Complexes of 2,4 Diamino 6-Hydroxy Pyrimidine PDF

Synthesis, spectral studies of Cr+3,Mn+2,Fe+3,Co+2,Ni+2,Cu+2 metal
Chapter II
ion chelates with 2 ,4,Diamino 6 Hydroxy Pyrimidine
Chapter-II
Synthesis, spectral studies of Cr+3,Mn+2,Fe+3,Co+2,Ni+2,Cu+2 metal ion chelates
with 2 ,4,Diamino 6 Hydroxy Pyrimidine
2.1. Chemistry of 2,4-Diamino 6 Hydroxy Pyrimidine (DAHP)
Pyrimidines are the six membered hetrocyclic compound containing two
nitrogen atoms1. 2,4 diamino pyridymine derivatives have received much attention
due to their wide application in antviral agent & modified to antitumor agent2.
Heterocyclic molecule containing pyrimidine moiety are of great interest & which is
useful for microbial activities3.Hetrocyclic compound are of great importance to life
in many natural products such as antibiotic, vitamins, harmones4. Pyrimidine
derivative are known to be antiinflimantory & analgesic5. 2-mercaptopyrimidine have
been studied as antitumor and antithyroid agents6. Pyrimidine derivatives having
mercapto group occupy a unique position in medicinal chemistry7. Literature survey
reveals the importance of pyrimidine derivatives containing nitrogen atom including
in nucleic acids, uracyl, cystosine and thymine with transition metal ions has been
reported8,9. The pyrimidines have been of great intrest in reaserchers for their
biological activities & HIV inhibitor10Certain reterences indicates that pyrimidine
11,12
ligands are catalyst in drug interaction with biomolecule . Literature did not
reveals synthesis characterisation of 2,4 Diamino 6 Hydroxy pyrimidine with
Cr+3,Mn+2,Fe+3,etc. The ligand 2,4 Diamino 6 Hydroxy Pyrimidine has good
chelating tendency and used to synthesis transition metal ion chelates.
The ligand DAHP contain primary amine tertiary amine & hydroxy group. Its
molecular formula is C4H6N4O.& mol.wt. 126.12. It is white colour solid crystalline
powder. It melts in the temperature range 285-2880C its boiling point 523.960C at 760
mmhg. It is a selective GTP cyclohydrolase inhibitor13.pyrimidinedaravative play an
important role in many biological process14-15and also it is used as drugs 16
a
pyrimidine derivatives shows antimicrobial activities like antiviral anti HIV17
antitumor18 antihypertensive19 are found to be an hetrocyclic compound containing
pyrimidine moiety20.
26
Chapter II
NH2
HO N NH2
Sructural Formula of ligand DAHP
The ligand DAHP 2,4 Diamino 6 Hydroxy pyrimidine was purchased from
sigma Aldrich. The purity of the ligand DAHP was checked by M.P. elemental
analysis & spectral data. All the chemical used for synthesis of metal chelates are of
BDH and AR grade. The metal ion chelates of ligands DAHP have been synthesis
and characterized by using elemental analysis, conductivity measurement ,infrared
spectra, electronic spectra, thermogravimetric analysis studies & X ray diffraction
studies.
2.2. Synthesis
(a) Synthesis of of Cr+3 metal ion chelates with 2,4 Diamino 6 Hydroxy
pyrimidine:
An ethanolic solution of 0.01M CrCl3 6H2O and ethanolic solution of ligand
0.02M 2,4 Diamino 6 Hydroxy pyrimidine were mixed in molar ratio 1:2 in an hot
condition in the presence of buffer solution (PH=10).The PH of the reaction mixture
was adjusted in between 6.2 to 6.8 by adding buffer solution. The resulting mixture
was refluxed over a water bath at about two & half hour a light gray coloured solid
was appered. After colling at room temperature, a gray coloured solid were separated
by filteration and ppt were washed with ethanol, dried in vaccum desicator.
(Yield : 69%)
(b) Synthesis of Mn+2 metal ion chelate with with 2,4 Diamino 6 Hydroxy
pyrimidine:
Into a 250 cm3 beaker containing alcoholic solution of 0.01 M of MnCl2 4H2O
was added a solution of 0.02 M of 2,4 Diamino 6 Hydroxy pyrimidine in ethanol
solution dropwise with constant stirring. The mixture was treated with buffer solution
27
Chapter II
, precipitate the golden brown product, which was suction filtered, washed with
ethanol to remove excess metal ion and unreacted ligand. (Yield : 58%)
(c) Synthesis of Fe+3metal ion chelates with 2,4 Diamino 6 Hydroxy
pyrimidine:
An ethanolic 50 ml of FeCl3.4H2O (0.1 M) solution is treated with 50 ml (0.2
M) ethanolic solution of ligand with constant stirring. pH of solution is maintained at
6.8 by the addition of buffer solution of PH=10. The reaction mixture is refluxed in
water bath for three hours using vertical water condenser. Precipitate is formed, it is
filtered through sintered glass crucible. Residue was washed with hot ethanol. The
residue was dried in vacuum desiccators over fused calcium chloride, yield were
recoded. (Yield:61%)
(d) Synthesis of Co+2 metal ion chelate with 2,4 Diamino 6 Hydroxy
pyrimidine:
The metal complexes were prepared by adding solution of CoCl2 .6H2O(0.01
M) in 50 mL absolute ethanol to 50 mL of an ethanolic solution of the ligand (0.02
M) (1:2 ratio) and heating under reflux conditions for about 80-90 °C to an extent of
2 to 4 h. Then the reaction mixture was concentrated into a small volume by
evaporation method, on cooling, the metal complexes purified out. The crystallized
metal salts were then filtered and washed it thoroughly with ethanol and dried under
vacuum over fused calcium chloride. (Yield:54%).
(e) Synthesis of Ni+2 metal ion chelate with 2,4 Diamino 6 Hydroxy
Pyrimidine:
50 ml of hot ethanolic solution of NiCl2.6H2O (0.01M ) was added to a hot
alcohol solution of 2,4 Diamino 6 Hydroxy Pyrimidine (0.02M) in the molar ratio 1:2
and refluxed on the water bath for 3h.The content were cooled to obtain precipitate.
The precipitate were filtered through whatman filter paper ,the residue were washed
with ethanol, dry it in a dessicator and weigh it. Yield of complex 57%.
(f) Synthesis of Cu+2 metal ion chelates with 2,4 Diamino 6 Hydroxy
Pyrimidine:
To a hot alcoholic solution solution of ligand DAHP (0.02M) in 25ml of
ethanol a suspension of respective metal salt CuCl2.2H2O(0.02M) was added drop
wise with constant stirring. After complete addition little amount of buffer solution
28
Chapter II
was added by maintaining PH 6.5.The reaction mixture was refluxed on a water bath
for 4-6 hrs. The precipitated complexes were filtered, washed with ethanol. Followed
by ether and dried over fused calcium chloride. Yield: 63%
2.3. Characterisation
After synthesis of metal complexes, they are characterized by physical
parameters, chemical analysis and spectral study. The prepared complexes are of
various colours varied from light gray, golden brown, mahagony , pista ,opaline green
different from ligand indicating that the colours formed depend upon the metal ions,
as an evidence for the chelation.
2.4. Physical parameters and chemical analysis
All the chemicals and solvents used were of A.R. grade. Elemental analysis
was done on Thermo Finnigan elemental analyzer. Molar conductance of the metal
ion chelates were determined in DMSO on conductivity meter Equip-tronics model
No-EQ661. The melting point were taken in an open capillary tube and are
uncorrected.
After synthesis of metal complexes they are characterized by physical
parameters like yield, colour, decomposition point, molar conductance were measured
and results are given in table 1. The estimation of metal is determined by gravimetric
methods as well as by EDTA method. Chloride was estimated by Volhards method21.
Metal-ligand ratio:
The weighed amounts of complex were ignited in preweighed crucible

