DETERMINATION OF COPPER COMPLEX COORDINATION II

A. BACKGROUND
1. GENERAL REVIEW
A very superficial examination of a large number of chemicals allows us to see that
they are very different in physical and chemical properties. Any acceptable bond theory must
explain these differences and allow us to estimate the properties of new materials. As the first
step towards solving problems, we need to know something about the arrangement of atoms
in chemicals. The structure of solid objects can be investigated using X-ray or neutron beams.
From the diffraction pattern obtained it is possible to find the arrangement of the particles that
make up it. Measuring the amount of heat needed to melt solid yield information about the
attraction between these particles, while the effects of electric current and simple chemical
tests on solids can tell whether it is metal or non-metal. If the material becomes non-
conductive solids, we can determine whether it consists of ions by investigating the effects of
electric current on liquid material (Jeffe, and Holliday, 1975: 25).
On each diagram, the atomic orbitals of the two atoms are represented on the right -
and the left hand diagram with the MOs in the middle. Correlation lines that connect atomic
and molecular orbitals are built to read diagrams that can be interpreted. Now consider the
situation for triatomic molecules such as CO 2. Molecular orbitals contain four sets of orbitals
and one atomic orbital of three atoms. An explanation of the bond in CF 4 involves five sets of
atomic orbitals and a set molecular orbitals, that is a six-component problem. Similarly, SF 6 is
an eight component problem. It is clear that MOs are complicated and, perhaps, difficult to
build and interpret. To overcome this difficulty, it is common to resolve MO descriptions of
polyatomic molecules into three-component problems, a method known as the ligand orbital
group (LGO) approach (Housecroft and Sharpe, 2001: 107).
The nature of block d transition metals is not different not only in the upper and lower
positions in the periodic table but also in the left and right groups. Groups 3 to 5 are often
referred to as initial transition metals and these metals are usually oxophilic and halophilic. In
the absence of bridge ligands, the formation of metal-metal bonds is difficult for these
elements. Organometallic compounds of these metals are known to be very powerful in
activating C-H bonds in hydrocarbons. The final transition metal in the right groups of the
periodic system is usually soft and has great activity in sulfur or selenium. Metal ion
compounds that coordinate with ligands are called complex compounds. Most ligands are
neutral or anionic substances but cations, such as tropylium cations are also known. Neutral
ligands, such as ammonia, NH3, or carbon monoxide, CO., Which are free, are also stable
molecules, whereas anionic ligands, such as Cl- or C5H5-, are stabilized only when
coordinated to a central metal atom. Ligands with one binding atom are called monodentate
ligands, and those with more than one binding atom are called polydentate ligands, which are
also called chelate ligands. The number of atoms tied to the central atom is called the
coordination number (Saito, 1996: 117-118).
To determination of copper as copper (I) thiocyanate this is an excellent
method, since most thiocyanates of other metals are soluble. Separation may thus be effected
from bismuth, cadmium, arsenic, antimony, tin, iron, nickel, cobalt, manganese, and zinc. The
addition of 2-3 g of tartaric acid is desirable for the prevention of hydrolysis when bismuth,
antimony, or tin is present. Excessive amounts of ammonium salts or of the thiocyanate
precipitant should be absent, as should also oxidising agents; the solution should only be
slightly acidic, since the solubility of the precipitate increases with decreasing pH. Lead,
mercury, the precious metals, selenium, and tellurium interfere and contaminate the
precipitate. The essential experimental conditions are, slight acidity of the solution with
respect to hydrochloric acid or sulphuric acid, since the solubility of the precipitate increases
appreciably with decreasing pH, the presence of a reducing agent, such as sulphurous acid or
ammonium hydrogensulphite, to reduce copper(II) to copper(l), a slight excess of ammonium
thiocyanate, since a large excess increases the solubility of the copper(l) thiocyanate due to
the formation of a complex thiocyanate ion, the absence of oxidising
agents (py et al. 1979: 455-456).
There are many ligands in addition to water, for example Cl-, NH3, CN-, NO2-, and
transition metal ions, in particular, form a large number of complex ions with different
ligands. The number of ligands surrounding the central atom, or ion, is called the
coordination number. The numerical value of the co-ordination number depends on a number
of factors, but one important factor is the sizes of both the ligands and central atom, or ion.
The shape of complex ions formed by typical elements can be determined by assuming each
ligand to be covalently bonded to the central ion and applying the theory of electron pair
