Synthesis, Characterization and Magnetic Studies of Cobalt (II),

Manganese (II) and Copper (II) Complexes containing

Nitrogen-Oxygen Donor Ligands

ASMAT ZAHRA1, TARIQ MAHMUD1, HAZOOR AHMAD SHAD2*, MUHAMMAD NAWAZ TAHIR3, HAJIRA REHMAN4,
TANZEELA GULAB SHAHZADY4, ZUFIQAR ALI4
1
Institute of Chemistry, University of Punjab Lahore, Pakistan
2
Department of Chemistry, Government Post Graduate College Jhang, Pakistan
3
Department of Physics, University of Sargodha, Sargodha Pakistan
4
Department of Chemistry, Lahore Garrison University Lahore, Pakistan

Transition metal complexes, [M(COOPh) 2(TMEDA)µ(OH 2 )], (where M=Co +2 and Mn +2 ) and
[Cu 3(COOPh) 2(TEA) 2(CH 3COO) 2] have been synthesized by using sodium benzoate, tetramethyl-
ethylenediamine and triethanolamine. The bonding nature and structure of complexes (1), (2) and (3) were
explored through X-ray crystallography, IR, elemental analysis and magnetic studies. Single crystal X-ray
analysis showed that in (1) and (2) complexes, each M (II) is bridged by two benzoate ions, one TMEDA and
one water molecule while in (3) complex, Cu1 is coordinated by four oxygen atoms, two from TEA and two
from carboxylate group while Cu2 is coordinated by three oxygen atoms and one nitrogen atom. All three
complexes displayed triclinic system with space group P-1. Vibrating sample magnetometer measurement
justified that these complexes are soft magnetic materials and can retain a certain value of magnetization
even when magnetic field is removed.

Keywords: Tetramethylethylenediamine; Triethanolamine; Binuclear complex; Soft magnetic material;

Metallo-enzymes.

Transition metal carboxylate clusters have attracted complexes have significance for the synthesis of copper
much attention because these clusters are a part of active containing superconducting ceramics [27]. Copper is an
sites of metallo-enzymes [1] and also show novel magnetic important trace metal for plants and animals [28,29] and
properties [2]. Tetranuclear Mn is the commonly known its mixed ligand complex are involved in a number of
oligo nuclear cluster present in active site of photo system biological processes [30–32]. Cu(II) complexes are used
II. It carries oxidation of water to molecular di-oxygen [3– in treatment of many diseases including cancer [33,34].
7]. In biology metallo-proteins having Mn+2 and Co+2 sites Numerous complexes having dinuclear µ-Oxo or µ-hydroxo
play an important role [8]. In addition to B12, cobalt proteins bridged by µ-O-O carboxylate ligands have already been
are also known. These proteins comprise methionine reported. Binuclear, trinuclear and tetranuclear complexes
amino peptidase 2. This enzyme occurs in human and other having O-and N- containing donar atoms have been
mammals not having B12 corrin ring. Nitriles hydratase is synthesized [35–47]. Keeping in view importance of these
another non corrin cobalt enzyme that metabolizes nitrile metal complexes, here we are reporting Co+2, Mn+2 and
in bacteria [9]. Other enzymes are methionyl amino Cu+2 complexes having µ bridging by O- and N- atoms.
peptidase, methylmalonyl-CoA mutase, isobutyryl-CoA Molecular structures of compounds (1), (2) and (3) have
mutase [10]. Active sites of all these metallo-enzymes may been determined by X-ray crystallographic method.
have mononuclear or dinuclear metal complexes [11, 12]. Tetramethylethylenediamine and triethanolamine are
In all these compounds ligation of metal ion is provided by bidentate ligands and form five membered chelate rings,
O and N donor atoms from various amino groups of metallo while benzoic acid is bidentate ligand and forms binuclear
proteins. Enzymes having Mn as co-factor are also known Co (II), Mn (II) and trinuclear complexes. These ligands
including: transferases, hydrolases, oxidoreductases, show variable coordination modes with various metal ions
isomerases, lyases, ligases, lectins, and integrins. because of presence of – COOH and –NH2 groups.
Pseudocatalases from Lactobacillus plantarum [13] and
Thermus thermophiles and certain ribonucleotides Experimental part
reductases (RNR), also have binuclear Mn sites these Physical Measurements
enzymes catalyze the disproportionate of H 2O 2 and All starting chemicals were of analytical grades used
reduction of ribonucleotides respectively. Arginase is without further purification. Metal ions were used as their
polypeptides having manganese metals [14]. acetate salts. C, H, N elemental analyses were carried out
Most commonly used metals Fe (II) Co (II) Ni (II), Zn by Perkin Elmer USA model analyzer. Infrared spectra were
(II) Mn(II) form low molecular weight complexes that have recorded (400–4000 cm -1 ) on SHIMADZU FT-IR
importance for molecular based magnets [15]. These spectrophotometer. Magnetic measurements were done
complexes possessed high catalyst activity; therefore, by using Vibrating Sample Magnetometer (Lakeshore’s
these are extremely important for biological chemists [16– 7407) at 298 K by applying field strength of 0–10000. Crystal
21]. Many dicarboxlylic and diamines based Cu (II) study of both complexes was done by single crystal X-ray
complexes have already been reported [22–26]. Such

