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J. Env. Bio-Sci., 2019: Vol. 33 (2): 291-302 ISSN 0973-6913 (Print), ISSN 0976-3384 (On Line)

SPECTRAL AND BIOLOGICAL PROFILE OF COMPLEXES OF 2, 4, 5-

TRIMETHOXYBENZALDEHYDE -S - BENZYLDITHIOCARBAZONE
Dayanand Prasad, Deepak Kumar1, Amit Kumar, B. N. Subhs, Vijay Kumar2 and Shivadhar Sharma*
1-
University Deptt. of Chemistry, Magadh University, Bodhgaya - 824234
2-
P. G. Deptt. of Chemistry, R. N. College, Hazipur.
B. R. A. Bihar University, Muzaffarpur
Email*: sharma.shivadhar@gmail.com
Received: 04-07-2019 Accepted: 25-12-2019
2,4,5-trimethoxybenzaldehyde was condensed with S-benzyldithiocarbazate to produce the Schiff base 2,4,5-trimethoxy
benzaldehyde-S-benzyldithiocarbazone, henceforth abbreviated as BBTC, which was used for complexation with Mn(II), Fe(II) and
Co(II). The complexes were formulated as M(BBTC)2X2 where X is Cl-, NO3- and CH3COO-. The FTIR spectra of complexes in
comparison to that of free ligand suggested the coordination through azomethine nitrogen and thion sulphur forming six membered
chelating with metal ion. The magnetic susceptibility and electronic spectral bands revealed octahedral symmetry (Oh) around
Mn(II) but tetragonally distorted octahedral symmetry (D4h) of Fe(II) and Co(II) complexes. The positive value of Dt for Fe(II) (68.42-
135.2 cm-1) and Co(II) (263-280 cm-1) clearly indicated elongation along z-axis in these complexes which was also supported by the
less value of Dq(z) than Dq(xy) for the complexes. The ligand as well as it complexes have been found active against the bacteria
Escherichia coli and Staphylococcus aureus.
Key words: D4h, Staphylococcus aureus, Racah Parameter B, C and Dt.

The synthesis, spectral investigation and biological activities
of carbazones, thiocarbazones and their metal complexes have
extensively been studied because of their wide variation in
modes of co-ordination, stereochemistry and beneficial
pharmacological activities [1-3]. Thiocarbazones have also been
reported as interesting chromogenic reagent that gives intense
coloured complexes, shows more bathochromic shift, more
sensitivity and more selectivity. That is why this field has
attracted the considerable attention of inorganic chemists [4-
9]. Schiff's bases of carbazones and thiocarbazones are very
good chelating agents. As chelation causes drastic changes
in the biological properties of the ligands as well as the metal
moiety, such complexes have been found potentially,
antibacterial, antifungal, anti-cancer etc [10-16]. Due to
pharmaceutical properties of carbazones and thiosemi-
carbazones which are frequently higher for metal complexes
than the free ligands, they have extensively been studied in
recent years [17-20]. Keeping the vasts spectrum of fascinating
properties of carbazones and thiocarbazones complexes and
in continuation of our previous work [21-26], we report here the
spectral and biological profile of complexes of 2,4,5-
trimethoxybenzaldehyde-S-benzyldehydedi-thiocarbazone
(BBTC).
2,4,5-trimethoxybenzaldehyde were procured from Lupin and
S-benzyldithiocarbazate was procured from Merk. The two
precursor were condensed together to produce the required
ligand according to the method reported by Md. A. Islam et al.
0.01 mole (1.96 g) of 2,4,5-trimethoxybenzaldehyde and 0.01
mole (1.98 g) of S-benzyldithiocarbazate were dissolved
together in 30 ml of ethanol and about 2 ml of conc. H2SO4
was added to it. The resulting solution was refluxed on water
bath using air condenser for about four hours, where by yellow
turbidity appeared which got solidified after living over night. It
was filtered and solid was recrystallized in ethanol acetone
mixture and dried in desicator on anhydrous CaCl2. The m.p.
was recorded 184°C and the yield was 79%. It has been given
below.

