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Abstract—A series of new copper(I) and mercury(II) complexes with 4-aminoantipyrine, semicarbazide, and
thiosemicarbazide ligands [(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)carbonohydrazonoyl
dicyanide (HL1), 2-cyano-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-[(E)-(3-methylphenyl)-
diazenyl]acetamide (H2L2), (Z)-2-cyano-N′-[(E)-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-
methylidene]-2-(2-phenylhydrazinylidene)acetohydrazide (HL3), 2-(anilinoacetyl)-N-phenylhydrazine-1-carbo-
thioamide (H2L4), 2-(anilinoacetyl)-N-(3-methylphenyl)hydrazine-1-carbothioamide (H2L5), and 2-anilino-N′-
[(E)-(2-hydroxyphenyl)methylidene]acetohydrazide (H2L6)] have been prepared and characterized by physical
and spectral data, including microanalysis, IR and UV-visible spectra, conductivity measurements, and thermal
analyses (DTG/TGA). The ligands H2L2 and HL3 produced dinuclear complexes. Thermal studies revealed that
the copper(I) complexes are thermally more stable than mercury(II) complexes. The copper complexes
exhibited potent inhibitory effect on the MCF7 human breast carcinoma cell line, as compared to mercury(II)
complexes.
Keywords: Anticancer activity, Cu(I) complexes, Hg(II) complexes, IR, UV, TGA
DOI: 10.1134/S1070363217060214
1256
SYNTHESIS, CHARACTERIZATION, AND ANTITUMOR ACTIVITY OF NEW COPPER(I) 1257
Scheme 1.
CN O
CN Me H CN
H N Me
N N H
NC N N Ph N
N Me Me N O N N N Me
N
N Me HN O N
O Me O
Ph Ph Ph
1 2
HL H2L H2L3
S OH
1H
H
Ph N 2 C3 4 Ph N
N N N R N N
H H H H
O O
4,
H2L H2L 5 H2L6
OH2
Cl CN Me
CN Me H
H Cu N
N CN H O N N
NC N N Me
X N Me N HN O
Ph N N AcO–
O M N N Ph Ph O
N O Me NH O H2O OH2 Ph
Y Ph N
Me N N CN Me Hg Hg
N Cu Me OH2
H2O O
Me H Cl OH2 OH
CN H
1, 2 3 4
S S
H H H Me H
H Ph N Ph
Ph N Ph Ph N N N N N
N N N N N H
H H H H O H H
O O S Hg
Cu M
OH2 AcO OAc
Cl OH
5 6 7
Ph N
N N
H
O
O
H2O M H
O O
Me
8
H2L4, R = H; H2L5, R = Me; 1, M = Cu, X = Cl, Y = H2O; 2, M = Hg, X = OAc, Y = OH.
hydroxyphenyl)methylidene]acetohydrazide (H2L6), and readily soluble in DMF and DMSO. The molar
characterize then by physical and spectral data, conductivities of 1–8 in DMF (c = 10–3 M; Table 1) show
including microanalysis, IR and UV-visible spectro- that the complexes (except for 4) are essentially non-
scopy, conductivity measurements, and thermal analyses electrolytes, indicating non-coordination of the anions;
(DTA/TG), and estimate their antitumor activity. complex 4 behaved as a 1 : 1 electrolyte [24].
