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

Article abstract of DOI:10.1081/SIM-120015080

Metal(II) complexes of the types [M(L)_mCl₂(H₂O)_n] and [Cu(L′)SO₄(H₂O)₂] [M=Co(II), Ni(II), Cu(II) and Cd(II), L=acetophenone salicyloylhydrazone (ASH) OHC₆H₄

Full text of DOI:10.1081/SIM-120015080

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Synthesis and Reactivity in Inorganic and Metal-Organic
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STUDIES ON COMPLEXES OF COBALT(II), NICKEL(II),
COPPER(II), AND CADMIUM(II) WITH ACETOPHENONE
AND 4-HYDROXYACETOPHENONE SALICYLOYL AND
ISONICOTINOYLHYDRAZONES
B. Singh a , K. K. Narang b & Rachana Srivastava1 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: 15 Feb 2007.
To cite this article: B. Singh , K. K. Narang & Rachana Srivastava1 (2002) STUDIES ON COMPLEXES OF COBALT(II),
NICKEL(II), COPPER(II), AND CADMIUM(II) WITH ACETOPHENONE AND 4-HYDROXYACETOPHENONE SALICYLOYL AND
ISONICOTINOYLHYDRAZONES, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 32:9, 1561-1581
To link to this article: http://dx.doi.org/10.1081/SIM-120015080
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 32, No. 9, pp. 1561–1581, 2002
STUDIES ON COMPLEXES
OF COBALT(II), NICKEL(II), COPPER(II),
AND CADMIUM(II) WITH
ACETOPHENONE AND
4-HYDROXYACETOPHENONE
SALICYLOYL AND
ISONICOTINOYLHYDRAZONES
B. Singh,1,* K. K. Narang,2 and Rachana Srivastava1
1Department of Chemistry and
2Department of Applied Chemistry,
Banaras Hindu University,
Varanasi 221 005, India
ABSTRACT
Metal(II) complexes of the types [M(L)mCl2(H2O)n] and
[Cu(L0)SO4(H2O)2] [M¼Co(II), Ni(II), Cu(II) and Cd(II),
L¼acetophenone salicyloylhydrazone (ASH) OHC6H4CO-
NHN¼C(CH3)C6H5, m ¼ 2, n ¼ 2; 4-hydroxyacetophenone
salicyloylhydrazone (4-HOASH), m ¼ 2, n ¼ 0; acetophenone
isonicotinoylhydrazone (AINH), NC5H4CONHN¼C(CH3)-
C6H5, m ¼ 1, n ¼ 2; 4-hydroxyacetophenone isonicotinoyl-
*Corresponding author. E-mail: bsingh@banaras.ernet.in
1561
DOI: 10.1081=SIM-120015080
Copyright # 2002 by Marcel Dekker, Inc.
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com

1562
SINGH, NARANG, AND SRIVASTAVA
hydrazone
(4-HOAINH),
NC5H4CONHN¼C(CH3)-
C6H4OH, m ¼ 1, n ¼ 2, and L0 ¼ 4-HOAINH and 4-HOASH]
were prepared and characterized by elemental and thermal
analyses, molar conductance, magnetic susceptibility, infra-
red, electronic, NMR, ESR and X-ray powder diffraction
studies. Some of the complexes were screened against E. coli
and Aspergillus niger to explore their biological activity.
INTRODUCTION
Salicylic- and isonicotinic acid hydrazides and their hydrazones form a
variety of complexes with metal ions.[173] INH is used as isoniazid for
treatment of tuberculosis and its activity is enhanced on chelation with
copper(II).[4] The salicylhydrazine is reported to have biological activity.
Acetophenone salicyloylhydrazone (ASH), 4-hydroxyacetophenone
salicyloylhydrazone (4-HOASH), acetophenone isonicotinoylhydrazone
(AINH) and 4-hydroxy acetophenone isonicotinoylhydrazone (4-
HOAINH) (Fig. 1) possess a number of potential bonding sites which
may form complexes with interesting structural and biological properties.
In this paper we report the synthesis, characterization and biological
activity of hitherto uninvestigated 3d- bivalent metal complexes of the title
hydrazones.
EXPERIMENTAL
Materials and Methods
The chemicals used were of analytical, reagent or equivalent grade.
Acetophenone and 4-hydroxyacetophenone were obtained from Central
Figure 1. Structures of the ligands.