at high temperature till the metal oxide is obtained. Using obtained weight of metal
oxide and weight of metal complex the M-L ratio of metal complex were
determined22-23.
Presence of lattice water molecules present in the coordination compounds

were determined by keeping the known weight of the complex in previously weighed
crucible in oven at about 110 for about one hour. The weight of difference gives
the amount of lattice water .
29
Chapter II
Table 1: Analytical data and physical properties of ligand (DAHP) and its metal 1ion chelates.
Ligand / Metal Molar Cond.

Colour D.P Yield (%) %Cl
Complexes (Ω-1 cm2 mol-1
DAHP white 285-286 - - -
[Cr(DAHP)2]Cl.2H2O 10.05
Light gray 241-252 69 41.59
(9.49)
[Mn(DAHP)2 ].H2O
Golden brown 222-242 58 8.12 -
[Fe(DAHP)2 ]Cl.H2O
9.16
Golden brown 252-290 61 39.14
(9.87)
[Co(DAHP)2 ]H2O Mahagony 227-280 54 11.16 -
-
[Ni(DAHP)2].2H2O Pista 235-262 57 10.57
19.20
[Cu(DAHP) .H2O].Cl Opaline green 242-250 63 39.82
(18.82)
30
Chapter II
Table 2.Percent C,H,N&metal ion in DAHP metal ion chelates
Empirical
Compounds M.W. %C %H %N %M
Formula
38.05 4.72 44.40
DAHP 126.12 C4H6N4O -
(38.02) (4.75) (44.35)
25.46 3.97 29.52 14.16
[Cr(DAHP)2]Cl.2H2O 373.73 C8H14N8O4ClCr
(25.68) (3.74) (29.96) (13.91)
29.48 3.86 34.97 16.15
[Mn(DAHP)2 ].H2O 323.17 C8H12N8O3Mn
(29.70) (3.71) (34.65) (16.99)
26.77 3.05 30.95 15.27

[Fe(DAHP)2 ]Cl.H2O 359.58 C8H12N8O3ClFe
(26.69) (3.33) (31.14) (15.52)
29.92 3.80 34.76 18.15

[Co(DAHP)2]H2O 327.17 C8H12N8O3Co
(29.34) (3.66) (34.23) (18.01)
27.02 4.58 32.57 17.14
[Ni(DAHP)2].2H2O 344.93 C8H14N8O4Ni
(27.83) (4.05) (32.47) (17.01)
19.14 2.54 23.52 26.27
[Cu(DAHP).H2O].Cl 242.16 C4H6N4O3ClCu
(19.82) (2.89) (23.12) (26.23)
31
Chapter II
2.5. Electronic and magnetic studies of metal ion chelates

The electronic spectra deals with transition in UV-Visible region. UV spectra
were recorded on UV-Vis spectrophotometer Thermo Evolution 300 in the 200-1000
nm ranges in DMSO solution (10-3). The electronic spectra of chelating agent 2,4-
Diamino 6-Hydroxy Pyrimidine (DAHP) and its metal chelates were obtained from
Vishnu Chemicals Hyderabad. The UV-Visible spectra of ligand and its metal
complexes were recorded in DMSO at room temperature. The electronic spectrum of
ligand showed only one intense band at 272 nm (36764cm-1) which is assigned to
n→π* transition of the C=N chromophore24.The magnetic moment were determined
at room temperature by Gouy’s method. The value of magnetic moment values of the
complexes are given in Table 1..The Cr(III) chelate shows a characteristic bands at
around 29411cm-1,21978 cm-1 and 17730 cm-1 which may be attributed to 4A2g → 4T2g
(F), 4A2g → 4T1g (F), 4A2g → 4T1g (P),transitions25-27,and the value of magnetic
moment of this Metal Chelate is 3.86 B.M. suggesting an octahedral geometry28. The
Mn (II) chelate shows characteristic band at 37313 cm-1,32781 cm-1,22624 cm-1 and
15384 cm-1.The first two intense maxima are due to intra ligand transitions of the
organic moiety. The other two transitions may be assigned to 4T1g → 4T1g (P) and 4T1g
→ 4T2g (F) transitions29-31. The electronic transitions together with a magnetic
moment value 5.77 B.M indicates an octahedral geometry32-33. Fe(III) complex
showed bands at 36101 cm-1 ,29585 cm-1 cm-1 and 20242 cm-1.The band 29585 cm-1
showed charge transfer band and last band assigned to 5T2g (F)→ 5Eg an octahedral
arrangement34.The Uv-Vis.spectra of Cobalt complex showed three bands 35714 cm-1
is assigned to π→π*/ n→π* transitions. The another band 1428 ,16949 cm-1 and
24691 cm-1 transitions due to 4A2g → 4T1g (P), 4A2g → 4T1g , 4A2g → 4T2g35. The room
temperature magnetic moments of the solid cobalt (II) complexes were found at 4.1 –
4.6 B.M., indicative an Co(II) ion is an octahedral environment36.The study of
magnetic moment indicating for the Ni(II) chelate (d8) were found to be 3.12 B.M
favouring an octahedral environment37. The Ni(II) complex exhibit four absorption
bands ,first first two intense maxima are due to intra ligand transitions of the organic
moiety. The other two transitions may be assigned to 4T1g → 4T1g (P) and 4T1g → 4T2g
(F) suggesting octahedral geometry38.The Copper chelate shows a single broad band
32
Chapter II
at 18939 cm-1 due to transition between 2

