Accepted Manuscript

Four copper(II) diclofenac complexes with pyridine derivatives: Synthesis,

crystal structures, spectroscopic properties, thermal analysis and catechol oxi
dase activities
Sema Caglar, Ismihan E. Aydemir, Ekrem Adgzel, Bulent Caglar, Serkan
Demir, Orhan Buyukgungor
PII:
DOI:
Reference:

S0020-1693(13)00487-8
http://dx.doi.org/10.1016/j.ica.2013.09.013
ICA 15641

To appear in:

Inorganica Chimica Acta

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Revised Date:
Accepted Date:

30 April 2013
12 August 2013
4 September 2013

Please cite this article as: S. Caglar, I.E. Aydemir, E. Adgzel, B. Caglar, S. Demir, O. Buyukgungor, Four copper(II)
diclofenac complexes with pyridine derivatives: Synthesis, crystal structures, spectroscopic properties, thermal
analysis and catechol oxidase activities, Inorganica Chimica Acta (2013), doi: http://dx.doi.org/10.1016/j.ica.
2013.09.013

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Four copper(II) diclofenac complexes with pyridine derivatives: Synthesis, crystal

structures, spectroscopic properties, thermal analysis and catechol oxidase activities
Sema Caglara*, Ismihan E. Aydemira, Ekrem Adgzela, Bulent Caglara,
Serkan Demirb, Orhan Buyukgungorc
a

Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100,

Erzincan, Turkey

Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55200,
Atakum, Samsun, Turkey
c

Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, 55200,
Atakum, Samsun, Turkey

Abstract
Four novel mononuclear copper(II) complexes [Cu(dicl)2(2-pic)2] 1, [Cu(dicl)2(3-pic)2] 2,
[Cu(dicl)2(4-pic)2] 3 and [Cu(dicl)2(2-ampy)2] 4 have been synthesized. The crystal structures
of the complexes 2 and 3 have been determined by X-ray crystallography. X-ray structure
analysis has shown that copper(II) ions have distorted octahedral geometry in 2 and 3 and
diclofenac coordinates to Cu(II) ion as a deprotonated ligand through carboxylato oxygens.
Four complexes have been characterized by elemental analysis and IR spectroscopy. Their
thermal stabilities have been determined by TG/DTA/DTG techniques. Four mononuclear
complexes have shown catalytic activity on the oxidation of 3,5-di-tert-butylcatechol to 3,5di-tert-butylquinone exhibiting saturation kinetics at high substrate concentrations.

Keywords: Diclofenac; Catechol oxidation; Copper(II) complex; Crystal structure

* Corresponding author. Tel.: +90 446 224 30 97 Fax: +90 446 224 30 16
E-mail address: semacaglar2002@hotmail.com (S. Caglar)

1. Introduction

The chemical classes of non-steroidal anti-inflammatory drugs (NSAIDs) consist of

salicylate derivatives, phenylalkanoic acids, oxicams, anthranilic acids, sulfonamides and
furanones [1]. NSAIDs are known as one of the most commonly used medications. In recent
years, the use of NSAIDs has continuously increased. As a result of this, synthesis and study
of metal complexes with NSAIDs has been a research area of considerable interest.
Diclofenac, (systematic (IUPAC) name 2-(2,6-dicholoroanilino)phenylacetic acid),
which consists of a phenylacetate group, a secondary amino group and a dichlorophenyl ring,
is a member of NSAIDs group of phenylalkanoic acids and currently one of the most widely
used drugs for the treatment of diverse diseases such as analgesic, anti-inflammatory,
antipyretic agents and sport injuries. In addition, NSAIDs are indicated to control pain and
inflammation of rheumatic and non-rheumatic origin [2-6]. Several studies have shown that
the influences of NSAIDs are essentially based on the inhibition of cyclooxygenase.
Cyclooxygenase converts the arachidonic acid into prostaglandins, prostacyclin, and
thromboxane [7-8]. However, the mechanisms responsible for these actions have not been
clearly demonstrated yet.
In previous papers, the crystal structures of metal complexes of diclofenac have been
reported [4, 10-12] as well as its own molecular structure has been characterized by various
techniques [9]. The literature overview have presented so far, synthesis and characterization
of mononuclear and dinuclear copper(II) complexes with NSAIDs phenylalkanoic acids,
tolmentin [13,14], naproxen [13,14], ibuprofen [13-15], suprofen [16,17], indomethacin
[18,19] and diclofenac [10].
Copper is one of the most important metals in the human body [20] because of its

