Spectrochimica Acta Part A 94 (2012) 312317

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

New hexadentate macrocyclic ligand and their copper(II) and nickel(II)

complexes: Spectral, magnetic, electrochemical, thermal, molecular modeling
and antimicrobial studies
Sulekh Chandra a, , Ruchi a , Kushal Qanungo b , Saroj. K. Sharma b
a
b

Department of Chemistry, Zakir Husain College (University of Delhi), J.L. Nehru Marg, New Delhi 110002, India
Department of Applied Science and Humanities, FET, Mody Institute of Technology and Science, Lakshmangarh 332311, Rajasthan, India

a r t i c l e

i n f o

Article history:
Received 28 July 2011
Received in revised form
16 November 2011
Accepted 15 December 2011
Keywords:
Macrocycles
Ni(II) and Cu(II) complexes
UVvis
EPR spectra
Molecular modeling
Cyclic voltammetry

a b s t r a c t
Ni(II) and Cu(II) complexes were synthesized with a hexadentate macrocyclic ligand [3,4,8,9tetraoxo2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L)] and characterized by elemental analysis,
molar conductance measurements, mass, NMR, IR, electronic, EPR spectral, thermal and molecular modeling studies. All the complexes are 1:2 electrolytes in nature and may be formulated as [M(L)]X2 [where,
M = Ni(II) and Cu(II) and X = Cl , NO3 , SO4 2 , CH3 COO ]. On the basis of IR, electronic and EPR spectral
studies an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II)
complexes. The antimicrobial activities and LD50 values of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against two different species of bacteria and plant pathogenic
fungi.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The eld of coordination chemistry of tetraaza macrocycles
has been studied extensively [15]. Macrocyclic compounds are
similar in structure and reactions to many naturally occurring
compounds, which are known to exhibit selective cation complexation [6,7]. Investigations of transition metal complexes with the
cyclic polyamine ligands are of current interest because they are
used as antiviral drugs [810] and as catalysts for various reactions (e.g., epoxidation or hydrolysis of DNA [1113]) and can
bind dioxygen [14,15]. The chemical properties of macrocyclic
complexes can be tuned to force metal ions to adopt unusual coordination geometry. Transition metal macrocyclic complexes have
been received much attention as an active part of metalloenzymes
[16] as biomimic model compounds [17] due to their resemblance with natural proteins like hemerythrin and enzymes. Also,
Schiff-bases have played an important role in the development
of coordination chemistry as they readily form stable complexes
with most of the transition metals. Synthesis of transition metal
complexes of new aza macrocycles with different cavity sizes,
donor types, ring substituents, etc., under different experimental

Corresponding author. Tel.: +91 11 22911267; fax: +91 11 23215906.

E-mail address: schandra 00@yahoo.com (S. Chandra).
1386-1425/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2011.12.028

conditions have resulted in a large number and variety of compounds [1822]. Because of the numerous areas of chemistry where
aza-macrocyclic complexes have found a niche, the preparation of
new macrocyclic ligands with ever more elaborate structures is also
a vital area of research. In the present paper we report the synthesis and characterization of nickel(II) and copper(II) complexes
of 3,4,8,9tetraoxo-2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L) (Scheme 1).

2. Experimental
All the chemicals used were of Anala R grade and procured from
SigmaAldrich. Metal salts were purchased from E. Merck and were
used as received.

2.1. Synthesis of ligand (L)

A hot ethanolic solution (20 mL) of pyridine 2,6 dicarboxylic acid
(3.34 g, 0.02 mol), and a hot ethanolic solution (20 mL) of thiourea
(1.52 g, 0.02 mol) are mixed slowly with constant stirring. The mixture is reuxed at 60 C (5) for 810 h in presence of few drops
of concentrated HCl (pH
= 34). On cooling, a solid yellow coloured
precipitate is formed, which is ltered, washed with cold EtOH,
and dried under vacuum over P4 O10. Yield: 75%, m.p: 180 C.

S. Chandra et al. / Spectrochimica Acta Part A 94 (2012) 312317

313

Scheme 1. Synthesis of ligand (L).

