Synthesis and characterization of mixed-ligand complexes of Cu(II), Ni(II), Co(II), Zn(II), Sm(III), and U(VI)O2, with a Schiff base derived from the sulfa drug sulfamerazine and 2,2′-bipyridine

Article abstract of DOI:10.1081/SIM-120021647

A new series of novel mixed-ligand complexes of Cu(II), Ni(II), Co(II), Zn(II), Sm(III) and U(VI)O₂ with the Schiff base derived from salicylaldehyde and the sulfa drag sulfamerazine, [N-(salicylidene)-sulfamerazine] (LH) and the heterocyclic base 2,2′-bipyridine (bpy) have been synthesized and characterized by IR, NMR, diffuse reflectance spectra and magnetic, thermal, and molar conductance measurements. The coordination by the azomethine nitrogen is inferred by the downfield shifting of the -CH=N- signal in the NMR spectra and the shift of v(C=N) to lower frequencies by 15-40 cm^-1 in the IR spectra upon complexation. Conductance measurements confirm the non-electrolytic nature of these complexes. The presence of lattice and coordinated water molecules are indicated by thermograms of the complexes. The general compositions of the complexes were found to be [M(L)(bpy)(OAc)(H₂O) {where M = Cu(II), Ni(II), Co(II) or Zn(II) and HOAc = acetic acid} and [Sm(L)(bpy)(OAc)₂(H₂O)·2H₂O and [UO₂(L)(bpy)(OAc)(H₂O)·H₂O.

Full text of DOI:10.1081/SIM-120021647

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Synthesis and characterization of Mixed‐Ligand
Complexes of Cu(II), Ni(II), Co(II), Zn(II), Sm(III), and
U(VI)O2, with a Schiff Base Derived from the Sulfa Drug
Sulfamerazine and 2,2′‐Bipyridine
R. C. Maurya a , P. Patel a & S. Rajput a
a Coordination Chemistry Laboratory, Department of P. G. Studies and Research in Chemistry,
R. D. University, Jabalpur, 482 001, India
Published online: 20 Aug 2006.
To cite this article: R. C. Maurya , P. Patel & S. Rajput (2003) Synthesis and characterization of Mixed‐Ligand Complexes
of Cu(II), Ni(II), Co(II), Zn(II), Sm(III), and U(VI)O2, with a Schiff Base Derived from the Sulfa Drug Sulfamerazine and
2,2′‐Bipyridine, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 33:5, 801-816, DOI: 10.1081/
SIM-120021647
To link to this article: http://dx.doi.org/10.1081/SIM-120021647
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 5, pp. 801–816, 2003
Synthesis and Characterization of
Mixed-Ligand Complexes of Cu(II), Ni(II),
Co(II), Zn(II), Sm(III), and U(VI)O2, with a
Schiff Base Derived from the Sulfa Drug
Sulfamerazine and 2,2’-Bipyridine
*
R. C. Maurya, P. Patel, and S. Rajput
Coordination Chemistry Laboratory, Department of P. G. Studies and
Research in Chemistry, R. D. University, Jabalpur, India
ABSTRACT
A new series of novel mixed-ligand complexes of Cu(II), Ni(II), Co(II),
Zn(II), Sm(III) and U(VI)O2 with the Schiff base derived from sali-
cylaldehyde and the sulfa drug sulfamerazine, [N-(salicylidene)-sulfa-
merazine] (LH) and the heterocyclic base 2,2’-bipyridine (bpy) have been
synthesized and characterized by IR, NMR, diffuse reflectance spectra
and magnetic, thermal, and molar conductance measurements. The coor-
dination by the azomethine nitrogen is inferred by the downfield shifting
of the –CH=N– signal in the NMR spectra and the shift of n(C=N) to
lower frequencies by 15–40 cm–1 in the IR spectra upon complexation.
*
Correspondence: R. C. Maurya, Coordination Chemistry Laboratory, Department of
P. G. Studies and Research in Chemistry, R. D. University, Jabalpur, 482 001, India;
E-mail: rcmaurya@sancharnet.in.
801
DOI: 10.1081/SIM-120021647
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