biological functionality, and synergetic activity with drugs as well [21]. Besides, as a cofactor,
copper(II) ion plays an important role in various enzymatic reactions, such as catechol
oxidase activity [22-32]. Catechol oxidase enzyme, also known as polyphenol oxidases, exists
widely in nature such as in plants, insects and crustaceans and plays an important role in
disease resistance in higher plants [33]. Catechol oxidase belonging to the polyphenol
oxidases oxidizes phenolic compounds to the corresponding quinone in the presence of
dioxygen [34]. In the present study, the catalytic activity of complexes for the oxidation of
3,5-di-tert-butylcatechol to the corresponding o-quinone in methanol medium has been
studied by UVVis spectroscopy technique (Fig. 1). Since several dinuclear copper(II)
complexes have featured the accomplished mimicry of the enzyme [30-32] both structurally

and functionally, a lot of mononuclear copper(II) complexes are known to display major
catecholase activity as well [27,35-37].
The mechanism of catechol oxidation by the natural enzyme, as proposed by Krebs
and co-authors were studied [38].
Our research has been focused on the coordination chemistry of diclofenac with metal
ions in an attempt to examine their mode of binding and catechol oxidase activity. Herein, we
have reported the synthesis, structural characterization and catechol oxidase activity of the
neutral copper(II) complexes with diclofenac in the presence of a nitrogen-donor heterocyclic
ligand such as 2-picolin (2-pic), 3-picoline (3-pic), 4-picoline (4-pic) and 2-aminopyridine (2ampy).

2. Experimental
2.1. Materials and methods
All reactions were performed with commercially available reagents and they were
used without further purification. The solvents were distilled and dried by standard
procedures. Infrared spectra of the complexes were recorded with a Bruker Vertex 80v FT-IR
spectrophotometer in the range of 4000-450 cm-1 and at a resolution of 4 cm-1 by using KBr
pellet. UVVis spectra were recorded on a PG 80+ UV-Vis spectrophotometer in the range of
200-900 nm in methanol. Elemental analyses of the complexes (carbon, hydrogen and
nitrogen) were determined with a LECO CHNS-932 analyzer. The TG and DTA curves were
scanned using a PRIS Diamond TG/DTG apparatus in a static air atmosphere (heating rate: 10
o

C min-1, platinum crucibles, mass: 10 mg and temperature range: 30-1000 oC).

2.2.

Synthesis

2.2.1. [Cu(dicl)2(2-pic)2] 1
Cu(CH3COO)2.2H2O (0.06g, 0.3 mmol) and Nadicl (sodium diclofenac) ligand (0.18g,
0.6 mmol) were dissolved in methanol-ethanol mixture ((1:1); 40 cm3) with continuous
stirring at 50 oC. Then 2-picoline (98L, 0.6 mmol) was added. The resulting solution was left
to stand for slow evaporation at room temperature, violet coloured micro-crystals appeared
after few days.
Yield: 80 %; microanalytical data for [C40H34N4O4Cl4Cu]: Found: C, 57.43; H, 4.11;
N, 6.72 %; calcd: C, 57.15; H, 4.05; N, 6.67 %).

