Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand

Article abstract of DOI:10.1016/j.saa.2015.02.006

A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been synthesized with newly synthesized biologically active macrocyclic ligand. The ligand was synthesized by condensation of β-diketone 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)propane-1,3-

Full text of DOI:10.1016/j.saa.2015.02.006

Accepted Manuscript
Synthesis, spectral, thermal and antimicrobial studies of transition metal com-
plexes of 14-membered tetraaza[ N ] macrocyclic ligand
4
Sunil G. Shankarwar, Bhagwat B. Nagolkar, Vinod A. Shelke, Trimbak K.
Chondhekar
PII:
S1386-1425(15)00158-4
http://dx.doi.org/10.1016/j.saa.2015.02.006
SAA 13296
DOI:
Reference:
To appear in:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
Received Date:
Revised Date:
Accepted Date:
27 June 2014
1 February 2015
3 February 2015
Please cite this article as: S.G. Shankarwar, B.B. Nagolkar, V.A. Shelke, T.K. Chondhekar, Synthesis, spectral,
thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[ N ] macrocyclic ligand,
4
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2015), doi: http://dx.doi.org/10.1016/j.saa.
2
015.02.006
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Synthesis, spectral, thermal and antimicrobial studies of transition metal
complexes of 14-membered tetraaza[ N ] macrocyclic ligand.
4
Sunil G. Shankarwar, Bhagwat B. Nagolkar, Vinod A. Shelke,
Trimbak K. Chondhekar*
Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University,
Aurangabad-431004, Maharashtra, India
E-mail: tkcchem@gmail.com
Abstract: A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been
synthesized with newly synthesized biologically active macrocyclic ligand. The ligand
was synthesized by condensation of β-diketone 1-(4-chlorophenyl)-3-(2-
hydroxyphenyl)propane-1,3-dione and o-phenylene diamine. All the complexes were
characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal
1
analysis, X-ray diffraction, IR, H-NMR, UV-Vis spectroscopy and mass spectroscopy.
From the analytical data, stoichiometry of the complexes was found to be 1:2 (metal:
ligand). Thermal behavior (TG/DTA) and kinetic parameters suggest more ordered
activated state in complex formation. All the complexes are of high spin type and six
coordinated. On the basis of IR, electronic spectral studies and magnetic behavior, an
octahedral geometry has been assigned to these complexes. The antibacterial and
antifungal activities of the ligand and its metal complexes, has been screened in vitro
against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma
respectively.

Keywords: macrocyclic ligand, transition metal complexes, thermal analysis, powder X-
ray diffraction. biological activity.
Introduction
Macrocyclic ligands and their metal complexes have a wide range of biological
activities [1]. Transition metal complexes containing macrocycles are of considerable
interest in terms of structural and coordination chemistry. The study of metal complexes
of macrocyclic ligands appears to be interesting in view of the possibility of obtaining
coordination compounds of unusual structure and stability. Transition metal macrocyclic
complexes have received special attention because of their active part in metalloenzymes
and as biomemitic model compounds due to their resemblance to natural proteins and
enzymes. Synthetic tetraaza macrocycle (N ) molecules are considered typically good
4
models for oxygen carriers due to the presence of four nitrogen donor sites confined to a
single four-fold or a slightly fourfold plane in a ring structure, appropriate for metal
ligand binding. A survey of the tetraaza macrocyclic ligand systems reported so far by
earlier workers indicates that the ring size of 12–16 is most common for molecular model
studies [2,3]. Aza-type ligands appear very promising for potential use as antifertile,
antifungal and antibacterial agents as well as due to their other biological properties [4-7].
The formation of macrocyclic complexes depends on the size of the macrocycles, nature
of its donor atoms and on the complexing behavior of the anions involved in coordination
[
8-10]. There is a continues interest in synthesizing macrocyclic complexes because of
their potential applications in fundamental and applied sciences and importance in the
area of coordination chemistry [11-14]. In view of the above applications, in the present
paper we report the synthesis, characterization and antimicrobial studies of Mn(II),

