Synthesis, characterization and structural study of new vanadium complexes with phenolic oxime ligands

Article abstract of DOI:10.1016/j.molstruc.2019.127597

In this work, three new vanadium complexes are reported. Their synthesis, crystallization and characterization are detailed. The complex (1) [VO(C₇H₆NO₂)₂] is a mononuclear and crystallizes in the monoclinic P2₁/n space group exhibiting a square pyramidal geometry around the vanadium. Dissolved in p-xylene (1–4 dimethylbenzene), this complex gives a binuclear complex (2) [V₂O₂(C₇H₆NO₂)₂(C₇H₅NO₂)₂]·C₈H₁₀ with a triclinic P-1 space group and an octahedral geometry around the vanadium. The complex (3) [VO₂(C₉H₉N₂O₃)] was obtained using the new iminoacylated oxime ligand (the result of the nucleophilic attack of 4-hydroxysalicylaldoxime with acetonitrile), it crystallizes in the triclinic P-1 space group with a trigonal bipyramidal geometry around the vanadium. All complexes were characterized by single crystal X-ray diffraction, FT-IR, NMR, UV–visible and TGA.

Full text of DOI:10.1016/j.molstruc.2019.127597

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Synthesis, characterization and structural study of new vanadium complexes with
phenolic oxime ligands
Ilyas Belkhettab, Sultana Boutamine, Hennia Slaouti, Med Faouzi Zid, Habib
Boughzala, Zakia Hank
PII:
S0022-2860(19)31706-5
DOI:
https://doi.org/10.1016/j.molstruc.2019.127597
MOLSTR 127597
Reference:
To appear in: Journal of Molecular Structure
Received Date: 28 September 2019
Revised Date: 7 December 2019
Accepted Date: 15 December 2019
Please cite this article as: I. Belkhettab, S. Boutamine, H. Slaouti, M.F. Zid, H. Boughzala, Z. Hank,
Synthesis, characterization and structural study of new vanadium complexes with phenolic oxime
ligands, Journal of Molecular Structure (2020), doi: https://doi.org/10.1016/j.molstruc.2019.127597.
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Graphical Abstract

Synthesis, characterization and structural study of new
vanadium complexes with phenolic oxime ligands
Ilyas Belkhettaba, Sultana Boutaminea, Hennia Slaoutia, Med Faouzi Zidb, Habib
Boughzalab, Zakia Hanka*
aUSTHB, Laboratoire d’Electrochimie-Corrosion, Métallurgie et Chimie Minérale, Faculté de
Chimie, BP 32 El Alia 16111 Bab-Ezzouar, Algiers, Algeria
bLaboratoire de Matériaux et Cristallochimie, et Thermodynamique appliqué, Faculté des
Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia
Abstract
In this work, three new vanadium complexes are reported. Their
synthesis, crystallization and characterization are detailed. The complex (1)
[VO(C7H6NO2)2] is amononuclear and crystallizes in the monoclinic P21/n
space group exhibiting a square pyramidal geometry around the vanadium.
Dissolved in p-xylene (1-4 dimethylbenzene), this complex gives a binuclear
complex (2) [V2O2(C7H6NO2)2(C7H5NO2)2].C8H10 with a triclinic P-1 space
group and an octahedral geometry around the vanadium. The complex (3)
[VO2(C9H9N2O3)] was obtained using the new iminoacylated oxime ligand
(the result of the nucleophilic attack of 4-hydroxysalicylaldoxime with
acetonitrile), it crystallizes in the triclinic P-1 space group with a trigonal
bipyramidal
geometry around the vanadium. All complexes were
characterized by single crystal X-ray diffraction, FT-IR, NMR, UV-visible
and TGA.
Keywords: vanadium complexes, salicylaldoxime, iminoacylation,
spectroscopic characterization, single crystal.
1. Introduction
The salicylaldoxime or phenolic oxime and its derivatives have been
the subject of extensive research in coordination chemistry, because of their
highly colored complexes with a large structural diversity, formed with the
majority of transition metals [1,2]. Oximes are compounds belonging to the

