Synthesis and structure of 3-{[aryl (hetaryl)amino]methylene}chromane-2,4-diones and their metal complexes

Article abstract of DOI:10.1134/S1070363216110153

3-{[Aryl(hetaryl)amino]methylene}chromane-2,4-diones (HL) were synthesized and used for chemical and electrochemical synthesis of Cu(II), Ni(II), and Co(II) complexes of the general formula ML2, as well as the ZnLOOCCH3 complex. The structure of the compl

Full text of DOI:10.1134/S1070363216110153

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 11, pp. 2492–2500. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.S. Burlov, V.G. Vlasenko, A.I. Uraev, G.G. Aleksandrov, E.V. Korshunova, I.N. Shcherbakov, D.A. Garnovskii, Yu.V. Koshchienko,
2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 11, pp. 1849–1858.
To the memory of G. G. Aleksandrov
Synthesis and Structure
of 3-{[Aryl (Hetaryl)amino]methylene}chromane-2,4-diones
and Their Metal Complexes
A. S. Burlova*, V. G. Vlasenkob, A. I. Uraeva, G. G. Aleksandrovc†,
E. V. Korshunovaa, I. N. Shcherbakovd, D. A. Garnovskiie, and Yu. V. Koshchienkoa
a Research Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
*e-mail: anatoly.burlov@yandex.ru
b Research Institute of Physics, Southern Federal University, Rostov-on-Don, Russia
c Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
d Southern Federal University, Rostov-on-Don, Russia
e Southern Research Center, Russian Academy of Sciences, Rostov-on-Don, Russia
Received May 10, 2016
Abstract—3-{[Aryl(hetaryl)amino]methylene}chromane-2,4-diones (HL) were synthesized and used for
chemical and electrochemical synthesis of Cu(II), Ni(II), and Co(II) complexes of the general formula ML2, as
1
well as the ZnLOOCCH3 complex. The structure of the complexes was studied by IR, Н NMR, and X-ray
absorption spectroscopy. Density functional theory (DFT) calculations showed that the energetically most
favored form of compounds HL is an aminoketone tautomeric form. The crystal structure of the solvate of bis-
{3-[(4-methylanilinato)methylene]chromane-2,4-dionato}copper(II) with two DMF molecules was determined
by X-ray diffraction analysis.
Keywords: 3-formyl-4-hydroxycoumarin, enamines, E/Z isomerization, tautomerism, metal complexes, X-ray
absorption spectroscopy
DOI: 10.1134/S1070363216110153
The enduring interest in natural and synthetic
derivatives of 2Н-1-benzopyran-2-one is explained by
their broad-spectrum biological and pharmacological
activity (antibacterial, antiviral, anticoagulation,
anticancer, anti-AIDS, etc.) [1–3]. In addition, such
derivatives are widely used as fluorescent probes and
chemosensors [4–6].
methylene derivatives of 2Н-chromene-2,4(3Н)-dione
were found to compare in the cytotoxic activity against
HL-60 and NALM-6 human leukemia cells [7, 8] with
the commercial drug Carboplatin. Therewith it was
shown that the activity of the complexes depends on
the configuration of the chelate entity and on the
nature of the substituents.
Over the past years much attention has been paid to
metal complexes of coumarin containing Schiff bases
[7–13]. The coordination of metals with such ligands
can give rise to new biologically active compounds
due to the enhancement or alteration of useful pro-
perties of the parent organic molecules [7, 8, 13–15].
The metal chelates formed by palladium with amino-
Even though the coordination chemistry of enamines
derived from 2H-chromene-2,4(3Н)-dione [7–11, 14]
has been well studied in view of the practical value of
such compounds, only few their metal chelates have
been structurally characterized. Rare examples are
provided by palladium [7, 8, 11] and cobalt complexes
[16]. Scarce information is also available on the
complexes containing a heterocyclic fragment in the
amine component [14].
† Deceased.
2492

SYNTHESIS AND STRUCTURE OF 3-{[ARYL (HETARYL)AMINO]METHYLENE}CHROMANE...
2493
Scheme 1.
O
O
O
O
CHNHR
O
N
O
O
N
M(CH3COO)2 nH2O
R
M
R
CH3ONa, BuOH
O
O
1a_1c
2_4
CH3
H3C
O
O
O
CH3
Ph
Zn
Zn(CH3COO)2 2H2O
CH3ONa, BuOH
N
N
1c
N
O
O
O
5
CH3
CH3
N
(c); M = Cu (2), Ni (3), Co (4).