Co(II), Ni(II), and cu(II) complexes with orthophenyl diamine containing nitrogen donor
N ] macrocyclic ligand having 14-membered backbone.
[
4
Experimental
All chemicals used were of the analytical grade (AR) and of highest purity. 4-
chlorobenzoic acid, ortho-hydroxy acetophenone and o-phenylenediamine were used for
synthesis of ligand. AR grade metal chlorides were used for complex preparation.
Spectroscopic grade solvents were used for spectral measurements. The carbon, hydrogen
and nitrogen contents were determined on Perkin Elmer (2400) CHNS analyzer. IR
-1
spectra in the range of 4000-400 cm were recorded on Jasco FT-IR-4100 spectrometer
1
using KBr pellets. H-NMR spectra of the ligand was recorded in DMSO using TMS as
an internal standard. The TG/DTA analysis was recorded on Perkin Elmer TA/SDT-2960
0
and XRD were recorded on Perkin Elmer employing CuKα radiation λ= 1.541A in the
0
rang 10-80 . The UV-Vis spectra of the complexes were recorded on ShimadzuUV-1800
Spectrophotometer. Magnetic susceptibility measurements of the metal complexes were
done on a Gouy balance at room temperature using Hg.[Co(SCN) ] as calibrant. Molar
4
conductance of complexes was measured on Elico CM-180 conductometer using 1 mM
solution in dimethyl sulphoxide.
synthesis of β-Diketone Step I
Equimolar amount of 4-chloro benzoic acid and ortho-hydroxy acetophenone
were dissolved in 50 mL dry pyridine. The reaction mixture was then cooled to 0°C. To
this, phosphorus oxychloride (0.06 mol) was added drop wise maintaining temperature
below 10°C. The reaction mixture was kept overnight at room temperature. It was then
poured on crushed ice with vigorous stirring. The crimson colored solid (ester) was

obtained which was filtered and washed several times with ice-cold water. Ester was then
crystallized with distilled ethanol. Purity of the compound was checked by TLC. Ester was
subjected to well known Baker-Venkatraman transformation. Ester (0.03 mol) was
dissolved in 15 mL dry pyridine. To this mixture, powdered KOH (1gm) was added and
the reaction mixture was stirred on magnetic stirrer at room temperature for 5 hours. Then
it was poured over crushed ice and acidified with concentrated hydrochloric acid. Finally
yellow colored product was obtained which was recrystallized from ethanol (Yield 55-
5
8%). Purity of all synthesized β-diketones were checked by TLC using silica gel G and
melting points.
Scheme1. synthesis of β-Diketone
Step II synthesis of macrocyclic ligand
A hot ethanolic solution, 25 ml of orthophenylene diamine 0.02M and an
ethanolic solution 25 ml of β-Diketone 0.02M were mixed slowly under constant stirring.
The resulting solution was refluxed for six hours in presence of 2-3 drops of concentrated
HCl. On cooling, light yellowish crystals separated out were filtered, washed with ethanol
and dried under vacuum.

Scheme 2. synthesis of macrocyclic ligand.
synthesis of metal complexes
A hot ethanolic solution, 25 ml of ligand (0.002M) and a hot ethanolic solution ,
5 ml of required metal salt (0.001M) were mixed together under constant stirring. The
2
mixture was refluxed for 8-9 hours. On cooling, a coloured solid precipitate formed was
filtered, washed with cold ethanol, chloroform and dried under vacuum (fig 1).
Where M = Mn (II), Co (II), Ni (II), Cu (II)

