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Macrocyclic Schiff Base Metal Complexes Derived from Isatin: Structural

Activity Relationship and DFT Calculations

Article in Tenside Surfactants Detergents · May 2017

DOI: 10.3139/113.110496

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Manickam Muthukkumar R. Rajavel

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 SYNTHESIS

y M. Muthukkumar1 , R. Rajavel2,* , G. Venkatesh3 and P. Vennila4

Macrocyclic Schiff Base Metal Complexes

Derived from Isatin: Structural Activity
Relationship and DFT Calculations

Macrocyclic metal complexes viz., Co(II), Ni(II), Cu(II) and Zn(II) Stichwörter: Makrozyklischer Komplex, Isatin, 4-Aminoantipy-
have been prepared using a macrocyclic Schiff base as ligand, rin, o-Phenylendiamin, antimikrobielle Aktivität, Dichtefunktio-
which was derived from Isatin, 4-aminoantipyrine and o-phenyl- naltheorie (DFT)
enediamine. Further, the complexes have been characterized by
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elemental analysis, magnetic susceptibility, molar conductance,

mass spectrometry, FT-IR-, Far-IR-, UV-Vis-, EDX spectroscopy, 1 Introduction
1H NMR and 13C NMR, ESR spectroscopy and SEM. The octahe-

dral geometry of the complexes has been revealed by the spec- Metal complexes of 4-aminoantipyrine Schiff base find ap-
tral data of UV-Vis and ESR as well as by the results of the mag- plications in various research areas including pharmacolo-
netic susceptibility measurements. Antimicrobial screening tests gical, clinical, corrosion science, analytical and biological
indicated that the Zn(II) metal complexes showed an excellent fields [1 – 6]. Studies of new kinds of chemotherapeutic
antimicrobial activity compared to the other studied metal com- Schiff bases and their functions receive the attention of bio-
plexes. The nuclease activity of the metal complexes showed chemists [7, 8]. Earlier reports revealed that some Schiff
that the Co(II) complex has effectively cleaved DNA. The opti- bases and their metal complexes showed a better activity
mized molecular structure, bond length, bond angle, dihedral when they existed as complexes rather than as ligands [9,
angle, chemical reactivity and total energy have been evaluated 10]. Macrocyclic compounds and their derivatives are inter-
For personal use only.

using the density functional theory (DFT) with B3LYP functional esting ligand systems which attracted the researchers in the
level. recent years to synthesize novel metal complexes that are
biologically important [11 – 13]. From the earlier reports it is
Key words: Macrocyclic complex, isatin, 4-aminoantipyrine, o- well known that, there must be an amine and a carbonyl
phenylenediamine, antimicrobial activity, density functional group containing system for synthesis of macrocyclic com-
theory (DFT) pounds. Among the several amines employed for the syn-
thesis of macrocyclic compounds, o-phenylenediamine is
one of the most intensively used compound and isatin is of-
Von Isatin abgeleitete, makrozyklische Schiff’sche Base- ten used as a reactant for preparation of the macrocyclic
Metallkomplexe: Struktur-Aktivitätsbeziehung und DFT- compounds, which is evidenced from the literature.
Berechnungen. Makrocyclische Metallkomplexe mit Co(II)-, In the present study, the novel tetradentate Schiff base
Ni(II)-, Cu(II)- bzw. Zn(II)-Zentralatom, wurden unter Verwen- has been synthesized using Isatin, 4-aminoantipyrine and
dung einer makrocyclischen Schiff’schen Base als Ligand herge- o-phenylenediamine ligand. The complexes have been
stellt, der aus Isatin, 4-Aminoantipyrin und o-Phenylendiamin formed by binding the metals through nitrogen atom of
erzeugt wurde. Ferner wurden die Komplexe durch Elementar- two azomethine grous of the same ligand. Further, the com-
analyse, magnetische Suszeptibilität, molare Leitfähigkeit, Mas- plexes have been characterized using standard analytical and
senspektrometrie, FT-IR-, Fern-IR-, UV-Vis-, EDX-Spektroskopie, spectral methods.
1H-NMR und 13C-NMR, ESR-Spektrometrie und Rasterelektro-

