bis-bidenticity of 2,4-dihydroxy-5-acetylacetophenone and its derivatives with divalent nickel and copper

Article abstract of DOI:10.1081/SIM-120016873

Cu(II) and Ni(II) complexes of 2,4-dihydroxy-5-acetylacetophenone (H₂L), 2,4-dihydroxy-5-acetylacetophenone dihydrazone (H₂L′) and 2,4-dihydroxy-5-acetylacetophenonedioxime (H₂L″) were synthesized and characterized by elem

Full text of DOI:10.1081/SIM-120016873

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bis-Bidenticity of 2,4-Dihydroxy-5-acetylacetophenone
and Its Derivatives with Divalent Nickel and Copper
B. S. Shyamala a & V. Jayatyagaraju b c
a S.N.V.M.V. College , Exhibition Grounds, Hyderabad, A.P., 500001, India
b Department of Chemistry , Nizam College , Osmania University , Hyderabad, A.P., 500001,
India
c Addis Ababa University , Addis Ababa, Ethiopia
Published online: 15 Aug 2006.
To cite this article: B. S. Shyamala & V. Jayatyagaraju (2003) bis-Bidenticity of 2,4-Dihydroxy-5-acetylacetophenone and Its
Derivatives with Divalent Nickel and Copper, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 33:1, 63-75,
DOI: 10.1081/SIM-120016873
To link to this article: http://dx.doi.org/10.1081/SIM-120016873
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 1, pp. 63–75, 2003
bis-Bidenticity of
2,4-Dihydroxy-5-acetylacetophenone
and Its Derivatives with Divalent Nickel
and Copper
2,#
B. S. Shyamala1, and V. Jayatyagaraju
*
1S.N.V.M.V. College, Exhibition Grounds, Hyderabad, A.P., India
2Department of Chemistry, Nizam College, Osmania University,
Hyderabad, A.P., India
ABSTRACT
Cu(II) and Ni(II) complexes of 2,4-dihydroxy-5-acetylacetophenone
(H2L), 2,4-dihydroxy-5-acetylacetophenone dihydrazone (H2L’) and
2,4-dihydroxy-5-acetylacetophenonedioxime (H2L@) were synthesized
and characterized by elemental analyses, conductance, magnetic suscept-
ibility measurements, UV-Vis and IR spectral studies. H2L’ and H2L@ were
synthesized by the reaction of H2L with hydrazine hydrate and hydro-
*
Correspondence: B. S. Shyamala, S.N.V.M.V. College, Exhibition Grounds,
Hyderabad, A.P. 500001, India; E-mail: bssdonge@hotmail.com.
#Current address: Addis Ababa University, Addis Ababa, Ethiopia.
63
DOI: 10.1081/SIM-120016873
0094-5714 (Print); 1532-2440 (Online)
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Copyright D 2003 by Marcel Dekker, Inc.

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64
Shyamala and Jayatyagaraju
xylamine, respectively, and were characterized using elemental analyses,
mass and IR spectral data. The ligands behave as dibasic bis-bidentates
yielding polymeric complexes. The coordination is octahedral for all
complexes except NiL’ which is square-planar.
INTRODUCTION
The structural[1–5] importance and applications[6] of metal complexes
derived from bis-bidentate and bis-multidentate chelates prompted us to
undertake the study of the coordination properties of such ligands. The
present work is devoted to the study of the coordination chemistry of 2,4-
dihydroxy-5-acetylacetophenone (H2L), its dihydrazone (H2L’) and dioxime
(H2L@) derivatives (Figure 1) with Ni(II) and Cu(II).
RESULTS AND DISCUSSION
The structures of the ligands H2L’ and H2L@ were determined by
elemental analyses, mass and IR spectral data. Analytical data of the li-
gands and metal complexes are presented in Table 1.
The molecular ion peaks in the mass spectra of the ligands H2L’ and
H2L@ were observed at m/e 220 and 224, respectively, which are the same
as the calculated M + values (220 and 224), for the molecular formulae
C10H12N4O2 and C10H12N2O4, respectively. The analytical data are con-
sistent with these molecular formulae.
IR Spectra of the Ligands
The IR spectral data for the ligands and metal complexes are listed in
Table 2. The IR spectra of H2L’ and H2L@ show the azomethine stretching
frequency as a sharp peak at 1610 and 1660 cm ꢀ 1, respectively.[7] A broad
Figure 1. Structures of the ligands.

