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Spectrophotometric Determination of Co(II), Ni(II) and Cu(II) Complexes with Schiff Base Containing Nitrogen and Sulphur Donor Sites

Volume 33, Number 6

Sanjay Kumar1, Ritika Kumari2 and B. K. Rai3

1Department of Chemistry, Jagdam College, Chapra, J. P. University, Chapra.

2Department of Chemistry, R. S. College, Chochahan, Muzaffarpur.

3Department of Chemistry, L. N. T. College, Muzaffarpur B.R.A. Bihar University, Muzaffarpur.

Corresponding Author E-mail: binodkrrai@yahoo.co.in

DOI : http://dx.doi.org/10.13005/ojc/330644

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ABSTRACT:

Coordination compounds of Co(II), Ni(II) and Cu(II) are synthesized by the reaction of 3-propyl-(N-ortho toludine) quinazoline thiosemicarbazone. An attempt has been made to probe the structures, bonding pattern and geometries of their coordination compounds by the molar mass, elemental analyses, infrared spectra, electronic spectra, molar conductance data and decomposition temperature.

KEYWORDS:

PTQT/ Co(II); Ni(II) and Cu(II) complexes/ Schiff Base

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Kumar S, Kumari R, Rai B. K. Spectrophotometric Determination of Co(II), Ni(II) and Cu(II) Complexes with Schiff Base Containing Nitrogen and Sulphur Donor Sites. Orient J Chem 2017;33(6).

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Kumar S, Kumari R, Rai B. K. Spectrophotometric Determination of Co(II), Ni(II) and Cu(II) Complexes with Schiff Base Containing Nitrogen and Sulphur Donor Sites. Orient J Chem 2017;33(6). Available from: http://www.orientjchem.org/?p=39689

Introduction

The chemistry of transition metal complexes has been rapidly expanding not only because their potential applications, but also due to the intriguing variety of architecture exhibited by these compounds1-5. Schiff base derivative incorporating a fluorescent moiety are a useful tool for optical sensing of metal ions. Thin organic and organometallic films have attracted research interest due to their technologically important optical and electronic properties. These materials exhibit luminescence, they are use as conductors, semiconductors and organic light emitting diodes (OLED)6-7. A considerable interest has been shown to biologically active transition metal complexes, largely due to their ability to interact with DNA8. The complexes which can bind or cleave DNA at specific sites, may play an important role in genomic research and in photodynamic therapy against cancer9. It is well known that some coordination compounds can inhibit the multiplication of cancer cells by binding and damaging DNA10.

Motivated from the above mentioned biochemical significance of Schiff base and their transition metal complexes with nitrogen and sulphur containing Schiff bases and in continuation of our earlier research work11-20 in this field we are hereby reported the synthesis and characterization of coordination compounds of Co(II), Ni(II) and Cu(II) with Schiff base ligand. 3-propyl-(N-ortho-toludine) quinazoline thiosemicarbazone (PTQT).

Experimental

All reagent were analytical grade and used without further purification. The metal contents were analysed by standard procedure21. The electronic spectra of the complexes were recorded on Cary-2390 spectrophotometer in the 10000-25000 cm-1. The infrared spectra of the ligand and metal complexes in the region 200-4000 cm_1 were recorded on Perkin Elmer 577 spectrophotometer. The magnetic susceptibility was measured using Gouy balance using mercury tetraisothicyanato cobaltate as a calibrant. The molar conductance was measured by Systronics conductivitymeter model 303 using DMF as a solvent.

Analytical data, electronic spectral data, molar conductance value, magnetic susceptibility value, decomposition temperature and molecular formula of the ligand as well as their complexes are recorded in Table-1 and the salient features of IR bands are recorded in Table-2.

Preparation of the ligand

Ethanolic solution of 3-propyl (N-ortho toludine) quinazoline (0.01m) in ethanol and thiosemicarbazide hydrochloride dissolved in 10% solution of sodium acetate in ethanol. The resulting mixture was refluxed on water bath for 2 h with occasional stirring. The solvent was concentrated to half of its volume and then poured in ice cold water. A solid precipitated out immediately which was filtered, washed with distilled water and cold ethanol.

Recrystallization of crude product from ethanol gave the Schiff Base, PTQT, Yield 70%, m.p. 183±1oC.

Preparation of the Complexes

The following general method was adopted for the pr eparation of the halide complexes of cobalt(II), nickel(II) and copper(II).

The complexes were prepared by reacting metal halides (0.05 g) of the cobalt(II), nickel(II) and copper(II) in ethanol with ethanolic solution of the ligand 3-propyl(N-ortho-toludine) thiosemicarbazone (0.1g). The mixture was then refluxed under stirring condition. The mixture was then refluxed for 3 h. The product was precipitated out and was collected by filteration followed by washing with cold water. Then the product was dried in oven. Yield 75-80%.