nenmikroskopie (SEM) charakterisiert. Die Oktaedergeometrie

2 Experimental
der Komplexe wurde durch die Spektraldaten der UV-Vis- und
der ESR-Messungen sowie durch die Ergebnisse der magnet-
ischen Suszeptibilitätsbestimmungen aufgezeigt. Antimikrobielle
2.1 Measurements
Screening-Tests zeigten, dass die Zn(II)-Metallkomplexe eine
ausgezeichnete antimikrobielle Aktivität im Vergleich zu den an-
All the chemicals including reagents and solvents viz., ben-
deren untersuchten Metallkomplexen zeigten. Die Nukleaseakti-
zil, 4-aminoantipyrine, o-phenylenediamine and various me-
tal(II) chlorides were purchased from Sigma Aldrich Com-
vität der obigen Metallkomplexe zeigte, dass der Co(II)-Komplex
pany in AR grade. Further, the purchased solvent was
die DNA wirksam gespalten hat. Die optimierte Molekülstruktur,
purified according to the standard procedures [14, 15].
die Bindungslänge, der Bindungswinkel, der Diederwinkel, die
The MS, 1H and 13C NMR spectra were recorded using
chemische Reaktivität und die Gesamtenergie wurden unter Ver-
Bruker DPX-300. The solvent MeOD was applied as an inter-
wendung der Dichtefunktionaltheorie (DFT) mit B3LYP-Funk-
nal standard TMS.
tionsniveau bewertet.
A Perkin-Elmer 783 spectrometer was used to record the
1
Department of Chemistry, Selvam Arts and Science College, Namakkal, Tamil- FT-IR spectra of the complexes in a range of 4 000 – 400 cm–1
nadu, India using KBr pellets. A Schimadzu UV spectrometer was used
2 ,*
Department of Chemistry, Periyar University, Salem-636011, Tamilnadu, India to record the UV-Vis spectra in the range 200 – 700 nm. A
3
Department of Chemistry, VSA Group of Institutions, Salem, Tamilnadu, India
4
Department of Chemistry, Thiruvelluvar Govt Arts College, Namakkal, Tamil- ELICO CM-180 instrument was used to measure the molar
nadu, India conductance at room temperature. DMSO was applied as

248 ª Carl Hanser Publisher, Munich Tenside Surf. Det. 54 (2017) 3

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

solvent. The SEM and EDX analysis for ligands and com- according to the reported procedure [17]: 250 mg agarose
plexes were also recorded. was completely dissolved in 25 ml of TAE buffer (4.84 g Tris
The antimicrobial activity of the ligand and the metal base, pH 8.0, 0.5 M EDTA/1 ltr). At 55 8C, a comb fitted gel
complexes was studied. Bacteria like E. coli, S. aureus and cassette was filled with the gel. After cooling when the gel
fungi like A. niger and A. flavas were examined in order to becomes a solid, it was placed in the chamber with the
find out whether they are susceptible to ligand and its metal DNA sample in 20 ll TAE buffer. Then it was loaded care-
complexes. The CT DNA cleavage ability of the newly fully into the well along with a standard DNA marker. Then
synthesized compound was examined by gel electrophoresis the electrical current has been passed for 45 min at 50 V. An
[14, 15]. UV transmitter was used to observe the bands of the re-
moved gel for 10 – 15 min which was stained with ETBR so-
2.2 Synthesis of Schiff base lution (10 lg/ml).

To the methanolic solution of 4-aminoantipyrine (0.4 g, 3 Results and Discussion

0.2 mmol), Isatin (1.46 g, 0.10 mmol) was added and the re-
action mixture was stirred for more than 3 h. The light The synthesized complexes are soluble in DMSO and
brown solid was filtered, recrystallized from methanol and methanol. Conductivity measurement of the complexes in
then vacuum dried. Then the obtained solid was refluxed 10–3 M solution of DMSO indicated the non-electrolytic be-
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with 40 ml ethanolic o-phenylenediamine solution (0.4 g, havior of the studied complexes (below 2 S cm2 mol–1). The
0.10 mmol) for 30 h. The light yellow coloured precipitated results are given in Table 1
solid was filtered off and dried over CaCl2.
3.1 IR spectra
2.3 Synthesis of Complexes
IR spectra of the ligand and the corresponding complex
A solution of metal(II) chloride in methanol (0.20 mmol) have been compared (Table 2). In the IR spectrum of ligand,
was refluxed in methanolic solution of the Schiff base no bands appeared at 1 700 cm–1 which showed the absence
(0.20 mmol) for 6 h. The volume of the solution was then of m(CO) whereas a band at 1 647 cm–1 is due to the presence
reduced to one third of its own volume by keeping it on a of m(C=N) [18, 19]. The observation confirmed the condensa-
hot plate. Then, the precipitated solid complex was washed tion of C=O group of isatin and NH2 group of o-Phenylene-
thoroughly with methanol and then dried in vacuum diamine. It is worth noting that, the frequencies of m(C=N)
For personal use only.