R =
CH3 (a),
(b),
N
N
O
C6H5
On the other hand, the presence in aminomethylene
derivatives of 2H-chromene-2,4(3Н)-dione of potential
donor centers, specifically, the oxygen atoms in the
coumarin component, and the possibility of modifica-
tion of the amine component (introduction of sub-
stituents with coordinately active groups) makes these
compounds promising models for studying competitive
coordination of metal ions [17–19].
by the reaction of 3-formyl-4-hydroxycoumarin with
4-aminoantipyrine in methanol [21].
The structure of compounds 1а–1c was studied by
1
IR and Н NMR spectroscopy. The IR spectra display
a ν(NH) band at 3550–3164 cm–1 [22, 23]. The carbonyl
bands of the chromene-2,4-dione and antipyrine frag-
ments appear at 1640–1720 cm–1.
The 1Н NMR spectra of compounds 1a–1c in
DMSO-d6 show two downfield doublet signals at
11.84–13.96 ppm, which can be assigned to the NН
protons. Such compounds in solutions exist as
mixtures of the E and Z isomers [24, 25]. The lower
field signals belong to the Е isomers which are
stabilized by an intramolecular hydrogen bond with the
С4=О oxygen. The higher field NH proton signals
belong to the Z isomers.
In the present work we studied the coordination of
polydentate N-aryl(hetaryl)aminomethylene derivatives
of 2Н-chromene-2,4(3Н)-dione 1а–1c with Cu(II),
Ni(II), Co(II), and Zn(II) to form complexes 2а–2c,
3a–3c, 4a–4c, and 5, respectively, under the conditions
of chemical and electrochemical synthesis. The
structure and properties of the synthesized compounds
were elucidated by various physicochemical methods,
including X-ray diffraction (XRD) analysis.
We performed DFT calculations of full energies of
tautomers A–D (Scheme 2) for a compound like 1а
(R = Ph) in the gas phase and DMSO and chloroform
solutions. The calculated relative stabilities of the
tautomers are listed in Table 1.
Compounds 1а–1c were synthesized by the con-
densation of 4-hydroxycoumarin with triethyl ortho-
formate and corresponding amines by a modified
procedure [20] (Scheme 1). Enamine 1c was obtained
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2494
BURLOV et al.
Table 1. Relative stability (kcal/mol) of isomers А–D of
compounds of type 1а (R = Ph) in the gas phase and DMSO
and CHCl3 solutions
results in a barrierless from the oxygen atom to the
azomethine nitrogen atom to form isomer C.
The chemical synthesis with metal acetates and the
electrochemical oxidation of cobalt, nickel, and copper
(used as anodes) in the presence of ligands 1а–1c in a
methanol–acetonitrile mixture give rise to mono-
nuclear complexes ML2 2–4. With M = Zn, complex
ZnLOOCCH3 (5) was obtained. The yields of the final
products in the electrochemical synthesis are higher by
7–10% than in the chemical synthesis.
Isomer
Gas phase
6.3
DMSO
8.4
CHCl3
7.8
А
B
C
D
0.0
0.0
0.0
0.7
0.6
0.6
12.4
–
–
The IR spectra of complexes 2–5 no longer show
ν(NH) bands of ligands 1 at 3160–3500 cm–1. The
strong ν(С=О) bands of ligands 1 at 1641–1647 cm–1
disappear from the spectra of complexes 2–4. The
medium ν(С=О) bands of the ligands at 1682–1686 cm–1
appear as strong bands shifted to 1695 cm–1 in the case
of in going to the complexes and appear in the spectra
of the latter at 1695 cm–1 (copper complex 2а) and
shifted by 22 cm–1 to 1660 cm–1 in the case of nickel
complex 3а and cobalt complex 4а.
According to the calculations, isomer B [(E)-keto-
enamine] is the most stable and (Z)-ketoenamine (tauto-
mer C) is less stable by as little as 0.6–0.7 kcal/mol
both in the gas phase and in DMSO and chloroform
solutions. From this the B/C ratio at room temperature
was estimated at 3 : 1 under the assumption of
thermodynamic equilibrium between the isomers.
Evidence showing that the E and Z isomers of different
azomethines derived from 3-formyl-4-hydroxy-
coumarin have close energies was obtained by
Kondratova et al. [26] by NMR spectroscopy. In
crystals of 3-(benzylaminomethylene)chromane-2,4-
dione both isomer exist in an equimolar ratio [27].
