Cobalt, nickel, and copper coordination compounds with 3-phenylpropenal benzoylhydrazone

Article abstract of DOI:10.1134/S1070363206100161

3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX ₂ ? nH₂O [M = Co, Ni, Cu; X = Cl, NO₃, HL = C₆H₅CH=CHCH=NNHC(O)C₆H₅; n = 0, 2] and ML₂ ? nH₂O (M = Co, Ni, Cu; n = 1-3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C₅H₅N, 2-CH₃C₅H ₄N, 3-CH₃C₅H₄N, 4-CH ₃C₅H₄N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (145-155°C) or deamination (145-185°C), and complete thermal decomposition (330-490°C). Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070363206100161

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 10, pp. 1595 1598.
Pleiades Publishing, Inc., 2006.
Original Russian Text N.M. Samus’, A.P. Gulya, V.I. Tsapkov, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 10, pp. 1664 1668.
Cobalt, Nickel, and Copper Coordination Compounds
with 3-Phenylpropenal Benzoylhydrazone
N. M. Samus’, A. P. Gulya, and V. I. Tsapkov
Moldovian State University, ul. Mateevicha 60, Kishinev, 2009 Moldova
Received June 29, 2006
Abstract 3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides,
nitrates, and acetates to give coordination compounds MX2 2HL nH2O [M = Co, Ni, Cu; X = Cl, NO3, HL =
C6H5CH=CHCH=NNHC(O)C6H5; n = 0, 2] and ML2 nH2O (M = Co, Ni, Cu; n = 1 3). Complexes MALCl
(M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C5H5N, 2-CH3C5H4N,
3-CH3C5H4N, 4-CH3C5H4N). All the compounds have a monomeric structure. Azomethine (HL) in them
behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70
90 C), deaquation (145 155 C) or deamination (145 185 C), and complete thermal decomposition (330
490 C).
DOI: 10.1134/S1070363206100161
Benzoylhydrazones of aromatic aldehydes and
ketones contain a broad range of donor atoms in their
composition and form with transition metal ions co-
ordination compounds with various composition,
structure, and properties [1 5]. Many of these sub-
stances are biologically active [6 8], which allows
them to be used as a basis for creation of selective
microbiological nutrient media, as well as potential
disifectants and antiseptics. In this connection syn-
thesis and study of new coordination compounds of
biometals with benzoylhydrazones are of both scien-
tific and practical interest.
(VIII), 2 (VI), 3 (VII)]. The above reactions in the
presence of sodium acetate, pyridine, or 2-, 3-, or
4-picoline (pH 7.0 7.5) result in the isolation of
complexes MALCl nH2O (IX XV) [M = Co (IX), Ni
(X), Cu (XI XV); A = H2O (XI), C5H5N (IX, X,
XII), 2-CH3C5H4N (XIII), 3-CH3C5H4N (XIV),
4-CH3C5H4N (XV); n = 0 (IX, X, XII XV), 1 (XI)].
Complexes I XV are insoluble in diethyl ether,
sparingly soluble in water, better soluble in alcohols,
and readily soluble in DMF, DMSO, and acetonitrile.
Their yields and certain physicochemical properties
are given in Table 1.
The aim of the present work was to find optimal
conditions for synthesis of cobalt, nickel, and copper
complexes with 3-phenylpropenal benzoylhydrazone
HL, to determine their composition and structure, and
to study their physicochemical properties.
The molecular conductivities of the synthesized
complexes in DMF show that compounds I, III, and
V XV are nonelectrolytes, and compounds II and IV,
ternary electrolytes. Magnetochemical study showed
that all the cobalt and nickel compounds are para-
magnetic, and, judging from the effective magnetic
moments, the central atoms in adducts I IV have a
pseudo-octahedral structure, and in complexes VI, VII,
IX, and X, a tetrahedral structure. Similar structures
were observed earlier [9] in nickel complexes with
3-phenylpropenal azomethines and were confirmed
by X-ray diffraction analysis. The magnetochemical
characteristics of copper complexes V, VIII, and XI
XV correspond to the spin value for one unpaired
electron and point to their monomeric structure.