Schiff base class. They can be synthesized by a simple reaction of aldehyde
or ketones with hydroxylamine [3]. The interaction of various donor atoms
in phenolic oxime ligand and its derivatives with transition metals gives
interesting structural features. For example, the 3,5-dichloro-2-
hydroxybenzaldehye oxime allied to platinum by mono and bidentate
coordination geometry [4]. Also, phenolic oxime generally forms
mononuclear complexes with most of divalent and lanthanide metal ions [5–
9]. In the binuclear compound [Nb2O(C7H5NO2)2(C2H5O)4], each
salicylaldoxime coordinates to niobium through phenolic oxygen and
nitrogen of the oxime group. The oxygen atom of the oxime function bridges
to the adjacent niobium [2], as found in the trinuclear compound of tin
[(C4H9Sn)3O(OH)(C7H6NO2)(C7H5NO2)] [10]. The flexibility in the
chelation of the oxime is responsible for the various structural packing with
chrome(III) [11]. In some hexanuclear cluster of manganese, the metallic
ions are linked by bridge and double coordination of the oxygen atom of
oxime [12,13]. Because of the potential physical and chemical properties of
polynuclear salicylaldoxime compounds, several studies were dedicated to
the synthesis and structural study of those materials. Milios et al. studied the
change from antiferromagnetic to ferromagnetic stems from (Mn3O)2 cage of
a series of analogous structural compounds with phenolic oximes [14]. In
addition, a review of literature shows various homometallic and
heterometallic complexes of phenolic oximes with interesting structural
features and various coordination behaviors[15–18]. As a polynuclear rare
earth clusters with the salicylaldoxime ligands, the octanuclear lanthanide
complexes of the general formula [Ln8(salox)4(OH)4(NO3)12(DMF)12] (Ln =
Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er), were studied revealing potential
magnetic proprieties [19].
The coordination chemistry of the Schiff base vanadium has also attracted a
great deal of attention because of its various field of application, such as in
medicine as an insulin-mimetic compound [20], or antitumor compound
[21]. In the biological activity field, it can be employed as an antimicrobial
agent, an antioxidant [22] and can also find application in catalyze [23] and
even in the extraction of metals [24].
The works of Zerbib et al. in 1994 [25] has drawn our attention for a number
of reasons. This work discloses a salicylaldoxime in various coordinations
around the vanadium metal. This diversity is caused by the recrystallization
conditions and the versatile coordination chemistry of phenolic oxime which
leads to the formation of different complexes confirming thereby the

instability of [VO(C7H6NO2)2] in organic solvent. Moreover, the
nucleophilic attack of this complex and similarly structured derivatives by
nitrile carbon R-C≡N ( R = CH3 or C6H5) results in the formation of an
iminoacylated oxime ligand [26,27].
In this paper, we report the structure study together with the spectroscopic
and thermal characterization of a new salicylaldoxime compound and
iminoacylated oxime ligand coordinated with vanadium.
1. Experimental
2.1. Materials and measurements
All the reagents: Salicylaldoxime, VCl3, VOSO4.5H2O, p-xylene and
solvents were obtained from commercial sources (Sigma Aldrich and Fluka)
and used without further purification. The infrared spectra were recorded on
a Jasco FTIR 4100 spectrophotometer in the 4000-400 cm-1 range.
Ultraviolet absorption spectra were obtained from UV-Jasco V-650
spectrophotometer. UV–Vis spectra were measured from 200 nm to 900 nm
at room temperature. Thermogravimetry (TGA) was carried on a Q500 TA
1
instrument under nitrogen at a heating rate of 10 °C min-1. H and 13C NMR
spectra were obtained on a Bruker 400 MHz spectrometer using DMSO-d6
and benzene C6D6-d6 as solvent. The single-crystal X-ray data were
collected using Xcalibur, Atlas diffractometer and Enarf-Nonius CAD-4
diffractometer.
2.2.
Synthesis
of
4-hydroxysalicylaldoxime
or
2,4-
dihydroxybenzaldoxime
The 4-hydroxysalicylaldoxime was synthesized according to the literature
[3]. A boiling solution of 2,4-hydroxybenzaldehyde (10mmol, 1.38g) in
30mL of methanol, a solution of hydroxylamonium chloride (10mmol,
0.69g) and sodium hydroxide (10mmol, 0.4g) in 30mL of water were mixed.
The reaction mixture was refluxed for 3h. The ligand was separated by ice,
added with vigorous stirring, then filtered and washed with hot water.