In the IR spectra of complexes 2b, 3b, and 4b, the
ν(С=О) band of the ligand at 1686 cm–1 is shifted and
appears as a strong broadened band at 1698 cm–1.
Furthermore, strong ν(СH=N) bands are observed at
1603–1606 cm–1.
4-Hydroxyimine А is destabilized by 6.3 kcal/mol
in the gas phase and even more stabilized in both
solvents, especially in the polar DMSO. The de-
stabilization of 2-hydroxyimine D, as predicted by the
calculations without inclusion of solvent effects, is
12.4 kcal/mol, whereas the inclusion of both solvents
With complexes 2c, 3c, and 4c, the ligand absorp-
tion band at 1686 cm–1 becomes stronger, and the
ν(С=О) absorption appears as three bands at 1719,
1750, and 1662 cm–1. Strong ν(СH=N) bands are also
observed at 1606 cm–1.
Scheme 2.
O
O
N
O
O
O
N
HO
H
A
B
H
O
O
O
O
O
H
N
N
O
D
C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 11 2016

SYNTHESIS AND STRUCTURE OF 3-{[ARYL (HETARYL)AMINO]METHYLENE}CHROMANE...
2495
Zinc complex 5 could only be prepared with ligand
1c. The Н NMR spectrum of complex 5 does not
2.5
2.0
1.5
1
contain the aminomethylene doublets of the ligand and
shows a singlet signal of the CH=N proton at 9.08 ppm
and a singlet of methyl group at 1.8 ppm assignable to
the acetate group. These findings suggest the
stabilization of the azomethine form А of the ligand in
the complex and the presence of a coordinated acetate
group.
1.0
0.5
1
Thus, the IR and Н NMR spectral data provide
evidence for the stabilization of the the azomethine
form А of ligands 1а–1c in complexes 2–5 and the
preservation of the acetate group in complex 5.
0
1
2
3
4
5
6
r, Å
Complexes 2–4 are paramagnetic. The effective
magnetic moments of the copper (1.9–2.0 B.M., 298 K),
nickel (3.11–3.25 B.M., 298 K), and cobalt complexes
(4.32–4.63 B.M., 298 K) does not change with
decreasing temperature, which points to a mononuclear
structure of the complexes.
Fig. 1. Fourier-transform moduli of the CuK-edge EXAFS
spectra of complexes (1) 2а and (2) 2c. (Solid line)
Experiment and (circles) theoretical FTM.
monoanionic ligands in the azomethine tautomeric
form А and two O atoms from the two structurally
The local atomic environment of the copper ions in
complexes 2а and 2c was elucidated from the CuK-
edge EXAFS spectra. Figure 1 shows the Fourier
transform moduli (FTM) of the EXAFS spectra of
complexes 2a and 2c, and Table 2 lists the parameters
of the local atomic environment of the copper ions in
these compounds. As the model for the calculation of
the photoelectron scattering phases and amplitudes we
chose the complex C34H24CuN2O2 which has a similar
atomic structure [28] (CSD code PHNPCV).
equivalent DMF molecules, thereby forming
a
distorted octahedral environment of the metal atom.
The six-membered chelate rings have an envelope
conformation with an almost planar fragment
comprising the N1, O1, C11, C19, and C20 atoms, and the
Cu atom deviates from this plane by 0.547(4) Å. The
dihedral angle along the N1O1 line is 23.0(1)°. By
symmetry reasons, Cu1 falls exactly on the
N1O1N1АO1А plane formed by the equatorial nitrogen
and oxygen atoms of the two ligands. The selected
bonds lengths (Å) and angles (deg) in complex 2а are
as follows: Cu1–O1 1.912(3), Cu1–N1 1.998(3),
Cu1–O11 2.675(4), C20–N1 1.294(4), C21–N1 1.426(4),
C11–O1 1.270(4), C18–O3 1.198(4), C18–O2 1.396(4),
C11–C19 1.403(5), C19–C20 1.421(5); O1Cu1O1A 180.0,
N1Cu1N1A 180.0, O11Cu1O11A 180.0, O1Cu1N1A
As seen from Fig. 1, the FTM of both samples
contain the main peaks at r = 1.44–1.48 Å and smaller
peaks at r = 2.49 Å. The best model of the local atomic
environments of the copper ions in these complexes,
found by multi-sphere fitting, corresponded to photo-
electron scattering on the four closest nitrogen and
oxygen atoms of the ligand, which form the first
coordination sphere appearing as the main peak in the
FTM. The average radii of the first coordination
spheres in complexes 2а and 2c, resulting from the
fitting procedure, proved to be close to each other
within the experimental error of 0.02 Å (Table 2). The
second peaks in the FTM can be associated with the
distances to the second coordination spheres (r ~3 Å)
including the carbon atoms of the ligands.
