Syntheses, spectra, thermal studies and crystal structures of vitamin B13 complexes of nickel(II) with N,N,N′,N′-tetramethylethylenediamine and 2,2-dimethylpropane-1,3-diamine

Article abstract of DOI:10.1002/zaac.200801313

Two nickel(II) complexes of vitamin B13 (H₃Or) with N,N,N′,N′-tetramethylethylenediamine (tmen) and 2,2-dimethylpropane- 1,3-diamine (dmpen) were synthesized and characterized by means of elemental and thermal analyses, magnetic susceptibility,

Full text of DOI:10.1002/zaac.200801313

ARTICLE
DOI: 10.1002/zaac.200801313
Syntheses, Spectra, Thermal Studies and Crystal Structures of Vitamin B13
Complexes of Nickel(II) with N,N,NЈ,NЈ-Tetramethylethylenediamine and
2
,2-Dimethylpropane-1,3-diamine
[a]
[a]
[b]
[b]
Okan Zafer Ye s¸ ilel,* Hakan Erer, Necmi Dege, and Orhan Büyükgüngör
Keywords: Orotato complexes; Vitamin B13 complexes; Amines; Nickel
Abstract. Two nickel(II) complexes of vitamin B13 (H
3
Or) with
tion. In the complexes, which crystallize in the triclinic system
¯
N,N,NЈ,NЈ-tetramethylethylenediamine (tmen) and 2,2-dimeth-
ylpropane-1,3-diamine (dmpen) were synthesized and characterized
by means of elemental and thermal analyses, magnetic suscepti-
bility, and IR and UV/Vis spectroscopic studies. The crystal
(space group P1 for 1) and the monoclinic system (space group
II
P2
1
/c for 2), the Ni ions exhibit a distorted octahedral coordi-
II
nation. Ni ions are chelated by the deprotonated nitrogen atom
of the pyrimidine ring and the oxygen atom of the carboxylate
group, the distorted octahedral coordination completed by one
2 2 2
structures of mer-[Ni(HOr)(H O) (tmen)]·H O (1) and [Ni(HOr)-
(
dmpen) ] (2) were determined by using single-crystal X-ray diffrac- tmen and two aqua ligands for 1 or two dmpen ligands for 2.
2
Introduction
[Ni(HOr)(H
2
O)
3
4
(na)]·2H O (na ϭ nicotine amide) [13],
2
[Ni(HOr)(H O) ]·H O [14], [Ni(HOr)(bipy)(H O) ]·2H O
2
2
2
2
2
Vitamin B13 (Orotic acid, H Or) is an important uracil
3
(bipy ϭ 2,2Ј-bipyridine) [15, 16], [Ni(HOr)(dpa)(H O) ]·
2 2
derivative, as the effective precursor in the biosynthesis of
uracil base of RNA in living organisms [1, 2]. In the last
years, research in bioinorganic chemistry has revealed the
important role of metal ions in most biological processes.
