Synthesis and characterization of new metal(II) complexes with formates and some nitrogen donor ligands

Article abstract of DOI:10.1007/s10973-006-7980-9

New mixed-ligands complexes with empirical formulae: M(2,4'-bpy) ₂L₂?H₂O (M(II)Zn, Cd), Zn(2-bpy) ₃L₂?4H₂O, Cd(2-bpy)₂L ₂?3H₂O, M(phen)L₂?2H

Full text of DOI:10.1007/s10973-006-7980-9

Journal of Thermal Analysis and Calorimetry, Vol. 90 (2007) 2, 557–564
SYNTHESIS AND CHARACTERIZATION OF NEW METAL(II)
COMPLEXES WITH FORMATES AND SOME NITROGEN DONOR
LIGANDS
*
D. Czakis-Sulikowska , A. Czylkowska, J. RadwaÕska-Doczekalska, R. Grodzki and
E. Wojciechowska
Institute of General and Ecological Chemistry, Technical University of ˜ódü, Poland
New mixed-ligands complexes with empirical formulae: M(2,4’-bpy)
2 2 2 3 2 2
L ·H O (M(II)=Zn, Cd), Zn(2-bpy) L ·4H O,
Cd(2-bpy) ·3H O, M(phen)L ·2H O (where M(II)=Mn, Ni, Zn, Cd; 2,4’-bpy=2,4’-bipyridine, 2-bpy=2,2’-bipyridine,
2
2
L
2
2
2
–
phen=1,10-phenanthroline, L=HCOO ) were prepared in pure solid state. They were characterized by chemical, thermal and X-ray
–
powder diffraction analysis, IR spectroscopy, molar conductance in MeOH, DMF and DMSO. Examinations of OCO absorption
bands suggest versatile coordination behaviour of obtained complexes. The 2,4’-bpy acts as monodentate ligand; 2-bpy and phen as
chelating ligands. Thermal studies were performed in static air atmosphere. When the temperature raised the dehydration processes
3 4
started. The final decomposition products, namely MO (Ni, Zn, Cd) and Mn O , were identified by X-ray diffraction.
Keywords: bipyridine isomers, IR spectra, mixed-ligands complexes, thermal decomposition, 1,10-phenanthroline, X-ray diffraction
Introduction
mal decomposition of these complexes in static air at-
mosphere. The single-crystal X-ray diffraction
Considerable attention has been devoted in recent
years to the study of mixed-ligands complexes of
metal(II) containing nitrogen donor ligands (among
others bipyridine isomers, 1,10-phenanthroline) with
biologically active carboxylates [1–7]. They are inter-
est both chemical and biological point of view. The
research of these types of complexes are motivated by
their potential applications (i.e. separation materials,
catalysis precursors, potential models of the catalyse
enzymes [4, 8–13]) and their interesting structures
method
of
copper(II)
compound
with
1,10-phenanthroline and formates exhibited the
dimeric structure with formate bridges [23].
Continuing our interest on mixed-ligands com-
plexes, we reported the synthesis of new metal(II)
complexes of bipyridine-formato (bipyridine=2-bpy
or 2,4’-bpy; M(II)=Zn, Cd) and 1,10-phenanthroline-
formato (M(II)=Mn, Ni, Zn, Cd). They have been
characterized by elemental analysis, IR spectroscopy,
molar conductivity, X-ray powder diffraction mea-
surements. Additionally, for nickel(II) complex elec-
tronic spectrum and effective magnetic moment (in
room temperature) was examined. Also the results of
thermal decomposition of obtained compounds are
described below.
[
14–16]. Very little is known on mixed-ligands com-
pounds with bipyridine isomers or 1,10-phenanthro-
line and formates (L). The complexes Cu(2-bpy)
HCOO ·H O and[Cu(2-bpy) (HCOO)]ClO were
2
(
2
2
2
4
prepared by Hathaway et al. [17] and
Cu(2-bpy) (HCOO)]BF ·0.5H O was studied by
Fitzgerald et al. [18]. The mixed-ligands complexes
[
2
4
2
of Mn(II), Co(II), Ni(II) and Cu(II) with
4
pared as five hydrates or anhydrous forms [19, 20].
