Synthesis, crystal structure, and characterization of thiophene-3- carboxaldoxime complexes with cobalt(II), nickel(II) and copper(II) halides

Article abstract of DOI:10.1016/j.molstruc.2012.02.055

The reaction of cobalt(II), nickel(II), copper(II) chlorides and bromides with thiophene-3-carboxaldoxime (3TCOH) leads to a series of new complexes: [CoCl₂(3TCOH)₄], [CoBr₂(3TCOH)₄], [NiCl₂(3TCOH)₄], [NiBr₂(3TCOH)₄], [CuCl₂(3TCOH)₄], [CuBr₂(3TCOH)₂] respectively. The crystal structures of [CoBr₂(3TCOH)₄], [NiBr₂(3TCOH)₄] have been determined by X-ray diffraction methods showing octahedral complex species. In all complexes, the oxime functional group remains protonated and the coordination occurs through the nitrogen atom of the oxime moiety.

Full text of DOI:10.1016/j.molstruc.2012.02.055

Journal of Molecular Structure 1019 (2012) 143–150
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, crystal structure, and characterization of thiophene-3-carboxaldoxime
complexes with cobalt(II), nickel(II) and copper(II) halides
a
a
b
a,
⇑
Kusaï Alomar , Jean-Jacques Hélesbeux , Magali Allain , Gilles Bouet
a
Laboratoire SONAS, EA 921, Université d’Angers, IFR QUASAV 149, UFR Sciences Pharmaceutiques et Ingénierie de la Santé, 16 Boulevard Daviers, F-49045 Angers Cedex 01, France
Institut des Sciences et Technologies Moléculaires d’Angers (MOLTECH-Anjou), UMR CNRS 6200, Université d’Angers, 2 Boulevard Lavoisier, 49045 Angers Cedex 01, France
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of cobalt(II), nickel(II), copper(II) chlorides and bromides with thiophene-3-carboxaldoxime
Received 16 January 2012
Received in revised form 20 February 2012
Accepted 21 February 2012
Available online 3 March 2012
(
[
3TCOH) leads to a series of new complexes: [CoCl
2
(3TCOH)
(3TCOH) ] respectively. The crystal structures of [CoBr
4
], [NiBr (3TCOH) ] have been determined by X-ray diffraction methods showing octahedral com-
4
], [CoBr
2
(3TCOH)
4
], [NiCl
2
(3TCOH)
4
],
NiBr
2
4
], [CuCl
2
(3TCOH)
4
], [CuBr
2
(3TCOH)
2
2
(3T-
COH)
4
2
plex species. In all complexes, the oxime functional group remains protonated and the coordination
occurs through the nitrogen atom of the oxime moiety.
Keywords:
Aldoxime
Ó 2012 Elsevier B.V. All rights reserved.
Thiophene
Metal complexes
Crystal structure
1
. Introduction
or E5FDH) complexes with cobalt and nickel halides; [MX
2 2
L ] and
[
MX ] complexes with copper chloride and bromide [6–9]. In
2 4
L
The syntheses, structures and solution chemistry of oxime and
these compounds, there is only one coordinating atom: N from
imine. In our continuing investigations about oximes, semicarba-
zones and thiosemicarbazones [10,11] deriving from heterocyclic
aldehydes (furan or thiophene) we described here the metal com-
plexes obtained with thiophene-3-carboxaldoxime (3TCOH) which
structure is given in Fig. 1.
oximato containing metal complexes have been extensively stud-
ied and described in many publications. Both aldoximes and ketox-
imes are known for their ability to complex metals. Ligands with
an oxime functional group linked to a heterocycle leads to many
complexes. Among these heterocycles bearing an oxime function
(
derived from an aldehyde or ketone as well) located in 2-position,
are the most numerous [1–3]. Heterocyclic mono-aldoximes and
their metal complexes were often described. Pyridyl oximes and
their metal complexes were recently reviewed [2].
Oximes and oximato group (obtained by deprotonation of the
hydroxyl moiety) contain two coordinating atoms: the nitrogen
atom of the imine and the oxygen atom of the hydroxyl, deproto-
nated or not [4,5].
