Thermal decomposition of new mononuclear NiII complexes with ONNO type reduced Schiff bases and Pseudo halogens

Article abstract of DOI:10.1002/zaac.200900499

Mononuclear nickel(II) complexes were prepared by reaction, of the three ONNO type reduced Schiff bases bis-N,N'-(2-hydroxybenzyl)-1,3-propanediamine (L^HH₂), bis-N,N'-(2-hydroxybenzyl)-2,2′-dimethyl-1, 3-propanediamine (LDM^HH₂), and bis-N,N'-[1-(2- hydroxyphenyl)ethyl]-1,3-propanediamine (LAC^HH₂) with Ni^II ions in the presence of pseudo halides (OCN^-, SCN^- and N₃^-). The complexes were characterized with the use of elemental analyses, IR spectroscopy, and thermal analyses. The molecular structure of one of the complexes was obtained by single-crystal X-ray diffraction. The obtained complexes are mononuclear, and a pseudo halide molecule is attached. One of the oxygen atoms of the ligand is in phenolate and the other was in phenol form. According to the thermogravimetry results, it was thought that the pseudo halide thermally detaches from the structure as hydropseudo halide. In azide-containing complexes an endothermic reaction was observed although the azide group usually decomposes with an exothermic reaction.

Full text of DOI:10.1002/zaac.200900499

ARTICLE
DOI: 10.1002/zaac.200900499
Thermal Decomposition of New Mononuclear NiII Complexes with ONNO
Type Reduced Schiff Bases and Pseudo Halogens
B. Meltem Ateş,[a] Bülent Zeybek,*[b] Mecit Aksu,[c] Ümit Ergun,[b] Filiz Ercan,[a]
M. Levent Aksu,[d] and Orhan Atakol[b]
Keywords: Azides; Nickel; Pseudo halides; Schiff bases; Thermal analysis
Abstract. Mononuclear nickel(II) complexes were prepared by reac- was obtained by single-crystal X-ray diffraction. The obtained com-
tion of the three ONNO type reduced Schiff bases bis-N,N'-(2-hydrox- plexes are mononuclear, and a pseudo halide molecule is attached. One
ybenzyl)-1,3-propanediamine (LHH2), bis-N,N'-(2-hydroxybenzyl)- of the oxygen atoms of the ligand is in phenolate and the other was in
2,2'-dimethyl-1,3-propanediamine (LDMHH2), and bis-N,N'-[1-(2-hy- phenol form. According to the thermogravimetry results, it was thought
droxyphenyl)ethyl]-1,3-propanediamine (LACHH2) with NiII ions in that the pseudo halide thermally detaches from the structure as hydrop-
the presence of pseudo halides (OCN–, SCN– and N3 ). The complexes seudo halide. In azide-containing complexes an endothermic reaction
–
were characterized with the use of elemental analyses, IR spectroscopy, was observed although the azide group usually decomposes with an
and thermal analyses. The molecular structure of one of the complexes exothermic reaction.
nes are also of ONNO type and give multinuclear complexes
Introduction
similar to those Schiff bases [15, 17, 18]. In a previous study,
Complexes with ONNO type Schiff bases and +2 valence
a mononuclear complex was obtained by the reaction of bis-
transition metal ions are known for more than 70 years [1–
N,N'-(salicylidene)-1,3-propanediamine with NiII in DMF in
14]. In all complexes, two of the phenol oxygen atoms are
–
the presence of N3 . The most interesting feature of this com-
coordinated as phenolate (Figure 1).
plex is that one of the phenol groups was converted into phe-
nolate, whereas the other remained intact and NiII was neutral-
ized by phenolate and azide groups [19]. A number of
complexes were prepared with the pseudo halides N3 , OCN–,
–
and SCN–, which were characterized by thermal analyses (Fig-
ure 2). Thermogravimetry studies concerning complexes that
contain azide groups and other pseudo halides have recently
been reported [20–33], which showed that azide groups de-
compose in exothermic reactions.