Table 2. Parameters of the local atomic structure of copper
complexes 2a and 2ca
Comp.
no.
Coordination
sphere
N
r, Å
σ2, Å2
Q, %
2а
2
2
2
6
1.87
1.99
2.70
3.17
0.0025
0.0027
0.0035
0.0035
O
N
O
C
6.5
The crystal structure of complex 2а was established
by XRD analysis. Compound 2а crystallizes in the
space group P-1 as a centrosymmetric mononuclear
complex (Fig. 2). The Cu1 atom coordinates two N and
two O atoms of the two chelate structurally equivalent
2c
2
2
6
1.87
2.01
2.96
0.0027
0.0027
0.0044
O
N
C
5.5
(N) Coordination number, (r) interatomic distance, (σ2) Debye–
Waller factor, and (Q) fitting function.
a
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2496
BURLOV et al.
Fig. 2. Molecular structure of complex 2а (hydrogen atoms are not shown, thermal ellipsoids are given at a 50% probability level).
89.46(13), O1Cu1N1 90.54(13), O1Cu1O11A 86.32(14),
N1Cu1O11A 95.57(11), O1Cu1O11 93.68(14), N1Cu1O11
84.43(11).
Thus, we prepared new paramagnetic Cu(II), Ni(II),
and Co(II) complexes ML2 on the basis of 3-{[aryl-
(hetaryl)amino]methylene}chromane-2,4-diones, and
also the ZnLOOCCH3 complex. The crystal and local
atomic structure of the copper complexes were studied
by XRD analysis and X-ray absorption spectroscopy.
The crystal structure of the solvate of bis{3-[(4-
methylanilinato)methylene]chromane-2,4-dionato}-
copper(II) with two DMF molecules was established to
show that the octahedral environment of the metal ion
is distorted due to additional coordination of two DMF
molecules.
The C20–N1 bond length is slightly larger compared
to the standard value (1.279 Å) for the azomethine
C=N [29, 30]. In its turn, the C11–O11 bond is
appreciably longer than the C18=O3 double bond,
which suggests that the ligand in the complex exists in
the monoanionic form А. The C11–C19 and C19–C20
bond lengths only slightly differ from each other,
unlike what is reported in the literature [31–34] for
Pd(II) complexes with structurally similar ligands,
where the C–C bonds in the metal rings fairly strongly
alternate in length (0.04–0.08 Å). The other geometric
parameters correspond to characteristic values [29].
EXPERIMENTAL
Elemental analysis for С, H, and N was performed
on a Carlo Erba Instruments TCM 480 instrument.
Analysis for metals was performed by gravimetry. The
In the crystal of complex 2а, no shortened inter-
molecular contacts were identified.
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SYNTHESIS AND STRUCTURE OF 3-{[ARYL (HETARYL)AMINO]METHYLENE}CHROMANE...
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ATR-IR spectra were measured on a Varian Еxcalibur-
3100 FTIR spectrometer for powders. The H NMR
three-parameter hybrid functional [38] (Becke
1
exchange functional [38] combined with Lee‒Yang‒
Parr correlation functional [40]) with full geometry
optimization without symmetry restrictions. The 6-
311G(d,p) split-valence basis set was used. The
calculations were performed at the Computing Center
cluster, South-Russian Regional Center for Informa-
tization, using the ORCA software [41]. Solvent
effects were included by the COSMO continuum
model [42] with standard parameters for the used solvents.
spectra were obtained on a Varian Unity-300
spectrometer (300 MHz) for DMSO-d6 solutions, the
1H chemical shifts are referenced against residual
proton signals of the solvent. The CuK edges were
obtained in the transmission mode on an EXAFS
spectrometer at the Structural Materials Science end-
station, Kurchatov Center for Synchrotron Radiation
and Nanotechnology (Moscow). The energy of the
electron beam used as the source of X-ray synchrotron
radiation was 2.5 GeV at a current of 80–100 µA. The
X-ray radiation was monochromatized with Si(111)
crystal. The spectra were processed by standard
procedures including background subtraction, K-edge
step normalization, and isolation of atomic absorption
µ0 [35], after which Fourier transform of the resulting
EXAFS χ spectra was performed in the photoelectron
wave-vector range k = 2.6‒12.6 Å–1 with the weight
function k3. The threshold ionization energy E0 was
chosen as the maximum of the first derivative K-edge,
and then it was varied in the course of the fitting
process. The exact structural parameters of the local
environment of the copper ions were determined by
nonlinear fitting the parameters of the corresponding
coordination spheres of the calculated EXAFS signals
to those isolated by Fourier transform filtering the full
EXAFS spectrum. The nonlinear fitting was performed
using the IFFEFIT-1.2.5 software [36]. The the
photoelectron scattering phases and amplitudes
required for constructing the model spectrum were
calculated using the FEFF7 software [37]. For the
starting atomic coordinates for calculating the
scattering phases and amplitudes and the subsequent
fitting we took the X-ray data for complexes having a
similar local environment of the copper ions, retrieved
from the Cambridge Structural Database.