According to the various modes of complexation, the oxime
group is involved in coordination through the imino nitrogen and
oxygen of the hydroxyl (bidentate ligand) or only using one of
these atoms [5]. In some cases the heteroatom of the heterocycle
could be involved in the coordination, especially when the oxime
group is located in 2 position.
2
. Experimental
2.1. Reactants
All reactants and solvents were analytical grade. Hydroxyl-
ammonium chloride and thiophene-3-carboxaldehyde were pur-
chased from Alfa Aesar (France). Cobalt, nickel and copper
hydrated halides (Prolabo) were used as received.
2.2. Measurements
Elemental analyses were carried out by the Service d’Analyses
1
(
ICSN, CNRS, Orsay, France). The H NMR spectra were recorded
In our laboratory, somes furan mono-aldoximes and their
complexes were described: 5-methyl furfuraldoxime (M5FDH)
and 5-ethyl-furfuraldoxime (E5FDH) giving [MX L ] (L = M5FDH
2 4
6
on a Jeol GSX WB spectrometer at 270 MHz in DMSO-D , the chem-
ical shifts are given in ppm, using TMS as internal reference. DSC
diagrams were recorded in the 25–400 °C range with a Mettler
DSC 822 unit, with the help of Mettler Toledo STAR SW 8.10 Sys-
tem software (Laboratoire de Physique, Faculté de Pharmacie, An-
gers); the heating rate was 10 °C per min. All measurements were
e
e
⇑
Corresponding author. Tel.: +33 2 41 22 66 00.
E-mail address: gilles.bouet@univ-angers.fr (G. Bouet).
0
022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2012.02.055

1
44
K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
precipitated [13,14]. The oxime was recrystallized from 75% etha-
nol and 25% distilled water. Translucent single crystals were ob-
OH
tained (MP = 129 °C).
N
HC
The mass spectrum of this ligand shows a major peak at m/
À1
z = 128.09 g mol corresponding to the molecular peak and one
+
proton [M + H] .
1
The H NMR of the ligand was recorded in DMSO-D
6
, the spectra
of the ligand exhibits signals due to: three ACH heterocyclic
protons, singulet d = 7.48 ppm, doublet d = 7.53 ppm, doublet d =
7.55 ppm; ACH@: singlet d = 8.22 ppm; AOH: singlet d = 11.53 ppm.
S
Fig. 1. Chemical structure of 3-thiophene aldehyde oxime (3TCOH).
2.5. Preparation of the complexes
3
made in 40 mm closed Al crucibles. The mass spectra were carried
out using Bruker Esquire 3000 Plus mass spectrometer (Plateforme
d’Ingénierie et Analyses Moléculaires, Université d’Angers, France).
The IR spectra were recorded with a Bruker FTIR Vector 22 spec-
All the complexes were prepared starting from 3TCOH (1.27 g,
0 mmol) dissolved in EtOH. The ethanolic solution of the metal
halide was added slowly while stirring.
1
À1
trometer between 4400 and 400 cm (KBr disks). The far IR spec-
tra were recorded with a Bruker Vertex FTIR spectrophotometer in
2
.5.1. Synthesis of [CoCl
The complex [CoCl
tion of 3TCOH (1.27 g, 10 mmol, 20 mL, EtOH) into a solution of co-
balt (II) chloride CoCl , 6H O (0.64 g, 2.5 mmol, 15 mL, EtOH) in a
2
(3TCOH)
4
] and [CoBr
] was prepared by adding a solu-
2 4
(3TCOH) ]
À1
the 650–50 cm
range, using polyethylene disks (Institut des
2
(3TCOH)
4
Matériaux Jean Rouxel, université de Nantes (France).