Elemental analysis found: C 46.43; H 3.46; N 20.34, Calculated for

C16 H10 N6 O4 S2 : C 46.37; H 2.41; N 20.28%.
2.2. Synthesis of complexes
A hot ethanolic solution (20 mL) of ligand L (0.001 mol, 0.82 g)
and hot ethanolic solution (20 mL) of corresponding metal salts
(0.001 mol) are mixed together with constant stirring. The mixture
was heated for 59 h at 6085 C. On cooling a coloured complex
is precipitated out. It is ltered, washed with cold EtOH and dried
under vacuum over P4 O10 [Fig. 1].

by MOPAC 2007 program in gas phase using level of theory at

department of Applied Science and Humanities, FET, Mody Institute of Technology and Science Lakshmangarh Rajasthan. Cyclic
voltammetric measurements were carried out using a BAS CV
50 W electrochemical analysis system at Delhi University. Thermal gravimetric analysis was carried out on model DTG60 thermal
gravimetric analyzer. Differential scanning calorimetry curves
were obtained using DSC Q200 V23.10 Build 79 model at USIC (Delhi
University). Antimicrobial studies of the compounds were carried
out at plant pathology department IARI (Delhi).
3. Result and discussion

2.3. Physical measurements

Elemental analysis of C, H and N were performed on a CarloErba EA1106 elemental analyzer. Molar conductance was evaluated
on an ELICO Conductivity Bridge (Type CM82T). Magnetic susceptibility was measured at room temperature on a Gouy balance
using CuSO4 5H2 O as a callibrant. IR spectra were recorded on
PerkinElmer-137 instrument as KBr pallets at Delhi University.
Electronic spectra were recorded in DMSO on a Shimadzu UV
mini-1240 spectrometer. 1 H NMR and 13 C NMR (300 MHz) spectra were recorded on a Bruker Advanced DPX-300 spectrometer
using D2 O as a solvent at IIT Delhi. EPR spectra of all the complexes were recorded at room temperature (RT) and liquid nitrogen
temperature (LNT) on an E4-EPR spectrometer using the DDPH as
the g-marker at SAIF, IIT (Bombay). The complexes were modeled

On the basis of elemental analysis, the complexes were found

to have the composition, as shown in Table 1. The molar conductance measurements of the complexes in DMSO correspond to
their 1:2 electrolytes in nature. These complexes may be formulated as [M(L)]X2 [where, M = Ni(II) and Cu(II) and X = Cl , NO3 ,
SO4 2 , CH3 COO ]. The IR spectrum of ligand (L) shows bands
mainly in the regions 1740, 1616, 1579, 1262, and 691 cm1 ,
which may be assigned to amide I [(C O)], [(CSNH)], amide
II [(CN) + (NH)], amide III [(NH)] and amide IV wagging
[(C O)] vibrations, respectively. A sharp band at 3185 cm1 shows
the presence of secondary  (NH) group. The IR band due to [(C N)
and (C C)] vibration from the pyridine ring are appeared at1542
and 1468 cm1 [23]. The mass spectrum of ligand (L) shows the
molecular ion peak at m/z 415 amu [M+ ] conrm the proposed formula corresponding to the macrocyclic moiety [(C16 H14 N6 O4 S2 )].
Mass spectrum [Fig. 2] shows the molecular ion peak at 393 amu.
It also shows a series of peaks, i.e. 317, 326, 344, 363, 347, 394,
416, 456, 527 amu, etc. corresponding to various fragments. Their
intensity conveys the idea of the stability of fragments. 1 H NMR
(D2 O) 8.368.53 (2d, 2H, ArH); 7.947 8.138.22 (1t, 2H, ArH);
(s, 4H, CO-NH) ppm [Fig. 3]. 13 C NMR (D2 O) 181 (C S); 172.501
(C O); 152.194, 132.627, 117.260 (Ar); ppm. All compounds gave
satisfactory elemental analysis. The higher melting points of the
complexes than the metal free ligand suggests the thermal stability
of the complexes.
3.1. Experimental/materials and methods section

Fig. 1. Structure of complexes with ligand (L).