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1563
Figure 2. Representative structures of the complexes.
(continued)

1564
SINGH, NARANG, AND SRIVASTAVA
Figure 2. Continued.

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1565
Drug House, New Delhi, and were used without further purification.
Acetophenone and 4-hydroxyacetophenone salicyloylhydrazones were pre-
pared by refluxing salicyloylhydrazine (10 mmol, 1.52 g) in ethanol (30 mL)
with acetophenone (10 mmol, 1.20 mL) or 4-hydroxyacetophenone
(10 mmol, 1.36 g, 20 mL) in ethanol (50 mL) for 7 h, respectively. Acet-
ophenone and 4-hydroxyacetophenone isonicotinoylhydrazones were
prepared by refluxing isonicotinoylhydrazine (10 mmol, 1.36 g) and acet-
ophenone (10 mmol, 1.20 g, 20 mL) in ethanol (30 mL) or 4-
hydroxyacetophenone (10 mmol, 1.36 g, 20 mL) in ethanol (50 mL) for
778 h, respectively. The compounds which precipitated during the reaction
were filtered and washed with ethanol. They were recrystallized from hot
ethanol. The hydrazones were characterized by elemental analyses, hydra-
zine determination, infrared and NMR spectra.
Synthesis of Complexes
The AINH and ASH complexes were synthesized by adding an
aqueous ethanol (50:50, v=v) solution (25 mL) of the metal chloride
(5 mmol) to a hot ethanol (50 mL) solution of AINH (10 mmol, 2.39 g) or
ASH (10 mmol, 2.54 g), respectively. The reaction solution was heated on a
water bath for ꢀ1 h. The compounds which precipitated during heating
were filtered and washed several times with distilled water, ethanol and
finally with ether before drying over anhydrous calcium chloride in a
desiccator.
The complexes of 4-HOASH and 4-HOAINH were prepared by
mixing an aqueous ethanol (50:50, v=v) solution (25 mL) of the metal
chloride=sulfate (10 mmol) and 4-HOASH (10 mmol, 2.70 g) or 4-HOAINH
(10 mmol, 2.56 g) in the same solvent (25 mL). The reaction solution was
refluxed for ꢀ8 h with shaking at regular intervals. The compounds which
precipitated during heating were filtered and washed several times with
distilled water to remove the unreacted metal salts, if any, then with ethanol
and finally with ether before drying over anhydrous calcium chloride in a
desiccator.
Analyses and Physical Measurements
The complexes were analysed for metal content using literature
procedures[5] after decomposing them with aqua regia followed by sul-
furic acid. Sulfate and chloride were determined gravimetrically as BaSO4
or AgCl, respectively. Hydrazine was determined volumetrically by

