A new Sulphur containing Schiff base ligand and its metal complexes –

synthesis, structural, spectroscopic and antimicrobial studies

P. Saritha Reddy

Department of Chemistry, University college for women, Osmania university,

Hyderabad, Andhra Pradesh, India-500095

INTRODUCTION

 Schiff basses and their metal complexes have attracted a great deal of attention in bio-
chemistry because of their vast applications as anticancer, anti tubercular, anticonvulsant,
insecticidal, antibacterial, antifungal, antiviral, antibiotic, anti-inflammatory and plant
growth regulating agents.
 In recent years there has been considerable interest in the synthesis and use of
functionalized polymers having chelating abilities due to their practical convenience,
operational flexibility and formation of coordination with high metal to polymer bond
energies.

 A class of multidentate ligands developed from symmetric aromatic diketones have

received investigation in our laboratory in view of their potentiality to simultaneously
bind at least two metal ions with the help of two chelating sequences. Such ligands have
been designated as bis-chelating ligands. The metal complexes synthesized from such
ligands have been observed to possess interesting structural features like polymerism,
antiferromagnetism and unusual geometries.
 Literature survey reveals that metal complexes of bis-bindentate oxygen, nitrogen donor
systems have not been much studied. 1,2,4,5 tetra substituted benzenes with all the four
substitutions containing metal binding centres are of great synthetic interest as they can
produce metal complex polymers.
  Res-diacetophenone or 2,4-Dihydroxy-5-acetylacetophenone(DAAP) is a symmetric
bisbidentate, ‘O.O’-‘O.O’ donor and some bis bidentate / multidentate ligands can be
synthesized by condensing H2 – DAAP with different amines. Infact some of such
ligands can be tailor made or designed to drive metal ions into suitable / preferred
coordination geometries.

EXPERIMENTAL

The ligand will be synthesized in the following steps.

1.Synthesis of 2, 4-Dihydroxy-5-acetylacetophenone (DAAP)

HO OH
HO O O
OH
ZnCI2
2 O O C C O

CH3 CH3

Yield 60% M.point 180OC. H2-DAAP is soluble in methanol, chloroform, carbon tetrachloride,
benzene, 1,4dioxane and dimethyl sulfoxide.

2. Synthesis of the ligand derived from 2, 4-Dihydroxy-5-acetylacetophenone and Ortho-

Aminothiophenol
To 0.05mol (9.7g) of H2 — DAAP dissolved in hot methanol, 0.1 mol (12.5ml) of Ortho Amino thio
phenol was added and refluxed for 3 hrs. After the completion of the reaction, water was added to
produce the product. The compound was filtered washed with methanol and Petroleum ether and dried in
vacuum.

Yield 80%
 NH2
HO OH HS
SH
HO OH SH
+ N C C N

O C C O
H3C CH3
H3C CH3

The 1NMR spectrum of the Ligand shows a signal at δ2.5 which corresponds to six protons of
H3C-C=N group. Complex multiplet in the region δ7.2 – 6.4 correspond to benzene protons.The
signal at δ5.4 correspond to SH protons.The signal corresponding to the phenolic OH adjacent to
azomethine moiety is indicated at δ12.6. The D 2O exchange studies also further confirm the
structure. The IR spectrum of the ligand shows the characteristic bands of the vibration
frequencies of the functional groups such as O-H, C=N, C-O, S-H, C=C.

SYNTHESIS OF METAL COMPLEXES

To the methanolic solution of divalent metal chloride(0.0025mol) 0.60g Cobalt(II),

0.59gNickel(II) and 0.43g Copper(II), 0.005mol methanolic solution of the ligand was added in
small amounts to get a clear solution. The pH of the reaction mixture was adjusted to 7 by adding
aqueous ammonia in methanol and the mixture was refluxed for 4 hrs. The colored product
obtained was filtered in hot condition and was washed thoroughly with small amounts of
methanol, petroleum ether and dried in vacuum.

TABLE 1: ANALYTICAL DATA AND PHYSICAL PROPERTIES OF COMPLEXES

Complex with M.Pt Yield Elements (found) calcd % ΏM

Mol.formula (mho cm2mol-1)
carbon hydrogen nitrogen metal
CoC22H22O4N2 >300 65% (59.91) (5.01) (6.35) (13.46) 12
60.41 5.03 6.40 13.50
NiC22H22O4N2 >300 70% (60.37) (4.99) (6.32) (13.31) 14
60.45 5.03 6.41 13.50

CuC22H22O4N2 >300 72% (59.68) (4.92) (6.28) (14.32) 22

59.79 4.98 6.34 14.38

TABLE 2: INFRARED SPECTRA RESULTS OF THE PRECURSOR, THE LIGAND

AND THE COMPLEXES

Band DAAP LIGAND Co(II)complex Ni(II)complex Cu(II)complex

assignments cm-1 cm-1 cm-1 cm-1
cm-1

υ O-H 3500- 3378 - - -

2700
υ (C=N) - 1607 1590 1591 1574

υ (C=O) 1645 - - - -

υ (C-O) 1258 1206 1254 1225 1246

New bands 626,572,532,448 614,582,474,448, 652,598,533,469,

416 422
 TABLE 3. MAGNETIC AND ELECTRONIC SPECTRAL DATA OF THE
COMPLEXES

Complex µeff B.M Electronic spectral

bands
Co(II) 4.62 8890,17543,25000

Ni(II) 2.89 10200,18518, 22222

26315

Cu(II) 1.94 12000,12987,14284

17241, 20000,

ESR SPECTRUM OF Cu(II) COMPLEX

g ll = 2.14 g┴ = 2.06 The g values indicate a distorted octahedral geometry.

 Biological activity and MIC50 of ligand and metal complexes

Sample Fungus Bacteria

G. -ve G. +ve
F. Solani A.Niger E.Coli P.Vulgaris B.Subtilis S.Pyogones
Ligand 1.1 0.9 -ve -ve -ve -ve

MIC50 >100µg/mL >100µg/mL -ve -ve -ve -ve

Co(II) complex 2.0 2.3 2.8 2.9 3.8 3.7

MIC50 >100µg/mL >100 µg/mL 50 µg/mL 50 µg/mL 25 µg/mL 25 µg/mL

Ni(II) complex 2.0 2.1 2.9 3.1 3.2 3.2

MIC50 >100µg/mL >100µg/mL 50 µg/mL 50 µg/mL 50 µg/mL 50 µg/mL

Cu(II) complex 3.0 3.0 -ve -ve -ve -ve

MIC50 50 µg/mL 50 µg/mL -ve -ve -ve -ve

CONCLUSION

Based on the analytical data, conductance, thermal, spectral and magnetic data octahedral
geometries have been proposed for Co(II), Ni (II) and Cu (II) complexes, wherein multidentate
ligand containing O and N donor system is found to behave as symmetric bis-bidentate system
employing two ON donor sequences. The tentative structure for the complexes can be as follows

OH2
OH2 OH2
O O
O O
M
M
M M

N=C C=N OH2

OH2 C=N OH2 N=C
CH 3 H 3C CH3 H 3C
SH SH

ACKNOWLEDGEMENT