Studies on complexes of cobalt(II), nickel(II), copper(II), and cadmium(II) with acetophenone and 4-hydroxyacetophenone oxaloyldihydrazones

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STUDIES ON COMPLEXES OF COBALT(II),
NICKEL(II), COPPER(II), AND CADMIUM(II) WITH
ACETOPHENONE AND 4-HYDROXYACETOPHENONE
OXALOYLDIHYDRAZONES
B. Singh a , K. K. Narang b & Rachana Srivastava a
a Department of Chemistry , Banaras Hindu University , Varanasi, 221 005, India
b Department of Applied Chemistry , Banaras Hindu University , Varanasi, 221 005, India
Published online: 09 Dec 2011.
To cite this article: B. Singh , K. K. Narang & Rachana Srivastava (2001) STUDIES ON COMPLEXES OF COBALT(II), NICKEL(II),
COPPER(II), AND CADMIUM(II) WITH ACETOPHENONE AND 4-HYDROXYACETOPHENONE OXALOYLDIHYDRAZONES, Synthesis and
Reactivity in Inorganic and Metal-Organic Chemistry, 31:8, 1387-1401, DOI: 10.1081/SIM-100107205
To link to this article: http://dx.doi.org/10.1081/SIM-100107205
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(8), 1387±1401 (2001)
STUDIES ON COMPLEXES
OF COBALT(II), NICKEL(II), COPPER(II),
AND CADMIUM(II) WITH
ACETOPHENONE AND
4-HYDROXYACETOPHENONE
OXALOYLDIHYDRAZONES
B. Singh,*,1 K. K. Narang,2 and Rachana Srivastava1
1Department of Chemistry, Banaras Hindu University,
Varanasi-221 005, India
2Department of Applied Chemistry, Banaras Hindu
University, Varanasi-221 005, India
ABSTRACT
The complexes [M(L1)nCl2] and [Cu(L2)SO4(H2O)2] [M ˆ
Co(II), Ni(II), Cu(II) and Cd(II); L1 ˆ acetophenone oxa-
loyldihydrazone (CONHN ˆ C(CH3)C6H5)2, n ˆ 2 and L2 ˆ
4-hydroxyacetophenone oxaloyldihydrazone (CONHN ˆ
C(CH3)C6H4OH-4)2 have been prepared. Analytical, molar
conductance, magnetic susceptibility, electronic, ESR and
NMR spectraldata have been used to investigate the structure
and bonding of the complexes. X-ray powder di€raction data
indicate the shape and size of the unit cell of the copper(II)
*Corresponding author. E-mail: bsingh@banaras.ernet.in
1387
Copyright # 2001 by MarcelDekker, Inc.
www.dekker.com

1388
SINGH, NARANG, AND SRIVASTAVA
complex. Some of the complexes were screened against E. coli
and Aspergillus niger for biological activity.
INTRODUCTION
Organic acid dihydrazides1 containing two CONHNH2 groups have
been reported to coordinate through two imine nitrogens (>NH) even in the
presence of potentialcoordinating >CˆO and -NH2 moieties. Strong in-
tramolecular hydrogen bonding as shown in Fig. 1, probably makes the
latter unavailable for coordination.
When the terminal-NH groups are condensed with aldehydes and
2
ketones, the resulting Schi€ bases have carbonyl oxygens and azomethine
nitrogens as donor sites and the above type of hydrogen bonding is likely to
be absent.
The 3d-metal complexes of oxaloyldihydrazide and its Schi€ bases
have been synthesized and the bonding and geometry around the metalion
has been reported276. Furthermore, 4-hydroxyacetophenone results in a
Schi€ base with an -OH group as an additionalbonding site.
In view of interesting bonding site of acetophenone oxaloyldihy-
drazone and 4-hydroxyacetophenone oxaloyldihydrazone (Fig. 2), the
hitherto uninvestigated cobalt(II), nickel(II), copper(II) and cadmium(II)
complexes of these ligands have been prepared and their structures have been
investigated. The results of these investigations are reported in this paper.
EXPERIMENTAL
Materials and Methods
The chemicals used in the present investigations were of analytical
reagent grade. Acetophenone and 4-hydroxyacetophenone (CentralDrug
House, New Delhi) were used as obtained. L1 and L2 were prepared by
re¯uxing oxalic acid dihydrazide (20 mmol, 2.36 g) with acetophenone
Figure 1. Structure of oxaloyldihydrazide.