802
Maurya, Patel, and Rajput
Conductance measurements confirm the non-electrolytic nature of these
complexes. The presence of lattice and coordinated water molecules are
indicated by thermograms of the complexes. The general compositions of
the complexes were found to be [M(L)(bpy)(OAc)(H2O) {where
M = Cu(II), Ni(II), Co(II) or Zn(II) and HOAc = acetic acid} and
[Sm(L)(bpy)(OAc)2(H2O)ꢀ2H2O and [UO2(L)(bpy)(OAc)(H2O)ꢀH2O.
Key Words: Schiff base; Sulfa drug; Sulfamerazine; Bipyridine; Cu(II);
Ni(II); Co(II); Zn(II); Sm(III); U(VI)O2 mixed ligand complexes.
INTRODUCTION
A large number of mixed-ligand complexes involving heterocyclic
bases such as pyridine, 2,2’-bipyridine, o-phenanthroline, etc. were reported
by many workers[1–3] due to their bio-inorganic applications and thermal
stability. Studies of formation constants of mixed-ligand systems [M(A)(L’),
where A = 2,2’-bipyridine or 2,2’-bipyridylamine and L’ = amino acids
have been carried out by earlier workers.[4–7] Schilt and Fritsch[8] prepared
a series of neutral, mixed-ligand complexes of the type (M(B)2(NCS)2],
where M = Fe(II), Co(II), Ni(II), Cu(II) or Zn(II) and B = a heterocyclic
base. Dutta and De[9] isolated solid, mixed-ligand complexes of copper(II)
containing 2,2’-bipyridine as primary ligand and glycine or alanine as
secondary ligands. A new series of eight mixed-ligand complexes of Cu(II),
and Co(II) with Schiff bases, viz., 2-hydroxybenzalidene-anthranilic acid or
2-hydroxybenzalidene-2-aminothiophenol and 2- or 3-pyrazoline-5-one
derivatives have been reported by Maurya et al.[10]
Chaturvedi et al. reported potentiometric and biocidal studies of some
mixed-ligand complexes of transition metals with N-pyridylanthranillic acid
and some bidentate ligands.[11] Complexes of thorium(IV) with heterocyclic
bases were reported by Manhas et al.[12] Copper(II) and zinc(II) complexes
of some bisheterocycles, viz., 2-[[5-substituted-1,3,4-oxadiazole-2-yl)-thio]-
methyl]-1H-benzimidazole, 2-[[5-substituted-4-amino1,2,4-triazol-3-yl)-
thio]methyl]-1H-benzimidazole and 2-[[5-substituted-1,3,4-thiadiazole-2-yl)-
thio]methyl]-1H-benzimidazole as fungicides have been studied by Mishra
et al.[13] It appears that the heterocycles, which have been observed to be least
biologically active, showed enhanced activities upon complexation.
EXPERIMENTAL
Materials
Salicylaldehyde, 2,2’-bipyridine, sulfamerazine (Sisco Chem. Industry,
Bombay), Cu(OOCCH3)2ꢀH2O, Ni(OOCCH3)2ꢀ4H2O, Co(OOCCH3)2ꢀ4H2O,

Complexes of Sulfamerazine
803
Zn(OOCCH3)2ꢀ2H2O and UO2(OOCCH3)2ꢀ2H2O (E. Merck); and Sm-
(OOCCH3)3ꢀ3H2O (Indian Rare Earth Ltd.), DMF (Sisco), ethanol and other
solvents of A.R. grade were used as received.
Synthesis of Schiff Base Ligand
A hot ethanolic solution (20 mL) of salicylaldehyde (50 mmol, 6.100 g,
5.32 mL) was added to a hot methanolic solution (25 mL) of sulfamerazine
(50 mmol, 13.215 g). This mixture was then refluxed on a water bath for 4–5
h. A coloured solid mass separated out on cooling which was filtered, washed
several times with ethanol, diethyl ether and, subsequently, dried over solid
CaCl2 in a desiccator. The purity of the ligand was checked by TLC. The
ligand is insoluble in non-polar solvents, viz., acetone, alcohol, and benzene
and soluble in polar solvents like DMF and DMSO. Yield, 14.7 g (80%).
Synthesis of Mixed-Ligand Complexes
A solution of the Schiff base ligand (5 mmol, 1.840 g) in the mini-
mum quantity ( ꢁ 30 mL) of DMF was mixed with a solution of 2,2’-
bipyridine (5 mmol, 0.780 g) in 20 mL ethanol. The resulting solution was
refluxed with stirring on a magnetic stirrer equipped with heater for 2 h.
Subsequently, an ethanolic solution ( ꢁ 40 mL) of the metal acetate (5
mmol) [0.995 g of Cu(OOCCH3)2ꢀH2O; 1.244 g of Ni(OOCCH3)2ꢀ4H2O;
1.100 g of Zn(OOCCH3)2ꢀ2H2O; 1.245 g of Co(OOCCH3)2ꢀ4H2O; 1.906 g
of Sm(OOCCH3)3ꢀ3H2O or 2.120 g of UO2(OOCCH3)2ꢀ2H2O] was added
drop-wise with stirring and the mixture was refluxed for 4 h on a heating
mantle. The bright-coloured mixed-ligand complexes separated out on
cooling, were filtered by suction, washed with ethanol and diethyl ether and
dried in vacuo over anhydrous CaCl2. The yields of the complexes were
60–70% with respect to ligand.
RESULTS AND DISCUSSION
Composition and Characterization of the Ligand
The sulfa drug based Schiff base ligand [N-(salicylidene)-sulfamera-
zine] (LH) was prepared as shown in Figure 1.
The composition of the ligand is consistent with the microanalytical
1
data (Table 1). The H NMR spectrum of LH is given in Figure 2, along
with the assignments of the various protons. The formation of this Schiff
base ligand is revealed by the appearance of the azomethine proton
(–CH=N–) signal at 8.96 ppm.[14] This is further supported by the
appearance of a band for n(C=N)(azomethine)[15] at 1590 cm–1 in the IR

