Indian Jownal of Chemistry
Vol. 38A, April 1999, pp. 385 - 387
Synthesis and structural studies of first row
transition metal complexes of a new
bi-ambidentate heterocyclic ligand
D Sandhya Rani & V Jayatyaga Raju*
Department of Chemistry, Osmania University,
Hyderabad 500 007, India
and
P V Ananthalakshmi
Dept. of Chemistry, University College for Women,
Koti, Hyderabad 500 001 , India
Received 13 November 1996; revised 18 August 1998
Chromium(llI), manganese(II), iron (III), cobalt(II),
nickel(II) and .copper(II) complexes of 3-(3,5-dirnethyl
pyrazole-l-yl) quinoxaline-2-one have been prepared and
characterised on the basis of analytical, electrical
conductance, IR electronic spectral and magnetic
susceptibility studies.
Transition metal complexes derived from neutral
heterocycli~ ligands have received relatively less
attention. Quinoxaline and pyrazoles form an
important class of nitrogen heterocyclics which have
been reported for a wide range of applicabilities l -4 .
They possess potential metal binding nitrogen centers
in the form of ring azomethine functions. A unique
combination of two types of nitrogen heterocyclics
namely quinoxalines and pyrazoles has been
investigated for the formation of transition metal
complexes. The present note deals with the synthesis
and characterisation of chromium(lIl), manganese(I1),
iron(III), cobalt(I1), nickel(Il) and copper(IJ)
complexes of 3-(3,5-dimethyl pyrazole-I-yl)
quinoxaline-2-one.
Experimental
All the chemicals used were either of AR or
chemically pure grade. Metal percentage was
estimated by decomposing the complexes through
evaporation of perchloric acid solutions first and then
dissolving the resultant salts in doubly distilled water
to make the solutions of known concentrations. The
metal contents were-estimated from these solutions on
an atomic absorption spectrometer Perkin Elmer-
2380. Analysis of C, H, and N were done at the
Central Instrumentation Laboratory, University of
Hyderabad. Chlorine contents were estimated after
igniting a definite weight of the complex in oxygen in
the presence of KOH and H20 2 (ref. 5). lR spectra
(KBr discs) were recorded in the 4000-400 cm- I
region on a Schimadzu. lR-435 and in nujol medium
in the 4000-200 cm- I on a Perkin-Elmer 288-13 . The
electronic spectra were recorded in solid state on a
Cary-2390 instrument. Magnetic susceptibilities of
the complexes at room temperature were measured on
a Faraday balance CAHN-7550-03 USA using
HgCO(NCS)4 as ·calibrant. Diamagnetic corrections
using pascal constants and temperature Independent
paramagnetic corrections were computedo. The
electrical conductance measurements were recorded
using 10-3 M solution in DMSO with an Elico
conducting bridge (Model CH-180) and a dip type
cell calibrated with KCI solutions.
Synthesis of quinoxaline-2,3-dione 7
Orthophenylene diamine (5.5 g), oxalic acid
dihydrate (6 .5 g) and 4 N HCI (30 cc) were heated to
boiling for 15 min. A crystalline solid appeared which
was cooled, collected, washed with water and dried .
The compound was dissolved in alkali and then
acidified with HC), so that, the pure quinoxaline-2,3-
dione was obtained as white needles. Yield: 3 g, m.p.
>350°C.
Synthesis of 3-hydrazino quinoxaline-2-one8
To a mixture of quinoxaline-2,3-dione ( 10 g) and
hydrazine hydrate (50 ml), water (50 ml) was added
and heated under reflux for 2 h and cooled . The
precipitate of 3-hydrazino quinoxaline-2-one was
filtered off, washed with water and crystallised from
butan-I-ol to give yellow needles. Yield: 9.4 g;
m.p.>360°C.
III
 386 INDIAN J CHEM, SEC A, APRIL 1999

Table I~haracterisation data of the complexes

Complex Found (Caled.), % Ileff
Metal C H N CI (8M)
8.30 48.87 3.75 17.52 16.63 4.23
(8.31 ) (48.86) (3:75) (17.54) (16.67)
9.0 1 51.39 3.95 18.47 11.69 5.51
(9.07) (51.49) (3 .95) (18.48) ( 11.71)
8.69 48.49 3.71 17.41 16.56 5.85
(8.71) (48.56) (3 .73) (17.43) ( 16.57)
9.65 51.12 3.91 18.35 11.78 4.12
(9.67) (51.15) (3.93) (18.36) (11.80)
9.65 51.13 3.93 18.36 11.79 2.78
(9.67) (51.15) (3 .93) (18.36) 11.80)
16.26 39.57· 3.04 14.21 18.03 1.81
(16.28) (39.69) (3 .05) (14.29) (18.06)