1
Colorless, mw: 153.14, H NMR (400 MHz, DMSO-d6,
N=OH), 10.08 and 9.70 (s, ArOH), 8.20 (s, CH=N), 7.22-6.29 (m, ArH). 13C
NMR (101 MHz, DMSO-d6, ppm): 158.20 (CH=N) 102.92-160.19 (ArC).
δppm): 10.92 (s,
δ
2.3. Synthesis of complex (1): [VO(C7H6NO2)2]
Complex (1) was prepared by mixing VCl3 (5mmol, 0.785g) dissolved in
20mL of H2O and salicylaldoxime (10mmol, 1.37g) dissolved in 20mL of
ethanol. The reaction mixture was refluxed for 2h at 60°C. The purple prism
crystals suitable for X-ray analysis were obtained by slow evaporation after
6 days. Purple crystal, mw : 339.2 , FT-IR (KBr pellet,
1601(C=N), 1283 (N-O), 987 (V=O), 592 (V-N), 487 (V-O), H NMR (400
ν
cm-1): 3310 (OH),
1
MHz, DMSO-d6, δppm): 11.29 (s, N=OH), 8.33(s, CH=N), 6.87-7.48 (m,
13
ArH). C NMR (101 MHz, DMSO-d6,
116.49 (ArC).
δppm): 148.13 (CH=N), 156.46-
2.4. Synthesis of complex (2): [V2O2(C7H6 NO2)2(C7H5 NO2)2].C8H10
Complex (2) was obtained by recrystallization of complex (1) in p-xylene at
120 °C for three hours and let for slow evaporation for 4 weeks. Black
crystal, mw: 729.47, FT-IR (KBr pellet,
1266 (N-O), 973 (V=O), 549 (V-N), 473 (V-O). 1H NMR (400 MHz, C6D6-
d6, ppm): 10.74 (s, N=OH), 8.91 and 7.88 (s, CH=N), 6.42- 7.75(m, ArH),
1.55 (s, CH3 xylene), C NMR (101 MHz, C6D6-d6,
ν cm-1): 3438 (OH), 1594(C=N),
δ
13
δppm) : 155.26 and
148.77 (CH=N) , 115.75-166.30 (ArC), 20.64 (CH3 xylene).
2.5. Synthesis of complex 3: [VO2(C9 H9N2 O3)]
Complex (3) was prepared by the reaction of VOSO4.5H2O (2mmol 0.506 g)
dissolved in 20mL of H2O and 4-hydroxysalicylaldoxime (4mmol 0.616g)
dissolved in 20mL of ethanol. The reaction mixture formed a green
precipitate immediately. This precipitate was dissolved in acetonitrile and
water for one hour at 60°C and let for slow evaporation. yield yellow crystal,
mw : 276.12, FT-IR (KBr pellet,
(C=N), 1229 (N-O), 938 and 924 (O=V=O), 634 (V-N), 457 (V-O), H
ν
cm-1): 3412 (OH), 3157 (N-H), 1604
1
NMR (400 MHz, DMSO-d6,
δppm) : 10.69 (s,NH), 9.59 (s,ArOH), 7.57(s,
CH=N ), 6.93-7.67(m, ArH), 2.42(s,CH3).13C NMR (101 MHz, DMSO-d6,