1566
SINGH, NARANG, AND SRIVASTAVA
titrating with KBrO3 after hydrolysing the complexes in ꢀ6N HCl using
methyl orange as an indicator.[6] Carbon, hydrogen and nitrogen were
determined microanalytically on a Perkin Elmer 240 DC elemental ana-
lyser. The water content in the complexes was determined by heating
a knownꢁ amount of sample to a constant weight at 100, 130, 150
and 180 C.
Molar conductances in DMSO solution (10ꢂ3 M) were measured at
room temperature on a Systronics 304 conductivity meter. Room tem-
perature magnetic susceptibilities were determined on a Cahn Faraday
balance using CoHg(SCN)4 as standard and were corrected for dia-
magnetism.[7] Electronic spectra of the ligands and complexes were recorded
on a Cary 2390 spectrophotometer in Nujol mulls. IR spectra were recorded
on a JASCO 5300 spectrophotometer KBr or Nujol mulls. ESR spectra of
the complexes were recorded on a Varian X band E4 spectrometer. NMR
spectra were recorded on a JEOL FX 90Q spectrometer in DMSO-d6 using
TMS as an internal reference. XRD data were collected on a Seifert ID-300
diffractometer using CuKa radiation.
RESULTS AND DISCUSSION
Reactions of AINH and 4-HOAINH with metal(II) salts yielded
complexes possessing a 1:1 metal-ligand ratio. ASH and 4-HOASH reacted
with metal(II) chloride and formed the complexes having only a 1:2 metal-
ligand stoichiometry. The complexes are insoluble in common organic
solvents such as ethanol, methanol, benzene, acetone, nitrobenzene,
dichloromethane and chloroform. However, they are slightly to fairly
soluble in DMF and DMSO.
H2O-EtOH
MCl2 ꢃnH2O þ 2AINH
½MðAINHÞCl2ðH2OÞ ꢄ
!
2
heat
þ AINH þ ðn ꢂ 2ÞH2O
H2O-EtOH
MCl2 ꢃnH2O þ 4-HOAINH
CuSO4 ꢃ5H2O þ 4-HOAINH
½Mð4-HOAINHÞCl2ðH2OÞ ꢄ
!
2
heat
þ ðn ꢂ 2ÞH2O
H2O-EtOH
½Cuð4-HOAINHÞSO4-
ðH2OÞ2ꢄ þ 3H2O
!
heat

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1567

1568
SINGH, NARANG, AND SRIVASTAVA

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1569
H2O-EtOH
MCl2 ꢃnH2O þ 2ASH
½MðASHÞ Cl2ðH2OÞ ꢄ þ ðn ꢂ 2ÞH2O
!
2
2
heat
H2O-EtOH
MCl2 ꢃnH2O þ 4-HOASH
CuSO4 ꢃ5H2O þ 4-HOASH
½Mð4-HOASHÞ Cl2ꢄ þ nH2O
!
2
heat
H2O-EtOH
½Cuð4-HOASHÞSO4ðH2OÞ ꢄ
!
2
heat
þ 3H2O
½MðIIÞ ¼ Co; Ni; Cu and Cd; n ¼ 0; 2; 6ꢄ
The complexes [M(ASH)2Cl2(H2O)2] and [M(AINH)Cl2(H2O)2] melt
ꢁ
in the 1807252 C temperature range while [M(4-HOASH)2Cl2] and [M(4-
ꢁ
HOAINH)Cl2(H2O)2] decompose in the 1907251 C temperature range.
The molar conductances (4.9728.7 OM cm2 molꢂ1) in DMSO of the
ꢂ1
complexes suggest non-electrolytic behaviour. The slightly higher values of
[Ni(AINH)Cl2(H2O)2] and [Cu(ASH)2Cl2(H2O)2] complexes are due to
partial dissociation of the anion by ꢁDMSO.[8] Dehydration studies of the
hydrated complexes in the 1007180 C temperature range showed the pre-
sence of coordinated water in the complexes.
Magnetic Measurements
The magnetic moment values of the cobalt(II) and nickel(II) com-
plexes are indicative of an octahedral geometry.[9] The meff values of the
copper(II) complexes correspond to one unpaired electron and give no
definite information regarding the coordination geometry around the
metal ion.
Electronic Spectra
In the spectra of ASHꢂ1absorption bands (Table II) are observed at
31,250, 41,322 and 45,870 cm while the spectrum of AINH shows bands at
34,246, 40,322 and 48,076 cmꢂ1, respectively. The bands are observed at
29,410, 40,650 and 46,290 cmꢂ1 in the spectrum of 4-HOASH and at 33,333,
42,016 and 47,169 cmꢂ1 in that of 4-HOAINH. The first two bands may be
assigned to n ! p* and p ! p* transitions of >C¼O and >C¼N moieties
and the third absorption band may be due to the p ! p* transition of the
benzene moiety. These bands were observed at lower energies in the spectra
of the complexes indicating involvement of the carbonyl oxygen and=or
azomethine nitrogen in bonding.