* email: [email protected]
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diffraction technique by using APEX2 BRUKER (1) and (2) are hexa-coordinated with four O-atoms and
diffractometer using SAINT program to solve structures. two N-atoms. In these complex, four oxygen atoms comes
from two bridging benzoate ligands and two monodentate
Synthesis of Complexes (1), (2) and (3) benzoate ligands, while two N-atoms come from a
Methanol (10 mL) solution of tetramethylethylene- chelated tetra-methylethelenediamine. The coordination
diamine 0.116 g (1.0 mmol) was mixed with aqueous (10 around each metal is completed by a water molecule
mL) solutions of tetra hydrated cobalt acetate 0.249 g (1.0 making a µ-bridging. In complex (3), two copper atoms
mmol). The mixture was stirred for 15 min. Meanwhile, are coordinated with four ligands. Cu1 is coordinated by
methanol (10 mL) solution of sodium benzoate 0.144 (1.0 four oxygen atoms while Cu2 is coordinated by three oxygen
mmol) was added drop wise and the mixture was further atom and one nitrogen atoms.
stirred for 1h at room temperature. The reaction was
monitored through TLC. After the completion of reaction, X-ray Crystal Structure
mixture was filtered. The filtrate was left for slow The molecular structure of [M (COOPh) 2
evaporation at room temperature. After a week, pink prisms (TMEDA)µ(OH 2)] (where M = Co +2 and Mn +2 ) and
of suitable size for crystallography were obtained. Crystals [Cu3(COOPh)2(TEA)2(CH3COO)2] with atom numbering
were collected and washed with methanol, dried in air scheme is shown in figures 1–3. The crystallographic data,
and used for characterization. Crystals were found stable selected bond lengths, bond angles and torsion angles are
under air, light and exposure to x-rays. Same method was given in tables 1–5, respectively. Crystal structures of
applied to prepare manganese (II) complex (2). On the complexes (1) and (2) are iso-structural. The coordination
other hand, for the synthesis of Cu (II) complex, methanol around each metal ion is similar with minor variations of
(10 mL) solution of triethanolamine 0.186g (1.25 mmol) bond distances and bond angles.
was used instead of TMEDA rest of the procedure was The crystallographic data showed that the Co1–O and
same as for complex (1) and (2). Co2–O bond distances are in the range [2.289(2) A to
2.554(2) A] and 2.289(2) A to 2.554(2) A], respectively.
Results and discussions The Co1–N and Co2–N bond distances are [2.289(2) A,
Chemistry 2.554(2) A] and [2.289(2) A, 2.554(2) A], respectively. Co1–
Complexes (1) and (2) were prepared by the reaction of N bond distance is 2.642(2) A. The Mn1–O and Mn2–O
equimolar quantity of tetramethylethylenediamine, cobalt bond distances are in the range [2.109(2) A to 2.209(2) A]
acetate and sodium benzoate in methanol. While the and [2.102(2) to 2.214(2) A], respectively. The Mn1–N and
complex (3), was synthesized by the reaction of Mn2–N bond distances are [2.334(3) A, 2.363(3) A] and
methanolic solution of copper acetate and triethanolamine [2.321(3) A, 2.371(3) A], respectively. The Co1…Co2 and
with sodium benzoate. The desired complexes were Mn1…Mn2 separations are 3.5870(5) A and 3.6100(7) A
obtained successfully in good yield (78–85%). The products respectively as shown in table 2. The coordination sphere
were obtained as crystalline solids and their purities were of Co (II) and Mn (II)-ions is six, four O-atoms and two N-
checked by thin layer chromatography. The complexes atoms (ORTEP figs. 1 and 3 respectively). The basal planes
were soluble in various solvents such as ethanol, methanol, of distorted octahedrons consist of three O-atoms and an
1, 4-dioxane, DMF and DMSO. The composition of the N-atom (O-atom of bridging water, its opposite N-atom,
complexes was consistent with their microanalytical data O-atom of mono-dentate benzoate and its opposite O-
as reported in tables 6 and 7. The metal ions in complex atom of bridging benzoate). The other N-atom and O-atom