Eg → 2T2g transitions . Further confirmed
magnetic moment between 1.83-1.98 B.M. favoring tetragonal geometry39-41.The
observed value of magnetic momemt is 1.87 B.M.
Table 3. Electronic spectral data in nm(cm)and magnetic moment of DAHP and
its metal ion complexes.
Compound μeff (B.M.) Assignment
Absorbance band
cm-1
DAHP 36764 (272) n→π*
4
3.86 29411(340) A2g → 4T2g (F),
[Cr(DAHP)2]Cl.2H2O 4
21978(455) A2g → 4T1g (F),
4
17330(564) A2g → 4T1g (P),
5.70 37313(268) n→π*
[Mn(DAHP)2].H2O 32781(305) π→π*
4
22624(442) T1g → 4T1g (P)
4
15384(650) T1g → 4T2g (F)
[Fe(DAHP)2]Cl.H2O 5.47 36101(277)
29585(338) LMCT
5
20242(494) T2g (F)→ 5Eg
4.42 35714(280)
4
24691(405) A2g → 4T1g (P),
[Co(DAHP)2]H2O 4
16949(590) A2g → 4T1g ,
4
14285(700) A2g → 4T2g
3.12 34246(292)
33112(302)
[Ni(DAHP)2].2H2O 4
24096(415) T1g → 4T1g (P)
4
15873(630) T1g → 4T2g (F)
2
[Cu(DAHP) .H2O].Cl 1.87 18939(528) Eg → 2T2g
33
Chapter II
Fig.1.UV visible spectra of ligand DAHP
Fig.2. UV visible spectra of [Cr(DAHP)2]Cl.2H2O
34
Chapter II
Fig.3. UV visible spectra of [Mn(DAHP)2 ].H2O
Fig.4. UV visible spectra of [Fe(DAHP)2 ]Cl.H2O
35
Chapter II
Fig.5. UV visible spectra of [Ni(DAHP)2].2H2O
Fig.6. UV visible spectra of [Cu(DAHP) .H2O].Cl
36
Chapter II
2.6. IR spectral characterisation

The characteristic infrared bonds which are assigned to most significant
functional groups of the chelating agent and its metal ion chelates are summarized in
table no.4 .It is very difficult to interpret IR spectra due to presence of similar groups
and absorption bands. Hence comparing spectral characterization of ligand with its
metal ion chelates, which gives valuable information regarding nature of chelating
agent as well as coordination sites through which metal ion is coordinated with
chelating agent. IR spectra were recorded on Brucker Alpha T IR spectrophotometer.
IR Spectral Analysis of [Cr(DAHP)2]Cl.2H2O :

The IR spectra of ligand shows the characteristic band at 3388 cm-1and 3334
cm-1 is due to υNH237. In [Cr(DAHP)2Cl2]Cl complex the band 3388 cm-1is shifted to
3341 cm-1 by lowering wave number ,υNH2 ranges from 3100-3412 cm-1 38.It indicates
υ NH2 invole for complex formation. The another same band is observed it indicates
that it does not coordinate with metal ion. Also another band found at 3232 cm-1it may
be due to υOH group present in ligand The complex showing disappearance of
phenolic υ(OH) band in the showing deprotonation of proton to coordinate with the
metal ion. This is further supported by the shifting of υ (C-O) phenolic band to lowers
frequency 1229 cm-1 in the metal complex, it suggests the co-ordination by the
phenolic oxygen after deprotonation indicates chelation of ligand to metal ion through
phenolic oxygen. The band observed at 1661 cm-1 indicates C=N group in ligand. This
band shifted by lowering wavenumber and shifted to 1641 cm-139.It indicates this
group involve for coordination with metal atom. The other band M-N observed 504
cm-1and M-O observed at 542 cm-1in metal ion chelates.
IR Spectral Analysis of [Mn(DAHP)2 ].H2O:
The IR band at 3388 cm-1and 3329 cm-1 is due to υNH2 and3388 cm-1 is
shifted to 3375 cm-1 and by lower wave number indicates involvement for complex
formation. The another band observed at 3329 cm-1in ligand it may be due to and
υNH2 , this band is found same in the complex. It suggests that this group does not
involve for bonding with metal ion. The spectrum of the free chelating agent exhibited
a medium intense band in the range 3232 cm-1 due to OH stretching vibration. This
37
Chapter II
band disappeared in the complexes spectra, indicates the deprotonation of the