1570
SINGH, NARANG, AND SRIVASTAVA

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1571
The spectra (Table II) of the cobalt(II) complexes show two absorption
4
4
4
bands. They are assigned to the T1g(F) ! A2g(F) (n2) and T1g(P) (n3)
transitions, respectively, assuming an octahedral stereochemistry for the
complexes.[10]
The [Ni(ASH)2Cl2(H2O)2] and [Ni(4-HOASH)2Cl2] complexes show
3
3
two absorption bands which are attributed to A2g(F) ! T1g(F) (n2) and
3T1g(P) (n3) transitions, respectively, while [Ni(AINH)Cl2(H2O)2] and
[Ni(4-HOAINH)Cl2(H2O)2] exhibit three absorption bands which are
3
assigned to 3A2g(F) ! T2g(F) (n1), 3T1g(F) (n2) and 3T1g(P) (n3), transitions,
respectively, on the basis of an octahedral geometry. The octahedral coor-
dination around nickel(II) is further supported by the n2=n1 ratio for AINH
(1.58) and 4-HOAINH (1.61) complexes which lies in the range reported for
the nickel (II) complexes with an octahedral geometry.[11]
The ligand field parameters such as crystal field splitting energy
(10Dq), inter-electronic repulsion parameters (B0), nephelauxetic ratio (b),
percentage covalency (b0) and ligand field stablization energy (LFSE) have
been evaluated for the cobalt(II) and nickel(II) complexes.[12] The values of
B0 and b are indicative of the reduction in inter-electronic repulsion which is
resulting due to the metal-ligand orbital overlap.
Only one broad band is observed in the spectra of the copper(II)
2
2
complexes at 10,810715,190 cmꢂ1 which may be assigned to the Eg ! T2g
(D) transition on the basis of an octahedral geometry.[13]
ESR Spectra
The spectra of [Cu(4-HOASH)SO4(H2O)2] and [Cu(4-HOAINH)-
SO4(H2O)2] are not resolved. They show peaks (Table III) which are used to
evaluate the g values. These are characteristic of interaction between copper
ions in the powder complex.
1H NMR Spectra
The spectrum of ASH shows peaks (Table IV) at d 2.52 (s), 11.36 (s)
and 7.4078.80 (m). AINH exhibits signals at d 2.52 (s), 10.06 (s) and
7.4078.43 (m). These peaks are attributed to 7CH3, NH and aromatic
protons, respectively. In the spectrum of [Cd(ASH)2Cl2(H2O)2], the 7NH
peak is observed at the same position and shows non-involvement of the
carbonyl oxygen in bonding. The spectrum of [Cd(AINH)Cl2(H2O)2] shows
signals at d 2.52 (CH3), 10.55 (7NH) and 7.4078.03 (aromatic protons).

1572
SINGH, NARANG, AND SRIVASTAVA
Table III. ESR Spectral Data of Complexes
Peak Position (G)
Complexes
g Values
[Cu(4-HOAINH)SO4(H2O)2]
[Cu(4-HOASH)SO4(H2O)2]
3400, 3485, 3560
3040, 3200, 3480
2.13, 2.07, 2.03
2.38, 2.26, 2.08
A downfield shift in the 7NH proton suggests bonding of the carbonyl
oxygen with the metal ions in these complexes.
13C NMR Spectra
The 22.49 MHz proton decoupled 13C NMR spectrum of ASH exhi-
bits signals (Table IV) at 13.92, 152.45 and 162.20 ppm and that of AINH
shows signals at 13.02, 150.03 and 152.25 ppm due to 7CH3, >C¼N
and >C¼O carbons, respectively.
The spectra of [Cd(ASH)2Cl2(H2O)2] show deshielding of the azo-
methine carbon indicating bonding through the azomethine nitrogen, while
that of [Cd(AINH)Cl2(H2O)2] exhibits signals at 13.28 (7CH3), 152.55
(>C¼N) and 152.88 (>C¼O) ppm. The downfield shifts in the carbonyl and
azomethine carbons, suggest participation of >C¼O and >C¼N moieties
in bonding.[15,16]
Infrared Spectra
The bands (Table V) appearing at 330073148, 169071640, 162071610
and 9907960 cmꢂ1 in the spectra of the hydrazones are attributed to n(NH),
Table IV. NMR Spectral Data of Ligands and Their Metal Complexes
1H NMR
13C NMR
Complexes
AINH
[Cd(AINH)Cl2(H2O)2] 10.55 2.52
ASH 11.36 2.52
[Cd(ASH)2Cl2(H2O)2] 11.36 2.52
7NH 7CH3 Aromatic Protons >C¼O >C¼N 7CH3
10.06 2.52
7.4078.43
7.4078.03
7.4078.80
7.0078.61
152.25 150.03 13.02
152.88 152.55 13.28
162.20 152.45 13.92
162.36 156.67 13.98