The reactions of copper(I) chloride and mercury(II) The 1H NMR spectra of ligands HL1–H2L6 have
acetate with HL1–H2L6 at a 1 : 1 molar ratio produced been reported in [25–29]. Comparison of the IR spec-
complexes 1–8; complexes 3 and 4 are dinuclear tra of the free ligands and their Cu(I) and Hg(II)
(Scheme 1). The complexes are air stable, non-hygro- complexes showed that HL1 is a bidentate ligand coor-
scopic, partially soluble in common organic solvents, dinating through the carbonyl oxygen and azomethine
Found, % Calculated, %
Yield, %
Ʌma
Compounds Color Formula M
C H M Cl C H M Cl
nitrogen atoms. Ligands H2L2 and HL3 produced remain at the same frequencies as in the spectra of the
dinuclear complexes 3 and 4. Ligands H2L4 and H2L5 free ligands or are slightly shifted, except for complex
are neutral bidentate (complexes 5, 7) or tridentate (6) 3 which showed lower frequencies. Thus, neither N–H
which coordinate through the side-chain carbonyl nor C≡N groups of the ligand participate in coor-
oxygen atom and NH nitrogen atom in complexes 5 dination in complexes 1 and 2. The side-chain C=O
and 7, and the sulfur atom is additionally involved in stretching band of the ligand disappears upon com-
complex 6. Ligand H2L6 in complex 8 is coordinated in plexation to form dinuclear complex 4. Ligands H2L4
a monobasic tridentate fashion through the azomethine and H2L5 show bands at 3310–3380, 3305– 3271, 3235–
nitrogen atom and enolic and phenolic oxygen atoms. 3165 (NH), 1690–1675 (C=O), and 750–761 cm–1 (C=S),
The IR spectra of the ligands and complexes 1–8 and three additional bands are observed for H2L6 at
are presented in Table 2. Generally, the IR spectra of 3400 (OH), 1605 (C=N), and 1275 cm–1 (C–O). The
free ligands HL1–HL3 showed four bands at 3200– ν(N–H) and ν(C=O) bands of complexes 5–7 appeared
3430, 2205–2210, 1630–1635, and 1590–1610 cm–1, at lower frequencies compared to the free ligands,
which were assigned to N–H, C≡N, C=O, and C=N indicating coordination through the corres-ponding
stretching vibrations; ligands H2L2 and HL3 addition- groups [33]. The IR spectrum of complex 8 showed
nally displayed bands at 1650–1660 and 1550– low-frequency shifts of the ν(C=N), ν(OH), ν(C–O),
1575 cm–1 due to side-chain C=O and N=N bonds, and δ(O–H) bands, whereas the ν(C=O) band
respectively. Metal complexes 1–3 are characterized disappeared. This means that the coordinated ligand
by reduced stretching frequencies of the pyrazolone has the enol imine structure. In addition, some new
and side-chain carbonyl groups and C=N bond, which medium to weak bands were observed in the IR spectra
is consistent with coordination through the corres- of all complexes at 655–455 and 510–420 cm–1, which
ponding donor atoms [30–32]. The bands corres- were tentatively assigned to ν(M–O) and ν(M–N)
ponding to ν(C≡N) and ν(N–H) in complexes 1–3 [34, 35].
The acetate ligand can coordinate to a metal center temperature, thermal decomposition begins, and the
in monodentate, bidentate, or bridging manner. The complexes melt together with decomposition in two
νas(COO–) and νs(COO–) frequencies of free acetate ion distinct stages. Complex 1 showed two endothermic
are ~1560 and 1416 cm–1, respectively. In the case of DTA peaks at 235–300 and 487–556°C due to loss of
monodentate coordination, the νas(COO–) frequency is H2O + Cl + C7H4N2 (weight loss 25.3%; calculated:
higher than 1560 cm–1, while the νs(COO–) frequency 25.0%). Complex 5 showed one endothermic and two
is lower than 1416 cm–1. As a result, the difference exothermic DTA peaks at 251–277, 382–428, and 456–
between the COO– stretching frequencies for mono- 578°C with weight losses of 20.0, 8.7, and 11.4%,
dentate coordination is much larger than for the free respectively (calculated: 20.1, 8.5, and 10.1%,
acetate ion, as found for complexes 2, 4, and 7 which respectively). Two endothermic and one exothermic
showed νas(COO–) at 1553–1605 cm–1 and νs(COO–) at DTA peaks were observed for complex 6 at 236–269,
1330–1385 cm–1 [36–38]. Complex 8 displayed two 461–541, and 553–590; the corresponding weight
bands at 1605 and 1418 cm–1 due to νas(COO–) and losses were 27.9, 16.3, and 6.9% (calculated: 27.8,
νs(COO–), respectively, and was assigned bidentate 16.7, and 6.6%, respectively). Complex 3 began to lose
coordination of the acetate ion [39]. In addition, the IR weight in the temperature range 46–80°C (one
spectra of 1, 3–6, and 8 showed a broad peak at 3390– endothermic DTA peak at 45–90°C, which was
3435 cm–1, indicating the presence of water molecules, assigned to loss of crystallization water; two exo-
and complex 4 showed one more band at 3437 cm–1 thermic DTA peaks at 238–350 and 419–492°C were
assigned to the coordinated hydroxy group [24]. related to weight losses of 16.3 and 18.0%, respec-
tively (calculated: 16.1 and 17.6%). The decomposi-
The thermal behavior of the obtained complexes
tion of complexes 1, 3, 5, and 6 was not complete until
was investigated by thermogravimetric and differential
600°C; i.e., these complexes may be regarded as mode-
thermal analysis (Table 3). Figure shows the DTA and
rately thermally stable.
