Synthesis and Spectral Study of Dicarboxylate of Cu (II) and Mn (II) metals with Heterocyclic Nitrogen Bases as Adducts
S. B. Kesrale*, Seema I. Habib and P. A. Kulkarni
P.G. Department of Chemistry and Organic Research Laboratory, Yeshwant Mahavidyalaya, Nanded -431602
*Corresponding Author E-mail: seemahabib12@gmail.com
ABSTRACT:
In the present paper an attempt was made to study dicarboxylate of Cu (II) and Mn (II) metals with heterocyclic Nitrogen bases as adducts in principle for their structure and properties. Salts of Cu++ and Mn++and dicarboxylic acids such as oxalic, succinic, Glutaric, Adipic acids were taken in 1:1 proportion and refluxed in heterocyclic bases such as pyridine, Quinoline, β-picoline or Nicotine. After filtration and cooling transition metal carboxylates with adducts of bases of Nitrogen and Nicotine were obtained. All the compounds were analysed by elemental analysis, solubility, magnetic susceptibility, IR, 1HNMR spectra and thermal analysis. All the synthesized compounds are paramagnetic. IR spectra showed that bonding of dicarboxylic acid to transition metal ion is through oxygen and of heterocyclic base and Nicotine is through Nitrogen.
KEYWORDS: Cu (II) and Mn (II) adducts, Elemental study and IR, 1H NMR spectra and TGA
INTRODUCTION:
An adduct is a result of interaction between lewis acids and lewis base1. Chemical study and structural study of Cu (II) propionate monoadduct with β-picoline was reported by Borel et.al2. Dicarboxylates are bidentate binegative chelating ligands forming chelates. Selected dicarboxylic acids are Oxalic, Succinic, Glutaric and Adipic acids, Pyridine and β-picoline are weaker ligands.
A literature survey on the adduct3 of transition metals/ carboxylates with nitrogen heterocyclic bases is as follows.
G. D. Baiju4 et.al studied Cu (II) aryl carboxylate compounds with cyano pyridine. L. Dubickii et.al studied magnetic properties with Cu (II) salts and the structure of Cu (II) salts, α, ω dicarboxlates of pyridine derivatives and amine derivatives. The thermal decomposition reactions of bivalent metal succinates in the solid state were carried out by K. Muraishi et.al5.
EXPERIMENTAL:
All the melting points were determined in an open capillary tube and are uncorrected. Completion of the reaction was monitored by thin layer chromatography on pre-coated sheets of silica gel-G. All the reagents used were chemically pure and are of AR grade. Solvents were dried and distilled before use according to standard procedure6.
Method of preparation of transition metal dicarboxylates heterocyclic nitrogen bases:
Transition metal ion such as Cu++ and Mn++salts were dissolved in minimum quantity of liquid heterocyclic nitrogen base in a beaker. In another beaker carboxylic acid such as oxalic, succinic Adipic, Glutaric acids were dissolved in heterocyclic nitrogen base such as pyridine,β-picoline, Quilone or Nicotine, which contain pyridine nucleus. Metal ion to dicarboxylic acid was taken 1:1 proportion. Both solutions were mixed and refluxed for 2-3 hours in round bottom flask. The hot solution was filtered and cooled. After cooling the crystals of transition metal dicarboxylates heterocyclic nitrogen base as adduct are obtained.
Table-1 Elemental analysis:
|
Sr. No |
Complex |
% Metal found (calc) |
% Carbon found (calc) |
% Hydrogen found (calc) |
% Nitrogen found (calc) |
Mol. Wt. |
Colour |
µeff B.M |
|
1 |
[Cu(II) Succ.(β-Pic.)2](β-Pic)2 |
11.48(11.52) |
21.50 (21.76) |
05.75 (05.80) |
10.12 (10.15) |
551.54 |
Green |
2.20 |
|
2 |
[Cu (II) Adip. (Quin)2] (Quin)2 |
08.71 (08.78) |
14.89 (14.93) |
04.92 (04.98) |
07.71 (07.74) |
723.54 |
Blue |
2.20 |
|
3 |
[Cu(II) Succ.(Py)2] (Py)5 |
08.81 (08.67) |
63.82 (63.88) |
05.01 (05.05) |
13.29 (13.38) |
732.54 |
Bluish Green |
2.20 |
|
4 |
[Cu(II)Adip.(β-Pic.)2] (-β-Pic)5 |
08.25 (08.30) |
65.81 (65.84) |
16.38 (16.53) |
10.91 (10.97) |
765.54 |
Green |
2.18 |
|
5 |
[Cu (II) Giut.] |
32.75 (32.81) |
30.91 (30.98) |
03.01 (03.09) |
----- |
193.65 |
Green |
2.20 |
|
6 |
Mn(II) Succ. (Quin) |
18.29 (18.31) |
51.09 (50.01) |
03.60 (03.61) |
04.62 (04.67) |
299.93 |
Yellow |
4.42 |
|
7 |
[Mn(II) Glut.0.5 (Quin) |
22.11 (22.60) |
44.21 (44.44) |
03.87 (03.91) |
02.82 (02.82) |
243.04 |
Fleshy |
4.30 |
|
8 |
Mn(II) Adip.0.5 (Quin) |
20.81 (20.85) |
47.79 (47.83) |
04.31 (04.37) |
02.61 (02.66) |
263.43 |
Reddish Orange |
1.50 |
RESULT AND DISCUSSION:
All the complexes are stable at room temperature insoluble in water and most of the common organic solvents but soluble in DMF and DMSO. The analytical data of the complexes (TABLE-1) indicates that their stoichiometry may be represented as 1:1. The molar conductance values of the complexes in DMF solvents suggesting their non-electrolytic nature 7.