phenolic groups and coordination of oxygen to the metal ions. In addition, the band at
1245 cm−1 due to ν(C–O) (phenolic) of the free ligand shifted by 1218 cm−1 lower
stretching frequency , indicates the coordination of the phenolic oxygen to the metal
ions. The strong absorption peak found at 1661 cm-1 C=N group in ligand and is
shifted to 1643 cm-1by lower wave number by 18 cm−1,it indicate this group involve
for complexation. The another one band found at405 cm-1 and 509 cm-1 shows that M-
N &M-O bonding40.
IR Spectral Analysis of[Fe(DAHP)2 ]Cl.H2O:
In the study of IR gives information regarding the intermolecular bonding in
complex. The new characteristic band appeared at 3388 cm-1 is to υNH2 in a ligand
and which is shifted at 3363 cm-1 by lower wavelength. This shows that the υNH2
group take part for participation with metal. The absence of the band in the region
3300–3200 cm−1 assigned to the phenolic –OH groups in the chelating agent and the
shift to lower wave number of ν (C-O) by ~40 cm-1 shows the the chelation of ligand
to metal ion through phenolic oxygen. This gives information that the phenolic –OH
group on deprotonation forms bond with central metal ion through oxygen atom.46-47.
The wavenumber 1648 cm-1 it may be due to C=N group in which is shifted by
lowering wave number by 15 cm−1.It suggest that C=N group take part bonding with
metal atom48.The new peak observed at 508 cm-1 & 636 cm-1 it may be due to M-N
and M-O.
IR Spectral Analysis of[Co(DAHP)2 ]H2O:
The IR spectrum of ligand shows strong band 3388 cm-1 is to υNH2 shifted to
lower frequency by 41 cm-1 attributed to involvement of complex formation. A
absorption band observed at 3332 cm-1 in the IR spectra of the ligand is due to the
stretching vibration of OH group which disappears in the spectra of the metal chelate,
suggests the deprotonation of the phenolic group and the coordination of these ligands
through the phenolic oxygen. It is also supported by the shift to lower wave numbers
-1 -1
of the band from 1245 cm to 1221 cm due to the stretching vibration of C–O
phenolic when compaired to the chelating agent49-51.
The another new band observed at 1661 cm-1 indicates C=N group in ligand. This
band shifted by lowering wavenumber and shifted to 1638 cm-1 52,53
.It indicates this
38
Chapter II
group involve for coordination with metal atom. The band appeared at 495 cm-1 and
543 cm-1 it may be due to M-N and M-O.
IR Spectral Analysis of [Ni(DAHP)2].2H2O :
Infra red spectra of ligand DAHP exhibit strong υNH2 stretch corresponds
amino group at 3388 cm-1shifted to 3342 cm-1 by decreasing wavenumber .It suggest
that complex formation of ligand with metal brought by change in wave number. The
IR spectra of the DAHP chelating agent exhibits a band in the region 3232cm-1, a
medium intensity band has disappeared in the complexes and indicates deprotonation
of the phenolic groups and coordination of oxygen to the metal ions It is also
supported by the shift to lower wave numbers of the band from 1245 cm -1 to 1228 cm
-1
due to the stretching vibration of C–O phenolic when compaired to the chelating
agent .The strong absorption peak found at 1637 cm-1 due to C=N group cm-1.This
frequency assigenable C=N group take part in formation of coordinate bond. This has
been further supported by appearance of new band at475 cm-1and 542 cm-1assigenable
to metal nitrogen stretching vibration and metal oxygen vibration.
IR Spectral Analysis of[Cu(DAHP) .H2O].Cl:
A strong υNH2 stretching at 3388 cm-1 and 3334 cm-1 in ligand .The C=N
stretching at 1661cm-1and υOH starching at3232cm-1is observed in ligand.The
complex formation of ligand with metal brought about significant changes in wave
numbers. The strong υNH2 stretch at 3388 cm-1 in ligand turned weak and shifted to
lower frequency by 62 cm-1 is indication of involvenment of amino group in complex
formation. The another band found at 3232 cm-1 it may be due to υOH group present
in ligand. This band disappeared in the complexes spectra, indicates the deprotonation
of the phenolic groups and coordination of oxygen to the metal ions. In addition, the
band at 1245 cm−1 due to ν(C–O) (phenolic) of the free ligand shifted by 1259 cm−1
higher stretching frequency , indicates the coordination of the phenolic oxygen to the
metal ions. similarly The C=N stretching is turned weak and shifted lower wave
number by 56 cm-1 reflecting that involvement of C=N group with metal. The new
band appeared at 3442 cm-1 indicated that the metal atom is coordinated with water
molecule which is not found in ligand. Also M-N,M-O band found at 459 cm-1& 524
cm-1 54-58.
39
Chapter II
Table 4: Infrared spectral data of ligand (DAHP) and its Cr(III), Mn(II), Fe(III),Co(II),Ni(II) and Cu(II) metal complexes.
υ(NH2) υ(NH2)
Compounds υ(H2O) υ(OH) υ(C=N) C-O υ(M-N) υ(M-O)
DAHP - 3388 3334 3232 1661 1245 - -
[Cr(DAHP)2]Cl.2H2O - 3341 3334 - 1641 1229 504 542
[Mn(DAHP)2 ].H2O 3375 3329 - 1643 1218 405 509

-
[Fe(DAHP)2 ]Cl.H2O 3363 3339 - 1648 1205 508 636

-
[CO(DAHP)2 ]H2O 3347 3332 - 1638 1221 543 495

-
[Ni(DAHP)2].2H2O 3342 3337 - 1637 1228 475 542

-
3442
[Cu(DAHP) .H2O].Cl 3354 3332 - 1605 1259 459 524
40
Chapter II
Fig.7.Infrared spectrum of ligand DAHP
Fig.8.Infrared spectrum of [Cr(DAHP)2]Cl.2H2O
41
Chapter II
Fig.9.Infrared spectrum of [Mn(DAHP)2 ].H2O
Fig.10. Infrared spectrum of [Fe(DAHP)2 ]Cl.H2O
Fig.11. Infrared spectrum of [Co(DAHP)2 ]H2O
42
Chapter II
Fig.12. Infrared spectrum of [Ni(DAHP)2].2H2O
Fig.13. Infrared spectrum of [Cu(DAHP) .H2O].Cl
2.7. Thermogravimetric analysis

Thermogravimetric analysis were recorded by Thermal Analyser(TG-
DSC)Instrument SDTQ 600 V20.9 in nitrogen atmosphere @ 100c/min.
Thermogravimetric Analysis of [Cr(DAHP)2]Cl.2H2O:
TGA curves of complex of [Cr(DAHP)2]Cl.2H2O reflects three stage of
decomposition. In the first step 18.06% weight is loss in the temperature range R.T. -
1280C.This loss is due to lattice water elimination of lattice chloride59. The second
step of decomposition 27.96% mass is loss in the temp.range 128-4010C which
corresponds to decomposition of some organic part from complex. In the third peak
13.53% mass is loss due decomposition of remaining organic moiety around the metal
43
Chapter II
atom from complex in the temperature range 401-6490C.The weight of residue is

found 40.40% Which is close agreement with theoretical value i.e.40.67%.
Thermogravimetric Analysis of [Mn(DAHP)2 ].H2O:
The thermogravimetric analysis data of complexes gives an information about
number and nature of decomposition of complex. loss of lattice water molecule
observed in temp. Room temp. to 1010C the 5.59% mass is loss. Above 1010c
complex begins to decompose upto 3890c 33.25% (cal.33.41%) weight is loss. This
loss may be of some part of complex. The next decomposition observed in the
temperature range from 389-7090C the maximum weight 38.16% is loss. This shows
good agreement with theoretical value (39.08%). Finally give corresponding metal
oxide. This complex are thermally stable and exhibit multistage decomposition
pattern.Lastly weight of residue remains i.e.22.99%(cal.21.94%).
Thermogravimetric analysis [Fe(DAHP)2 ]Cl.H2O:
The TGA curve for [Fe(DAHP)2 ]Cl.H2O pattern shows weight loss initially
from R.T.to 1160C 4.935% (cal.5.00%) loss may be due to lattice water molecule of
complex . the next stage of decomposition occurs in the temp. range 116 to 1570C
9.503%(9.873%) weight is loss . This loss corresponds to elimination of chloride from
complex. From 157 to 333 0C 23.67% mass is loss this loss may be due to loss of
some part of the complex. The next peak observed in the range 333 to 7430C with
18.07% mass is loss this loss may be due to remove remaining pyrimidine moiety
around central metal atom. From 7740C the weight of residue remain unchanged upto
1000 Fe2O3.The % of residue Fe2O3 found to be 43.81% (44.40%). This shows good
agreement with calculated value.
Thermogravimetric Analysis of [Co(DAHP)2 ]H2O:
Cobalt complex exhibit three steps of decomposition. First step is observed in
the temp.range R.T.to 1310C, 5.311% mass is loss,this loss in mass is due to
elimination of water from the complex.This value gives close agreement with
theoretical value.From temperature range 131 to 3120C 31.14% mass is loss .This loss
in mass may be due to elimination of some part of pyrimidine group from the
complex compound. Third step of decomposition occurred in the temperature range
312 to 697 0C 41.48% weight is loss .This loss in weight is due to major part of
pyrimidine molecule is to be removed. The weight of residue found to be
44
Chapter II
22.06.%.The percent losses in massas observed in TG curve are equivalent to the

