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 CO2. Molecular orbitals contain four sets of orbitals and one
atomic orbital of three atoms. An explanation of the bond in CF4 involves five sets of atomic
orbitals and a set molecular orbitals, that is a six-component problem. Similarly, SF6 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
3 8 3 8
1

2 9
11

2 9
1 1
0
CuCl2.2
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

32
4 5
1 6 7
11
8
9 32
4 5
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)
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