Their structural and magnetic properties were studied.
However, thermal behaviour data of these complexes
were not published. We have recently reported of
Experimental
,4’-bipyridine (4-bpy) and formates have been pre-
Materials
2
,4’-Bipyridine (m.p.=61°C), 2,2-bipyridine (m.p.=
72°C), dimethylsulfoxide (DMSO), formic acid
were obtained from Aldrich; 1,10-phenanthro-
line·H O from POCh Gliwice, methanol (MeOH)
=
4
(
,4’-bipyridine-formato complexes of M(II) ions
M(II)=Mn, Co, Ni, Cu, Zn, Cd) and 2,2’-bipyridine
2
anhydroscan and dimethylformamide (DMF) from
Lab-Scan and Chempur, respectively; hydroxylamine
or 2,4’-bipyridine-formato complexes of Mn(II),
Co(II), Ni(II) and Cu(II) [21, 22]. In these papers
were examined physico-chemical properties and ther-
(
50% water solution) from Fluka; other chemicals
*
Author for correspondence: dczakis@p.lodz.pl
1
388–6150/$20.00
Akadémiai Kiadó, Budapest, Hungary
Springer, Dordrecht, The Netherlands
©
2007 Akadémiai Kiadó, Budapest

CZAKIS-SULIKOWSKA et al.
were p.a. products of POCh-Gliwice. Water solutions
of metal(II) formates were prepared by adding
2
carbonates in ca. stoichiometric quantities.
plexes were identified by the X-ray diffraction pat-
terns using a D-5000 diffractometer with a nickel- fil-
tered CuK radiation. The curves were recorded in the
–
mol L formic acid to freshly precipitated metal(II)
1
a
range of 2q angles 2–80°.
Complex synthesis
Results and discussion
The mixed-ligand complexes with 2,4’-bipyridine or
2
,2’-bipyridine and formates were prepared by meth-
The new fine-crystalline complexes with the empiri-
ods described earlier [22]. 1,10-Phenanthroline-
formato compounds were synthesized by reaction of
freshly obtained solutions of appropriate metal(II)
formates with solutions of 1,10-phenanthroline. A so-
lution 5 mmol of phen in 15.6 mL of 96% v/v ethanol
was added to solution of metal(II) formates (5 mmol
in 14.4 mL water). In case of nickel(II) complex,
cal
Cd(2,4’-bpy) L ·H O (II), Zn(2-bpy) L ·4H O (III),
formulae
Zn(2,4’-bpy) L ·H O
(I),
2
2
2
2
2
2
3
2
2
Cd(2-bpy) L ·3H O (IV), Mn(phen)L ·2H O (V),
2
2
2
2
2
Ni(phen)L ·2H O (VI), Zn(phen)L ·2H O (VII),
2
2
2
2
Cd(phen)L ·H O (VIII) were isolated. All the com-
2
2
pounds are stable at room temperature (expect com-
plex of Mn(II)). The X-ray diffraction patterns of
6
mmol of phen dissolved in 27.1 mL of 96% v/v etha-
nol was mixed with 3 mmol of nickel(II) formate in
2 mL of water. The mixtures were heated up to 70°C.
Zn(2,4’-bpy) L ·H O and Cd(2,4’-bpy) L ·H O indi-
2 2 2 2 2 2
cate that they are isostructural. The molar conductiv-
ity for all complexes in MeOH, (V)–(VIII) in DMF
and (V) in DMSO exhibited a behaviour intermediate
between those of non-electrolytes and 1:1 electro-
lytes. The compounds (I)–(IV) in DMF and all except
1
During several days the compounds were crystallized.
The products were washed with 40% v/v ethanol and
then with ethanol and diethyl ether mixture (1:1). All
compounds were dried in open air and analysed. C, N,
(
V) in DMSO are non-electrolytes (Table 1) [25].