TG curves of complexes 1–3, 5, and 6 recorded under
nitrogen atmosphere. No weight loss was found for Likewise, mercury(II) chelates 2, 7, and 8 decom-
complexes 1, 5, and 6 up to 235, 223, and 194°C, posed in two distinct stages starting at 169, 136, and
respectively, indicating the absence of solvent/water 157°C (Table 3). Complex 2 showed a strong exo-
molecules, which was also evident from their ele- thermic DTA peak at 169–213°C with a weight loss of
mental analyses and IR spectra. Above that 73.7% (calculated: 73.95%). Complex 7 displayed three
Table 4. Cytotoxicity of some ligands and complexes against MCF-7 cell line
Inhibition, %
Compound IC50, μM
1 µM 10 µM 100 µM
HL1 62.6±11.7 65.5±11.3 66.7±12.1 0.78
1
Cu(HL )2Cl(H2O) 88.8±15.6 93.6± 13.1 93.3±15.1 0.56
1
Hg(HL )2(OH)(OAc) 83.3±11.3 85.9±21.1 88.5±18.2 0.60
4
H2L 59.3±11.0 62.5±10.6 64.7±11.3 0.84
4
Cu(H2L )Cl(H2O) 85.0±14.6 88.5±14.0 88.2±14.1 0.59
5
H2L 58.8±11.0 62.0±10.4 63.5±11.0 0.85
5
Cu(H2L )(OH) 89.0±16.0 94.5±14.3 94.2±15.3 0.56
5
Hg(H2L )(OAc)2 80.0±11.2 82.0 ±19.7 83.7±17.3 0.63
6
H2L 64.0 ±11.8 65.6±11.5 67.6±11.7 0.78
6
Hg(HL )(OAc)(H2O) 81.3±11.3 83.5±15.3 85.7±15.0 0.62
Doxorubicin 75.5±12.4 80.4±17.0 87.3±18.3 0.66
weak exothermic and one weak endothermic DTA plex 8 with weight losses of 6.4 and 68.9%, respec-
peaks at 163–195, 224–262, 444–485, and 485–570°C tively (calculated: 6.2 and 68.9%). Complex 4 showed
(weight loss 9.0, 24.3, and 21.5%; calculated: 9.3, three exothermic DTA peaks at 189–244, 278–358,
24.0, and 21.2%, respectively). Two exothermic DTA and 514–594°C (weight loss: 15.6, 25.1, and 8.1%;
peaks appeared at 228–257 and 431–481°C for com- calculated: 15.3, 25.0, and 8.0%).
2
TGA, mg
TGA, mg
1
1
2
Temperature, °C Temperature, °C
(c) Sample weight 3.2 mg (d) Sample weight 3.2 mg
1
TGA, mg
TGA, mg
2
1
Temperature, °C Temperature, °C
Temperature, °C
(1) TG and (2) DTA curves of copper(I) complexes (a–d) 1–3, 5, and (e) 6.