Table 1: Analytical, colour, magnetic susceptibility, molar conductivity and decomposition temperature of ligand PTQT and its metal complexes

Compounds        (Colour) % Analysis found (calculated) lmax electronic  cm-1 Wm ohm-1 cm2 mol-1 meff B.M. DT  oC
M C N H
PTQT         (Colourless) 64.81 (64.95) 19.80 (19.94) 5.93 (5.98)
[Co(PTQT)2Cl2]         (Yellow) 6.93 (7.08) 84.21 (84.38) 16.70 (16.82) 4.97 (5.04) 8720, 17200, 20040 6.3 4.83 219
[Co(PTQT)2Br2]      (Yellow) 5.73 (5.80) 76.09 (76.24) 15.13 (15.20) 4.48 (4.56) 8700, 17060, 20080 6.1 4.89 209
[Co(PTQT)2I2]        (Red) 5.73 (5.80) 69.06 (69.18) 13.68 (13.79) 4.07 (4.13) 8910, 11010, 20100 6.9 4.67 224
[Co(PTQT)2(NO3)2] (Red) 6.58 (6.65) 79.14 (79.32) 15.70 (15.82) 4.68 (4.74) 8800, 17040, 20020 7.3 5.02 202
[Co(PTQT)2(ClO4)2] 6.04 (6.13) 73.01 (73.13) 14.49 (14.58) 4.30 (4.37) 8860, 17210, 19940 5.9 5.10 211
[Ni(PTQT)2Cl2]   (Brown) 6.96 (7.06) 84.22 (84.40) 16.70 (16.82) 4.98 (5.04) 10300, 14400, 24310 5.2 3.06 213
[Ni(PTQT)2Br2]  (Brown) 6.29 (6.37) 76.09 (76.26) 15.10 (15.20) 4.50 (4.56) 10260, 14100, 25980 4.9 3.11 207
[Ni(PTQT)2I2] 5.70 (5.78) 69.07 (69.19) 13.69 (13.79) 4.06 (4.13) 10190, 14.080, 25100 4.7 3.02 228
[Ni(PTQT)2(NO3)2]  (Red) 6.57 (6.63) 79.16 (79.34) 15.69 (15.82) 4.68 (4.74) 10220, 14200, 25800 5.2 3.09 216
[Ni(PTQT)2(ClO4)2] 6.02 (6.11) 72.99 (73.14) 14.44 (14.58) 4.68 (4.74) 10100, 14160, 24900 4.9 3.01 204
[Cu(PTQT)2Cl2]  (Blue) 7.68 (7.59) 83.78 (83.91) 16.65 (16.73) 4.96 (5.02) 14600, 24640 9.2 1.84 221
[Cu(PTQT)2Br2]  (Blue) 6.78 (6.86) 75.70 (75.86) 15.04 (15.12) 4.47 (4.53) 14380, 24310 10.8 1.89 217
[Cu(PTQT)2(NO3)2] (Blue) 6.05 (7.14) 78.78 (78.91) 15.62 ((15.73) 4.68 (4.72) 14510, 24210 10.2 1.86 212
[Cu(PTQT)2(ClO4)2] 6.49 (6.58) 72.66 (72.75) 14.39 (14.51) 4.29 (4.35) 14700, 24700 11.3 1.92 203

 

DT = Decomposition Temeperature

Table 2:  Salient features of IR spectral data (cm-1) for ligand PTQT and its metal complexes

Compounds

nC=N

nC = S

nM – O

nM – N

nM – S

nM – X

PTQT

1560 s,b3260 s,b

800 s,b1740 s,b

 

 

 

[Co(PTQT)2Cl2]

1530 m,b

790 m,b

520 m

470 m,b

420 m

325 m

[Co(PTQT)2Br2]

1535 m,b

780 m,b

515 m

470 m

420 m

315 m

[Co(PTQT)2I2]

1535 m,b

775 m,b

510 m

470 m

420 m

325 m

[Co(PTQT)2(NO3)2]

1535 m,b

775 m,b

505 m

465 m

425 m

320 m

[Co(PTQT)2(ClO4)2]

1530 m,b

775 m,b

510 m

465 m

415 m

320 m

[Ni(PTQT)2Cl2]

1530 m,b

775 m,b

510 m

460 m

415 m

275 m

[Ni(PTQT)2Br2]

1535 m,b

780 m,b

515 m

470 m

410 m

280 m

[Ni(PTQT)2I2]

1530 m,b

780 m,b

515 m

470 m

410 m

280 m

[Ni(PTQT)2(NO3)2]

1530 m,b

780 m,b

510 m

460 m,b

415 m

280 m

[Ni(PTQT)2(ClO4)2]

1530 m,b

775 m,b

510 m,b

465 m

420 m

275 m

[Cu(PTQT)2Cl2]

1530 m,b

780 m,b

515 m,b

465 m

415 m

270 m

[Cu(PTQT)2Br2]

1535 m,b

770 m,b

515 m,b

470 m

415 m,b

275 m

[Cu(PTQT)2(NO3)2]

1525 m,b

770 m,b

520 m,b

470 m

410 m

275 m

[Cu(PTQT)2(ClO4)2]

1535 m,b

775 m,b

520 m,b

470 m

415 m

275 m

 

m = medium,   s = strong,   b = broad

The following general method was adopted for the preparation of nitrate and perchlorate complexes. The complexes were prepared by using metal nitrates/ perchlorate salts of cobalt(II), nickel(II) and copper(II) to a hot ethanolic solution of the ligand 3-propyle (N-ortho toludine) thiosemicarbazone. The mixture was in the molar ratio 1:2. The mixture was then refluxed under stirring condition. The mixture was then refluxed for 4 h. The product was precipitated out and was collected by filtration followed by washing with cold water. Then the product was dried in oven. Yield 75-80%.

