Complexes of Fe(II) and Mn(II) with N-(2-Hydroxybenzamido)phthalimide

Article abstract of DOI:10.1134/S1070363218030362

Complexes of Fe(II) and Mn(II) with N-(2-hydroxybenzamido)phthalimide of the general formula [M(LH)₂] were synthesized and studied by IR, electronic absorption, and ESR spectroscopy and thermogravimetry. The ligand coordinates to Fe(II) and Mn(II) through the oxygen atom of the amido group which is present in the enolic form.

Full text of DOI:10.1134/S1070363218030362

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 3, pp. 607–609. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © G.G. Gondolova, A.A. Medzhidov, P.A. Fatullaeva, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 3, pp. 517–
520.
LETTERS
TO THE EDITOR
Complexes of Fe(II) and Mn(II)
with N-(2-Hydroxybenzamido)phthalimide
G. G. Gondolovaa, A. A. Medzhidovb, and P. A. Fatullaevab
a Institute of Ecology and Natural Resources, Gyanja Branch, National Academy of Sciences of Azerbaijan,
pr. G. Alieva 153, Gyanja, AZ 2003 Azerbaijan
*е-mail: gulnargondolova@gmail.com
b Nagiev Institute of Catalysis and Inorganic Chemistry, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received September 18, 2017
Abstract—Complexes of Fe(II) and Mn(II) with N-(2-hydroxybenzamido)phthalimide of the general formula
[M(LH)2] were synthesized and studied by IR, electronic absorption, and ESR spectroscopy and thermo-
gravimetry. The ligand coordinates to Fe(II) and Mn(II) through the oxygen atom of the amido group which is
present in the enolic form.
Keywords: N-(2-hydroxybenzamido)phthalimide, iron complexes, manganese complexes
DOI: 10.1134/S1070363218030362
Carboxylic acid hydrazide derivatives and their
metal complexes exhibit biological activity and are
used in medicine and technics. Hydrazides that act as
antitubercular [1, 2], anticancer [3–5], antimalarial [6],
and antimicrobial agents are known [7, 8]. The anti-
microbial activity is characteristic of such phthalimide
derivatives of hydrazides as N-(arylcarboxamido)-
phthalimides [9, 10]. The structure of one of the
specimens of this class of compounds was studied in
[11]. Carboxylic acid hydrazides show nootropic and
antidepressant properties and improve brain function
[12]. Metal complexes of hydrazides are environ-
mentally friendly compounds, and they have found
application in agriculture as efficient plant growth
regulators. Many hydrazides are applied for metal
extraction from industrial wastewater [13].
are few in number; in particular, the synthesis of
derivatives of salicylhydrazide and phthalic anhydride
and their metal complexes has never been reported.
We synthesized N-(2-hydroxybenzamido)phthalimide
[N-(1,3-dioxo-1,3-dihydro-2Н-isoindol-2-yl)-2-hydroxybenz-
amide] 1 (LH2) and its Fe(II) and Mn(II) complexes
and studied their structure by physicochemical methods.
N-(2-Hydroxybenzamido)phthalimide 1 was syn-
thesized by the reaction of salicylhydrazide with
phthalic anhydride in DMF at 85°С for 3.5 h (Scheme 1).
The IR spectrum of ligand 1 displays bands at 3378
and 2200–3500 cm–1, which are assignable to the
amide NH and phenol OH groups. The absorption
bands at 1794 and 1725 cm–1 correspond to symmetrical
and antisymmetrical vibrations of the phthalimide
carbonyls and the band at 1654 cm–1 is associated with
the amide С=О group.
Literature search showed that the publications of
the synthesis of carboxylic acid hydrazide derivatives
Scheme 1.
O
C
O
C
O
H
N
NH2
O
C
H
+ O
C
N
N
_H2O
C
O
C
O
OH
OH
1
607