(Fig. 9). have been shifted to lower frequencies (40 – 80 cm–1). The
observation revealed the involvement of the nitrogen atom
2.4 Antimicrobial activity of C=N in coordination with the metal ion [21]. The results
confirmed the formation of macrocyclic frame. The band ap-
The antimicrobial activity of the studied compounds against peared at 3 247 – 3 364 cm–1 could be due to the presence of
the bacteria (E. coli, S. aureus) and fungi (A. niger and A. fla- m(N-H) [20 – 23].
vas) was determined by the well diffusion method [16] using The results of Far IR spectrum of each complex revealed
an agar nutrient as medium. In order to prepare a stock so- that the bands in the range 440 – 460 cm–1 are due to m(M-
lution, the synthesized complexes (100 mg) were dissolved N) [24, 25]. The bands appeared at 340 – 314 cm–1 in all com-
in DMSO. The well was prepared by using agar medium fol- plexes are assigned to m(M-Cl) [26]. The formation of M-N
lowing a typical procedure. The well was filled with the test and M-Cl bonds is supported by these bands.
solution and the plate was incubated at 35 8C. The incuba-
tion period for bacteria and fungi were 24 and 72 h, respec- 1
3.2 H NMR Spectra
tively. During this period, the test solution diffused and af-
fected the growth of the inoculated microorganisms. The 1H-NMR spectrum of the ligand recorded in MeOD is
shown in Fig. 1a. From the figure, signals at d/ppm: 2.9 (s,
2.5 DNA cleavage activities 6H, =C-CH3)2, due to six protons of two methyl groups at-
tached to double bond carbon atom, 3.34 (s, 7H, N-CH3)2
Gel electrophoresis was used to examine the ability of DNA correspond to seven protons of two methyl groups attached
cleavage of the studied complexes. The samples were treated to N-substitute methyl group. 7.34 – 7.84 (m, 18H, aromatic

Compound Carbon Hydrogen Nitrogen Metal Yield Electrolytic Nature

(%) S · cm2 · mol–1
Co(C36H31N9)Cl2 (1) Calcd. 60.09 4.34 17.52 8.19 65 0.101
Found 64.16 4.31 17.54 8.02
Ni(C36H31N9)Cl2 (2) Calcd. 60.11 4.34 17.53 8.16 70 0.111
Found 60.25 4.32 17.57 8.16
Cu(C36H31N9)Cl2 (3) Calcd. 59.71 4.31 17.41 8.78 65 0.093
Found 59.83 4.29 17.45 8.52
Zn(C36H31N9)Cl2 (4) Calcd. 59.56 4.3 17.6 9.01 65 0.083
Found 59.75 4.25 17.42 8.95

Table 1 Analytical data of the reported complexes

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 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

proton) due to the protons of four phenyl rings and 8.45 (s, 128.97 due to the aromatic carbon, 48.14 for (N-CH3) and
1H, NH of istain) were arrived [26 – 29]. 35.99 corresponding to (C-CH3) of ring [30].

3.3 13C NMR Spectra 3.4 NMR Studies of zinc complex

The 13C-NMR (Fig. 1b) spectral analysis showed signals at d/ In the spectrum (Fig. 2) of the zinc complex, it is observed
ppm: 161 (C=O) attributed to carbon atom of carbonyl that azomethine proton signal is shifted to low field. The
groups, 139.56 (C=N) for carbon atoms azomethine groups, peak at d 7.5 found in the ligand is shifted to d 7.8 in com-

Compound Complex m(N-H)/ m(C=N)/ m(C=C)/ m(C-N)/ m(M-N)/ m(M-Cl)/

cm–1 cm–1 cm–1 cm–1 cm–1 cm–1
1 (C36H31N9)Cl2 3 244 – 3325 1647 1491 – 1591 1238 – –
2 CO(C36H31N9)Cl2 3 250 1606 1489 1243 448 341
3 Ni(C36H31N9)Cl2 3247 1606 1490 1244 451 311
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4 Cu(C36H31N9)Cl2 – 1594 1490 1206 455 314

5 Zn(C36H31N9)Cl2 3 364 1629 1590 1267 460 327

Table 2 Infrared spectral data m/cm–1, of the divalent of Co(II), Ni(II), Cu(II) and Zn(II) complexes derived from isatin, 4-aminoantipyrine and o-phenylene-
diamine
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(a)

(a)

(b) (b)

Figure 1 Spectra of the ligand, (a): 1H NMR, (b): 13C NMR Figure 2 Spectra of the Zn(II) complex, (a): 1H NMR, (b): 13C NMR