calculated values of mass loss, from 6970C the residue (CoO) remains unchanged .
Thermogravimetric Analysis of [Ni(DAHP)2].2H2O:
Thermal study of [Ni(DAHP)2].2H2O showed three steps of decomposition. In
case of Ni(II) metal complex first step of weight loss observed in the temperature
range R.T. to 1120C with 9.820% weight loss due to loss of lattice part of the
complex .after that the weight loss started in the temperature 112 to 319 0C with
weight loss 31.32%. This weight loss may be due to removel of some part of the
complex. The third step of decomposition is observed at the temperature 319 to
6210C with 38.64% mass loss due to loss of remaining moiety around central atom
from complex..From 6210C to 10000C the complex get converted into NiO. The
observed value close agreement with calculated values.
Thermogravimetric Analysis of[Cu(DAHP) .H2O].Cl:
The % of loss of chloride molecule at R.T.to 146 0C was found to be 14.31%
which is very close to the calculated value 14.66%. The decomposition continues at
the temp. 146-2280C,the weight loss were found 6.45(cal.mass 7.43%) which
indication that the coordinated water molecule. Further complex decomposes from
228-3660C with 21.31% (cal.22.29%) -NH2 group and some part from complex.The
last step of decomposition observed in the temperature range 366 to 6250C, 24.99%
mass loss observed which indicates elimination of remaining pyrimidine moiety from
the complex. At 6250C horizontal nature of curve shows the presence of thermally
stable metal oxide and which is found 32.87%(cal.32.84) 60
Table 14. Thermogravimetric Analysis of [Cr(DAHP)2]Cl.2H2O
Temp.range0c % Loss Nature of Decomposition
R.T.-128 18.06 Decomposition of Lattice
water & Chloride from the
complex
128-401 27.96 Some organic part of the
complex
401-649 13.53 Remaining organic moiety
around metal atom
649-1000 40.40(40.67) Residue(Cr2O3)
45
Chapter II
Table 15.Thermogravimetric Analysis of [Mn(DAHP)2 ].H2O

R.T.-101 5.59 Lattice part of the complex&
coordinated water
101-389 33.25 Some organic part of
complex
389-709 38.16 Remaining Pyrimidine part
of the ligand
709-1000 22.99(21.94) Residue(MnO)
Table 16.Thermogravimetric analysis of [Fe(DAHP)2 ]Cl.H2O

R.T.-116 4.93 Lattice water
116-157 9.50 chloride
157-333 23.67 NH2 group and some part of
complex
333-743 18.07 Remainingpyrimidine moiety
743-1000 43.81(44.40) ResidueFe2O3
Table 17.Thermogravimetric Analysis of [Co(DAHP)2 ]H2O

R.T.-131 5.311 Lattice part of the complex
complex
312-697 41.48 Remaing part of ligand
around the metal atom
697-1000 22.06(22.90) Residue (CoO)
Table 18.Thermogravimetric Analysis of [Ni(DAHP)2].2H2O
46
Chapter II

R.T.-112 9.82 Lattice water
complex
319-621 38.64 Remaining pyrimidine
moiety
621-1000 20.20(21.67) Residue (NiO)
Table 19.Thermogravimetric Analysis of [Cu(DAHP) .H2O].Cl

R.T.-146 14.31 Lattice part
146-228 6.45 Coordinated water
228-366 21.31 Some organic part
366-625 24.99 Pyrimidine part of the ligand
625-1000 32.87(32.84) Residue (CuO)
47
Chapter II
Fig.14. TGA of [Cr(DAHP)2]Cl.2H2O
Fig.15.TGA of[Mn(DAHP)2 ].H2O
48
Chapter II
Fig.16.TGAof[Fe(DAHP)2]Cl.H2O
Fig.17. TGA of [Co(DAHP)2 ]H2O complex
49
Chapter II
Fig.18.TGA of [Ni(DAHP)2].2H2O
Fig.19. TGAof[Cu(DAHP).H2O].Cl
50
Chapter II
2.8. Powder X ray analysis

Powder X ray diffractograms of selected complexes were recoreded in 2θ
range from 10 to 900 using Cuka radiation source at a wavelength of 1.54060 A0 At
room temp. are shown in fig.Observed diffractogram of the complexes shows
crystalline nature . The diffractograms and associated data depict the 2θ value for
each peak, the relative intensity and interplanar spacing (d-values). The X-ray
diffraction pattern of these complexes with respect to major peaks of relative intensity
using a computer programme61. Major reflexes were used to determine corresponding
interplaner distances.Independent indexing calculation of miller indices and
evaluation of lattice parameter a,b,c and interfacial angles α, β and γ were determined
by computer based powder X programme. Unit cell volume were determined by
standard formula. . This indexing method also yields the Miller indices (hkl), the unit
cell parameters and the unit cell volume. The unit cell of Mn(II) complex yielded
values of lattice parameters: a = 5.65370 Å, b =5.65370Å and c = 5.98640 Å, and a
unit cell volume V =165.71502,% . The unit cell of the Cu(II) complex yielded values
of lattice constants: a =4.98450 Å, b =4.98450 Å, c =5.98450 Å, and a unit cell
volume V volume=128.76614 ,%.
51
Chapter II
XRD of [Mn(DAHP)2 ].H2O

Crystal system : Hexagonal
Lattice type: P
Lattice parameters A=5.65370 b= 5.65370 c=5.98640 α =90 β =90 γ =120
Radiation: Cu, Wavelength : 1.54060 A0 Theta start=10 2Theta end =90
Unit cell volume: 165.71502.
Table.20
Theta Theta d d
h k l
(observed) (calculated) (observed) (calculated)
0 0 2 15.14784 14.91234 2.96820 2.99330

1 1 0 15.82766 15.74023 2.84288 2.83954
1 0 2 17.69122 17.53301 2.54967 2.55697
2 0 1 19.71034 19.79405 2.29587 2.27468
2 0 3 29.83961 29.80949 1.55314 1.54953
2 1 3 34.61897 34.49391 1.35954 1.36019
1 1 4 35.78779 35.57707 1.32064 1.32400
2 2 2 37.04224 36.90496 1.28187 1.28279
4 0 0 39.00432 38.79132 1.22672 1.22956
4 0 1 39.89585 39.75922 1.20365 1.20442
1 0 5 41.47445 41.46348 1.16554 1.16334
3 2 0 43.07087 43.05476 1.13023 1.12832
52
Chapter II
Fig.20. X-Ray Difractogram of [Mn(DAHP)2 ].H2O
[Cu(DAHP) .H2O].Cl
Crystal system : Hexagonal
Lattice type: P
Lattice parameters A=4.98450 b= 4.98450 c=5.98450 α =90 β =90 γ =120
0
Radition: Cu, Wavelength 1.54060 A Theta start=10 2Theta end =90
Unit cell volume128.76614 ,% porosity 2.39938
Table.21.
Theta Theta
h k l d (observed) d (calculated)
(observed) (calculated)
0 0 1 6.99846 7.66881 5.90063 5.77233
1 0 0 10.36651 10.44561 4.08502 4.24871

