Vitamin B13 complexes of nickel(II) and copper(II) with ethanolamine: Syntheses, crystal structures, spectroscopic and thermal studies

Article abstract of DOI:10.1002/zaac.200700049

Fac-bis(ethanolamine)orotatonickel(II), [Ni(HOr)(ea)₂] and mer-bis(ethanolamine)orotatocopper(II) dihydrate, [Cu(HOr)(ea)₂] ·2H₂O were synthesized and characterized by elemental analysis, FT-IR, UV-Vis Spectroscopy and thermal analysis. In addition, their solid-state structures were determined by single crystal X-ray diffraction studies. Both the fac-[Ni(HOr)(ea)₂] (1) and mer[Cu(HOr)(ea) ₂]·2H₂O (2) complexes are isomorphous and crystallize in the triclinic space group P1 The Ni²⁺ and Cu²⁺ ions are coordinated by two neutral ea ligands and one orotate dianion in a distorted octahedral fashion. The ea ligand acts as a bidentate donor through the amine N and hydroxyl O atoms, while orotate dianion is coordinated through deprotonated N3 pyrimidine atom and carboxylate oxygen atom as a bidentate ligand. Thermal decompositions of the complexes are studied in over the range 20-600°C on heating in a static air atmosphere.

Full text of DOI:10.1002/zaac.200700049

DOI: 10.1002/zaac.200700049
Vitamin B13 Complexes of Nickel(II) and Copper(II) with Ethanolamine:
Syntheses, Crystal Structures, Spectroscopic and Thermal Studies
Okan Zafer Yesilela,* and Ertan Sahinb
¸
¸
a Eskis¸ehir/Turkey, Eskis¸ehir Osmangazi University, Faculty of Arts and Sciences, Department of Chemistry
b Erzurum/Turkey, Atatürk University, Faculty of Arts and Sciences, Department of Chemistry
Received January 18th, 2007.
Abstract. Fac-bis(ethanolamine)orotatonickel(II), [Ni(HOr)(ea)2] and
mer-bis(ethanolamine)orotatocopper(II) dihydrate, [Cu(HOr)(ea)2]·
2H2O were synthesized and characterized by elemental analysis,
FT-IR, UV-Vis Spectroscopy and thermal analysis. In addition,
their solid-state structures were determined by single crystal X-ray
diffraction studies. Both the fac-[Ni(HOr)(ea)2] (1) and mer-
a distorted octahedral fashion. The ea ligand acts as a bidentate
donor through the amine N and hydroxyl O atoms, while orotate
dianion is coordinated through deprotonated N3 pyrimidine atom
and carboxylate oxygen atom as a bidentate ligand. Thermal de-
compositions of the complexes are studied in over the range
20Ϫ600 °C on heating in a static air atmosphere.
[Cu(HOr)(ea)2]·2H2O (2) complexes are isomorphous and crys-
2ϩ
tallize in the triclinic space group P1. The Ni and Cu2ϩ ions are
Keywords: Nickel; Copper; Ethanolamine; Orotic acid; Orotato
¯
coordinated by two neutral ea ligands and one orotate dianion in
complexes; Vitamin B13
1 Introduction
25], 1,10-phenanthroline-N,N [14, 26, 27], triethanolamine-
N,O,OЈ [28], triethanolamine-N,O,OЈ,OЉ [29] appear in re-
cent literature. In some transition metal complexes, the
orotate ligand acts as a counter ion [30Ϫ34].
In the present paper, we describe the syntheses, spectro-
scopic, thermal behavior and crystal structure of the new
vitamin B13 complexes of nickel(II) and copper(II) with
ethanolamine (Scheme 1 b.).