The ligand field-spectrum for Ni(phen)L ·2H O in
solid state was recorded. It exhibits three bands at
H was determined by elementary analysis with V O
2 5
2
2
as oxidizing agent (Carlo-Erba instrument), contents
of M(II) in mineralized samples by complexometric
titration with EDTA.
–1
24940, 16460 and 11620 cm which may be attributed
to transitions A ® T (P), A ® T (F) and
3
3
3
3
2
g
1g
2g
1g
3
1
A ® E , respectively. The room temperature effective
2g
g
magnetic moment of Ni(phen)L ·2H O is equal 3.36
2
Methods
2
B.M. Above observations are in accordance with dis-
torted octahedral geometry around nickel(II) [26, 27].
Conductivity measurements were performed on
OK-102/1 conductometer with OK 0902 electrode at
2
5±0.5°C. The molar conductivity (L ) of the com-
M
–3
–1
Infrared spectra
plexes was measured for 1.0·10 mol L solutions in
MeOH, DMF and DMSO. IR spectra were recorded on
FTIR-8501 Shimadzu spectrophotometer over the range
IR spectra of all obtained complexes were investi-
gated. As result of the formation of complexes with
metal(II) ions, the IR spectra of 2-bpy and 2,4’-bpy
undergo changes. They were found to be similar to
–1
4
000–400 cm using KBr pellets. VIS spectra (only for
nickel(II) complex) were obtained in Nujol mull on
–1
n
M-40 SPECORD over the range 29500–11000 cm .
The magnetic susceptibility of Ni(II) complexes was
measured on magnetic balance (Sherwood Scientific
those obtained for other complexes of d metals
[
14, 22, 28–30]. Spectrum of 2,4’-bpy (unsymmetri-
cal isomer of bpy) changes only, following
complexation [28], in the region of vibration modes
of the 4-substituted (4-sub) pyridine. The stretching
vibration of 4-sub pyridine nCC, nCN, nCCinter ring
MSB MK 1) using Co[Hg(SCN) ] as a calibrant. Exper-
4
imental magnetic susceptibility was corrected by dia-
magnetism data [24].
The thermal decomposition was studied by
means of Q-1500 derivatograph. The samples of
1
atmosphere. a-Al was used as standard material.
–
1
(
1595 cm for free ligand [31]) was shifted to higher
value in the spectrum of the complex (II) by about
–
5 cm . The characteristic ring breathing vibration of
1
00 mg were heated in ceramic crucible in static air
O
3
1
4
–
-sub pyridine (band as a shoulder at 990 cm in
1
2
All thermal investigations were carried out to the tem-
perature range 20–1000°C at heating rate of
1
products of decomposition were determined. In
sinters (prepared during the heating sample of com-
plex up to temperatures definite from TG curves) the
presence of carbonates were analyzed. The obtained
final solid thermal decomposition products of com-
unbonded 2,4’-bpy [31]) is observed in spectra of the
–
complexes (I) and (II) at 1016.4 and 1012.6 cm , re-
1
–
0°C min . From TG curves the solid intermediate
1
spectively. Also the band (assigned as ring stretching
–
1
mode for 4-sub pyridine) at 1405 cm in free 2,4’-bpy
–
1
is displaced for complexes by ca. 10 cm toward
higher frequencies. From these observations and liter-
ature data [14, 28, 32] it is possible to state, that
558
J. Therm. Anal. Cal., 90, 2007

METAL(II) COMPLEXES WITH FORMATES AND SOME NITROGEN DONOR LIGANDS
–
1
2
–1
M
Table 1 Analytical data, molar conductivity L (W cm mol ) in MeOH, DMF and DMSO
–
c=1·10 mol L at 25°C
3
–1
Analysis: found (calculated)/%
L
M
No.