Fig.1 Structure of Metal Complexes.
Results and Discussion
All the complexes were colored solids, air stable and soluble in polar solvents like
DMF and DMSO. The elemental analysis show 1:2 (metal: ligand) stoichiometry for all
the complexes. Micro analytical data and molar conductance values are given in (Table
1
). The metal contents in complexes were estimated by gravimetric analysis [15]. All the
complexes show low conductance which indicates their non-electrolytic nature. The
magnetic measurement studies show that the Mn(II), Co(II), and Cu(II), complexes
exhibit paramagnetic whereas the Ni(II) shows diamagnetic behavior (Table 1).
1
H-NMR spectra of ligand
1
The H NMR spectra of the ligand was recorded in DMSO. It shows following
signals at 2.55, (s,4H -CH ), 8.55  (s,2H,-OH),6.9-8.5 corresponding to phenyl ring
2
protons (m,24H).
Mass Spectra of the ligand
Mass spectral data confirmed the structure of ligand HL as indicated by the peaks
corresponding to their molecular mass.
FTIR spectra
-1
The IR spectra of ligands (Table 2) do not show any band at 1700 cm (υ C=O)
-1
-1
3
380 cm (υas NH ) and 3250 cm (υs NH ) corresponding to carbonyl groups and free
2 2
amine[16]. There are two main features in the infrared spectrum of the macrocyclic
ligand. The first feature is the disappearance of the two characteristic between the

primary amine group –NH of the diamine and >C=O of the diketone. It also confirmed
2
the elimination of a water molecule and complete condensation[17]. A band
-1
corresponding to the (υ C=N) (azomethine linkage) appers at 1641-1658 cm in the
spectra. The structure suggested to the ligand is shown in (scheme 2). The position of this
band is shifted to lower frequency in the complexes as compared to free macrocyclic
ligand suggesting that the coordination takes place through the nitrogen of (υ C=N) group
[
18].
Electronic absorption spectra and magnetic measurements
Electronic spectra of Mn(II) complex in DMSO solution, display four weak
-1
intensity absorption bands (Table 3) in the range of 18,100–18,587 cm , 23,200–24,570
-1
-1
-1
cm , 27,000–29,412 cm and 30,950–33,003 cm . These bands may be assigned to the
6
4
4
6
4
4
4
6
4
4
6
4
4
transitions, A → T ( G), A → E , A ( G), A → E ( D) and A → T ( P),
1
g
1g
1g
g
1g
1g
g
1g
1g
respectively. The magnetic moment recorded at room temperature was 5.86 B.M.
corresponding to five unpaired electrons [19,01].
-1
-
The Co(II) complex shows three bands at 12,360-12,509 cm , 16,051-17,123 cm
1
-1
4
4
4
4
and 22,026-22,229 cm corresponding to the transitions T (F) → T (F), T → A
1
g
2g
1g
2g
4
and T (F) → T (P) respectively. These electronic tranisitions and observed magnetic
1
g
2g
moment of 4.8 B.M. indicated high spin octahedral geometry [20].
The electronic spectra of Ni(II) complex exhibited three bands in the 13,333–
-1
3
3
1
4,390, 18,587–18,621, and 26,385–27,700 cm regions corresponding to A (F) → T
2g 2g
3
3
3
3
(
F), A (F)→ T (F), and A (F)→ T (P) transitions respectively. The observed
2g g 2g 1g
magnetic moment of Ni(II) complex at room temperature was 2.95 BM. These values are