2.2.2. [Cu(dicl)2(3-pic)2] 2
Cu(CH3COO)2.2H2O (0.06g, 0.3 mmol) and Nadicl ligand (0.18g, 0.6 mmol) were
dissolved in methanol-ethanol ((1:1); 40 cm3) mixture with continuous stirring at 50 oC. Then
3-picoline (98L, 0.6 mmol) was added. X-ray quality dark blue crystals of [Cu(dicl)2(3pic)2] were obtained by slow evaporation of the solution at room temperature within few day.
Yield: 75 %; microanalytical data for [C40H34N4O4Cl4Cu]: Found: C, 56.73; H, 4.21;
N, 6.70 %; calcd: C, 57.15; H, 4.05; N, 6.67 %).

2.2.3. [Cu(dicl)2(4-pic)2] 3
Complex 3 was prepared following the same procedure carried out for 1 using 4picoline instead of 2-picoline. The solution was left to stand for slow evaporation. The dark
green crystal suitable for X-ray structure determination was collected after two weeks.
Yield: 83 %; Analytical data for [C40H34N4O4Cl4Cu]: Found: C, 56.89; H, 4.18; N,
6.72 %; calcd: C, 57.15; H, 4.05; N, 6.67 %).

2.2.4. [Cu(dicl)2(2-ampy)2] 4
CuCl2.2H2O (0.05g, 0.3 mmol) and Nadicl ligand (0.18g, 0.6 mmol) were dissolved in
methanol-ethanol ((1:1); 40 cm3) mixture with continuous stirring at 50 oC. Then 2aminopyridine (0.056g, 0.6 mmol) was added. After slow evaporation of the resulting solution
in few days, dark green micro-crystals appeared.
Yield: 80 %; Analytical data for [C38H32N6O4Cl4Cu]: Found: C, 53.25; H, 3.81; N,
9.70 %; calcd: C, 54.17; H, 3.80; N, 9.97 %).

2.3. X-ray crystallography

The diffraction data were collected on a STOE IPDSII image plate detector using Mo
K radiation ( = 0.71073, T = 293 K). A summary of the key crystallographic information
is given in Table 1. Data collection: Stoe X-AREA [39]. Cell refinement: Stoe X-AREA [39].
Data reduction: Stoe X-RED [39]. The structure was solved by direct-methods using
SHELXS-97 [40] and anisotropic displacement parameters were applied to non-hydrogen
atoms in a full-matrix least-squares refinement based on F2 using SHELXL- 97 [40]. All H
atoms attached to carbon were positioned geometrically and refined by a riding model
assigning Uiso equals to 1.2 times that of attached atoms and remaining H atoms were located
from the Fourier difference map.

2.4. Methodology for catechol oxidase activity of complexes

The catalytic oxidation of substrate 3,5-di-tert-butylcatechol (DTBCH2) by four
complexes were evaluated in air saturated methanol at room temperature. The reaction was
performed spectrophotometrically by choosing the strongest absorbance value. Because, the
oxidation product (3,5-di-tert-butylquinone (3,5-DTBQ)) is significantly stable and has a
strong absorption at 395 nm. The initial reaction rate was determined from the slope of the
trace at 395 nm first 30 sec. of the reaction. While the initial rate was being determined,
different ratios of complex and substrate were studied. The minimum complex to substrate
rate was 1:5, the maximum complex to substrate rate was 1:30. Km, Vmax, kcat values were
determined by Lineweaver-Burk plots and Michaelis-Menten equation.

3. Result and Discussion

Complexes 14 are stable at the same environment conditions. They are insoluble in
water, hexane and diethyl ether, but they are soluble in methanol, chloroform, tetrahidrofuran
and dimethylsulfoxide. Based on the experimental data (IR spectroscopy, elemental and
thermal analysis), 1 and 4 show structural similarity with [Cu(dicl)2(3-pic)2] 2 and
[Cu(dicl)2(4-pic)2] 3, respectively. Selected geometrical parameters for 2 and 3 are listed in
Table 1. High purity of the complexes was confirmed by elemental analysis data being in
good agreement with these calculated for the suggested stoichiometries.

