Co(II), Ni(II), and Cu(II) Complexes of N-(2-Hydroxybenzamido)phthalimide

Article abstract of DOI:10.1134/S1070363219030307

Co(II), Ni(II), and Cu(II) complexes with N-(2-hydroxybenzamido)phthalimide (LH₂) were synthesized and studied by IR, electron absorption, EPR spectroscopy, and thermogravimetry. In the case of Cu(II) ions, binuclear Cu₂L₂ complexes are formed, in which the ligand acts as a dianion, while Co(II) and Ni(II) ions form M(LH)₂ complexes.

Full text of DOI:10.1134/S1070363219030307

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 3, pp. 546–548. © Pleiades Publishing, Ltd., 2019.
Russian Text © G.G. Gondolova, S.Z. Ismailova, P.A. Fatullaeva, A.A. Mejidov, 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 3,
pp. 479–482.
LETTERS
TO THE EDITOR
Co(II), Ni(II), and Cu(II) Сomplexes
of N-(2-Hydroxybenzamido)phthalimide
G. G. Gondolovaa*, S. Z. Ismailovab, P. A. Fatullaevab, and A. A. Mejidovb
a Institute of Ecology and Natural Resources, Ganja Department of the National Academy of Sciences of Azerbaijan,
pr. G. Aliyeva 153, Ganja, AZ 2003 Azerbaijan
*e-mail: gulnargondolova@gmail.com
b M. Nagiyev Institute of Catalysis and Inorganic Chemistry
of the National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received September 13, 2018; revised September 13, 2018; accepted September 27, 2018
Abstract—Co(II), Ni(II), and Cu(II) complexes with N-(2-hydroxybenzamido)phthalimide (LH2) were
synthesized and studied by IR, electron absorption, EPR spectroscopy, and thermogravimetry. In the case of
Cu(II) ions, binuclear Cu2L2 complexes are formed, in which the ligand acts as a dianion, while Co(II) and
Ni(II) ions form M(LH)2 complexes.
Keywords: N-(2-hydroxybenzamido)phthalimide, copper complexes, nickel complexes, cobalt complexes
DOI: 10.1134/S1070363219030307
Compounds based on hydrazides of carboxylic
acids and their metal complexes possess anti-
tuberculosis [1–2], anti-cancer [3–5], anti-malarial [6],
and antimicrobial [7, 8] activity. Phthalimide deri-
vatives of hydrazides are known to exhibit anti-
microbial activity [9, 10]. Earlier we have synthesized
Fe(II) and Mn(II) complexes with N-(2-hydroxy-
benzamido)phthalimide (LH2) based on salicyl-
hydrazide and phthalic anhydride [11]. In continuation
of the work on synthesis and study of salicylhydrazide
and phthalic anhydride derivatives and their complexes
with metals, in this work we have synthesized Co(II),
Ni(II), and Cu(II) complexes with N-(2-hydroxy-
benzamido)phthalimide and studied them by IR,
electronic absorption, EPR spectroscopy and thermo-
gravimetry.
anhydride in a DMF solution at 85°C within 3.5 h [11].
As shown earlier, this ligand is able to play the roles of
mono- and dianions as a result of its existence in the
keto- and enol forms (Scheme 1). Oxygen atoms of the
amide group and of phthalimide fragment can
participate in the coordination with metal ions
Co(II), Ni(II), and Cu(II) complexes were
synthesized by reactions of Co(CH3COO)2·4H2O,
Ni(CH3COO)2·4H2O, and Cu(CH3COO)2·H2O, respec-
tively, with N-(2-hydroxybenzamido)phthalimide in
methanol at 50–60°C. Composition and structure of
the resulting compounds were confirmed by the data of
elemental analysis, IR, UV, and EPR spectroscopy,
and thermogravimetry. According to the elemental
analysis (Table 1), Co(II) and Ni(II) ions form M(LH)2
complexes, whereas in the case of Cu(II) Cu2L2 com-
plexes are formed (Scheme 2).
N-(2-hydroxybenzamido)phthalimide was synthe-
sized by reacting salicylhydrazide with phthalic
Scheme 1.
O
O
O
OH
N
N
N
N
H
O
O
OH
OH
546