in tune with a high spin configuration and show the presence of an octahedral
environment around Ni(II) [21].
The electronic spectra of Cu(II) complex exhibits three bands in the 10,020-
-1
-1
-1
1
0,143 cm , 14,684-14,788 cm , and 22,075-23,154 cm regions. These bands may be
4
4
4
4
4
assigned to the transitions T (F) → T (F), T (F) → A (F) and T (F) → T (P)
1
g
2g
1g
2g
1g
1g
respectively. The positions of bands indicated that the Cu(II) complex have an overall
octahedral geometry. Electronic spectral data coupled with observed maganetic moment
of 1.94 B. M. further supports the octahedral geometry [22]. On the basis of analytical
and spectral data, octahedral structures have been proposed for all the complexes (Table
3
).
Thermal analysis.
The simultaneous TG/DT analysis of some representative metal complexes was
done from ambient temperature to 1000 ºC in nitrogen atmosphere using α-Al O as
2
3
reference. In the thermogram curve of Mn(II) complex, the first step shows a steep slope
between 140–230 °C with a mass loss of 5.65 %(calculated 5.89%), indicating the
removal of two molecules of coordinated water[18, 19]. An endothermic peak in the
range 140–200 °C (ΔTmax = 195°C) on DTA curve corresponds to dehydration step. The
anhydrous complex then shows slow decomposition from 200-300°C in first step with
1
5.00% (calcd. 14.10%) mass loss and a broad exotherm (ΔTmax = 252°C) in DTA
which may be attributed to removal of noncoordinated part of the ligand. The second step
decomposition is from 400 to 600°C with 11.70% (calcd 12.09%) mass loss
corresponding to decomposition of coordinated part of ligand. A broad endotherm in
DTA is observed for this step. The mass of final residue 28.04% corresponds to stable

MnO. The thermogram of Co(II) complex shows in first step a steep slope between
40–230 °C with a mass loss of 6.35 %(calculated 6.89%) indicating the removal of two
molecules of coordinated water. An endothermic peak in the range 140–230 °C (ΔTmax
225°C) on the DTA curve corresponds to dehydration step. The anhydrous complex
1
=
then show slow decomposition from 200-300°C, with 10.00% (calcd. 11.92%) mass loss
and a broad exotherm (ΔTmax = 245°C) in DTA may be attributed to removal of
noncoordinated part of the ligand. The second step decomposition from 400 to 600°C
with 18.00% (calcd 17.09%) mass loss corresponds to decomposition of coordinated part
of ligand. A broad endotherm in DTA is observed for this. The mass of final residue
3
4.01 % corresponds to stable CoO.
Powder X-ray diffraction analysis
The X-ray powder diffractogram of the metal complexes (fig 2) were used for the
structural characterisation and determination of lattice dimensions. The observed data of
complexes under investigation was compared with other literature data having analogous
cell and subsequently indexed to similar geometry. The X-ray diffractogram of metal
complexes was scanned in the range 20–80 at wavelength 1.540A˚. The diffractogram
and associated data depict 2θ values for each peak, relative intensity and interplanar
spacing (d-values). The X-ray diffraction pattern of these complexes with respect to
major peaks having relative intensity greater than 10% have been indexed by using
computer programme[10]. The diffractogram of Mn(II) complex shows 27 reflections
with maxima at 2θ =70.660 corresponding to d value 1.33A. The observed values of
o
lattice constants, a= 8.67A˚, b = 8.56A˚, c = 9.99A˚ and α =β =γ = 90 . Mn(II) complex
o
satisfies the condition a≠ b≠c and α =β =γ = 90 required for the compound to be

orthorhombic lattice type. The diffractogram of Co(II) complex shows 21 reflections with
maxima at 2θ =18.124 corresponding to d value 4.89A˚. The values of lattice constants,
o
a= 9.55A˚, b = 9.55A˚, c = 10.23A˚ and α =β =γ = 90 . These values satisfy the condition
o
a=b≠ c and α =β =γ = 90 required for the compound to be tetragonal lattice type. The
diffractogram of Ni(II) complex shows 19 reflections with maxima at 2θ =43.726
corresponding to d value 2.06A˚ and observed values of lattice constants, a= 5.46A˚, b =
o
o
5
.46A˚, c = 6.33A˚ and α =β =γ = 90 satisfy the condition a= b≠c and α =β =γ = 90
required for the compound to be tetragonal lattice type. The diffractogram of Cu(II)
complex shows 26 reflections with maxima at 2θ =23.075 corresponding to d value
3
.85A˚ and observed values of lattice constants, a= 6.46A˚, b = 7.21A˚, c = 6.32A˚ and α
o
o
=
β =γ = 90 satisfy the condition a≠ b≠c and α =β =γ = 90 required for the compound to
be orthorhombic lattice type.