0 0 2 15.32804 15.47950 2.82372 2.88617
1 1 0 17.71828 18.30193 2.46352 2.45299
1 1 1 19.27555 19.95017 2.27643 2.25760
2 0 0 20.50688 21.26021 2.14853 2.12435
2 0 1 22.02793 22.72946 2.01030 1.99363
53
Chapter II
0 0 3 23.04197 23.59946 1.92834 1.92411
2 0 2 26.04786 26.75893 1.72332 1.71087

2 1 0 28.36566 28.66452 1.59549 1.60586
2 1 1 29.27105 29.86094 1.55122 1.54711
3 0 1 33.79800 34.05839 1.36690 1.37544
Fig.21. X-Ray Difractogram of [Cu(DAHP) .H2O].Cl
2.9. Result and discussion

The 2,4 Diamino 6 Hydroxy pyrimidine is an heterocyclic chelating agent
used to synthesis d block metal ion complexes.The elemental analysis agreed with 1:2
metal to ligand stoichimetry for all the metal ion chelates except Cu+2 metal ion
chelates. The metal ion chelates are of various colours varied from light gray, golden
brown, mahagony , pista ,opaline green different from ligand indicating that the
colours formed depend upon the metal ions,the melting point of the metal ion chelates
are higher than the chelating agent,as an evidence for the chelation. In all the metal
ion chelates of 2,4 Diamino 6 Hydroxy pyrimidine acts as tridentate and binds
through NH2 and oxygen of the phenoxyl group and nitrogen of C=N azomethine to
metal ion and to give octahedral geometry while Cu(II) give an tetrahedral geometry.
54
Chapter II
Research study indicates that this chelating agent act as tridentate.

Thermogravimetric analysis of synthesized metal ion complexes indicates that these
complexes are thermally stable. The some ‘d’ block Cr+3,Mn+2,Fe+3,Co+2,and Ni+2
metal ion chelates of 4 Diamino 6 Hydroxy pyrimidine ligand aquires octahedral
arrangement while Cu+2chelate aquires tetrahedral arrangement.
The results of physical, chemical and spectral parameters of synthesized metal

ion chelates agrees with proposed synthesized metal ion chelates
2.10. Symmary and conclusion

(1) [Cr(DAHP)2]Cl.2H2O complex coordination no. of central metal ion is 6.Central
metal ion Cr+3.Primary valency is+3.Ligand act as uninegative charge species
after reacting with central metal ion Cr+3.Ligand DAHP behaves as tridentate
ligand. Two lattice water molecules are present outside the coordination sphere.
High decomposition point of the complex suggest good thermal stability.
Complex shows electrolyte in nature. M:L ratio, TGA study of synthesized metal
ion chelates also supports the proposed empirical formula of synthesized
compounds.
(2) 2,4 Diamino 6 Hydroxy pyrimidine is an heterocyclic organic compound and used
for preparation of Mn+2metal ion complex. In [Mn(DAHP)2].H2O Complex
coordination of central metal ion is 6.Central metal ion Mn+2.Primary valency
+2.Ligand act as uninegative charge species after reacting with central metal ion
Mn+2. Ligand DAHP behaves as tridentate nature. One lattice water molecule
present outside the coordination sphere. Complex is non electrolyte in nature.
TGA of synthesized metal ion complexes indicates that these complexes are
thermally stable. The physicochemical analysis of these metal ion complex, M:L
ratio and thermogravimetric analysis also support the empirical formula of
prepared metal ion chelates.
(3) [Fe(DAHP)2 ]Cl.H2O complex coordination no. of central metal ion is 6.Central
metal ion Fe+3.Primary valency is +3.Ligand act as uninegative charge species
after reacting with central metal ion Fe+3.Ligand DAHP behaves as tridentate
55
Chapter II
ligand. One lattice water molecules are present outside the coordination sphere.
Complex shows electrolyte in nature. Geometry of the complex Octahedral.
(4) [Co(DAHP)2]H2O coordination of central metal ion is 6.Central metal ion
Co+2.Primary valency +2.Ligand act as uninegative charge species after reacting
with central metal ion Co+2. Ligand DAHP behaves as tridentate nature. One
lattice water molecule present outside the coordination sphere. Complex is non
electrolyte in nature. on the basis of the results obtained from elemental analysis,
infrared and electronic spectra ,TGA analysis it is clear that the octahedral
complex is formed.
(5) [Ni(DAHP)2].2H2O coordination of central metal ion is 6.Central metal ion
Ni+2.Primary valency +2.Ligand act as uninegative charge species after reacting
with central metal ion Ni+2. Ligand DAHP behaves as tridentate nature.
Thermogravimetric analysis support the presence of water molecule. Two lattice
water molecule present outside the coordination sphere. Complex is non
electrolyte in nature .on the basis of the results obtained from elemental analysis,
infrared and electronic spectra ,TGA analysis it is clear that the octahedral
complex is formed.
(6) [Cu(DAHP)H2O].Cl coordination of central metal ion is 4.Central metal ion
Cu+2.Primary valency +2.Ligand act as uninegative charge species after reacting
with central metal ion Cu+2. Ligand DAHP behaves as tridentate nature. Complex
is electrolyte in nature. on the basis of the results obtained from elemental
analysis, infrared and electronic spectra ,TGA analysis it is clear that the
tetrahedral complex is formed. M:L ratio, TGA study of synthesized metal ion
chelates also supports the proposed empirical formula of synthesized compounds.
56
Chapter II
2.11. Proposed structure of metal ion chelates
NH2
N
H2 N O
Cr
Cl.2H2O
O NH2
N
NH2
Proposed structure of [Cr(DAHP)2]Cl.2H2O Complex
3D view of [Cr(DAHP)2]Cl.2H2O complex
57
Chapter II
NH2
N
H 2N O
Mn
H 2O
O NH2
N
NH2
Proposed structure of [Mn(DAHP)2 ].H2O
3D view of [Mn(DAHP)2 ].H2O Complex
58
Chapter II
NH2
N
H2N O
Fe
Cl.H2O
O NH2
N
NH2
Proposed structure of [Fe(DAHP)2 ]Cl.H2O
3D view of [Fe(DAHP)2 ]Cl.H2O Complex
59
Chapter II
NH2
N
H2N O
Co
H2O
O NH2
N
NH2
Proposed structure of Co(DAHP)2]H2O
3D view of [Co(DAHP)2]H2O Complex
60
Chapter II
NH2
N
H2 N O
Ni
2H2O
O NH2
N
NH2
Proposed structure of [Ni(DAHP)2].2H2O
3D view of [Ni(DAHP)2].2H2O Complex
61
Chapter II
H2O
Cu
O NH2
N
NH2
Proposed structure of [Cu(DAHP)H2O].Cl Complex
3D view [Cu(DAHP)H2O].Cl Complex
62
Chapter II
2.12. References
(1) Adroju A.Osowole& Reuben O.Yoade, Scientific Journal of Applied
Research 4, 101-106. (2013).
(2) Hiroukietal. Anticancer Research 26: 91-98(2006).
(3) R.C. Elderfield, Hetrocyclic compounds vol.6 John Wiley & sons, New
York,NY USA (1957).
(4) Y.Ju,D.Kumar and R.S.Verma,Journal of Organic Chemistry ,Vol.71 pp
6697-6700,(2000).
(5) Sham M Sondhi,MonicaDinodia,ReshmaRani,Rakesh Shukla & Ram
Raghubir, Indian Journal of Chemistry, Vol.49(B), 273-281.Feb.(2009)
(6) Hadjakou S K,Demetzis M.A.,KubickiM,Kovala-DemetziD.Applied
organometallic Chemistry,14(11),727-734,(2000).
(7) Nigam S.C.,Saharia G.S et al.Ind.Chem.Soc.60,583(1997).
(8) ReinertH,Weiss R and Seylers H,Z Physiol.Chem. Vol.350 no.11 p.1310.
( 1969).
(9) Garg B.S. and KapurL,Inorg.Chem.Acta.Vol.173,no.2.p.223, (1990).
(10) Hafez H.N.,El-Gazz ABA, Biorganic& medicinal Chemistry
19(15),4143-4147,(2009).
(11) Y Nagel,WBeck,ZNaturforsch,B Anorg.Chem.,4,1447, (1986).
(12) JMSalas,M.A.Romero,M.P.Sanchez,M,Quiros.Coord.Chem.Rev.,1119,193-
195, (1995).
(13) Gal E.M.et.al, ,Neuro Chem.Res.3,69-88,(1978).
(14) Kenner G.W.et al J.Chem.Soc.652(1944).
(15) Baddiley J et al J.Chem.Soc.657(1944)
(16) CentolellaA.P.&Nelson J.W.J.Am.Chem.Soc.65,209(1943).
(17) Okabe M,Sun R.C.et al J.org.Chem.56,4393,(1991).
(18) HeidelbergerC.C.&ChaudharyN.C.etal sachinerNature,179,663(1957).
(19) Rushell R.K.&Ramprilla R.A,J.Med.Chem.31,1786(1988).
(20) P.A.Shah et al Ultra Chemistry Vol.6(1)15-18(2010).
(21) Vogel A.I. Textbook of Inorganic Analysis, Vth edition ELBS, London (1996).
(22) KlaymanD.L.&Joseph F.J.Med.Chem.,22,855 (1979).
(23) RanaA.K.Dabhi H.R. and Pancholi A.M. J.Polymer Mater., 235(1998).
63
Chapter II
(24) Anita Sharma ,Tushar Mehta and ManshiK.shah.