804
Maurya, Patel, and Rajput
Figure 1. Synthesis of the Schiff base ligand.
spectrum of the ligand. The ligand also exhibits a signal for the phenolic
(OH) proton at 12.55 ppm and NH proton at 11.81 ppm.[16] The aromatic
proton signals appear as a multiplet at 6.90 to 8.33 ppm.
Composition and Characterization of the
Metal Complexes
The mixed-ligand metal complexes of LH and 2,2’-bipyridine were
prepared according to the following equations:
MðOOCCH3Þ2 ꢀ nH2O þ LH þ bpy
EthanolÀDMF
Reflux
þ½MðLÞðbpyÞðOAcÞðH2OÞꢂ þ ðn À 1ÞH2O þ CH3COOH
ð1Þ
Where, M = Cu(II), n = 1 (1); Ni(II), n = 4 (2); Co(II), n = 4 (3); Zn(II),
n = 2 (4)
SmðOOCCH3Þ3ꢀ 3H2O þ LH þ bpy
EthanolÀDMF
Reflux
ð2Þ
ð3Þ
½SmðLÞðbpyÞðOAcÞ2ðH2OÞ ꢀ 2H2O ð5Þ CH3COOH
UO2ðOOCCH3Þ2 ꢀ 2H2O þ LH þ bpy
EthanolÀDMF
Reflux
½UO2ðLÞðbpyÞðOAcÞðH2OÞꢂꢀH2O ð6Þ CH3COOH

Complexes of Sulfamerazine
805

806
Maurya, Patel, and Rajput
Figure 2. 1H NMR spectrum of the Schiff base ligand HL.
Some physical properties such as melting points, % yields, colours, etc.
of the complexes are given in Table 1. The complexes were characterized
by the following physical studies.
Infrared Spectra
The important IR spectral bands of the Schiff base ligand LH and its
metal complexes are given in Table 2. The ligand LH contains five poten-
tial donor sites: 1) the phenolic oxygen, 2) the azomethine nitrogen, 3) the
sulfonamide oxygen, 4) the sulfonamide nitrogen and 5) the ring nitrogen.
In the IR spectrum of this ligand a sharp band observed at 1590 cm–1 is
assigned to the n(C=N)[15] mode of the Schiff base and medium-broad
bands observed at 3540 and 3030 cm–1 are due to n(O–H) phenolic and
n(NH) stretching, respectively.[17] Evidence of nitrogen bonding of the
azomethine (C=N) group to the central metal ion stems from the shift of
the n(C=N) frequency to lower frequencies by 15–40 cm–1 in all of the