δ
ppm ) : 173.00 (O-C=NH), 165.50 (Ar-O-V), 159.62 (Ar-OH), 137.44
(CH=N), 115.56- 134.84 (Ar), 16.42(CH3).
2.6. Data refinement
The single-crystal X-ray data of complexes (1) and (2) were obtained by an
Oxford Diffraction Xcalibur four-circle diffractometer (Rigaku Oxford
Diffraction, 2015 ) using Mo Kα radiation (λ = 0.71073 Å) [28]. Data
collection was done using the CrysAlis program. Empirical absorption
correction was performed using spherical harmonics, implemented in the
SCALE3ABSPACK scaling algorithm. The data of complex (3) were
collected by Enraf-Nonius CAD-4 automatic four circle using Mo K
α
radiation ( = 0.71073 Å) [29,30]. Data collection was performed using the
λ
XCAD4 [31].The empirical absorption was corrected by psi-scan [32]. All
structures were solved by direct methods using the SHELXT, and refined by
full-matrix least-squares calculations on F2 using SHELXL-2014 [33]
integrated in WingX program [34]. The crystallographic data collection of
the samples and the results of the solution structures are summarized in
(Table.1). Diamond software was used for molecular graphics [35].
3. Results and Discussion
3.1. Crystal structures of complex (1)
The reaction between salicylaldoxime and vanadium(III) under aerobic
condition, in the presence of water, ledto the oxidation of vanadium(III) into
oxo-vanadium(IV) [36,37]. Complex (1) crystallizes in monoclinic space
group P21/n. This structure is similar to the complex reported by Li et al
[38], who used a different method of synthesis. The structural unit consists
of a discrete neutral monomer complex with selective atom numbering
scheme as shown in (Figure.1). The oxo-vanadium(IV) is coordinated to
two independent mono-deprotonated salicylaldoximato by the phenolic
oxygen and the oximato nitrogen atoms, forming a planar base with a V=O
bond in an apical position.

The polyhedral environment around the vanadium ion can be described as a
slightly distorted square-pyramidal geometry. The value of parameter is
equal to 0.11, which explains the slightly distorted geometry ( =0 for ideal
τ
τ
square-pyramidal) [39]. The five coordinate bond lengths and their angular
values are noted in Table.2. The vanadium atom is lifted by 0.575(6) Å from
the pyramidal base.
The two phenyl rings (C1–C6) and (C8–C13) have a r-m-s deviation of the
fitted atoms of 0.0037(2) Å and 0.0124(2) Å, respectively with a dihedral
angle of 6.75(1)°. The V=O bond length is 1.5951(5) Å. Selected bond
distances and angles are summarized in Table.S1.
The crystal packing view (Figure.2) shows a neighboring antiparallel
stacking of the structural unit. This face-to-face arrangement is maintained
by intermolecular hydrogen interactions between C-H···O and C-H···π,
which contribute to the stability and cohesion of the structure build
(Table.S2).
3.2.
Crystal structures of complex (2)
The salicylaldoxime and its derivatives form with transition metals,such as
iron and manganese, a large family of complexes[40,41]; due to the
presence of several donor atoms. The work of Zerbib et al.[25] proves the
instability of vanadium and salicylaldoxime complex in conventional
solvents; for example, the solubilization of [VO(C7H6NO2)2] in ethanol
gives a trimer [V3O3(C7H6NO2)2(C2H5O)5]. In this work, this instability is
demonstrated by the solubilization of [VO(C7H6 NO2)2] in para-xylene,
which gives a dimer [V2O2 (C7H6NO2)2(C7H5NO2)2].C8H10. In parallel, we
have the oxidation of vanadium(IV) to vanadium(V).

Complex (2) with selective atom numbering scheme in (Figure.3),
crystallizes in the triclinic space group P-1. The structural unit consists of
four salicylaldoximato coordinated to two oxo-vanadium(IV) and para-
xylene (1,4-dimethylbenzene). The oxo-vanadium(V) is coordinated to two
deprotonated salicylaldoximato by phenolic oxygen atoms and
oximatonitrogen atoms. The deprotonated oxygen atom of the oxime
function bridges to the adjacent vanadium and occupies the sixth coordinate
site. This double coordination between the two vanadium ions forms the
dimer. The atomscoordinated to the vanadium cations form two independent
octahedrawith the oxygen atom of vanadyl in a cis arrangement. The
distance between the two vanadium ions is 4.0689(3) Å, the coordinate bond
lengths and their angular values are summarized in Table.3.
The two phenyl rings (C1–C6) and (C8–C13) have an r-m-s deviation of the
fitted atoms of 0.0044(4) Å and 0.0101(4) Å, respectively with a dihedral
angle of 62.60(2)°. The r-m-s deviations of the fitted atoms of (C15-C20)
and (C22-C27) are 0.0093(4) Å and 0.0017(4) Å, respectively, with a
dihedral angle between the two rings of 86.24(2)°. In the crystal packing
illustrated in (Figure.4), the network structure is maintained through
intermolecular C—H···O and C—H···
π
hydrogen interactions (Table.S4).
Moreover, the presence of
π–π interactions in the structure between Cg3
[C22-C23/C27] and Cg3V (Symmetry code 1-x, -y, 2-z), which are 4.068(3)
Å apart, contribute to the cohesion and stability of the structure build.