The XRD analysis of compound 2а was performed
at an Enraf‒Nonius CAD4 automated diffractometer
(MoKα radiation, λ 0.71073 Å, graphite mono-
chromator, ω-scanning) at room temperature. The
structure was solved by the direct method and refined
refined by full-matrix least-squares on F2 for all non-
hydrogen atoms (SHELXTL [43]). Hydrogen atoms
were located and refined by the rider model. The
crystal parameters of complex 2а at 295(2) K are as
follws: М 766.28, C40H38CuN4O8, crystal dimensions
0.40×0.05×0.05 mm, space group P-1, triclinic
syngony, a 9.334(8), b 11.168(7), c 11.221(6) Å,
α 118.94(4)°, β 108.09(6)°, γ 99.13(6)°, V 903.5(11)
Å3, Z 1, ρ 1.408 g/cm3, μ 0.664 mm–1, θ 2.12°–26.50°,
–2 ≤ h ≤ 11, –14 ≤ k ≤ 13, –14 ≤ l ≤ 13; total
reflections 4508, unique 3743 (Rint 0.0521), R1 0.0718,
wR2 0.1828 [for 3019 reflections with I ≥ 2σ(I)] and
R1 0.0879, wR2 0.1963 (for the entire experimental
dataset), GoF 1.103, Δρmin/Δρmax –1.251/2.569 е/Å–3.
The total set of XRD data is deposited at the Cambridge
Crystallographic Data Centre (CCDC 1470638).
Commercial 4-hydroxycoumarin, 2-aminopyridine,
4-aminoantipyrine, and triethyl orthoformate (Alfa
Aesar) were used.
Compounds 1а–1c were synthesized by a modified
procedure [20]. A solution of 1.48 g (0.01 mol) of
triethyl orthoformate and 0.01 mol of the corres-
ponding amine in 10 mL of ethylene glycol was added
to 1.62 g (0.01 mol) of 4-hydroxycoumarin. The
mixture was heated at 150°С with stirring with a
descending water-cooled condenser until the alcohol
that formed no longer distilled. Then the reaction
mixture was heated to 180°С and kept at that
temperature for 20 min. After cooling to room
temperature, the precipitate was filtered off, washed
with ethanol (2×5 mL), and recrystallized from DMF.
The goodness-of-fit function
Q
which was
minimized to find the local environment parameters
was calculated by the following formula:
Σ[kχexp(k) – kχth(k)]2
Q(%) = —–——————– ×100%.
Σ[kχexp(k)]2
The specific magnetic susceptibilities of solid com-
plexes were measured by the Faraday method in the
temperature range 78–300 K. The calibration reference
standard was Hg[Co(CNS)4].
3-[(4-Tolylamino)methylene]chromane-2,4-dione
(1а). Yield 1.31 g (47%), yellow powder, mp 198–
Quantum-chemical calculations were performed by
the density functional theory method with the B3LYP
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BURLOV et al.
199°С. IR spectrum, ν, cm–1: 3155 (N–H), 1682
(C=O), 1647 (C=O). 1H NMR spectrum, δ, ppm: 2.36 s
(3H, CH3), 7.21–7.3 m (4H, СHAr), 7.46 d (2H, СHAr,
J = 8.0 Hz), 7.58–7.65 m (1H, СHAr), 7.96 dd (1H,
СHAr, J = 7.8, J = 1.5 Hz), 8.83 d (1Н, CHNH, J =
13.8 Hz), 8.88 d (1Н, CHNH, J = 14.7 Hz), 11.84 d
(1Н, CHNH, J = 14.7 Hz), 13.58 d (1Н, CHNH, J =
13.8 Hz). Found, %: С 73.10; Н 4.60; N 5.10.
C17H13NO3. Calculated, %: С 73.11; H 4.69; N 5.01.
of the synthesis, the precipitate was filtered off,
washed with hot methanol (3×5 mL), and dried in a
vacuum at 150°С.
