Copper(II) and zinc(II) complexes of thiophene/furan carboxamides: Synthesis, structure and properties

Article abstract of DOI:10.1134/S0036023610070168

Cu(II) and Zn(II) complexes were synthesized from equimolar amounts of carboxamides; 1,8-bis(2-thiophenecarboxamido)-p-menthane (tkdam) and 1,8-bis(2-furancarboxamido)-p-menthane (furdam). The structure of the carboxamides were determined by elemental ana

Full text of DOI:10.1134/S0036023610070168

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 7, pp. 1094–1102. © Pleiades Publishing, Ltd., 2010.
COORDINATION COMPOUNDS
Copper(II) and Zinc(II) Complexes of Thiophene/Furan
Carboxamides: Synthesis, Structure and Properties1
Ayla Balaban Gündüzalp and Birgül Erk
Chemistry Department, Faculty of Science and Arts, Gazi University, Ankara, Turkey
eꢀmail: balaban@gazi.edu.tr
Received September 19, 2008
Abstract—Cu(II) and Zn(II) complexes were synthesized from equimolar amounts of carboxamides; 1,8ꢀ
bis(2ꢀthiophenecarboxamido)ꢀpꢀmenthane (tkdam) and 1,8ꢀbis(2ꢀfurancarboxamido)ꢀpꢀmenthane (furꢀ
dam). The structure of the carboxamides were determined by elemental analysis; 1H NMR, 13C NMR, FTꢀ
IR and LCꢀMS spectra. The relative energies and the electronic properties (LUMO, HOMO, LUMOꢀ
HOMO gap) of the ligands were investigated theoretically by performing Semiꢀempirical molecular orbital
theory PM3 method in Hyperchem 7 (Release). Carboxamide complexes having general formula as; monoꢀ
meric, [ML]Cl2 and dimeric [Cu(tkdam)Cl]2Cl2 5H2O were synthesized and characterized by using element
⋅
analysis; FTꢀIR, LCꢀMS spectra; magnetic susceptibility, molar conductivity and thermal (TGA/DTA
curve) studies. It was found that the coordination number of the monomeric complexes is four whereas
dimeric’s is six. The changes in the selected vibration bands in FTꢀIR indicate that, carboxamides behave as
tetradentate ligands and coordinate to metal ions from acyl ring (through S/O) and amide carbonyl (C=O).
Molar conductivity measurements indicate the 1 : 2 ionic nature of the carboxamide complexes.
DOI: 10.1134/S0036023610070168
1
INTRODUCTION
boxamides were determined by spectral methods (1H
NMR, 13C NMR, LCꢀMS, FTꢀIR). The relative
energies: total energy, binding energy, heat of formaꢀ
tion and the electronic properties: the highest occuꢀ
pied molecular obital (HOMO) energy, lowest unocꢀ
cupied molecular orbital (LUMO) energy and
The carboxamide linkages (–CO–NH–) are an
essential building unit in proteins, which has attracted
much attention because of its high resistance to
hydrolysis. This fact is of crucial importance in biologꢀ
ical systems, since it permits for the building of peptides
from relatively simple amino acid precursors [1–4].
LUMOꢀHOMO gap ( E) of the ligands were calcuꢀ
Δ
lated by using Semiꢀempirical PM3 method in Hyperꢀ
chem 7 (Release). The coordination behaviour of
ligands towards transition metal ions was investigated
via the FTꢀIR, molar conductance, magnetic moment
and thermal analysis.
The continuing interest in the study of carboxamꢀ
ide complexes are derived from their ability to model
active sites present in some metalloproteins and the
search for a better understanding of physicochemical
properties of such complexes, especially the stereꢀ
ochemistry of the metallic centers. In order to expand
on the function of the metal ions in the biological sysꢀ
tems, we are involved in a study of the impact of strucꢀ
ture changes on the physicochemical properties of the
model complex of the first row transition metal [5, 6].
