
3.96 (3.99)
9.55 (9.60)
195
14.72 (14.78)
nitrogen was involved in coordination with the metal
ion. The molar conductance values of the Ni(II),
Co(II), and Cu(II) complexes are in the range 5 to
32 Ω–1 cm2 mol–1 in 10–3 M DMF solutions indicating
the non–electrolytic nature of these compounds [18].
The theoretical mass of the remaining NiO is 7.12%
in agreement with 7.87% from the TG studies. The
theoretical mass losses in the second, third, and fourth
decomposition stages are 24.19, 54.33, and 72.24%
respectively in agreement with the experimental values
24.33, 54.08, and 72.44.
The thermogravimetric analysis was carried out in
the temparature range 0–1100°C. The samples were
placed in platinum crucibles and α-Al2O3 was used as
the reference material. Heating was performed under
N2 atmosphere at a flow rate of 60 ml min–1. The
sample size was limited to 2–8 mg, and the heating
rate was adjusted to 10°C/min in all cases.
The DTA/TG diagrams of the Co(II) complex are
shown in Fig. 1b. It was found from TG analysis that
the sample starts losing mass at 200°C and ends at
900°C after losing 93.6% of its mass and becoming a
black-brown residue which correspond to 6.40% of the
total mass. The examination of TG curve showed that
the sample decomposes in three stages. The sample
loses 10.40% of mass between 100 and 200°C, 25.15%
of the mass between 200 and 270°C, and 94.88%
It is noted from the TG analysis that the Ni(II)
complex of H2L loses 92.13% of its original mass
between 198 and 650°C and the 7.87% residue is a
greenish-black solid. The DTA/TG data for the Ni
complex are shown in Fig. 1a. The sample decomposes
in four stages.The first decomposition occurs between
198 and 250°C with 11.21% mass loss, the second
decomposition occurs between 250 and 300°C with
24.33% mass loss, the third decomposition occurs
between 300 and 450°C with 54.08% mass loss, and
the fourth decomposition stage between 425 and 640°C,
with 72.44% mass loss.
Table 4. Magnetic moments and electronic spectral data of
the Schiff base ligand and its metal complexes
Compound
μeff
λmax, nm
–
430, 399, 359, 335, 322, 267, 211
430, 332, 266, 251, 232
III
Ni3[H2L]2·4H2O
Co3[H2L]2·10H2O
Cu[H2L]2
2.51
3.62
1.69
430, 335, 265, 251, 231
651, 502, 431, 401, 321, 247
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

942
KAYA et al.
(a)
DTA UV/mg
2.00
TG, %
exo
100
90
80
70
60
50
40
30
1.50
1.00
0.50
0.00
200
400
600
800
1000
Temperature, °C
(b)
DTA UV/mg
100
90
80
70
60
50
40
30
20
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
200
400
600
Temperature, °C
(c)
800
1000
DTA UV/mg
TG, %
100
exo
7
6
5
4
3
2
1
0
80
60
40
20
200
400
600
800
1000
Temperature, °C
Fig. 1. DTA/TG diagrams of H2L with (a) Ni(II), (b) Co(II), (c) Cu(II).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

