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Powder diffraction study of some mixed ligand complexes of Mn(II), Ni(II), Cu(II), Zn(II), and Cd(II)

Published online by Cambridge University Press:  05 March 2012

Ranjana Ghose  and
Rajesh Kumar
Ranjana Ghose*
Affiliation:
Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi, Uttar Pradesh 221005, India
Rajesh Kumar
Affiliation:
Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi, Uttar Pradesh 221005, India
*
a)Author to whom correspondence should be addressed. Electronic mail: rghose.apc@itbhu.ac.in
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Abstract

The mixed ligand complexes of manganese(II), nickel(II), copper(II), zinc(II), and cadmium(II) involving aspartic acid and benzoic acid have been synthesized. The complexes were studied by various spectroscopic techniques such as infrared, electronic, X-ray diffraction, and magnetic measurements. The complexes were found to have octahedral geometry. The X-ray powder diffraction results show that the crystal systems of Mn(II)-Asp-Ben complex are hexagonal, and Ni(II)-Asp-Ben, Cu(II)-Asp-Ben, Zn(II)-Asp-Ben, and Cd(II)-Asp-Ben complexes are found to be triclinic. The value of unit-cell parameters and XRD data for the five mixed ligand complexes are reported.

Keywords

aspartic acidbenzoic acidmixed ligand complexes
Type
New Diffraction Data
Information
Powder Diffraction , Volume 26 , Issue 1 , March 2011 , pp. 82 - 87
Copyright
Copyright © Cambridge University Press 2011

INTRODUCTION

Benzoic acid has its biological importance (Buhler et al., Reference Buhler, Pucher, Wenk and Broz2009). Benzoic acid or its sodium, potassium, or calcium salt is intentionally added to certain food as food preservative or may naturally be present in specific foods. Sodium benzoate is used as one of the main antimicrobial preservatives in foods and beverages.

Benzoic acid is used as an antiseptic, antimycotic, and antipyretic. Estimation of intake of benzoic acid in Belgium adult population was investigated by Vandevijvere et al. (Reference Vandevijvere, Andjelovic, De Wil, Vinkx, Huybrechts, Van Loco, Van Oyen and Goeyens2009). The effects of toxic and nontoxic metals on the aromatic system of benzoic acid have been studied by Raman, infrared spectra, and ultraviolet spectroscopic techniques (Lewandowski, Reference Lewandowski1988). Hofmann-type complexes M(Ben)2Ni(CN)4 were studied using benzoic acid, where M is Ni, Cd, Co, and Mn (Kartal and Senturk, Reference Kartal and Senturk2005). The amino acid aspartic acid is well known for its biological values. The complexes of some amino acids with vanadium(III) were reported (Bukietyńska et al., Reference Bukietyńska, Podsiadly and Karweeka2003). Metal complexes of aspartic acid were studied by various methods (Yasui and Ama, Reference Yasui and Ama1975; Ishizuka et al., Reference Ishizuka, Yamamoto, Arata and Fujiwara1973; Battaglia et al., Reference Battaglia, Corradi, Antolini, Marcotrigiano, Menabue and Pellacani1982; Wojciechowska et al., Reference Wojciechowska, Lomozik and Zielinski1987).

In biological systems there is a possibility of the formation of mixed ligand complexes by the interaction of protein and food intake with the metal ions present. The present paper deals with the synthesis, spectroscopic, and powder X-ray diffraction studies of mixed ligand complexes of Mn(II), Ni(II), Cu(II), Zn(II), and Cd(II) with benzoic acid (Ben) and aspartic acid (Asp).

EXPERIMENTAL

All the chemicals and reagents used were of analytical grade. Asp was obtained from E. Merck, while Ben and metal sulphates were from Fluka.

Figure 1. X-ray diffraction pattern of Mn(II)-Asp-Ben complex.

Figure 2. X-ray diffraction pattern of Ni(II)-Asp-Ben complex.

Figure 3. X-ray diffraction pattern of Cu(II)-Asp-Ben complex.

To synthesize the various mixed ligand complexes, aqueous solution of metal(II) sulphate was added to an aqueous solution of Asp in 1:1 molar ratio in hot condition. Further an equimolar amount of methanolic solution of Ben was added to it. The pH values of the resultant mixtures were raised to between 6.0 and 7.5 by adding sodium hydroxide solution depending on the metal ion. The pH for Mn(II) was 7.2, for Ni(II) 7.5, for Cu(II) 6.05, for Zn(II) 7.2, and Cd(II) 6.8. Each of the resultant solution was heated until it boils and concentrated to half of its initial volume; precipitates of the complexes appeared which were filtered off and washed with hot water several times and with acetone. The precipitates were dried in an oven ∼50 °C.

TABLE I. X-ray diffraction data of Mn(II)-Asp-Ben [Mn2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

TABLE II. X-ray diffraction data of Ni(II)-Asp-Ben [Ni2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 4. X-ray diffraction pattern of Zn(II)-Asp-Ben complex.

Figure 5. X-ray diffraction pattern of Cd(II)-Asp-Ben complex.

All the complexes were analyzed for metal, sulphate, carbon, hydrogen, and nitrogen by standard methods.