Almost all complexes were obtained in crystal form but only
Figure 1. Most common complexes with ONNO type Schiff bases.
crystals of complex X grew to appropriate dimensions to ob-
tain its molecular structure with single-crystal X-ray diffraction
methods. Attempts to grow single-crystals of complex III in
DMF were unsuccessful. Recrystallization from DMSO
yielded complex X. Complexes I–X were characterized by IR
spectroscopy and elemental analyses; their thermal degradation
behaviors were examined by thermogravimetric measurements.
ONNO type Schiff bases are easily reduced with the help of
NaBH4 and turn into phenolamines [15–17]. These phenolami-
* Dr. B. Zeybek
Fax: +90-312-2232395
E-Mail: bzeybek@science.ankara.edu.tr
[a] Department of Physics Engineering
Hacettepe University
Results and Discussion
06800 Beytepe, Ankara, Turkey
[b] Department of Chemistry
Faculty of Science
The results of elemental analyses and important IR spectro-
scopic data are tabulated in Table 1. The asymmetric stretching
vibrations of azide ligands, νN3 and νCN are in good agreement
with the literature [30, 33]. The molecular structure of complex
X is shown in Figure 3 and selected bond lengths and bond
angles are listed in Table 2 and Table 3, respectively. In previ-
ous studies, the X-ray diffraction models of complexes I and
IV were given [19]. Complex III did not give crystals suitable
Ankara University
06100 Tandoğan, Ankara, Turkey
[c] Department of Chemistry
Faculty of Arts and Science
Bozok University
66200, Yozgat, Turkey
[d] Faculty of Gazi Education
Gazi University
06500 Beşevler, Ankara, Turkey
840
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 636, 840–845

Thermal Decomposition of New Mononuclear NiII Complexes
Figure 2. Formula of complexes I–X.
Table 1. Elemental analyses and important IR spectroscopic data of complexes I–X.
Complex
Elemental analyses
Expected %
Important IR data /cm–1
Found %
Ni
C
N
H
C
N
H
Ni
νO–H νN–H νC–H (Ar) νC–H Aliph
νN3 (OCN) (SCN) νC=O (DMF) νC=C (Ar) δCH2
δC–H (Ar)
[NiLH·N3·
DMF]2·DMF (I)
52.20 18.40 6.22 11.87 51.94 17.68 6.18 11.94 3370 3269 3037–3056 2861–2927
2036
2208
2094
2035
2194
2093
2027
2189
2082
2088
1646
1645
1650
1651
1646
1646
1649
1647
1650
1651
1598
1597
1598
1601
1598
1599
1600
1598
1598
1601
1460 757
1459 758
1468 756
1470 758
1460 760
1463 761
1469 757
1465 757
1490 758
1478 757
NiLH·OCN·DMF 55.17 12.25 5.95 12.84 54.69 13.41 5.21 12.73 3497 3270 3019–3058 2863–2928
(II)
NiLH·SCN·DMF 53.20 11.81 5.73 12.38 52.77 10.96 5.26 12.24 3491 3273 3021–3063 2866–2931
(III)
[NiLDMH·N3·
DMF]2·2DMF (IV)
NiLDMH·OCN·
DMF (V)
53.99 17.41 6.64 11.23 54.07 16.82 5.94 10.79 3501 3268 3021–3058 2860–2929
56.82 11.52 6.42 12.07 56.37 10.91 6.24 11.92 3510 3282 3024–3061 2855–2931
54.99 11.15 6.22 11.69 55.33 10.78 5.64 11.33 3504 3300 3022–3058 2864–2930
54.35 17.29 6.42 12.07 53.89 16.86 5.89 12.01 3449 3260 3018–3049 2865–2924
56.82 11.52 6.42 12.07 56.43 11.36 6.04 11.57 3469 3266 3017–3051 2865–2931
54.99 11.15 6.22 11.69 54.51 10.59 5.78 11.51 3475 3264 3018–3052 2864–2932
50.03 10.14 6.02 10.63 49.59 10.24 5.76 10.46 3416 3270 3028–3057 2848–2939
NiLDMH·
SCN·DMF (VI)
NiLACH·N3·
DMF (VII)
NiLACH·OCN·
DMF (VIII)
NiLACH·SCN·
DMF (IX)
[NiLH·SCN·
DMF]·DMSO (X)
Table 2. Selected bond lenghts /Å of complex X.