608
GONDOLOVA et al.
Scheme 2.
O
O
O
C
OH
C
C
C
C
C
NH
N
N
N
OH
OH
O
O
Due to the enolization of the amide group (Scheme 2),
ligand 1 can be present both as a monoanion (LH1–)
and a dianion (L2–). Metal ions can coordinate to the
phenolic, amide, and phthalimide oxygen atoms.
The electron absorption spectrum of a solution of
Fe(II) complex 2 in ethanol shows, along the ligand
bands at 218 (ε 3×104 mol L–1 cm–1), 228 (ε 2.7×
104 mol L–1 cm–1), and 300 nm (ε 8.1×102 mol L–1 cm–1),
a charge-transfer band at 370 nm and a broad band at
~469 nm corresponding to the d'‒d transition [14].
Complexes 2 and 3 were prepared by the reaction
of N-(2-hydroxybenzamido)phthalimide 1 with FeSO4
(NH4)2SO4·6H2O or Mn(OAc)2 in methanol at 50–60°С
for 30 min. According to the elemental analyses (Table 1),
Fe(II) and Mn(II) form complexes of the composition
M(LH)2.
The electron absorption spectrum of Mn(II) com-
plex contains, along with the absorption bands on the
ligand, a charge-transfer band at 370 nm and a low-
intensity visible band at 454 nm assignable to a transi-
tion to 4G term components [14]. The ESR spectrum of
this complex in the polycrystalline state displays a
nearly symmetrical singlet with the line width
(between the steepest slope points) 320 Hz and g factor
2.125.
The carbonyl and amide groups in the IR spectrum
of the Fe(II) complex are slightly shifted red (1723 and
1651 cm–1, respectively). The stretching vibration band
of the amide N–H group at 3272 cm–1 completely
disappears. In view of the large shift of the phenolic νС‒О
band (Table 2) we can suggest the involvement of
phenolic oxygen in bridging to the metal atom.
According to the thermogravimetry (TG) data,
complexes 2 and 3 decompose in 2 stages. The major
weight loss takes place in the first stage in the
temperature range 250–350°С (55–75%). Complete decom-
position to form oxides takes place in the second stage
at 400–600°С. The oxide residue after decomposition
corresponds to the metal content of the complexes
(Table 1).
O
OH
C
C N N
C
O
O
Thus, we prepared a new ligand, N-(2-hyd-
roxybenzamido)phthalimide, which can behave as a
monoanion bidentate or dianion tridentate ligands
depending of the nature of the metal ion. As shown by
IR and electron absorption spectroscopy, Fe2+ and
Mn2+ ions form complexes M(LH)2, where the LH
M
O
C
O
C
N N
C
O
OH
Table 1. Melting points and elemental analyses of compounds 1–3
Calculated/found, %
Comp.
no.
Elemental formula
C15H10N2O4
mp, °С
М
C
H
N
O
M
–
1
251
63.83
63.77
58.46
59.38
58.19
57.72
3.57
3.64
2.60
2.47
2.58
2.44
9.93
9.96
9.09
8.19
9.05
9.49
22.67
22.63
20.78
19.44
20.07
20.23
282.00
615.85
618.70
–
2
3
C30H16N4O8Fe
C30H16N4O8Mn
>255
>255
9.07
10.52
9.48
10.12
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018

COMPLEXES OF Fe(II) AND Mn(II)
609
Table 2. IR spectral data for compounds 1‒3
ν, cm–1
Comp.
no.
νas(С=О)
(phthalimide)
νs(С=О)
(phthalimide)
O–H (phenol)
N–H (amide)
С=О (amide)
С–О (phenol)
1
2
3
3400 br
3378 br
3416 br
3272 m
1795 sh
1794 sh
1794 sh
1734 s
1723
1654 сs
1651 s
1651 s
1212
1206
1153
–
–
1722
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ligand is present in the enol form and coordinates to
the metal ions via the phenolic oxygen and amide
nitrogen atoms.
N-(1,3-Dioxo-1,3-dihydro-2Н-isoindol-2-yl)-2-
hydroxybenzamide (1). A mixture of 50 mL of DMF,
salicylhydrazide (0.02 mol), and phthalic anhydride
(0.02 mol) was stirred for 3.5 h at 85°С. After cooling
to room temperature the reaction mixture was diluted
with 2 L of distilled water and left to stand for 1 day.
The colorless crystals that formed were separated,
washed with ethanol, and dried in a vacuum.
Complex Fe(LH)2 (2). A mixture of 0.04 mol of
N-(2-hydroxybenzamido)phthalimide 1, 0.04 mol of
FeSO4 (NH4)2SO4·6H2O, and 35 mL of methanol was
vigorously stirred at 50–60°С for 30 min and then left
to stand overnight. The dark violet crystals that formed
were separated, washed with water and methanol, and
dried at room temperature.
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Complex Mn(LH)2 (3) was synthesized in a similar
way from manganese acetate.
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The melting points, IR spectral data, elemental
analyses of the synthesized compounds are listed in
Tables 1 and 2.
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Yan-Hong, Li, J. Mol. Struct., 2012, vol. 1014, p. 110.
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The IR spectra were measured on a Nicolet IS10
spectrometer. The electron absorption spectra were
obtained on an Evolution 60S UV-VİS spectrophoto-
meter. The thermogravimetric analysis was performed
on a NETZSCH STA 449 Fс derivatograph. The EPR
spectra were run on a Brukеr BioSpin spectro-
photometer.
11. Sutradhar, M., Martins, L.M.D.R.S., Guedes, da Silva M.F.C.,
Alegria, E.C.B.A., Liu, C.-M., and Pombeiro, A.J.L.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018