Table 1
CRYSTALLOGRAPHIC
DATA FOR COMPLEXES
(1), (2) AND (3)

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 Table 2
IMPORTANT BOND LENGTHS (AO)
OF COMPLEXES (1) AND (2)

Table 3
IMPORTANT BOND ANGLES (O) OF
COMPLEX (3)

Table 4
SELECTED TORSION
ANGLES (O) OF
COMPLEXES (1)
AND (2)

are at apical positions. In each bi-nuclear complex one of 0.662(5):0.338(5). The role of water molecule is to provide
the tetramethylethylenediamine and mono-dentate bridging between metal ions through O-atom and to
benzoate (attached to same metal ion) are disordered due stabilize the orientation of mono-dentate benzoate groups
to ethyl and benzene ring with occupancy ratio of due to H-bonding.
1724 http://www.revistadechimie.ro REV.CHIM.(Bucharest)♦69♦ No. 7 ♦ 2018
 Table 5
SELECTED TORSION
ANGLES (O) OF
COMPLEX (3)

Fig. 2. ORTEP Diagram of Complex (2)

Fig. 1. ORTEP Diagram of Complex (1)

In both complexes none of the benzoate ligand is planar. group A(C9/O6/Cu2) and benzene ring B(C10-C15) is
For example, the dihedral angle between the carboxylate 17.625 o.
group A (O1/C7/O2) and benzene rings B (C8a–C13a) is
12.5(6) °. The minor part of disordered benzene ring C (C8b– Infrared Spectroscopy
C13b) is oriented at a dihedral angle of 2.6(7) ° with its Several characteristics bands have been observed in IR
major counterpart B. For other benzoates the dihedral angle spectrum of complexes (1), (2) and (3). Sodium benzoate,
between D (O3/C14/O3)/ E (C15–C20), F (O5/C21/O6)/ TMEDA and TEA ligand have a tendency to coordinate with
G(C22–C27) and H(O7/C28/O8)/I(C29–C34) is 20.5(2)°, metal due to donar atoms. Co and Mn Complexes showed
9.9(5)° and 18.9(3) °, respectively. The dihedral angles bands at 3387 and 3352 respectively which are assigned
between B/E , E/G and G/I is 86.8 (2) °, 64.99(11) ° and to –OH group indicates the presence of H2O molecule in
84.8(1)° respectively. both the complexes. Bands observed at 1541, 1544, 1540
Crystallographic data of complex (3) shows that the and at 1394, 1400, 1402 are assigned to C=O and C–O in
bond distances between Cu1–O1, Cu1–O1i and Cu–O3i Co, Mn and Cu complexes respectively that indicates the
are in the range of 1.963(32), 1.963(3) and 1.902(3), presence of carboxylic group in these complexes. In
respectively. Similarly, the bond distances between Cu2- addition to these two new bands appeared due to the
O3, Cu2–O6 and Cu2–O2 are 1.922(2), 1.948(3) and presence of M–N and M–O in these complexes (table 6).
1.965(3) respectively as shown in table 2. Bond distance Appearance of these peaks indicates the coordination of
of Cu1–O3 from triethanolamine is 1.902(3) while Cu2–N1 Co, Mn and Cu with ligands.
from triethanolamine is 2.064(3). The geometry around
the Cu atom is square planar due to three oxygen atoms Elemental Analyses