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1573

1574
SINGH, NARANG, AND SRIVASTAVA
Table VI. X-Ray Powder Diffraction Data of [Cu(4-HOAINH)SO4(H2O)2]
D
Irel.
1=d2 Qobs.
1=d2 Qcal.
h
k
l
8.4892
7.2613
6.8038
6.1453
5.5141
5.1920
4.8700
4.6283
4.2975
4.1114
4.0113
3.8742
3.6274
3.4697
3.3298
3.2115
2.9414
2.8962
2.8166
2.6977
2.5746
2.3545
2.3096
2.2612
2.0176
1.9510
1.8981
1.8794
1.7899
1.7340
1.6577
1.6484
1.6130
1.5745
1.5646
1.5359
1.5154
1.5047
1.4892
1.4506
1.3916
1.3856
1.3631
1.3531
1000
302
287
190
55
106
178
203
169
56
0.01388
0.01897
0.02160
0.02480
0.03289
0.03710
0.04216
0.04668
0.05415
0.05916
0.06215
0.06662
0.07600
0.08306
0.09019
0.09696
0.11558
0.11922
0.12605
0.13741
0.15086
0.18039
0.18747
0.19558
0.24566
0.26272
0.27756
0.28311
0.31214
0.33258
0.36391
0.36802
0.38435
0.40338
0.50850
0.42391
0.43546
0.44167
0.45091
0.47523
0.51638
0.52086
0.53820
0.54619
0.01355
0.01896
0.02165
0.02727
0.03295
0.03721
0.04196
0.04717
0.05419
0.05890
0.06226
0.06672
0.07630
0.08299
0.08944
0.09685
0.11553
0.11933
0.12649
0.13746
0.15081
0.18066
0.18717
0.19569
0.24567
0.26266
0.27742
0.28129
0.31238
0.33265
0.36420
0.36829
0.38439
0.40317
0.40852
0.42373
0.43546
0.44170
0.45098
0.47527
0.51637
0.52103
0.52820
0.54614
1
0
2
0
0
0
1
2
ꢂ2
ꢂ2
2
1
2
ꢂ1
1
2
3
1
2
3
2
0
ꢂ3
ꢂ1
ꢂ2
0
0
2
2
1
ꢂ1
62
0
ꢂ4
379
116
515
70
99
58
93
49
62
54
45
62
55
58
66
59
52
56
66
42
49
53
47
76
49
33
45
37
45
77
55
67
59
ꢂ4
2
1
4
2
2
4
ꢂ1
2
1
1
2
0
5
5
2
0
3
6
5
ꢂ2
3
4
2
2
0
ꢂ4
ꢂ5
3
2
3
ꢂ3
0
ꢂ6
3
1
ꢂ4
ꢂ2
ꢂ1
2
ꢂ6
5
4
6
6
5
5
ꢂ6
7
5
1
1
ꢂ7
1
4
1
7
9
2
6
8
ꢂ3
ꢂ7
5
5
1
ꢂ8
6
2
8
6
2
6
3
4
9
4
ꢂ1
ꢂ8
5
4
1
1
8
ꢂ10
6
6
ꢂ5
ꢂ11
4
8
ꢂ12
3
ꢂ8
1
1
5
ꢂ11
4

