Synthesis and Characterization of Tetrakis2-Amino

IOP Conference Series: Materials Science and Engineering
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Synthesis and Characterization of Tetrakis(2-amino-3-

methylpyridine)copper(II) Sulfate Tetrahydrate
To cite this article: S B Rahardjo et al 2018 IOP Conf. Ser.: Mater. Sci. Eng. 349 012056
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The 12th Joint Conference on Chemistry IOP Publishing
IOP Conf. Series: Materials Science and Engineering 349 (2018) 012056 doi:10.1088/1757-899X/349/1/012056
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Synthesis and Characterization of Tetrakis(2-amino-3-

methylpyridine)copper(II) Sulfate Tetrahydrate
S B Rahardjo1, T E Saraswati1, A Masykur1, N N F Finantrena1, H Syaima2

1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas
Sebelas Maret, Surakarta, 57126, Indonesia
2
Chemistry Graduate Program, Graduate School, Universitas Sebelas Maret, Surakarta,
57126, Indonesia
E-mail: sentotbr@yahoo.com
Abstract. The complex of Tetrakis(2-amino-3-methylpyridine)copper(II) sulfate tetrahydrate

has been synthesized in a ratio of 1: 6 metal to ligand in methanol. The percentage of copper in
the complex measured by Atomic Absorption Spectrometer (AAS) showed the complex formula
was Cu(2-amino-3-metilpyridine)4SO4(H2O)n (n = 3, 4, or 5). The analysis of TG/DTA showed
that 1 mole of complex contains 4 moles of H2O. The conductivity measurement indicated that
the complex is in 1 to 1 electrolyte. The formula of the complex was estimated as [Cu(2-amino-
3-metilpyridine)4]SO4∙4H2O. The complex was paramagnetic with µeff of 1.85 BM. The UV-Vis
spectra showed a band peak at 730 nm with an electronic transition Eg⟶T2g. IR spectral data
indicated that the functional groups of N-pyridine 2-amino-3-metilpyridine coordinated to ion
Cu(II). The geometry of the complex was probably square planar.
1. Introduction
Pyridine derivative which has antibacterial activity [1] is able to act as ligands. It is due to the availability
of free electron pair to bond with a metal ion. Pyridine derivative ligands can form complexes with
different types of donor atoms coordinated to the metal ion. In case the complex of [Ag(2-amino-3-
methylpyridine)2]NO3, the ligand has an electron donor atom N in the primary amine and N-pyridine.
Coordinated donor atoms are N in pyridine [2]. After complexing, the effectivity of ligands as
antibacterial increase significantly. The complex of Cu(II)-2,4-dinitro-6(pyridine-2-
ylmethylamino)methyl-phenolate has better bactericidal activity than complex of Fe(II), Zn(II), Ni(II)
and 2,4-dinitro-6(pyridine-2-ylmethylamino)-methylphenolate as ligands [3]. Therefore, complexing
copper ion with pyridine derivative ligands seems promising due to the improvement of both
antibacterial activities.
Copper is one of transition metal elements with 3d9 electron configuration that can form complexes
because they have d orbitals are not fully charged electrons. Copper has the oxidation number of +1 and
+2, copper in the form of Cu(II) is more stable than Cu(I). Cu(II) can form a wide variety of geometries
in the complex include square planar [4], square pyramidal [5], and octahedral [6] but generally Cu(II)
has a coordination number of four bonded to ligands forming complexes with square planar structure.
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2. Experimental
2.1. Materials
All chemicals were purchased from E.Merck.
2.2. Physical measurements

The copper content was determined by Atomic Absorption Spectrometer (AAS) Shimadzu AA-6650.
Infrared spectra were recorded on Prestige-21 Shimadzu spectrophotometers using KBr disc. The
thermogravimetric analysis of the metal complex was recorded on Thermogravimetric/Differential
Thermal Analysis (TG/DTA) Diamond Perkin Elmer analyzer. Spectra UV-VIS was performed on
Shimadzu UV-3601 spectrophotometer. Molar conductivity (Λ*m) of 1 mM solution in methanol was
measured on Jenway CE 4071 conductivity meter at 25 oC. The magnetic moment was measured with
Auto Sherwood Scientific 10169 Magnetic Susceptibility Balance.
2.3. Synthesis of Cu(II) complex