for XRD analysis in DMF. It was recrystallized from DMSO
and crystals suitable for XRD analysis as a result of the solvati-
zation of a DMSO molecule with the complex were obtained.
This new complex was described as compound X.
N1–Ni
2.107(4)
N2–Ni
N3–Ni
Ni–O1
Ni–O2
Ni–O3
C18–N3
C18–S1
2.101(5)
2.034(6)
2.046(4)
2.061(3)
2.134(4)
1.148(7)
1.632(8)
Elemental analyses and the molecular structure of the com-
plex show that NiII has mononuclear and octahedral coordina-
tion spheres similar to those reported in literature. As seen
from the data listed in Table 4, the coordination sphere around
NiII is an almost ideal octahedron with no significant deforma-
tion. The lengths of the coordinative bonds around NiII are
2.034, 2.046, 2.061, 2.101, 2.107, and 2.134 Å and the bond
angles are approximately 90 °. Only the N2–Ni–O3 and, N1–
Ni–O3 angles were found to amount 82.99 and 85.62 °. The
N3–Ni–O3, O2–Ni–N1 and O1–Ni–N2 angles were observed
to amount 176.70, 174.51, and 173.02 °, respectively, and de-
viate only slightly from the ideal value of 180 °.
Figure 3. Molecular structure of NiLH·SCN·DMF·DMSO (X).
Z. Anorg. Allg. Chem. 2010, 840–845
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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841

B. Zeybek et al.
ARTICLE
Table 3. Selected bond angles /° of complex X.
gen atoms of the phenol group. However, the bond angle
amounts 102.93 °, which is far from the expected value. There-
fore, this is not a real hydrogen bond formation. It can be
described as agnostic interaction [37].
N3–Ni–O1
N3–Ni–O2
O1–Ni–O2
N3–Ni–N2
O1–Ni–N2
O2–Ni–N2
N3–Ni–N1
O1–Ni–N1
O2–Ni–N1
N2–Ni–N1
N3–Ni–O3
O1–Ni–O3
O2–Ni–O3
N2–Ni–O3
N1–Ni–O3
N3–C18–S1
92.61(19)
90.17(18)
87.14(15)
93.80(2)
173.02(18)
89.96(17)
94.90(2)
Table 5. Hydrogen bonding parameters for complex X.
D–H···A
D–H
H···A
D···A
D–H···A
90.41(16)
174.51(18)
91.92(18)
176.70(2)
90.63(16)
89.49(15)
82.99(18)
85.62(17)
179.00(7)
O2–H2(B)···O1 0.93 Å
1.52 Å 2.412(5) Å
158 °
Table 4. Crystallographic data of complex X.
Chemical formula
C23H34N4NiO4S2
Formula mass
553.37
Temperature /K
293
Wavelength /Å
0.71073 Mo-Kα
Monoclinic, I2/a
Crystal system, space group
Unit cell dimensions /Å, °
a
18.7698 (2)
11.8211 (2)
24.5208 (16)
109.923 (4)
5115.3 (3)
8
b
c
β
Volume /Å3
Z
Calculated density /g·cm–3
Absorption coefficient /mm–1
F(000)
1.437
Figure 4. Dimerization of two molecules of complex X by hydrogen
bonding.
0.958
2336
Crystal size /mm
θmax /°
0.30 × 0.25 × 0.20
24.02
Table 6 lists the thermogravimetric data of complexes I–X.