Thermogravimetric analysis:
Thermogravimetric analysis (TGA) allows to quantitative study that is changes in weight of solid as a function of temperature. TGA is useful tool for the study of solid state reactions. DTA measures heat changes due to transformations in the sample relative to an inert reference.
Magnetic moments:
The magnetic moments of the compounds at room temperature were calculated by Gouy method using Hg [Co(NCS)4] as a calibrant. Diamagnetic corrections were applied using pascal’s constant.
All the Cu (II) compounds show magnetic moments near to 2.2 BM which are very close to standard range of 1.9 to 2.1 BM, they are having one unpaired electron. Mn (II) Adip 0.5 Quin. show magnetic moments of 1.5 B. M, showing one unpaired electron, low spin compound having intense reddish brown colour probably due to charge transfer. Mn (II) Succinate Quin. Shows Magnetic moments of 4.42 B. M.
Infra red Spectra:
Infrared spectra of compounds were obtained by using KBr pellets in solid state.
1) [Cu (II) Succ.(β-Pic.)2] (β-Pic)2 Succinic acid absorbs at 1780 cm-1. In complex it absorb at 1773 cm-1. There is negative shift of absorption indicating bond formation. Β-Picoline absorbs at 790 cm-1. In complex peak is at 696 cm-1.
2) [Cu (II) Adip. (Quin.)2] (Quin.)2 Adipic acid shows single band at 1700 cm-1. In complex it absorbs at 1685cm-1. Quinoline absorbs at 1660 cm-1 – 1550 cm-1. In complex it is shifted to 1648, 1618 cm-1, 1584 cm-1, 1570 cm-1, 1560 cm-.
3) [Cu (II) Succ.(Py)2] (Py)5 Succinate absorb at 1774 cm-1. Pyridine absorbs at 1654 cm-1, 1647 cm-1, 1629 cm-1, 1618 cm-1, 1605 cm-1, 1576 cm-1 and 1560.2 cm-1.
4) [Cu (II) Adip. (β-Pic.)] (-β-Pic)5 Adipic acid shift from 1700 cm-1 to 1691.2 cm-1 on complexation. β-Picoline shift from 790 cm-1 to 736 cm-1.
5) [Cu (II) Glut.)] In complex peak is observed at 925 cm-1, where as in glutaric acid it is at 950 cm-1.
6) Mn (II) Succ.(Quin.)There is a peak at 1774 cm-1 for succinate and 1654 cm-1, 1636 cm-1, 1621 cm-1, 1597 cm-1 for Quinoline.
7) Mn (II) Glut.0.5(Indol)The free N-H absorption of Indol is at 3491 cm-1. In complex, Indol absorbs at 3249 cm-1.
8) Mn (II) Adipate 0.5 QuinolineAdipate absorbs at 1701 cm-1, 1684 and Quinoline 1654 cm-1, 1618 cm-1, 1588 cm-1, 1560 cm-1, 1528 cm-1 and 1499 cm-1.
1HNMR Spectra:
1HNMR spectra of synthesized compounds and their adducts were recorded in DMSO. The 1HNMR spectra of complexes shows broad signals and the conformation of each signal in the aromatic region is difficult due to complex pattern of splitting.
CONCLUSION:
The Cu(II) and Mn(II) adducts are coloured, insoluble in most of the organic solvent but soluble in in DMF and DMSO. The stoichiometry of the adducts obtained has been found to be 1:1. All the synthesized adducts are paramagnetic.
ACKNOWLEDGMENT:
The authors are thankful to the principal, yeshwant Mahavidyalaya, Nanded for providing laboratory facilities. The authors are also thankful to the Head IICT Hyderabad, for providing spectral data.
REFERENCES:
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2. Borel M. M., Busnot A. and Leclaure A. Journal of Inorganic Nuclear Chemistry. Pergamon Press, 38, 1976, 235-238.
3. Miss RR. Kulshretha and Mukhtar Singh. Indian Journal of Chemistry. 24A, Oct. 1985, 852-854
4. Baiju G. D. Indian Journal of Chemistry. 41A, 2002, 767-770.
5. Yokobayashi H., Nagase K. and Muraishi K.Bull of Chemical Society. Japan, 48, 1975, 2789-2792.
6. (a) Sakamoto M., Itose S., Ishimori T., Matsumoto N., Okawa H and Sigeo Kida. Bull Chem. Soc. Japan, 1990, 63, 1830-1831. (b) Sakamoto M., Itose S., Ishimori T., Matsumoto N., Okawa H. and Sigeo Kida. Bull Chem. Soc. Japan, 1990, 63, 1830.
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Received on 23.03.2013 Modified on 05.04.2013
Accepted on 12.04.2013 © AJRC All right reserved
Asian J. Research Chem. 6(5): May 2013; Page 459-460