Co(II), Ni(II), AND Cu(II) СOMPLEXES OF N-(2-HYDROXYBENZAMIDO)PHTHALIMIDE
547
Scheme 2.
O
C
N
Cu
Cu
N
C
O
C
C
OH
O
O
C N N
C
O
O
O
O
M
O
O
C
O
O
C
N N C
C
C
O
C
O
N
OH
N
M = Co(II), Ni(II).
The IR spectra of the Co(II) and Ni(II) complexes
in the regions of amide group vibrations and
symmetric stretching vibrations of the C=O bond are
characterized by a noticeable shift to the low-
frequency region as compared with the free ligand. At
the same time the vibrational band of the phenol OH
group, which is observed in the original ligand
spectrum at 3400 cm–1, is absent from these spectra
(Table 2). In the IR spectra of the Cu(II) complex the
following changes are observed: a weak band at
1795 cm–1 almost disappears, the band at 1725 cm–1 is
slightly shifted in the low-energy region (1721 cm–1),
and the amide band at 1653 cm–1 disappears
completely. The band of the N-H stretching vibrations
of amide group, which is present in the free ligand
spectrum at 3272 cm–1, is also absent. These data point
to the participation of phenol oxygen, enol oxygen, and
phthalimide fragment oxygen in the coordination with
Cu(II) ions.
(1 : 10), absorption bands at 347 nm (a charge transfer
band) and a very wide band at ~667 nm are observed
in addition to the ligand bands [λmax = 218 (ε = 3×
104 M−1 cm−1), 228 (ε = 2.7×104 M−1 cm−1), and 300 nm
(ε = 8.1×102 M−1 cm−1). The ESR spectrum of this
complex in the polycrystalline state appears as an
almost symmetric singlet with a line width of 450 Hz
(between maximal slope points) and g-factor of 2.03.
In the spectrum of the cobalt(II) complex along
with ligand absorption bands there are a charge
transfer band at 365 nm (ε = 1.3×102 M−1 cm−1) and
two low-intensity bands in the visible region: at 540 nm
(ε = 27 M−1 cm−1) and 649 nm (ε = 6 M−1 cm−1).
Spectrum of the nickel(II) complex contains three
absorption bands in the visible region: 485 nm (ε =
85 M−1 cm−1), 649 nm (ε = 8 M−1 cm−1), and 740 cm–1
(ε = 7 M−1 cm−1).
According to the thermogravimetric analysis, the
decomposition of the synthesized Co(II), Ni(II), and
Cu(II) complexes with N-(2-hydroxybenzamido)-
phthalimide proceeds in two stages. The main weight
In the electronic spectra of the solution of the
Cu(II) complex in a mixture of DMF and alcohol
Table 1. Melting points and elemental analysis data for Co(II), Ni(II), and Cu(II) complexes with N-(2-hydroxybenzamido)-
phthalimide
Found, %
N
Calculated, %
mp,
°С
М,
g/mol
Complex
Formula
C
H
O
M
C
H
N
O
M
Сu2L2
>255 52.40 2.33 8.15 18.62 18.50 C30H16N4O8Cu2 51.70 2.47 8.19 18.44 19.20 688.0
Ni(LH)2
Со(LH)2
>255 58.19 2.58 9.05 20.07
>255 58.16 2.58 9.04 20.70
9.48
C30H16N4O8Ni
57.72 2.44 9.49 20.23 10.12 618.7
9.52 C30H16N4O8Co 57.74 2.81 8.82 21.06 9.57 618.9
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 3 2019