Vitamin B13 (C5H4N2O4, 1,2,3,6-tetrahydro-2,6-dioxo-4-
pyrimidine carboxylic acid or orotic acid, Scheme 1 a.) and
other derivatives are of great importance in biological sys-
tems and are found in cell and body fluids of many living
organisms [1Ϫ3]. In the last years, search in bioinorganic
chemistry has revealed the important role of metal ions in
most biological processes. Nickel, magnesium, palladium
and platinum orotate complexes have been screened as
therapeutic agents for cancer [4, 5]. Orotic acid (H3Or) is
also an interesting ligand in coordination chemistry. It may
coordinate through the two nitrogen atoms of the pyrim-
idine ring, the two carbonyl oxygen atoms and the carboxyl
group. In all the cases described so far, coordination of or-
otic acid is coordinated to a different metal atom and either
mono-dimensional chain or bi-dimensional or tri-dimen-
sional polymers are obtained. Diaqua, triaqua and tetra-
aqua complexes of H2OrϪ and HOr2Ϫ with transition met-
als were reported [6Ϫ15]. Synthesis and structural charac-
terization of mixed-ligand transition metal complexes of
HOr2Ϫ with mono-, bi-, tri- and tetradentate N- and/or
O- donor ligands such as imidazole-N [16], 4(5)-methylimi-
dazole-N [17], nicotinamide [18, 19], amine-N [5, 20Ϫ22],
ethylenediamine-N,N [11, 23], 2,2Ј-bipyridine-N,N [14, 24,
Scheme 1 Structures of the ligands: (a) Vitamin B13 (b) Ethanol-
amine
2 Results and Discussion
2.1 UV-vis spectra and magnetic susceptibility
* Okan Zafer Yes¸ilel
Eskis¸ehir Osmangazi University,
Faculty of Arts and Sciences,
Department of Chemistry,
TRϪ26480, Eskis¸ehirϪTurkey
EϪmail: yesilel@ogu.edu.tr
Tel.: ϩ90 222 2393750
The UV-vis spectra of 1 in H2O display three absorption
bands at 402 (ε ϭ 78 LmolϪ1cmϪ1), 604 (ε ϭ 28
LmolϪ1cmϪ1) and 889 nm (ε ϭ 13 LmolϪ1cmϪ1). These
3
3
3
3
values were assigned to A2g Ǟ T1g (P), A2g Ǟ T1g and
3A2g Ǟ 3T2g, respectively. The ∆o value for 1 was calculated
Z. Anorg. Allg. Chem. 2007, 633, 1087Ϫ1093
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O. Z. Yes¸ilel, E. S¸ahin
as 11,249 cmϪ1. However, the electronic spectrum of 2 exhi-
2.3 Thermal analyses
bit an absorption band at 638 nm (ε ϭ 53 LmolϪ1cmϪ1
)
The thermal decomposition behavior of the complexes was
followed up to 600 °C in static air atmosphere. TG, DTG
and DTA curves for 1 and 2 are presented in Figures 1 and 2.
2
due to a dϪd transition (2B1g
Ǟ
2Eg, B1g
Ǟ
2B2g and
2B1g Ǟ A1g lie within one broad envelope). The ∆o value
2
for the complex was calculated as 15,674 cmϪ1
.
The complexes 1 and 2 exhibit the magnetic moment val-
ues of 2.77 and 1.61 BM which corresponds to two and one
unpaired electrons, respectively, which are consistent with a
weak field octahedral coordination as expected.
Fac-[Ni(HOr)(ea)2]
The NiII complex is thermally stable up to 242 °C and then
begins to decompose (Fig. 1.). The decomposition of 1.5
moles ea ligands takes place in the temperature range
243Ϫ335 °C with an endothermic DTA peak at 317 °C
(found 26.68, calcd. 27.35 %). In the [Ni(sac)(ea)2] complex,
this type of behaviors has been reported earlier [38] (where
sac ϭ saccharinate ion). The decomposition of the HOrϪ
and residue ea ligand occurs between 373 and 457 °C with
extremely exothermic DTA peak at 453 °C. The final green-
yellow product of the thermal decomposition was identified
as NiO. The total mass loss observed is 76.70 %, in agree-
ment with the expected value (77.00 %).
