Transition Metal Chemistry, 19 (1994) 75-77
Structural elucidation of manganese(II), iron(III), cobalt(II),
nickel(II), copper(II) and zinc(II) complexes of a new multidentate
dihydrazino quinoxaline derivative
Dikonda S. Rani, Parupalli V. A. Lakshmi and Vuppalapati Jayatyagaraju*
Department of Chemistry, Osmania University, Hyderabad 500 007, India
Summary
Manganese(II), iron(III), cobalt(II), nickel(II), copper(II)
and zinc(II) complexes of a new multidentate oxygen-
nitrogen donor, bis(N-salicylidene)-2,3-dihydrazino-l,4-
quinoxaline (HzBSDHQ) were prepared and characterised
by elemental analysis, conductance, thermal, spectral and
magnetic data. H2BSDH Q deprotonates to give a dibasic
O N N O donor set in a trivalent iron(III) complex, which
binds to the divalent metal ions in a bis-tridentate fashion,
using two monobasic O N N donor sets, and resulting in
polymeric complexes. Octahedral geometries are proposed
for all these complexes, and preliminary studies show that
they possess potential antimicrobial activity.
Introduction
Quinoxalines are a class of fused six-membered heterocycles
containing two nitrogens para to each other. Substituted
quinoxalines have featured widely in antimicrobial,
pharmacological, pesticidal, insecticidal and herbicidal
studies "-4). The preparation of multidentate oxygen
nitrogen donor systems containing 1,4-quinoxaline and
their metal complexes was undertaken to further investigate
their antimicrobial applications. This paper discusses the
synthesis and characterization of bis(N-salicylidene)-2,3-
dihydrazino-l,4-quinoxaline (H2BSDHQ) (Figure 1) and
its complexes with manganese(II), iron(III), cobalt(II),
nickel(II), copper(II) and zinc(II).
Experimental
Materials
AnalaR Grade metal chlorides were used as supplied.
Silicylaldehyde and NzH4"HzO were obtained from E.
Merck. Solvents were purified by established procedures (5).
Physical measurements and analysis
Mass spectra were recorded on a Perkin-Elmer Hitachi
RMU-6L spectrometer. 1H n.m.r, spectra were recorded on
a Varian XL-200 MHz in DMSO-d 6. I.r. spectra (KBr
discs) were recorded in the 4000-200 cm-~ region on a
Perkin-Elmer 283-B. Reflectance spectra of solids were
recorded on a Cary-2390. Magnetic susceptibilities were
measured on a Faraday balance CAHN-7550-03, at room
temperature using HgCo(NCS)4 as the calibrant. Dia-
magnetic corrections using Pascal's constants and tem-
perature-independent paramagnetic corrections were
computed (6). The electrical conductance measurements
were recorded using 10-3 molar solutions in D M S O with
an Elico conductivity bridge (Model CM-180) and a dip
type cell calibrated with KC1 solutions.
Carbon, hydrogen and nitrogen analyses was carried
* Author to whom all correspondenceshould be directed.
0340-4285 9 1994Chapman& Hall
Metal dihydrazino quinoxaline complexes 75
out on a microanalytical Perkin-Elmer 240C elemental
analyser. Chloride contents were estimated argentometri-
cally after igniting a definite weight of the complex in
oxygen in the presence of K O H and HzOz tv). For metal
estimations, the complexes were decomposed by slow
evaporation of HC104 and H N O 3 solutions and the
resulting metal salts were dissolved in H 2 0 to give
aqueous solutions of known dilution. The metal contents
were estimated by the emission spectrophotometry tech-
nique using a Lab tam plasma Scan-8410.
Synthesis of H2BSDH Q
The H2BSDH Q ligand was prepared by a four step
process from the synthesis of quinoxaline-2,3-dione (QD) ~8~
and 2,3-dichloro quinoxaline (DQ) t9).
2,3-Dihydrazino quino xaline ( QD H )
M e O H (t 00 cm 3) was added to 2,3-dichloro quinoxaline
(10 g), NzH4" H 2 0 (50 cm 3) and the mixture boiled under
reflux in a steam bath for 8 h. The orange-yellow com-
pound which separated was removed by filtration, washed
with small amounts of M e O H and dried in vacuo. Yield
65%; m.p. 240~ (dec) (found: C, 47.6; H, 5.2; N, 40.42,
CaHx2N60 calcd: C, 46.15; H, 5.8; N, 40.4%). 1H n.m.r.
(DMSO-d6): 6 11.0 (ring NH) (2), 6 6.8-7.5 (aromatic) (4),
65.4-5.8 (NH2) (4). Q D H - H 2 0 re~z=208. I.r. 3150-
3300 c m - 1, v(NH2) (sym and asym); 1625 c m - 1 v(C=-N)
(exo) and v(C=C); 1600 cm-1 v(NH)(def) and v ( C = C )
and 1500cm- 1 v(C=N)(ring). U.v.-vis (VmaX in cm 1)
37174 (benzene ring), 26178 (ring NH), 24875 (azomethine),
23474 and 22075 ( N 2 H 4 chromophore).
Bis(N-salic ylidene )-2,3-dih ydrazino-1,4-quinoxaline
Salicylaldehyde (0.73 c m 3) w a s added to a solution of
2,3-dihydrazino quinoxaline (1.14g) in D M F (50cm3),
and the mixture boiled under reflux for 3 h. The mixture
was then poured into H 2 0 (150cm 3) and the pale green
compound which separated was removed by filtration,
washed with a small amount of aqueous E t O H and dried
in vacuo. Yield 70%; m.p. 142 ~ C. (Found: C, 64.85; H, 4.1;
N, 20.9, C22HlsN602 calcd: C, 66.3; H, 4.5; N, 21.1%),
m/z = 398. 1H n.m.r. (DMSO-d6): 6 8.5 (azomethines CH)
(2), b 6.6 (NH) (2), 6 6.9-7.5 (aromatic) (12), 6 12.1 (OH) (2).
l.r. bands (cm-~): 3300-3000 br I v ( O H ) + v(NH)], 1620 s
v(C=N)(exo), 1540s, v(C~N)(ring), 1240s v(C O)
(phenolic) and 1030 v(N--N). U.v.-vis. (Vm,x in cm-1):
37174 (ring rc ~ n* transition) and a multiple bond 25974-
21739 with components 25974, 25000, 22988 and 21739
(~z--, g* and r/---,n* transitions). The data are consistent
with the expected structure (Figure 1).
Preparation of the complexes
The following general procedure was adopted. A M e O H
solution of the metal chloride (1 mol) was mixed with
76 Rani et al. Transition Metal Chemistry, 19 (1994) 7 5 - 7 7