250 Tenside Surf. Det. 54 (2017) 3

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

plex and the rest of the peaks (s, 6H, =C-CH3)2, & (s, 7H, N- type [34]. The results of the ligand (a) & Cu(II) complex (b)
CH3)2 appear in the same region 2.82, 3.33, respectively. The study are shown in Fig. 3.
peaks at d 8.24 and d 8.43 are due to benzylidenium hydro-
gen. 3.7 SEM- EDX analysis

3.5 Magnetic Measurement and Electronic Spectra Figures 4 and 5 show the SEM-EDX analysis of the studied
complexes. The surface morphology of ligand and Cu(II)
Magnetic susceptibility of the complex was measured by complex has been examined using scanning electron micro-
Guoy balance using copper sulphate as calibrant. UV-Vis scope at a magnification of 2000 X. The distinct morphology
spectra of complexes were recorded using 10–3 M methano- of ligand and Cu(II) complex has been observed. The size of
lic solution of complexes. the flakes is greater for Cu(II) complex than the free ligand.

Cobalt complex:
The magnetic moments of Co(II) complex was found in the
range 4.60 – 5.21 lb, which is consistent with three unpaired
electrons. The solution spectra of Co(II) complexes exhibit
three bands at 11 300 cm–1, 15350 cm–1 and 24 100 cm–1
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which are assigned to 4T1g[ f ] ? 4T2g[ f ], 4T1g[ f ] ? 4A2g[F],

and 4T1g ? 4sA2g[P] transition respectively. These spectral
data suggested that the complex have octahedral geometry
[31].

Nickel complexes:
The magnetic moments of Ni(II) complex was found in the
range 2.92 – 2.98 lb, which is consistent with two unpaired
electrons. The solution spectra of Ni(II) complex exhibited
three bands in the region 11 850 cm–1 (m1), 16 750 cm–1 (m2)
and 23 850 cm–1 (m3) and are assigned to 3B1g ? 3B2g,
3
A2g ? 3A2g[F], and 3A2g ? 3T1g[P], transition respectively.
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From this spectral data it is clear that the complex posses a

distorted octahedral geometry [32]. (a)

Copper complex:
The magnetic moments Cu(II) complex was found in the
range 1.70 – 1.82 lb, which is consistent with one unpaired
electron. The transition 2B1g ? 2B2g assigned the solution
spectra of Cu(II) as 18 550 cm–1 and broad band at 14 250,
16 750 cm–1 which are assigned to 2B1g ? 2B2g and
2
B1g ? 2A2g transition, respectively. This shows that the
complex structure is distorted octahedral [33]. The results
of the study are shown in Table 3.

3.6 Mass spectra

The stoichiometry composition at room temperature has

been compared using the mass spectra of the ligand [L] and
its copper complexes. The Schiff base showed a molecular
ion peak at m/z 589 which was also supported by the nitro-
gen rule. Since the compound possess nine nitrogen atoms, (b)
the copper complex exhibited molecular ion peak at m/z 725
which confirmed the stoichiometry of metal chelates as ML Figure 3 Mass spectrum of the ligand (a) and its Cu(II) complex (b)

Compound Frequancy/ cm–1 Transition Geometry leff/lb

Co(C36H31N9)Cl2 (1) 11300 4T g[f] ? 4T
1 2g[f], Octahedral 4.60 – 5.21
15 350 4T 4
1g[f] ? A2g[F],
24100 4T g ? 4A g[P]
1 2

Ni(C36H31N9)Cl2 (2) 11850 3B g ? 3B g, Distorted octahedral 2.92 – 2.98

1 2
16750 3A g ? 3A g[F],
2 2
23 850 3A g ? 3T g[P]
2 1

Cu(C36H31N9)Cl2 (3) 18 550 2B 2B

1g ? 2g, Distorted octahedral 1.70 – 1.82
14 250 2B 2B
1g ? 2g,
16750 2B 2
1g ? A2g

Table 3 Electronic spectral data and magnetic moments of the prepared compounds

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 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

EDX analysis is used to calculate the percentage level of var-

ious elements present in the metal complex. The results of
energy dispersive X-ray analysis (EDX) indicated that no
contamination existed in complexes. The percentages of ele-
ments present in the complex are in good agreement with
the proposed structure.