COMPLEXES WITH ACETOPHENONE
1389
Figure 2. Structure of ligands.
(20 mmol, 2.40 g) or 4-hydroxyacetophenone (20 mmol, 2.72 g) in ethanol
(100 mL) for ꢀ 7 h. The hydrazones precipitated during the reaction were
®ltered and washed with ethanol. They were recrystallized form hot ethanol.
The parent hydrazide was prepared by the reported method7. They were
characterized by C, H and N analyses, IR and NMR spectra.
Synthesis of Complexes
The complexes of L1 were obtained by adding an ethanolsoultion
(50 mL) of the hydrazone (10 mmol, 3.22 g) to an aqueous ethanol (50:50,
v=v) solution (50 mL) of the metal salts (10 mmol) and heating on a water
bath for ꢀ 1 h. The compounds precipitated during the reaction were
®ltered and washed with distilled water, ethanol and ®nally with diethyl
ether and dried over anhydrous calcium chloride in a desiccator under
reduced pressure.
The complexes of L2 were obtained by mixing an ethanolsoultion
(50 mL) of the hydrazone (10 mmol, 3.38 g) and an aqueous ethanol (60:40,
v=v) solution of the metal salt (10 mmol) and re¯uxing the solution for ꢀ 8 h.
With re¯uxing the compounds precipitated and were ®ltered and washed
several times with distilled water to remove unreacted metal salts followed
by ethanol and ®nally diethyl ether and dried in a desiccator.
Analysis and Physical Measurements
The metal, chloride and sulfate contents were determined by literature
procedures8. Carbon, hydrogen and nitrogen were determined micro-
analytically on a Perkin Elmer 240 C elemental analyzer. Hydrazine was
determined volumetrically by titrating against KBrO3 after acid catalysed

1390
SINGH, NARANG, AND SRIVASTAVA
Figure 3. Representative structures of complexes.

COMPLEXES WITH ACETOPHENONE
1391
hydrolysis of the complexes of the complexes for ꢀ 2 h using methylorange
as indicator9. Molar conductances in DMSO solution (l0À3 M) were mea-
sured at room temperature on a Systronics 304 conductivitymeter. Magnetic
susceptibilities were determined at room temperature on a Cahn-Faraday
balance using [CoHg(SCN)4] as a standard and corrections were made for
diamagnetism10. IR spectra were recorded on a JASCO 5300 spectro-
photometer in Nujol mulls or KBr discs. NMR spectra were recorded on a
JEOL FX-90Q spectrometer in DMSO-d6 solution using tetramethylsilane
as an internal reference. Electronic spectra of the ligands and complexes
were recorded on a Cary 2390 spectrophotometer in Nujol mulls. The ESR
spectrum of [Cu(L2)SO4(H2O)2] was recorded on a Varian X-band E4
spectrometer. X-ray di€raction data were collected on a Seifert ID 3000
di€ractometer using Cu-Ka radiation.
RESULTS AND DISCUSSION
A summary of the analytical results and some physical properties are
shown in Table I. The complexes are insoluble in common organic solvent
such as ethanol, methanol, acetone and chloroform. However, the L1
complexes are slightly or fairly soluble in DMF and DMSO. The electrical
conductance of the nickel(II), zinc(II) and cadmium(II) complexes of L1
indicate their non-electrolytic behaviour while those of the cobalt(II) and
copper(II) complexes suggest partial dissociation of the anion in DMSO
solution11.
Magnetic Moments
Magnetic moments of the nickel(II) and cobalt(II) complexes favour
an octahedralarrangement of ligands around metalions 12. The me€ values of
the copper complexes are indicative of the presence of one unpaired electron
but give no de®nite information regarding the stereochemistry.
Electronic Spectra
The absorption bands observed in the spectrum of L1 at 28,409, 43,246
and 47,619 cmÀ1 and in that of L2 at 28,901, 40,971 and 45,454 cmÀ1 may be
assigned to the n?p* and p?p* transitions of >CˆO, >CˆN and the
p?p* transition of the benzene moiety.
These bands are observed at lower energies at 29,410730,400,
39,330740,310 and 44,650745,450 cmÀ1 in the spectra of the L1 complexes