3.3.
Crystal structures of complex (3)
Complex (3) was synthesized using a similar procedure to that reported by
Grigg et al [26]. The X-ray diffraction study reveals an iminoacylation
reaction of 4-hydroxysalicylaldoxime by acetonitrile, leading to formation of
a new iminoacylated ligand. The complex is obtained by the nucleophilic
attack of oxygen of the oxime function on the unsaturated carbon atom of
the nitrile group of the MeCN solvent, resulting in the formation of
iminoacylated ligand [42]. In parallel, during the reaction, vanadium
undergoes oxidation (VIVO to VVO2)due to the presence of water.
Complex (3) crystallizes in triclinic space group P-1. The structural unit
consists of a discrete monomer complex with selective atom numbering
scheme in (Figure.5). The structural unit consists of tridentate iminoacylated
ligand monodepronated, coordinated to dioxo-vanadium(V). The bond
lengths of V=O4 and V=O5 are 1.6300(2) Å and 1.6169(3) Å, respectively.
These are,according to the literature,typical distances of V=O double bonds
with an angle of 108.0715(1)° [43]; the coordination bond lengths and their
angular values are shown in Table.4. The vanadium ion adopts a trigonal
bipyramidal environment with five atoms (N2O3). The trigonal base is
formed by two oxygen atoms of dioxo-vanadium and one nitrogen atom
from oxime. The r-m-s deviation of the fitted atoms(V1, N1, O4, O5), which
isequal to 0.0465(7) Å,reveals acoplanar vanadium with a trigonal base. The
iminoacyled ligand is planar with anRMS deviation of the fitted atoms equal
to 0.0517(2) Å. The crystal structure can be described as a packing of
parallel layers of a planar complex along the aaxis with a linear coordination
of the structural units, and that are arranged parallel to each other at a
distance of 3.867(2) Å (Figure.6). The cohesion of the structure and stability
are ensured by intermolecular N—H···O and C—H···O hydrogen bonds
(Table.S6).

3.4.
UV–Vis spectral study
The UV–Vis absorption spectra study of complexes 1–3 and ligands,
recorded in the 200-900 nm region in DMSO solution at room temperature,
are presented in (Figure.7). In the ultraviolet region, the spectrum displays a
strong band around 260 nm and 310 nm for complexes (1) and (2) as well as
for the salicylaldoxime ligand. These bands are attributed to π→π*and
n
→π* intramolecular transitions of the ligand. For complexes (3) and 4-
hydroxysalicylaldoxime, the spectrum presents transitions at 275 nm and
310 nm, respectively due to the intramolecular π→π* and n→π* transitions
[6]. In the visible region, one can observe very weak intensity band around
565nm for complex (1) [VO(HL)2] attributed to the d-d transition of
vanadium(IV) [44]. For complex (2) [VO(HL)2(L)2].C8H10 and complex (3)
[VO2(L’)], no d-d transition absorption appears in the spectrum. This
absence is due to the d0 of the electronic configuration of vanadium(V) [45].
3.5. Thermal analysis
Thermogravimetric analysis (TGA) was employed to study the thermal
proprieties of the complexes. Itwas carried out at a heating rate of 10 C/min
under nitrogen. All the complexes exhibit stabilityat room temperature but
decompose differently according to the nature and number of ligands
(Figure.8). Complex (1) gradually decomposes in two steps, the melting
point is just before the first partial weight loss of 32% at 165°C and the
second weight loss of 43% at 470°C, due to the major decomposition.
Complex (2) degrades in three steps. The first loss of 21%is between 152°C-
210°C and the second of 13% at 286°C while the third and the major one is
observed at 392°C with 39%. Complex (3) begins to degrade at 197°C with
16% of weight loss,followed by asmaller weight loss of 9.5% at 250°C, to
end up with the last and largest weight loss of 41% at 350°C.