For these reasons, some metal complexes of vitamin B13
and its derivatives have recently attracted growing attention
in medicine for applications in curing syndromes related
with some metal deficiencies. In addition, nickel, mag-
nesium, palladium, and platinum orotato complexes have
been screened as therapeutic agents for cancer [3, 4]. Studies
showed that the presence of three different functional
groups such as pyrimidine nitrogen atoms, carbonyl oxygen
atoms, or carboxylate oxygen atoms makes orotate a poly-
functional ligand in coordination chemistry [5Ϫ19]. The
H O (dpa ϭ 2,2Ј-bipyridylamine) [16], [Ni(HOr)(dpa) ]·
2
2
0
.5H O [16], [Ni(HOr)(phen)(H O) ]·2H O (phen ϭ 1,10-
2 2 2 2
phenanthroline) [16], [Ni(HOr)(dmphen)(H O)] (dmphen ϭ
2
2,9-dimethyl-1Ϫ1,10-phenanthroline) [16], and [Ni(HOr)(-
mea) ] (mea ϭ monoethanolamine) [17], where orotate acts
2
as a bidentate ligand. In the polymeric [Ni(HOr)(H O) ]
2
3 n
2Ϫ
[
16, 18] and [Ni(HOr)(NH )(H O) ] [19] complexes, HOr
3
2
2 n
acts as a bridging ligand. In [Ni(H O) ](H Or) ·2H O [20],
2
6
2
2
2
Ϫ
H Or does not coordinate the metal ion and behaves as a
2
counterion. Recently, we reported the thermal decompo-
II
II
II
II
sition of Ni , Co , Cu , and Cd -1,10-phenanthroline
complexes with orotato counterions [21]. In this study,
we describe the preparation and spectroscopic characteriz-
II
ation (IR and UV/Vis) of orotato complexes of Ni
2
Ϫ
most common coordination mode of HOr
is ligation
with N,N,NЈ,NЈ-tetramethylethylenediamine (tmen) mer-
through a deprotonated nitrogen atom of the pyrimidine
ring and a carboxylate oxygen atom so forming a five-
[
Ni(HOr)(H O) (tmen)]·H O (1) and 2,2-dimethylpropane-
2 2 2
1
,3-diamine (dmpen), [Ni(HOr)(dmpen) ] (2). The thermal
2
membered chelate ring. Crystal structures have been
decomposition pathway of the complexes was followed by
the help of thermal analysis (TG, DTG and DTA). The
crystal structures of both complexes were also determined
by single-crystal X-ray diffraction.
II
described for the mononuclear Ni
complexes,
[
[
Ni(HOr)(H O)(tea)]·H O (tea ϭ triethanolamine) [10],
2 2
Ni(HOr)(H O)(4-mim) ] ·5H O (4-mim ϭ 4(5)-methyl-
2
3 2
2
imidazole) [11], [Ni(HOr)(H O) (im) ] (imidazole) [12],
2
2
2
Results and Discussion
Magnetic Susceptibility and UV/Vis Spectra of 1 and 2
*
Prof. Dr. O. Z. Ye s¸ ilel
Fax: ϩ90-222-2393578
E-Mail: yesilel@ogu.edu.tr
The electronic spectroscopic data, the assignment of the
[
a] Faculty of Arts and Sciences, Department of Chemistry
Eski s¸ ehir Osmangazi University
dϪd transitions and the magnetic moment values of the
II
complexes are given in Table 1. The Ni complexes exhibit
26480 Eski s¸ ehir, Turkey
magnetic moment values of 2.90 and 2.88 BM, which corre-
spond to two unpaired electrons, respectively.
[
b] Faculty of Arts and Sciences, Department of Physics, Ondokuz
Mayıs University, Samsun, Turkey
Z. Anorg. Allg. Chem. 2009, 635, 577Ϫ581
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
577

O. Z. Ye s¸ ilel, H. Erer, N. Dege, O. Büyükgüngör
Table 1. Electronic spectra and magnetic moment values of 1 and 2. Thermal Analyses of 1 and 2
ARTICLE
1
2
[Ni(HOr)(H O) (tmen)]·H O (1)
2 2 2
λ
max /nm
621
In the first stage, endothermic loss of crystal water occurs
in the 65Ϫ135 °C temperature range (DTGmax. ϭ 107 °C,
mass loss found 4.98 %, calcd. 4.71 %). The second stage
884
ε /L·cmϪ1 ·molϪ1
11
6
3
3
3
Assignment of dϪd transitions
A
2g Ǟ T1g
2g Ǟ T2g
[
Ni(HOr)(H O) (tmen)] is related to the release of the aqua
2 2
3
3
3
A
ligands between 148 and 233 °C (DTGmax ϭ 206 and
17 °C, mass loss found 8.98 %, calcd. 9.42 %). These stages
Δ
μ
o
/cmϪ1
11,300
2.90
2
eff /BM
show thermochromism, blue Ǟ green. The anhydrous com-
plex is rehydrated immediately after cooling in an open at-
mosphere. In the 234Ϫ421 °C temperature range, tmen and
HOr ligands are lost in two endothermic steps. The follow-
ing stage involves the burning of the organic residues
Table 2. IR spectra of complexesa) /cmϪ1
.