3.1. Description of crystal structures

3.1.1. [Cu(dicl)2(3-pic)2] 2
A molecular view of [Cu(dicl)2(3-pic)2] with the atom numbering scheme is shown in
Fig. 2. The selected bond lengths and angles are given in Table 2. The coordination geometry
of Cu(II) ion in 2, can be described as distorted octahedral, with two neutral 3-pic ligands and
two anionic dicl ligands. 2 crystallizes in monoclinic space group C2/c and shows a disorder
in four carbon atoms of benzene (C17A/C17B C20A/C20B and Cl2A/Cl2B) and carboxyl
groups (C14A/C14B O1A/O1B O2A/O2B) in dicl ligands. These atoms are treated as
split atoms during the refinement to account for the disorder.
As expected, Cu-O(1A)dicl (2.609(6) ) and Cu-O(2B)dicl (2.429(6) ) bonds are
longer than Cu-O(1B)dicl (1.966(5) ), Cu-O(2A)dicl (2.020(7) ) and Cu-N(1)3-pic (1.996(2)
) bonds and shows a Jahn-Teller elongated octahedral geometry along Cu(II).

Cu-N3-pic bond distance is 1.996(2) , and similar to that in [Cu(bba)2(3-pic)2]

1.999(2) [41], [cis-Cu(p-hydroxybenzoate)2(3-picoline)2] (1.99(2) ) [42] and [Cu(2-Cl-5FC7H3O2)2(3-pic)2(H2O)2] (2.009(4) ) [43] where 2-Cl-5-FC7H3O2 is 2-Chloro-5fluorobenzoate.
Attractive C2-H2Cg2i (C7, C8, C9, C10, C11 and C12) (i: x,-y,1/2+z) (2.92 )
interactions between the phenyl rings of the dicl ligand and C-H group of 3-pic ligands are
shown in Fig. 3.
Intramolecular hydrogen bond between hydrogen atom of dicl ligand and the
carboxylate oxygen of the same ligand is given in Table 3.

3.1.2. [Cu(dicl)2(4-pic)2] 3
A molecular view of [Cu(dicl)2(4-pic)2] with the atom numbering scheme is shown in
Fig. 4. The selected bond lengths and angles are given in Table 2. Single-crystal X-ray
diffraction study reveals that complex 3 crystallizes in the orthorhombic Pna21 space group.
The asymmetric unit consists of one Cu(II) ion, two neutral 4-pic ligands and two anionic dicl
ligands. Cu(II) center exhibits a distorted octahedral coordination environment, completed by
two nitrogen atoms of two 4-pic (CuN 2.032(2) 2.043(2) ) and four carboxyl oxygen
atoms from two dicl (CuO 2.1934(2) 1.941(2); 2.715(2) - 2.741(2) ) ligands. The longer
Cu-O2 and Cu-O4 bonds in 3 also indicate Jahn-Teller distortion by elongation.
Cu-N4-pic bond distances are 2.032(2) - 2.043(2) , which are slightly longer than
these in [Cu(bba)2(4-pic)2] (1.997(15) ) [44], [Cu(dipic)(4-picoline)]n (1.920(15) and
1.890(11) ) [45], [Cu(pmpa)(4-methylpyridine)(H2O)](H2O)(ClO4) (1.986(4) ) [46], and
(PEPA)(4-methylpyridine)(H2O)](ClO4) (2.001(4) ) [47] and [CuBr(C9H16N2Si)]4 (2.013 )
[48]. But Cu-N4-pic bond distance is shorter than that in [Cu2(3-ClC2H4COO)4(4-pic)]
(2.170(2) ) [49] where bba, (H2dipic), pmpa, PEPA, (3-ClC2H4COO), (C9H16N2Si) are 2benzoylbenzoic acid, Pyridine-2,6-dicarboxylic acid, N-(2-picolyl)picolinamide, N-(2pyridylethyl)picolinamide, 3-chloropropionato, trimethylsilyl-(4-methylpyridine-2-yl)amine,
respectively.
Cu-Odicl bond distances are 1.941(2) - 2.1934(2) , which are close to their
counterpart in [Cu(dicl)2(py)2] (1.9446(15) ) [50].
The intra-molecular hydrogen bond between N-H group of dicl ligand and carboxylate
oxygen (N3H3AO1, N4H4AO3) of dicl ligand, together with non-conventional
hydrogen bond between the hydrogen of a dicl and chlorine of another dicl ligand and (C16
H16Cl4), (Table 3, Fig. 5) stabilize the crystal packing.