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Complexes with Divalent Nickel and Copper
65

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66
Shyamala and Jayatyagaraju

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Complexes with Divalent Nickel and Copper
67
band centered at 2550 cm ꢀ 1 in H2L’ is assigned to phenolic stretching
n(OH).[8]
The corresponding band in H2L@ is observed at 2800 cm ꢀ 1. The
lowering and broadening of this band in both ligands is attributed to in-
tramolecular H-bonding between the phenolic hydrogen and azomethine
nitrogen.[9] The n(OH) (oxime) band is shown as a distinct peak at 3400
cm ꢀ 1. The n(N–H) (asy and sy) and n(N–N) bands in H2L’ are identified
at 3400, 3300 and at 1050 cm ꢀ 1, respectively.[10,11] The n(N–O) band of
the oxime moiety[12] in H2L@ is observed at 960 cm ꢀ 1. Based on these
observations, the structures assigned to the ligands are given in Figure 1.
Synthesis of the Complexes
The metal complexes are air-stable, sparingly soluble in DMF and 1,4-
dioxane and are completely soluble in DMSO. They were characterised on
the basis of elemental analyses, conductance, thermal, IR and UV-Vis-near-
IR spectral and magnetic data.
Analysis, Conductance and Thermal Studies of the Complexes
The analytical data suggest a 1:1 metal to ligand ratio. A conductance
measurement in 1ꢁ 10 ꢀ 3 M DMSO solution reveals the complexes to be
non-electrolytes. Hence, the formation of metal complexes can be given by
the following representative equations.
H2L þ M2þ ! ML þ 2Hþ
H2L0 þ M2þ ! ML0 þ 2Hþ
H2L00 þ M2þ ! ML00 þ 2Hþ
Thermal data of NiL shows an endotherm at 210 °C indicating the
presence of a single coordinated water molecule per metal ion.[13] The
thermograms do not indicate the presence of water in all of the other
complexes. All the complexes start decomposing around 300 °C as indicated
by the exotherms.
The n(OH) bands identified in the free ligands were absent in the IR
spectra of all the complexes. This is attributed to deprotonation of pheno-

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68
Shyamala and Jayatyagaraju
lic groups during complexation.[14] Further, a shift in the n(C–O) band by
10–20 cm ꢀ 1 to higher frequency confirms coordination through the phe-
nolic oxygen in the ligands.[15]
In NiL, a broad band in the region 3500–3100 cm ꢀ 1 is due to co-
ordinated water.[16] The rocking mode of the coordinated water was
observed[16] at 820 cm ꢀ 1. The acetyl stretching vibration in H2L and the
azomethine stretch in H2L’ and H2L@ have under-gone shifts to lower
frequency confirming their participation in coordination.[11,17] While the
–NH2 bands are intact in NiL’, these bands in CuL’ and the n(OH) (oxime)
band in H2L@ complexes have broadened and undergone a shift to lower
frequency as compared with the free ligand. This is attributed to in-
tramolecular hydrogen bonding.[11] Non-ligand bands observed in the region
of 870–440 cm ꢀ 1 are assigned to M–O and M–N vibrations.[18]
Based on these observations the ligands are concluded to be dibasic
and bis-bidentate donors. H2L coordinates through the acetyl and phenolic
oxygens. H2L’ and H2L@ coordinate through the azomethine nitrogen and
phenolic oxygen.
Electronic Spectra and Magnetic Moments of the Complexes
The magnetic moments of NiL and NiL@ are close to the spin-only
value of 2.83 B.M. for octahedral Ni(II) complexes. The electronic spectral
data comprising the observed band positions, 10Dq and the calculated
values of b35, B35 and meff (B.M. units) for the Ni(II) complexes are listed
in Table 3. Table 4 presents the assigned transitions and magnetic data for
the Cu(II) complexes.
The values of the first spin allowed band (v1) was taken as 10Dq. The
values, v2, v3 and B35 were calculated using standard equations, which
include configurational interaction[19] as detailed below, adopting the pro-
cedures (a), (b) and (c).
(a) Fitting the second band:
10Dq ¼ v1
B ¼ ð2v21 þ v22 ꢀ 3v1v2Þ=ð15v2 ꢀ 27v1Þ
(b) Fitting the third band:
10Dq ¼ v1
B ¼ ð2v21 þ v32 ꢀ 3v1v3Þ=ð15v3 ꢀ 27v1Þ

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Complexes with Divalent Nickel and Copper
69