Complexes of Sulfamerazine
807

808
Maurya, Patel, and Rajput
complexes.[18] This is further confirmed by the appearance of new bands at
405–440 cm–1 due to the n(M–N)[19] band.
The coordination through the phenolic oxygen after deprotonation is
revealed by the disappearance of the n(OH) phenolic band at 3540 cm–1 and
the appearance of a band due to n(C–O) phenolic at much lower frequencies
(1440–1465 cm–1)[20] in all the complexes as compared to that of the ligand
at 1480 cm–1. This is further confirmed by the appearance of a new non-
ligand band at 510–560 cm–1 due to n(M–O)[20] in all the complexes. The
bands in the ligand due to nas(SO2) and ns(SO2) appear at 1340 and 1155
cm–1, respectively. These remain almost unchanged in the complexes,
indicating that this group is not participating in coordination.[21] This is
supported by the unchanged n(S–N) and n(C–S) modes appearing at 965
cm–1 and 845 cm–1, respectively, in the ligand after complexation.[22] The
band due to n(=N–) ring appearing at 1565 cm–1 in the Schiff base, does
not show any appreciable change in the complexes. In some complexes this
mode seems to be merged with the n(C=N) azomethine band, which is
indicated by the appearance of a broad band in this region. This suggests that
the ring nitrogens of the ligand are not taking part in coordination.[23] In all
the complexes the lattice/coordinated[24] water molecules are indicated by
the appearance of a broad band in the region 3350–3460 cm–1. The
coordination of an acetato group in all the complexes is indicated by the
appearance of two new bands in the regions 1606–1660 and 1320–1360
cm–1 assignable to nas(COO) and ns(COO) modes, respectively. The
value of Dn = nas(COO) À ns(COO) = 286–300 cm–1 suggests the uni-
dentate coordination of the acetato group.[25] In the uranium complex (6)
two additional sharp bands are observed at 940 and 820 cm–1, which are
assigned to nas(UO2) and ns(UO2) modes, respectively. This observation
suggests that the O=U=O moiety is virtually linear in this complex.[26] The
IR spectra of all the complexes show a change in the ring (=N–) nitrogen
frequencies of the 2,2’-bipyridine (bpy). The bands in bpy at 1570 and 415
cm–1 have shifted to higher frequencies at 1577–1595 cm–1 and 440–465
cm–1, respectively, in all the complexes. This suggests that both nitrogens
of bipy are coordinated to the metal ion.[27] A new band in the region 210–
250 cm–1 due to n(M–N) of bpy further confirms its bidentate coordination
to the metal centre.
Conductance Measurements
The observed molar conductances (LM = 8.2–11.8 ohm–1cm2 mole–1)
of all the complexes in 10–3 M DMF solutions are given in Table 1. This
suggests the non-electrolytic nature of these complexes.[28]

Complexes of Sulfamerazine
Magnetic Susceptibility Measurements
809
The room temperature magnetic moment values of the complexes are
given in Table 1. The magnetic moment value of 1.80 B.M. measured
for the copper complex (1) lies in the range expected for a d9 system, which
contains one unpaired electron with octahedral geometry.[29] The measured
value of 3.13 B.M. for the nickel complex (2) suggests octahedral geometry
for this complex.[30] The observed magnetic moment of 4.91 B.M. is
consistent with a high-spin octahedral cobalt(II) complex.[30] The room
temperature magnetic moment value (1.67 B.M.) of the samarium complex
(5) is consistent with the presence of five unpaired electrons and indicates
only slight participation of 4f electrons in bonding.[31] The Zn(II) and
UO2(VI) complexes were found to be diamagnetic as expected.
1H NMR Spectra
Proton NMR spectra of the ligand LH (Figure 2) and the [Zn(L)-
(bpy)(OAc)(H2O) complex (Figure 3) were recorded in DMSO-d6. The
absence of the phenolic (OH) proton signal (at 12.55 ppm in the ligand
Figure 3. 1H NMR spectrum of [Zn(L)(bpy)(OAc)(H2O)] (4).

810
Maurya, Patel, and Rajput
LH) in the Zn complex indicates the coordination by phenolic oxygen to the
metal ion after deprotonation.[37] The coordination of the azomethine
nitrogen is inferred by the downfield shifting of the –CH=N– proton
signal from 8.96 ppm in the ligand to 9.8 ppm in the complex.[16] The
aromatic proton signals and –CH3 proton signal are seen at 6.8–8.4 ppm
and 2.32 ppm, respectively. The 1H NMR spectra of these two com-
pounds, along with the assignment of proton signals, are given in Figures 2
and 3.
Electronic Spectra
The diffuse reflectance spectra of a few representative compounds
were recorded in the wave length range 260 to 800 nm. Compound (2)
exhibits five absorption maxima (Figure 4) at 274, 314, 338, 406 and 545
nm. The first three absorption maxima are most probably due to n !s*,
p! p* and n !p* intraligand transitions, respectively. Considering the
high intensity of the fourth band at 406 nm, it may be assigned as
ligand ! metal charge transfer transition The last absorption maximum at
3
3
545 nm is due to a d–d transition assignable to A2g(F) ! T1g(F). This
suggests an octahedral[32] stereochemistry around the nickel(II) ion. The
diffuse reflectance spectrum of compound (6) displays three spectral bands
at 265, 342 and 480 nm. These are assigned to p !p* and n! p* and
1P
! pu transitions,[33] respectively. The last one of the transition is
+
3
g
typical of the O=U=O symmetric stretching frequency of the first excited
state.[3] The diffuse reflectance spectrum (Figure 4) of the Sm(III) complex
Figure 4. Diffuse reflectance spectrum of [Ni(L)(bpy)(OAc)(H2O)] (2).