repulsion (Chambers, and Holliday, 1975: 46).
Apart from forming molecular compounds with water (hydrate) certain salts have the
properties of combining with the second salt either with or without water. In this combination,
the character of each salt is somewhat modified but not completely changed. Because that's
the name, "double salt". In physical properties such as crystal shape, solubility, and, in some
cases, color, double salt crystals differ from simple salts. This compound follows the laws of
certain proportions. Ammonium sulfate crystallizes from the solution as anhydrous salt,
(NH4)2SO4; copper sulfate as hydrate, CuSO4-5H2O; but when an equivalent amount of two
salts is in a joint solution of double salt, (NH4) 2SO4-CuSO4-6H2O, separate first because it is
more soluble than each single salt (Arthur et al, 1922: 61).
2. Results Review
Based on experiments conducted (Setiawan, et al. 2017: 2) qualitative tests of nitrate
ions were carried out by reacting the solution of complex compounds with concentrated iron
(II) ammonium sulfate and concentrated sulfuric acid. (Vogel, 1979). Calculation of free
energy is done by optimizing the possibility of the structure of complex compounds using the
Gaussian vol program. 5.0. The crystals of complex compounds produced are colorless
because the central atom Cd (II) has d orbitals which are filled with electrons so there is no
transition d-d. The reaction between cadmium nitrate and 1,3-bis (difenilfosfino) propane
(dppp) with stoichiometry 1:1 in methanol solvents produces complex monomer compounds
[Cd(ONO2)2 (dppp)] with distorted tetrahedral structures. Dppp acts as a bidentate septic
ligand and nitrate ion acts as a monodentate ligand.
The formation of the metal complex is dictated by its stability. This stability of the
metal
complex depends both on the metal ion and the ligand. In general, stability of the complex
increases with decreasing size and increasing electron affinity of the central metal. Thus
highly polarizing transition metal ions have greater tendency to form complex ,regardless of
the nature of the ligand, the stability of the bivalent transition metal complexes increase in the
order Mn+2<Fe+2<Co+2<Ni+2< Cu+2 <Zn+2 . The chemistry of Cu(II) ion is considered in this
work. Cu(II) will be presented in terms of its dn configuration. The (+II) state is the most
stable and important for copper. The cupric ion Cu+2 has electronic configuration d9 and has an
unpaired electron. Its compounds therefore are colored and paramagnetic. Distorted
octahedral arrangement is common in copper compounds with two long bonds and four short
ones (Kumar, et al. 2014: 2).
According to (Namdeo, et al. 2017: 3) The complex has been prepared from the
reaction of copper nitrate (0.01 mol, 2.41 gm) dissolved in 50 ml of ethanol with
thioacetamide (0.01 mol, 0.75gm) dissolved in 50 ml of ethanol and 2-[(4- methyl phenyl
imino) methyl]-6-methoxy phenol (0.01 mol, 2.41 gm) in 250 ml of round bottom flask fitted
with reflux condensor and was refluxed at 60-700C on water bath for 2-3 hours. The product
was cooled at room temperature and kept overnight. Then filtered to get crystals. Washed with
hot etanol. The complex is then recrystallized with methanol and dried to get purified
compound. The complex was stored in a desiccator over anhydrous calcium chloride.
According to (Krstic, et al. 2015: 9) Biometals achieve interaction with acid-type anti
inflammatory drugs at micromolar and millimolarlevels. R-COOH behaves as monodentate,
bidentate or a bridge ligand, which can be reliably determined based ona model system, where
in the complexes are formed with different stoichiometric compositions, and the geometric
structures, which can be determined using various analytical techniques (UV/VIS, FTIR,
EPR, X-ray, ESI-MS, etc.). The associates obtained are important for the following reasons:
theory of coordination chemistry, significance of the development of new methods for
determining micro amounts of active components, to achieve more balanced therapeutic
dosing, biodistribution of medicine, monitoring its pharmacokinetics including excretion;
reduction of unwanted responses, improvement of anti-microbial activity, synergistic effect of
the metals and medicine, as well as improved anti-ulcerous, antitumor and anti-bacterial
activity.
Based on the research that has been done (Setiawan and Iwan, 2014: 2) The reaction
that occurs in the synthesis of NOTA is a bimolecular nucleophilic substitution reaction, this
is because the structure of the R-X compound (bromo acetic acid) is the primary alkyl halide.
The condition of bromine which has electronegative properties is smaller than nitrogen
(electronegativity of nitrogen = 4.03; whereas bromine = 2.96), so that nitrogen is easier to
replace the position of bromine in bonds, and bromine is released (bromine is a loose group
well).
B. OBJECTIVE OF EXPERIMENT
Determine the coordination number of the complex with CuCl2.2H2O material
C. APPARATUS AND CHEMICALS
1. Apparatus
a. Beaker 50 mL 2 units
b. Beaker 100 mL 4 units