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70
Shyamala and Jayatyagaraju
Table 4. Electronic spectral data and magnetic data of the Cu(II) complexes.
Complex
[CuL]n
nmax (cm ꢀ 1
)
Assignment
meff (B.M.)
2
17,860, 14,290, 12,350
2B1g ! Eg,
1.40
2
2
2
2B1g ! B2g B1g ! A1g
[CuL’]n
[CuL@]n
Multiple band
in the region
Same as above
0.00
1.77
23,300 ꢀ 16,670
25,500; 22,720; 15,630
Same as above
(c) Fitting the sum of second and third bands:
10Dq ¼ v1
B ¼ ðv2 þ v3 ꢀ 3v1Þ=15
Out of the three adopted procedures, the best fit for the transitions v2
and v3 was achieved using method (a) for NiL and method (c) for NiL@. In
view of the ligand structure of H2L’, the diamagnetic nature and the
observed electronic transitions of NiL’, the complex is predicted to be a
linear polymer with a square-planar geometry around the nickel ion.[20]
The magnetic moments and electronic transition pattern support square-
planar geometry around Cu(II) ions, with strong metal-metal inter-
actions[20,21] in CuL and CuL’.
The proposed structures based on these observations are depicted in
Figure 2.
EXPERIMENTAL
Materials
The reagents and chemicals used were of BDH (AR) or E. Merck (AR)
grade. All solvents were distilled under anhydrous conditions before use.
Synthesis of Ligands
Synthesis of 2,4-Dihydroxy-5-acetylacetophenone (H2L)
The compound was prepared as reported by Anjaneyulu et al.[22]

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Complexes with Divalent Nickel and Copper
71
Figure 2. Suggested structures of complexes.

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Shyamala and Jayatyagaraju
Synthesis of 2,4-Dihydroxy-5-acetylacetophenone Dihydrazone (H2L’)
A solution of hydrazine (5 mL, 0.1 mol) in methanol (25 mL) was
added slowly to a hot methanolic solution (100 mL) of 2,4-dihydroxy-5-
acetylacetophenone (9.7 g, 0.05 mol). The resultant solution was refluxed
on a water bath for 3 h. The bright-yellow crystalline product obtained was
filtered and washed successively with methanol and petroleum ether and
then dried in vacuo.(decomposition point > 260 °C). Yield, 12 g (80%).
Synthesis of 2,4-Dihydroxy-5-acetylacetophenone Dioxime (H2L@)
A solution of hydroxylamine hydrochloride (7 g, 0.1 mol) in aqueous
methanol (1:1 v/v, 50 mL) was added to a hot methanolic solution (100
mL) of 2,4-dihydroxy-5-acetylacetophenone (9.7 g, 0.05 mol) and the re-
sulting solution was refluxed for 4 h on a water bath. The white crystalline
product obtained was washed with hot aqueous methanol, petroleum ether
and dried in vacuo.(decomposition point >250 °C). Yield, 13 g (75%).
Synthesis of Complexes
The following general procedure was adopted for the synthesis of the
metal complexes. To a hot methanolic sodium hydroxide solution (1%, 100
mL) of the ligand (H2L =0.97 g, H2L’ =1.11 g, H2L@=1.22 g, 0.005 mol) a
methanolic solution of the divalent metal chloride (NiCl2ꢂ6H2O =1.189 g,
CuCl2ꢂ2H2O = 0.855 g, 0.005 mol, in 50 mL) was added. A distinct lowering
of the pH was observed. The pH of the solution was then increased to 6
using a methanolic ammonia solution and the contents were refluxed for 6 h.
The separated solid complex was filtered, washed with methanol, petroleum
ether and dried in vacuo. Yield, 1.09–1.35 g (40–60%).
Analytical and Physical Measurements
The mass spectra of the ligands were recorded on a VG-Micromass
7070-H spectrometer. Elemental analyses were carried out by micro ana-
lytical methods. Metal contents were determined using a Varian Spectra 30/
40 atomic absorption spectrometer, employing the necessary standards.
DTA studies were carried out on a Leeds and Northrup, U.S.A. instrument.
Thermal decompositions were effected at normal atmosphere in Robert–
Grimshaw ceramic sample holders at a testing rate of 10 °C/min using

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Complexes with Divalent Nickel and Copper
73
a–alumina as reference. Conductance measurements were carried out on a
Digisun D1-909 digital conductometer. IR spectra were recorded on a Per-
kin-Elmer-783 spectrophotometer using KBr pellets. Reflectance electronic
spectra were recorded in Nujol mulls on a Cary 2390 UV spectrometer.
Magnetic susceptibilities were measured on a vibrating sample magnetome-
ter of EG & G Princeton, research model.
ACKNOWLEDGMENTS
One of the authors (B.S.S) is thankful to the Head, Department of
Chemistry, Osmania University, for extending laboratory facilities; and to
the Director, Indian Institute of Chemical Technology, Hyderabad, for ex-
tending Differential Thermal Analysis and library facilities; and to the
Director, Geological Survey of India, Hyderabad, for recording atomic ab-
sorption spectra. Thanks are extended to RSIC, Madras for certain spectral
facilities and to the Principal, Sarojini Naidu Vanita Maha Vidyalaya Col-
lege for cooperation extended in pursuing research activity.
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Complexes with Divalent Nickel and Copper
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Received June 21, 2001
Accepted September 3, 2002
Referee I: M. A. Green
Referee II: D. Rabinovich