2.2 Infrared spectra
The most important IR absorption bands of the complexes
are listed in Table 1. The strong band at 3484 cmϪ1 is
characteristic for the OH stretching vibration of the water
molecules in 2. The observed strong bands at 3314 cmϪ1
for 1 and 3322 cmϪ1 for 2, respectively, are assigned to the
hydroxyl group of ea ligand. The stretching bands for NH2
group of ea ligand appear at 3289 cmϪ1 for 1 and 3283,
3238 cmϪ1 for 2. The weak band at 3183 cmϪ1 for 1 and
3158 cmϪ1 for 2 correspond to the stretching vibration of
the N(1)H group of HOr ligand. The relatively weak bands
2945Ϫ2972 cmϪ1 region are assigned to the CH stretching
vibration of ea and HOr ligands. The νN(3)H and νOHacid
Mer-[Cu(HOr)(ea)2]·2H2O
The CuII complex shows a seven step mass loss and the first
steps in the 46Ϫ98 °C temperature range corresponds to the
endothermic elimination of two moles crystal water mol-
ecules (found 9.61, calcd. 9.59 %). The ea ligands decom-
pose consecutive two stages; between 140Ϫ190 °C the com-
plex decompose 0.5 mole ea ligand with two endothermic
and one exothermic effect on DTA (149, 165 and 184 °C,
found 9.32, calcd. 8.13 %) and in the temperature range of
191Ϫ295 °C (DTA ϭ 255 °C), 22 % weight loss was ob-
served in the complex, which correspond to the release of
1.5 moles ea ligands (Calcd 24.38). This type of decompo-
sition behavior in the [Cu(sac)(ea)2] [38], [Cu(ox)(ea)2] [39]
and [Cu(sq)(ea)2]n [40] complexes has been reported (sac ϭ
saccharinate, ox ϭ oxalate, sq ϭ squarat). The last de-
composition stage between 296 and 495 °C is due to de-
composition of the HOrϪ ligand release CO/CO2 [17]
(found 35.85, calcd. 36.74 %) to form CuO. The overall
mass loss 77.02 % (calcd. 78.84 %) agrees with the propose
structure well.
vibration of H3Or appeared at 3154 and ca. 2500 cmϪ1
,
respectively, are disappeared in the both complexes. The
carbonyl stretching bands of orotic acid observed at 1729,
1719 cmϪ1 of [νCϭO(acid)ϩνC(2)ϭO] and 1700, 1653 cmϪ1 of
[νC(6)ϭOϩνringϩνCϭC], respectively [35, 36]. These bands
overlapped in the complexes were shifted to 1674 and
1646 cmϪ1 for 2, while the [Ni(HOr)(ea)2] complex give a
strong single band at 1648 cmϪ1, indicating that orotate li-
gand coordinates to metal ions through carboxyl oxygen
and nitrogen atoms of pyrimidine ring as a bisdeprotonated
bidentate ligand. The ν(C(2)ϭO) bands shift towards lower
frequencies, when the orotate ligand coordinates through
N(3) atom of pyrimidine ring to the metal ions [14, 28, 29].
The weak bands observed in the 445Ϫ553 cmϪ1 region are
due to MϪO and MϪN stretching vibrations [37].
On the basis of the fist temperature of decomposition
stage of anhydrous complexes, thermal stability of the NiII
complex (243 °C) is higher than the CuII complex (140 °C).
This temperature were showed 162, 141 and 203 °C in the
[Cu(sac)2(ea)2] [38], [Cu(ox)(ea)2] [39] and [Cu(sq)(ea)2]n [40]
complexes, while decomposition temperature of ea molecule in
the [Ni(sac)2(ea)2] complex [38] was observed at 248 °C.
Table 1 Selected IR spectral data for 1 and 2 /cmϪ1 *
Assignment
H3Or
1
2
ν(OH)
Ϫ
Ϫ
Ϫ
Ϫ
3484 m
3322 s
3283, 3238 s
Ϫ
3158 m
2945-2972 w
Ϫ
ν(OH)ea
ν(NH2)
ν(N(3)H)
ν(N(1)H)
ν(CH)
3314 s
3289 s
Ϫ
3183 m
2881-2942 w
Ϫ
3154 m
3137 m
3099 s
2500 m, b
ν(OH)acid
2.4 Crystal structures
Fac-[Ni(HOr)(ea)2] (1)
ν(CϭOacidϩC(2)ϭO) 1729 vs, 1719 vs
1674 vs
ν(C(6)ϭOϩring)
ν(CϭC)
ν(CϪN), δ(N(1)H)
MϪO, MϪN
1700 vs
1653 vs
1435 s, b
1648 vs
1646 vs
Ǟ
·
·
1475 s
445Ϫ550 w
1483 s
448Ϫ553 w
Crystal structure of fac-bis(ethanolamine)orotatonickel(II)
with the atom labelling is shown in Figure 3. The complex
is described as a distorted octahedron. Each Ni2ϩ ion is
coordinated by two neutral ea ligands and one orotate di-
Ϫ
* Abbreviations: w Ϫ weak; m Ϫ medium; s Ϫ strong; vs Ϫ very strong, b
Ϫ broad.