N NH
O
HL
It was shown that the reactions of hot (50 55 C)
ethanol solutions of cobalt, nickel, and copper chlo-
rides, nitrates, and acetates with hydrazone (HL) in a
1:2 molar ratio yield compounds I VIII as fine crys-
tals. On the basis of the elemental analysis (Table 1)
we proposed the compositions MX2 2HL nH2O [M =
Co (I, II), Ni (III, IV), Cu (V); X = Cl (I, III, V),
NO3 (II, IV); n = 0 (I, III, V), 2 (II, IV)] and ML2
nH2O [M = Co (VI), Ni (VII), Cu (VIII); n = 1
Thermal analysis of compounds I XV (Table 2)
showed their thermolysis involves the stages of de-
hydration (60 90 C), deaquation (160 190 C) or
deamination (170 210 C) up to complete thermo-
1595

1596
SAMUS’ et al.
Table 1. Physicochemical characteristics of cobalt, nickel, and copper coordination compounds I XV with 3-phenylpro-
penal benzoylhydrazone
Found, %
Mb
Calculated, %
Mb
a
a
Comp.
no.
Yield,
%
,
,
eff
Formula
1
BM
1 cm2 mol
Cl
N
Cl
N
I
II
69
74
75
66
87
56
57
65
74
64
84
59
91
90
93
4.98
5.06
3.06
2.98
1.78
4.12
4.55
1.83
4.02
4.64
1.75
1.89
1.80
1.94
1.79
3
136
5
144
2
11.07
11.16
11.29
9.16
7.95
9.49
8.05
9.90
8.60 C32H28Cl2CoN4O2
11.51 C32H32CoN6O10
8.99 C32H28Cl2N4NiO2
11.46 C32H32N6NiO10
8.59 C32H28Cl2CuN4O2
9.28 C32H30CoN4O4
8.98 C32H32N4NiO5
9.39 C32H28CuN4O3
10.05 C21H18ClCoN3O
9.80 C21H18ClN3NiO
6.99 C16H17ClCuN2O3
9.65 C21H18ClCuN3O
9.25 C22H20ClCuN3O
9.64 C22H20ClCuN3O
9.30 C22H20ClCuN3O
11.30
11.30
9.37
8.89
8.21 11.68
9.37 8.89
8.21 11.68
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
11.18 10.08
9.95
8.82
9.44
9.17
9.66
9.94
9.94
7.28
9.82
9.51
9.51
9.51
2
4
3
6
3
2
3
3
10.11
9.37
9.66
11.03
10.77
14.16
13.71
16.45
15.7
14.70
14.79
14.90
8.26
8.19
8.98
8.03
7.81
8.16
7.93
8.40 13.96
8.40 13.96
9.23 16.64
8.30 14.97
8.04 14.97
8.04 14.97
8.04 14.97
4
3
a
b
At 293 K.
M is metal.
Table 2. Thermal analysis of cobalt, nickel, and copper coordination compounds I XV with 3-phenylpropenal benzoyl-
hydrazone
Weight loss
Kinetic parameters
Number of
the endo effects of maximum
in DTA curve effect,
Temperature
Temperature of
complete decom-
Comp.
no.
C
position,
C
found,
%
calculated, corresponds to
Ea,
logZ
1
%
detachment of kJmol
I
II
460
410
440
400
400
360
360
330
490
480
440
1
1
155
145
5.3
4.9
5.0
5.0
2H2O
2H2O
55.2
49.7
6.6
5.8
III
IV
V
VI
VII
VIII
IX
X
1
1
1
1
1
1
2
1
1
1
1
85
75
70
6.0
9.0
3.4
18.5
18.6
4.5
6.1
8.8
3.1
18.7
18.7
4.7
2H2O
3H2O
H2O
C5H5N
C5H5N
H2O
38.2
35.9
32.7
89.2
75.4
34.1
48.6
68.9
67.2
75.1
72.5
4.6
4.5
4.4
9.4
8.6
4.5
5.7
7.8
7.7
8.5
8.4
185
170
90
155
160
145
175
160
XI
5.0
4.7
H2O
XII
18.8
21.5
21.3
21.2
18.5
21.1
21.1
21.1
C5H5N
C6H7N
C6H7N
C6H7N
460
445
475
465
XIII
XIV
XV
oxidative decomposition (360 530 C). The complete
decomposition temperature (t) depends on the central
atom and changes in the following order at the same
inner-sphere composition of the coordination com-
pound: t(Co) > t(Ni) > t(Cu). The decomposition
temperature is also affected by the nature of inner-
sphere ligands. It increases when nitrate ion is re-
placed by chloride ion and the inner-sphere water is
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COBALT, NICKEL, AND COPPER COORDINATION COMPOUNDS
1597
replaced by amines, and for amine complexes IX, X,
and XII XV with the same central atom the following
order is observed: t(3-CH3C5H4N t(4-CH3C5H4N)
t(C5H5N) > t(2-CH3C5H4N). Using the Horowitz
Metzger method [10] with the Topor additions [11],
we estimated kinetic parameters for deaquation and
deamination of the complexes under study. The result-
ing data (Table 2) show that the activation energies
(Ea) and preexponential factors (Z) are close to those
for similar reactions described in the literature [12 14].