EXPERIMENTAL
Materials and Methods
1,8ꢀdiaminoꢀpꢀmenthane, 2ꢀthiophenecarbonyl
chloride and 2ꢀfurancarbonyl chloride, metal salts as
chlorides (all from Aldrih) and solvents (all from
Merck) were used without further purification. All
chemicals and solvents used in syntheses were of anaꢀ
lytical grade. The elemental analyses (C, H, N, S)
were performed on a LECO–CHSNOꢀ9320 type eleꢀ
mental analyzer. Geometry optimization of ligands
were performed by Semiꢀempiricai molecular orbital
theory PM3 method in Hyperchem 7 (Release). The
IR spectra (4000–400 cm–1) were recorded on a Mattꢀ
sonꢀ1000 FTꢀIR spectrophotometer with samples
prepared as KBr pellets. NMR spectra were recorded
on a Bruker–Spectrospin Avance DPXꢀ400 Ultra–
Shield (400 MHz) using DMSOꢀd6 as a solvent. UVꢀ
There is a considerable interest in the pharmacolꢀ
ogy of heterocyclic ligands containing nitrogen, oxyꢀ
gen, sulfur etc. and their metal chelates [7, 8] as antiꢀ
tumor, antibacterial, antifungal and antiviral agents.
Copper complexes have been widely used in metalmeꢀ
diated DNA cleavage to obtain the activated oxygen
species [9].
In this paper, we report the synthesis and characterꢀ
ization of thiopheneꢀ2ꢀcarboxamide and furanꢀ2ꢀcarꢀ
boxamide by the reaction of the acide chlorides with
1,8ꢀdiaminoꢀpꢀmenthane. The structures of the carꢀ
1
The article is published in the original.
1094

COPPER(II) AND ZINC(II) COMPLEXES
Table 1. Elemental analysis data of ligands and their complexes; found/(calculated
1095
)
Compound
C, %
H, %
N, %
S, %
M, %
–
Cl, %
–
tkdam
[Cu(tkdam)Cl]2Cl2
61.37(61.54) 6.50(6.66)
41.78(42.14) 5.23(5.44)
45.34(45.61) 4.65(4.94)
66.77(67.06) 7.54(7.26)
48.36(48.76) 5.09(5.28)
48.13(48.58) 5.47(5.26)
7.10(7.18)
5.12(4.92)
4.95(5.32)
8.23(7.82)
5.95(5.69)
5.91(5.67)
15.98(16.38)
⋅
5H2O
10.61(11.24) 10.57(11.15) 11.74(12.47)
11.78(12.18) 12.34(12.42) 12.49(13.36)
[Zn(tkdam)]Cl2
furdam
–
–
–
–
–
[Cu(furdam)]Cl2
[Zn(furdam)]Cl2
12.72(12.90) 13.45(14.39)
12.68(13.24) 15.23(14.37)
Table 2. Physical properties of carboxamides and their complexes
Λm
(cm–1 mol–1
Compound
Formula
FW (g/mol)
Yield (%)
μeff (B.M.)
–1
Ω
)
tkdam
C20H26N2O2S2
5H2O C40H62N4O9S4Cu2Cl4
C20H26N2O2S2ZnCl2
C20H26N2O4
390.33
1139.04
526.69
358.17
492.62
494.47
70
63
60
67
64
62
–
1.67
dia
–
–
98
87
–
[Cu(tkdam)Cl]2Cl2
[Zn(tkdam)]Cl2
furdam
⋅
[Cu(furdam)]Cl2
[Zn(furdam)]Cl2
C20H26N2O4CuCl2
C20H26N2O4ZnCl2
1.88
dia
96
90
Vis spectra were recorded on UNICAMꢀUV 2ꢀ100 appropriate metal chloride (1.00 mmol) in 25 mL
spectrophotometer. Magnetic susceptibility data for methanol to the hot solution (40 ) of ligand
°C
the metal complexes was recorded on a Sherwood Sciꢀ (1.00 mmol) in the same solvent (25 mL). The resultꢀ
entific magnetic balance. The molar conductance ing mixture was stirred under reflux whereupon the
measurements were carried out using a Siemens WPA complexes precipitated. They were recrystallized from
CM 35 conductometer. A Du Pont Instrument 951 methanol and than dried in dessiccant [10].
thermal analyzer was used to record simultaneously
TG and DTA curves. The experiments were carried
out in dynamic nitrogen atmosphere (20 mL min–1
)
RESULTS AND DISCUSSION
with a heating rate of 10°C min–1 in the temperature
range 30–400°C using platinum crucibles.