and one nitrogen atom. It is coordinated with one oxygen The observed and experimental values of CHN analysis
atom from carboxylate ion (Cu2–O6), second from acetate are given in table 7. These elemental analyses showed
ion (Cu2–O2) and third from triethanolamine (Cu2–O3). that % of C, % H and % N are almost same in all three
The angles around the copper atom, O6/Cu2/N1, N1/Cu2/ complexes with small variation up to 5%.
O3, O3/Cu2/O2 and O2/Cu2/O6 are 93.58 (12), 85.96 (11),
92.68 (11) and 87.79 (11) respectively which are deviated Magnetic Measurements
from normal angle (90o) to some extent due to presence Vibrating sample magnetometer (VSM) was used to
of different groups attached at four corners of square planar carry out magnetic measurement. Magnetic behavior of
geometry. In the same way, Cu1 is also coordinated by complexes (1), (2) and (3) are shown in figures 4, 5 and 6
four oxygen atoms i.e. two from acetate groups (Cu1– respectively. The plot between magnetic field (G) and
O1and Cu1–O1i) while other two from triethanolamine magnetic moment (emu) indicates that these complexes
(Cu1–O3 and Cu1–O3i). are ferromagnetic in nature and magnetism is reversible.
Benzoate ligand in copper complex is non-planar from These materials are magnetically anisotropic. Low value
the basal plane. The dihedral angle between corboxylate of coercivity and retentivity indicate that all three
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 Table 6
IMPORTANT IR PEAKS (CM-1) OBSERVED FOR
COMPLEXES (1), (2) AND (3

Table 7
ELEMENTAL ANALYSES FOR COMPLEXES (1),
(2) AND (3)

Table 8
VSM CALCULATION FOR
COMPLEXES (1), (2)
AND (3)

Fig. 3. ORTEP Diagram of Complex (3)

Fig. 4. Hysteresis Loop for Complex (1) Fig. 6. Hysteresis Loop for Complex (3)

complexes are soft magnetic materials. Coercivity of a

magnetic material is related with its microstructure. At
9685.95 G field complex (1) showed a magnetic moment
of 2.232×10 -3 emu, complex (2) showed a magnetic
moment of 2.235emu while complex (3) showed a
magnetic moment of 2.345×10-3 emu. Value of saturation
of magnetization and squareness ratio obtained from VSM
analysis are presented in table 8.
Conclusions
Three complexes of Co (II), Mn (II) and Cu (II) were
synthesized. Magnetic studies of complexes proved that
all three complexes are soft magnetic materials. These
complexes showed certain values of magnetization
saturation that is property of ferromagnetic and
Fig. 5. Hysteresis Loop for Complex (2) antiferromagnetic materials. These materials can show a
1726 http://www.revistadechimie.ro REV.CHIM.(Bucharest)♦69♦ No. 7 ♦ 2018
certain value magnetic moment even in the absence of 23.O’BRIEN, P., STAFFORD, C., YOUNG, L.C., J.Inorg.Chim.Acta 147,
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Manuscript received: 6.06.2017

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