Infrared spectra in nujol mulls were recorded on a Hitachi 270-50 IR spectrophotometer in the range from 4000 to 250 cm−1, and electronic spectra in the solid state were recorded with a Hitachi 330 spectrophotometer in the range from 200 to 2500 nm. The magnetic moment measurements were carried out by the Gouy method using Hg[Co(SCN)4] as a calibrant. X-ray diffraction patterns were taken with a Seifert-Rich ID 3000 X-ray diffractometer operated at 40 kV and 30 mA. Cu K α X-rays (λ=1.540 598 Å) with a Ni filter were used. Ito’s method was used for automatic indexing of the observed diffraction patterns (Azaroff and Buerger, Reference Azaroff and Buerger1958).

RESULTS AND DISCUSSION

The analytical data of the complexes show that the mixed ligand complexes are of the composition M 2(C4H5NO4)(C7H5O2)(OH)(H2O)4. All the synthesized

TABLE III. X-ray diffraction data of Cu(II)-Asp-Ben [Cu2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

complexes are coloured except those of Zn(II) and Cd (II) which are white. The complexes were insoluble in water and common organic solvents. The complexes did not melt up to 300 °C.

In the mixed ligand complexes Asp behaves as a bidentate ligand. Asp forms bonds with the α-carboxylate and β-carboxylate O atoms. The presence of multiple bands in the mixed ligand complexes in the region of asymmetric and symmetric modes of the carboxylate groups (Battaglia et al., Reference Battaglia, Corradi, Marcotrigiano, Menabue and Pellacani1980) shows that both the carboxylate groups of Asp are coordinated to the metal ions. The benzoate ion behaves as a bidentate ligand in the mixed ligand complexes.

TABLE IV. X-ray diffraction data of Zn(II)-Asp-Ben [Zn2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

A sharp band about 3600 cm−1 in the complexes suggests νOH stretching band, and the band appearing at 950 cm−1 indicates a bridging OH bonding in the complexes. This suggests the polymeric structure of the complexes, which is also reflected from the insolubility of various complexes.

In all the synthesized complexes a broad band appears in the region between 3500 to 3200 cm−1, showing the presence of aquo group in the complexes. ν M-O aquo bands at about 440 cm−1 in the complexes confirm the coordination of water molecule. The assignments (Nakamoto, Reference Nakamoto1970) of ν M-O around 280 cm−1 (Goodgame and Johns, Reference Goodgame and Johns1978) favours the coordination number six for the metal ions.

The magnetic moment value for Mn(II) complex is in the range of 5.2 to 6.0 B. M., indicating that the Mn(II) complex is typically high spin complex and having octahedral structure. The Ni(II) complex exhibits the magnetic moment value in the range of 2.8 to 3.2 B. M., indicating octahedral coordination of the ligands around Ni(II) ion. The Cu(II) complex shows magnetic moment in the range of 1.61 to 1.85 B. M., suggesting distorted octahedral nature for the complex. The UV-visible spectra also show octahedral geometry for the complexes.

X-ray powder diffraction patterns for the mixed ligand complexes of Mn(II), Ni(II), Cu(II), Zn(II), and Cd(II) involving Asp and Ben are plotted in Figures 1–5. The observed and calculated values of 2θ, d, I, and Δ2θ of the diffraction peaks and their (h k l) Miller indices determined by Ito’s method are listed in Tables I–V. The unit-cell parameters were also obtained from the automatic indexing results for the mixed ligand complexes. The crystal systems of Mn(II)-Asp-Ben complex is hexagonal, while Ni(II)-Asp-Ben, Cu(II)-Asp-Ben, Zn(II)-Asp-Ben, and Cd(II)-Asp-Ben complexes are triclinic. The values of unit-cell parameters for the five mixed ligand complexes are listed in Table VI.

TABLE V. X-ray diffraction data of Cd(II)-Asp-Ben [Cd2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

TABLE VI. The unit-cell parameters for M(II)-Asp-Ben complexes.

References

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Figure 0

Figure 1. X-ray diffraction pattern of Mn(II)-Asp-Ben complex.

Figure 1

Figure 2. X-ray diffraction pattern of Ni(II)-Asp-Ben complex.

Figure 2

Figure 3. X-ray diffraction pattern of Cu(II)-Asp-Ben complex.

Figure 3

TABLE I. X-ray diffraction data of Mn(II)-Asp-Ben [Mn2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 4

TABLE II. X-ray diffraction data of Ni(II)-Asp-Ben [Ni2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 5

Figure 4. X-ray diffraction pattern of Zn(II)-Asp-Ben complex.

Figure 6

Figure 5. X-ray diffraction pattern of Cd(II)-Asp-Ben complex.

Figure 7

TABLE III. X-ray diffraction data of Cu(II)-Asp-Ben [Cu2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 8

TABLE IV. X-ray diffraction data of Zn(II)-Asp-Ben [Zn2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 9

TABLE V. X-ray diffraction data of Cd(II)-Asp-Ben [Cd2(C4H5NO4)(C7H5O2)(OH)(H2O)4] complex.

Figure 10

TABLE VI. The unit-cell parameters for M(II)-Asp-Ben complexes.