3.8 ESR spectra

The ESR spectra of Cu(II) complex has been recorded at

room temperature (300 K). The four well resolved peaks in
the low filed region are corresponding to g|| (2.230) and g\
(2.085). The trend g|| (2.230) > g\ (2.085) > ge (2.0023) ob-
served for copper complex suggested that the unpaired elec-
trons are localized in dx2-y2 orbital of the Cu(II) ion. As per
Hathaway exchange interaction is negligible when G is
greater than 4 (G > 4) and when it is less than 4 (G < 4) ex-
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change interaction is considerable in the complex. It is ob-

served that G values of these complexes are less than four
(G < 4), indicating considerable exchange interaction the
complexes [35 – 38]. The spin orbit coupling constant (k) val-
(a) ue (–650 cm–1) calculated using the relations gav = 1/3(g|| +
2 g\) and gav = 2(1 – 2k/10Dq is less than that of the free
Cu(II) ion (–832 cm–1) which also supported the covalent
character of M-L bond in the complex. The covalence param-
eter a2 is calculated using the following equation (Fig. 6).
a2 ðCuÞ ¼ ðAjj =0:036Þ þ ðg j j  2:0023Þ

þ 3=7ðg ?  2:0023Þ þ 0:04

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A complete covalent bonding is obtained when the value

a2 = 0.5, whereas it will be termed as complete ionic bond-
ing when the value a2 = 1.0. The observed value of a2 (0.92)
of the complex is less than unity, which confirmed the cova-
lent character of the complex [37, 38].

3.9 DNA cleavage activity

It is evident from gel electrophoresis analysis (Fig. 7) that,

the difference in molecular weight of the control and the
treated DNA samples influenced the action of the ligand
and its metal complexes on DNA. Compared to control
DNA, the difference in the migration of the lanes of Schiff
base ligand (L) and its metal(II) complexes is shown clearly
in the present gel electrophoresis (Fig. 7). It has been shown
(b) that, ligand and its [Co(L)Cl2] complexes completely cleaved
Figure 4 SEM image of the ligand (a) and its Cu(II) complex (b)

Figure 5 EDX spectrum of the Cu(II) complex Figure 6 ESR spectrum of the Cu(II) complex

252 Tenside Surf. Det. 54 (2017) 3

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

the super coil. On the other hand, there is only partial cleav- gi. From the results of the antimicrobial studies it is clear,
age of super coil by [Ni(L)Cl2], [Cu (L) Cl2] and [Zn(L)Cl2] that the metal complexes are found as highly effective
complexes. From the studies, it is evident that only the con- against bacteria compared to that of the free ligand. Overlap
trol DNA does not show any apparent cleavage but the li- of the ligand orbital reduces the polarity of the metal ion and
gand and its metal complexes show the apparent cleavage. partial sharing of the positive charge of the metal ion with
From the finding of this study, it could be concluded that donor groups (Chelation theory) [38]. This causes enhance-
all the synthesized compounds are good inhibitors of patho- ment in delocalization of the p-electrons over the whole che-
genic micro organisms, which is evident from the observa- late ring and the penetration of the complexes into lipid
tion of the DNA cleavage. membranes and blocks are enhanced by the metal binding
sites in the enzymes of micro organisms. The synthesis of
proteins is blocked and further growth of organisms is re-
3.10 Antimicrobial studies stricted by the complexes and the respiration process of the
cell is also disturbed. The results of the study are shown in
In-vitro antimicrobial activity tests were carried out with Plate 1: Anti bacterial activity, Plate 2: Anti Fungal activity
metal chloride solutions, DMSO solvent, free ligand and (Fig. 8).
DMSO solution of metal complexes. The tests were studied
against E. coli, S. aureus, bacteria and A. niger, A. flavas fun-
3.11 Molecular geometry
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The molecular structural modeling and numbering of

(Cu(C36H31N9)Cl2) (Table 4), (Co(C36H31N9)Cl2), (Ni
(C36H31N9) Cl2), (Zn(C36H31N9)Cl2) complex are listed in
Figs. 10 – 15 and the values calculated from the same are
presented in Table 5. From the theoretical values, it can be
seen that, most of the optimized bond lengths are slightly
deviated from experimental values. The parameters viz.,
bond length, bond angles and dihedral angles were depicted
in Table 5 and 6.

3.12 Global and Local Reactivity descriptors

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The highest occupied molecular orbital (HOMO) and the

lowest unoccupied molecular orbital (LUMO) of a molecule
are called the frontier orbitals [39]. Fukui et al. [40] first no-
ticed the important role of HOMO and LUMO in governing
molecular chemical reactions. It is clear from recent investi-
gations that, the gap in energy between the HOMO and
Figure 7 DNA cleavage: Agarose gel electrphoretic pattern of CT-DNA in- LUMO is a vital stability index. The difference in energy be-
duced by H2O2 and metal complexes M: DNA alone (lane 1), C: Control DNA
(lane 2), L1: Ligand (lane 3), Co: [CoL]Cl2 (lane 4), Ni: [NiL]Cl2 (lane 5), Cu: tween these two frontier orbitals can be used to predict the
[CuL]Cl2 (lane 6), Zn: [ZnL]Cl2 (lane 7) strength and stability of transition metal complexes. The sta-