Assignments
H
3
Or [23]
1
2
ν
ν
ν
ν
ν
ν
ν
ν
ν
ν
OH
3241 sh
Ϫ
3154 m
3137 m
3099 s
Ϫ
1729, 1719 vs
1700 vs
1653 vs
1435 s
3383 s
Ϫ
3132 s
Ϫ
3074 w
2853 w
1636 vs, b
1636 vs, b
1589 m
1472 m
Ϫ
NH2
N(3)H
N(1)H
CH
3447, 3415 s
3280 s
Ϫ
3157 m
2996, 2874 m
1653 vs
1623 vs
1568 sh
1463 s
(DTGmax. ϭ 519 °C), leading finally to NiO. The overall
weight loss of 80.03 % (calcd. 80.49 %) agrees with the pro-
posed pathway.
CH3
CϭOacidϩνC(2)ϭO
C(6)ϭOϩνring
CϭCϩνring
[
Ni(HOr)(dmpen) ] (2)
2
CϭN
The complex is thermally stable up to about 285 °C. In
a)
Abbreviations: w Ϫ weak; m Ϫ medium; s Ϫ strong; vs. Ϫ very
the temperature range of 285Ϫ400 °C, the three stages of
strong, b Ϫ broad, sh Ϫ shoulder.
II
the Ni complex are related to the successive decompo-
sition of the neutral dmpen ligands and partial decompo-
sition of orotates by giving exothermic contribution (DTA-
The electronic spectra of complexes 1 and 2 in H O exhi-
2
Ϫ1
Ϫ1
bit absorption bands at 621 (ε ϭ 11 L·mol ·cm ), 652
Ϫ1
Ϫ1
Ϫ1
Ϫ1
ϭ 318, 377 and 400 °C. The final solid product of the
(
ε ϭ 16 L·mol ·cm ) and 884 (ε ϭ 6 L·mol ·cm ),
max
Ϫ1
Ϫ1
3
thermal decomposition was identified as NiO. The total
mass loss of the decomposition process was 84.05 %
(calcd. 82.09 %).
8
95 nm (ε ϭ 13 L·mol ·cm ), assigned to the A2g Ǟ
3
3
3
T1g and the A Ǟ T dϪd transitions, respectively. The
2g
2g
Ϫ1
Δ value was calculated as 11300 for 1 and 11230 for 2 cm
o
[
22]. The absorption bands below 350 nm are due to intra-
ligand transitions.
Table 3. Crystal data and structure refinements for 1 and 2.
1
2
Infrared Spectra of 1 and 2
Empirical formula
Temperature /K
Crystal system
Space group
Unit cell dimensions
a
NiC11
296 (2)
triclinic
H O N
22 6 4
2
·H O
30 6 4
NiC15H N O
The most significant frequencies in the IR spectra of 1
and 2 are given in Table 2. The broad band at 3383 cm
is characteristic of water molecules involved in moderately
strong hydrogen bonding. The observed NH stretching fre-
296 (2)
monoclinic
P2 /c
Ϫ1
¯
P1
1
2
8.491 (1)
10.086 (1)
18.667 (1)
11.621 (1)
Ϫ1
quencies in the region 3447Ϫ3415 cm clearly reveal the
b
10.206 (1)
11.570 (1)
68.198 (5)
70.022 (5)
75.826 (5)
866.9 (1)
2
1.16
1.467
2.58Ϫ27.89
presence of dmpen ligand in 2. The bands at 3132 and c /A˚
Ϫ1
3
280 cm are attributed to the NH stretching vibration in
Ͱ
β
2
Ϫ
118.171 (3)
the HOr ligand for 1 and 2, respectively. The weak bands
γ /°
Ϫ1
Ϫ1
between 3074Ϫ2853 cm for 1 and 3157Ϫ2874 cm for 2
are due to the ν(CϪH) vibrations. The position of carbonyl
3
˚
V /A
1928.6 (2)
4
1.04
1.437
1.99Ϫ27.98
Z
Ϫ1
and carboxylate groups of orotate moiety can be used to Absorption coefficient /mm
Ϫ3
Dcalc /mg·m
characterize the coordination mode. The carbonyl
Theta range for data
stretching bands of the free orotic acid observed at 1729
collection /°
Ϫ1
Ϫ1
and 1719 cm
(νCϭO(acid)ϩνC(2)ϭO) and at 1700 cm
Measured reflections
18759
32322
[
νC(6)ϭOϩνring] [23]. These bands appear as strong broad Independent reflections
4051 [Rint ϭ 0.043]
11, 13, 15
4579 [Rint ϭ 0.053]
13, 24, 15
Integration X-RED
Integration
Ϫ1
bands at 1636 cm , as a broad band in 1, and at 1653 and h / k / l
1
Ϫ1
Absorption correction
Refinement method
Final R indices [F >2σ(F )]
623 cm in 2. These shifts indicate that the orotate li-
gands are coordinated as bidentate ligands. The bands with
2
2
R
1
ϭ 0.052,
wR ϭ 0.152
1.02
0.42; Ϫ0.50
R
1
ϭ 0.030,
wR ϭ 0.078
1.04
0.28; Ϫ0.33
strong intensity around 1575 cmϪ1 correspond to the
2
2
ν(CϭC) vibrations of the pyrimidine ring of orotate, whereas Goodness-of-fit on F2
the ν(
1
Largest difference peak and
hole /e·A
vibrations are observed at approximately
466 cm in both complexes.