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1575
Table VII. X-Ray Powder Diffraction Data of [Cd(AINH)Cl2(H2O)2]
D
Irel.
1=d2 Qobs.
1=d2 Qcal.
h
k
l
8.3426
7.8421
7.5165
6.7880
6.4861
6.3277
5.8325
5.5268
5.3382
5.2057
4.8796
4.6597
4.6117
4.4782
4.1804
3.8621
3.5862
3.4265
3.3267
3.2012
2.8555
2.8113
2.6379
2.6082
2.5346
2.4452
2.3962
2.3543
2.2532
2.2097
2.1823
2.1117
2.0366
1.9962
1.9559
1.9104
1.8936
1.8717
1.7200
681
214
911
107
169
232
106
1000
153
152
201
166
166
207
135
127
229
97
0.01437
0.01626
0.01770
0.02170
0.02377
0.02498
0.02940
0.03274
0.03509
0.03690
0.04200
0.04606
0.04702
0.04986
0.05722
0.06704
0.07776
0.08517
0.09036
0.09758
0.12264
0.12653
0.14371
0.14700
0.15566
0.16725
0.17416
0.18042
0.19697
0.20480
0.20998
0.22425
0.24110
0.25095
0.26140
0.27400
0.27888
0.28545
0.33802
0.01415
0.01602
0.01752
0.02177
0.02370
0.02488
0.02954
0.03258
0.03503
0.03694
0.04191
0.04585
0.04893
0.04978
0.05721
0.06688
0.07786
0.08531
0.09010
0.09757
0.12261
0.12651
0.14374
0.14701
0.15561
0.16724
0.17418
0.18042
0.19688
0.20478
0.20985
0.22431
0.24110
0.25070
0.26150
0.27401
0.27885
0.28547
0.33795
1
2
2
1
1
ꢂ2
1
1
ꢂ2
ꢂ3
1
1
2
2
ꢂ1
2
ꢂ2
2
ꢂ1
ꢂ2
3
2
4
2
3
2
2
3
ꢂ2
3
ꢂ1
ꢂ2
2
3
1
ꢂ4
2
3
1
3
4
5
5
0
2
3
4
1
6
1
6
6
1
4
2
ꢂ3
3
ꢂ3
3
3
0
3
6
3
6
ꢂ2
343
287
73
135
96
1
ꢂ6
ꢂ4
ꢂ6
8
0
3
5
6
1
1
3
ꢂ1
139
137
188
140
139
157
125
121
103
132
136
147
99
5
7
ꢂ5
ꢂ4
ꢂ7
4
7
9
6
8
1
5
1
2
8
ꢂ3
9
2
ꢂ8
10
6
7
8
2
3
1
ꢂ3
ꢂ10
7
ꢂ2
133
121
92
4
5
4
8
ꢂ11
2
ꢂ9
2
(continued)

1576
SINGH, NARANG, AND SRIVASTAVA
Table VII. Continued
1=d2 Qobs. 1=d2 Qcal.
D
Irel.
h
k
l
1.6970
1.6798
1.6678
1.6467
1.6350
1.6148
1.5590
1.5500
1.5403
1.5275
1.5043
1.4870
1.4785
1.4697
1.4615
1.4458
1.4344
1.4261
1.4071
1.3995
1.3812
1.3582
1.3478
133
107
123
93
97
80
0.34725
0.35439
0.35951
0.36878
0.37408
0.38350
0.41144
0.41623
0.42149
0.42859
0.44191
0.45225
0.45746
0.46296
0.46817
0.47839
0.48603
0.49170
0.50507
0.51057
0.52419
0.54209
0.55049
0.34724
0.35442
0.35953
0.36889
0.37408
0.38352
0.41144
0.41623
0.42147
0.42860
0.44191
0.45230
0.45748
0.46293
0.46810
0.47833
0.48603
0.49174
0.50502
0.51056
0.52419
0.54207
0.55038
ꢂ10
4
0
9
1
11
10
11
9
10
ꢂ5
ꢂ8
2
3
ꢂ11
6
6
1
1
9
2
ꢂ9
1
160
173
245
189
236
119
120
158
153
131
164
177
170
161
107
97
ꢂ11
13
1
3
11
13
4
ꢂ5
9
8
12
9
5
9
2
ꢂ3
ꢂ9
ꢂ4
11
10
ꢂ10
4
3
7
12
3
10
14
ꢂ10
ꢂ7
5
11
ꢂ7
9
8
4
5
9
11
4
13
ꢂ9
7
4
5
120
14
n(C¼O), n(C¼N) and n(N7N) modes, respectively. A band at 3260, 3325
and 3320 cmꢂ1 is assigned to n(OH) (phenolic) in the spectra of ASH, 4-
HOASH and 4-HOAINH, respectively. The appearance of n(OH) at lower
frequency may be due to inter- and=or intramolecular hydrogen bonding.
In the spectra of [M(ASH)2Cl2(H2O)2] and [M(4-HO-
AINH)Cl2(H2O)2], the absorption band due to n(C¼O) is shifted towards
higher frequency or remained unaltered indicating non-participation of the
carbonyl oxygen in bonding. In the spectra of [M(4-HOASH)2Cl2],
[M(AINH)Cl2(H2O)2], [Cu(4-HOASH)SO4(H2O)2] and [Cu(4-HOAINH)-
SO4(H2O)2] complexes, n(C¼O) is observed at lower frequency
(166271635 cmꢂ1) indicating coordination of the carbonyl oxygen to the
metal ion.[17]
In all of the complexes n(C¼N) is observed in the 161571595 cmꢂ1
region indicating that the azomethine nitrogen is involved in bonding.[18]