Figure 8 Antimicrobial studies: the two Petri dishes on the left: antibacterial activity; the two Petri dishes on the on the right: antifungal activity

Figure 9 Synthesis of isatin Schiff base ligand

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 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

C2-C1 1.546 C3-C2-C1 116.8 C4-C3-C2-C1 6.9

C3-C2 1.339 C4-C3-C2 123.4 C5-C4-C3-C2 –9.8
C4-C3 1.532 C5-C4-C3 120.2 C6-C1-C2-C3 –0.4
C5-C4 1.344 C6-C1-C2 120.2 C7-C3-C2-C1 –171.3
C6-C1 1.376 C7-C3-C2 131.8 N8-C4-C3-C2 170.4
C7-C3 1.498 N8-C4-C3 112.3 C9-N8-C4-C3 14.6
N8-C4 1.506 C9-N8-C4 101.9 N10-C7-C3-C2 3.3
C9-N8 1.481 N10-C7-C3 138.4 N11-C9-C8-C4 167.2
N10-C7 1.293 N11-C9-C8 135.7 C12-N10-C7-C3 –6.5
N11-C9 1.301 C12-N10-C7 139.5 C13-C12-N10-C7 –176.7
C12-N10 1.451 C13-C12-N10 112.2 N14-C13-C12-N10 –5.2
C13-C12 1.482 N14-C13-C12 115.6 C15-N14-C13-C12 –178.5
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N14-C13 1.311 C15-N14-C13 135.8 C16-C15-N14-C13 –177.8

C15-N14 1.488 C16-C15-N14 114.1 C17-C15-N14-C13 1.5
C16-C15 1.392 C17-C15-N14 126.0 C18-C16-C15-N14 –179.9
C17-C15 1.525 C18-C16-C15 121.3 C19-C17-C15-N14 –178.1
C18-C16 1.525 C19-C17-C15 118.7 C20-C18-C16-C15 –2.4
C19-C17 1.364 C20-C18-C16 118.5 C21-N11-C9-N8 –2.7
C20-C18 1.354 C21-N11-C9 139.2 C22-C21-N11-C9 –179.0
C21-N11 1.461 C22-C21-N11 112.9 N23-C22-C21-N11 –4.1
C22-C21 1.506 N23-C22-C21 115.4 N24-C13-C12-N10 173.5
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N23-C22 1.314 N24-C13-C12 107.5 C25-N24-C13-C12 147.0

N24-C13 1.462 C25-N24-C13 114.0 C26-C25-N24-C13 –147.1
C25-N24 1.464 C26-C25-N24 120.6 C27-C25-N24-C13 32.7
C26-C25 1.535 C27-C25-N24 119.2 C28-C26-C25-N24 179.5
C27-C25 1.355 C28-C26-C25 119.8 C29-C27-C25-N24 –179.6
C28-C26 1.356 C29-C27-C25 120.0 C30-C28-C27-C25 0.1
C29-C27 1.538 C30-C28-C27 119.9 C31-C12-N10-C7 3.5
C30-C28 1.355 C31-C12-N10 139.3 C32-C31-C12-N10 –11.8
C31-C12 1.337 C32-C31-C12 126.2 N33-N24-C13-C12 23.6
C32-C31 1.547 N33-N24-C13 102.3 C34-N33-N24-C13 –154.0
N33-N24 1.445 C34-N33-N24 111.2 N35-C22-C21-N11 175.7
C34-N33 1.468 N35-C22-C21 107.9 C36-N35-C22-C21 143.4
N35-C22 1.455 C36-N35-C22 114.1 C37-C36-N35-C22 31.4
C36-N35 1.466 C37-C36-N35 119.7 C38-C36-N35-C22 –148.4
C37-C36 1.354 C38-C36-N35 120.3 C39-C37-C36-N35 –179.8
C38-C36 1.540 C39-C37-C36 120.0 C40-C38-C36-N35 179.9
C39-C37 1.541 C40-C38-C36 119.9 C41 – 40-C37-C36 –0.3
C40-C38 1.358 C41 – 40-C37 120.0 C42-C21-N11-C9 2.4
C41-C40 1.355 C42-C21-N11 138.8 C43-C42-C21-N11 –13.1
C42-C21 1.333 C43-C42-C21 126.7 C43-C42-C22-C21 21.7
C43-C42 1.536 C43-C42-C22 102.1 N44-C45-N35-C22 –153.4
N44-C45 1.452 N44-C45-N35 110.9 C45-N44-C6-C5 176.7
C45-N44 1.473 C45-N44-C6 120.1 C1-H46-C1-C6 –179.6
C1-H46 1.070 C1-H46-C1 121.7 C2-H47-C4-C3 –175.2