Fig. 2. X-ray diffractograms of Mn (II), Co (II), Ni (II), and Cu (II) complexes.
Kinetic calculations
The kinetic and thermodynamic parameters viz order of reaction (n), energy of
activation (E ), pre-exponential factor (z), entropy of activation (ΔS) and free energy
a
change (ΔG) together with correlation coefficient (r) for non-isothermal decomposition of
metal complexes have been determined by Horowitz-Metzer (HM) approximation
method and Coats-Redfern integral method [29,24].

Horowitz-Metzer (HM) approximation method
1n
2



1(1)



Ea
2.303RTs
ZRTs
E
log

 log

2
2
(1 n)
E
2.303RTs
o
Where α = Fraction decomposed.
 = heating rate (10 C/min.)
R = Molar gas constant.
k = Boltzman constant.
h = Plank’s constant.
n = order of reaction.
Ts = Temperature at half wt. loss.
Z = Frequency factor.
The equation used for calculating entropy change (ΔS) is given below.
Z h
S  2.303Rlog
k Ts
0
Where, k - Boltzman constant, h- Planck’s constant, β – Rate of heating 10 C/min., R-
Molar gas constant and T -Peak temperature.
s
Coats Redfern Method
The thermodynamic activation parameters of decomposition processes of
complexes were calculated by this method. The activation energy (E ), enthalpy (∆H*),
a
entropy (∆S) and Gibbs free energy change of the decomposition (∆G*) were evaluated
by employing the Coats –Redfern relation
log{W /W W}
ZR
2RT
E*
E*
f
f
log[
 log[
(1
)]
2
T
E*
2.303RT
Where W -is the mass loss at the completion of the reaction.
f
W is the mass loss up to temperature T
R- Gas constant
E*- Activation energy in KJ/mol
-is the heating rate


1
(
1-(2RT/E*)
A plot of L.H.S. of equation against 1/T gave a slope from which E* was calculated
H* E*RT
S*  2.303R[(log

Zh

)]
KT
G* H *TS*
The data is given in (Table 4). The results show that the values obtained by two methods
are comparable. The calculated values of energy of activation of Mn(II), Co(II), Ni(II)
and Cu(II) complexes are relatively low indicating the autocatalytic effect of metal ions
on the thermal decomposition of metal complexes [24-25]. The negative values of
entropy of activation indicates that the activated complex is more ordered than the
reactant and that the reaction is slow. The more ordered nature may be due to the
polarization of bonds in activated state which might happen through charge transfer
electronic transitions.
Antimicrobial activity
The antibacterial activities of ligand and its metal complexes were tested in vitro
against bacteria such as Staphylococcus aureus and Escherichia coli by paper disc plate
-3
method [26]. The compounds were tested at the concentration 250 and 500 µg cm in
DMSO and compared with known antibiotics viz Rifampicin (Table 5). For fungicidal
activity, compounds were screened in vitro against Aspergillus niger and Trichoderma by
mycelia dry weight method [27] with glucose nitrate media. The compounds were tested
-3
at the concentration 250and 500 µg cm in DMSO and compared with control (Table 6).
From Table 5 and 6, it is clear that the inhibition by metal chelates is higher than that of
their parent ligand and metal salts. The results are in good agreement with previous