Methanolic solution (10 mL) of CuSO4∙5H2O (0.748 g; 3 mmol) was added dropwise to methanolic
solution (20 mL) of 2-amino-3-methylpyridine (1.944 g; 18 mmol) with constant stirring for 3 hours.
CuSO4∙5H2O solution initially blue and then after the addition of ligand 2-amino-3-methylpyridine, the
solution becae green. The solution was then concentrated 1/3 of the previous volume. Furthermore, the
solution was diffused using diethyl ether and left to stand for 72 hours. The precipitate was filtered, then
dried in a desiccator for 48 hours.
3. Result and Discussion

3.1. Electronic spectra
Figure 1 shows the shift of CuSO4∙5H2O maximum absorption wavelength (818 nm) towards smaller
wavelengths in the complex Cu(II)-2-amino-3-methylpyridine (730 nm). Shifting λmax indicates the
formation of the complex due to the substitutions of H2O molecules with 2-amino-3-methylpyridine. It
was estimated that 2-amino-3-methylpyridine have greater powers than the H2O. Electronic spectra of
the complex [Cu(2-amino-3-methylpyridine)4]SO4.4H2O shows a wide absorption at λmax 730 nm (13700
cm-1). A low-intensity absorption band of a copper complex at 740 nm is assigned to the Eg⟶T2g
transition which attributed to square planar geometry [7], so is 720 nm [8]. Therefore, it indicated the
square planar geometry around metal ion in the formed complex.
CuSO4.5H2O(a)
0,8 Cu(L)(b)
0,7
0,6 a
Abs
0,5
Absorbansi
0,4
0,3
0,2
0,1 b
0,0
500 600 700 800 900
Panjang Gelombang
Wavelenght (nm)
Figure 1. Electronic spectra of CuSO45H2O solution (a) and the complex solution (b)
3.2. Analysis of the amount of copper with Atomic Absorption Spectroscopy (AAS)
AAS was used to determine the total copper content of the complex shown in table 1. The result of
copper content in the complex was 9.53±0.06%. This result of the measurements was compared to the
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calculation results of the proposed complex formula. It can be estimated that the complex formula is
Cu(2-amino-3-methylpyridine)4SO4(H2O)n (n=3, 4 or 5).
Table 1. Percentage of copper in the complex theoretically.
Empirical Formula Molecular weight (g/mol) % Cu

Cu(2-amino-3-metylpyridine)4SO4(H2O)3 645.5 9.84
3.3. Thermal analysis by TG/DTA

Thermogram of complex in figure 2 shows the endothermic reaction in the area of 129 °C followed by
10.89% mass reduction in the temperature range 135-174 °C, which corresponds to the loss of four
molecules H2O. Something similar happened at the complex Cu(II)-sepamet that showed a mass
reduction in 79.9 to 146.4 °C 9.50 % indicating loss of four molecules of lattice water [9]. The complex
[Cu(en)(phen)2]Br2∙2phen∙8H2O, en=ethylenediamine, phen=[bis (1,10 Phenanthroline) also
experienced a reduction in mass at 170 °C indicating the release of H2O molecules as hydrates [10].
Based on the analysis TG/DTA can be estimated that the complex formula is Cu(2-amino-3-
methylpyridine)4SO4.4H2O.
14
. o
135 C, 13,626
12 . o
174 C, 12,098
Penurunan berat (mg)
10
Weight loss (%)
o
4 129 C o
163 C
100 200 300 400 500

A
Figure 2. TG/DTA analysis of the complex
3.4. Analysis of electrical conductivity

The molar conductivity of the complex and standard solution were determined in methanol (10-3 M) at
room temperature. The value of molar conductivity is shown in table 2. The molar conductance values
of the complex lie in 12.7 ± 0.1 S.cm2.mol-1, thus indicating that is an electrolyte. By comparing the
conductivity values of the complex sample with a molar conductivity of the standard solution, it can be
seen that the charge ratio of cationic: anions= 1:1. This shows that the ion SO42- is not coordinated to
the central metal ion Cu(II) and only acts as an anion [11-12]. Thus, the formula is probably [Cu(2-
amino-3-methylpyridine)4]SO4∙4H2O.
3
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Table 2. Molar conductivity of metal salts and Cu(II)-ranitidine in water

Solution Ʌm (S cm2 mol-1) Total ions
Metanol - -
CuSO4∙5H2O 7.63 ± 0.2 2
NiSO4∙6H2O 4.40 ± 0.1 2
FeSO4∙7H2O 16,50 ± 0.1 2
CuCl2∙2H2O 73.73 ± 0.2 3
MgCl2 83.76 ± 0.15 3
AlCl3∙6H2O 192.26 ± 0.15 4
FeCl3∙6H2O 241.63 ± 0.15 4
The complex. 12.7 ± 0.1 2
3.5. Infrared (IR) analysis