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Vitamin B13 Complexes of Nickel(II) and Copper(II) with Ethanolamine
Fig. 1 TG, DTG and DTA curves of 1
Fig. 2 TG, DTG and DTA curves of 2
anion in distorted octahedron fashion. The ea ligand acts
as a bidentate donor through the amine N and hydroxyl O
atoms creating a five membered chelate ring. Orotate di-
anion is coordinated through deprotonated N3 pyrimidine
atom and carboxylate oxygen atom as a bidentate ligand.
The two NiϪOea and NiϪNea bond distances are almost
equivalent to each other [NiϪO1 2.090(3), NiϪO2 2.148(4),
[33] and 5.0(2) [32]]. The bond lengths of carbonyl groups
C8ϪO5 and C9ϪO6 are even less than the nickel(II) com-
˚
plex [Ni(HOr)(im)2(H2O)2] [1.257(2) and 1.252(2) A] [16].
The carboxylate groups (CϪO) are asymmetric due to the
˚
difference [1.252(5)Ϫ1.269(5) A] in coordination and par-
ticipation in the hydrogen bonding. Off all the nitrogen-car-
bon bonds in the uracilate ring of the orotate ligand, the
N3ϪC9 and N3ϪC6 bond lengths are the shortest, 1.358(5)
˚
NiϪN1 2.057(4), NiϪN2 2.085(4) A].
˚
˚
Orotate moiety is planar with slightly more rotated car-
boxylate group in the coordinated one [N3/C6/C5/O3 10.3°,
N3/C6/C5/O4 Ϫ167.6°]. This torsion angles indicate that
distortion of the orotate ligand caused by coordination to
and 1.360(5) A, respectively (N4ϪC9, 1.381(5) A). This
indicates a considerable π-electron delocalization within the
C7ϪC6ϪN3ϪC9 skeleton. The C2ϪN3 bond determined
˚
in this study, 1.381(5) A is longer than that reported pre-
viously, 1.368(4) A [15].
Ni2ϩ ion is more than in uncoordinated orotic acid [5.9(4)
˚
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www.zaac.wiley-vch.de
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O. Z. Yes¸ilel, E. S¸ahin
The crystal structure is stabilized through strong inter-
molecular hydrogen bonding involving the coordinated hy-
droxyl O atoms and amine groups of N atoms and orotate
N atom. Two orotate molecules are joined by two N4···O5
hydrogen bonds (Table 2), which leads to the formation of
centro-symmetric dimer of the title complex in the crystal
values are found to be longer than that of the related study
of [Cu(mea)2(ox)] [39], [Cu(sq)(ea)2] [40] and [Cu(sac)2(ea)2]
[42] (Table 5). The orotate intraligand bond lengths are
similar with those in the metal-HOr complexes [8, 11, 17].
Crystal structure of the complex was given in Figure 4b.
The water molecules complete the 3D dimension of the
complex through number of hydrogen bond interactions
(Table 4.). The hydrogen bonds are very close to linear. Lat-
tice water molecules stabilize the structure also with hydro-
gen bonds by playing the role of donors to the exocyclic
oxygen atoms.
˚
unit cell. The distance N4···O5 is 2.902(7) A and the hydro-
gen bonds are nearly linear (166°). Similar behaviours were
also reported in the work of Wysokinski et. al. [41] and
Uc¸ar et. al. [16]. The bond lengths and angles of hydrogen
bonding are listed in Table 3. The results obtained indicate,
that the extensive network of intermolecular hydrogen
bonds are of prime importance in the crystal packing. O6
oxygen atom of the orotic acid is also involved in intra-
molecular hydrogen bond with the coordinated amine N2
˚
atom, N2ϪH···O6 ϭ 2.855(6) A.
Fig. 3 (a) ORTEP view of facϪbis(ethanolamine)orotatonickel(II)
with displacement ellipsoids drawn at the 50 % probability level.
(b) Hydrogen bonded geometry. Dashed lines represent HϪbonds
Fig. 4 (a) The molecular structure of mer-[Cu(HOr)(ea)2]·2H2O,
showing the atomϪlabelling scheme. Displacement ellipsoids are
drawn at the 50 % probability level. (b) The crystal structure of
mer-[Cu(HOr)(ea)2]·2H2O, viewed down the c axis.