The carboxamide compounds were prepared as
described in the experimental part, crystallized, dried
and subjected to elemental analysis. The results of eleꢀ
mental analysis (C, H, N, S) and analytical data are
presented in Tables 1 and 2.
The results obtained are in good agreement with
those suggested formula below. In all of the syntheꢀ
sized carboxamides behave as tetradentate ligands.
The preparation of the ligands are given in Fig. 1.
Synthesis of the Ligands
To a solution of acide chlorides (30.00 mmol) in
dichloromethane (20 cm3), triethylamine (30.00 mmol)
was added then 1,8ꢀdiaminoꢀpꢀmenthane (15.00 mmol)
in dichloromethane (10 cm3) was added dropwise by
cooling the balloon in the ice bath. The reaction mixꢀ
ture was stirred magnetically under reflux for a day.
The precipitate was filtered and dried on vacua. The
crude product was dissolved in a 30 mL of MeOH by
heating on a magnetic stirrer. The solvent was evapoꢀ
rated to half of its original volume. The solution was
filtered warmly to remove impurities, then left for
crystallization at room temperature. Recrystallization
from methanol yielded a white solid ligands and than
these crystals were dried on A4 molecular sieve [8].
In general, 1 : 1 (M : L) solid complexes were isoꢀ
lated and found to have the general formula given as
MXm ·
Cl;
n
m
H2O + L
[ML]X2 where M = Cu, Zn; X =
= 2;
n
= 0.2 whereas dimeric complex
(tkdamCu) has the general formula as
[Cu(tkdam)Cl]2Cl2 5H2O
⋅
.
NMR Spectra
1H NMR and 13C NMR data of carboxamide
ligands are collected in Table 3.
Synthesis of Metal Complexes
1
The H NMR spectra of carboxamides in deutero
The metal complexes of the carboxamides were form of DMSO displayed the expected resonances.
prepared by the addition of hot solution (40 ) of the The integration which is in accordance with 1 : 2 forꢀ
°
C
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

1096
GÜNDÜZALP, ERK
H
CH3
CH3
H
CH3 H O−
N+
CH3 H Cl
O–ꢀ
C
CH3
O
H
+N
H
+
C NH2
C Cl NH2
C
C
••
••
X
X
X
CH3
Cl
X = S, O
O
C Cl
2(C2H5)3N
X
••
H
H
CH3
CH3
H
H
OH
OH
CH3
C
O+
C
+O
CH3
C
–Cl
N
C
C
N
H
N
C
N
H
X
X
X
X
X
CH3 H
CH3 H
Cl
Cl
CH3
H
CH3
O
O
+ 2(C2H5)3NHCl
C
NH C
C NH
X
CH3
Fig. 1. Preparation of the carboxamide ligands.
mulation proposed by elemental analysis, allows the carboxamide leads to less decrease in E (9.05 eV),
Δ
assignment of them. In general, the multiplates this means that in any excitation process of thiophene
observed between 7.11–7.85 ppm and 7.06–7.79 ppm carboxamide needs less energy than furan carboxamꢀ
are asigned to thiophene and furan ring protons, ide [6–18] LUMO, HOMO orbitals and energy specꢀ
respectively. N(1)H and N(2)H protons are observed tra of tkdam molecule are shown in Figs. 2 and 3.
between 7.43–7.66 ppm as singlet [11–14]. In the
13CꢀNMR spectra, carbonyl C(5), C(16) groups have
the highest chemical shifts and observed between
FTꢀIR Spectra and Mode of Bonding
161.46 ppm, 161.11 ppm for tkdam and 158.10 ppm,
157.74 ppm for furdam [8, 15]. The functional groups
at each side of the menthane ring have similar or very
close chemical shifts because of asymetry.