The ligand molecule was modeled by MOPAC 2007 [24] program

in gas phase using PM6 level of theory [25]. The molecule was rst
preoptimised using molecular mechanics methods. Several cycles
of energy minimization had to be carried out. Geometry was optimized by using Eigen Vector. The Root Mean Square Gradient for the
molecule was 0.00876. Self Consistent Field was achieved. The nal

314

S. Chandra et al. / Spectrochimica Acta Part A 94 (2012) 312317

Table 1
Molar conductance and elemental analysis data of the complexes.
Complexes

[Ni(L)]Cl2
NiC16 H14 N6 O4 S2 Cl2
[Ni(L)](NO3 )2
NiC16 H14 N8 O10 S2
[Ni(L)]SO4
NiC16 H14 N6 O10 S3
[Ni(L)](CH3 COO)2
NiC18 H20 N6 O8 S2
[Cu(L)]Cl2
CuC16 H14 N6 O4 S2 Cl2
[Cu(L)](NO3 )2
CuC16 H14 N8 O10 S2
[Cu(L)]SO4
CuC16 H14 N6 O10 S3
[Cu(L)](CH3 COO)2
CuC18 H20 N6 O8 S2

Molar conductance
(1 cm2 mol1 )

Colour

Yield (%)

m.p./dec. ( C)

Elemental analysis%, found (calculated %)

35.89
(35.80)
32.21 (32.17)

1.90
(1.86)
1.61
(1.67)
1.79
(1.75)
2.75
(2.70)
1.88
(1.82)
1.62
(1.66)
1.77
(1.74)
1.71
(1.67)

15.62
(15.66)
18.70
(18.76)
14.71
(14.77)
14.27
(14.21)
15.36
(15.31)
18.65
(18.62)
14.71
(14.64)
14.15
(14.10)

176

Green

64

270

10.88 (10.94)

188

Green

60

202

192

Green

58

210

9.88
(9.83)
10.27 (10.32)

191

Green

62

255

158

Light
Blue
Sky
Blue
Blue

67

260

65

254

69

250

63

258

161
166
170

Shiny
Blue

heat of formation was 30.06979 kcal/mol. Attempts to optimize

the metal complexes were not successful.

4. Results and discussion

The ligand adopts a chair like conformation with the two pyridine rings is parallel to each other. The electrostatic potential
surface of molecule is shown in Fig. 4. Notice that the electron
density is concentrated on the sulphur and oxygen atoms in the
molecule (red shading). The ligand has 70 lled molecular orbitals,
and the orbitals of the HOMO and LUMO level are shown in Fig. 5a
and b. Notice that the HOMO orbitals are concentrated on the
sulphur atoms while the LUMO orbitals are concentrated on the
carbons of the pyridine rings. The HOMO and LUMO energy was
found to be 9.238 eV and 1.743 eV.
C
The pyridine C (sp2 )N(sp2 ) bond lengths are 1.36 A,
2
The C(sp2 ) O(sp2 ) bonds are 1.21
(sp )C(sp2 ) is 1.41 and 1.40 A.
All bond lengths are close
The C(sp3 ) S(sp2 ) is 1.64 A.
and 1.20 A.
to standard bond lengths.

Fig. 4. Electrostatic potential surface of the PM6 geometry optimised structure (red
negative, green neutral and blue positive) of the ligand. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version
of the article.)

9.89
(9.93)
11.51 (11.57)
10.61
(10.55)
11.02
(11.07)
10.60
(10.66)

33.81
(33.76)
40.67 (40.60)
35.05
(35.00)
31.99 (31.92)
33.41 (33.47)
33.15 (32.24)

4.1. IR spectra of the complexes

On complexation positions of (NH) , (amide II and III) and
[(C N)py, (CC)py] bands [26,27] are shifted toward lower or
higher side; this indicates that the nitrogen of NH group and
pyridine are participated in coordination. The band due to thione
sulphur is at same position as in ligand; this indicates that there is
no coordination with sulphur. Thus it is implied that ligands [L] act
as hexadentate [28].
The IR spectra of nitrate complexes of Ni(II) and Cu(II) with
L show broad absorption band in the region of 13901333 cm1 ,
which corresponds to uncoordinated nitrate group. Thus the nitrate

Fig. 5. (a) HOMO orbitals of the PM6 geometry optimised structure of the ligand.
(b) LUMO orbitals of the PM6 geometry optimised structure of the ligand.