Complex
M
C
N
H
MeOH
53.0
DMF
10.2
DMSO
9.2
(
(
(
(
(
(
(
(
I)
Zn(2,4’-bpy)
2
L
2
·H
·H
·4H
·3H
·2H
·2H
·2H
·H
2
O
13.64
(13.46)
54.01
(54.34)
11.43
(11.53)
4.11
(4.15)
(
white)
II)
Cd(2,4’-bpy)
white)
2
L
2
2
O
21.20
(21.09)
49.23
(49.09)
10.51
(10.42)
3.77
(3.78)
47.5
74.7
69.7
74.7
74.7
67.7
64.6
9.8
10.1
11.4
16.5
12.3
17.7
19.4
16.6
8.8
(
III)
IV)
V)
Zn(2-bpy)
white)
3
L
2
2
O
12.00
(12.07)
55.10
(55.12)
9.08
(9.15)
4.96
(4.92)
(
Cd(2-bpy)
white)
2
L
2
2
O
19.76
(19.78)
46.38
(46.45)
9.82
(9.85)
4.19
(4.25)
(
a)
Mn(phen)L
yellow)
2
2
O
15.35
(15.21)
45.99
(46.55)
7.71
(7.77)
3.29
(3.35)
28.3
(
VI)
VII)
Ni(phen)L
green)
2
2
O
16.08
(16.50)
46.12
(46.07)
7.65
(7.67)
3.36
(3.31)
37.6
24.2
20.2
(
Zn(phen)L
white)
2
2
O
17.70
(17.59)
45.01
(45.24)
7.23
(7.54)
3.19
(3.25)
(
VIII)
Cd(phen)L
(white)
2
2
O
28.40
(28.15)
41.76
(41.97)
6.88
(6.99)
1.49
(1.51)
9.2
a)
–4
.0·10 mol L
–1
6
2,4’-bpy coordinated via least hindered 4’(N) atom as
monodentate ligand.
The spectrum of free 1,10-phenanthroline [30] un-
dergoes modification on coordination to metal(II)
[1, 30]. Similar results have been obtained for IR spectra
of investigated complexes with 1,10-phenanthroline and
formates. The principal IR spectra bands of phen in iso-
lated compounds are collected in Table 2. There occur
changes of complexes spectra in the ranges
In spectra of Zn(2-bpy) L ·4H O and
2
3
2
Cd(2-bpy) L ·3H O complexes the bands attributed
2
2
2
to ring stretching vibrations n , n , n and ring
CCinter ring
CC
CN
breathing mode (in unbonded ligand at 1599 and
–
91 cm , respectively [29]) are moved towards
1
9
higher frequencies in comparison to free 2-bpy; these
–1
ca. 1615–1423 and ca. 795–730 cm . The bands at
–1
615 and 1423 cm (attributed to n
1
vibrations of
free phen) [30] appear for complexes between
–
1
(CN,CC)
bands occurred at 1596.9 and 1018.3 cm (for Zn(II))
and 1603.1 and 1012.6 (for Cd(II)), respectively. The
band gCH out-of-plane deformation modes are ob-
served at higher waven numbers (781.1, 763.8 for
–1
596.9–1591.2 and 1429.2–1427.2 cm . Presence of
1
strong band at 1519.8–1515.9 cm (1505 cm for free
–1
–1
phen) is associated with carbocyclic ring vibrations.
There are observed also absorption bands (g ) in the
–
1
(
unbonded N-donor ligand (753 cm ). Also weak sat-
III) and 769.5 cm for (IV)) in comparison to
–
1
CH
–1
range 794.6–783.0 and 731.0–727.1 cm (in free phen
–
1
ellite of this band at 738 cm gains intensity and is
strongly moved away from the parent peak. These ob-
servations suggested that 2-bpy is coordinated to
metal ions [29, 30, 33].
–1
at 767 and 734 cm ).
