Transition Metal Chemistry, 19 (1994) 25-27
Physicochemical studies of (o-vanillin thiosemicarbazonato)-
nickel(II) chelate
Badri V. Agarwala*, Sunita Hingorani ~ and Vanita Puri
Department of P.G. Studies and Research in Chemistry, R.D. University, Jabalpur 482001, India
Chunni L. Khetrapai and Gowda A. Naganagowda
Sophisticated Instruments Facility, Indian Institute of Science, Banffalore-560012, India
Summary
Five- and six-membered rings result from the chelation of
nickel(II) by the dibasic tridentate Schiff base ligand,
o-vanillin thiosemicarbazone(o-VTSC), a new chelate
prepared and characterized. The structural results are
discussed in the light of spectroscopic and other data.
Introduction
The number and diversity of sulphur nitrogen chelating
agents used to prepare new coordination compounds,
have increased recently (~'2~ and thc pronounced biological
activity of the metal chelates obtained from thiosemi-
carbazide has created considerable interest ~3~. The com-
plexes formed with transition metals and uranium with
various thiosemicarbazones and their analogues have
been described earlier (4-m. In this paper thc results of the
i.r., u.v.-vis, spectroscopic investigations, molar conduc-
tance, t.g.a, and n.m.r, data on the nickel chelate of
o-VTSC are reported.
Experimental
Materials
o-vanillin-thiosemicarbazide (SISCO), Ni(OAc)24H20
(E. Merck) and the reagent grade solvent D M F and EtOH
were used as supplied.
Physical measurements
Carbon, hydrogen and nitrogen content were analysed at
the RSIC, Central Drug Research Institute, Lucknow,
India, and nickel content in the laboratory at Jabalpur,
India. 1H n.m.r, spectra of the ligand and chelate were
recorded on a WH-270 F T N M R spectrometer equipped
with an A S P E C T 2000 computer at Bangalore, lndia. The
i.r. spectra were recorded on a Perkin-Elmer model 1430
in the 4 0 0 0 - 2 0 0 c m - t range using CsI pallets and the
electronic spectrum on a Pye-Unicam SP 8-100 spectro-
photometer.
Magnetic susceptibilities were measured by Gouy's
method using Hg[Co(SCN)4] as a calibrant. The con-
ductivity measurements were made on a direct reading
Toshniwal conductivity bridge employing a 10-3M
solution of the chelate in DMF. T.g.a. were made at RSIC
Nagpur employing D u P o n t Instrument.
Presented at 29th ICCC, Lausanne, Switzerland, 1992.
* Author to whom all correspondence should be directed.
t Present Address:Department of Chemical Engineering, Universityof
Florida, FL 32611, USA.
0340-4285 (C) 1994 Chapman & Hall
o-VTSC Ni(II) chelate 25
Nickel( l l ) - o - V T S C chelate
The Schiff base ligand o-VTSC (0.005tool, 1.13g) was
prepared by condensation of o-vanillin with a equimolar
ratio ofthiosemicarbazide ~6)dissolved in 1 : 1 D M F - E t O H
(100 cm 3) and added to an aqueous solution of Ni(OAc)2
(0.005 mol, 1.24 g). The mixture was boiled under reflux
for 6 h and cooled overnight, after which a brown preci-
pitate formed. This was removed by filtration, washed
thoroughly several times with E t O H and EtzO, and
finally dried. The chelate was insoluble in H 2 0 , EtOH,
M e O H and common organic solvents, but soluble in
polar solvents such as DMF, D M S O and Dioxan. The
product was rccrystallizcd from D M F ; m.p. > 360 ~ C.
The chelate is formed in a 1 : 1 stoichiometry, having the
formula [Ni(o-VTSC)H20], as revealed by microanaly-
tical data (Table 1).
Results and discussion
l.r. spectral studies
I.r. spectral data of the ligand and the chelate exhibit
characteristic bands as shown in Table 2. The ligand is
present in the thione form in the solid state and enolizes
in solution during chelation. A specific band (azomethine)
at 1580 c m - 1 confirms the formation of the Schiff base by
condensation ofo-vanillin with thiosemicarbazide (m. The
coordination sites are as follows. (a) Phenolic oxygen: ab-
sence of a v(OH) band at ca. 3420 c m - 1 in the complex
spectrum and the v ( C = O ) shift by 20 25 c m - 1 to higher
wavenumber clearly indicate the deprotonation and sub-
sequent coordination of o-VTSC via phenolic oxygen.
The presence of a v ( M - - O ) band in the far i.r. region
at ca. 590cm -1 further confirms this bonding site.
(b) Azomethine nitrogen: the positive v(C---N) shift by
10cm-1 to 1 5 8 0 c m - t in the ligand and the higher shift
of v ( N - - N ) at ca. 1050cm -1 is observed. New bands
appear duc to the chelate [ v ( C ~ N - - N ~ C ) skeleton] at
ca. 1530cm - l a n d v ( M N) atca. 365cm - ~ f u r t h e r c o n -
firming the participation of azomethine nitrogen ~7).
(c) Thiolic sulphur atom: absence of v ( C z S ) band in the
spectrum of the chelate at 1480 c m - 1 and presence of new
band due to v(C--S) and v ( N i - - O ) at 850 and 580cm -1
respectively confirm that coordination occurs through the
thiolic sulphur atom C8).(d) Coordinated water: presence of
v(OH), 6(HzO ) and 7(HzO) in the i.r. spectrum of chelate
at 3420, 960 and 650 c m - 1 shows the presence of coordi-
nated H 2 0 in the complex (9). The - - O C H 3 group does
not take part in coordination as the v(OCH3) band
observed at ca. 2800 c m - 1 in the ligand remains unaltered
on chelation (~~
26 Agarwala et al. Transition Metal Chemistry, 19 (1994) 25-27