CϭN)
Ϫ1
˚
Ϫ3
578
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 577Ϫ581

Vitamin B13 Complexes of Nickel(II) with Diamines
sphere. An additional uncoordinated water molecule is pre-
sent in the structure. The NiϪN
bond lengths are
tmen
˚
˚
2
.154(2) and 2.144(2) A. The NiϪN
[2.073(2) A] and
HOr
˚
NiϪOHOr [2.026(1) A] bond lengths are noticeably longer
than those found in [Ni(HOr)(H O)(4-mim) ] ·5H O
2
3 2
2
˚
2.084(2) and 2.078(2) A] [11] and [NiHOr(H O) (ata) ]
2 2 2
2.108(2) and 2.100(2) A] [24], and somewhat shorter than
[
[
˚
the values reported for [Ni(HOr)(H O) ]·H O [25] [2.049(3)
2
4
2
˚
and 2.023(3) A]. The orotato intraligand bond lengths are
Figure 1. Ortep III view of 1 with the atom numbering scheme.
Displacement ellipsoids are drawn at the 50 % probability level. For comparable with those in similar nickel complexes [11, 19,
clarity, only the major part of the disordered fragment is shown.
2
[
4Ϫ26]. The discrepancy between the carboxylate C7ϪO3
˚ ˚
1.261(2) A] and C7ϪO4 [1.234(2) A] distances reflects the
coordination as well as the participation in hydrogen bond-
ing.
The details of hydrogen bonding are given in Table 5.
Crystal Structures of 1 and 2
Ni(HOr)(H O) (tmen)]·H O (1)
[
2
2
2
The details of the crystal structure are given in Table 3. Both water molecules (coordinated and uncoordinated)
Selected bond lengths and angles are given in Table 4. The participate in hydrogen bonding of O···O type (ranging
˚
crystal structure of the complex is presented in Figure 1. In from 2.680 to 2.793 A), whereas the orotato ligands are in-
˚
the structure two water molecules, the orotato dianion and cluded in the hydrogen bonds of N···O type (2.859 (2) A].
tmen act as ligands, saturating the metal coordination Each of the HOr ligand is doubly hydrogen-bonded to a
Ϫ
corresponding HOr2 ligand. These DA:AD-type hydrogen
bonds involve the pyrimidine carbonyl oxygen atom and the
˚
Table 4. Selected bond lengths /A and angles /° for 1 and 2.
Compound 1
i
˚
i
amide NϪH group [N(3)···O(5) 2.859(2) A, H(3)···O(5)
˚
i
2.00 A, N(3)ϪH(3)···O(5) 174°; i: Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ
1]. A strong intramolecular hydrogen bond connects O1-
H1A···O6 (2.630 (2)) and O7ϪH7A···O5 (2.702 (2) A] (Fig-
Ni1ϪO3
Ni1ϪN4
Ni1ϪO1
Ni1ϪO2
Ni1ϪN2B
Ni1ϪN2A
2.026(1)
2.073(2)
2.106(1)
2.130(2)
2.144(2)
2.145(2)
Ni1ϪN1A
Ni1ϪN1B
O3ϪC7
O4ϪC7
O5ϪC10
O6ϪC11
2.154(2)
2.154(2)
1.261(2)
1.234(2)
1.246(2)
1.251(2)
˚
ure 2).