2
2
2
.3. Crystal data collection and processing
1/4 metal salt/ligand molar ratio. The mixture was refluxed in eth-
anol for 24 h. After standing at room temperature for 1 week, the
complex crystallized. It was filtered and washed with ethanol
and dried. It was recrystallized from ethanol and orange crystals
Several tests with 3TCOH were performed at various tempera-
tures, but all results show static disorder for the sulfur atoms of
the thiophene ring, within three molecules among the four inde-
pendent molecules in the cell. Finally, the crystal structure of
were obtained. Similarly, the complex [CoBr
pared from a mixture of 3TCOH (1.27 g, 10 mmol, 20 mL, EtOH)
and CoBr (0.59 g, 2.5 mmol, 15 mL, EtOH).
2 4
(3TCOH) ] was pre-
3
TCOH consists in four independent molecules in which three of
2
them undergo a disorder so that the atoms positions cannot be
determined with a sufficient accuracy.
All complexes were recrystallized from ethanol. Several at-
2 4
tempts at various temperatures for the complex [CoCl (3TCOH) ],
show significant static disorder for the thiophene ring mainly.
The oxime group and the halide ions show a weaker disorder as
well. The same phenomenon was observed in the case of the com-
2
.5.2. Synthesis of [NiCl
2 4 2 4 2 4
(3TCOH) ], [NiBr (3TCOH) ], [CuCl (3TCOH) ]
and [CuBr (3TCOH)
2
2
]
All theses complexes were prepared in the same way, by adding
TCOH (1.27 g, 10 mmol, EtOH) into a solution the corresponding
3
metal halogenide (EtOH, 1:4 or 1:2 metal to ligand ratio. All com-
pounds precipitated after standing at room temperature.
plex [CuCl
Crystals of the complexes [CoBr
COH)
] are isostructural and triclinic with P À 1 space group.
X-ray single-crystal diffraction data were collected at 293 K on a
Brüker-Nonius Kappa CCD diffractometer for [CoBr (3TCOH)
and on a STOE-IPDS diffractometer for [NiBr (3TCOH) ], both
equipped with a graphite monochromator using Mo K radiation
k = 0.71073 Å) (MOLTECH-Anjou, UMR CNRS 6200, Université
2 4
(3TCOH) ].
2 4 2
(3TCOH) ] and [NiBr (3T-
4
Table 1
Crystallographic data for [CoBr
2 4
(3TCOH) ] and [NiBr
2
(3TCOH)
4
].
2
4
]
2
4
Name
[CoBr (3TCOH) ]
2
4
[NiBr (3TCOH) ]
2
4
a
Formula
C
60
H
60 Br
6
3
Co N
12
O
12
S
12
C
60
6 3 12 12 12
H60 Br Ni N O S
(
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
2182.17
Triclinic
P À 1
2169.41
Triclinic
P À 1
d’Angers). The structures were solved by direct methods and re-
2
fined on F by full-matrix least-squares method, using SHELX97
11.203(1)
11.834(2)
16.689(2)
100.15(1)
104.88(1)
11.218(1)
11.874(2)
16.669(2)
99.89(1)
105.55(1)
100.84 (1)
2042.2(4)
1
package [12]. All non-H atoms were refined anisotropically and
the H atoms were included in the calculation without refinement.
Absorption was corrected by gaussian technique for [NiBr
COH) ] and by SADABS program (Sheldrick, Bruker, 2000) for
CoBr (3TCOH) ].
2
(3T-
a
(°)
b (°)
(°)
4
c
100.848(8)
2040.5(5)
1
[
2
4
3
V (Å )
Z
D
À3
calc (g cm
2.4. Synthesis of the ligand 3TCOH
)
1.764
1.764
Crystal size (mm)
0.43 Â 0.37 Â 0.2
0.19 Â 0.19 Â 0.15
Absorption coeff.