Table 1. Analytical, conductancea and magnetic data for o- is found to be 2.30 B.M., which is intermediate of tetrahedral
VTSC chelate. (3.2-4.1 B.M.) and square planar (diamagnetic) complexes,
suggesting that this chelate shows the rare phenomenon
Compound Found (Calcd.)(%) Am ~eff of spin-state equilibrium between the spin-free tetrahedral
M C H N (B.M.) and the spin-paired square planar configurations (~3). This
o-VTSC b - 48.1 5.0 18.7 - - rules out the possibility of octahedral geometry where
(48.0) (4.9) (18.7) - magnetic moment values lie in the range 2.9-3.3 B.M.
[Ni(o-VTSC).H20] 20.1 37.0 3.4 14.3 3.83 2.23 Similar high spin-low spin equilibrium has been noticed
(20.8) (36.1) (3.7) (14.1) in the nickel(II) complex formed with a macrocyclic tetra-
dentate ligand derived from 2-aminobenzaldehyde by
aMolar conductance, measured in ca. I 0 - 3 M D M F solution and Busch et al. (la) The D4h symmetry is preferred rather than
expressed in o h m - 1 cm 2 m o l - i; bo_VTSC = o-Vanillinthiosemicarbazone: Oh for the complex and a singlet-triplet equilibrium may
C9H11N302S.
Occur.

Table 2. Prominent i.r. spectral data (cm- 1) for o-VTSC and Ni--o-VTSC chelate.

Compound v(NH) v(C=N) v(C--N--N=C) v(N--N) v ( C : S ) v(C--S) v(M--O) v(M--S) v(M--N)

[o-VTSC] 3130 1580 - 1050 1460 . . . .

[Ni(o-VTSC).HzO] 3140 1590 1530 1070 - 850 580 440 390

v(H20) ca. 3480, 5(H20) ca. 1660 and ?(H20) at ca. 680cm-1 in the chelate.

110 0.6 H
lOO ~ I- 275.49~
1 H N I
90 288.96~ t.1291.39~
o~ 80 -8.724% r~1349.21o C
0.4~ o~ i
~" 70 I ~ 377.70~ (I)

o 60 tt/ -~ OCH3 I
H
5o 0.2 g
>
Figure 2. Structure of Ni--o-VTSC chelate.
40 I I \ \\ 788.56oc _ Pi
30 W 50074~ ~
20 I I , I I 150774(c ~ - - ~ ' - - ~ 0.0
100 200 300 400 500 600 700 800
T.g.a.
Temperature (~
The t.g.a, data shows a percentage weight loss of 6.00
Figure 1. T.g.a. of Ni--o-VTSC complex. (calcd 6.40) for N i - - o - V T S C chelate, corresponding to
one molecule of coordinated HzO, which is consistent
with the analytical and i.r. spectral data. The pyrolytic
Electronic spectra and magnetic susceptibilities curve for this chelate is shown in Figure 1.
In the electronic spectrum of o-VTSC, three intense
maxima are observed at 235, 268 and 350nm due to 1H n.m.r, spectra
n - a*, a - a* and n - n* transitions, respectively(11).
The latter two bands show blue shift by 40-60 nm in the 1H n.m.r, spectra of N i - - o - V T S C chelate were recorded
brown coloured nickel(II) chelate. The three bands observed and the spectral lines assigned for all protons with the help
at 420, 570 and 870nm are assigned as 1Bzo*--1A1 o, of the deuterium exchanged spectrum. The chemical shift
values are given in Table 3. The disappearance o f - - N H
1A20*-- 1A1~ and 1E0*- 1Alg transitions, respectively(~2).
and - - O H proton signals in the spectrum clearly shows
The magnetic moment ofmonomeric N i - - o - V T S C chelate
the sites of coordination with nickel. Also the aromatic
protons signals at 6.95 and 7.55 p.p.m, of the ligand have
shifted to 6.90 p.p.m., the proton at 6.75 shifted to 6.45 p.p.m.
Table 3. H a n.m.r, spectral data of o-VTSC and its nickel(II) Olefinic CH shifted from 8.4p.p.m. in the ligand to
chelate. 7.9p.p.m. The - - N H 2 and - - O C H 3 have shifted from
8.0 to 6.35 p.p.m, and 3.8 to 3.75 p.p.m., respectively. The
Nuclei Chem shift (p.p.m.) Chem shift (p.p.m.)
results are in agreement with the proposed structure
nickel(II) chelate o-VTSC
(Figure 2).
Aromatic protons 6.45(0,6.9(d) 6.75(0, 6.95(d),
7.55(d)
Alkene-CH 7.9 8:4 Conclusions
Alkene-NH2 6.35 7.9, 8.1
Alkene-OCH 3 3.75 3.80 The ligand o-VTSC behaves as a dibasic tridentate ligand
Alkene-OH - 11.4 towards nickel(II) and the three bonding sites are con-
Alkene-NH - 9.2 firmed to be phenolic oxygen, azomethine nitrogen and
thiolo sulphur atom based on spectral, magnetic and t.g.a.
Transition Metal Chemistry, 19 (1994) 25-27
studies. The formation of five- and six-membered rings
are shown. The chelate has been evaluated for in vitro
anti-HIV activity and found to be cytotoxic in AIDS
antiviral screen.
Acknowledgements
The authors are grateful to National Institute of Health,
Bethesda, Maryland, USA, for anticancer testing and
their interest in the work.
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(Received 27 N o v e m b e r 1992) T M C 2915