The IR spectra of investigated complexes
II–VII) show bands arising from asymmetric nas(OCO)
(
–
1
Table 2 Principal IR bands for 1,10-phenanthroline in free ligand and their complexes/cm
Compound
phen [30]
n
CN, CC
n
CC
*
n
CN, CC
g
CH
1615
1505
1423
767
34
7
(
(
(
(
V)
Mn(phen)L
2
·2H
·2H
·2H
·2H
2
O
1595.0
1593.1
1596.9
1591.2
1515.9
1515.9
1519.8
1515.9
1427.2
1427.2
1429.2
1427.2
788.8
31.0
7
VI)
VII)
VIII)
*
Ni(phen)L
Zn(phen)L
2
2
O
794.6
27.1
7
2
2
O
792.7
29.0
7
Cd(phen)L
2
2
O
783.0
30.0
7
associated with carbocyclic ring vibrations
J. Therm. Anal. Cal., 90, 2007
559

CZAKIS-SULIKOWSKA et al.
and symmetric ns(OCO) vibrations of OCO groups in
ble after the determination of crystal structure. The
presence of water molecules in isolated complexes is
shown by a strong and broad band in the region
–
1
the ranges 1631.7–1604.7 and 1375.9–1348.1 cm ,
respectively (Table 3). However, the analysis of these
regions of spectrum, in the case of I and VIII com-
pounds does not permit an interpretation of the nature
of the metal(II)-formate bonds; nas(OCO) (from
–
1
3400–3200 cm .
Thermal studies
Zn(2,4’-bpy) L ·H O) and n (from Cd(phen)L2·
s(OCO)
2
2
2
H O) overlaid by 2,4’-bpy frequencies and the ab-
2
The thermal decomposition data are collected in Ta-
ble 4. Thermoanalytical curves of Zn(2-bpy) L ·4H O
sorption p +rr(OCO), respectively. The frequencies of
CH
3
2
2
asymmetric (nas(OCO)
)
and symmetric (ns(OCO)
)
and Zn(2,4’-bpy) L ·H O (Fig. 1) and Mn(phen)L ·
2 2 2 2
carboxylate vibrations in the IR spectra, and the mag-
nitude of separation Dn=nas(OCO)–ns(OCO), are often
used as spectroscopic criterions to determine the
mode of carboxylate binding [34–39]. Values of Dn
between nas(OCO) and ns(OCO) for II, III and IV are
higher than those for sodium formate (DnNaHCOO=
2H O and Ni(phen)L ·2H O (Fig. 2) are presented as
2 2 2
examples. All the compounds decompose progres-
sively. Thermal decomposition started by dehydration
process and is accompanied by endothermic effect.
The compounds lose molecules of water in one step.
The complexes with 2,4’-bpy are thermally more sta-
ble than 2-bpy compounds. The complexes (I) and
(II) begin to decompose at 200 and 130°C, respec-
–
1
=
240 cm [38]). Thus, we state that carboxylate
groups in these complexes are probably monodentate.
The Dn values of formates for M(phen)L ·2H
O
tively. Zn(2-bpy) L ·4H O and Cd(2-bpy) L ·3H O
3 2 2 2 2 2
2
2
–
1
are equal 233.3 (Mn), 228.8 (Ni) and 235.3 cm (Zn).
It suggests, that carboxylate groups in
,10-phenanthroline complexes of Mn(II), Ni(II) and
Zn(II) behave as bidentate chelate ligands. Full inter-
pretation of mode of coordination between metal(II)-
carboxylates in obtained compounds would be possi-
are stable up to 90 and 70°C. When the temperature
increases the intermediate anhydrous complexes
Zn(2,4’-bpy)2L2 (310–510°) and Zn(2-bpy)3L2
(205–520°C) convert to ZnO with residue of organic
fragments. The TG curves show rapid mass loss.