Results and Discussion

Infrared Spectral Study

The IR spectrum of the complexes was compared with those of the free ligand in order to determine the involvement of the coordination sites in the chelation. Analysis by IR results in the absorption spectra in the IR region and registered bands or signals. IR spectra of the ligand, PTQT exhibited the characteristic strong band at 1560 cm‑1 assignable22,24 to azomethine (>C=N). In the spectra of the complex this band shows red shift with slightly reduced intensity. The shift of the band and change in intensity proposes possible linkage of the azomethine nitrogen with metal ions. The infrared spectra of the ligand shows a strong and broad band at 780 cm‑1    assigned22-25 to nC=S. After complex formation this band also shows red shift proposes coordination of metal through thione sulphur atom of thiosemicarbazone moiety.

The evidence of bonding ligand, PTQT to metal ion through oxygen atom of either nitrate or perchlorate ion, N-atom of azomethine group and thione sulphur of thiosemicarbazone moiety is supported by the appearance of bands due to nM–O22-26 at 540-515 cm-1, nM–S22-26 at 475-455 cm-1 and nM–N22-26 at 435-410 cm-1 respectively. The evidence of metal-halogen coordination is supported by the low molar conductance values27 of the complexes in the range 4.7-11.3 ohm-1 cm2 mol-1 and appearance of a band in the region 325-265 cm-1 assigned22-26 to nM–X.

The evidence for nitrate complexes indicated by presence of characteristic medium intensity bands at 1280 and 1120 with separation of 160 cm-1 due to monodentate linkage of nitrate group. Presence of combination bands at 1680 and 1660 with a separation of 20 cm-1 confirming the monodentate behavior of the nitrate group28. The monodentate behavior of perchlorate complexes were confirmed due to the presence of four IR spectra bands at 1130, 1050, 650 and 620 cm-1 proposing monodentate behavior of perchlorate in group29.

Hence on the basis of above discussion on IR spectra data, it proposes that the ligand PTQT acts in a neutral bidentate manner. The remaining coordination positions of metal ions are satisfied by negative ions such as Cl–, Br–, I–, NO3– and ClO4–.

Electronic Spectra and Magnetic Susceptibility of the Complex

The cobalt(II) complexes exhibit three spectral bands in the regions at 8800-8900 cm-1, 17000-17200 cm-1 and 19940-20100 cm-1 assignable to the transitions 4T2g (F) ← 4T1g (F), 4A2g (F) ← 4T1g (F) and 4T1g (P) ← 4T1g (F) respectively which proposes octahedral30 geometry. The proposed octahedral geometry of the cobalt(II) complexes is supported31,32 by high magnetic susceptibility value in the range of 4.67-5.02 BM. The Ni(II) complexes exhibits three spectra bands in the region at 10100-10300, 14080-14400 and 24310-25980 cm-1 assignable to transitions 3T2g (F) ← 3A2g(F), 3T1g(F) ← 3A2g(F) and 3T1g(P) ← 3A2g(F) respectively which proposed octahedral30 geometry for Ni(II) complexes. The proposed octahedral geometry of Ni(II) complexes is further supported31,32 by magnetic susceptibility value of all the Ni(II) complexes in the range 3.01-3.11 BM. The Cu(II) complexes display two ligand field bands in the position 14300-14700 cm-1 and 24210-24700 cm‑1 assignable to the transition 2T2g ← 2Eg  and charge transfer band, respectively. The electronic spectra of all the Cu(II) complexes suggesting octahedral30 geometry around central metal ion. The magnetic moment value of Cu(II) complexes are lie in the range of 1.84-1.92 BM.

Molar Conductivity Measurement

Molar conductance data of the complexes were measured in the solvent DMF and all the complexes were found to be non electrolytic in nature. The molar conductance value27  of the complexes are lies in range 4.7-11.3 ohm-1 cm2 mol‑1.

Figure 1: [M(PTQT)2X2] M = Co(II), Ni(II) and Cu(II); R= propyl R' = o-toludine; X = Cl-, Br- , I-, NO3- and ClO4- Figure 1:  [M(PTQT)2X2] M = Co(II), Ni(II) and Cu(II); R= propyl  R’ = o-toludine; X = Cl–,  Br– , I–, NO3– and ClO4–

Click here to View figure

 

Conclusion

Based on the above physico-chemical and spectroscopic studies it is proposes that the ligand PTQT acts in a bidentate manner and coordination is proposed through azomethine N and thione S of thiosemicarbazone moiety. The remaining coordination centre of metal ions are satisfied by negative ion such as Cl–, Br–, I–, NO3– and ClO4–.

The proposed geometry of the Co(II), Ni(II) and Cu(II) are shown as Fig.1.

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