2-Hydroxy-1-naphthaldehyde S-(alkyl)-N4-phenylthiosemicarbazone complexes with Fe(III), Co(III), Ni(II), and Cu(II) ions

Article abstract of DOI:10.1081/SIM-120021929

2-Hydroxy-1-naphthaldehyde S-(alkyl)-N⁴-phenyl-thiosemicarbazones (alkyl = CH₃, C₂H₅, n-C₃H₇ and C₆H₅CH₂) were synthesized according to common procedures. T

Full text of DOI:10.1081/SIM-120021929

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2‐Hydroxy‐1‐naphthaldehyde
S‐(Alkyl)‐N4‐phenylthiosemicarbazone Complexes with
Fe(III), Co(III), Ni(II), and Cu(II) Ions
a
İrfan Kızılcıklı & Yılmaz Mesut a
a Istanbul University, Engineering Faculty, Chemistry Department, 34850, Avcilar, Istanbul,
Turkey
Version of record first published: 15 Feb 2007.
To cite this article: İrfan Kızılcıklı & Yılmaz Mesut (2003): 2‐Hydroxy‐1‐naphthaldehyde S‐(Alkyl)‐N4‐phenylthiosemicarbazone
Complexes with Fe(III), Co(III), Ni(II), and Cu(II) Ions, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 33:6,
949-963
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 6, pp. 949–963, 2003
2-Hydroxy-1-naphthaldehyde
S-(Alkyl)-N4-phenylthiosemicarbazone Complexes
with Fe(III), Co(III), Ni(II), and Cu(II) Ions
*
˙
Irfan Kızılcıklı and Yılmaz Mesut
Istanbul University, Engineering Faculty, Chemistry Department,
Avcilar, Istanbul, Turkey
ABSTRACT
2-Hydroxy-1-naphthaldehyde S-(alkyl)-N4-phenyl-thiosemicarbazones
(alkyl = CH3, C2H5, n-C3H7 and C6H5CH2) were synthesized according
to common procedures. The 1:1 and 1:2 metal to ligand complexes with
Fe(III), Co(III), Ni(II), and Cu(II) salts were synthesized and charac-
1
terized by analytical data, IR, H NMR spectroscopy, magnetic suscep-
tibility, molar conductivity and TGA analysis. It was determined that the
tridentate behavior of the ligands is accomplished via the phenolic
hydroxy group, the azomethine and thioamide nitrogens.
*
˙
Correspondence: Irfan Kızılcıklı, Istanbul University, Engineering Faculty, Chem-
istry Department, 34850, Avcilar, Istanbul, Turkey; E-mail: irfrank@istanbul.edu.tr.
949
DOI: 10.1081/SIM-120021929
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

950
Kızılcıklı and Mesut
INTRODUCTION
2-Hydroxy-1-naphthaldehyde thiosemicarbazone and its S-alkyl deri-
vatives belong to multidentate thiosemicarbazone compounds having wide
biological activities, and thus, they are used widely in pharmacology.[1–9] It
is found that they function as antimicrobial, antimalarial, antitumor and
antileukemic agents in compounds with transition metals and other metal
ions.[10–13] It should be noted that 2-hydroxy-1-naphthaldehyde thiosemi-
carbazone and its derivatives are used as selective reactants with glucose,
cholesterol, uric acid and amino acid in fluorometric determinations, as well
as of Fe(III) and Cu(II) in spectrophotometric methods.[14–19] The mole-
cular geometries of S-alkyl derivatives, which are obtained by alkylation of
the sulfur atom in thiosemicarbazones, and the bonding mode to the metal
ion are changed on coordination, and, consequently, the terminal nitrogen
(N4) is involved in coordination instead of the sulfur atom, the donor pro-
perty of which is very diminished.[20]
This study consists in the preparation and identification of 2-hydroxy-
1-naphthaldehyde S-alkyl-N4-phenylthiosemicarbazones (Figure 1) and
their Fe(III), Co(III), Ni(II), and Cu(II) complexes. The coordination be-
havior of the ligands are discussed and structures for the metal complexes
are suggested.
RESULTS AND DISCUSSION
Synthesis and Some Properties of the Compounds
The interaction of metal salts with the ligands in 1:1 and 1:2 molar
ratio in ethanol yielded stable solid complexes corresponding to the general
Figure 1. The ligands (R = CH3: H2L1; C2H5: H2L2; n-C3H7: H2L3; C6H5CH2: H2L4).