Copper(II) bis{3-[(4-methylanilinato)methylene]-
chromane-2,4-dionate} (2а). Yield 0.3 g (48%,
method а), 0.34 g (50%, method b), dark green
powder, mp >250°С, µeff 1.92 B.M. (298 K). IR
spectrum, ν, cm–1: 1695 vs (С=О). Found, %: С 65.75,
65.81; Н 3.99, 4.05; N 4.48, 5.00; Cu 10.16, 10.10.
C34H24СuN2O6. Calculated, %: С 65.85; H 3.90; N
4.52; Cu 10.25.
3-[(4-Pyridylamino)methylene]chromane-2,4-dione
(1b). Yield 1.2 g (45%), yellow powder, mp 215–216°С.
IR spectrum, ν, cm–1: 3220–3187 w (N–H), 1687 m
Copper(II) bis[4-hydroxy-3-(2-pyridyliminomethyl)-
chromen-2-onate] (2b). Yield 0.30 g (50%, method
а), 0.36 g (60%, method b), green powder, mp >250°С,
µeff 1.98 B.M. (298 K). IR spectrum, ν, cm–1: 1698 m
br (С=О). Found, %: С 60.56, 60.59; Н 3.01, 3.08; N
9.49, 9.52; Cu 10.60, 10.59. C30H18CuN4O6. Calculated,
%: С 60.66; H 3.05; N 9.43; Cu 10.70.
1
(C=O), 1641 vs (C=O). H NMR spectrum, δ, ppm:
7.21–7.33 m (3H, СHAr), 7.63–7.74 m (2H, СHAr),
7.82–7.89 m (1H, СHAr), 7.97 d (1H, СHAr, J =
7.8 Hz), 8.42–8.46 m (1H, СHAr), 9.62 d (1Н, CHNH,
J = 14.0 Hz), 9.82 d (1Н, CHNH, J = 13.8 Hz), 11.83 d
(1Н, CHNH, J = 13.8 Hz), 13.22 d (1Н, CHNH, J =
14.0 Hz). Found, %: С 67.5; Н 3.90; N 10.65.
C15H10N2O3. Calculated, %: С 67.67; H 3.79; N 10.52.
Copper(II) bis[2,3-dimethyl-5-oxo-4-phenylcyclo-
penten-1-yl)iminomethyl]-4-hydroxychromen-2-onate]
(2c). Yield 0.37 g (45%, method а), 0.44 g (53%,
method b), green powder, mp >250°С, µeff 2.01 B.M.
(298 K). IR spectrum, ν, cm–1: 1719 s (С=О), 1694 m,
1662 s. Found, %: С 62.15, 62.09; Н 3.99, 3.81; N
10.22, 10.39; Cu 7.75, 7.84. C42H32CuN6O8.
Calculated, %: С 62.10; H 3.97; N 10.35; Cu 7.82.
3-{[(1,5-Dimethyl-3-oxo-2-phenylpyrazol-4-yl)-
amino]methylene}chromane-2,4-dione (1c). Yield
1.83 (49 %), light yellow powder, mp 211–212°С. IR
spectrum, ν, cm–1: 3551–3504 w (N–H), 1686, 1698 s
(C=O), 1633 s (C=O). 1H NMR spectrum, δ, ppm: 2.49
s (3H, СHAr), 3.22 s (3H, СHAr), 7.21–7.39 m (5H,
СHAr), 7.45–7.61 m (3H, СHAr), 7.92–7.98 m (1H,
СHAr), 9.33 d (1Н, CHNH, J = 14.1 Hz), 9.37 d (1Н,
CHNH, J = 13.7 Hz), 11.66 d (1Н, CHNH, J =
14.1 Hz), 13.96 d (1Н, CHNH, J = 13.7 Hz). Found,
%: С 66.56; Н 4.67; N 11.30. C21H17N3O4. Calculated,
%: С 67.19; H 4.56; N 11.20.
Nickel(II) bis{3-[(4-methylanilinato)methylene]-
chromane-2,4-dionate} (3а). Yield 0.25 g (40%,
method а), 0.3 g (50%, method b), dark green powder,
mp >250°С, µeff 3.11 B.M. (298 K). IR spectrum, ν,
cm–1: 1660 vs (С=О). Found, %: С 66.25, 66.21; Н
3.98, 4.02; N 4.69, 4.42; Ni 9.42, 9.64. C34H24NiN2O6.