3.909
3.988
This ligand was prepared by reacting equimolar amounts of thi-
À1
(
mm
)
ophene-3-carboxaldehyde and hydroxylamine. The hydroxylamine
was generated by reacting potassium hydroxide with hydroxylam-
monium chloride in methanol. Hydroxylammonium chloride
F (000)
hkl limits
1083
1074
À15 6 h 6 15
À16 6 k 6 16
À23 6 l 6 22
23437/
10450[R(int) = 0.0486]
10450/1/514
13 6 h 6 13
À14 6 k 6 14
À20 6 l 6 20
23941/
7430[R(int) = 0.0734]
7430/1/514
(
9
0.6 g, 9 mmol, 10 mL) reacted with potassium hydroxide (0.5 g,
mmol, 10 mL) for 10 min, potassium chloride then precipitated
Reflections collected/
unique
Data/restraints/
parameters
and was removed by filtration and hydroxylamine was added to
thiophene-3-carboxaldehyde (1 g, 9 mmol, 10 mL, EtOH) in the
presence of pure acetic acid (1 mL). The mixture was kept at
h
min, hmax (°)
for I > 2
wR for I > 2
3.59, 30.03
0.0603
0.1716
1.80, 26.01
0.0624
0.1727
R
1
r
(I)
3
0 °C for 20 h. After cooling to room temperature, the solution
2
r(I)
was concentrated under reduced pressure, and small white crystals

K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
145
2 4
Fig. 2. Crystal structure and atoms numbering for [CoBr (3TCOH) ].

1
46
K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
Table 2
ions and thiophene cycle in two of the four ligands (Fig. 2). The
occupation rates are 0.817 for Br1 and 0.183 for Br5; 0.943 (Br2)
and 0.057 (Br6). For the thiophene rings, S3/C16/H16/H13A/H14A
and S9/C15/H15/H13B/H14B the rates are 0.820 and 0.180 while
for S4/C22/H22/H19A/H20A and S8/C21/H21/H19B/H20B, the
rates are 0.787 and 0.213.
2 4
Selected bond lengths (Å) and angles (°) for [CoBr (3TCOH) ].
Bond lengths (Å)
Bond angles (°)
C1AN1
C6AN2
1.276(8)
1.275(8)
1.278(8)
1.258(8)
1.278(8)
1.200(10)
1.378(7)
2.179(6)
1.373(7)
2.155(6)
1.393(7)
2.193(6)
1.390(7)
2.185(5)
1.381(7)
2.201(6)
1.462(10)
2.158(7)
2.615(13)
2.634(2)
2.6343(12)
2.654(12)
2.6747(11)
2.690(4)
N2ACo1AN1
N2ACo1AN4
N1ACo1AN4
N2ACo1AN3
N1ACo1AN3
N4ACo1AN3
N2ACo1ABr1
N1ACo1ABr1
N4ACo1ABr1
N3ACo1ABr1
N2ACo1ABr2
N1ACo1ABr2
N4ACo1ABr2
N3ACo1ABr2
Br1ACo1ABr2
N6ACo2AN5
N6ACo2ABr3
N5ACo2ABr3
C1AN1AO1
177.5(2)
89.5(2)
93.0(2)
89.9(2)
87.6(2)
179.2(2)
88.15(16)
92.45(15)
88.22(16)
91.28(15)
91.39(15)
88.02(15)
91.79(16)
88.70(15)
179.53(7)
89.1(2)
C11AN3
C17AN4
C23AN5
C28AN6
N1AO1
N1ACo1
N2AO2
N2ACo1
N3AO3
N3ACo1
N4AO4
N4ACo1
N5AO5
N5ACo2
N6AO6
N6ACo2
Co1ABr6
Co1ABr1
Co1ABr2
Co1ABr5
Co2ABr3
Co2ABr4
2 4
In the complex [CoBr (3TCOH) ], the four ligands coordinate
through the imino nitrogen atom. The complex shows an octahedral
geometry and the cobalt is located at the symmetry center of a
slightly distorted octahedron. Thus, linked to four nitrogen atoms
of four 3TCOH molecules and two bromine ions, the cobalt(II) ion
a six coordination number [15].
Its coordination polyhedron is a slightly distorted octahedron in
which the bromine ions are in trans position with respect to the
equatorial plane defined by the four nitrogen atoms of the ligands.