Phenylthiosemicarbazone Complexes
951
formulae[M(HL)2]ClxꢀnH2O(M = Fe,Co,Ni;x = 0,1;n = 0–2),[Fe(HL)Cl2]
and [Cu(HL)H2O]NO3. The metal/ligand stoichiometry of the Fe(III) com-
plexes is 1:1 for H2L1and H2L2, and 1:2 for H2L3 and H2L4, and 1:1 for
Cu(II) and 1:2 for Ni(II) complexes with H2L1, H2L2, H2L3 and H2L4 (see
Table 1).
Typical complexation reactions are given below.
FeCl3ꢀ6H2O þ 2H2L ! ½FeðHLÞ2ꢁClꢀH2O þ 2HCl þ 5H2O
FeCl3ꢀ6H2O þ H2L ! ½FeðHLÞCl2ꢁ þ HCl þ 6H2O
2CoCl2ꢀ6H2O þ 4H2L þ 1=2O2 ! 2½CoðHLÞ2ꢁCl þ 2HCl þ 13H2O
NiCl2ꢀ6H2O þ 2H2L ! ½NiðHLÞ2ꢁ þ 2HCl þ 6H2O
CuðNO3Þ2ꢀ3H2O þ H2L ! ½CuðHLÞH2OꢁNO3 þ HNO3 þ 2H2O
The ligands H2L1, H2L2, H2L3 and H2L4are insoluble in alcohols, but
soluble in polar organic solvents such as DMF and MeCN. The metal com-
plexes are easily soluble in DMSO and DMF, sparingly soluble in etha-
nol and methanol, whereas they are insoluble in chlorinated hydrocarbons.
The metal complexes generally have 70–100 °C higher melting points
than the corresponding ligands. The Fe(III) complexes are black, Co(III)
complexes are brown, Ni(II) complexes are deep yellow and Cu(II) com-
plexes are green.
Molar Conductivity and Magnetic Susceptibility
Conductivity measurements were made in acetonitrile for the Cu(II)
complexes, while methanol was used for the other complexes. (L: O–1
cm2mol–1, at 25
1 °C).
[Fe(HL4)2]ClꢀH2O and [Fe(HL3)2]ClꢀH2O have conductivity values of
112 and 108, respectively, indicating their electrolytic nature. The con-
ductivity of all other complexes are between 40 and 80 O–1cm2mol–1,
indicating that these complexes are non-electrolytic.
The 1:1 Fe(III) complexes with H2L1 and H2L2 and 1:2 complexes with
H2L3 and H2L4 are paramagnetic and high-spin, the meff values are 5.58,
5.60, 5.80, 5.66 B.M., respectively. The Co(III) complexes are low-spin and
diamagnetic, and the probable distorted octahedral structure is [Co(HL)2]-
ClꢀnH2O (for H2L = H2L1, H2L2 and H2L3, n = 0; for H2L = H2L4,
n = 2). It is determined that the stoichiometric ratio for Ni(II) complexes is