Compound 2
Ni1ϪN3A
Ni1ϪO4
Ni1ϪN5
Ni1ϪN4A
Ni1ϪN6
Ni1ϪN1
2.078(6)
2.082(1)
2.084(1)
2.089(3)
2.112(1)
2.124(1)
Ni1ϪN4B
Ni1ϪN3B
O1ϪC1
O2ϪC2
O3ϪC5
2.170(4)
2.193(9)
1.239(2)
1.237(2)
1.233(2)
1.269(2)
O4ϪC5
Compound 1
O3ϪNi1ϪN4
O3ϪNi1ϪO1
N4ϪNi1ϪO1
O1ϪNi1ϪN2A
N4ϪNi1ϪO1
O1ϪNi1ϪO2
O3ϪNi1ϪN1A
O2ϪNi1ϪN1A
80.06(5)
170.80(6)
92.20(6)
93.64(8)
92.20(6)
87.70(7)
94.73(8)
171.30(8)
O3ϪNi1ϪO2
87.61(6)
96.72(9)
94.00(7)
91.93(6)
91.09(8)
173.99(7)
86.91(8)
84.57(9)
N4ϪNi1ϪN1A
O3ϪNi1ϪN2A
N4ϪNi1ϪO2
O1ϪNi1ϪN1A
N4ϪNi1ϪN2A
O2ϪNi1ϪN2A
N2AϪNi1ϪN1A
Compound 2
N3AϪNi1ϪO4
N3AϪNi1ϪN5
O4ϪNi1ϪN5
N3AϪNi1ϪN4A
O4ϪNi1ϪN4A
N5ϪNi1ϪN4A
N3AϪNi1ϪN6
O4ϪNi1ϪN6
N5ϪNi1ϪN6
N4AϪNi1ϪN6
N3AϪNi1ϪN1
O4ϪNi1ϪN1
N5ϪNi1ϪN1
N4AϪNi1ϪN1
89.9(4)
93.5(4)
175.0(1)
89.9(2)
83.0(1)
100.6(1)
175.8(4)
86.0(1)
90.7(1)
88.8(1)
86.1(1)
78.8(1)
97.7(1)
161.3(1)
N6ϪNi1ϪN1
93.9(1)
84.6(2)
96.7(1)
87.4(1)
14.7(1)
95.1(1)
169.6(1)
0.1(8)
89.8(5)
93.5(5)
89.9(2)
175.7(5)
86.0(2)
84.6(2)
N3AϪNi1ϪN4B
O4ϪNi1ϪN4B
N5ϪNi1ϪN4B
N4AϪNi1ϪN4B
N6ϪNi1ϪN4B
N1ϪNi1ϪN4B
N3AϪNi1ϪN3B
O4ϪNi1ϪN3B
N5ϪNi1ϪN3B
N4AϪNi1ϪN3B
N6ϪNi1ϪN3B
N1ϪNi1ϪN3B
N4BϪNi1ϪN3B
Figure 2. Packing diagram of 1 viewed along [-100].
[Ni(HOr)(dmpen) ] (2)
2
The molecular structure is shown in Figure 3 and selected
bond lengths and bond angles are given in Table 4. In the
II
complex, the Ni ion exhibits a distorted octahedral coordi-
nation defined by four nitrogen atoms from two chelating
dmpen ligands together with the bidentate orotato ligand.
Z. Anorg. Allg. Chem. 2009, 577Ϫ581
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
579

O. Z. Ye s¸ ilel, H. Erer, N. Dege, O. Büyükgüngör
ARTICLE
Table 5. Hydrogen-bonding lenghts and angles for 1 and 2.