These four nitrogen atoms N1, N2, N3, and N4 are coplanar and are
arranged in a quite square geometry with N1AN3, N3AN2, N2AN4
and N4AN1 distances of 3.0260(88), 3.0723(89), 3.0537(90) and
3.1639(87) Å respectively. In the mean time the angles N1A
Co1AN3 (87.6(2)°), N3ACo1AN2 (89.9(2)°), N2ACo1AN4
90.4(2)
88.26(16)
112.9(6)
128.2(5)
118.8(4)
112.1(6)
129.0(5)
118.9(4)
C1AN1ACo1
O1AN1ACo1
C6AN2AO2
C6AN2ACo1
O2AN2ACo1
(
89.5(2)°) and N4ACo1AN1 (93.0(2)°) are closed to 90°. The two
bonds CoABr1 and CoABr2 are quite orthogonal to this plane; their
deviation to the normal axis of this square plane N1N2N3N4 are
2
.58° and 2.22° respectively.
The bond lengths C1AN1, N2AC6, C11AN3, N4AC17, C23AN5,
N6AC28 are 1.276(8), 1.275(8), 1.278(8), 1.258(8), 1.278(8) and
.200(10) Å, respectively (Table 2). These lengths are typical of a
3
. Results and discussion
1
C@N double bond [16]. Each 3TCOH molecule in the complex is
plane, with a small deviation for the oxygen atoms of the oxime
moiety. The four ligands are located in two intersecting planes,
with a 88.03° angle between these two planes.
3
.1. Crystal structure of [CoBr (3TCOH) ]
2 4
The main crystal parameters are reported in Table 1. The struc-
ture of one structural unit and atoms numbering scheme are given
in Fig. 2. The complex [CoBr (3TCOH) ] crystallized in a triclinic
system in P À 1 space group and with a single unit per cell
Z = 1). This unit consists in three molecules in which one and half
In the crystal structure, the first molecule is associated with an
half of the other complex molecule through a weak hydrogen
bond: O4AH4AÁ Á ÁO6 showing a 2.965 Å length and a 105.07° angle
2
4
(
(Fig. 3). This weak hydrogen bond ensures the cohesion of the crys-
are independent and the other defined by symmetry. Inside an
independent molecule, we observed a static disorder for bromine
tal and the stability of the stacking, as no other interaction was ob-
served (Fig. 4).
2 4
Fig. 3. Hydrogen bonding for [CoBr (3TCOH) ].

K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
147
2 4
Fig. 4. Cell packing for [CoBr (3TCOH) ].
3
.2. Crystal structure of the nickel complex [NiBr
2
(3TCOH)
4
]
The complex has an octahedral geometry with the nickel lo-
cated at the symmetry center of the slightly distorted octahedron,
linked to four nitrogen atoms of four 3TCOH molecules and two
bromine ions (Fig. 5) [17]. This compound is very similar to the co-
balt complex described above.
The main crystal parameters are reported in Table 1. The bond
distances and angles are listed in Table 3 and the structure and
the numbering scheme are given in Fig. 5. The complex [NiBr (3T-
COH)
] crystallizes in a triclinic system with a P À 1 space group
and we note the presence of three molecules per unit cell forming
a single unit (Z = 1), as in the case of the complex [CoBr (3TCOH) ].
2
4
Each molecule of ligand in the complex has a planar geometry
with a small deviation to this plane observed for the oxygen atoms
(oxime). The four ligands are grouped two by two, belonging to
two secant planes. These two planes exhibit a 85.5° angle between
them. The nickel ion stands at the symmetry center of the struc-
2
4
It also undergoes a disorder for bromide ions and thiophene rings.
The occupation rates are 0.708 for Br1 and 0.292 for Br5; 0.900
2
+
(
Br2) and 0.100 (Br6). For the thiophene rings, S3/C16/H16/
H13A/H14A and S9/C15/H15/H13B/H14B the rates are 0.818 and
.182 while for S4/C22/H22/H19A/H20A and S8/C21/H21/H19B/
ture; the bromide ions, the Ni ion are located along the cross line
of the two planes containing the ligand molecules.
0
In the crystal structure, the first complex molecule is linked to
the second part of the molecule through a hydrogen bond
O6AH6AÁ Á ÁO4 with a 3.086 Å length and a 96.57° angle (Fig. 6).