S. Chandra et al. / Spectrochimica Acta Part A 94 (2012) 312317

Table 2
Magnetic moment and electronic spectral data of the complexes.

315

Table 5
Electrochemical data of Cu(II) complexes in DMSO.

Complexes

eff (B.M.)

max (cm1 )

Complexes

Ec (mV)

Ea (mV)

E1/2 (mV)

[Ni(L)]Cl2
[Ni(L)](NO3 )2
[Ni(L)]SO4
[Ni(L)](CH3 COO)2
[Cu(L)]Cl2
[Cu(L)](NO3 )2
[Cu(L)]SO4
[Cu(L)](CH3 COO)2

2.91
2.97
3.08
2.97
1.95
1.94
2.04
1.96

9718, 15337,19646, 30395

9285, 14792, 18621, 31847
9661, 14792, 18621, 37174
9293, 14880, 18621, 33783
9587, 12562, 22939, 32467
12804, 22876, 16276
12836, 18621, 27777, 34722
13245, 18621, 22827, 32467

[Cu(L)]SO4
[Cu(L)](CH3 COO)2

700
410

95
270

340

Table 6
Antibacterial activities data of the ligand (L) and their [Ni(L)](CH3 COO)2 ,
[Cu(L)](CH3 COO)2 complexes.
Bacterial inhibition (%) (conc. in g mL1 )

Compounds

Basillus subtilis

Table 3
Ligand eld parameters of Ni(II) complexes.
1

Complexes

Dq

B (cm

[Ni(L)]Cl2
[Ni(L)](NO3 )2
[Ni(L)]SO4
[Ni(L)](CH3 COO)2

971
928
966
929

388
295
370
374

LFSE (kJ mol

0.37
0.35
0.28
0.35

139
133
138
133

L
[Ni(L)](CH3 COO)2
[Cu(L)](CH3 COO)2
Streptomycin

Xenthomonas compestris

0.05

0.075

0.1

15.29
16.47
32.94

17.64
20
37.64

22.35
23.52
41.17

0.05

0.075

0.1

16.47
21.17
80

20
23.52
85.88

25.88
31.76
91.76

B. subtilis: Cu > Ni > L.

X. compestris: Cu >Ni > L.

group is uncoordinated and present outside the coordination

sphere [29].
The sulphato complexes of Ni(II) and Cu(II) with L show sharp
band in the region of 11081165 cm1 [30] and there is no splitting
of 3 and 5 which indicates that SO4 2 ion is uncoordinated to the
metal ion.
The IR spectra of acetate complexes of Ni(II) and Cu(II) with
ligand L show absorption bands in the region of 15541448 (1 ),
14111306 cm1 (2 ). This indicates that the acetate group is uncoordinated and present outside the coordination sphere [31].
4.2. Electronic spectra of the complexes
Magnetic moment of Ni(II) complexes at room temperature lies
in the range 2.913.08 BM, (Table 2). Electronic spectra of complexes show bands in the region of 92939661, 14,79215,337 and
18,62119,647 cm1 . An examination of these bands indicates that
the complexes have an octahedral geometry and might possess D4h
symmetry [32]. The ground state of Ni(II) in an octahedral coordination is 3 A2g . Thus, these bands may be assigned to the three spin
allowed 3 A2g (F) 3 T2g (F) (1 ), 3 A2g (F) 3 T1g (F) (2 ) and 3 A2g
(F) 3 T1g (P) (3 ) transitions, respectively [33,34], corresponding
to an octahedral geometry of Ni(II) complexes.
Magnetic moment of Cu(II) complexes at room temperature
lies in the range 1.942.04 BM (Table 2). The electronic spectra of the complexes show three bands in range of 958713,245,
16,27618,621 and 22,87627,777 cm1 which can be assigned to
2B 2A , 2B 2B
2
2
1g
1g
1g
2g and B1g Eg transitions, respectively,
corresponding to tetragonal geometry [35]. Various ligand eld
parameters were calculated for Ni(II) complexes and are listed in
Table 3.