Figure 5 shows the TG and DTA curves of complex
NiLH·N3·DMF (I). This complex is reported in literature. Two
units of NiLH·N3·DMF form a dimer with one DMF solvate
molecule. Four endothermic reaction steps are observed in the
TG and DTA curves of this complex. The first reaction is the
breakage of the solvatized DMF molecule from the
(NiLH·N3)2·DMF dimer. The theoretical mass of DMF is
7.38 %, whereas the experimental mass loss is 6.50 0.44 %.
The second weight loss step amounts 8.75 0.14 %. This is
probably due to dissociation of HN3 from the complex. Azides
are known to be explosive and can easily turn into nitrogen.
The explosion reaction of azide is highly exothermic [38].
θmin /°
2.07
Index range
0 ≤ h ≤ 21
0 ≤ k ≤ 13
–28 ≤ l ≤ 26
3966
Number of reflections used
Number of parameters
290
Rint
0.0286
R
0.0545
Rw
0.1247
Goodness of fit
1.012
Δρmin, Δρmax /e·Å–3
–0.712, 1.037
The most interesting phenomenon observed is the fact that However, the reaction observed here is endothermic and can-
one of the phenol groups of the ligand is coordinated as phe- not be the explosion reaction of azide. HN3 is a liquid com-
nolate and the other remains in phenol form. The 2+ charge of pound at room temperature and their salts are stable up to
NiII is neutralized by the negative charges of phenolate and ~200 °C [39]. In the NiLH·N3·DMF octahedral unit one phenol
pseudo halide. The hydrogen atom of the phenol group has a group of the ligand LH is in phenolate and the other is in phe-
very strong tendency to form hydrogen bonds and phenol hy- nol state.
drogen atoms form hydrogen bonds with phenolate groups of
The azide group coordinative bonded to hydrogen of this
neighboring molecules. The characteristics of this hydrogen phenol group thermally detaches from the structure as HN3. In
bond are shown in Table 5. Under these circumstances, two the remaining part of the molecule NiII is coordinated between
complex molecules are bonded to each other with two hydro- two amine nitrogen atoms and two phenolate oxygen atoms of
gen bonds through a dimerization process (Figure 4). As seen the LH molecule and oxygen atoms of the DMF group. The
in Table 5, there is an intramolecular hydrogen bond formed third weight loss step is related to the removal of DMF from
between hydrogen attached to amine nitrogen atoms and oxy- the remaining part of the complex. The expected and experi-
842
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 840–845

Thermal Decomposition of New Mononuclear NiII Complexes
Table 6. Thermoanalytical data of complexes I–X.
Complex
1st Thermal Reaction: Dissociation of DMF molecules 2nd Thermal Reaction: Degradation of the complex
Residue NiO
Temp. range /°C
Expected mass loss /% Found mass loss /% Temp. range /°C Found mass loss /% Expected /% Found /%
[NiLH·N3·DMF]2·DMF (I)a)
NiLH·OCN·DMF (II)
126–240, DTG: 127, 166, 207 30.83
29.76 0.52
25.28 0.14
26.56 0.46
42.31 1.17
23.09 0.30
26.65 1.20
22.42 0.35
23.36 0.27
25.93 1.14
36.45 0.24
240–430
270–440
210–380
190–440
270–445
275–430
245–420
250–430
235–445
240–395
21.70
24.60
15.30
13.90
36.04
13.60
18.60
47.80
36.90
28.60
15.10
16.34
15.75
11.54
15.34
14.87