findings with respect to comparative activity of free ligand and its complexes [26-27].
The metal chelates have higher antibacterial activity than the corresponding free ligand
and control against the same microorganism under identical experimental conditions.This
increased activity of metal chelates can be explained on the basis of chelation theory [26].
Such enhanced activity of metal chelates is due to increased lipophilic nature of the metal
ions in complexes [27]. Transport of both, metal and ligand across lypophilic membranes
to vital intramolecular sites is favoured by chelation. Once intracellular, the fully
coordinated complex or one of its derivatives, including the dissociated metal or ligand
may be the active entity.The increase in activity with concentration is due to the effect of
metal ions on the normal process. The microbial results are presented in (Tables 5 and
6
). In case of antibacterial studies it was observed that, the ligand is moderately active
towards Stapylococcus and less active to E. coli. However, all the metal complexes show
enhanced antibacterial activity against both bacterial species.
The ligand and its metal complexes show fungal growth inhibition in the
following order: Co(II) > Ni(II) > Cu(II) > Mn(II) > HL. The antibacterial capacity of the
ligand and its metal complexes show following order: Ni(II) > Co(II) > Mn(II) > Cu(II) >
HL.
Conclusion
Metal complexes of Mn(II), Co(II), Ni(II), and Cu(II) with novel macrocyclic
ligand were synthesized. The structure of macrocylic ligand have been proposed on the
1
basis of IR, H NMR mass spectra which acts as a tetradentate ligand by coordinating
through four azomethine nitrogens. The elemental analysis, magnetic measurements, IR
and electronic spectra revealed the formation of monomeric complexes. Octahedral

structures were assigned to these complexes on the basis of elemental and spectral data.
Presence of two coordinated water molecules was proved by TG/DTA, analysis x-ray
diffraction study showed that the Mn(II), Cu(II) complexes have orthorhombic and
Co(II), Ni(II) complexes have tetragonal crystal structures. All these complexes were
found to have enhanced antibacterial and antifungal activities than the parent ligand.
ACKNOWLEDGEMENT
One of the Authors (T. K. Chondhekar) is thankful to UGC, New Delhi for
awarding UGC-BSR Faculty Fellowship. Thanks are also due to CSIR New Delhi for
financial support.
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2
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Figure Captions:
Scheme 1. Synthesis of β-Diketone
Scheme 2. Synthesis of macrocyclic ligand.

Fig.1 Synthesis of Metal Complexes.
Where M = Mn (II), Co (II), Ni (II), Cu (II)

Fig. 2. X-ray diffractograms of Mn (II), Co (II), Ni (II), and Cu (II) complexes.

Table .1.
Physical characterization, analytical and molar conductance data of ligand and its
metal complexes.
M.P. / Magnetic
Decomp. moment
Molar
conduc.
Mho
% Found
(Calculated)
Ligand/Complexes
F. W.
Temp.
μeff
C
H
N
M
0
2
-1
C
(B.M.)
cm mol
7
2.12
4.88
7.50
(
HL)
693.631
784.569
752.564
752.321
757.177
185 ----
----
(
72.72) (4.35) (8.07) _
4.60 4.07 6.80 7.40
64.29) (4.36) (7.14) (8.15)
6.81 4.10 7.10 8.05
67.03) (4.55) (7.44) (8.50)
7.10 4.09 7.60 7.70
67.05) (4.55) (7.44) (7.80)
6.95 4.84 7.20 8.50
66.62) (4.52) (7.39) (8.45)
6
[
MnL(H O) ]
>300
5.86
4.81
2.95
1.94
28.00
27.04
12.06
23.04
2
2
(
6
[
CoL(H O) ]
>300
>300
>300
2
2
(
6
[
NiL (H2O)2 ]
(
6
[
CuL (H2O)2]
(

Table.2
FTIR Spectra of the ligand (HL) and its macrocyclic metal complexes (cm ).
-1
Ligand/Complexes (OH)
(C=N)
1658
1645
1600
1604
1602
(C-N)
1055
1066
1091
1014
1064
(C-Cl)
754
(C-O)
1219
1259
1245
1257
1250
(M-N)
HL
3664
3695
3736
3680
3712
[
[
[
[
MnL(H O) ]
742
455
465
449
473
2
2
CoL(H O) ]
742
2
2
NiL(H O) ]
750
2
2
CuL(H O) ]
740
2
2