4. Conclusion
In summary, we studied three complexes of vanadium with oxime ligands,
twomonomer and a binuclear. All complexes structures were elucidated by
single crystal x-ray diffraction and characterized by spectroscopic methods
and thermal analysis. Complex (1) exhibits a classical square pyramidal
coordination. Complex (2) has
a
new dimeric vanadium
[VO(HL)2(L)2].C8H10 structure, the bridge connecting two doubly
deprotonated salicylaldoxime ligand. Complex (3) was synthesized by
iminoaclylation reaction between 4-hydroxysalicylaldoxime vanadium
complex and acetonitrile, which produces the tridentate iminoacylated ligand
dioxovanavium. The packing of all the complexes is ensured by various
intermolecular interactions; H-bonds and
π–π serve the stabilization and
cohesion of the structure build. The UV-visible spectroscopy study and
thermal analysis showed a good agreement with the structures of the
complexes.
Further applications are under way, including the biological application such
as antimicrobial, antioxidant and antitumor activity. Further research is
plannedfor the synthesis of new complexes in this category.
5. Supplementary Material
CCDC 1851810, CCDC 1857553 and CCDC 1938771contain complete
supplementary crystallographic data for complexes (1), (2) and (3),
respectively. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_ request/cif
Supplementary information (SI): Tables.
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Table.1: Crystal data and refinement results for complexes (1), (2) and (3).
complex (1)
complex (2)
complex (3)
crystal data
Chemical formula
Mr
C14H12N2O5V
339.20
C32H27N4O10V2
729.45
C9H9N2O5V
276.12
Crystal
space
system,
Monoclinic
P21 /n
Triclinic
P-1
Triclinic
P-1
group
Temperature (K)
a (Å)
293
100
293
14.718 (4)
7.182 (3)
14.781 (5)
90
10.196 (6)
11.895(7)
14.201 (9)
83.614 (5)
69.880 (6)
72.708 (6)
7.9703 (3)
8.251 (2)
9.105 (2)
82.285 (10)
82.015 (10)
65.797
b (Å)
c (Å)
α (°)
113.120 (5)
90
β (°)
γ (°)
1437.1 (9)
1544.0 (16)
538.87 (19)
2
V (Å3)
4
2
Z
purple
black
yellow
Color
0.46 × 0.31 × 0.19
0.32 × 0.28 × 0.17
Xcalibur,
diffractometer
0.41 × 0.14 × 0.10
Atlas Enraf–Nonius
diffractometer
Crystal size (mm)
Xcalibur,
Atlas
CAD-4
diffractometer
Diffractometer
R1, wR2
0.048, 0.128
1.100
0.074, 0.198
1.095
0.032, 0.092
1.075
GOF
0.695
0.650
0.660
(sin θ/λ)max(Å−1)
No. of reflections
(ꢀ/σ)max
3710
5971
2573
0.001
< 0.001
3.241
ꢀρmax,
ꢀρmin
0.59, −0.50
1.14, −0.65
0.32, −0.21
(eÅ−3)