Calculated, %: С 66.37; H 3.93; N 4.55; Ni 9.53.
Synthesis of complexes 2–5 (general procedure).
а. A solution of the corresponding metal salt in 20 mL
of methanol was added to a boiling solution of 2 mmol
of ligand 1 and 0.1 g (2 mmol) of sodiu methylate in
10 mL of n-butanol. The mixture was refluxed for 2 h.
After cooling, the precipitate was filtered off, washed
with methanol, and dried in a vacuum oven at 150°С.
Nickel(II) bis[4-hydroxy-3-(2-pyridyliminomethyl)-
chromen-2-onate] (3b). Yield 0.28 g (47%, method
а), 0.32 g (55%, method b), green powder, mp >250°С,
µeff 3.15 B.M. (298 K). IR spectrum, ν, cm–1: 1700 vs
(С=О). Found, %: С 61.21, 61.29; Н 2.99, 3.03; N
9.47, 9.49; Ni 9.81, 9.99. C30H18NiN4O6. Calculated,
%: С 61.16; H 3.08; N 9.51; Ni 9.96.
b. The electrochemical synthesis was performed by
a standard procedure [44] using an EG&G PAR/173
potentiostat in a 1 : 1 methanol–acetonitrile mixture
with a platinum cathode and a metal (Cu, Ni, and Co)
plate anode. The working solution (25 mL) contained
0.5 mmol of ligand 1а–1c and 0.01 g of Et4NClO4
(conducting additive). The synthesis was carried out in
a U-shaped glass tube with unseparated anode and
cathode compartments with a constant current of
40 mA and a voltage of 15 V for 1 h. After completion
Nickel(II) bis[2,3-dimethyl-5-oxo-4-phenylcyclo-
penten-1-yl)iminomethyl]-4-hydroxychromen-2-onate]
(3c). Yield 0.36 g (45%, method а), 0.44 g (55%,
method b), green powder, mp >250°С, µeff 3.25 B.M.
(298 K). IR spectrum, ν, cm–1: 1718 s (С=О), m 1700,
s 1662. Found, %: С 62.35, 62.39; Н 4.12, 3.81; N
10.57, 10.36; Ni 7.37, 7.15. C42H32NiN6O8. Calculated,
%: С 62.48; H 3.99; N 10.40; Ni 7.27.
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SYNTHESIS AND STRUCTURE OF 3-{[ARYL (HETARYL)AMINO]METHYLENE}CHROMANE...
2499
2. Stanković, N., Mladenović, M., Mihailović, M.,
Arambašić, J., Uskoković, A., Stanković, V.,
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2014, vol. 55, p. 20. doi 10.1016/j.ejps.2014.01.004
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Gomes, L.R., and Low, J.N., Chem. Commun., 2015,
vol. 51, no. 14, p. 2832. doi 10.1039/C4CC08798D
4. Kaur, K., Saini, R., Kumar, A., Luxami, V., Kaur, N.,
Singh, P., and Kumar, S., Coord. Chem. Rev., 2012,
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5. Advances in Chemical Sensors, Wen Wang, Ed., Rijeka:
InTech, 2012, ch. 6, p. 6.
Cobalt(II) bis{3-[(4-methylanilinato)methylene]-
chromane-2,4-dionate} (4а). Yield 0.28 g (45%,
method а), 0.34 g (56%, method b), orange powder,
mp >250°С, µeff 4.35 B.M. (298 K). IR spectrum, ν,
cm–1: 1660 о. s (С=О). Found, %: С 66.29, 66.38; Н
3.99, 4.01; N 4.57, 4.49; Co 9.43, 9.51. C34H24CoN2O6.
Calculated, %: С 66.35; H 3.93; N 4.55; Co 9.57.
Cobalt(II) bis[4-hydroxy-3-(2-pyridyliminomethyl)-
chromen-2-onate] (4b). Yield 0.27 g (45%, method
а), 0.33 g (56%, method b), red-orange powder, mp
>250°С, µeff 4.32 B.M. (298 K). IR spectrum, ν, cm–1:
1702 vs (С=О). Found, %: С 61.20, 61.18; Н 3.15,
3.04; N 9.45, 9.49; Co 9.89, 9.95. C30H18CoN4O6.
Calculated, %: С 61.13; H 3.08; N 9.51; Co 10.00.