The most chracteristic vibrations of carboxamide
compounds are selected by comparing the vibrational
frequencies of the ligands with those of their metal
complexes and recorded in IR spectra gives enough
information to elucidate the way of bonding of the
ligands to the metal ions. Carboxamides have three
donor sites: thiophene ring S/furan ring O; carbonyl O
and amide N. As tetradentate ligands the bonding
takes place through either the ring donors (S/O) and
Geometry Optimization
Geometry optimization calculations for the free
ligands were performed by Semiꢀempirical PM3
method in Hyperchem 7 (Release) whereas this
method is not satisfactory for the complexes. Table 4
shows the PM3 optimized total energy, binding energy,
semiꢀempirical heats of formation and the highest
occupied molecular orbital (HOMO), the lowest
unoccupied molecular orbital (LUMO) energies and
the interꢀfrontier molecular orbital energy gap
carbonyl O (Amide
characteristic amide bands such as: Amide
Amide II, Amide III etc. Amide occurs as a strong
band between 3335–3367 cm–1 by the vibration of N–H
bond (νN–H). Amide band which results from comꢀ
I
) [19, 20]. Carboxamides have
A, Amide
I,
A
I
posite N–C=O vibriation consists mainly of carbonyl
C=O vibriation (νC=O). Amide II and Amide III bands
arise from νC–N as well as δN–H, these modes are couꢀ
pled to one another [7, 8, 21]. The carbonyl frequenꢀ
(LUMOꢀHOMO,
ΔE) with the lowest and highest
level energy values of the carboxamide ligands.
Thiophene carboxamide molecule has a heat of cies (Amide I) of the ligands are observed between
formation of about –31.86 kcal/mol, while furanꢀ2ꢀ 1632–1654 cm–1. In the complexes, a significant negꢀ
carboxamide has the value of about –102.46 kcal/mol ative shift of the carbonyl frequency takes place,
by PM3 method. As shown in Table 4 the heat of forꢀ because of coordination through the carbonyl O [22,
mation of the molecules change with variation of 23]. The other bonding mode is supported by these
donors (S, O etc.). On the other hand, the values of additional observations: (i) the shift of νCS
HOMO, LUMO and energies may be affected by lower wawenumbers and δC–S–C to higher wawenumꢀ
the variety of the donors. Furan carboxamide leads to bers by coordination through thiophene ring [14]. (ii)
+ δring to
ΔE
more increase in
ΔE
gap (9.52 eV), while thiophene the shift of in plane ring deformation mode of furan
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

COPPER(II) AND ZINC(II) COMPLEXES
Table 3. The NMR data for carboxamides using d6ꢀDMSO as solvent
1097
7
8
14
10 H
12
CH3
18 19
2
3
O
CH3
O
6
1
C NH
1
C HN C
20
4
17
5
(2)
16
(1)
9
11
X
X = S, O
X
CH3
15
1H NMR (ppm)
tkdam
13C NMR (ppm)
Assignment
N(1)H
furdam
tkdam
furdam
7.66 (s, 1H)
7.59 (s, 1H)
7.69 (d, 1H)
7.14 (m, 1H)
7.85 (d, 1H)
–
7.53 (s, 1H)
7.43 (s, 1H)
7.79 (d, 1H)
7.06 (m, 1H)
7.66 (d, 1H)
–
–
–
–
N(2)H
–
C(1)H
130.76
128.32
141.98
128.67
161.46
56.67
27.84
145.12
112.93
113.95
148.69
158.10
56.85
C(2)H
C(3)H
C(4)
C(5)
–
–
C(6)
–
–
C(7)H3
C(8)H2–C(11)H2
C(12)H
C(13)
1.39 (s, 3H)
2.02–1.21 (m, 8H)
2.17 (m, 1H)
–
1.31 (s, 3H)
24.59
2.47–1.12 (m, 8H)
2.09 (m, 1H)
–
36.06–22.65
43.13
43.72–22.02
36.81
56.09
54.09
C(14)H3, C(15)H3
C(16)
1.33 (s, 6H)
–
1.27 (s, 6H)
–
24.38
23.42
161.11
128.63
141.90
128.32
130.70
157.74
147.50
113.82
112.64
145.02
C(17)
–
–
C(18)H
C(19)H
C(20)H
7.82 (d, 1H)
7.11 (m, 1H)
7.69 (d, 1H)
7.66 (d, 1H)
7.06 (m, 1H)
7.79 (d, 1H)
ring, νC–C + νC–O to lower wawenumbers and the shift occurs by the removal of the amine (dam) as fragment
of βC–H(ring) to higher wawenumbers by coordination
through the furan ring [24, 25].