Next, the combustion of the remaining organic prod-
1
2 2 2 3 2 2
Fig. 1 Thermoanalytical curves for a – Zn(2,4’-bpy) (HCOO) ×H O and b – Zn(2-bpy) (HCOO) ·4H O (mass sample 100 mg)
560
J. Therm. Anal. Cal., 90, 2007

METAL(II) COMPLEXES WITH FORMATES AND SOME NITROGEN DONOR LIGANDS
–
1
Table 3 Principal IR bands for OCO groups in free ligand and obtained complexes/cm
Compound
n
as(OCO)
n
s(OCO)
pCH+rr(OCO)
Dn=nas–n
s
HCOONa [40]
1597
1357
1389
240
2
,4’-bipyridine-formato complexes
1373.2
(
(
I)
Zn(2,4’-bpy)
2
L
2
·H
2
O
1390.0
1385.0
*
II)
Cd(2,4’-bpy)
2
L
2
·H
2
O
1631.7
1370.0
261.7
2
,2-bipyridine-formato complexes
(
(
III)
IV)
Zn(2-bpy)
3
L
2
·4H
2
O
1631.7
1631.7
1348.1
1352.0
1384.8
1380.9
283.6
279.7
Cd(2-bpy)
2
L
2
·3H
2
O
1
, 10-phenanthroline-formato complexes
(
(
(
(
V)
Mn(phen)L
Ni(phen)L ·2H
Zn(phen)L ·2H
2
·2H O
2
·2H
2
O
1608.5
1604.7
1610.5
1631.7
1375.2
1375.9
1375.2
1388.7
1380.9
1390.6
233.3
228.8
235.3
*
VI)
VII)
2
2
O
2
2
O
VIII) Cd(phen)L
2
*
the nature of the M-formate bonds does not interpreted
ucts takes place and pure ZnO is formed. The strong
and broad exothermic peaks originating from oxida-
tion of organic residues are observed (Table 4). In the
range 320–570°C the intermediate product
thermic peaks on DTA are at 410 and 540°C. The
anhydrous compound (IV) lose one mol of 2-bpy be-
tween 160–380°C. The decomposition of intermedi-
ate Cd(2-bpy)L to CdCO takes place at 380–480°C.
2 3
Cd(2,4’-bpy)
mixture of CdCO with CdO occurs. A constant mass
level for CdO begins at 760°C. The appropriate endo-
2
L
2
begins to decompose and formation
In higher temperature (~760°C) pure CdO is ob-
served. The DTA curve shows endothermic peaks at
360 and 440°C.
3
2 2 2 2
Fig. 2 Thermoanalytical curves for a – Mn(phen)(HCOO) ×2H O and b – Ni(phen)(HCOO) ×2H O (mass sample 100 mg)
J. Therm. Anal. Cal., 90, 2007
561

CZAKIS-SULIKOWSKA et al.
Table 4 Thermal decomposition data of obtained complexes in air; mass sample 100 mg
Ranges of
decomposition/°C
DTA peaks/
°C
Mass loss/%
found calc.
Intermediate and final solid
products
No.
Complex
(
(
(
(
I)
Zn(2,4’-bpy)
2
L
2
·H
2
O
200–240
230 endo
395 exo
4.0
3.71
2 2
Zn(2,4’-bpy) L
a
3
5
10–510
10–920
ZnO+organic fragments
ZnO
850 exo br
205 endo
410, 540 endo
900 exo
75.0
3.5
75.54
3.38
–
II)
III)
IV)
Cd(2,4’-bpy)
2
L
2
·H
2
O
130–220
20–570
760
90–200
2 2
Cd(2,4’-bpy) L
a
3
69.5
3.0
mixture of CdCO
CdO
3
and CdO
>
72.52
10.53
Zn(2-bpy)
3
L
2
·4H
2
O
170 endo
400 exo
10.5
3 2
Zn(2-bpy) L
a
2
05–520
20–920
ZnO + organic fragments
ZnO
5
900 exo
71.0
9.0
70.96
9.50
27.45
32.73
7.74
9.98
24.94
43.97
9.87
12.35
–
Cd(2-bpy)
2
L
2
·3H
2
O
70–150
140 endo
360 endo
440 endo
770 exo
Cd(2-bpy)
2 2
L
1
60–380
80–480
80–760
27.0
33.0
8.0
Cd(2-bpy)L
2
3
4
CdCO
3
CdO
(
(
V)
Mn(phen)L
2
·2H
2
O
80–120
110 endo
260 endo
440–630 exo
160 endo
220 endo
400–560 exo
10.0
24.0
43.5
10.0
12.0
58.0
+2.0
10.0
25.0
43.0
4.0
Mn(phen)L
2
2
30–380
80–660
Mn(phen)0.5L
2
3
3 4
Mn O
VI)
Ni(phen)L
2
·2H
2
O
100–180
Ni(phen)L
2
1
2
80–250
50–560
Ni(phen)0.75L
2
NiO with traces of Ni
NiO
>570
57.31
9.69
24.24
43.17
4.49
–
(
(
VII)
Zn(phen)L
2
·2H
2
O
90–125
100 endo
200 endo