Complexes of Sulfamerazine
811
(5) displays three absorption bands in the visible region at 505, 692 and
6
4
6
6
6
4
716 nm. These are assigned to H5/2 ! F9/2, H5/2 ! P5/2, H5/2 ! I13/2
,
respectively.[34]
Thermogravimetric Analysis
The TG curves of two representative compounds, [Sm(L)(bpy)(OAc)2-
(H2O)ꢀ2H2O and [UO2(L)(bpy)(OAc)(H2O)ꢀH2O, were recorded in the tem-
perature range from ambient to 810 °C at a heating rate of 15 °C /min.
The TG curve of the compound (5) shows a first weight loss at 116 °C of
4.0% (calc. 4.1%) corresponding to two lattice water molecules.[35] The
second weight loss at 142 °C was observed to be 2.5% (calc. 2.2%)
corresponding to the elimination of one coordinated water molecule.[36]
The dehydrated compound is stable up to 322 °C and shows a sudden
weight loss of 34% (calc. 34.5%), which may be due to removal of two
acetato groups and one 2,2’-bipyridine molecule in the temperature range
322–390 °C. At subsequent higher temperatures the TG curve consists of
greatly overlapped decomposition steps which prevent the accurate
correlation of these steps with the proper decomposition products. The
TG curve of complex (6) shows a first weight loss of 2.0% (calc. 2.02%)
at 110 °C due to elimination of one lattice water[35] molecule. It shows a
further weight loss of 2.4% (calc. 2.6%) at 143 °C corresponding to
removal of one coordinated water[36] molecule. The third weight loss of
7.0% (calc. 6.9%) was observed at 290 °C and may be due to loss of one
acetato group from the coordination sphere. The fourth weight loss of
Figure 5. Suggested structure of [M(L)(bpy)(OAc)(H2O)].

812
Maurya, Patel, and Rajput
20% (calc. 19.6%) in the temperature range 290–416 °C may be due to
the elimination of one bpy molecule. The following equations represent
these processes:
110 °C
½UO2ðLÞðbpyÞðOAcÞðH2OÞꢀH2O
! ½UO2ðLÞðbpyÞðOAcÞðH2OÞꢂ
ÀH2O
ð4Þ
ð5Þ
143 °C
½UO2ðLÞðbpyÞðOAcÞðH2OÞꢂ
!½UO2ðLÞðbpyÞðOAcÞꢂ
ÀH2O
290 °C
!
½UO2ðLÞðbpyÞðOAcÞꢂ
½UO2ðLÞðbpyÞðOAcÞꢂ
½UO2ðLÞðbpyÞꢂ
ð6Þ
ð7Þ
ÀOAc
290À416 °C
!
½UO2ðLÞꢂ
Àbpy
CONCLUSIONS
From the satisfactory analytical data, magnetic studies, conductance
measurements, thermal and various spectral studies it is concluded that
the metal: ligand stoichiometric ratio is 1:1 in all the complexes. The
general compositions of the transition metal complexes are [M(L)(bipy)-
(OAc)(H2O) (where M = Cu(II), Ni(II), Co(II) or Zn(II) and OAc = CH3-
COO) and the complexes derived from the inner transition metals have
the composition [Sm(L)(bipy)(OAc)2(H2O)ꢀ2H2O and [UO2(L)(bipy)-
(OAc)(H2O)ꢀH2O. The overall spectral studies indicate that the Schiff
Figure 6. Suggested structure of [Sm(L)(bpy)(OAc)2(H2O)]ꢀ2H2O (5).

Complexes of Sulfamerazine
813
Figure 7. Suggested structure of [UO2(L)(bpy)(OAc)(H2O)]ꢀH2O (6).
base ligand behaves in a monobasic bidentate (O,N) manner. The pro-
posed structures of the synthesized complexes are shown in Figures 5, 6
and 7.
ACKNOWLEDGMENTS
The authors are thankful to Professor S. D. Tripathi, Vice-Chancellor
of this University, for encouragement, and Professor K. K. Mishra, Head,
Department of Chemistry, for laboratory facilities and helpful discussions.
Analytical facilities provided by the Central Drug Research Institute,
Lucknow, India, and the Regional Sophisticated Instrumentation Centre, In-
dian Institute of Technology, Chennai, India, are gratefully acknowledged.
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Received August 17, 1998
Accepted January 31, 2003
Referee I: F. T. Greenaway
Referee II: R. A. Faltynek