SYNTHESIS AND CHARACTERISTICS OF N-(GLYOXYLDIOXIME)-...
943
between 270 and 900°C. The TG analysis showed that
the Co(II) complex yields in pyrolysis a solid product
of mass 6.40% corresponding to the theoretical mass
of 6.42% for CoO. The Co(II) complex decomposition
in three stages predicts theoretical losses of 10.16,
25.60, and 94.91% of its mass during pyrolysis,
respectively in good agreement with the mass losses
derived from TG curve: 10.40, 25.15, and 94.88%. The
TG studies on the Cu(II) complex of H2L showed that
the initial mass loss occurred at 195°C. Decomposition
ends with a total mass loss of 90.80% at 650°C leaving
a black solid residue corresponding to a mass of
9.80%. DTA/TG diagrams of the Cu(II) complex are
shown in Fig. 1c. It was observed from the TG curve
that the sample decomposes in three stages and it loses
4.52%, 29.03 and 67.20% of its mass in each stage,
respectively. The temperatures ranges of these decom-
position are 195–240, 240–330, and 330–615°C,
respectively. The theoretical mass losses of each stage
are as follows; 4.48, 28.26, 67.26% where the
corresponding experimental percent mass losses are
4.52, 29.08, 67.20%, respectively. It was concluded
from TG studies that all the Ni(II), Co(II) and Cu(II)
complexes examined were converted on pyrolysis to
the corresponding oxides [22].
and refluxed for 24 h. After cooling, the resulting
precipitate was filtered off, recrystallized from
anhydrous ethanol, washed several times with diethyl
ether, and dried over calcium chloride under a vacuum.
Yield: 61% , mp 155°C, in the FAB–MS m/z: 291.8
(M+).
Synthesis of 2-[(4-aminonaphthalen-1-ylimino)
methyl]phenol (II). For 0.5 h, 0.5 g of FeO(OH) was
activated in water as catalyst and then it was added to
the solution of I (5.35 g, 0.018 mol in 130 ml of
anhydrous ethanol). Into the mixture a solution of
hydrazinium hydroxide (N2H4·H2O, 1.37
g
in
anhydrous ethanol) was added dropwise in 5 min and
refluxed for 5 h. Catalyst was filtered off after cooling
the reaction mixture to room temprature. Excess
ethanol was removed under a vacuum to give yellow
solid residue. The product was recrystalcized from
anhydrous ethanol. Yield: 92%, mp 120°C, in the
FAB–MS m/z: 262.7 (M+).
Synthesis of N-(glyoxyldioxime)-N'-(2-hydroxy-
benzylidene)-1,4-diaminonaphthalene (III, H2L). A
water solution of NaHCO3 (0.84 g, 10 mmol) was
added to a solution of II (1.32 g, 5 mmol in 40 ml of
anhydrous ethanol), then a solution of anti-chloro-
glyoxime (0.613 g, 5 mmol in 30 ml of anhydrous
ethanol) synthesized by the method described pre-
viously was added dropwise to the mixture at room
temperature within 2 h. The mixture heated on a water
bath at 60–70°C was stirred for 5 h more. The yellow
mixture was filtered and excess of ethanol was
removed by evaporation on a rotary evaporator. The
product was precipitated by the addition of diethyl
ether. The product was filtered off, washed with
diethyl ether several times, and dried under a vacuum
for 24 h. Yield: 57%, mp: 160°C, in the FAB–MS
m/z: 347.9 (M+).
EXPERIMENTAL
Elemental analyses for carbon, hydrogen, and nitro-
gen were obtained on a Carlo Erba 1106 analyser.
Jasco FT/IR–300E spectrometer was used for
characterization of compounds by IR spectra. The
electronic spectra in the 200-800 nm range were
recorded in DMF on a spectrophotometer Shimadzu
UV–160A. Conductivities were measured in DMF at
24°C using a conductivity meter LF330/SET. Mag-
netic moments were measured by the Gouy metod
1
using Hg[Co(SCN)4] as calibrant. H NMR spectrum
of the ligand H2L was recorded on a Bruker Avance-
500 NMR instrument. DTA/TG spectra of the com-
plexes were recorded by A Setaram Setys Evolution
TGA–DTA/DSC 1750 thermal analysis system. Chem-
icals used in the study were purchased from Sigma-
Aldrich, and all of them were purified by published
procedures [23].
Synthesis of Ni3(H2L)2 · 4H2O complex (IV). A so-
lution of 3 mmol of the metal salt [Ni(CH3COO)2·6H2O,
0.357 g] in 20 ml of distilled water was added to the
solution of the ligand III (2 mmol, 0.696g) in 20 ml of
ethanol. The pH of the mixture was adjusted to 4.5–5.0
with the addition of 0.100 N NaOH solution. In order
to complete the precipitation, the mixture was kept on
a water bath at 25°C for 2 h. The complex formed was
filtered off, washed with water, diethyl ether, and cold
ethanol, then dried in a vacuum at 70°C. Yield: 77%,
mp 230°C (decomposition point), in the FAB–MS m/z:
1058.1 (M+).
Synthesis of 2-[(4-nitronaphthalen-1-ylimino)
methyl]phenol (I). 4-Nitro-1-naphthylamine (5.64 g,
0.03 mol) dissolved in anhydrous ethanol (50 ml) was
added with constant stirring to a solution of
salicylaldehyde (3.66 g, 0.03 mol) in anhydrous
ethanol. The mixture was stirred with a magnet stirrer
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

944
KAYA et al.
2+
OH2
H
H
C
H2O
N
Ni
O
N
O
C
N
H
(CH3COO_)2
N
N
C
H
O
O
Ni
N
H
C N
H
Ni
C
OH2
O
O
N
C
H
OH2
H
IV
Synthesis of Co3(H2L)2 · 10H2O complex (V). A so-
lution of 3 mmol of the metal salt [Co(CH3COO)2·4H2O,
0.747 g] in 20 ml of distilled water was added to the
solution of the ligand (H2L, 2 mmol, 0.696g) in 20 ml
of ethanol. The pH of the mixture was adjusted to 4.5–
5.0 with the addition of 0.100 N NaOH solution. In
order to complete the precipitation the mixture was
kept on a water bath at 25°C for 2 h. The complex
formed was filtered off, washed with water, diethyl-
ether, and cold ethanol, then dried under a vacuum at
70°C. Yield: 71%, mp >300°C, in the FAB–MS m/z:
1167.2 (M+).
2+
OH2
H
H
N
H2O
H2O
OH2
O
C
Co
N
O
C
N
H
H
N
(CH3COO_ )2
C
O
OH2
Co
N
_
H2O
O
N
C
H
N
C
H
OH2
OH2
OH2
Co
O
O
N
C
H2O
H
H
V
Synthesis of the Cu(H2L)2 complex (VI). A so-
lution of 1 mmol of the metal salt [Cu(CH3COO)2·H2O,
0.199 g] in 20 ml of distilled water was added to the
solution of the ligand (H2L, 2 mmol, 0.696g) in 20 ml
of ethanol. The pH of the mixture was adjusted to
4.5–5.0 with the addition of 0.100 N NaOH solu-
tion. To complete the precipitation the mixture was
kept on a water bath at 25°C for 2 h. The complex
formed was filtered off, washed with water,
diethylether, and cold ethanol, then dried in a vacuum
at 70°C. Yield: 55%, mp 195°C, in the FAB–MS m/z:
757.2 (M+).
H
H
N
C
C
HO
O
N
N
H
N
N
H
O
C
Cu
N
H
O
C N
H
C
O
N
OH
C
H
H
VI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

SYNTHESIS AND CHARACTERISTICS OF N-(GLYOXYLDIOXIME)-...
945
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