Table 3.
Magnetic and Electronic absorption spectral data of compounds.
-1
Frequency in cm
Compound
Band Assignment
Geometry
Octahedral
6
6
6
6
4
4
4
3
3
4
1
8,100-18587
A → T
1g 1g
4
4
[
MnL(H O) ]
23,200-24,570
A1g → E , A
2
2
g
1g
4
2
3
1
7,000-29,412
0,950-33,003
2360-12509
A → E
1
g
g
4
A → T
1
g
1g
4
T (F) → T (F),
Octahedral
Octahedral
Octahedral
1
g
2g
4
[
[
[
CoL(H O) ]
16051-17123
T → A
1g 2g
2
2
2
1
2026-22229
T (F) → T (P),
1g 2g
3
3333–14390
A (F) → T (F),
2g 2g
3
NiL(H O) ]
18587–18621
A (F)→ T (F),
2g g
2
2
3
3
2
6385–27700
A (F)→ T (P),
2g 1g
4
4
1
0020-10143
T (F) → T (F),
1g 2g
4
4
CuL(H O) ]
14684-14788
2075-23154
T (F) → A (F)
1g 2g
2
2
4
2
T (F) → T (P),
1g 1g

Table 4. The kinetic parameters of metal complexes calculated by Horowitz-Metzger
HM) and Coats-Redfern (CM) methods.
(
Corelation
coefficient
Ea
A
ΔS#
ΔG#
Complex Step
n
Method
-1)
-1
-1
-1
-1
(
kJmol
(S )
JK mol
(kJmol )
(r)
3
HM
CR
4.47
2.84×10
11.353
-172.50
-175.90
-170.76
-159.689
-173.68
-161.87
-160.45
-142.57
-179.62
-178.51
-156.097
-142.698
-174.71
-161.87
-166.74
-149.86
18.63
18.66
38.01
36.51
20.22
19.34
52.90
50.25
16.22
16.14
52.38
50.25
20.29
19.34
47.94
45.51
0.9994
0.9975
0.9998
0.9969
0.9919
0.9975
0.9938
0.9979
0.9948
0.9915
0.9985
0.9967
0.9919
0.9998
0.9997
0.9953
I
0.45
0.45
0.45
0.45
0.46
0.46
0.40
0.40
24.18
14.75
8.97
Mn(II)
-
2
HM
CR
8.37×10
3.30
II
HM
CR
7.31
0.11
I
19.78
29.11
23.53
2.94
32.86
0.605
1.43
Co(II)
HM
CR
II
2
HM
CR
1.77×10
5.376
0.6054
2.41
I
16.62
29.11
20.37
7.31
Ni(II)
II
HM
CR
HM
CR
0.118
1.168
6.251
7.900
I
10.8
Cu(II)
HM
CR
23.29
13.57
II

Table 5.
Antibacterial activity of HL and its metal complexes.
inhibition Zone diameter (mm)
Staphylococcus aures
E.coli
Ligand/Complexes 250ppm
500ppm
40
250ppm
42
500ppm
Rifampicin
40
08
14
15
16
12
42
14
19
20
28
17
(
[
[
[
[
HL)
11
12
MnL(H O) ]
26
11
2
2
CoL(H O) ]
16
17
2
2
NiL(H O) ]
21
31
2
2
CuL(H O) ]
22
14
2
2
Table 6.
Antifungal activity of compounds yield of mycelia dry weight in mg (% inhibition)
Aspergillus niger Trichoderma
Ligand/Complexes 250ppm 500ppm 250ppm
500ppm
40
Control
40
40
40
(
[
[
[
[
HL)
14(65)
11(72)
30(25)
27(33)
25(38)
11(72)
09(78)
11(73)
10(75)
04(90)
13(68)
14(65)
17(58)
12(70)
19(53)
10(75)
07(83)
09(78)
10(75)
11(73)
MnL(H O) ]
2
2
CoL(H O) ]
2
2
NiL(H O) ]
2
2
CuL(H O) ]
2
2

Graphical Abstract

ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Metal complexes of Mn(II), Co(II), Ni(II), Cu(II),
Synthesized by condensation of β-diketone
All the synthesized compound Characterized by spectroscopy techniques.
The complexes was found to be 1:2 (metal: ligand).
The antibacterial and antifungal activities of the ligand and its metal complexes.