Table.2: Bond distances and bond angles for complex (1).
Bond distances (Å)
V—O05
V—O3
V—O1
1.5951 (17) V—N2
1.9174 (16) V—N1
1.9216 (17)
2.060 (2)
2.060 (2)
Bond angles (°)
O05—V—O3
O05—V—O1
O3—V—O1
O05—V—N2
O3—V—N2
108.55 (8)
108.95 (9)
142.50 (8)
106.00 (9)
85.97 (7)
O1—V—N2
83.14 (8)
104.46 (9)
84.82 (7)
86.70 (7)
149.54 (8)
O05—V—N1
O3—V—N1
O1—V—N1
N2—V—N1
Table.3: Bond distances and bond angles for complex (2).
Bond distances (Å)
V01—O05
V01—O01
V01—O03
V01—O09
V01—N02
V01—N01
Bond angles (°)
1.591 (4)
1.823 (4)
1.864 (4)
1.952 (4)
2.111 (5)
2.318 (5)
V02—O10
V02—O06
V02—O08
V02—O04
V02—N04
V02—N03
1.600 (4)
1.833 (4)
1.875 (4)
1.939 (4)
2.121 (5)
2.313 (5)
O05—V01—O01 102.6 (2)
O10—V02—O06 103.9 (2)
O05—V01—O03 100.25 (19) O10—V02—O08 100.78 (18)
O01—V01—O03 95.76 (18)
O05—V01—O09 95.13 (19)
O01—V01—O09 96.31 (17)
O06—V02—O08 91.75 (18)
O10—V02—O04 93.28 (19)
O06—V02—O04 97.97 (17)
O03—V01—O09 157.86 (17) O08—V02—O04 160.50 (16)
O05—V01—N02 92.6 (2) O10—V02—N04 94.7 (2)
O01—V01—N02 164.80 (17) O06—V02—N04 161.22 (18)
O03—V01—N02 80.97 (18)
O09—V01—N02 82.52 (18)
O05—V01—N01 170.6 (2)
O01—V01—N01 81.44 (18)
O03—V01—N01 87.69 (17)
O09—V01—N01 75.86 (17)
N02—V01—N01 83.58 (18)
O08—V02—N04 81.84 (18)
O04—V02—N04 83.62 (17)
O10—V02—N03 171.1 (2)
O06—V02—N03 81.26 (19)
O08—V02—N03 86.16 (17)
O04—V02—N03 78.71 (17)
N04—V02—N03 80.72 (19)

Table.4: Bond distances and bond angles for complex (3).
Bond distances (Å)
V001—O5
V001—O4
V001—O1
V001—N2
V001—N1
1.6170 (15)
1.6300 (17)
1.8972 (15)
2.0546 (19)
2.1185 (17)
Bond angles (°)
O5—V001—O4
O5—V001—O1
O4—V001—O1
O5—V001—N2
O4—V001—N2
108.07 (9)
100.21 (7)
101.69 (8)
94.98 (8)
95.87 (8)
O1—V001—N2
O5—V001—N1
O4—V001—N1
O1—V001—N1
N2—V001—N1
151.83 (7)
130.73 (8)
120.08 (8)
80.66 (7)
71.47 (7)

Figure.1: The structural unit of complex (1), showing the atomic numbering scheme.
Displacement ellipsoids are shown at 50% probability level; H atoms have been omitted
for clarity.
.
Figure.2: Crystal packing of complex (1) viewed along the [100] direction.

Figure.3: The structural unit of complex (2), showing the atomic numbering scheme.
Displacement ellipsoids are shown at 50% probability level, H atoms have been omitted
for clarity.

Figure.4: Crystal packing of complex (2) viewed along the [100] direction.
Figure.5: The structural unit of complex (3), showing the atomic numbering scheme.
Displacement ellipsoids are shown at 50% probability level, H atoms have been omitted
for clarity.

Figure.6: Crystal packing of complex (3) viewed along the [010] direction.

Figure.7: UV-Visible absorption spectra in DMSO, comparison between ligand and their
complexes.

Figure.8: TGA-Curves of vanadium complexes.

Highlights
- Synthesis of new vanadium complexes with phenolic oxime.
- The complexes were determined by X-ray diffraction and
characterized by thermal and spectroscopic analysis.
- The instability of the complex in organics solvent p-xylene.
- The iminoacylation reaction by acetonitril result a new
compound.

Ilyas Belkhettab
Study, conception and design.
Sultana Boutamine Supervision, original draft preparation.
Hennia Slaouti Interpretation of results and Contribution to the interpretation of the results.
Med Faouzi Zid Data collection of single crystal and structural resolution.
Habib Boughzala Refinement structures and representation of crystallographic results.
Zakia Hank
procedure.
Involvement in the drafting of the manuscript - Reviewing and Submission

Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.