952
Kızılcıklı and Mesut

Phenylthiosemicarbazone Complexes
953

954
Kızılcıklı and Mesut
1:2. These complexes are paramagnetic and high-spin (meff = 2.84–3.1
BM). The 1:1 Cu(II) complexes are paramagnetic (meff = 1.65–1.80 B.M.).
TGA Analysis
TGA analyses of the Fe(III), Co(III), Ni(II) and Cu(II) complexes with
H2L1, H2L2, H2L3 and H2L4 were conducted in air within the range 25–800 °C
at 10 °C/min heating rate. The results of the TGA analyses indicated the
presence of crystal water molecules in the compounds [Ni(HL1)2]ꢀH2O,
[Ni(HL2)2]ꢀH2O, [Ni(HL3)2]ꢀH2O, [Ni(HL4)2]ꢀH2O, [Fe(HL3)2]ClꢀH2O,
[Fe(HL4)2]ClꢀH2O and [Co(HL4)2]Clꢀ2H2O. Elimination of the water mole-
cules were observed at 110–140 °C. Table 2 shows representative thermal
degradations of the Co(III) complexes. The Co(III) complexes were found
to decompose in three main steps like the other complexes. The first step
Table 2. TGA data of Co(III) complexes.
Actual weight loss %
Temperature range
for each step (°C)
Compound
weight (mg)
Compounds
Found
Calculated
[Co(HL1)2] Cl
25
11.15
9.00
5.32
1.27
1st step 25–279
2ndstep 279–524
3rdstep 524–603
Residue
19.3
33.0
36.3
11.4
20.2
31.5
38.3
10.0
[Co(HL2)2] Cl
25
12.81
10.41
6.05
1st step 25–270
2ndstep 270–514
3rdstep 514–581
Residue
18.8
34.0
36.1
11.1
19.5
34.1
35.5
10.9
1.42
[Co(HL3)2]Cl
25
10.82
8.86
4.94
1.24
1st step 25–270
2ndstep 270–505
3rdstep 505–571
Residue
18.1
36.2
34.2
11.5
18.8
36.5
33.6
11.1
[Co(HL4)2]Clꢀ2H2O
25
11.90
11.30
9.40
1st step 25–132a
2ndstep 132–246
3rdstep 246–480
4thstep 480–627
Residue
5.0
16.0
40.4
29.2
9.4
4.8
16.1
40.7
29.5
8.9
4.59
1.12
aIndicates the presence of crystal water.

Phenylthiosemicarbazone Complexes
955
ends at 280 °C by the elimination of phenyl rings attached to the terminal
N4 atom. The next step at 525 °C involves chloride loss and a decom-
position of the thiosemicarbazone structure, and finally, in the last step at
ca. 650 °C, decomposition of the naphthaldehyde moiety is observed.[3]
The Co2O3 residue is stable beyond this temperature. Only the Co(III)
complex with H2L4 shows elimination of two molecules of water at 132 °C.
Electronic Spectra
UV-Vis spectra of the ligands and their metal complexes were obtained
in 2ꢀ10–5 M ethanolic solutions between 200 and 700 nm.
The bands at 232–242 nm, attributed to the p !p* transitions, did not
change in the Co(III) complexes, but underwent a shift to 314–319 nm for
the Fe(III) and 276–285 nm for the Cu(II) complexes. The bands of n ! p*
transitions at 378–380 nm showed a bathochromic shift to 427–430 nm for
the Co(III) complexes, while hypsochromic shifts were seen to 360–370
nm for the Fe(III), and to 335–345 nm for the Cu(II) complexes. The charge
transfer bands of the Fe(III), Co(III) and Cu(II) complexes were observed at
359–372, 443 and 412–417 nm, respectively. The data regarding d–d bonds
could not be obtained clearly at the studied concentration
IR Spectra
IR spectra was obtained as KBr disks in the 4000–400 cm–1 range. The
spectra of the ligands contain the expected n(N4H) and n(OH) vibrations are
seen as broad, strong bands between 3257–3423 cm–1. The medium-
intensity bands at 3048–3122 cm–1 and 2868–2998 cm–1 are attributed to
aromatic n(C–H) and aliphatic n(C–H) vibrations, respectively. The d(NH)
and d(OH) bands of the ligands are observed at 1621–1609 cm–1, while the
n(C =N1) bands are at 1570
7 cm–1. The (N4H) rocking band at 719
cm–1 as well as in-plane aromatic (C–H) bands at 1031–1081 cm–1 and out-
of-plane aromatic (C–H) bands at 827–646 cm–1 have been determined.
The d(C–OH) bands are seen at 1356
2 cm–1 in the ligands.[2,9,13,20] The
d(OH) band at 1356
2 cm–1 can also be seen in the spectra of the com-
plexes, by undergoing higher-field shifts of about 7–15 and 2–12 cm–1,
respectively.[9]
The n(C=N1) band of the ligands is observed to undergo a 5–12 cm–1
shift to lower frequency on coordination to the metal ion.[21]
The (N4–C) streching band at 1242
2 cm–1 in the ligands undergoes
a 20–23 cm–1 shift to lower frequency which enhances the possibility of
decreasing the electron delocalization on the N4–C system and the change
in the electron density in the region.[2,13]