We found that the nature of the central atom and
inner-sphere ligands affect Ea and log Z of the pro-
cesses under study, and for complexes with the same
composition they vary as follows: Zn > Co > Ni,
3-H3C5H4N > 4-H3C5H4N > C5H5N > 2-H3C5H4N.
The revealed order parallels the above sequence of
complete decomposition temperatures and the order of
amine basicities. The only outlier in the latter order is
2-H3C5H4N, probably, by steric reasons.
respectively. The fact that the oxygen atom of the
ligand in the deprotonated thiocarbamide form co-
ordinates with the central atoms is confirmed by the
1
disappearance of the (C=O) band at 1630 cm and
1
the (NH) bands at 3230 3200 and 3170 3150 cm
from the IR spectra of complexes VI XV and also by
the appearance of a new absorption band at 600
1
580 cm , assignable to (C=O) [15], and by the split-
1
ting the (C=N) band at 1595 1590 cm into two
components. Further evidence for the above coordina-
tion of hydrazone HL comes from the appearance of a
number of new absorption bands in the region of 550
1
1
400 cm [ (M N) at 530 510 and 425 405 cm and
1
(M O) at 490 470 cm ] in the IR spectra of all the
complexes. Participation of the other functional
groups of the Schiff base in the coordination with
metal ions is excluded, since their characteristic ab-
sorption bands appear in the same regions as in the
spectrum of the starting hydrazone. The presence of
coordinated molecules of water and amines in the
complexes is confirmed by the presence of the cor-
responding absorption bands in their IR spectra
[ (H2O) 3595 3580, (H2O) 1580 1575, and (H2O)
To determine the mode of ligand coordination with
central ions, we compared the IR spectra of complexes
I XV, starting hydrazone HL, and coordination com-
pounds of transition metals with similar Schiff bases
described in the literature [1 9]. Azomethine HL in
the complexes under study behaves as a bidentate
electroneutral or monodeprotonated N,O-ligand at-
tached to the complex-forming ion through the azo-
methine nitrogen atom and the oxygen atom of the
carbamide fragment to form a five-membered metal
cycle. Evidence for this conclusion is provided by a
1
920 915 cm in the case of aqua complexes II, IV,
and XI and (CC) + (CN) + (CCH) 1640 1635,
1530 1525, (CN) 1310 1305, (CCN) 1230 1225,
(CCN) 1230 1225, (CCH) + (CC) + (CNC)
1060 1055, 1030 1025, (CCC) + (CNC) 730 725,
1
and (CH) 830 825 cm in the case of amine com-
plexes IX, X, and XII XV].
1
30 25 cm low-frequency shift of the (C=N) and
The obtained physicochemical data allow us to
present the distribution of chemical bonds in com-
plexes I XV by schemes A D.
(C=O) absorption bands compared to analogous ab-
sorption bands in the spectrum of the starting hydra-
zone, where they are observed at 1600 and 1630 cm ,
1
R
R
H2O
Ph
Ph
NH
O N
NH
O N
Cl M Cl
Cl M Cl
(NO3)2
N
O
HN
R
N
O
OH2
B
HN
R
Ph
Ph
A
M = Co, Ni, Cu.
R
M = Co, Ni.
Ph
Ph
X
O
O N N
M
M
nH2O
nH2O
N N Cl
N N
O
Ph
R
R
C
D
M = Co, Ni, Cu;
M = Co, Ni, Cu; n = 0, 1;
X = H2O, C5H5N, 2-, 3-, 4-CH3C5H4N.
R = C6H5CH=CH, Ph = C6H5.
n = 1 3.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

1598
SAMUS’ et al.
2. Garnovskii, A.D., Koord. Khim., 1993, vol. 19, no. 5,
EXPERIMENTAL
p. 394.