525 exo br
120 endo
250 endo
680 exo br
Zn(phen)L
2
1
80–335
35–630
Zn(phen)0.5
ZnO
L
2
3
VIII) Cd(phen)L
2
·H
2
O
110–190
Cd(phen)L
2
a
1
3
90–370
70–770
38.0
25.0
mixture of CdCO
CdO
3
and CdO
63.01
br – broad
a
–
quantitative composition does not investigated
During heating, the Mn(phen)L ·2H O (V),
2
tion process with endothermic effect on DTA curve at
120°C. With increasing of temperature (190–370°C)
mixture of CdCO and CdO exists. The final solid
product of decomposition is CdO accompanied by
broad exothermic effect at 680°C. The lines for all fi-
nal products corresponded to those reported in Pow-
der Diffraction File [41].
2
Ni(phen)L ·2H O (VI) and Zn(phen)L ·2H O (VII)
2
2
2
2
complexes lose molecules of water in the ranges
0–120 (V), 100–180 (VI) and 90–125°C (VII). After
that, elimination of 1,10-phenanthroline begins and
the intermediate products:
230–380°C), Ni(phen)0.75L2 (180–250°C) and
Zn(phen) L (180–335°C) were formed. On DTA
3
8
Mn(phen)0.5L
2
(
0
.5 2
curve endothermic effects at 260 (V), 220 (VI) and
2
3
00°C (VII) exist. Between 380–660 (V) and
35–630°C (VII) the Mn and ZnO occur, respec-
Conclusions
O
4
3
tively. Further heating Ni(phen)0.75L2 causes decom-
position to mixture NiO with trace of Ni. X-ray dif-
fraction patterns indicate that NiO with Ni are pre-
sented in the sinter of complex (VI) heated up to
In this paper we described in solid state mixed-ligands
metal(II) complexes with N-donors (2-bpy, 2,4’-bpy or
phen) and formates. On basis of our previous papers
[21, 22], the literature data [19, 20] and present studies
stated, that metal(II) complexes with bipyridine isomers
or phen and formates formed compounds of the princi-
5
60°C. A plateau for NiO in the TG curve being ob-
tained above 570°C. Thermal decomposition of
Cd(phen)L ·H O is started at 110°C. First is dehydra-
pally following empirical formulae: M(2-bpy) L ·nH O
2 2 2
2
2
562
J. Therm. Anal. Cal., 90, 2007

METAL(II) COMPLEXES WITH FORMATES AND SOME NITROGEN DONOR LIGANDS
(Co, Cu [22], Cd), M(2-bpy) L ·nH O (Ni [22], Zn),
M(2,4’-bpy) L ·nH O (Mn, Co, Ni, Cu [22], Zn, Cd)
8 C. Kaes, A. Katz and M. W. Hosseini, Chem. Rev.,
00 (2000) 3553 and references therein.
3
2
2
1
2
2
2
9
G. Psomas, C. Dendrinou-Samara, P. Philippakopoulos,
V. Tangoulis, C. P. Raptopoulou, E. Samaras and
D. P. Kessissoglou, Inorg. Chim. Acta, 272 (1998) 24.
and M(4-bpy)L ·nH O (Mn, Co, Ni, Cu [19–21]). They
2
2
were prepared as solid state with various degree of
hydration or in anhydrous form [21]. The IR spectros-
copy confirms, that the metal ions are bonded to N-do-
nor ligands. The carboxylate groups have versatile the
mode of coordination to metal(II). These groups in the
obtained complexes with 2-bpy or 2,4’-bpy are bonded
as monodentate (or ‘pseudomonodentate’) ligands [22],
whereas bidentate chelating or bridging formates exist
in the major 4,4’-bipyridine complexes [19–21]. The
mode of metal-carboxylate coordination probably de-
pends on the nitrogen atoms position in the bipyridine
isomers [14, 32, 33]. The carboxylate groups in
1
1
0 P. Losier and M. J. Zaworotka, Angew. Chem. Int. Edit.
Engl., 35 (1996) 2779.