6. Wang, K., Ma, L., Liu, G., Cao, D., Guan, R., and Liu, Z.,
Dyes Pigments, 2016, vol. 126, p. 104. doi 10.1016/
j.dyepig. 2015.11.019
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Kufelnicki, A., and Nawrot, B., Eur. J. Inorg. Chem.,
2004, vol. 2004, no. 22, p. 4412. doi 10.1002/
ejic.200400483
8. Budzisz, E., Malecka, M., Lorenz, I.P., Mayer, P.,
Kwiecien, R.A., Paneth, P., Krajewska, U., and
Rozalski, M., Inorg. Chem., 2006, vol. 45, no. 24,
p. 9688. doi 10.1021/ic0605569
Cobalt(II) bis[2,3-dimethyl-5-oxo-4-phenylcyclo-
penten-1-yl)iminomethyl]-4-hydroxychromen-2-onate]
(4c). Yield 0.36 g (45%, method а), 0.43 g (54%,
method b), red powder, mp >250°С. IR spectrum, ν,
cm–1: 1662 s (С=О), 1715 m, 1700 m. Found, %: С
62.55, 62.39; Н 4.15, 4.05; N 10.32, 10.37; Co 7.48,
7.25. C42H32CoN6O8. Calculated, %: С 62.46; H 3.99;
N 10.41; Co 7.30. µeff 4.63 B.M. (298 K).
9. Joseph, J. and Mehta, B.H., Asian J. Chem., 2007,
vol. 19, no. 1, p. 401.
3-[2,3-Dimethyl-5-oxo-4-phenylcyclopenten-1-yl)-
iminomethyl]-4-hydroxychromen-2-onato]zinc(II)
acetate (5). Yield 0.20 g (40%, method а), yellow
powder, mp >250°С. IR spectrum, ν, cm–1: 1620 vs
(С=О), 1673 s. 1H NMR spectrum, δ, ppm: 1.83 s (3H,
CH3), 3.66 s (3H, CH3), 3.23 s (3H, CH3), 7.14–7.56 m
(8H, СHAr), 7.86–8.04 m (1H, СHAr), 9.08 s (1H,
CH=N). Found, %: С 55.42; Н 3.95; N 8.39; Zn 13.15.
C23H19ZnN3O6. Calculated, %: С 55.38; H 3.84; N
8.42; Zn 13.11.
10. Jevtić, V.V., Pešić, M., Radić, G.P., Vuković, N.,
Sukdolak, S., Klisurić, O., Podolski-Renić, A., Tanić, N.,
and Trifunović, S.R., J. Mol. Struct., 2013, vol. 1040,
p. 216. doi 10.1016/j.molstruc.2013.03.013
11. Ilić, D.R., Jevtić, V.V., Radić, G.P., Arsikin, K., Ristić, B.,
Harhaji-Trajković, L., Vuković, N., Sukdolak, S.,
Klisurić, O., Trajković, V., and Trifunović, S.R., Eur. J.
Med. Chem., 2014, vol. 74, p. 502. doi10.1016/
j.ejmech.2013.12.051
12. Prabhakara, C.T., Patil, S.A., Kulkarni, A.D., Naik, V.H.,
Manjunatha, M., Kinnal, S.M., and Badami, P.S.,
J. Photochem. Photobiol. B, 2015, vol. 148, p. 322. doi
10.1016/j.jphotobiol.2015.03.033
ACKNOWLEDGMENTS
13. Abou-Hussein, A.A. and Linert, W., Spectrochim. Acta,
Part A, 2015, vol. 141, p. 223. doi 10.1016/
j.saa.2015.01.063
14. Rehman, S.U., Chohan, Z.H., Gulnaz, F., and Supuran, C.T.,
J. Enzyme Inhib. Med. Chem., 2005, vol. 20, no. 4,
p. 333. doi 10.1080/14756360500141911
15. Patil, S.A., Unki, S.N., Kulkarni, A.D., Naik, V.H., and
Badami, P.S., J. Mol. Struct., 2011, vol. 985, nos. 2–3,
p. 330. doi 10.1016/j.molstruc.2010.11.016
The research was performed using the equipment of
the Centers for Collective Use of the Kurnakov
Institute of General and Inorganic Chemistry and
“Kurchatov Institute” National Research Center, as
well as “Molecular Spectroscopy” Center for Collective
Use of the Southern Federal University.
The work was financially supported by the Southern
Federal University (grant no. 213.01-2014/005VG).
16. Ketata, I., Mechi, L., Ayed, T.B., Dusek, M., Petricek, V.,
and Hassen, R.B., Open J. Inorg. Chem., 2012, vol. 2,
no. 2, p. 33. doi 10.4236/ojic.2012.22006
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