˚
˚
˚
DϪH···A
d(DϪH) /A
d(H···A) /A
d(D···A) /A
<(DHA) /°
Graphset Descriptor
Complex 1
N3ϪH3···O5i
O1ϪH1A···O6
0.86
2.00
2.859(2)
2.630(2)
2.793(3)
2.793(2)
2.680(2)
2.702(2)
2.758(2)
174
R
2(8)
S(6)
2
0.77(4)
0.85(3)
0.82(3)
0.78(3)
0.78(3)
0.83(3)
1.87(4)
1.96(3)
2.00(3)
1.91(3)
1.97(3)
1.93(3)
168(3)
169(3)
163(3)
174(3)
157(3)
170(3)
ii
1
O1ϪH1B···O7
O2ϪH2B···O7
O2ϪH2A···O4
O7ϪH7A···O5
R
2
R
2
R
2
R
2
R
2
(6)
ii
iii
1
2
4
4
(6)
(12)
(16)
(16)
i
O7ϪH7B···O6
Symmetry codes: (i) Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 1; (ii) x, yϪ1, z; (iii) Ϫx ϩ 2, Ϫy ϩ 1, Ϫz.
Complex 2
N2ϪH2···O3i
N5ϪH5A···O2
N5ϪH5B···O1
0.86
0.90
0.90
2.18
2.19
2.11
3.007(2)
2.970(2)
2.912(2)
162
144
149
C(7)
C(7)
S(6)
ii
Symmetry codes: (i) x, Ϫy ϩ 1/2, z ϩ 1/2; (ii) x ϩ 1, Ϫy ϩ 1/2, z ϩ 1/2.
The NiϪN3/N4/N5/N6 distances are different from each
The crystal packing is stabilized by intra- and intermolec-
˚
other and lie in a wide range [2.078(6)Ϫ2.193(9) A]. The ular hydrogen bonding between the N2ϪH2, N5ϪH5
II
orotato ligand is coordinated to the Ni ion through nitro- atoms from dmpen and O1, O2, and O3 atoms form the
˚
i
ii
gen and oxygen atoms [Ni1ϪO4 ϭ 2.082(1) A and orotato ligand [N2···O3 ϭ 3.007(2), N5···O2 ϭ 2.970(2)
˚
˚
NiϪN1 ϭ 2.124(1) A]. The angle O4ϪNi1ϪN5 [175.00(5)°] and N5···O1 ϭ 2.912(2) A, (i) x, Ϫy ϩ 1/2, z ϩ 1/2;
is virtually linear, whereas N1ϪNi1ϪN4 [169.61(11)°] and (ii) x ϩ 1, Ϫy ϩ 1/2, z ϩ 1/2] (Figure 4).
N4ϪNi1ϪN1 [161.29(11)°] deviate much from linearity. On
this basis, atoms O4, N1, N4 and N5 can be chosen to form
the basal plane of the octahedron, and the equatorial posi-
tions are occupied by atoms N3 and N6. The equatorial
plane and the orotato ligand are approximately planar. The
Ni1ϪN1 and Ni1ϪO4 bond lengths are similar to that
II
found in other Ni -orotato complexes [11, 24, 25] and the
angle of N1ϪNi1ϪO4 [78.77(5)°] is nearly equal with pre-
viously reported complexes [11, 24, 25].
Figure 4. Packing diagram of 2 viewed along [-100].
Experimental Section
Materials and Measurements
All chemicals used were of analytical reagent grade and were com-
mercially purchased. IR spectra were obtained with a Bruker Ten-
sor 27 FT-IR spectrometer using KBr pellets in the
Ϫ1
4
000Ϫ400 cm range. Elemental analyses for C, H and N were
performed by using a Carlo Erba 1106 microanalyzer. Magnetic
susceptibility measurements at room temperature were performed
by using a Sherwood Scientific MXI model Gouy magnetic bal-
ance. The UV/Vis spectra were obtained for aqueous solutions of
Ϫ3
the complexes (10 m) with a Unicam UV2 spectrometer in the
Figure 3. Ortep III view of 2 with the atom numbering scheme.