1392
SINGH, NARANG, AND SRIVASTAVA

COMPLEXES WITH ACETOPHENONE
1393
and at 29,330732,330, 40,040740,540 and 45,450745,490 cmÀ1 in those of
the L2 complexes, indicating bonding of >CˆO and >CˆN moieties to the
metalions.
The bands observed at 14,478 (n2) and 18,115 (n3) cmÀ1 in the spec-
trum of [Co(L1)2Cl2] and at 19,220 (n2) and 22,440 (n3) cmÀ1 in that of
4
4
[Co(L2)Cl2] are assigned to T1g (F)?4A2g (F) (n2) and T1g (P) (n3) tran-
sitions, respectively, assuming an octahedral geometry13.
[Ni(L1)2Cl2] shows two adsorption bands at 18,226 (n2) and 26,836 (n3)
cmÀ1 and [Ni(L2)Cl2] exhibits two absorption bands at 18,625 (n2) and
26,795 (n3) cmÀ1. They are attributed to A2g(F)?3T1g(F) (n2) and T1g(P)
(n3) transitions, respectively, on the basis of an octahedral stereochemistry14.
The ligand ®eld parameters such as crystal ®eld splitting energy
(10 Dq) interelectronic repulsion parameter (B0), nephalauxetic ratio (b),
percentage covalency (b0) and ligand ®eld stabilization energy (LFSE) have
been evaluated for the cobalt(II) and nickel(II) complexes15. The values of
B0, b and b0 are indicative of metal-ligand orbital overlap. Only one
absorption band is observed at 12,760 and 14,815 cmÀ1 in the copper(II)
3
3
complexes of L1 and L2, respectively. This is assigned to the Eg?2T2g(D)
transition, indicating octahedralgeometry for the compelxes
2
16
.
ESR Spectra
The spectrum of [Cu(L2)SO4(H2O)2] gives gzz ˆ 2.196, gyy ˆ 2.002 and
gxx ˆ 2.003 indicating rhombic symmetry around the metalion in the
complex17.
Infrared Spectra
The bands observed at 3270, 1685, 1665 and 980 cmÀ1 in the spectrum
of L1 and at 3225 m 1680, 1635 and at 975 cmÀ1 in that of L2 are attribute to
n(N-H), n(CˆO), n(CˆN) and n(N-N), respectively.
In the spectra of the L2 complexes n(CˆO) shifts to lower frequencies
(166071630 cmÀ1) suggesting interaction of the carbonyloxygen with the
metalions. The n(CˆO) band shifted towards higher frequencies in the L1
complexes or remained unaltered and thus indicates non-participation of the
18
carbonyloxygen in bonding
.
The weakening, splitting and broadening of the band due to n(CˆN)
in all the complexes suggest bonding through the azomethine nitrogen19.
Further, the appearance of n(N-N) at higher frequencies (98571020 cmÀ1
)

1394
SINGH, NARANG, AND SRIVASTAVA

COMPLEXES WITH ACETOPHENONE
1395

1396
SINGH, NARANG, AND SRIVASTAVA
Table IV. Important IR SpectralBands (cm À1) of L1, L2 and Their Complexes
Complexes
n(OH)phenolic
n(NH)
n(CˆO)
n(CˆN)
n(N-N)
a
L1
7
7
7
7
7
3350 w
3350 w
3345 w
3350 w
3345 w
3345 w
3270 m
3275 m
3270 w
3325 w
3270 w
3225 w
3222 w
3224 w
3230 w
3220 w
3220 w
1685 s
1690 s
1690 s
1690 m
1685 m
1680 s
1630 m
1630 m
1635 m
1640 m
1660 m
1665 s
980 m
995 m
1005 m
l000 m
1000 m
975 m
1005 m
1010 m
1015 m
1000 m
985 m
[Co(L1)2Cl2]a
[Ni(L1)2Cl2]a
[Cu(L1)2Cl2]a
1620 m
1640 m
1635 m
1635 m
1635 s
1625 m
1620 m
1630 m
1605 m
1620 m
[Cd(L1)2Cl2]a
b
L2
[Co(L2)Cl2]b
[Ni(L2)Cl2]b
[Cu(L2)Cl2]b
[Cu(L2)SO4(H2O)2]b
[Cd(L2)Cl2]b
aIn KBr.
bIn Nujol mulls.
compared to its position in the free hydrazone favours involvement of the
azomethine nitrogen derived form the hydrazine moiety in bonding20.
The bond due to n(OH) observed at 3350 cmÀ1 in the spectrum of L2
is observed at the same position in the complexes and suggests non-
involvement of the phenolic oxygen in bonding. In [Cu(L2)SO4(H2O)2] three
new bands due to chelating sulfate are observed at 965, 1065 and
1245 cmÀ1 21
.
1H NMR Spectra
The spectrum of L1 at 27 ꢁC exhibits signals at 10.12, 2.22 and
6.4077.00 due to -NH, CH3, and aromatic protons, respectively. The
spectrum of [Cd(L1)2Cl2] shows up®eld shifting of the -NH signal and
suggests non-participation of >CˆO in bonding.
13C NMR Spectra
The spectrum of L1 exhibits signals at 160.22, 150.00 and 13.61 ppm
due to >CˆO, >CˆN and -CH3 carbons, respectively. In the spectrum of
22,23
[Cd(L1)2Cl2] the >CˆN signalshows a down®edl shift ans suggests inter-
action of the azomethine nitrogen with the metalion
.