15.36
15.35
14.87
13.53
14.48 1.18
15.12 2.05
14.24 1.22
10.92 1.09
14.71 1.16
15.04 0.52
16.22 1.46
16.06 0.94
14.33 1.16
12.79 0.83
118–230, DTG: 190
138–202, DTG: 198
25.36
27.83
41.44
23.85
26.28
23.85
23.85
26.29
38.03
NiLH·SCN·DMF (III)
[NiLDMH·N3·DMF]2·2DMF (IV) 184–294, DTG: 231
NiLDMH.OCN.DMF (V)
NiLDMH·SCN·DMF (VI)
NiLACH·N3·DMF (VII)
NiLACH·OCN·DMF (VIII)
NiLACH·SCN·DMF (IX)
[NiLH·SCN·DMF]·DMSO (X)
175–265, DTG: 235
165–266, DTG: 221
165–268, DTG: 232
172–250, DTG: 214
149–230, DTG: 192
146–228, DTG: 219
a) In [NiLH·N3·DMF]2·DMF. 1st Thermal Reaction: Dissociation of solvated DMF at 119–146 °C Expected: 7.38 % Found: 6.50 0.44 %. 2nd
Thermal Reaction: Loss of HN3 at 149–185 °C Expected: 8.69 % Found: 8.75 0.14 %. 3rd Thermal Reaction: Loss of DMF at 185–234 °C
Expected: 14.76 % Found: 14.78 0.94 %. 4th Thermal Reaction: Degradation of NiL at 280–345 °C. Degradation range of NiL 314–360 °C
DTG: 340 °C. Degradation range of NiLDMH 337–421 °C DTG: 390 °C.
Preparation of Ligands
LHH2, LDMHH2, and LACHH2 were obtained the reduction of corre-
sponding Schiff base. Bis-N,N'(salicylidene)-1,3-propanediamine
(1.410 g, 0.005 mol), bis-N,N'(salicylidene)-2,2'-dimethyl-1,3-propan-
ediamine (1.540 g, 0.005 mol), or bis-N,N'(2-hydroxyacetophenyli-
dine)-1,3-propanediamine (1.540 g, 0.005 mol) was dissolved in
MeOH (50 mL) under heating. Solid NaBH4 was slowly added to this
solution. Twice the volume of ice was added to yield a colorless solu-
tion, which was left to stand for one day. The colorless precipitate was
filtered off and dried in air.
1H NMR (LHH2): δ = 6.67–6.73 and 7.03–7.09 (HAr), 2.48–2.65 (HCH2
,
,
neighbor to nitrogen), 1.58–1.69 (HCH2, methylene), 3.75–2.86 (HCH2
benzyl), 4.75 (HN–H). (LDMHH2): δ = 6.72–6.77 and 7.12–7.18 (HAr),
3.88–4.34 (HCH2, benzyl), 2.38–2.54 (HCH2, neighbor to nitrogen),
0.98–1.22 (HCH3), 5.26 (HN–H). (LACHH2): δ = 6.66–6.82, 7.15–7.26,
Figure 5. TG and DTA curves for NiLH·N3·DMF (I).
and 7.48–7.59 (HAr), 1.52–1.68 (HCH2, methylene), 2.32–2.40 (HCH2
neighbor to nitrogen), 3.68–3.78 (HC–H, benzyl), 2.14–2.28 (HCH3),
5.31 (HN–H).
,
The Schiff bases were prepared from the corresponding aldehyde and
amine compounds in EtOH. Bis-N,N'(salicylidene)-1,3-propanediam-
ine was prepared from salicylaldehyde and 1,3-propanediamine, bis-
N,N'(salicylidene)-2,2'-dimethyl-1,3-propanediamine was prepared
from salicylaldehyde and 2,2'-dimethyl-1,3-propanediamine and bis-
N,N'(2-hydroxyacetophenylidine)-1,3-propanediamine was prepared
from 2-hydroxyacetophenone and 1,3-propanediamine.
mentally found mass losses are 14.76 % and 14.78 0.94 %,
which nearly similar. The total mass loss expected from the
first three thermal reactions is 30.83 % and the experimentally
found value is 29.76 0.52 %. The fourth weight loss is the
decomposition of the NiLH molecule, which takes place in a
non-uniform manner. In other complexes thermal HSCN for-
mation such as HN3 is not clearly observed. Figure 6 illustrates
the TG and DTA curves of complexes II, III, V, and IX. In
these TG and DTA curves the formation of HN3, HOCN and
HSCN and the loss of coordinative DMF appears as a single
endothermic reaction.