3.2. IR Spectra
(NH) band is observed at 3250 cm-1 in Nadicl. In complexes, the band shifts to 3264,
3252, 3232 and 3212 cm-1, respectively. The sharp (NH) vibration of 2-ampy ligand in
[Cu(dicl)2(2-ampy)2] is found to be a doublet at 3370-3335 cm-1 range. The weak bands
around 3080-3011 cm-1 are assigned to aromatic (CH) of phenyl rings. The relatively weak
bands between 2975 and 2880 cm-1 are assigned to aliphatic (CH) vibrations of Nadicl and
other ligands. asym(COO-) at 1572 cm-1 in free Nadicl, has shifted in complexes to 1577,
1573, 1573 and 1585 cm-1, respectively. While sym(COO-) at 1399 cm-1 has shifted in
complexes to 1387, 1395, 1450 and 1391 cm-1, respectively. The difference (asym(COO) sym(COO)), a useful characteristic tool for determining the coordination mode of carboxylato
group is calculated as 190, 178, 123 and 194 cm-1, respectively and is coherent with bidentate
coordinated ( < 200 cm-1) carboxylate ligands [51]. The bands appear around 1608-1588 cm-1
arises from phenyl ring stretching vibrations of the Nadicl and other ligands. Medium
intensity bands within 1315-1305 cm-1 may be assigned to (CN-C) asymmetric stretching
while the weak bands at around 1235 cm-1 assigned to (CN-C) symmetric stretching of
Nadicl ligand. The band occurs in 934 cm-1 is attributed to in plane deformation vibration of
the CH groups. The bands at around 768 cm1 correspond to (C-Cl) vibration of Nadicl. The
band under 600 cm-1 in complexes, may be attributed to metal-oxygen and metal-nitrogen
stretching vibrations (Fig. 6, Table 4).

3.3. Thermal Analysis

It is pointed that thermal analysis plots of powder complexes 1 and 4 are quite similar
with that of crystalline complexes 2 and 3. The thermal analysis measurements give
satisfactory results for the suggested stoichiometries of 1 and 4.
Complexes 1, 3 and 4 are thermally stable up to 166, 183, and 183 C, respectively
and decompose in two steps. In the first step, between 123-209 C, two coordinated 2-picoline
molecules (observed weight loss 22.90%, calculated 22.14%) are released at 165 C
(endothermic peak on the DTA curve) for 1; between 136-216 C, two coordinated 4-picoline
molecules (observed weight loss 21%, calculated 22.14%) are released at 183 C
(endothermic peak on the DTA curve) for 3; and between 133-254 C, two coordinated 2aminopyridine molecules (observed weight loss 23.4%, calculated 22.32%) are released at
183 C (endothermic peak on the DTA curve) for 4. The second step is continues with the loss
of two coordinated diclofenac anions over the ranges 209-675 C, (observed weight loss