1 T. TÓaczaÓa, Wiadomoíci Chem., 45 (1991) 439.
12 A. B. Rovinsky and A. M. Zhabotynskii, J. Phys. Chem.,
88 (1984) 6081.
13 L. P. Tikhonova, K. B. Yatsymirskii and W. Zajac, Teor.
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1
4 R. KruszyÕski, B. Kuünik, T. J. Bartczak and
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5 Jian-Min Li, Yu-Gen Zhang, Jing-Hua Chen, Lei Rui,
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1
19 (2000) 1117.
1
,10-phenanthroline-formato complexes of Mn(II),
1
6 J.-H. Liao, S.-H. Chehg and C.-T. Su, Inorg. Chim.
Commun., 5 (2002) 761.
Ni(II) and Zn(II) behave as bidentate chelating ligands.
The investigated mixed-ligands metals(II) com-
plexes with N-donors and formates are more stable
than the major formate dihydrates of M(II) [42]. Ther-
mal decomposition of obtained complexes started
with the release of water molecules. The pyrolysis of
transition anhydrous complexes is multistage and
yields oxides as final products. Among obtained com-
plexes the most stable are 2,4’-bipyridine-formato
17 B. J. Hathaway, I. M. Procter, R. C. Slade and
A. A. G. Tomlinson, J. Chem. Soc., 2219 (1969).
1
1
2
8 W. Fitzgerald and B. J. Hathaway, J. Chem. Soc. Dalton
Trans., 657 (1981).
9 X.-Y. Wang, H.-Y. Wei, Z.-M. Wang, Z.-D. Chen and
S. Gao, Inorg. Chem., 44 (2005) 572.
0 I. L. Manson, I. G. Leher, J. Y. Gu, R. Geiser,
J. A. Schlueter, R. Henning, X. P. Wang, A. J. Schultz,
H. J. Koo and M. H. Whangbo, J. Chem. Soc. Dalton
Trans., 2905 (2003).
(
initial
Zn(2,4’-bpy)
,4’-bipyridine-formato compounds [21]. The
temperature
of
decomposition
of
L
·H
O
is 200°C) and some
21 D. Czakis-Sulikowska, M. Markiewicz and
J. RadwaÕska-Doczekalska, Pol. J. Chem.,
2
2
2
4
7
7 (2003) 1255.
phenathroline-formato complexes are somewhat more
stable than compounds with 2,2-bipyridine.
Additionally, in this paper we stated, that the
2
2
2 D. Czakis-Sulikowska, J. RadwaÕska-Doczekalska,
A. Czylkowska, M. Markiewicz and A. Broniarczyk,
J. Therm. Anal. Cal., 86 (2006) 327.
complexes
of
Zn(2,4’-bpy)
2
L
2
·H
2
O
Cd(2,4’-bpy) L ·H O are isostructural. The magnetic
and
3 T. Tokii, N. Watanable, M. Nakashima, Y. Muto,
M. Marooka, S. Ohba and Y. Saito, Bull. Chem. Soc. Jpn.,
2
2
2
moment and the ligand field spectrum of complex
Ni(phen)L ·2H O is characteristic of octahedral envi-
ronment around Ni(II).
6
3 (1990) 364.
2
2
24 E. KÞnig, Magnetic Properties of Coordination and
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2
2
5 W. J. Geary, Coord. Chem. Rev., 7 (1971) 81.
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Received: October 19, 2006
Accepted: January 4, 2007
OnlineFirst: April 29, 2007
DOI: 10.1007/s10973-006-7980-9
564
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