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1577
Table VIII. X-Ray Powder Diffraction Data of [Cd(4-HOAINH)Cl2(H2O)2]
D
Irel.
1=d2 Qobs.
1=d2 Qcal.
h
k
l
8.1493
6.1931
5.8722
5.5007
5.1271
3.3788
2.5687
2.4033
1.8298
1.6798
1.5986
1.5811
1.5708
1.5656
1.5268
1.4753
863
1000
452
446
394
343
271
308
401
327
360
264
313
305
467
424
0.01506
0.02607
0.02900
0.03305
0.03804
0.08759
0.15156
0.17313
0.29867
0.03544
0.39131
0.40002
0.40528
0.40798
0.42898
0.45945
0.01508
0.02621
0.02892
0.03306
0.03789
0.08760
0.15158
0.17303
0.29869
0.35427
0.39133
0.40004
0.40523
0.40808
0.42895
0.45941
2
ꢂ1
2
2
1
0
0
0
2
6
7
4
9
0
ꢂ7
ꢂ1
5
0
1
0
0
0
ꢂ1
0
2
3
7
6
6
2
0
9
ꢂ2
0
ꢂ1
ꢂ3
0
1
6
7
1
6
ꢂ9
0
7
2
9
ꢂ10
The n(N7N) band shifted to higher frequency (10157980 cmꢂ1) in the
spectra of the complexes compared to the free hydrazones. This further
supports bonding through the azomethine nitrogen.[19] The band due to
n(OH) shifted to higher frequency or remained unaltered indicating non-
involvement of the phenolic oxygen in bonding.
The bands observed at 680 cmꢂ1 due to in-plane deformation and at
415 cmꢂ1 due to out-of-plane deformation modes in the spectrum of 4-
HOAINH shifted towards higher frequencies in the spectra of the complexes
except in that of [Cu(4-HOAINH)SO4(H2O)2]. This suggests involvement of
the pyridine nitrogen in bonding. In the spectrum of AINH these bands are
observed at 685 and 415 cmꢂ1 which remain unaltered in the spectra of the
complexes and suggest non-participation of the pyridine nitrogen in
bonding.
In the spectra of [Cu(4-HOASH)SO4(H2O)2], and [Cu(4-HOAINH)-
SO4(H2O)2] three new bands appear at 9607985, 104071060 and
121071250 cmꢂ1 and indicate chelate bonding of SO24ꢂ
.
A broad band at 355573405 cmꢂ1 is assigned to n(OH) of water in the
hydrated complexes. The coordinated nature of water is shown by the
presence of bands in the 8807860 and 7807770 cmꢂ1 regions due to rr(H2O)
and rw(H2O), respectively.