H complexes was established by d.t.a. E n d o t h e r m s indicate

N~N--N ~CH -- C6H4OH --O
N N -- N ~ CH -- C6H4OH -- O I.r. studies
H
Figure 1. Ligand structure: H2BSDHQ.
H 2 B S D H Q (1 mol). T o this a 5% M e O H solution of
a m m o n i a was added to maintain the reaction at p H 7, and
the mixture was boiled under reflux in a steam bath for
3 h. The complex which precipitated was r e m o v e d by
filtration, washed with M e O H and dried in vacuo. The
purities of H z B S D H Q and metal complexes were checked
by t.l.c. The analytical data and p r o p o s e d formulae for the
complexes are given in Table 1.
Results and discussion
The H 2 B S D H Q complexes are coloured and oxygen
stable. They are insoluble in c o m m o n organic solvents but
soluble in D M F and D M S O . They decompose at high
temperatures. Analytical data are c o m m e n s u r a t e with a
1 : i metal to ligand stoichiometry in all complexes, except
in the zinc(II) complex (2:1). They have low m o l a r
conductances (f~M = 2.0-4.0 mhos m o l - 1 cm 2) in 1 x 10 3
molar D M S O solutions at r o o m temperature and are
therefore nonelectrolytes ~ m. The chloride in iron(III) and
zinc(II) complexes lies within the c o o r d i n a t i o n sphere.
The presence of coordinated H 2 0 in iron(III) zinc(II)
deaquation in a one step process for each complex in the
265-300 ~ C range.
The i.r. spectral data of the complexes are given in Table 1.
The manganese(II), cobalt(II), nickel(II), copper(II) and
zinc(II) complexes show changes in v ( C - - O ) , v ( C = N )
(ring) and v(C~-N)(exo), indicating binding to the metal
t h r o u g h an O N N sequence involving phenolic oxygen
and azomethine nitrogens (x ~-~ 3). As these complexes are
isolated from neutral media, d e p r o t o n a t i o n of phenolic
oxygen has p r o b a b l y occurred. Indeed, the ~Hn.m.r.
spectrum of the zinc(II) complex confirms this fact (dis-
appearance of the 6 12.1 signal). The u p w a r d v ( N - - N )
shift in all the complexes in the 1 0 - 3 0 c m ~ range
supports involvement of one of the nitrogens in bonding ~14);
the iron(III) complex being the exception in v ( C = N )
(ring) ~'~ The b a n d at 2 9 0 0 - 3 4 0 0 c m - ~ in the iron(III)
complex is assumed to be due to side chain v(OH) and
v(NH) ~s) and the m e d i u m intensity b a n d observed at
8 5 0 c m - ~ is assignable to the rocking m o d e (x6) of coor-
dinated H 2 0 molecule. However, in the zinc(II) complex
the b r o a d b a n d at 2 9 0 0 - 3 4 0 0 c m - i is a v(OH) and
v(NH) c o m b i n a t i o n and shows the presence of H 2 0 and
ammonia ~ in c o o r d i n a t i o n sphere as established by
M - - O H 2 and M--NH3(XT) rocking modes (850 and
910 c m - ~, respectively).
The new bands in the far i.r. region (Table 1) are
attributed to v ( M - - O ) , v ( M - - N ) and v ( M - - C 1 ) (ls'19).