Mer-[Cu(HOr)(ea)2]·2H2O (2)
Figure 4 shows a drawing of the molecular complex. The
structure is similar to compound (1) except that complex
mer-[Cu(HOr)(ea)2] has two uncoordinated water molecules
3 Experimental
3.1 Materials and Measurements
All chemicals used were analytical reagent and were commercially
purchased. IR spectra were obtained with a Bruker Tensor 27 FT-IR
˚
in the structure. CuϪOHOr distance is 1.984(2) A, while the
˚
CuϪOea distances range from 2.477(2) to 2.526(2) A. These
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Vitamin B13 Complexes of Nickel(II) and Copper(II) with Ethanolamine
˚
Table 2 Crystal data and structure refinement for 1 and 2
Table 4 Selected bond lengths /A, and bond angles /° and hydro-
gen bonding geometry for 2
1
2
Cu1ϪO3
Cu1ϪN3
Cu1ϪO1
O2ϪC4
O4ϪC5
O1ϪC1
N3ϪC9
1.984 (2)
2.004(2)
2.477(2)
1.432(4)
1.226(3)
1.433(4)
1.362(3)
Cu1ϪN2
Cu1ϪN1
Cu1ϪO2
O6ϪC9
O3ϪC5
C5ϪC6
1.998(2)
2.033(2)
2.526(2)
1.233(3)
1.274(3)
1.518(3)
Chemical formula
Formula weight /gmolϪ1
Temperature /K
C9H16N4O6Ni
334.9
293(2)
C9H20N4O8Cu
375.8
293(2)
˚
Wavelength /A
0.71073
triclinic, P1
0.71073
triclinic, P1
¯
¯
Crystal system, space group
˚
Unit cell dimensions /A, °
a
b
c
7.935(5)
8.581(5)
11.086(6)
106.07(5)
109.38(6)
99.40(5)
656.58(25)
2
8.203(5)
8.240(5)
O3ϪCu1ϪN2
N2ϪCu1ϪN3
N2ϪCu1ϪN1
C5ϪO3ϪCu1
O4ϪC5ϪC6
173.45(8)
98.73(8)
93.34(9)
116.5(2)
119.8(2)
O3ϪCu1ϪN3
O3ϪCu1ϪN1
N3ϪCu1ϪN1
O4ϪC5ϪO3
81.54(7)
87.37(8)
165.56(8)
125.0(2)
12.781(6)
67.135(5)
76.918(5)
76.901(6)
766.05(20)
2
1.63
1.471
390
Ͱ
β
γ
3
˚
Volume /A
Z
Hydrogen bonds
Density (calculated) /mg/m3
1.69
Absorption coefficient /mmϪ1 1.510
DϪH···A
d(DϪH)
d(H···A)
d(D···A)
<DϪH···A
F(000)
348
Crystal size /mm
θ Range for collection /°
Index ranges
0.20, 0.17, 0.15
2.1Ϫ30.6
Ϫ10Յ h Յ11,
Ϫ12Յ k Յ12,
Ϫ15Յ l Յ15
19435
3991(Rintϭ0.118)
2647(I>2σ I)
186
0.18, 0.20, 0.25
2.6Ϫ30.5
Ϫ11Յ h Յ11,
Ϫ11Յ k Յ11,
Ϫ18Յ l Յ18
22914
4679(Rintϭ0.055)
3941(I>2σ I)
208
O1ϪH···O4i
0.82
0.87
0.82
0.86
0.98
0.92
0.94
0.94
0.93
0.91
0.90
1.92
2.23
2.00
2.00
1.96
1.90
1.99
2.54
1.96
1.85
1.94
2.701(4)
3.063(4)
2.750(3)
2.842(4)
2.921(4)
2.798(4)
2.827(4)
3.197(3)
2.792(4)
2. 749(4)
2.827(4)
158
161
151