MATERIAL AND METHODS

All the reagents used were of Anal-R-grade. The precursor

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 PRASAD, KUMAR, KUMAR, SUBHS, KUMAR AND SHARMA
The ligand has been used for complexation with Mn(II), Fe(II)
and Co(II) metal ions by used method of reflux. The ligand as
well as complexes were microanalysed by Perkin-Elmer-2400-
CHN elemental analyser. Mn(II) and Co(II) were estimated
gravimetrically while Fe(II) was estimated volumetrically after
decomposition of the complexes. The FTIR spectra of the ligand
and complexes were recorded on Perkin-Elmer-FTIR
spectrometer using KBr are disc between 4000 to 400 cm-1.
The magnetic susceptibility of complexes has been determined
by Gouy's balance at room temperature using mercuric
tetrathiocyanatocobaltate(II) as calibrant. The electronic spectra
of metal complexes were recorded on Shimadzu UV-Visible
spectrophotometer (UV-160). The molar conductivity of
complexes was determined in DMF solution 10 -3 M
concentration using Toshiniwal CL-01-06 conductivity bridge.
The ligand as well as complexes were assayed against the
bacteria Bascillus subtills and Klebsiella pneumoniae using
Ciprofloxacin as reference.
RESULTS AND DISCUSSIONS
The percentage composition of ligand and its complexes has
been given in Table-1.
The extremely low value of conductivity (18-23 ohm-1 cm2 mol-1)
of complexes clearly indicates their nonelectrolytic nature [28-
30]. The percentage composition and molar conductivity of
complexes reveal their formation as [ML2X2] where, M = Mn(II),
Fe(II) and Co(II), L = BBTC and X = Cl-, NO3- and CH3COO-
FTIR-SPECTRAL STUDY: The free ligand absorbs at 3455 cm
1
which is assigned to ν N-H [31-33] stretching vibration of the
ligand, which remains intact in complexes. It indicates that ν N-
, nitrogen of the ligand is not involved in coordination. The free
ligand absorbs at 2620 cm-1 due to  C  S  CH 2 vibration which
H
doesn't undergo any change in complexes, which is indicative
of non participation of thio ether group of the ligand in
coordination. A medium band appears at 1650 cm-1, which
undergoes negative shift by 32-35 cm-1 and appears at 1615-
1650 cm-1 in the FTIR spectra of complexes. It is a distinct
indication of co-ordination through azomethine nitrogen of the
ligand in complexes [34-36]. The coordination through
azomethine nitrogen of the ligand is further supported by an
increase by 15 cm-1 in absorption frequency of ν N-N which
absorbs at 1013 cm-1 in FTIR spectrum of free ligand [37]. The
methoxy group of free ligand absorbs at 1160 cm-1 with medium
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intensity and remains almost intact in the spectra of
complexes. It shows the non-participation of methoxy oxygen
of ligand in co-ordination. The medium band appearing at
1045 cm-1 due to ν C-S stretching vibration of free ligand
undergoes red shift appearing at 1010-1020 cm-1 in complexes
which indicates coordination through thionyl sulphur of the
ligand to the metal ions [38]. The coordination through sulphur
and azomethine nitrogen of the ligand is furthur supported by
the appearance of new band at 530-535 cm-1 due to ν M-N
and 445-450 cm-1 due to ν M-S in the FTIR spectra of the
complexes [39]. In addition to these bands some new bands
appear in complexes. In complexes number 1, 4 and 7 new
band appears at 420-425 cm-1 due to ν M-Cl stretching
showing the presence of chloride in their co-ordination
sphere[40]. In complexes number 2, 5 and 8 two new bands
appear at 1380-1384 cm-1 and 840-848 cm-1, which shows
the presence of mono co-ordinated NO3- ion in these
complexes [41]. The new bands appearing at 1560-1565 cm-
1
and 1320-1330 cm-1 in FTIR spectra of complexes no. 3, 6
and 9 may be attributed to ν asyCOO- and ν syCOO- respectively
[42]. The between symmetric and asymmetric vibrations of
acetate is more than 200 cm-1 which is typical of monodentate
co-ordination of acetato group in these complexes [43]. The
tabular form of FTIR bands in ligand and complexes have
been presented in table-2 and the graphs have also been
presented in Fig. 1 to 14.
MAGNETIC MOMENT AND ELECTRONIC SPECTRA OF
- COMPLEXES : Magnetic moment of Mn(II) complexes are
found 5.80-5.83 BM. The values are very close to the magnetic
moment corresponding to five unpaired electrons. This is
indicative of the fact that Mn++ complexes are high spin
magnetically dilute octahedral complexes [44]. The slightly
low value of magnetic moment may be due to spin-orbit
coupling, which further restricts the spin as well as orbital
motion of the electron to the little extent. The Mn(II) complexes
display four very weak bands in their electronic spectra. The
bands have been given in Table-3.
The weak bands of electronic spectra of Mn(II) complexes
are assigned to the following spin forbidden transitions, ν 1
= 6A1g 4T1g (4G), ν 2 = 6A1g  4T2g or 4A1g or 4Eg (4G), ν 3
= 6A1g  4Eg (4D) and ν 4 = 6A1g  4T1g (4P)
Using Tanabe-Sugano diagram the values of different crystal
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Table 1: % Composition, Physical properties and molar conductivity of ligand

and complexes.