Derchemica Sinica, , 4(1) 141-146,(2013).
(25) S.Santhi and C.G.radhakrishnnan Namboori,Orient.J.Chem.
Vol.27(3)1203-1208,(2011).
(26) F.M.Morad,M.M.Elajaily,S.BenGweirif,J.ofSci& its applications,
1:72(2007).
(27) R.K.Dubey,etal.IndianJ.Chem,Sec IA.47:1210,(2008). .
(28) B.S.Shyamala,P.V. Anantha Lakshmi and V. Jayatyaga Raju ,
Vol.2, No.2, pp 1332-1339, Int.J. ChemTech Res.,2(2)(2010).
(29) Anupama B and GyanaKumari C. Int.J.Research.Chem.Environ.
Vol.3 Issue 2 April (172-180)( 2013).
(30) MukherjiG,PoddarS.N.andDeyK.Indian J.Chem,25A,275(1986).
(31) Raman N,Kulandaisamy A and Jeyasubramanian K,
Synth.React.Inorg.Met-org&Nano-Metal,32(9),1583(2002).
(32) A. B. P. Lever, Inorganic Electronic Spectroscopy,
Elsevier, Amsterdam, p. 275 (1968).
(33) L. Sacconi, Transition Met. Chem. 61, 943 (1968).
(34) NagajothiA,KiruthikaA,Chitra S and ParmeswariK.
Research Journal of Chemical Sciences.Vol.3(2),35-43,Feb.(2013).
(35) H.Haribabu,P.V.AnanthaLakshmi,V.JayatyagaRaju,
Int.J.ChemTech Res.,5(4).1512-1518 (2013).
(36) Lever A.B.P. Inorganic Electronic Spectroscopy , Elsevier,
Amsterdam,23, (1984).
(37) Vishnukant Budhewar , F.B.Bux , Lochan Vishwas Vyavahare and
Arun Singh , IJCEPR,Vol.3, No.2, 178-183(2012)
(38) MukherjiG,PoddarS.N.andDeyK.Indian J.Chem,25A,275(1986).
(39) E.M.Govege and J.E.Gedard,Inorganic Chem, ,17,270(1978).
(40) W.G.Hanna,M.M.Moawad,Trans.Met.Chem,26,644-651,(2001).
(41) S. Belaid, A. Landrau, S. Djebbar, O. Benali- Baitich, G. Bouet, J. Inorg.
Biochem, 102, 63-69, (2008).
(42) G.Rajadurai,A.Puhal Raj and S.Pari, Arch.Phy.Res. 4(3):61-66. (2013).
64
Chapter II
(43) FAO Adeunale, Jao Woods and OA Odunola, Oct-Dec. RJPBCS.Vol.3,