956
Kızılcıklı and Mesut
It is seen that the vibration, deformation and out-of-plane bands of the
N4H group at 3240
15, 1620
2 cm–1 and 719 cm–1 respectively, dis-
appear. This observation indicates that the coordination may occur with
deprotonation of the N4H donor group.[2,13,21]
1H NMR Spectra
The spectra of the ligands and their Co(III) complexes were recorded in
DMSO-d6 (see Table 3). The methyl protons appear as a singlet at 2.5 ppm
in the spectra of H2L1, and for H2L2 they are seen as a triplet at 1.8–1.2
ppm. The CH2 groups of H2L3 are a triplet at 3.6–3.0 ppm and a quartet at
1.2–0.8 ppm.
The ligands H2L3 and H2L4 in which no isomerization is seen in their
1H NMR spectra are relatively more easily coordinated. It is apparent from
the yields that these ligands are more effective in the isolation of 1:2
chelates. However, it was not possible to isolate the 1:2 complexes of the
ligands H2L1and H2L2, containing lower homologues (CH3 and C2H5) with
Fe(III) in even low yields. This is probably caused by isomer mixtures due
to the C=N bond with relatively higher solubility.[20]
The azomethine proton (CH=N1) gives a doublet for H2L1 showing cis/
trans isomerism (with an approx. 65/35 ratio) at 9.38 ppm, whereas a doublet
is seen at 9.43 ppm, having an isomer ratio of 55/45 for H2L2. However,
H2L3 and H2L4 show singlets only at 9.41 and 9.39 ppm, respectively.
The fact that the chemical shifts of the azomethine protons change not
in an assessable size is caused by the back-donation of the azomethine
system for coordination. Since the p electrons of the azomethine group are
not affected, the chemical environment of the proton is not changed.
However, the appearance of doublets for the proton g (Figure 1) at 9.38 and
9.43 for H2L1and H2L2, respectively, as singlets at 9.41 and 9.35 in the
complexes shows that the complexation occurs with only one isomer.
The disappearance of thioamide (N4H) resonance peaks in the spectra
of the complexes with the ligands definitely proves that the coordination
is occurring involving this region with deprotonation. In contrast, the
OH groups are involved in the coordination without deprotonation (see
Figures 2 and 3). The shifts of the OH group from 8.5–8.9 ppm to 6.0–
6.2 ppm support the data obtained from IR spectra.
It is known that the complexation of the thiosemicarbazone-ligands via
their OH groups affects the conjugated backbone of the ligand and, thus,
the p-system of the aromatic ring.[23] Since the coordination is observed
without deprotonation, this effect is only seen as small shifts, i.e., the
resonance of the proton Ha shifts by 0.25 ppm for H2L1 and H2L2, and 0.52
ppm for H2L3 and H2L4 (Figure 1).

Phenylthiosemicarbazone Complexes
957

958
Kızılcıklı and Mesut
Figure 2. 1:2 complexes (R = CH3, C2H5, n-C3H7 and C6H5CH2).
Figure 3. 1:1 complexes (R = CH3, C2H5, n-C3H7 and C6H5CH2).