Table 2: FTIR bands in Ligand and complexes (in cm-1)

 PRASAD, KUMAR, KUMAR, SUBHS, KUMAR AND SHARMA (294)

Table 3: Electronic Spectral bands (cm-1) and Magnetic moment of Mn(II) complexes

Table 4: The values of crystal Field parameters for Mn(II) Complexes

Sl. Complexes 2 Dq(cm–1) B(cm –1 ) C(cm –1) C/B 

1
I [Mn(BBTC) 2Cl2] 1.35 1254.442 896.03 3098 3.45413 6.66354

II [Mn(BBTC)2(NO3) 2] 1.34017 1649.238 916.243 3005.51 3.2802 4.55795

III [Mn(BBTC) 2(CH3COO)2] 1.33022 1427.450 892.156 3057.68 3.4273 7.06699

Table 5: Electronic Spectral bands (cm-1) and Magnetic moment of Fe(II) complexes

Table 6: Electronic Spectral bands (cm-1) and Magnetic moment of Fe(II) complexes
Sl. Complexes Dq (x y ) Dq (z) Ds Dt
(cm – 1 ) (cm – 1 ) (cm – 1 ) (cm – 1 )
I [Fe(BBTC) 2 Cl 2 ] 1927 1690.4 3042 135.2
II [Fe(BBTC) 2 (NO 3 ) 2 ] 1900 1766.72 2983.6 76.16
III [Fe(BBTC) 2 (CH 3 COO) 2 ] 1870 1750.00 2950.70 68.42
Table 7: Electronic Spectral bands and Magnetic moment of Co(II) complexes

Table 8: Values of various crystal field parameter of Co(II) complexes

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field parameters have been derived and values have been
presented in Table- 4.
The ratio of Racah Parameter C/B derived for Mn(II) complexes
(3.28-3.45) is very close to the theoretical value (3.5)[45]. The
values of different crystal field parameters support octahedral
geometry around Mn(II) in these complexes [30, 46].
The magnetic moment of Fe(II) complexes exhibit magnetic
moment 5.00-5.10 BM, which shows the presence of four
unpaired electrons in the complexes. The values are a bit higher
than that corresponding to four unpaired electrons (4.89 BM)
which may be attributed to the ground state term 5T2g which
being orbitally degenerate contributes to the magnetic moment
of six coordinate Fe(II) complexes. The magnetic moment of
six coordinate Fe(II) complexes also show enhancement due
to deviation from octahedral symmetry [47-49]. The Fe(II)
complexes display three bands in their electronic spectra which
is indicative of tetragonal distortion in octahedral symmetry of
Fe(II) complexes. Under the influence of tetragonal distortion
both the ground state crystal field terms 5T2g and the excited
crystal field term 5Eg of its ground term 5D undergo further
splitting causing the possibility of three spin allowed transition
bands. The electronic spectral bands [50] and their assignment
have been presented in Table - 5.
These bands were assigned to the following spin allowed
transitions, 1  5Eg  5B2g, 2  5Eg  5A1g and  3  E g  B1 g
5 5
On the basis of these transitions and energy associated with
different transitions the various crystal field parameters have
been derived and values have been presented on Table - 6.
From the table it is obvious that Dq(z) for all the complexes is
less than Dq(xy) which shows that the axial ligands are slightly
away from the metal ion in respect of the planer ligands in all
the complexes. It predicts the tetragonally elongated
octahedral symmetry (D4h) for all the Fe(II) complexes. The
elongation along Z-axis is further supported by the positive
value of the radial integral Dt for all the Fe(II) complexes [25].
ELECTRONIC SPECTRA OF Co(II) : The magnetic moment
of Co(II) complexes has been found 4.72 - 4.79 BM. Co(II) is a
d7 system having three unpaired electrons and hence the spin
only value of magnetic moment is expected to be 3.87 BM.
The abnormality in the magnetic moment of Co(II) complexes
may be attributed to 4T1g ground state crystal field term in
octahedral symmetry which appreciably contribute to the
magnetic moment of Co(II) complexes in octahedral symmetry
[23,51,52]. The electronic spectra of Co(II) complexes display
four bands which has been given in Table - 7.
The bands have been assigned to the following spin allowed
transitions,  2  Eg  B2 g ,  3  Eg  Eg ,
4 a 4 4 a 4 b
 4  4 E ga  4 B1g and  5  4 E ga  4 E gc
The first band ν 1 due to 4 E ga  4 A 2a g is not
observed due to small gap between the two levels causing
absorption energy in I.R. range. The value of 10Dq(xy) has been
derived from ν 4 - ν 2 and Dt has been derived from 354 (   ) ,
Dq(xy) was derived from the popular equation, Dt = 7 Dq  Dq .
3 2
4
( xy ) ( z)
The values of the different crystal field parameter derived from
the spectral bands have been presented in Table - 8.
The electronic spectral graph of Mn(II), Fe(II) & Co(II) complexes
may be seen in Figures 12-14.
From the values of Ds and Dt the value of ν 1 has been derived
which were found 6,694 - 6,919 cm-1, which falls in I.R. region.
The +ve value of Dt and Ds are indicative of tetragonally elongated
octahedral geometry of all the Co(II) complexes [53,54]. The
tetragonal elongation along z-axis in all Co(II) complexes is
also supported by the smaller value of Dq(z) than Dq(xy) [55,56].
Antimicrobial activity: The ligand as well as its metal
complexes were screened against bacterial species
Escherichia coli and Staphylococcus aureus using
ciprofloxacin as reference for the evaluation of their antibacterial
activity. The bacteria was incubated for 24 hours at 35°C and
the activity was determined by measuring the diameter of
inhibition zone by agur diffusion method. The results have been
shown in Table - 9. From the table it may be inferred that the
free ligand is active against both E. Coli and S. aureus, but it
is less active than the standard ciprofloxacin. The metal
complexes of the ligand are found more active against both,
E. Coli and S. aureus strains. The positive effect of almost all
the complexes is comparable to ciprofloxacin.
The grater inhibitory effect of metal complexes than the ligand
for the bacterial strains may be attributed to overtone concept
and chelation theory [57-59].
CONCLUSION
The ligand BBTC is found to act as neutral bidentate one
coordinating through azomethine nitrogen and thionic sulphur.
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 PRASAD, KUMAR, KUMAR, SUBHS, KUMAR AND SHARMA (300)