IV is observed at
spectra of [Cu(tkdam)Cl]2Cl2
m
/
z
= 171.1 (100.0%) [27]. The mass
⋅
5H2O is scanned up to
1200 (m/z), molecular ion peak was observed at
1050.6 (3.5%), [Cu(tkdam)Cl]2Cl+ fragment is
Molar Conductivity
The molar conductivity (Λm) of 10–3 M solutions of the
complexes were measured in MeOH at 25°C and exhibitꢀ
observed at 1013.0 (6.3%) by lossing of one chlorine
2+
atom, [Cu(tkdam)Cl]2 fragment was observed at
ted in Table 2. It is concluded that all the complexes have 978.7 (weakly) by lossing of two chlorine atoms and
the molar conductivity of 87–98
Ω
–1 mol–1 cm2 indicatꢀ
ing the ionic nature of these complexes. The molar
conductivity of 10–3
also measured as 88
M
Ω
CaCl2 solution in methanol was
Table 4. Semiꢀempirical PM3 calculation results of ligands
–1 mol–1 cm2 which is around the
Assignment
tkdam
furdam
molar conductivity of complexes. It means that all
complexes have 1 : 2 electrolyte type by comparing
CaCl2 solution and two chloride anions bonds to the
coordination sphere of the complexes as counter
ions [26].
Total energy (kcal/mol)
Binding energy (kcal/mol)
Heat of formation (kcal/mol)
HOMO energy (eV)
–93497.89 –98438.58
–5582.23 –5339.15
–31.86
–9.74
–0.69
9.05
–102.46
–9.65
–0.13
9.52
Mass Spectra
LUMO energy (eV)
Mass spectra of tkdam gives the molecular ion peak
LUMOꢀHOMO gap (ΔE, eV)
as fragment
I at m/z= 391.2 (4.3%). The main peak
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

1098
GÜNDÜZALP, ERK
LUMO
HOMO
Fig. 2. The shape of LUMO and HOMO of tkdam. Balls and cylinders model was used for the geometry optimization by Semiꢀ
empirical PM3 method.
30]. Mass spectra of [Cu(furdam)]Cl2 and [Zn(furꢀ
dam)]Cl2 are scanned up to 1200 ( , molecular ion
peaks with bonded fragment which belongs to menꢀ
thane ring (
= 82.1), [ML + 2Cl + 82.1]+ are
observed around 573.0 (6.3%) and 577.0 (4.7%) which
are the highest fragment ( ) values in the spectra.