165
166
165
147
128
149
173
167
N2ϪH···O8W
O2ϪH···O3ii
N4ϪH···O8Wiii
N1ϪH···O5iv
O7WϪH···O6iii
N2ϪH···O6
Refl. Collected
Independent reflections
Observed reflections
Parameters
N2ϪH···O6iii
O8WϪH···O5iv
O8WϪH···O7Wv
O7WϪH···O1
GoodnessϪofϪfit on F2
Final R indices [I >2σ(I)]
1.104
1.084
R1ϭ0.069, wR2ϭ0.176 R1ϭ0.040, wR2ϭ0.095
0.627 and 1.049
Ϫ3
˚
Largest diff. peak and hole /A
0.410 and 0.554
Symmetry transformations used to generate equivalent atoms; (i) ϭ
Ϫx,1Ϫy,1Ϫz; (ii) ϭ Ϫx, Ϫy,1Ϫz; (iii) ϭ Ϫx,1Ϫy, Ϫz; (iv) ϭ 1ϩx, Ϫ1ϩy,z;
(v) ϭ 1Ϫx,1Ϫy,Ϫz
˚
Table 3 Selected bond lengths /A, and bond angles /° and hydro-
gen bonding geometry for 1
model Gouy magnetic balance. The UV-Vis. spectra were obtained
for the aqueous solution of the complex (10Ϫ3 M) with a Unicam
UV2 spectrometer in the range 900Ϫ190 nm. Diamond TG/DTA
thermal analyzer was used to record simultaneous TG, DTG and
DTA curves in the static air atmosphere at a heating rate of
10 KminϪ1 in the temperature range 20Ϫ600 °C using platinum
crucibles.
NiϪN3
NiϪN2
NiϪO1
O2ϪC4
O3ϪC5
N4ϪC9
2.045(3)
2.085(4)
2.090(3)
1.433(6)
1.269(5)
1.381(5)
NiϪN1
NiϪO3
NiϪO2
O4ϪC5
N4ϪC8
N3ϪC6
2.057(4)
2.088(3)
2.148(4)
1.252(5)
1.379(5)
1.360(5)
N3ϪNiϪN1
N1ϪNiϪN2
N1ϪNiϪO3
N3ϪNiϪO1
N2ϪNiϪO1
N2ϪNiϪO2
95.0(2)
100.6(2)
94.7(2)
171.1(2)
91.9(2)
81.44(10)
N3ϪNiϪN2
N3ϪNiϪO3
N2ϪNiϪO3
N1ϪNiϪO1
O3ϪNiϪO1
96.4(2)
79.3(1)
164.4(2)
80.2(2)
93.5(2)
3.2 Preparation of the Complexes
A solution of ethanolamine (0.25 g, 4 mmol) in isopropanol (5 mL)
was added dropwise upon stirring to
a
solution of
Hydrogen bonds
[M(HOr)(H2O)4]·H2O (M ϭ NiII [10] and CuII [11] (2 mmol, 0.61 g
for NiII and 0.62 g for CuII in isopropanol (20 mL). The solution
was heated to 50 °C in a temperature-controlled bath and stirring
for 4 h at 50 °C. The reaction mixture was then slowly cooled to
room temperature. The blue crystals formed were filtered and
washed with 5 mL of ethanol and dried in air. Fac-[Ni(HOr)(ea)2]
Yield ca. 67.5 %; dp 299 °C. Anal. Calcd. for [Ni(C5H2N2O4)-
(C2H7NO)2] (C9H16N4O6Ni, 334.94 gmolϪ1) (%): C, 32.27; H, 4.81;
N, 16.73. Found: C, 32.57; H, 4.82; N, 16.71 and mer-
[Cu(HOr)(ea)2]·2H2O. Yield ca. 71 %; dp 33 °C. Anal. Calcd.