Though this interaction is weak, it is the only way to stabilize
the structure [18]. The packing is given on Fig. 7.
H20B, these rates are 0.742 and 0.258 respectively.
Table 3
2 4
Selected bond lengths (Å) and angles (°) for [NiBr (3TCOH) ].
Bond lengths (Å)
Bond angles (°)
C1AN1
C6AN2
1.258(9)
1.253(9)
1.249(9)
1.235(9)
1.275(10)
1.124(11)
1.389(7)
2.138(5)
1.370(7)
2.111(5)
1.411(8)
2.158(6)
1.388(8)
2.158(6)
1.392(8)
2.160(6)
1.530(13)
2.091(8)
2.577(8)
2.601(2)
2.5910(11)
2.597(7)
2.6460(13)
2.684(3)
N2ANi1AN1
N2ANi1AN3
N1ANi1AN3
N2ANi1AN4
N1ANi1AN4
N3ANi1AN4
N2ANi1ABr1
N1ANi1ABr1
N4ANi1ABr1
N3ANi1ABr1
N2ANi1ABr2
N1ANi1ABr2
N4ANi1ABr2
N3ANi1ABr2
Br2ANi1ABr1
N6ANi2AN5
N6ANi2ABr3
N5ANi2ABr3
C1AN1AO1
178.4(2)
90.3(2)
88.3(2)
89.0(2)
92.5(2)
179.0(2)
88.65(16)
91.85(16)
89.00(17)
90.34(16)
90.73(15)
88.76(15)
91.01(17)
89.64(17)
179.38(7)
88.8(2)
3.3. Structures of the complexes
C11AN3
C17AN4
C23AN5
C28AN6
N1AO1
N1ANi1
N2AO2
N2ANi1
N3AO3
N3ANi1
N4AO4
N4ANi1
N5AO5
N5ANi2
N6AO6
N6ANi2
Ni1ABr6
Ni1ABr1
Ni1ABr2
Ni1ABr5
Ni2ABr3
Ni2ABr4
3.3.1. Analytical data
The elemental analysis of the ligand and its complexes is sum-
marized in Table 4. A good fit is observed between the experimen-
tal and calculated values and the formulae of the complexes are
[
CoCl
2
(3TCOH)
4
2
], [CoBr (3TCOH)
4
], [NiCl
2
(3TCOH)
4 2
], [NiBr (3T-
COH)
4
], [CuCl (3TCOH)
2
4
] and [CuBr
2
(3TCOH)
2
] respectively.
3.3.2. DSC
The DSC patterns allowed us to determine the melting point of
the ligand, appearing as a typical endothermic peak at 129 °C. All
diagrams for the metal complexes do not show any endothermic
peak. On the opposite side we observed in each case a fine exo-
thermic peak corresponding to crystallization at 175 °C
88.3(3)
88.72(17)
112.8(5)
129.7(5)
117.3(4)
111.9(6)
130.4(5)
117.7(4)
(
[CoCl
COH)
CuCl
2
(3TCOH)
]), 165 °C ([NiBr
(3TCOH) ] and [CuBr
4
]), 166 °C for [CoBr
(3TCOH) ]), 125 °C and 123 °C for
(3TCOH) ] respectively. The same
2 4 2
(3TCOH) ], 271 °C ([NiCl (3T-
C1AN1ANi1
O1AN1ANi1
C6AN2AO2
C6AN2ANi1
O2AN2ANi1
4
2
4
[
2
4
2
2
behavior has been observed for complexes with 5-substituted fur-
furaldoxime [6].

1
48
K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
2 4
Fig. 5. Crystal structure and atoms numbering for [NiBr (3TCOH) ].
3.3.3. Infrared spectra
2 4 2 2
[CuCl (3TCOH) ] and [CuBr (3TCOH) ] confirm that the oxime is
The main infrared vibration bands are reported in Table 5. The
not ionized as indicated by the presence of the
m
(OH) band be-
À1
infrared spectra of the complexes [CoCl
2
4 2 4
(3TCOH) ], [NiCl (3TCOH) ],
tween 3227 and 3261 cm in all spectra. The
m
(C@N) vibration

K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
149
Table 4
Analytical data.