1578
SINGH, NARANG, AND SRIVASTAVA
X-Ray Powder Diffraction Studies
The X-ray powder diffraction patterns of the complexes
[Cd(AINH)Cl2(H2O)2], [Cu(4-HOAINH)SO4(H2O)2] and [Cd(4-HOAINH)
Cl2(H2O)2] are indicative of their crystalline nature. The diffraction patterns
have been successfully indexed by Ito’s method.[21] The shape of the unit
lattice and parameters are given in Table IX.
Biological Activity
Acetophenone and 4-hydroxyacetophenone salicyloylhydrazones and
their copper(II) and zinc(II) complexes were screened against E. coli and
Aspergillus niger at the three concentrations 500, 1000 and 1500 mg=mL.
Table IX. The Shape of Unit Lattice and Parameters
Complex
Crystal Lattice
V (A3)
[Cd(AINH)Cl2(H2O)2]
Rhombohedral
a 21.34 A a 89ꢁ
9318.3970
b 21.31 A b 93ꢁ
c 20.93 A g 101ꢁ
a 16.45 A a 84ꢁ
b 14.86 A b 115ꢁ
c 16.15 A g 102ꢁ
a 53.90 A a 51ꢁ
b 16.44 A b 161ꢁ
c 35.52 A g 133ꢁ
[Cu(4-HOAINH)SO4(H2O)2]
[Cd(4-HOAINH)Cl2(H2O)2]
triclinic
3471.1381
7050.7761
triclinic
Table X. Antifungal Activity of ASH, 4-HOASH, and Their Metal Complexes
% Germination
Complexes
500 mg=mL
1000 mg=mL
1500 mg=mL
ASH
4-HOASH
[Cu(ASH)2Cl2(H2O)2]
[Zn(ASH)2Cl2(H2O)2]ꢃH2O
[Cu(4-HOASH)2Cl2]
[Zn(4-HOASH)2Cl2]ꢃH2O
þþþ
þþ
þþ
þ
þþ
þþ
þþ
þ
þþ
þþ
þþ
þ
þþþ
þþ
þþ
þþ
þþ
þþ
þþþþ ¼ 100% germination, þþþ ¼ 75% germination, þþ ¼ 50% germination,
þ ¼ 25% germination.

COMPLEXES OF Co(II), Ni(II), Cu(II), AND Cd(II)
1579
Table XI. Antibacterial Activity of ASH, 4-HOASH, and Their Metal Complexes
Zone of Inhibition (cm)
Complexes
500 mg=mL
1000 mg=mL
1500 mg=mL
ASH
4-HOASH
[Cu(ASH)2Cl2(H2O)2]
[Zn(ASH)2Cl2(H2O)2]ꢃH2O
[Cu(4-HOASH)2Cl2]
[Zn(4-HOASH)2Cl2]ꢃH2O
0.52
0.66
0.89
0.77
0.61
0.69
0.58
0.68
0.91
0.69
0.60
0.66
0.69
0.71
0.98
0.70
0.79
0.78
From Tables X and XI it may be inferred that the metal complexes of 4-
HOASH and ASH have greater activity than the parent hydrazones which
may be due to the chelation effect.[22]
The ligand containing the phenolic moiety is found more effective as
compared to other ligands reported earlier.[23] The ligand 4-HOASH con-
taining two phenolic groups shows poor germination and better inhibition
against E. coli than ASH which is due to the presence of only one phenolic
group. The complexes show better inhibitory effect compared to the parent
hydrazones. This may be explained as follows. In the complexes the ligands
have some uncoordinated donor atoms which enhance the activity of the
complexes by bonding with trace element present in biosystem. Thus, the
microquanitity of trace elements presents in microorganisms may combine
with the uncoordinated site and may inhibit the growth of fungi and
bacteria.
ACKNOWLEDGMENT
The authors thank the Head, Department of Chemistry, Banaras
Hindu University, Varanasi, India, for laboratory facilities.
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1580
SINGH, NARANG, AND SRIVASTAVA
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Received October 4, 2001
Accepted June 15, 2002
Referee I: D. Rabinovich
Referee II: R. U. Kirss