Table l. Analytical and i.r. data of the metal complexes of H2BSDHQ a'b.
Complex/ Found (calcd.)(%) v(NH) v((OH) +(NH)) v(C~N) v(C~N) v(C--O) v(N N) New bands
Stoichiometry M N (exo) (ring) (phenolic)
[MnUL] 12.55 18.5 3000-3300 - 1600 1520 1250 1260 1060 630, 490
(12.2) (18.6)
[FemLCI(H20)] 11.3 16.7 - 3000-3400 1600 1550 1240 1260 1040 850, 640, 385
(11,0) (16.6)
[ConL] 11.95 18.9 3000 3300 - 1600 1520 1240-1250 1040 620
(12.95) (18.5)
[NiUL] 13.1 18.4 3000-3300 - 1600 1520 1240-1250 1040 620
(12.9) (18.5)
[CunL] 14.1 18.7 3000, 3200, - 1600 1500 1230-1260 1040 640, 620
(13.8) (18.3) 3300
[Zn~L(NH3)z(H20)2Clz] 19.4 16.5 - 2900-3300 1600 1520 1240-1260 1050 910, 850, 630,
(19.6) (16.77) 610, 300
aAll i.r. bands in cm- 1; babbreviation: H2BSDHQ = bis(N-Salicylidene)-2,3-dihydrazino- 1,4-quinoxaline (C22H 18N602), L = C22H1 6 N 6 0 2 '

Table 2. Magnetic moment and electronic spectral data of metal-H2BSDHQ complexest

Complex ~eff (B.M.) Vmax Assignment

(temperature in K) (cm-1)

[MnIIL] 5.85 25316, 23255, 22222, -

(295) 19607, 17543, 15625,
15151, 13888, 12987
[FemLCI(H20)] 6.06 25641, 22727, 21737,
(295) 16393, 15625, 14925,
13888, 12820
[foUL] 3.95 25000-20000 4 Z i g --4 4Tlg(p )
(295)
[-NinL] 3.03 23255 3A20 ~ 3Tla(P )
(295) 17543 3A2 --~3T1
10869 3A g __+3T g
~2g 20 *

16393-15151 SA2_-* 1E_

[CuIIL] 1.73 18181 2Bf---~ZE"
(295) 17241 2 B Ig~ 2 Bz.
g
15625 2Big ~ 2Alg

"HeBSDHQ = bis(N-salieylidene)-2,3-dihydrazino-l,4-quinoxaline (C22HlsN602) , L = C22H16N602.

 Transition Metal Chemistry, 19 (1994) 75-77 Metal dihydrazino quinoxaline complexes 77

azomethine chromophore-metal binding. The broad bands

in this range may also have d - d component transitions
corresponding to the complexed transition metal ions.
The electronic spectra of manganese(II) and iron(III)
exhibit several weak absorptions due to doubly forbidden
N'N"U N''- N. d - d transitions (2~). As such, no specific assignments for
the electronic transition could be made, The nephalauxetic
and inter electron repulsion parameters for the nickel(II)
complex are B = 546.06 and fl = 0.524, which indicate a
strong ligand field around the metal ion. The analytical,
conductivity, thermal and spectral characteristics correlate
to suggest a bis-tridentate mode towards divalent metal
ions and a tetradentate mode towards iron(Ill). The
dependence of this binding mode on charge is interesting.
U = Un II, CuI], NiH, CoH In manganese(II), cobalt(II), nickel(lI) and copper(II)
complexes these interactions can be justified in terms of
(2) polymers and the proposed structures of complexes are
Figure 2. H z B S D H Q - M n u, - C o u, - N i n and - C u H complexes. given in Figures 2-4.
Preliminary studies on the bactericidal properties of
H z B S D H Q , its metal complexes, QD, DQ, Q D H and
related compounds, indicate promising activity against
Staphylococcus Aureus and Escherichia Colt. Detailed
studies are in progress.
N N
Acknowledgements
HN NH One of the authors (P. V. A. L.) thanks the CSIR, India,
\ Cl I for the Senior Research Fellowship.
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This result may be attributed" to the changes in the
electronic environment of the ligand as a consequence of (Received 20 January 1993) T M C 2957