Table 4 contains the results of studying the and H2L4), their copper(I) and mercury(II) complexes
cytotoxic activity of some ligands and complexes in demonstrated significant inhibitory action against
vitro, which was expressed as percentage of inhibition MCF7 cell line in dose-dependent manner. Copper(I)
of MCF7 proliferation. In contrast to the ligands (HL1 complexes 1 and 6 exhibited a significant increase in
the cytotoxicity against MCF7 as compared to doxo- a solution of the corresponding ligand (HL1, H2L2,
rubicin taken as reference anticancer drug. H2L4, or H2L5 for copper complexes or HL1, HL3,
H2L5, or H2L6 for mercury complexes) in anhydrous
In summary, we have synthesized and structurally
ethanol. The mixture was magnetically stirred at 60°C
characterized new copper(I) and mercury(II) com-
for 2–5 h. The resulting solid was filtered off, washed
plexes with 4-aminoantipyrine, thiosemicarbazide, and
several times with ethanol, and dried over P4O10 in a
hydrazide ligands. The thermal study revealed that the
vacuum.
copper(I) complexes are more thermally stable than
mercury(II) chelates. The copper complexes showed
Antitumor activity. Potential cytotoxicities of
higher cytotoxicity against human breast carcinoma
ligands HL1, H2L4, H2L5, and H2L6 and complexes 1, 2,
MCF7 cell line as compared to mercury complexes and
and 5–8 against human breast adenocarcinoma cell line
are therefore promising as anticancer drugs.
MCF7 (ATCC, cat. no. HTB-22) were evaluated at the
EXPERIMENTAL National Cancer Institute (Cairo University, Egypt) by
the colorimetric sulforhodamine B (SRB) assay accord-
All organic reagents and solvents were purchased ing to [40, 41]. The cells were grown in Dulbecco’s
from Fluka or Merck (Nasr City, Egypt) and were used Modified Eagle’s Medium with 4.5% of glucose
without further purification. The elemental analyses (DMEM, PAA Laboratories) supplemented with 10%
(C, H, Cl) were obtained as the Microanalytical Unit of fetal calf serum (FCS). Cells were seeded into 96-well
the Cairo University, Egypt. The Fourier Transform microliter plates at a density of 5000 cells per 0.1 mL
Infrared (FT-IR) spectra (4000–400 cm–1) were per well and 24 h after seeding were exposed in
recorded in KBr on a Thermo Nicolet Nexus 670 FTIR triplicate to three dilutions (1, 10, 100 μM) of samples
spectrometer (Central Lab, El Minufiya University, dissolved in dimethyl sulfoxide (DMSO). Control and
Egypt). The 1H NMR spectra were recorded in DMSO-d6 blank wells were included in each plate. After 72 h,
using a Varian NMR spectrometer (300 MHz; Micro- cells were fixed in trichloroacetic acid (TCA) (25 μL
analytical Lab, Cairo University, Egypt). The molar of 50% w/v TCA per well) for 1 h at 4°C, washed five
conductivity measurements were made in DMF (10–3 M) times with distilled water, and stained with 50 μL of
using a Tacussel Conductometer type CD6N. 0.4% SRB in 1% acetic acid for 30 min. The cells were
washed five times with 1% acetic acid and air-dried.
Thermal analyses (DTA/TG) were obtained using a The stain was solubilized in 10 mM TRIS (pH 10.5),
Shimadzu DTA/TG-50 Thermal analyzer (Central Lab, and light absorption was measured using a microplate
El Minufiya University, Egypt) at a heating rate of reader (Thermo Lab Systems) at λ 492 nm with
10 deg/min in a nitrogen atmosphere (nitrogen flow reference wavelength λ 690 nm. The cytotoxicity was
rate 20 mL/min) in the temperature range from 25 to expressed as a percentage of the corresponding control
800°C using platinum crucibles. value (non-treated cells) obtained in two independent
The ligands, (1,5-dimethyl-3-oxo-2-phenyl-2,3-di- experiments. The original data was analyzed by a one
hydro-1H-pyrazol-4-yl)carbonohydrazonoyl dicyanide way ANOVA, followed by Duncan’s multiple-range
(HL1), 2-cyano-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3- post-hoc test. Differences were considered significant
dihydro-1H-pyrazol-4-yl)-2-[(E)-(3-ethylphenyl)di- at P <0.05.
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