The positions along z-axis are occupied by chloride or nitrate

Grants Commission for granting Rajiv Gandhi National
or acetate ions. All the complexes of Mn(II), Fe(II) and Co(II)
Fellowship vide Registration ID : RGNF-2017-18-SC-BIH-41422.
are found to possess D4h symmetry with elongation along z-
Authors' are thankful to Prof. S. K. Singh, Head, P. G.
axis. The free ligand and its complexes are found active against
Department of Zoology for allowing the microbiological lab of
E. Coli and S. aureus. The antibacterial of free ligand is found
his department to carry out the antimicrobial study.
to have enhanced after complexation with metals.
REFERENCES
ACKNOWLEDGEMENTS
1. J. P. Holland, F. I. Albrithio, H. M. Betts, P. D. Bonnitcha, P. Burka, M.
One of the author, Deepak Kumar is thankful to University Christlieb, G. C. Churchill, A. R. Cowlry, J. R. Dilworth, P. S. Donnelly,
(301) SPECTRAL AND BIOLOGICAL PROFILE OF COMPLEXES OF 2, 4, 5-TRIMETHOXYBENZALDEHYDE

Table 9: Zone of Inhibition of Ligand and Complexes

Ciprofloxacin Ciprofloxacin
E. Coli Test zone S. aureus Test zone
Sl. Test Compound Control zone of Control zone of
of Inhibition (mm) of Inhibition (mm)
Inhibition (mm) Inhibition (mm)
1 BBTC (Ligand) 25 35 26 34
2 [Mn(BBTC) 2Cl 2] 34.6 28 42 30
3 [Mn(BBTC) 2(NO 3 )2 ] 33 35 37 32
4 [Mn(BBTC) 2(CH 3COO)2 ] 29 24 31 30
5 [Fe(BBTC) 2Cl 2] 31 32 34 32
6 [Fe(BBTC) 2(NO 3 )2] 30.8 33 32 30
7 [Fe(BBTC) 2(CH 3COO)2 ] 28.9 33 30 31
8 [Co(BBTC) 2Cl 2] 26.4 30 29 30
9 [Co(BBTC) 2(NO 3 )2 ] 26 31 28.8 31
10 [Co(BBTC) 2(CH 3COO)2 ] 26 31 28.6 32

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