Displacement ellipsoids are drawn at the 50 % probability level. For range 900Ϫ190 nm. A PerkinϪElmer Diamond TG/DTA Thermal
clarity, only major part of disordered fragment is shown. Analyzer was used to record simultaneous TG, DTG and DTA
580
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 577Ϫ581

Vitamin B13 Complexes of Nickel(II) with Diamines
curves in static air atmosphere at a heating rate of 10 °C·minϪ1 in
the temperature range 20Ϫ1000 °C using platinum crucibles.
Acknowledgement
The authors acknowledge the Faculty of Arts and Sciences,
Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS-
II diffractometer (purchased under grant F.279 of the University
Research Fund).
Preparation of 1 and 2
A solution of tmen (0.58 g, 5 mmol) or dmpen (0.51 g, 5 mmol) in
water (10 mL) was added dropwise with stirring to a solution of
2 4 2
[Ni(HOr)(H O) ]·H O [14] (0.76 g, 2.5 mmol) in distilled water
(25 mL). The solutions were heated to 60 °C in a temperature-con-
trolled bath and stirred for 5 h at 60 °C. Afterwards, the reaction
mixtures were cooled to room temperature. The blue Ni complex
References
II
crystals were filtered and washed with cool distilled water (15 mL)
[1] I. Leberman, A. Kornberg, E. S. Simms, J. Biol. Chem. 1955,
215, 403.
and acetone, and dried in air. C11
C 34.49, H 6.32, N 14.63 %; found: C 34.42, H 6.33, N 14.76 %.
Ni (417.13): calculated C 43.19, H 7.25, N 20.15 %;
24 4 7
H N O Ni (383.02): calculated
[
[
[
[
2] A. Lehninger, Principles of Biochemistry Worth Publishers,
New York, 1970, p. 661.
15 30 6 4
C H N O
3] H. Schmidbaur, H. G. Classen, J. Helbig, Angew. Chem. 1990,
found: C 43.21, H 7.23, N 20.15 %.
102, 1122.
4] P. Castan, S. Wimmer, E. Colacio-Rodriguez, A. L. Beau-
champ, J. Inorg. Biochem. 1990, 38, 225.
5] C. P. Raptopoulou, V. Tangoulis, V. Psycharis, Inorg. Chem.
Crystallographic Analysis
Single-crystal X-ray data were collected with a Stoe X-AREA
2000, 39, 4452.
single crystal diffractometer using monochromated MoK
α
radi-
[6] X. Li, R. Cao, D. Sun, Q. Shi, M. Hong, Y. Liang, Inorg.
Chem. Commun. 2002, 5, 589.
[7] T. T. B. Ha, A. M. Larsonneur-Galibert, P. Castan, J. Jaud, J.
Chem. Crystallogr. 1999, 29, 565.
ation at 296 K. The structures were solved by direct methods and
conventional Fourier methods. The program used for cell refine-
ment was Stoe X-AREA [27], SHELXS-97 and SHELXL-97 [28]
were used for solving and refining the structures. Molecular
graphics: ORTEP-3 for Windows [29]. Software used to prepare
material for publication: wingx [29] publication routines. Further
details concerning data collection and refinement are given in
Table 3.
[
[
[
[
8] S. Bekiroglu, O. Kristiansson, J. Chem. Soc., Dalton Trans.
2002, 1330.
9] X. Li, R. Cao, D. Sun, Q. Shi, W. Bi, M. Hong, Inorg. Chem.
Com. 2003, 6, 815.
10] H. Ölmez, H. I c¸ budak, O. Z. Yesilel, C. Arıcı, D. Ülkü, Z.
Kristallogr. 2004, 219, 300.
11] O. Z. Ye s¸ ilel, M. S. Soylu, H. Ölmez, O. Büyükgüngör, Poly-
hedron 2006, 25, 2985.
Inspection of the displacement ellipsoids of tmen ligand in com-
pound 1 and dmpen ligand in compound 2 shows a large aniso-
tropy of the ligand atoms. This suggests that the two ligand atoms
[12] I. U c¸ ar, A. Bulut, O. Z. Yesilel, H. Ölmez, O. Büyükgüngör,
Acta Crystallogr., Sect. C 2004, 60, m563.
show positional disorder, therefore, a split model is necessary. The [13] D. A. Kose, B. Zumreoglu-Karan, C. Unaleroglu, O. Sahin, O.