at liquid nitrogen temperature (LNT). A polycrystalline spectrum

shows a well-resolved anisotroic broad signal [36]. The analysis
of spectra give g|| = 2.092.24 and g = 2.022.11 (Table 4). The
trend g|| > g > 2.0023, observed for the complexes indicate that
the unpaired electron is localized in the dx2 y2 orbital of the Cu(II)
ion and spectral gures are characteristic for the axial symmetry.
Tetragonally elongated structure are thus conrmed for the Cu(II)
complexes [37]. G = (g|| 2)/(g 2), which is the measurement of
the exchange interaction between the metal centers in a solid sample of the complex has also been calculated. According to Hathway
and Billing [38], if G > 4, the exchange interaction is negligible but
G < 4 indicates the considerable exchange interaction in the solid
complexes. The complexes reported here gives the G value in the
range 1.313.63, which is < 4, indicating exchange interaction in the
solid complexes.
4.4. Cyclic voltammetric
The cyclic voltammograms of all the complexes are recorded
in DMSO. Tetra butyl ammonium perchlorate (0.1 M) is used as
the supporting electrolyte. A three electrode conguration composed of Pt working electrode (3.1 mm2 area), a Pt wire counter
electrode, and a Ag/AgNO3 electrode reference electrode are used
for the measurement.
The [Cu(L)](OAc)2 complexes show a quasi reversible redox
wave [Fig. 7] due to the Cu(II)/Cu(I) couple. E1/2 value of this redox
couple is found to be 340 mV. This value is more cathodic than
other Cu(II) complexes [39], which indicate the stability of coordination sphere of Cu(II) (Table 5). In contrast to above complex the
[Cu(L)]SO4 show a irreversible cathodic/anodic wave [Fig. 8] [40].
4.5. Thermal analysis

4.3. EPR spectra of the Cu(II) complexes

EPR spectra of the Cu(II) complexes [Fig. 6] were recorded at
room temperature as polycrystalline samples and in DMSO solution

The thermal stability of the complexes with ligand was investigated using TGA. The thermogravimetric analyses (TGA) were
carried out at a heating rate of 10 C/min in a nitrogen atmosphere

Table 4
EPR spectral data of the Cu(II) complexes in DMSO at room temperature and liquid nitrogen temperature.
Complxes

[Cu(L)]Cl2
[Cu(L)](NO3 )2
[Cu(L)]SO4
[Cu(L)](CH3 COO)2

At RT

At LNT

g1

g2

g3

g||

giso

g1

g2

g3

g||

giso

45
36
96
92

3240
3201
3190
3071

3290
3235
3220
2980

3350
3263
3250
3142

2.09
2.12
2.23
2.21

2.02
2.08
2.09
2.16

2.04
2.10
2.14
2.17

3.63
1.44
2.40
1.31

30
48
36
56

2900
2910
2920
3141

3000
2990
2950
3250

3100
3080
3100
3327

2.24
2.23
2.12
2.07

2.09
2.11
2.08
2.04

2.14
2.15
2.10
2.05

2.48
2.11
1.44
1.78

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S. Chandra et al. / Spectrochimica Acta Part A 94 (2012) 312317

Table 7
Antifungal activities data of the ligand (L) and their [Ni(L)](Cl)2 , [Cu(L)](Cl)2 complexes.
Fungal inhibition (%) (conc. in g mL1 )

Compounds

LD50 value R. solani/R.blast

Rizactonia solani
0.05
L
[Ni(L)](Cl)2
[Cu(L)](Cl)2
Ciplooxamin for
R. solani (standard)
Tricyclozole for
R. blast (standard)

5.88
15.29
10.58

0.075
15.29
20
21.63

Rice blast
0.1
22.35
36.47
31.76

0.5
69.95
85.88
76.47
12

1
100
100
100

0.05
24.70
37.64
29.41

0.075
36.47
45.88
38.82

0.1

0.5

41.17
54.70
43.52

74.11
85.88
76.47

100
100
100

0.2391/0.1766
0.2126/
0.2139/0.01766

28

17

R. solani: Ni > Cu > L.

R. blast: Ni > Cu > L.

over a temperature range of 25500 C. The thermograms of the

complexes of Cu(II) and Ni(II) do not show any peak below 230 C
which indicate that their is no water molecule inside or outside the
coordination sphere. On heating, for the complex of Copper sulphate exhibit mass loss curve beyond 226 C and continues to a
temperature around 243 C and for the complex of Nickel sulphate
exhibit mass loss curve beyond 257 C and continues to a temperature around 291 C, after which the TG becomes parallel to the
temperature axis. The percentage of the residue left was found to
be the respective metal oxide, CuO and NiO [41].
Decomposition reactions are shown below;
243 C