Cl
Cl
μ
ꢀdichloro bridging dicopper (
) fragment
Cu
Cu
m/z)
is observed at 198.1 (7.1%) [28, 29]. These fragmentaꢀ
tions support the proposed dimeric nature of tkdamCu
complex in which other fragments are as follows: 882.1
(3.7%), 803.2 (17.5%), 488.0 (18.7%), 453.0 (36.4%),
128.0 (100%). In mass spectra of [Zn(tkdam)]Cl2 comꢀ
plex, molecular ion peak is observed at 544.2 (3.8%),
[Zn(tkdam)]+ fragment occurs by lossing of two chloꢀ
m/z
m/z
This shows that furdam complexes are monomeric
[14, 27]. [Cu(furdam)]2+ and [Zn(furdam)]2+ fragꢀ
ments which occur by losing of two chlorine atoms are
observed at 422.5 (4.1%) and 424.5 (5.5%). The proꢀ
posed fragmentation route of complexes and the main
rine atoms at
intensity. Mass spectra of furdam gives the molecular
ion peak as fragment at = 359.2 (12.3%) and
other fragments are as follows: fragment II (C4H3O
CO) is at = 95.1 (23.8%), fragment III
C15H22N2O2) is at 265.2 (35.0%) resulting from the
elimination of 2ꢀthiophene carbonyl group. Also the
removal of the amine(dam) fragment IV from fragꢀ in nitrogen atmosphere (20 ml min–1) with a heating
ment III can be observed at C.
= 171.2 (76.3%) [27, rate of 10°C min–1 in the temperature range 30–400
(m/z) 455.2 with 58.5% strong peak
fragments (I, II, III, IV) of ligands are shown in Fig. 4.
I
m/z
⋅
m/z
Thermal Studies
Thermal behaviour of complexes was determined
(
m/
z
°
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

COPPER(II) AND ZINC(II) COMPLEXES
1099
0 eV
0 eV
LUMO
HOMO
Fig. 3. The molecular orbital energy spectra of tkdam, Semiꢀempirical PM3 results.
As seen in Fig. 5, there are mainly two continuous mula as suggested from the analytical data (Tables 1
and 2) and proposed structure of complexes shown in
Fig. 6.
mass loss steps in the TGA curve of [Cu(tkdam)Cl]2Cl2
⋅
5H2O. The first step with mass loss of 9.525% from
90.57 to 132.13°C may be assigned to the loss of the
five crystal water molecules of hydration. There is
mainly large mass loss step which starts at 260.08°C
and ends at 300.14°C with loss percentage of 68.798%
which is attributed to the organic decomposition. In
CONCLUSION
In this study, we have reported the synthesis of carꢀ
boxamide ligands which contain N, S and O donors
and their tetradentate complexes. The structure of
ligands were determined by using elemental analysis,
several spectral methods (NMR, FTꢀIR, LCꢀMS).
the DTA curves, [Cu(tkdam)Cl]2Cl2
different heat effects on heating such as two intense
exothermic peak at 119.77°C ( = –598.50 J/g) and
270.04°C (
mic peak at 284.23°C (
⋅
5H2O behaves
Δ
H
Δ
H
= –93.42 J/g), one intense endotherꢀ The relative energies and the electronic properties of
Δ
H
= 230.63 J/g). In the TGA ligands were calculated by Semiꢀempirical molecular
orbital theory PM3 method in Hyperchem 7
(Release).
curves of other complexes, there are no mass loss up to
250°C because of non hydration. For [Zn(tkdam)]Cl2
and [Cu(furdam)]Cl2 complexes, there are observed
mainly one intense exothermic peak with mass loss of
The spectral, conductivity, thermal and magnetic
studies of complexes have been discussed. Carboxamꢀ
ides act as a tetradentate through the two amide carboꢀ
nyl (C=O) and two S/O donors of thiophene/furan
ring according to vibrational shifts on IR spectra.