4,.1120 ( 2012).
(44) T.Noorjahan Begum,J.Sreeramulu,IJSID, ,2(1),23-35( 2012).
(45) SunitaGarud&L.P.Shinde Oct.-Dec. RJPBCS,Vol.4,4. No.1285(2013).
(46) Abdel-Latif S A and Hassib H B, J Ther Anal Calorimet., 68(3), 983-99(2002).
(47) S. G. Wanale, S. P. Pachling and S. D. Deosarkar, Chem Sci Trans., 2(2), 395-
402 ( 2013).
(48) Dr.MohammedFakruddin,AliahmedV.MohmmadYunu,World Journal of
Pharmaceutical Research,Vol.3,Issue2,2590-2599(2014).
(49) Mohapatra R K, Mishra U K, Mishra S K, Mahapatra A and Dash D C, J
Korean Chem Soc. , 55(6) , 926( 2011).
(50) Mirela C, Emilia I and Adrian M S, Revue Roumaine de Chimie , 53(10) , 903-
909. (2008).
(51) Mohapatra R K, Dash M P, Patjoshi S B and Dash D C, Acta Chim Pharm
Indica , 2(4) , 156-162(2012).
(52) Pen land R.B.MizushinaS.Curran C and Onagliano J.V. Am. Chem. Soc.,
79,1575. (1957).
(53) K. B. Guldasi and M.S.Patil, Trans Mat Chem.,72,128,( 1987).
(54) R.Shakru,N.J.P. Subhini,Satishkumar K.Shivraj,J.Chem.Pharm.Res.,2(1),38-
46(2010).
(55) N. Sadeghy, and S. Amani, Polish J. Chem,79,1749( 2005 ).
(56) N. Nassirinia, G. Shahmoradi, N. Sadeghi and S. Amani , J. Coord. Chem.
60,2581. (2007).
(57) N. Nassirinia, N. Sadeghi and S. Amani, J. Coord. Chem. 61,796( 2008)
(58) G. A. van Albada, M. T. Lakin, N. Veldman, A. L. Spek and Reedijk, Inorg.
Chem. 34, 4910,(1995).
(59) JoshiKrushnalalT,PancholiA.M.,PandyK.S.and Thakur A.
J.Int.J.Res.Chem.Environ.Vol.1,Issue 2, 63-69.Oct-(2011)
(60) RajendraK.Jain,D.K.Mishra,Derpharma chemical,l3(1),8-21(2011).
(61) J. R. Carvajal, T. Roisnel, Winplotr, A Graphic Tool for Powder Diffraction,
Laboratoire Leon Brillouin (ceal/cnrs) 91191 Gif sur Yvette Cedex, France,
(2004).
65

Complexes of 2,4 Diamino 6-Hydroxy Pyrimidine PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Complexes of 2,4 Diamino 6-Hydroxy Pyrimidine PDF

Uploaded by

Copyright:

Available Formats

Synthesis, spectral studies of Cr+3,Mn+2,Fe+3,Co+2,Ni+2,Cu+2 metal

Sructural Formula of ligand DAHP

The weighed amounts of complex were ignited in preweighed crucible

Presence of lattice water molecules present in the coordination compounds

Ligand / Metal Molar Cond.

DAHP white 285-286 - - -

[Co(DAHP)2 ]H2O Mahagony 227-280 54 11.16 -

Table 2.Percent C,H,N&metal ion in DAHP metal ion chelates

26.77 3.05 30.95 15.27

29.92 3.80 34.76 18.15

2.5. Electronic and magnetic studies of metal ion chelates

at 18939 cm-1 due to transition between 2

DAHP 36764 (272) n→π*

Fig.1.UV visible spectra of ligand DAHP

Fig.2. UV visible spectra of [Cr(DAHP)2]Cl.2H2O

Fig.3. UV visible spectra of [Mn(DAHP)2 ].H2O

Fig.4. UV visible spectra of [Fe(DAHP)2 ]Cl.H2O

Fig.5. UV visible spectra of [Ni(DAHP)2].2H2O

Fig.6. UV visible spectra of [Cu(DAHP) .H2O].Cl

2.6. IR spectral characterisation

IR Spectral Analysis of [Cr(DAHP)2]Cl.2H2O :

band disappeared in the complexes spectra, indicates the deprotonation of the

DAHP - 3388 3334 3232 1661 1245 - -

[Cr(DAHP)2]Cl.2H2O - 3341 3334 - 1641 1229 504 542

[Mn(DAHP)2 ].H2O 3375 3329 - 1643 1218 405 509

[Fe(DAHP)2 ]Cl.H2O 3363 3339 - 1648 1205 508 636

[CO(DAHP)2 ]H2O 3347 3332 - 1638 1221 543 495

[Ni(DAHP)2].2H2O 3342 3337 - 1637 1228 475 542

Fig.7.Infrared spectrum of ligand DAHP

Fig.8.Infrared spectrum of [Cr(DAHP)2]Cl.2H2O

Fig.9.Infrared spectrum of [Mn(DAHP)2 ].H2O

Fig.10. Infrared spectrum of [Fe(DAHP)2 ]Cl.H2O

Fig.11. Infrared spectrum of [Co(DAHP)2 ]H2O

Fig.12. Infrared spectrum of [Ni(DAHP)2].2H2O

Fig.13. Infrared spectrum of [Cu(DAHP) .H2O].Cl

2.7. Thermogravimetric analysis

atom from complex in the temperature range 401-6490C.The weight of residue is

22.06.%.The percent losses in massas observed in TG curve are equivalent to the

Table 15.Thermogravimetric Analysis of [Mn(DAHP)2 ].H2O

Table 16.Thermogravimetric analysis of [Fe(DAHP)2 ]Cl.H2O

Table 17.Thermogravimetric Analysis of [Co(DAHP)2 ]H2O

Table 18.Thermogravimetric Analysis of [Ni(DAHP)2].2H2O

Temp.range0c % Loss Nature of Decomposition

Table 19.Thermogravimetric Analysis of [Cu(DAHP) .H2O].Cl

Fig.14. TGA of [Cr(DAHP)2]Cl.2H2O

Fig.15.TGA of[Mn(DAHP)2 ].H2O

Fig.17. TGA of [Co(DAHP)2 ]H2O complex

2.8. Powder X ray analysis

XRD of [Mn(DAHP)2 ].H2O

0 0 2 15.14784 14.91234 2.96820 2.99330

Fig.20. X-Ray Difractogram of [Mn(DAHP)2 ].H2O

0 0 1 6.99846 7.66881 5.90063 5.77233

1 0 0 10.36651 10.44561 4.08502 4.24871

0 0 3 23.04197 23.59946 1.92834 1.92411

2 0 2 26.04786 26.75893 1.72332 1.71087

Fig.21. X-Ray Difractogram of [Cu(DAHP) .H2O].Cl

2.9. Result and discussion

Research study indicates that this chelating agent act as tridentate.

The results of physical, chemical and spectral parameters of synthesized metal

2.10. Symmary and conclusion

2.11. Proposed structure of metal ion chelates

Proposed structure of [Cr(DAHP)2]Cl.2H2O Complex

3D view of [Cr(DAHP)2]Cl.2H2O complex