Table 4 Optimized geometrical parameters of obtained by B3LYP/6-31 density functional calculations (Cu(C36H31N9)Cl2)

254 Tenside Surf. Det. 54 (2017) 3

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

C2-H47 1.068 C2-H47-C4 121.1 C5-H48-C1-C2 176.6

C5-H48 1.069 C5-H48-C1 119.5 C6-H49-C4-C3 –102.2
C6-H49 1.066 C6-H49-C4 111.0 N8-H50-C25-N24 62.9
N8-H50 1.005 N8-H50-C25 139.5 C27-H51-C36-N35 62.0
C27-H51 0.911 C27-H51-C36 129.3 C37-H52-C17-C15 177.9
C37-H52 1.013 C37-H52-C17 119.7 C19-H53-C18-C16 –178.5
C19-H53 1.079 C19-H53-C18 119.3 C20-H54-C25-N24 –0.2
C20-H54 1.067 C20-H54-C25 120.1 C26-H55-C15-N14 8.5
C26-H55 1.071 C26-H55-C15 72.4 C17-H56-C26-C25 –179.8
C17-H56 0.974 C17-H56-C26 119.8 C28-H57-C27-C25 –179.9
C28-H57 1.072 C28-H57-C27 120.1 C29-H58-C29-C27 179.6
C29-H58 1.070 C29-H58-C29 120.1 C30-H59-C31-C12 158.9
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C30-H59 1.069 C30-H59-C31 83.2 C32-H60-C31-C12 18.7

C32-H60 1.069 C32-H60-C31 83.4 C32-H61-C31-C12 88.7
C32-H61 1.075 C32-H61-C31 140.3 C32-H62-C33-N24 179.4
C32-H62 1.072 C32-H62-C33 109.6 C34-H63-C33-N24 59.5
C34-H63 1.071 C34-H63-C33 109.3 C34-H64-C33-N24 –60.5
C34-H64 1.070 C34-H64-C33 109.4 C34-H65-C16-C15 –163.9
C34-H65 1.070 C34-H65-C16 72.3 C18-H66-C36-N35 0.0
C18-H66 0.987 C18-H66-C36 120.2 C38-H67-C37-C36 179.8
C38-H67 1.069 C38-H67-C37 120.2 C39-H68-C38-C36 180.0
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C39-H68 1.070 C39-H68-C38 119.9 C40-H69-C39-C37 –179.8

C40-H69 1.072 C40-H69-C39 120.2 C41-H70-C42-C21 148.9
C41-H70 1.070 C41-H70-C42 109.4 C43-H71-C42-C21 –90.8
C43-H71 1.073 C43-H71-C42 109.6 C43-H72-C42-C21 29.5
C43-H72 1.064 C43-H72-C42 109.2 C43-H73-N44-N35 –179.9
C43-H73 1.072 C43-H73-N44 109.5 C45-H74-N44-N35 –59.8
C45-H74 1.069 C45-H74-N44 109.7 C45-H75-N44-N35 60.1
C45-H75 1.072 C45-H75-N44 109.4 C45-H76-C13-C12 4.1
C45-H76 1.070 C45-H76-C13 112.7 N14- Cu77-N10-C7 178.6
Cu77-N10 1.842 N10- Cu77-N14 91.42 C12-N10-Cu77-N11 –178.5
Cu77-N11 1.826 N11- Cu77-N14 176.4 C16-N23-Cu77-N11 177.2
Cu 77-N23 1.931 N23- Cu77-N11 92.3 N23-Cu77-N14-C13 178.6
Cu 77-N14 1.912 N14- Cu77-N23 88.9 N23-Cu77-N14-C15 –0.6
Cu 77-Cl78 2.123 Cl78- Cu77-Cl79 179.6 – –
Cu 77-Cl79 2.159 – – – –

Table 4 (Continued)

Tenside Surf. Det. 54 (2017) 3 255

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship
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Figure 10 Molecular structure of metal

complexes

Figure 11 Isatin Schiff base ligands

Figure 12 Metal complexes i) HOMO

ii) LUMO iii) HOMO-LUMO of
(Cu(C36H31N9)Cl2)