for [Cu(C5H2N2O4)(C2H7NO)2]·2H2O (C9H20N4O8Cu, 375.83
gmolϪ1) (%): C, 28.76; H, 5.36; N, 14.71. Found: C, 28.67; H, 5.04;
N, 14.76
D؊H···A
d(D؊H)
d(H···A)
d(D···A)
<D؊H···A
N1ϪH···O6i
N1ϪH···O5ii
O1ϪH···O4iii
N2ϪH···O6
N2ϪH···O4iv
O2ϪH···O3iii
N4ϪH···O5v
C1ϪH···O5vi
C1ϪH···O6vii
0.90
0.90
0.74
0.90
0.90
0.87
1.07
0.97
0.97
2.16
2.16
1.96
2.16
2.27
1.90
1.85
2.45
2.56
2.988(6)
3.036(6)
2.681(6)
2.855(6)
3.133(6)
2.749(6)
2.902(7)
3.320(8)
3.326(9)
152
163
165
133
162
164
166
149
136
Symmetry transformations used to generate equivalent atoms; (i) ϭ Ϫx,1Ϫy,
Ϫz; (ii) ϭ Ϫx, 2Ϫy, Ϫz; (iii) ϭ Ϫx, 2Ϫy,1Ϫz; (iv) ϭ x, Ϫ1ϩy, z; (v) ϭ 1Ϫx,
2Ϫy, Ϫz ; (vi) ϭ Ϫ1ϩx, Ϫ1ϩy, z; (vii) ϭ Ϫ1ϩx, y, z
spectrometer using KBr pellets in the 4000Ϫ400 cmϪ1 range.
Elemental analysis for C, H and N were performed using a Carlo
Erba 1106 microanalyser. Magnetic susceptibility measurement at
room temperature was performed using a Sherwood Scientific MXI
3.3 X-ray structure analyses
For the crystal structure determination, the single-crystal
of the compounds the fac-[Ni(HOr)(ea)2] (1) and mer-
Z. Anorg. Allg. Chem. 2007, 1087Ϫ1093
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1091

O. Z. Yes¸ilel, E. S¸ahin
Table 5 Comparison of the bond distances and angles of the orotato and ethanolamine complexesa
Complexes
MϪOHOr
MϪNHOr
,
OHOrϪMϪNHOr
MϪOmea
MϪNmea
OmeaϪMϪNmea
[Ni(HOr)(ea)2] (1)
2.088,
2.045
1.984,
2.004
Ϫ
79.32
81.54
Ϫ
2.090, 2.148
2.057, 2.085
2.526, 2.033
2.477, 1.998
2.093,
80.17,
81.62
78.36,
78.80
97.29
[Cu(HOr)(ea)2]·2H2O (2)
[Ni(sac)2(ea)2] [43]
2.075
2.326,
1.992
2.162,
[Cu(sac)2(ea)2] [42]
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
80.97
81.84
[Zn(sac)2(ea)2] [38]
Ϫ
2.087
[Hg(sac)2(ea)2] [44]
Ϫ
2.657, 2.759
2.121, 2.106
2.433,
2.023
2.373,
74.04
72.44
78.17
[Cu(ox)(ea)2] [39]
Ϫ
[Cu(sq)(ea)2] [40]
Ϫ
81.15
Ϫ
1.983
Ϫ
[Ni(HOr)(H2O)4]·H2O [10]
[Ni(HOr)(H2O)2(im)2] [16]
[Ni(HOr)(H2O)(tea)]·H2O [28]
[Cu(HOr)(tea)]·H2O [29]
[Cu(HOr)(en)H2O]·H2O [11]
2.023,
2.049
2.064,
2.072
2.029,
2.085
1.944,
1.952
1.990,
1.986
80.0
80.12
80.08
84.07
81.9
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
a sac ϭ saccharinate, ox ϭ oxalate, sq ϭ squarato, im ϭ imidazole, tea ϭ triethanolamine, en ϭ ethylenediamine.
[Cu(HOr)(ea)2]·2H2O (2) was used for data collection on a four-
circle Rigaku R-AXIS RAPID-S diffractometer equipped with a
two-dimensional area IP detector. The graphite-monochromatized
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Mo Kα radiation (λ ϭ0.71073 A) and oscillation scans technique
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for 1 and 2 were taken successfully by varying ω with three sets of
different χ and ϕ values. For each compounds the 108 images for
six different runs covering about 99.8 % of the Ewald spheres were
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squares methods on the basis of all reflections with F2>2σ(F2). In-
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ture factors) for the structures of 1 and 2 in this paper have been
deposited with the Cambridge Crystallographic Data centre as
supplementary publication numbers 632854 and 632853 respec-
tively. Copies of the data can be obtained, free of charge, on appli-
cation to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
[fax: ϩ44 1223 336033 or e-mail:deposit@ccdc.cam.ac.uk]
G. Jovanovski, A. R. Ibrahim, A. Usman, H. K. Fun, S. Chan-
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Acknowledgements. This work was supported by the Eskis᝺ehir
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