.. • Ct(lIQ ,'.UI'
Ull
Ulrl
Synthesis of 3-(3,5-dimethyl pyrazole-l-yl) quin-
oxaline-2-one9
A mixure of 3-hydrazino quinoxaline-2-one (8.8 g)
and acetyl acetone (20 ml) was refluxed fiJr 2 h. The
colourless product that separated out was filtered and
recrystallised from benzene. Yield: 6.5 g;
m.p.> 168°C.
[Found: C, 64.48; H, 5.10; N, 23.31; C\3H I2N 40
Calcd.: C, 65.00; H, 5.00; N, 23.33%]. mlz 240.
IH NMR (OMSO-d6): 82.3, 82.2 {methyl protons
(6)}, 86.·1 {-CH-proton (l)}, 87.3-7.9 (NH and
phenol protons confirmed by 0 20 exchange (5). UV-
Vis (vmax in cm- I): 43478 (ring 1Ht* transition) and
31746, 28169 (1t-1t* and n-1t* transition) and 31746,
28169 (1t--1t* and n-1t* transition). The data are
consistent with the expected structure (Structure I).
Preparation of complexes
The ligand (1.20 g, 0.005 mol) was dissolved in
methanol (25 ml) and to this solution, methanolic
solution (25 m\) of divalent/trivalent metal chloride
(0.0025 mol) was added. The pH of the mixture was
adjusted to 7 with I % alcoholic ammonia and the
reaction mixture was refluxed for 3-4 h. The coloured
product thus obtained was filtered in hot condition,
washed successively with methanol and petroleum
ether and dried in vacuo. The purity of the complexes
was checked by TLC using methanol and solvent
mixtures.
Results and discussion
. Analytical data of C, H, N, CI and metal are in
good agreement with 1:2 metal-ligand stoichiometry
for all the complexes except for Cu(U) complex
where it is 1: 1 (Table 1).
All the complexes neither melt nor decompose
upto 300°C. Except chromium(III) and iron(III), all
complexes show negligible conductivity thus proving
that they are non-electrolytes. Chromium(III) and
iron(I1I) complexes show conductance values of 74
mhos and 67 mhos respectively indicating to be 1: I
electrolytes IO • The analytical and conductivity data
shows that one chloride is in the ionization sphere,
while the other two chloride ions are in coordination
 NOTES
sphere for chromium(Ill),and iron(Ill) complexes. In
case of manganese(II), cobalt(Il), nickel(Il) and
copper(II) complexes, the two chloride ions are in the
coordination sphere.
In the IR spectrum the free ligand shows vNH at
2900 cm·! vC=O at 1670 cm-! and two azomethine
groups show sharp peaks at 1574 and 1556 cm-!.
Comparison of the infrared spectrum of free ligand
with that of each metal complex suggests two
possible modes of chelation. Manganese(Il),
cobalt(II) and nickel(II) complexes belong to the first
category in which the infrared spectrum show notable
downward shift!! in vC=O by about 40 cm-!,
indicating that the exocyclic, lactam carbonyl oxygen
is the bindipg site in these complexes. Further, there
is a downward shift in vC=N (non-quinoxaline ring)
to the extent of 10-15 cm-! in these complexes
suggesting coordination through the corresponding
nitrogen 12.
Chromium(ID), iron(ID) and copper(II) com-plexes
belong to the second category in which the infrared
spectra show no change in vC=O. Instead, the
azomethine stretching frequencies show notable
downward shifts 12. These changes suggest the non-
participation of carbonyl oxygen and participation of
only the azomethine nitrogens in metal binding
process. Weak non-ligand peaks observed in the
range 494-310 cm-! are due to vM-O, vM-N and
vM-C1 vibrations 13,!4 in the corres-ponding complexes.
The magnetic susceptibility measurements and the
calculated magnetic moments show that all the
complexes are paramagnetic with high spin
configurations l2 ,15 of the central metal ions (Table I).
The electronic spectra assignments are based on
high-spin octahedral geometry for all the complexes
except the copper(II) complex in which the three
component band structure characteristic of square
planer geometry is seen l6 • The inter electron repulsion
parameter and nephelauxetic parameter have been
evaluated for chromium(ill) and nickel(lI) complexes
[for chromium(ill) B=831 and p=O.806; for nickel(II)
B=883 and P=O.818] 17. The transition patterns and
V2/ VI ratio (2 .19) are both supportive of octahedral
geometry in the case of cobalt(II) complex l 8 •
The ESR spectrum of copper(II) complex shows
that the g parameter is highly an isotropic and exhibits
three components. The values are g12=2.652 1,
gyy=2.1925, g",,=2.0088.
Copper(II) ion in this complex seems to be totally
387
free from the influ~nce of the nearest neighbouring
copper ions of the adjacent complex molecules which
coexist in the solid state the possible explanation for
this could t>e the presence of bulky tricyclic ligand
molecules in the coordination sphere due to which the
interaction between consecutive copper ions of
different complex molecules is initiated and such
systems wherein metal-metal interaction is almost
totally inhibited are referred as magnetically dilute
systems. Further, the high g12 value can be explained
on the basis of large energy separation between d z1
and d x 1 - y 1 orbitals.
The biambidenticity of the ligand is a notable
feature. It acts as NN donor in chromium(ID),
iron(ID) and copper(n) complexes and as ON donor
in manganese(II), cobalt(II) and nickel(n) complexes.
On the basis of elemental, conductance, magnetic
and spectral data, octahedral geometrics have been
proposed for all the complexes except for copper(II)
complex to which square plane geometry is proposed
(Structures II-IV).
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