Büyükgüngör, J. Coord. Chem. 2006, 59, 2125.
disordered atoms of the two ligands were modelled over two orien-
tations and the refined site-occupancy factors of the disordered
parts, viz. (N1A/N2A/C1AϪC6A)/(N1B/N2B/C1BϪC6B) and
[
[
[
14] A. Karipides, B. Thomas, Acta Crystalogr., Sect. C 1986, 42,
1705.
15] L. Xing, C. Rong, S. Dao-Feng, H. Mao-Chun, Chin. J. Struct.
Chem. 2002, 21, 374.
16] M. J. Plater, M. R. S. J. Foreman, J. M. S. Skakle, R. A. Howie,
Inorg. Chim. Acta 2002, 332, 135.
[17] O. Z. Ye s¸ ilel, E. S¸ ahin, Z. Anorg. Allg. Chem. 2007, 633, 1087.
18] D. Sun, R. Cao, Y. Liang, M. Hong, Y. Zhao, J. Weng, Aust.
(N3A/N4A/C6AϪC10A)/(N3B/N4B/C6BϪC10B), are 0.679(3)/
0.321(3) % and 0.572(3)/0.428(3) %, respectively. The disordered
atoms were refined by using the following restraints: SIMU, DELU
and SADI [28].
[
In compound 1, the five-membered chelate ring formed by atoms
J. Chem. 2002, 55, 681.
˚
Ni1/O3/C7/C8/N4 is planar [maximum deviation Ϫ0.021(3) A for
[19] I. Mutikainen, Finn. Chem. Lett. 1985, 5, 193.
[20] L. R. Falvello, D. Ferrer, T. Soler, M. Tom a´ s, Acta Crystallogr.,
Sect. C 2003, 59, m149.
atom N4], whereas the other five-membered chelate ring formed
by atoms Ni1/N1/C3/C4/N2 is twisted on the C3ϪC4 bond with
˚
[21] O. Z. Ye s¸ ilel, H. Ölmez, J. Ther. Anal. Calorim. 2006, 86, 211.
puckering parameters [30] of Q ϭ 0.4560 A and ϕ ϭ 267.10° for
[
[
[
22] D. Sutton, Electronic Spectra of Transition Metal Complexes,
McGraw-Hill, London, 1968, pp. 208.
23] A. Hernanz, F. Billes, I. Bratu, R. Navarro, Biopolymers
the atom sequence Ni1/N1A/C3A/C4A/N2A and with puckering
˚
parameters of Q ϭ 0.4466 A and ϕ ϭ 93.99° for the atom sequence
Ni1/N1B/C3B/C4B/N2B. In compound 2, the five-membered che-
(Biospectroscopy) 2000, 57, 187.
late ring formed by atoms Ni1/O4/C5/C4/N1 is planar [maximum
24] O. Z. Ye s¸ ilel, K. Akda gˇ , H. Pa s¸ ao gˇ lu, O. Büyükgüngör, Z.
Naturforsch. 2007, 62b, 818.
˚
deviation Ϫ0.038(3) A for atom N1], whereas the two six-mem-
bered chelate rings formed by atoms Ni1/N3/C6/C7/C8/N4 and
Ni1/N5/C11/C12/C13/N6 adopt a chair conformation as is evident
from the puckering parameters: Q ϭ 0.5598 A, θ ϭ 12.36° and ϕ ϭ
˚
1
0
85.17° for the atom sequence Ni1/N3A/C6A/C7A/C8A/N4A, Q ϭ
˚
.8396 A, θ ϭ 93.61° and ϕ ϭ 101.47° for the atom sequence Ni1/
˚
N3B/C6B/C7B/C8B/N4B, and Q ϭ 0.5280 A, θ ϭ 158.75° and ϕ ϭ
356.15° for the atom sequence Ni1/N5/C11/C12/C13/N6.
Crystallographic data for the structure reported here have been de-
posited (CCDC-638270 for 1 and -656858 for 2). Copies of the data
can be obtained free of change from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Z. Anorg. Allg. Chem. 2009, 577Ϫ581
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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