COMPLEXES WITH ACETOPHENONE
1397
Table V. X-ray Powder Di€raction Pattern of [Cu(L2)SO4(H2O)2]
d
Irel.
1=d2obs
1=d2cal
hkl
8.1488
6.9502
6.3191
4.9346
4.5420
3.9969
3.8280
3.3851
3.2870
3.1441
3.0691
2.9212
2.8365
2.7576
2.6008
2.5537
2.4722
2.4281
2.3813
2.3421
1.9791
1.8397
1.8267
1.8062
1.5755
1.5193
1.4753
1.4379
1.4268
1.4069
1.3850
1.3666
1.3570
1.3495
842
938
618
631
710
530
708
538
600
557
668
709
665
660
510
459
827
1000
614
681
764
780
787
987
388
418
658
411
789
421
660
727
669
901
0.01506
0.02070
0.02504
0.04107
0.04847
0.06260
0.06824
0.08727
0.09025
0.10116
0.10616
0.11719
0.12429
0.13150
0.14784
0.15334
0.16362
0.16962
0.17635
0.18230
0.25531
0.29546
0.29969
0.30656
0.41223
0.43322
0.45945
0.48366
0.49122
0.50521
0.52132
0.53545
0.54305
0.54910
0.01529
0.02077
0.02512
0.04105
0.04829
0.06269
0.6779
112
021
022
210
233
121
132
242
314
225
232
342
421
231
302
404
456
205
312
251
314
506
487
205
194
371
3310
2105
8710
253
966
6712
784
741
0.08854
0.09075
0.10108
0.10611
0.11590
0.12475
0.13167
0.14780
0.15319
0.16368
0.16964
0.17629
0.18191
0.25505
0.29545
0.29958
0.30654
0.41216
0.43395
0.45922
0.48364
0.49129
0.50515
0.52143
0.53545
0.54294
0.54922

1398
SINGH, NARANG, AND SRIVASTAVA
X-Ray Power Di€raction Studies
The X-ray powder lines observed for the [Cu(L2)SO4(H2O)2
complex have been successfully indexed by Ito's method. The indexing
of the lines yields the lattice constant a ˆ 13.01, b ˆ 15.04 and
c ˆ 16.54 A, a ˆ 132.010, b ˆ 122.00 and g ˆ 68.890 for a triclinic unit
lattice24.
Fungicidal Activity
The antifungalactivity of the copper(II) and zinc(II) compelxes in
DMSO solution at 500, 1000 and 1500 mg=mL were evaluated against
Aspergillus niger using the slide germination method25. In this method the
fungus culture was placed on di€erent slides and two drops of a solution of
the compounds of di€erent concentrations was added. The slides were in-
cubated in a humidity chamber and the percentage of germination was re-
corded after ꢀ 48 h.
Table VI indicates a gradual decrease in germination with increasing
dose of the metal complexes. The ligands were found less e€ective than their
complexes. The copper(II) and zinc(II) complexes showed appreciable
toxicity26. This may be due to the chelation of the ligand which increases the
lipid solubility, thereby facilitating its passage through the lipid layer of the
fungus membrane. The [Zn(L2)Cl2] complex showed poor germination,
possibly due to its polymeric nature.
1
Table VI. AntifungalActivity of L , L2 and Their Complexes
Percentage of Germination
Complexes
500 mg=mL
1000 mg=mL
1500 mg=mL
L1
‡‡‡
‡‡‡
‡‡‡
‡‡
‡‡
‡
[Cu(L1)2Cl2]
[Zn(L1)2Cl2]
L2
‡‡‡
‡‡‡
‡‡‡
‡‡
‡‡
‡‡
‡
‡‡‡‡
‡‡‡
[Cu(L2)Cl2]
[Zn(L2)Cl2]
‡‡‡‡
‡‡‡
‡
‡‡‡‡ ˆ 100% germination, ‡‡‡ ˆ 75% germination, ‡‡ ˆ 50% germination,
‡ ˆ 25% germination.