Preparation of the Complexes
The Ligand (LHH2, LDMHH2 or LACHH2) (0.001 mol) was dissolved
in DMF (40 mL) whilst heating. Afterwards, a solution of NiCl2·6H2O
(0.237 g) in hot MeOH (20 mL) and a solution of the sodium pseudo
halide salt (0.002 mol) in hot water (5 mL) was added. The resulting
mixture was left to stand for 1–5 days and the precipitated crystals
were filtered off and dried in air.
Experimental Section
General
1H-NMR spectra were obtained with a Bruker DPX FT NMR
(500 MHz) spectrometer (SiMe4 as internal standard and 85 % H3PO4
Preparation of Complex X for XRD Studies
as an external standard). The concentration of solute molecules was All complexes were obtained as blue crystals. However, the crystals
150 mg in 1.0 mL CDCl3.
were not big enough for XRD studies. Therefore, the complex
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de 843
Z. Anorg. Allg. Chem. 2010, 840–845

B. Zeybek et al.
ARTICLE
NiLH·SCN·DMF (III) (200 mg) was dissolved in DMSO (10 mL)
whilst heating. DMF (10 mL) was added and the final mixture was
left to stand for 5–6 days. The resulting crystals were filtered off and
used for XRD studies.
The C, H, and N analyses of the complexes were carried out with a
Leco 932 CHNS analyzer. Ni analysis was performed with a GBC
Avanta PM Model AAS apparatus.
Thermogravimetric analyses were performed with a Shimadzu DTG-
60 H apparatus under N2 atmosphere in Pt pans. The TG and DTA
curves were taken between 30 °C and 750 °C at a heating rate of
10 °C·min–1. The pans were cleaned with oxygen at 750 °C.
A
blue prismatic crystal with approximate dimensions
0.20 × 0.25 × 0.30 mm was attached to a glass fiber and mounted on
an Enraf–Nonius CAD4 diffractometer [34]. X-ray diffraction data of
single crystal were collected at room temperature with graphite mono-
chromated Mo-Kα radiation. The cell parameters were determined from
a least-squares refinement of 25 centered reflections. Cell refinement
was carried out using CAD4 EXPRESS [34]. During data collection,
three standard reflections were periodically measured every 120 mi-
nutes and showed no significant intensity variation. With ω/2θ scan
mode 2052 unique reflections having I ≥ 2σ(I) were measured in the
range of 2.07 ≤ θ ≤ 24.02°. Data reduction was carried out using
SHELXL97 [35]. The structure was solved by direct methods using
SHELX97 [35] in the WinGX package [36] and refined by full-matrix
least-square method on F2 using SHELXL97 [35]. All non-hydrogen
atoms were refined with anisotropic thermal parameters and the hydro-
gen atoms were included at calculated position using a riding model
with Ueq = 1.2 Uiso (C, N). Selected crystallographic data are given in
Table 4, selected bond lengths and angles are given in Table 2 and
Table 3, respectively.
Crystallographic data for the structural analysis have been deposited
with the Cambridge Crystallographic Data Center, CCDC-751983 for
complex X. Copies of this information can be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge, CB2, 1EZ, UK
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk).
Acknowledgement
We also thank the Ankara University Scientific Research Fund (Project
No: 20070705118) for their support. Furthermore, we also thank Ana-
dolu University and Medicinal Plants and Medicine Research Center
of Anadolu University, Eskişehir, for allowing us to use the NMR facil-
ity.
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Figure 6. TG and DTA curves for (a) NiLH·OCN·DMF (II), (b)
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Thermal Decomposition of New Mononuclear NiII Complexes
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