c. Erlenmeyer 100 mL 8 units

d. Burette 2 units

e. Measuring Pipette 5 mL 1 unit

f. Measuring Pipette 10 mL 1 unit

 g. Bulb pipette 1 unit

h. Funnel 1 unit

i. Stir road 2 unit

j. Gauze and tripod 1 unit

k. Thermometer 1 unit

l. Spray bottle 1 unit

m. Volumetric flask 100 mL 3 units

n. Volumetric flask 250mL 1 unit

2. Chemicals
a. Ammonium NH3
b. Copper (II) Chloride CuCl2.5H2O

c. Ethanol C2H5OH

d. Ammonium hydroxide NH4OH

e. Crystal Sodium Borax Decahydrate Na2B4O7.10 H2O

f. Metil orange

g. Chloride acid HCl

h. Indicator PP

D. WORK PROCEDURE
1. Determination of Coordination Complex Number by CuCl2.2H2O
 Preparation of CuCl2 solution and NH3 8.5 M solution
 CuCl2.2H2O

CuCl2
Solution

25 mL of
alcohol
8.5g 96%
4567 4567

CuCl2.2
3 8 3 8
1 11

2 9 2 9
1 1
0

4.25g of H2O
CuCl2.2H2O

25 mL of
25 ml` of NH4OH 17 M alcohol
96% NH3 8,5 M Solution

 Standaridization of NH3 solution

1,87 gram of Na2B4O7.10H2O
Na2B4O7.10H2O. aquadest
solution

3
2
4 5
1
6 7
1 1
8
9
3
4 5
2 1
6 7
8
10 9 1,87 gram
ofNa2B4O7.10H2O
.

HCl

10 mL Na2B4O7
10 mL Na2B4O7 solution
2 drops methyl solution
orange

titrate until 3 times

2. Determination of Coordination Complex Number of Cu(NH3)2+ by Titrimometry

Method
 0 NH
0
1
1 NH3 solution 2
0
3
2
0 3
0
3
0 4
0
4
0 5
0
5
0 0
0

10 mL of CuCl2 Note the

temperature and
color change

Volume of NH3
solution that use by
the comparing of 1:1,
1:2, 1:3, 1:4, 1:5, and
1:6 (Cu:NH3)

BIBLIOGRAPHY

Blanchard, Arthur., Joseph W. Phelan S.B and Arthur R. Davis, Ph.D. 1922. Synthetic
Inorganic Chemistry : A Course of Laboratory and Classroom Study for First Year
College Students. United States: John Wiley & Sons, Inc.

Chambers, C and A.K Holliday. 1975. Modern Inorganic Chemistry. Great Britain:
Bufferworth & Co

Housecroft, Cathrine E and Alan G. Sharpe. 2001. Inorganic Chemistry. United Kingdom:
Pearson Education Limited

Jeffery, GH., J Basset., J Mendham and R C Denney. 1978. Vogels Textbook of Quantitative
Chemical Analysis Fifth Edition. United States: Longman Scientific & Technical

Kumar,T. Sravan., A. Satya Kuamr and Kashi Reddy Methuku. 2014. Multi Dentate Ligands
and Metal Complexes Derived from Ninhydrin and Ethylen Diamine. International
Journal of Modern Chemistry and Applied Science. Vol. 1 No. 4 ISSN 2349 – 0594

Krstic, Nenad S., Ružica S Nikolić., Maja N Stanković., Nada G Nikolić and Dragan M
Đorđević. 2015. Coordination Compounds of M(II) Biometal Ions with AcidType
 Anti-inflammatory Drugs as Ligands. Tropical Journal of Pharmaceutical
Research. Vol. 14 No.2 ISSN: 1596-5996

Namdeo, Pratibha., Arpan Bhardwaj and S.K. Verma. 2017. Synthesis Of Mixed Ligand
Metal Complex Of Cu (II) With Schiff Base And Thioacetamide. International
Journal of Engineering Technologies and Management Research. Vol. 4 ISSN
2454-1907

Saito, Taro. 1996. Kimia Anorganik. Tokyo: Iwanami Shoten

Setiawan, Duyeh and Iwan Hastiawan. 2014. Sintesis Dan Karakterisasi 1,4,7
Triazasiklononana-1,4,7-Asam Triasetat (Nota) Sebagai Ligan Dalam Senyawa
Kompleks Sediaan Radioterapi. Chimica et Natura Acta. Vol.2 No.1

Setiawan, Wawan., Fariati and Effendy. 2017. Sintesis dan Karakterisasi Senyawa Kompleks
dari Kadmium Nitrat dan 1,3-bis(difenilfosfino)propana dengan Stoikiometri 1 : 1.
Journal Cis-Trans (JC-T). Vol 1, No 2, e-ISSN 2549-6573