>500 C

[Ni(L)]SO4 [Ni(L)] Nio

SO4

257 C

>500 C

[Cu(L)]SO4 [Cu(L)] CuO

SO4

Graph 1. Comparison of the percentage inhibition of compounds with standard

antibacterial drug at 0.1 ppm concentration.

The dehydration processes are interpreted by endothermic

peaks in DSC curves. DSC curves presented melting process for the
complex of copper acetate at 102.05 C, 193.89 C, 285.39 C and for
the nickel complex at 101.97 C and 180.37 C.
4.6. X-ray diffraction studies for [Ni(L)]SO4 complex
X-ray powder diffraction pattern for [Ni(L)]SO4 complex is
recorded by powder method. Lipsons method [42] has been used
to calculate the lattice constant. These are as follows;
A = 0.0209
B = 0.0429
C = 0.0107
The calculated values for unit dimensions are;
a = 16.8082 A
b = 11.7465 A
c = 7.4814 A

Bacillus sublitis Gram (+) and Xanthomonas compestris Gram () bacteria, as growth inhibitor by the DUAL CULTURE METHOD [45]. NSA
(nutrient sucrose agar) medium (nutrient broth 8 g L1 , sucrose
50 g L1 and agar 18 g L1 ) is used for isolation, cutting and maintenance of bacterial culture. Streptomycin is used as standard drug
[Graph 1]. The results of the antibacterial screening show the order
of percentage inhibition has been observed to be presented in
Table 6. Antibacterial studies data show that metal complexes show
moderate activities as compared to free ligands.
4.7.2. Antifungal screening
The ligand (L) and their complexes with NiCl2 and CuCl2 for antifungal studies were screened against Rhizoctonia solani and Rice
blast fungi, as growth inhibitor by FOOD POISON TECHNIQUE [46].
Potato dextrose agar (39 g L1 ) for Rhizoctonia solani and oat meal
(50 g L1 oatmeal, 20 g L1 agar) sucrose medium for Rice blas are
used for are used for isolation, cutting and maintenance of fungal culture. Amphotericin-B and Tricyclozole are used as standard
drugs [Graph 2]. The results of the antibacterial screening show the
order of percentage inhibition has been observed to be presented
in Table 7. Antifungal studies and their (Probit analysis) LD50 data
show that metal complexes show moderate activities as compared
to free ligands. The Probit analysis studies are shown in Graph 3, 4
and 5.

4.7. Antimicrobial study

The ligand (L), ligand free metal ions and its complexes were
evaluated against different species of bacteria and fungi as per the
procedure reported earlier [43,44]. In both, antibacterial and antifungal studies ligand free metal ions in solution show inhibition
capacity slightly more than the ligand but much less than complexes against all the species under study.
4.7.1. Antibacterial screening
The ligand (L) and their complexes with Ni(CH3 COO)2 and
Cu(CH3 COO)2 for antibacterial studies were screened against

Graph 2. Comparison of the percentage inhibition of compounds with standard

antifungal drugs at 0.5 ppm concentration.

S. Chandra et al. / Spectrochimica Acta Part A 94 (2012) 312317

5. Conclusion
Ni(II) and Cu(II) complexes with a hexadentate macrocyclic ligand have been prepared and characterized. On the basis of above
spectral studies and molecular modeling a distorted octahedral
geometry has been assigned for Ni(II) and tetragonal geometry for
Cu(II) complexes. Various ligand eld and bonding parameters have
been calculated and discussed. Electrochemical, thermal, antimicrobial studies have been discussed.
Acknowledgements
We thank the Principal, Zakir Husain College for providing laboratory facilities, SAIF, IIT (Bombay) for recording ESR spectra and
DRDO, New Delhi for nancial support, the Head, App Sci. and Dean
FET for recording molecular modeling data.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.saa.2011.12.028.
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