Compound
Color
Yield (%)
Elemental analysis found (Calc.)
C (%)
H (%)
N (%)
3
TCOH
CoCl (3TCOH)
CoBr (3TCOH)
(3TCOH)
(3TCOH)
(3TCOH)
(3TCOH)
White
Orange
Orange
Green
Green
Green
Orange
86
70
67
74
71
81
78
46.97
3.79
(3.96)
3.06
(3.16)
2.76
(2.77)
3.17
(3.16)
2.73
(2.77)
2.96
(3.13)
2.12
10.68
(11.01)
8.81
(8.77)
7.56
(7.70)
8.70
(8.78)
7.77
(7.70)
8.83
(8.71)
5.71
(
47.23)
37.66
37.62)
32.76
33.02)
37.83
37.64)
33.36
33.30)
37.54
37.35)
24.43
[
[
[
[
[
[
2
4
]
(
2
4
]
(
NiCl
2
4
]
(
NiBr
2
4
]
(
CuCl
2
4
]
(
CuBr
2
2
]
(
24.23)
(2.44)
(5.65)
Table 5
À1
Infrared data for the ligand and its complexes (cm ).
Fig. 6. Hydrogen bonding for [NiBr
2
(3TCOH)
4
].
Compound
m
(OH)
m
(C@N)
m
(NAO) Resp.
m
(MAN)
m
(MAX)
cycle
3
TCOH
3180
3236
1642
1648
1643
1653
1646
1657
1656
959
962
960
966
962
946
943
1147
86
1156
83
1156
780
1155
785
1155
–
–
7
band is slightly shifted to higher values compared to the ligand: it
[
CoCl (3TCOH)
2
4
]
303
298
309
303
273
315
184
168
193
178
186
209
À1
appears between 1643 and 1657 cm in the cases of the com-
7
plexes. The
m
(NAO) vibration is located between 943 and
[CoBr (3TCOH) ] 3249
2
4
À1
9
2
66 cm [19]. The wavenumber of the bands appearing between
73 and 315 cm are typical of the
À1
[NiCl (3TCOH) ]
3227
3232
3227
3261
m
(MAN) vibration. The wave-
2
4
À1
number of the bands appearing between 168 and 209 cm corre-
spond to MAX stretching vibrations [19,20]. These results agree
with (i) the oxime functional group is not deprotonated, (ii) the ha-
lides are present in all complexes, (iii) in all cases, the coordination
occurs through N imino atom.
[
NiBr
[CuCl
CuBr
2
(3TCOH)
(3TCOH)
(3TCOH)
4
]
7
83
1157
87
1156
85
2
4
]
7
[
2
2
]
7
3.3.4. Proposed structures
The proposed structures of the complexes [CoCl
2
(3TCOH)
4
],
The structures of the complexes [CoCl
2
(3TCOH)
4
], [NiCl
2
(3T-
[
2 4 2 4 2 2
NiCl (3TCOH) ], [CuCl (3TCOH) ] and [CuBr (3TCOH) ] are shown
COH)
4
], [CuCl
2
4
(3TCOH) ] were determined on the basis of the crystal
on Fig. 8.
Fig. 7. Cell packing for [NiBr
2
(3TCOH)
4
].

1
50
K. Alomar et al. / Journal of Molecular Structure 1019 (2012) 143–150
S
the N imino atom and these complexes show a typical octahedral
geometry.
2
The structure of the complex [CuBr (3TCOH) ] has been already
2
observed for many cupric complexes in which the heteroatom
from the heterocycle could not be involved in the coordination be-
cause it is too far from the metal ion. The Cu(II) ion stands at the
center of a distorted tetrahedron with a quite square-planar geom-
etry [21].