70.2%, calculated 70.0%; exothermic peaks at 455, 499 and 605 C on the DTA curve) 216678 C (observed weight loss 71.2%, calculated 70.0%; exothermic peaks at 218, 470 and 612
C on the DTA curve) and 254-678 C (observed weight loss 70.02%, calculated 70.08%)
(exothermic peaks at 477, 524 and 588 C on the DTA curve) for 1, 3 and 4 respectively. The
total mass loss of whole decomposition process is 93.1 %, (calcd. 92.14 %), 92.2 %, (calcd.
92.14 %) and 93.42 % (calcd. 92.40 %) for 1, 3 and 4 respectively. The final decomposition
product estimated is CuO.
The thermal behaviour of 2 was followed up to 900 oC in a static air atmosphere.
Complex decomposes in two steps. The first step between 133-545 oC corresponds to the
removal of two coordinated 3-picolin and one coordinated diclofenac ligands with the
endothermic and exothermic DTA signals at 183, 478, 500 and 511 oC. The observed mass
loss of 58.30 % agrees with the calculated mass loss of 57.14 %. The degradation of one
coordinated diclofenac ligand takes place in the second stage (545-650 oC, DTA 620 oC) with
a mass loss of 34.0 % (calcd. 35.0 %). The total observed mass loss of 92.30 % agrees well
with the calculated one of 92.14 % and the final decomposition product estimated is CuO.

3.4. Catechol oxidase studies

The catalytic oxidation of 3,5-DTBCH2 was studied to investigate the catechol oxidase
activity of the four mononuclear complexes and it was found that all complexes showed
catechol oxidase activity in methanol media at room temperature. For the whole catalytic
process, 1x10-4 M solutions of the complexes were treated with different ratios of substrate
under aerobic conditions.
In these studies, measured absorbance values were time dependent (Fig. 7). 5x10-3 M
substrate and 1x10-4 M complexes 1-4 were stirred equal volumes (1ml) and absorbance
values were recorded for 30 min., every 1 min.
The kinetics of the 3,5-DTBCH2 oxidation was determined by the initial rate method
by monitoring the increase of the product 3,5-DTBQ (395 nm for all cases). The rate
determining step was found to change with the substrate to complex ratio. While the
complexes concentrations were kept constant, substrate concentration was changed. Constant
concentrations of complexes and different concentration of substrate were prepared (complex:
1x10-4 M, substrate: 30-20-15-10-5x10-4 M). A linear relationship observed between the
initial rate and complex concentration showed a first order dependence on the catalyst
concentration for the system (Fig. 8). All complexes exhibited saturation kinetics. With the

help of LineweaverBurk curves shown in Fig. 9, Km, Vmax and kcat values for all complexes
were calculated and given in Table 5.
It was found that all complexes show catechol oxidase activity but 4 does less than
three picoline derivatives complexes. This result is expected to be dependent on a number of
factors that need to be considered, such as electrochemical properties, the geometry imposed
by the ligands on the metal ion, the nature of any exogenous donors, the basicity of the donor
atom, and the steric features of the ligands [23,52].
The turnover number is for catechol oxidase enzyme 2.29x103 s-1. All mononuclear
copper(II) complexes displayed much less turnover number. But these results are quite
comparable to reported in literature [53-57].

4. Conclusion

The chemical classes of non-steroidal anti-inflammatory drugs of diclofenac

complexes with copper(II) and pyridine derivatives have been synthesized and characterized
by elemental analyses, FT-IR, thermal analyses and X-ray diffraction. Elemental and thermal
analysis data show that powder complexes 1 and 4 are quite similar in structure to crystalline
complexes 2 and 3. X-ray crystal structure analysis demonstrated that 2 and 3 have a distorted
octahedral geometry. Thermal analysis data shows that all complexes decompose above 166
o

C within two stages. Catechol oxidase activity of these complexes have been investigated by

using 3,5-DTBCH as substrate in methanol. Our study indicates that 1, 2 and 3 showed good
catechol oxidase activity but 4 showed less than three picoline derivatives complexes.