The resistance of solutions of complexes I XV in
DMF (20 C, c 0.001 M) was measured by a Þ-38
slide-wire bridge. The IR spectra of Nujol suspensions
of samples preliminarily dried at 105 C to constant
weight were recorded on a Specord M-80 spectropho-
tometer. The effective magnetic moments of com-
pounds I XV were determined by the Gouy method.
The molar magnetic susceptibility corrected for dia-
magnetism was calculated on the basis of theoretical
magnetic susceptibilities of organic compounds. The
themoanalytical curves of complexes I XV were
taken on a Paulik Paulik Erdey derivatograph in the
range 20 1000 C in air (standard Al2O3, corundum
crucible).
3. Kogan, V.A. and Lukov, V.V., Koord. Khim., 1993,
vol. 19, no. 6, p. 476.
4. Samus’, N.M., Tsapkov, V.I., and Kravchenko, V.N.,
Zh. Obshch. Khim., 1997, vol. 67, no. 12, p. 2044.
5. Samus’, N.M., Tsapkov, V.I. and Kerner, A.V., Zh.
Obshch. Khim., 2003, vol. 73, no. 10, p. 1704.
6. Samus’, N.M., Prisakar’, V.I., Tsapkov, V.I., Bura-
cheva, S.A., and Gulya, A.P., Khim.-Farm. Zh., 2004,
vol. 38. 7, p. 27.
7. Samus’, N.M., Tsapkov, V.I., Burdenko, T.A., Martin
Mazvimba Tongai, Tarkodzhiel’ Mianperem, and
Vakarash, N.A., Khim.-Farm. Zh., 1993, vol. 27, no. 7,
p. 39.
The starting 3-phenylpropenal benzoylhydrazone
was prepared by the published procedure [16.]
8. Samus’, N.M., Tsapkov, V.I., Burdenko, T.A., Bura-
cheva, S.A., Martin Mazvimba Tongai, and Shandzhai
Candra Sokhan, Khim.-Farm. Zh., 1994, vol. 28. 7,
p. 41.
Dichlorobis[N-(3-phenylprop-2-enylidene)-N -
benzoylhydrazine)cobalt. To a hot (50 55 C) solu-
tion of 10 mmol of cobalt dichloride hexahydrate in
25 ml of ethanol, 25 ml of a solution of 20 mmol of
3-phenylpropenal benzoylhydrazone in ethanol. The
reaction mixture was heated for 30 40 min with
continuous stirring. A dark brown substance was
precipitated from it on cooling and was filtered off on
a glass filter, washed with small amounts of alcohol
and ether, and dried in air to constant weight.
9. Chumakov, Yu.M., Samus’, N.M., Bochelli, G., and
Suponitskii, K.Yu., Koord. Khim., 2006, vol. 32,
no. 1, p. 16.
10. Horowitz, H.H. and Metzger G.A., Anal. Chem., 1963,
vol. 35, p. 1464.
11. Topor, N.D., Vestn. Mosk. Gos. Univ., Ser. Geol.,
1967, no. 1, p. 84.
12. Kukushkin, Yu.N., Budanova, V.F., and Sedova, G.N.,
Termicheskie prevrashcheniya koordinatsionnykh
soedinenii v tverdoi faze (Thermal Transformations
of Coordination Compounds in Solid Phase), Lenin-
grad: Leningr. Gos. Univ., 1981.
Complexes II VIII were synthesized in a similar
way starting from benzoylhydrazone HL and hydrates
of cobalt, nickel, or copper chlorides, nitrates, or
acetates. Complexes IX, X, and XII XV were ob-
tained by the above-described procedure by the reac-
tions of the salts and azomethine HL in a 1:1 molar
ratio in the presence of pyridine or 2-, 3-, or 4-pi-
coline (pH 8). Compound XI was synthesized si-
milarly, using ethanolic sodium acetate (pH 7.5) as
proton acceptor.
13. Kukushkin, Yu.N., Khodzhaev, O.F., Budanova, V.F.,
and Parpiev, N.A., Termoliz koordinatsionnykh soe-
dinenii (Thermolysis of Coordination Compounds),
Tashkent: Fan, 1986.
14. Logvinenko, V.A., Termicheskii analiz koordinatsion-
nykh soedinenii i klatratov (Thermal Analysis of
Coordination Compounds and Clathrates), Novo-
sibirsk: Nauka, 1982.
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