1. STUDIES ON METAL COMPLEXES WITH NSO DONOR LIGAND
Presented by
Shehnaz H Solanki
Guide
Dr. Sujit Baran Kumar
Department of Chemistry
Faculty of Science
The Maharaja Sayajirao University of Baroda

2. Contents: Introduction Objectives Experimental Work
Results and Discussion
Conclusion
References

3. INTRODUCTION
Schiff bases derived from an amino and carbonyl compound are an important class of ligands that coordinate to metal ions via azomethine nitrogen and have been studied extensively.
In azomethine derivatives, the C=N linkage is essential for biological activity and several azomethine has been reported to possess remarkable antibacterial, antifungal, anticancer and antimalarial activities [1].
Schiff-base complexes are considered to be among the most important stereo chemical models in main group and transition metal coordination chemistry due to their preparative accessibility and structural variety[2].
It is well known that N and S atoms play a key role in the coordination of metals at the active sites of numerous metallobiomolecules [3]. Schiff base metal complexes have been widely studied because they have industrial, antifungal, antibacterial, anticancer and herbicidal applications [4].
Chelating ligands containing N, S and O donor atoms show broad biological activity and are of special interest because of the variety of ways in which they are bonded to metal ions.

4. OBJECTIVES
Syntheses and characterization of monoprotic tridentate N, O and S-coordinated ligand 2-((E)-(2,2dimethoxyethylimino)methyl)phenol (L).
Syntheses of square planer and octahedral complexes of the type [ML2] where M = Cu2+ and Ni2+ and square planar complexes of the type [CdLX], where X = NCS-, NCO-, N3-.
Characterization of the ligand and complexes by physico-chemical methods and different spectroscopic techniques such as 1H NMR, FTIR, UV-VIS and single crystal X-ray diffraction study etc.
Chelating ligands containing N, S and O donor atoms show broad biological activity and are of special interest because of the variety of ways in which they are bonded to metal ions. .

5. Synthesis of 2-((E)-(2-(methylthio)phenylimino)methyl)phenol
Experimental Work
Synthesis of 2-((E)-(2-(methylthio)phenylimino)methyl)phenol
Ligand
Mol.Wt.
Solubility
Color
M.P(⁰C)
% Yield L
243.32
CH₃CN,
CH2Cl2
Yellow
188
82 %

6. Synthesis of complexes
Syntheses of [ML2] type complexes [M = Cu(II) and Ni(II)]

7. Synthesis of [CdLX] type complexes

8. Molecular Formula (Mol.Wt.)
RESULTS AND DISCUSSIONS
Microanalysis data
Compound
Colour
Molecular Formula (Mol.Wt.)
% Yield
% C
% H
% N
Theo.
Prac.
Ligand
Yellow
C14H13NOS
243.32
82%
69.11
69.42
5.39
5.32
5.76
5.55
[CuL2]
Green
C28H24N2CuO2S2
548.18
64%
61.35
61.68
4.41
4.4
5.11
5.12
[NiL2]
C28H24N2NiO2S2
543.33
67%
61.9
61.56
4.45
4.46
5.16
5.18
[CdLN3]
C15H15CdN4O5
411.78
60%
43.75
43.9
3.67
3.66
13.61
13.71
[CdLNCO]
C15H15CdN2O2S
66%
46.67
46.48
3.61
6.8
6.68
[CdLNCS]
C16H15CdN2OS2
427.84
62%
44.92
44.61
3.53
3.49
6.39

9. 1H NMR Spectrum of Ligand

10. 1H NMR Spectrum of Ligand

11. IR Spectrum of [CuL2]

12. IR Spectrum of [NiL2]

13. IR Spectrum of [CdLN3]

14. IR Spectrum of [CdLNCO]

15. IR Spectrum of [CdLNCS]

16. IR data of complexes Compound (C=N) cm-1 (C-S) cm-1
(N3)/NCO/NCS cm-1
Ligand
1610
643 -
[CuL2]
1604
645
[NiL2]
1601
[CdLN3]
1603
635
2059
[CdLNCO]
625
2162
[CdLNCS]
1605
664
2063

17. Electronic spectra of the complexes

18. Electronic spectral data, conductance and magnetic property of complexes
Compounds
Electronic spectra
λmax ( ε (mol-1cm-1)
Conductance
M (Ω-1mol-1cm2)
in CH3CN
Magnetic
moment
μeff (BM)
[CuL2]
231(25563),398(5969), 679(127) 8
1.79
[NiL2]
227(23633), 398(6677), 679(1314) 12
2.88
Ligand
211(12671),266(10839), 353(05155) -