5. Supplementary Material
Supplementary data CCDC-919580 and CCDC-919579 contains the supplementary
crystallographic data for complex 2 and 3, respectively. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223336-033; or e-mail: deposit@ccdc.cam.ac.uk.

Acknowledgement
This work was supported by the Erzincan University by project No. 110205.

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Figure Captions
Fig. 1. Oxidation of the 3,5-di tert-butyl catechol by the catalyst.
Fig. 2. ORTEP III diagram and atom numbering scheme of 2. Displacement ellipsoids are
drawn at the 20% probability level.
Fig. 3. A crystal packing diagram of 2.
Fig. 4. ORTEP III diagram and atom numbering scheme of 3. Displacement ellipsoids are
drawn at the 20% probability level.
Fig. 5. A crystal packing diagram of 3.
Fig. 6. FT-IR spectrum of complexes (a) 1 (b) 2 (c) 3 (d) 4
Fig. 7. Plot of absorbance time for the oxidation of 3,5-DTBCH2 performed at 25 oC in
CH3OH and catalyzed by complexes 1-4.
Fig. 8. Dependence of the initial reaction rates on the concentration of complexes [(a) 1 (b) 2
(c) 3 (d) 4] at constant concentration of 3,5-DTBCH2, 5x10-3 M.
Fig. 9. Lineweaver-Burk plot for the catalysis by (a) 1 (b) 2 (c) 3 (d) 4

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Table 1. Crystal data and structure refinement parameters for (2) and (3) complexes
(2)

(3)

Empirical formula

C40H34N4O4CI4Cu

C40H34N4O4CI4Cu

Formula weight

840.05

840.05

Temperature (K)

293

293

Wavelength ()

0.71073

0.71073

Crytal system

monoclinic

orthorhombic

Space group

C2/c

P n a 21

a ()

22.7734(12)

22.4110(5)

b ()

10.8490(7)

7.7627(2)

c ()

17.1457(10)

21.8007(4)

(o)

90

90

(o)

114.087(4)

90

(o)

90

90

V ()3

3867.3(4)

3792.66(15)

A. coefficient (mm-1)

0.888

0.905

Dcalc (mg m-3)

1.4428(1)

1.471

Crystal size (mm)

0.34; 0.48; 0.72

0.07;0.34;0.78

Unit cell dimensions

Theta range for data collection (o) 1.85; 27.27

1.30;27.28

Measured reflections

10854

55884

Indepen. reflections

2863

8054

Absorpt. correction

Integrationa

Integrationa

Refinement method

Full-matrix least-squares
on F2

Full-matrix least-squares
on F2

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Final R indices

0.0609

0.0461

Goodness-of-fit on F2

1.011

0.970

Largest difference peah and hole

(e/3)

-0.283; 0.533

-0.280; 0.581

[F2 > 2(F2)]

Stoe and Cie (2002)

Table 2. Selected bond distances () and angles (o) for 2 and 3

(2)
Cu1-N1

1.996(2)

Cu1-O2A

2.020(7)

Cu1-O1A

2.609(6)

Cu1-O2B

2.429(6)

Cu1-O1B

1.966(5)

O1B-Cu1-O2B

58.7(2)

O2B-Cu1-O1Bi

164.5(2)

136.3(3)

O2B-Cu1-N1

94.13(13)

O1B-Cu1-O1B

O1B-Cu1-N1

88.60(15)
i

87.09(13)

O2B-Cu1-N1

90.64(15)

O2B-Cu1-O2B

O1B-Cu1-O2Bi

164.5(2)

O1A-Cu1-N1

84.35(14)

O1A-Cu1-N1i

94.49(15)

O1A-Cu1-O2A

55.3(3)

O2A-Cu1-N1i

93.6(2)

O2A-Cu1-O2Ai

138.6(3)

N1-Cu1-N1i

177.96(9)

O1B-Cu1-N1

106.7(2)

(3)
Cu1-N1

2.043(2)

Cu1-O3

1.9339(19)

Cu1-N2

2.032(2)