256 Tenside Surf. Det. 54 (2017) 3

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

bility is directly related to energy gap. The high stability in The v and g can be determined by the following expressions
turn indicates low chemical reactivity and small gap indi- from calculation of IP and EA.
cates high chemical reactivity.
Koopman’s theorem [41] specifies that the energy of the IP þ EA
v¼ ð3Þ
highest occupied molecular orbital (EHOMO) and the energy 2
of the lowest unoccupied molecular orbital (ELUMO) corre- 1
The S is defined as the inverse of the g (3). S ¼
spond to ionization energy and electron affinity, respectively. g
According to Koopman’s Theorem, electronegativity, global l2
hardness and softness may be defined via the following The electrophilicity index (x) formula is x ¼
2g
equations in terms of the energy of HOMO and LUMO. In
Calculated quantum chemical parameters of (Cu
this stage, it should be noted that softness (r) is defined as
(C36H31N9)Cl2), (Co(C36H31N9)Cl2), (Ni (C36H31N9) Cl2) and
physically inverse of hardness [41 – 45].
(Zn(C36H31N9)Cl2) metal complexes were listed in Table 6.
IP ¼ EHOMO ð1Þ According to the HOMO-LUMO energy gap values, the sta-
bility of metal complexes are in the following order Ni(II) >
EA ¼ ELUMO ð2Þ Zn(II) > Co(II) > Cu(II).
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Figure 13 Metal complexes i) HOMO

ii) LUMO iii) HOMO-LUMO of
(Co(C36H31N9)Cl2)

Figure 14 Metal complexes i) HOMO

ii) LUMO iii) HOMO-LUMO of
(Ni (C36H31N9)Cl2)

Figure 15 Metal complexes i) HOMO

ii) LUMO iii) HOMO-LUMO of
(Zn(C36H31N9)Cl2)

Tenside Surf. Det. 54 (2017) 3 257

 M. Muthukkumar et al.: Macrocyclic schiff base metal complexes derived from isatin: structural activity relationship

Bond Length/Å Bond angle Angle/Å Dihedral angle Angle/Å

Ni77-N10 1.844 N10- Ni77-N14 98.6 N14- Ni77-N10-C7 178.7
Ni 77-N11 1.825 N11- Ni77-N14 175.9 C12-N10-Ni77-N11 –176.2
Ni 77-N23 1.841 N23- Ni77-N11 98.6 C16-N23-Ni77-N11 177.6
Ni 77-N14 1.821 N14- Ni77-N23 87.7 N23-Ni77-N14-C13 –178.2
Ni 77-Cl78 2.132 Cl78- Ni77-Cl79 173.5 N23-Ni77-N14-C15 –2.1
Ni 77-Cl79 2.144 – – – –
Zn77-N10 1.912 N10- Zn77-N14 87.6 N14- Zn77-N10-C7 178.3
Zn77-N11 1.864 N11- Zn77-N14 171.4 C12-N10-Zn77-N11 –176.8
Zn77-N23 1.854 N23- Zn77-N11 98.6 C16-N23-Zn77-N11 176.9
Zn77-N14 1.921 N14- Zn77-N23 87.9 N23-Zn77-N14-C13 175.2
Zn77-Cl78 2.312 Cl78- Zn77-Cl79 174.6 N23-Zn77-N14-C15 –2.8
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Zn77-Cl79 2.231 – – – –
Co77-N10 1.964 N10- Co77-N14 91.6 N14- Co77-N10-C7 178.4
Co77-N11 1.821 N11- Co77-N14 178.9 C12-N10-Co77-N11 179.2
Co77-N23 1.961 N23- Co77-N11 92.6 C16-N23-Co77-N11 178.6
Co77-N14 1.831 N14- Co77-N23 88.7 N23-Co77-N14-C13 179.2
Co77-Cl78 2.124 Cl78- Co77-Cl79 179.5 N23-Co77-N14-C15 0.5
Co77-Cl79 2.023 – – – –

Table 5 Selectded optimized geometrical parameters of obtained by B3LYP/6-31 density functional calculations ([Ni(C36H31N9)Cl2], [Zn(C36H31N9)Cl2] and
[Co(C36H31N9)Cl2])
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Metal Complexes HOMO LUMO DE g/eV r/eV v x e

Isatin Schiff base ligand –6.9964 –0.9967 –5.9997 6.40377 0.15616 –7.4948 28.0859 0.03561
[Cu(C36H31N9)Cl2] –6.04 –6.4544 0.41442 5.50173 0.18176 13.992 97.8882 0.01022
[Co(C36H31N9)Cl2] –8.0783 –8.2685 0.1902 3.70936 0.26959 8.96538 40.189 0.02488
[Ni(C36H31N9)Cl2] –6.3692 –1.1271 –5.2421 6.20673 0.16112 11.0187 60.7062 0.01647
[Zn(C36H31N9)Cl2] –6.7763 –2.1181 –4.6582 6.20673 0.16112 11.0187 60.7062 0.01647

Table 6 Quantum chemical parameters of metal complexes

4 Conclusion References

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