In order to find binding modes of the ligand with transition metal ions, infrared spectra of compounds
were recorded. Table 3 shows the infrared absorption of functional groups in the ligand and the complex.
On comparison of infrared spectra of 2-amino-3-methylpyridine and the complex, the C=N band at 1583
cm-1 in ligand was shifted by 66 cm-1 to a higher frequency on complexation indicated coordination of
N-pyridine in 2-amino-3-methylpyridine to the metal ion. It was evidenced by an absorption at 475 cm-
1
which indicated the presence of Cu-N bond. A similar case also occurred in the complex
[Cu4(Salicilydene-Cefotaxime)(OH)6] which has an absorption of N-pyridine at 1600 cm-1 and shift
towards higher at 1640 cm-1 in the complex and there was a new absorption at 490 cm-1 indicated the
presence of Cu-N bond [13]. In the complex [Cu(L5)2Cl2], L5=(E)-1-(2-amino hydroxy benzylidene)
quinoline-2(1H)-one) also indicate the presence of Cu-N bond in the absorption at 471 cm-1 [14].
Table 3. Infrared absorption of ranitidine hydrochloride and the complex

Compounds IR absorption (cm-1)
(C=N) (C=C) (N-H) (Cu-N)
2-amino-3-methylpyridine 1583 1472 3193 -
1453 3192
[Cu(2-amino-3-methyl- 1649 1479 3187 475
pyridine)4] SO4∙4H2O 1460 3157
3.6. Magnetic properties (μeff)

The μeff value measured for the present Cu(II) complex is 1.85 B.M., this value shows that the complex
is paramagnetic which has one unpaired electron BM [15]. The square planar complex of Cu(II) showed
magnetic moment BM 1.81 to 1.86 BM [16-17], indicated that [Cu(2-amino-3-methyl-
pyridine)4]SO4∙4H2O was present in square planar geometry. Based on the above results, the structure
in figure 3 is suggested for the complex.
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H3C
NH2 CH3
N N
NH2
Cu2+ SO4.4H2O
H2 N
N N
H3 C
H2 N CH3
Figure 3. Suggested structure of [Cu(2-amino-3-methylpyridine)4]SO4∙4H2O
4. Conclusion
The complex [Cu(2-amino-3-methylpyridine)4]SO4∙4H2O was able to be synthesized by mixing a
methanolic solution of Cu(II) and a methanolic solution of 2-amino-3-methylpyridine solution with a
mole ratio of 1:6 and stirring for 3 hours. The functional group coordinated to the Cu(II) was possibly
N-pyridine, forming square planar geometry. The complex is paramagnetic has one peak at maximum
UV-Vis absorption of 730 nm.
Acknowledgement
Authors gratefully express acknowledgments to Ministry of Research, Technology and Higher
Education (RISTEKDIKTI) of the Republic of Indonesia for financial support.
References
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Toxicology 2(1) 5-11

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IOP Conference Series: Materials Science and Engineering

PAPER • OPEN ACCESS

Synthesis and Characterization of Tetrakis(2-amino-3-

View the article online for updates and enhancements.

This content was downloaded from IP address 139.81.245.213 on 02/05/2018 at 01:44

Synthesis and Characterization of Tetrakis(2-amino-3-

S B Rahardjo1, T E Saraswati1, A Masykur1, N N F Finantrena1, H Syaima2

Abstract. The complex of Tetrakis(2-amino-3-methylpyridine)copper(II) sulfate tetrahydrate

2.2. Physical measurements

2.3. Synthesis of Cu(II) complex

3. Result and Discussion

Table 1. Percentage of copper in the complex theoretically.

Empirical Formula Molecular weight (g/mol) % Cu

3.3. Thermal analysis by TG/DTA

100 200 300 400 500

Figure 2. TG/DTA analysis of the complex

3.4. Analysis of electrical conductivity

Table 2. Molar conductivity of metal salts and Cu(II)-ranitidine in water

3.5. Infrared (IR) analysis

Table 3. Infrared absorption of ranitidine hydrochloride and the complex

3.6. Magnetic properties (μeff)

Figure 3. Suggested structure of [Cu(2-amino-3-methylpyridine)4]SO4∙4H2O

Toxicology 2(1) 5-11

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