COMPLEXES WITH ACETOPHENONE
1399
1
Table VII. AntibacterialActivity of L , L2 and Their Complexes
Zone of Inhibition (cm)
Complexes
500 mg=mL
1000 mg=mL
1500 mg=mL
L1
0.018
0.880
0.780
0.022
0.660
0.650
0.022
0.899
0.770
0.024
0.668
0.655
0.024
0.931
0.699
0.026
0.668
0.678
[Cu(L1)2Cl2]
[Zn(L1)2Cl2]
L2
[Cu(L2)Cl2]
[Zn(L2)Cl2]
Antibacterial Activity
1
The antibacterialactivity of the hydrazones L and L2 and their
copper(II) and zinc(II) complexes was studied against E. coli by the
Kirby Baur method27. Each of the compounds was dissolved in the
minimum amount of DMSO and diluted with water to obtain solutions
containing the compounds at the following concentrations: 500, 1000 and
1500 mg=mL. Paper discs of Whatman ®lter paper of uniform diameter
(0.5 cm) were cut and sterilized in an autoclave. The paper discs soaked
in the desired test solutions were placed aseptically in the Petri dishes
containing Luria bertani agar culture media seeded with the bacteria. The
solvent used for preparing the above solutions of di€erent concentrations
was diluted with water in the same way as the complexes to serve as
control. The Petri dishes were incubated at 37 ꢁC and the inhibition zones
were recorded after 18 h of incubation. Each treatment was replicated
three times. The inhibitory e€ect of the complexes increases with in-
creasing concentration of the complexes. The copper(II)-L1 complex
shows higher toxicity than the other complexes. The complexes show a
better inhibitory e€ect than their ligands, which may be due to the
presence of uncoordinated sites in the complexes. The results are de-
scribed in Table VII.
ACKNOWLEDGMENTS
The authors thank the Head, Department of Chemistry, Banaras
Hindu University, for providing laboratory facilities. Thanks are also due to
the RegionalSophisticated Instrumentation Centre, CentralDrug Research
Institute, Lucknow for microanalyses.

1400
SINGH, NARANG, AND SRIVASTAVA
REFERENCES
1. Ahmad, A.-Dutta; Mandal, P.K.; Chaudhary, N.R. Malonyldihy-
drazide Complexes of the 3d Elements. J. Inorg. Nucl. Chem. 1966, 28,
295172959.
2. Narang, K.K.; Lal, R.A. Copper(II), Nickel(II) and Cobalt(II)
Complexes of Acylhydrazine Schi€ Bases. Curr. Sci. 1977, 46 (12),
4017403.
3. Narang, K.K.; Lal, R.A. Zinc(II) Complexes of Acylhydrazine Schi€
Bases. Trans. Met. Chem. 1977, 2, 1007103.
4. Aggarwal, R.C.; Singh, B. Synthesis and Structural Studies of Simple
and Mixed Acid Dihydrazide Complexes of Oxovanadium(IV). Trans.
Met. Chem. 1976, 1, 1617166.
5. Aggarwal, R.C.; Singh, B. Synthesis and Structural Studies of Oxalyl
Acetone Dihydrazone Complexes of Some Divalent Transition Metal
Ions. J. Coord. Chem. 1978, 7, 2457248.
6. Aggarwal, R.C.; Singh, B. Synthesis and Structural Studies of Oxalyl
Dihydrazide Complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and
Zn(II). Z. Anorg. Allg. Chem. 1978, 445, 2277232.
7. Narang, K.K.; Pandey, J.P.; Singh, V.P. Synthesis, Characterization
and PhysicochemicalStudies of Some Copper(II) Tetrathiocyanato-
dithallate(I). Polyhedron 1994, 13 (4), 5297538.
8. Vogel, A.I. A Text Book of Quantitative Inorganic Analysis; Longmass:
London, 1969; 4597587.
9. Narang, K.K.; Lal, R.A. Copper(II), Nickel(II) and Cobalt(II) Com-
plexes of Disalicylaldiimine Succinamide and Di(o-hydroxyaceto-
phenoneimine) Succinamide. Trans. Met. Chem. 1976, 1, 2607263.
10. Earnshaw, A. Introduction to Magneto Chemistry, Academic Press:
London, 1968; 35736.
11. Geary, W.J. The Use of Conductivity Measurements in Organic Sol-
vents for Characterization of Coordination Compounds. Coord.
Chem. Rev. 1971, 7, 817l22.
12. Figgis, B.N.; Lewis, J. Magnetochemistry of Compounds in Modern
Coordination Chemistry. Lewis, J., Wilkins, R.G., Eds.; Interscience:
New York, 1960; 45747.
13. Lever, A.B.P. Inorganic Electronic Spectroscopy; Elsevier: Amsterdam,
1968; 2997300.
14. Sacconi, L. Electronic Structure and Stereochemistry of Nickel(II).
Trans. Met. Chem. 1968, 4, 1997298.
15. Lever, A.B.P. Electronic Spectra of Some Transition Metal Com-
plexes. Derivation of Dq and B. J. Chem. Educ. 1968, 45 (11),
7117712.