Phenylthiosemicarbazone Complexes
959
It can be accepted that the appearance of new bands at 1008 and 810
cm–1 in the IR spectra of the Cu(II) complexes is indicative of ionic bonding
of NO3ꢂ to Cu(II), moreover, X-ray diffraction studies of the Cu(II) complex
of salicylaldehyde-S-methyl-N4-phenylthiosemicarbazone confirm the struc-
ture as [Cu(HL)H2O]ꢀNO3.[21,24]
The analytical and especially spectral data indicate that the ligands
have an ONN donor set. All of the ligands function as tridentate (ON1N4)
for Fe(III), Co(III), Ni(II), and Cu(II) ions. That the proton of the N4H
group rather than OH is dissociated makes 5- and 6-membered chelate
structures possible. The structures proposed and based on these approaches
are presented in Figures 2 and 3.
EXPERIMENTAL
Chemicals and Apparatus
1
The chemical used were reagent grade. H NMR spectra were recorded
in DMSO-d6 solutions on a Bruker AC-200 MHz FT-NMR spectrometer
(TUBITAK, Turkey) and chemical shifts were referenced relative to Me4Si.
IR spectra were recorded in KBr discs on a Mattson 1000 FT-IR spec-
trometer. Elemental analyses were obtained with a Carlo-Erba 1106 ana-
lyser (TUBITAK, Turkey) and a Hitachi 180/80 model atomic absorption
spectrometer. The molar conductances of the compounds were measured in
methanol and acetonitrile on a 712 Metrohm conductometer. Chloride ions
were determined by a Jenway 3040 ion analyser multimeter. Magnetic
measurements were carried out on a Sherwood Scientific apparatus at room
temperature by Gouy’s method using CuSO4ꢀ5H2O as calibrant. Water
contents and TGA analyses of the compounds were determined on a
Shimadzu 50 Model TGA. pH measurements and melting points were
carried out on a Jenway 3040 ion analyser and a Bu¨chi melting point B-545
instrument, respectively.
Synthesis of 2-Hydroxy-1-naphthaldehyde
S-Methyl-N4-phenylthiosemicarbazone (H2L1)
To the suspension of N4-phenylthiosemicarbazide (1 g, 6 mmols) in 10
mL ethyl alcohol, 0.8 mL (12 mmols) of MeI was added dropwise and the
mixture was refluxed on an 80 °C water bath for 3–4 hours. The cooled
reaction mixture was treated dropwise with 8 mL of a warm ethanolic
solution of 2-hydroxy-1-naphthaldehyde (0.86 g, 5 mmols). The yellow
product separated was washed with small portions of cold ethanol and

960
Kızılcıklı and Mesut
diethyl ether. The free ligand was obtained by adding a sufficient amount of
aqueous NaHCO3 solution (10%, w/w) before it was recrystallized from
ethanol. The final product was dried in a vacuum dessicator over CaCl2.
The other ligands, H2L2 , H2L3 and H2L4, were prepared in a similar
manner by using the corresponding alkyl halides[25,26] (see Figure 1).
Synthesis of 2-Hydroxynaphthaldehyde
S-Methyl-N4-phenylthiosemicarbazonatoiron(III) Complex
A quantity of 335 mg (1 mmole) 2-hydroxy-1-naphthaldehyde-S-
methyl-N4-phenyl thiosemicarbazone (H2L1) was dissolved in a mixture of
acetone (10 mL) and ethanol (20 mL) by means of an ultrasonic water bath.
This solution was treated drop-wise with 8 mL of an ethanolic solution of
FeCl3ꢀ6H2O (324 mg, 1,2 mmols). The reaction was continued for at least
one hour at ambient temperature, and the flask was placed in a refrigerator
and kept overnight. The formed black crystalline product was filtered,
washed two times with ethanol and one time with diethyl ether, and was
dried over CaCl2 in a vacuum dessicator.
The other complexes were prepared similarly using the appropriate
ligands and metal salts.[27]
ACKNOWLEDGMENTS
¨
The authors thank Dr. Bahri Ulku¨seven for his kind remarks on the
interpretation of the experimental data, and Mr. Barbaros Akkurt for ob-
taining analytical and spectral data.
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Received June 22, 2002
Accepted February 20, 2003
Referee I: D. X. West
Referee II: N. V. Duffy