Cl
OH
N
OH
OH
Appendix A. Supplementary material
Crystallographic data have been deposited with the CCDC (12
Union Road, Cambridge, CB2 IEZ, UK (fax: +44 1223 336033; e-
mail: deposit@ccdc.cam.ac.uk or at http://www.ccdc.cam.ac.uk),
and are available on request quoting the deposition numbers CCDC
N
M
S
N
S
OH
N
8
62503 (cobalt complex) and 862504 (nickel complex). Supple-
Cl
mentary data associated with this article can be found, in the on-
line version, at doi:10.1016/j.molstruc.2012.02.055.
References
[
1] A. Chakravorty, Coord. Chem. Rev. 13 (1974) 1–48.
S
[2] C.J. Milios, T.C. Stamatatos, S.P. Perlepes, Polyhedron 25 (2006) 134–194.
[3] V.Y. Kukushkin, A.J.L. Pombeiro, Coord. Chem. Rev. 181 (1999) 147–175.
(
a)
[
4] T.C. Stamatatos, A. Bell, P. Cooper, A. Terzis, C.P. Raptopoulou, S.L. Heath, R.E.P.
Winpenny, S.P. Perlepes, Inorg. Chem. Commun. 8 (2005) 533–538.
5] C.P. Raptopoulou, V. Psycharis, Inorg. Chem. Commun. 11 (2008) 1194–1197.
6] G. Bouet, J. Jolivet, C.R. Acad, C.R. Acad. Sci. Paris, Ser. II (292) (1981) 1139–
M = Co, Ni and Cu
[
[
1
142.
OH
N
[
[
7] G. Bouet, J. Coord. Chem. 15 (1986) 1139–1142.
8] G. Bouet, J. Dugué, Trans. Met. Chem. 14 (1989) 356–360.
[9] G. Bouet, J. Dugué, F. Keller-Besrest, Trans. Met. Chem. 15 (1990) 5–8.
10] K. Alomar, M.A. Khan, M. Allain, G. Bouet, Polyhedron 28 (2009) 1273–1281.
11] K. Alomar, A. Landreau, M. Kempf, M.A. Khan, M. Allain, G. Bouet, J. Inorg.
Biochem. 104 (2010) 397–404.
S
[
[
Br
Cu
N
Br
[
[
12] G.M. Sheldrick, SHELX97 – Program for Crystal Structure Analysis (Release 97–
S
2
), University of Göttingen, Göttingen, Germany, 1998.
13] N. Gharah, S. Chakraborty, A.K. Mukherjee, R. Bhattacharyya, Inorg. Chim. Acta
62 (2009) 1089–1100.
[14] J.T. Li, X.L. Li, T.S. Li, Ultrason. Sonochem. 13 (2006) 200–202.
15] P. Chadha, B.D. Gupta, K. Mahata, Organometallics 25 (2006) 92–98.
[16] A. Gupta, R.K. Sharma, R. Bohra, V.K. Jain, J.E. Drake, J. Organomet. Chem. 645
2002) 118–126.
3
HO
[
(
b)
(
[
[
[
17] S. Mukherjee, B.A. Patel, S. Bhaduri, Organometallics 28 (2009) 3074–3078.
18] C.B. Aakeröy, A.M. Beatty, D.S. Leinen, Cryst. Growth Des. 1 (2001) 47–52.
19] L. Croitor, E.B. Coropceanu, E. Jeanneau, I.V. Dementiev, T.I. Goglidze, Y.M.
Chumakov, M.S. Fonari, Cryst. Growth Des. 9 (2009) 5233–5243.
Fig. 8. Proposed structures for [CoCl
a) and [CuBr (3TCOH) ] (b).
2
(3TCOH)
4
], [NiCl
2
(3TCOH)
4
2 4
], [CuCl (3TCOH) ]
(
2
2
[
[
20] I. Georgieva, N. Trendafilova, G. Bauer, Spectrochim. Acta A 63 (2006) 403–415.
21] Y.Y. Scaffidi-Domianello, K. Meelich, M.A. Jakupec, V.B. Arion, V.Y. Kukushkin,
M. Galanski, B.K. Keppler, Inorg. Chem. 49 (2010) 5669–5678.
structures of [CoBr
spectroscopic data. In all species, the coordination occurs through
2
(3TCOH)
4
] and [NiBr
2
4
(3TCOH) ] and from their