Conductivity measurements showed that all comꢀ
plexes are electrolite (1 : 2 type) and contain two Cl
atoms out of coordination sphere. The structures of
87.927% at 290.74°C (
Δ
H
= –598.50 J/g) and
74.753% at 288.28°C (
Δ
H = –778.72 J/g) depending
on organic decomposition. There are different mass
loss rates starting at 259.33°C and finishing at
287.32°C which is predicted as the continuous organic
decomposition of [Zn(furdam)]Cl2 [31, 32]. Thermal
results shows good agreement with the theoretical forꢀ monomeric complexes are proposed as tetragonal
Table 5. Characteristic IR bands (4000–400 cm–1) of carboxamides and their complexes
Thiophene ring
Furan ring
νC–O βC–H(ring)
Compound
Amide
A
Amide
I
Amide II
ν
(CS) +
δ
(ring), δC–S–C νC–C
+
,
tkdam
3338
3337
3335
3363
3358
3367
1632
1623
1621
1654
1645
1644
1537
1540
1542
1597
1596
1597
717, 611
–
[Cu(tkdam)Cl]2Cl2
[Zn(tkdam)]Cl2
furdam
⋅
5H2O
706, 643
–
–
706, 636
–
–
–
1019, 1253
1012, 1270
1012, 1272
[Cu(furdam)]Cl2
[Zn(furdam)]Cl2
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1100
GÜNDÜZALP, ERK
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

COPPER(II) AND ZINC(II) COMPLEXES
1101
DTA,
uV
TGA,
mg
6
Temp,
°
C
400
300
200
100
20
0
25.50 min
284.23°C
5
4
3
2
1
–0.566 mg
–9.525%
Weight Loss
–20
–4.088 mg
–68.798%
Weight Loss
119.77°C
Peak
Onset 90.57°C
132.13°C
Endset
Heat
–40
–60
24.48 min
270.04°C
–3.56 J
–598.50 J/g
30
0
10
20
Time, min
Fig. 5. TGAꢀDTA curve of [Cu(tkdam)] Cl
⋅
5H O complex.
2
2
2
H3C
H3C
CH3
CH3
NH
CH3
HN
NH
C
NH
C
CH3
C
S
C
C
S
Cl
Cl
O
O
O
O
X
Cu
Cu
S
O
C
O
M
CH3
CH3
C
HN
S
C
X
C
CH3
NH
tkdamCu
[ML]Cl2 (M = Cu, Zn; X = S, O)
Fig. 6. The proposed structure of the carboxamide complexes.
geometry. Two extra bonding to tetragonal geometry and spectral data support the proposed dimeric strucꢀ
are provided by the coordinated two bridging chlorine
atoms in distorted octahedral dimeric complex,
[Cu(tkdam)Cl]2Cl2 ⋅ 5H2O [33, 34]. In the physicoꢀ
chemical aspects magnetic properties of dicopper
complexes are differ from monocopper complexes
with their antiferromagnetic coupling depending upon
the bridging and distortion. This is in agreement with
bridging tkdamCu complex and its magnetic moment
ture [28, 29].
In our previous work, 1,3ꢀbis(2ꢀthiophenecarboxꢀ
amido)ꢀpropane, 1,3ꢀbis(2ꢀfuran carboxamido)ꢀproꢀ
pane and their Cu(II), Zn(II), Co(III) complexes
were synthesized and their antimicrobial activities
were screened against several bacteria and fungi
(
C. albicans) [14]. In our further applications, the antiꢀ
(
µ
= 1.67 B.M.) is lower than other synthesized monoꢀ
copper complex, furdamCu ( = 1.88 B.M.) [35, 36].
In the mass spectra, the peak at
bacterial activies of the newly synthesized carboxamꢀ
ide compounds presented in this paper will be investiꢀ
gated.
µ
(m
/
z
) 198.1 correꢀ
Cl
sponds to
µ
ꢀdichloro bridging dicopper (
)
Cu
Cu
Cl
fragment. The electronic spectra of dinuclear copper
chelate showed an extra band at 422 nm between 10Dq
band for distorted octahedral geometry corresponding
ACKNOWLEDGMENTS
The authors are thankful to the Gazi University,
vide Project no. 05/2007ꢀ09 for financial support.
to the transitions 2Eg
2T2 [19]. These magnetic
g
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 7 2010

1102
GÜNDÜZALP, ERK
18. S. Silva, R. M. Silva, and K. N. Silva, J. Mol. Struct.
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