548
GONDOLOVA et al.
Table 2. Data of the IR spectra of Co(II), Ni(II), and Cu(II) complexes with N-(2-hydroxybenzamido)phthalimide
ν, cm–1
Compound
OHphenol
3400 br
3377 br
3377
NHamide
3272 m
3274 w
3274 w
–
νas(СОphtal
1795 w
1794 w
1795
)
νs(СОphtal
1734 s
1725
)
СОamide
1654 s
1651 s
1648 s
–
СОphenol
1212
LH2
Co(LH)2
Ni(LH)2
Cu2L2
1210
1725
1210
3416
1721
1626
1156
loss occurs in the first stage in the temperature range
300–400°C (55–75%, depending on the metal nature).
In the second stage at 400–600°C the final decom-
position takes place to form corresponding oxides.
Amounts of NiO and CuO remaining after decom-
position of the Ni(II) and Cu(II) complexes correspond
to the metal contents in the complexes (Table 2).
REFERENCES
1. Patole, J., Sandbhor, U., Padhye, S., Dileep, D.N.,
Anson, C.E., and Powell, A., Bioorg. Med. Chem. Lett.,
2003, vol. 13, no. 1, p. 1. doi 10.1016/S0960-894X(02)
00855-7
2. Terzioğlu, N. and Gürsoy, A., Eur. J. Med. Chem.,
2003, vol. 38, no. 2, P.781. doi 10.1016/S0223-5234
(03)00138-7
3. Cocco, M.T., Congiu, C., Lilliu, V., and Onnis, V.,
Bioorg. Med. Chem., 2006, vol. 14, no 2, p. 366. doi
10.1016/j.bmc.2005.08.012
4. Easmon, J., Puerstinger, G., Roth, T., Feibig, H., Jenny, M.,
Jaege, W., Heinish, G., and Hofmann, G., Int. J.
Cancer, 2001, vol. 94, no. 1, p. 89. doi 10.1002/ijc.1427
Thus, new complexes of Co(II), Ni(II), and Cu(II)
complexes with N-(2-hydroxybenzamido)phthalimide
were obtained, in which it acts as a monoanion
bidentate or a dianion tridentate ligand depending on
the metal nature. It was found that Co2+ and Ni2+ ions
form M(LH)2 complexes, whereas Cu2+ ions form
Cu2L2 complexes.
5. Walcourt, A., Loyevsky, M., Lovejoy, D.B., Gor-
deuk, V.R., and Richardson, D.R., Int. J. Biochem. Cell
Biol., 2004, vol. 36, no. 3, p. 401. doi 10.1016/S1357-
2725(03)00248-6
6. Vicini, P., Zani, F., Cozzini, P., and Doytchinova, I.,
Eur J. Med Chem., 2002, vol. 37, no. 7, p. 64. doi
10.1016/S0223-5234(02)01378-8
7. Shunsheng, Z., Sijiao, W., Xiangrong L., and Li, K.,
J. Coord. Chem., 2012, vol. 65, no. 24, p. 4277. doi
10.1080/00958972.2012. 738813
Synthesis of the Cu2L2 complex. A mixture of
0.04 mol of N-(2-hydroxybenzamido)phthalimide and
35 mL of methanol was intensely stirred at 50–60°C
for 30 min. The crystalline precipitate was filtered off,
multiply washed with water and methanol, and dried.
The Ni(LH)2 and Co(LH)2 complexes were syn-
thesized similarly using the mole ratio ligand : metal =
2 : 1.
The IR spectra were taken on a Nicolet IS10
spectrophotometer in KBr tablets. The electronic
absorption spectra were obtained on a UV-vis Evolu-
tion 60S spectrophotometer. The ESR spectra were
recorded on a Bruker BioSpin GmbH spectrophoto-
meter. The thermogravimetric analysis was carried out
using a NETZSCH STA 449 Fc derivatograph.
8. Ming-Li, L., Jian-Min, D., Da-Cheng, L., Jian-Zhong, C.,
and Da-Qi, W., J. Mol. Struct., 2012, vol. 1011, p 140.
doi 10.1016/j.molstruc.2011.12.024
9. Tian, Y.P., Duan, C.Y., and Zhao C.Y., Inorg. Chem.,
1997, vol. 36, no. 6, p. 1247. doi 10.1021/ic9603870
10. Shi-Liang, C., Zheng, L., Jie, L., Guo-Cheng, H., and
Yan-Hong, L., J. Mol. Struct., 2012, vol. 1014, p. 110.
doi 10.1016/j.molstruc. 2012.02.011
CONFLICT OF INTEREST
11. Gondolova, G.G., Medzhidov, A.A., and Fatullaeva, P.A.,
Russ. J. Gen. Chem., 2018, vol. 88, no. 3, p. 607. doi
10.1134/S1070363218030362
No conflict of interest was declared by the authors.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 3 2019