COMPLEXES WITH ACETOPHENONE
1401
16. Patel, K.C.; Goldberg, D.E. N-Aralkylamine Complexes. Formation
0
Constant of Coordination Compounds of N-Benzyland N,N -Di-
benzylethylenediamine with Transition Metal Ions. J. Inorg. Nucl.
Chem. 1972, 34 (11), 358373584.
17. Hathaway, B.J.; Billing, D.E. Electronic Properties and Stereo-
chemistry of Mononuclear Complexes of Copper(II) Ions. Coord.
Chem. Rev. 1970, 5 (2), 1437207.
18. Nagano, K.; Kinoshita, H.; Hirakawa, A.Y. Infrared Absorption
Spectra of Isonicotinoylhydrazine and Related Compounds. Chem.
Pharm. Bull. 1964, 12 (10), 119871206.
19. Braibanti, A.; Dallawale, F.; Pellinghelli, M.A.; Leporati, E. The
Nitrogen-Nitrogen Stretching Band in Hydrazine Derivatives and
Complexes. Inorg. Chem. 1968, 7 (7), 143071433.
20. Narang, K.K.; Singh, V.P. Synthesis of Characterization of Cobalt-
(II), Nickel(II), Copper(II) and Zinc(II) Complexes with Acylacetone
Bis-Benzoylhydrazine and Acetylacetone Bis-Isonicotinoylhydrazine.
Trans. Met. Chem. 1993, 18 (3), 2877290.
21. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Co-
ordination Compounds; Wiley Interscience: New York, 1978; 2847286.
22. Haworth, D.T.; Mass, D.L.; Das, M. Carbon-l3 and Fluorine-19
Nuclear Magnetic Resonance Studies of some Monothio-b-Diketonate
Complexes. J. Inorg. Nucl. Chem. 1981, 43 (3), 5157518.
23. Domiano, P.; Pelizzi, C.; Predirri, G.; Vignali, C.; Palla, G. Aroylhy-
drazone as Chelating Agents-d10-MetalCompelxes of Pyridine-2-car-
baldehyde, Salicyloylhydrazone and X-ray Structure of the Zn(II)
Derivatives. Polyhedron 1984, 3 (3), 2817286.
24. Azaro€, L.V.; Buerger, M.J. The Powder Method in X-ray Crystal-
lography; McGraw Hill: New York, 1958; 1197121.
25. Kandsen, R.; Michael, V. Manual of Environmental Biology. Chris-
ton, Hurst, J., Ed.; American Society for Microbiology: Washington,
1997; 3497357.
26. Rao, D.S.; Ganorkar, M.C. Synthesis and Biological Studies of Some
Metal Complexes of Benzaldehyde Salicyloylhydrazone. J. Ind. Chem.
Soc. 1981, LVIII (3), 2177219.
27. Bauer, A.W.; Kirby, W.M.M.; Sherris, J.C.; Turck, M. Antibiotic
Susceptibility Testing by a Standardized Single Disc Method. Am. J.
Clin. Pathol. 1966, 45 (4), 4937496.
Received October 29, 2000
Accepted June 23, 2001
Referee I: D. T. Haworth
Referee II: E. S. Gould