19. Single crystal structure of [CuL2] complex

20. Single crystal structure of [NiL2] complex

21. Absorption coefficient (mm-1) 1.085 1.087 2.945 F(000) 499 1698 1128
Ligand
[CuL2]
[NiL2]
Empirical formula
C14H13NOS
C42H36Cu1.5N3O3S3
C28H24N2 Ni O2S2
Formula weight
243.32
822.23
543.33
Temperature (K)
293(2)
Wavelength (Ǻ)
Crystal system
Monoclinic
Space group
P21/n
P21/c
a (Ǻ)
(4)
(4)
(3)
b (Ǻ)
(3)
(8)
(3)
c (Ǻ)
(19)
(6)
(4)
()
90.00
()
(4)
95.573(2)
()
Volume (Ǻ3)
(5)
3691.3(2)
(10) Z 4
Density (Mg/m3)
1.265
1.480
1.461
Absorption coefficient (mm-1)
1.085
1.087
2.945
F(000)
499
1698
1128
Theta range for data collection() to to to
Index ranges
-16≤h≤13,
-13≤k≤14,
-6≤l≤8
-13≤h≤14,
-29≤k≤29,
-19≤l≤20
-15 ≤ h ≤ 15,
-14 ≤ k ≤ 14,
-19 ≤ l ≤ 16
Reflections collected
3118
26416
23763
Independent reflections
2120
[R(int) = ]
8683
[R(int) = ]
4822
[R(int) = ]
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
and
and
and
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
2120 / 0 / 155
8683/ 0 / 487
4822/0/324
Goodness-of-fit on F2
1.051
1.052
1.043
Final R indices [I>2sigma(I)]
R1 = ,
wR2 =
R1 = ,
wR2 =
R1 =
wR2 =
R indices (all data)
R1 = ,
wR2 =
R1 = ,
wR2 =
R1 = ,
wR2 =

22. Selected bond lengths and angles of complexes [CuL2] and [NiL2]
Bond Angles (°)
Cu(1)–O(1)
1.9222(18)
O(1)-Cu(1)-O(1)i
180.0
Cu(1)–O(1)i
O(1)-Cu(1)-N(1)i
90.74(8)
Cu(1)–N(1)
1.985(2)
N(1)-Cu(1)-N(1)i
Cu(1)–N(1)i
O(3)-Cu(2)-N(2)
153.12(18)
Cu(2)–O(2)
1.9104(16)
N(3)-Cu(2)-N(2)
97.24(8)
Cu(2)–O(3)
1.9117(17)
O(2)-Cu(2)-N(2)
91.17(8)
Cu(2)–N(3)
1.9994(19)
O(3)-Cu(2)-N(3)
91.81(8)
Cu(2)–N(2)
2.008(2)
O(2)-Cu(2)-O(3)
89.38(7)
O(1)-Cu(1)-N(1)
89.26
[NiL2]
Ni(1)-O(1)
1.9944(17)
O(1)-Ni(1)-N(1)
92.13(8)
Ni(1)-O(2)
2.0231(17)
N(1)-Ni(1)-N(2)
174.75(8)
Ni(1)-N(1)
2.028(2)
O(1)-Ni(1)-S(1)
171.37(5)
Ni(1)-N(2)
2.036(2)
O(2)-Ni(1)-S(2)
168.74(5)
Ni(1)-S(1)
2.4748(7)
S(1)-Ni(1)-S(2)
88.08(2)
Ni(1)-S(2)
2.4810(7)
N(2)-Ni(1)-S(2)
93.76(6)

23. CONCLUSION
We have synthesized tridentate NOS co-ordinated ligand 2-((E)-(2 (methylthio)phenylimino)methyl) and the ligand was characterized by different spectroscopic studies such as 1H NMR, FT-IR and single crystal diffraction studies.
Two mononuclear bis copper(II) complexes of the type [CuL2] and Nickel(II) complexes of the type [NiL2] and three mononuclear cadmium(II) complexes of the type [CdLX] where X = NCS-, N3-, NCO- have been synthesized by the reaction of the ligand in combination of different halide or pseudohalides.
The complexes were characterized by elemental analyses, FT-IR, UV-Visible spectroscopic, conductivity measurement, magnetic studies and crystal structure of the ligand and complexes [CuL2] and [NiL2] have been solved by single crystal X-Ray diffraction studies and it shows that [CuL2] complex have distorted square planar geometry and [NiL2] complex have distorted octahedral geometry.

24. References : [1] [2] [3] [4] [5] [6] [7]
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L.-J. Liu, Synth. React. Inorg. Met. Org. Chem. 41 (2011) 531.
Singh; M.S. Barwa; P. Tyagi; Eur. J. Med. Chem .42( 2007)
M. Yildiz.; B. Dulger; S. Y. Koyuncu ; B. M.Yapici .J. Indian Chem. Soc 81(2004)7-12.
L. J. Farrugia, J. Appl. Cryst. 32(1999) 837.
S. Mandal, A.K. Rout, M. Fleck, G. Pilet, J. Ribas, D. Bandyopadhyay, Inorg. Chim. Acta 363 (2010) 2250.
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