Cu1-O2

2.714(2)

Cu1-O1

1.9409(18)

Cu1-O4

2.745(2)

O1-Cu1-N1

89.48(9)

O3-Cu1-N2

90.86(9)

O1-Cu1-N2

89.64(9)

O3-Cu1-O1

179.24(10)

O3-Cu1-N1

90.03(9)

N2-Cu1-N1

178.45(10)

O2-Cu1-O1

53.68(7)

O2-Cu1-O4

179.27(8)

O4-Cu1-O1

126.72(7)

O2-Cu1-N1

81.62(9)

O2-Cu1-O3

126.81(7)

O2-Cu1-N1

96.84(9)

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O4-Cu1-N1

98.95(9)

O4-Cu1-N2

82.58(9)

Symmetry code: (i) -x,y,1/2-z

Table 3. Hydrogen-bonding geometries for 2 and 3 (,o)

DH A

DH

H A

D A

DH A

N2-H2AO2B

0.86

1.97

2.6673

138

C4-H4O2B

0.93

2.58

3.1876

123

0.86

2.26

2.853(3)

126

0.86

2.18

2.822(3)

132

0.93

2.81

3.726(4)

169

(2)

(3)
N3-H3AO1
N4-H4AO3
i

C16-H16Cl4

Symmetry code: (i) 1-x,1-y,-1/2+z

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Table 4. Selected IR spectral dataa for the dicl ligand, (1), (2), (3) and (4)
dicl

(1)

(2)

(3)

(4)

(NH)

32250m

3264

3252

3232

3212

(NH)

3370-3335s

aro(CH)

3060w

3066-3039w

3058-3035w

3082w

3066w

alf(CH)

2980w

2963-2888w

2974-2924w

2920w

2956w

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asym(COO-)

1572s

1577s

1573s

1573s

1585s

sym(COO-)

1399w

1387w

1395w

1450w

1391w

asym(CNC)

1306s

1310s

1312s

1315s

1316s

sym(CNC)

1236vw

1236w

1237w

1241w

1235w

(CCl)

768mw

765mw

780m

767w

768w

w, weak; m, medium; s, strong; vs, verystrong

a

Frequencies in cm

-1

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Table 5. Km, Vmax and kcat values for complexes
Vmax (Ms-1)

Km (M)

kcat (s-1)

[Cu(dicl)2(2-pic)2]

3.91x10-6

6.91x10-5

3.89x10-2

[Cu(dicl)2(3-pic)2]

3.17x10-6

1.078x10-4

3.17x10-2

[Cu(dicl)2(4-pic)2]

2.82x10-6

9.84x10-5

2.81x10-2

2.65x10-6

3.44x10-4

2.64x10-2

[Cu(dicl)2(2-ampy)2]

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Four copper(II) diclofenac complexes with pyridine derivatives: Synthesis, crystal

structures, spectroscopic properties, thermal analysis and catechol oxidase activities
Sema Caglara*, Ismihan E. Aydemira, Ekrem Adgzela, Bulent Caglara, Serkan Demirb
Orhan Buyukgungorb

Four diclofenac complexes with copper(II) and pyridine derivatives have been
synthesized.
Four complexes have been characterized by elemental analysis, FT-IR, thermal
analysis and X-ray diffraction.
This study demonstrates that, four complexes show good catechol oxidase activity.

30

Four copper(II) diclofenac complexes with pyridine derivatives: Synthesis, crystal

structures, spectroscopic properties, thermal analysis and catechol oxidase activities
Sema Caglara*, Ismihan E. Aydemira, Ekrem Adgzela, Bulent Caglara, Serkan Demirb
Orhan Buyukgungorb

Four diclofenac complexes with copper(II) and pyridine derivatives have been
synthesized and characterized by elemental analysis, FT-IR, thermal analysis and Xray diffraction.
Four complexes show good catechol oxidase activity.

31