Synthesis, characterization, and X-ray crystal structures of oxovanadium(V) complexes with hydrazone and 8-hydroxyquinoline ligands

Article abstract of DOI:10.1134/S1070328414120112

Three new oxovanadium(V) complexes with the general formula [VO(L) ⁿ (HQ)] (n = 1-3) were prepared by the reaction of [VO(Acac)₂] (Acac = acetylacetonate) and 8-hydroxyquinoline with similar benzohydrazide ligands in methanol. Crysta

Full text of DOI:10.1134/S1070328414120112

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ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2014, Vol. 40, No. 12, pp. 948–953. © Pleiades Publishing, Ltd., 2014.
Synthesis, Characterization, and Xꢀray Crystal Structures
of Oxovanadium(V) Complexes with Hydrazone
and 8ꢀHydroxyquinoline Ligands1
S. S. Qiana, Y. T. Yeb, J. Q. Renb, Z. Youb, *, and H. L. Zhua, **
a School of Life Sciences, Shandong University of Technology, Zibo, 25504 P.R. China
b Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 P.R. China
eꢀmail: youzhonglu@126.com*; hailiang_zhu@163.com**
Received May 5, 2014
Abstract—Three new oxovanadium(V) complexes with the general formula [VO(L)n(HQ)] (
n = 1–3) were
prepared by the reaction of [VO(Acac)2] (Acac = acetylacetonate) and 8ꢀhydroxyquinoline with similar benꢀ
zohydrazide ligands in methanol. Crystal and molecular structures of the complexes were determined by eleꢀ
mental analysis, infrared and UVꢀVis spectra and single crystal Xꢀray diffraction (CIF file CCDC
nos. 1004087 (I), 1004088 (II), and 1004089 (III)). The V atoms are in octahedral coordination. Thermal
stability of the complexes were studied.
DOI: 10.1134/S1070328414120112
1
INTRODUCTION
EXPERIMENTAL
Vanadium plays an important role in biological proꢀ
Materials and measurements. Commercially availꢀ
able salicylaldehyde, 3ꢀmethoxysalicylaldehyde,
4ꢀmethoxysalicylaldehyde and 3ꢀmethylbenzohyꢀ
drazide were purchased from Aldrich and used without
further purification. C, H, and N elemental analyses
were performed with a PerkinꢀElmer elemental anaꢀ
cesses [1–3]. In human beings, vanadium complexes
have shown promising activity for the treatment of diabeꢀ
tes [4, 5]. In recent years, a large number of vanadium
complexes with various ligands have been prepared [6–
10]. Among the complexes, those derived from hydraꢀ
zones have been received particular attention in biologiꢀ
cal and medicinal chemistry [11–15]. 8ꢀHydroxyquinoꢀ lyzer. Infrared spectra were recorded on a Nicolet
line is a widely used bidentate ligand. As a continuation of
the work to extend vanadium complexes, in the present
paper, three new hydrazone oxovanadium(V) complexes
AVATAR 360 spectrometer as KBr pellets in the
4000–400 cm–1 region. UVꢀVis spectra were recorded
on a Lambdar 900 spectrometer with acetonitrile as
the solvent. Thermal stability analysis was performed
[VO(L1)(HQ)]
[VO(L3)(HQ)]
(
I
), [VO(L2)(HQ)]
III
(H2L1
(
II), and
'ꢀ(2ꢀhydroxybenꢀ
'ꢀ(2ꢀ
hydroxyꢀ4ꢀmethoxybenzylidene)ꢀ3ꢀmethylbenzohydraꢀ
zide, H2L3 =
'ꢀ(2ꢀhydroxyꢀ3ꢀmethoxybenzylidene)ꢀ3ꢀ
(
)
= N
zylidene)ꢀ3ꢀmethylbenzohydrazide, H2L2
= N
on a PerkinElmer Pyris Diamond TG
−
DTA thermal
analyses system.
N
Synthesis of the complexes. The three complexes
were prepared by the similar method. Equimolar
quantities (0.1 mmol each) of 3ꢀmethylbenzohyꢀ
drazide and various aldehydes were reacted at room
temperature in methanol (15 mL) for 30 min. Then,
the solid of 8ꢀhydoxyquinoline (0.1 mmol) and
[VO(Acac)2] (0.1 mmol) were added to the mixture.
The final mixture was further stirred for 30 min at
room temperature to give a deep brown solution. The
resulting solution was allowed to stand in air for a few
days. Brown blockꢀshaped crystals suitable for Xꢀray
single crystal diffraction were formed at the bottom of
the vessel. The isolated products were washed three
methylbenzohydrazide), bearing 8ꢀhydroxyquinoline
(HHQ) ligands, have been presented. The hydrazone
ligands are the following:
H
N
N
O
X
OH
Y
1
2
H L : X = Y = H; H L : X = OMe, Y = H;
2
2
3
H L : X = H, Y = OMe
2
1
The article is published in the original.
948

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SYNTHESIS, CHARACTERIZATION, AND XꢀRAY CRYSTAL STRUCTURES
949
Table 1. Crystallographic data and refinement parameters for complexes
I–III
Value
Parameter
I
II
III
Formula weight
Crystal color; habit
Crystal size, mm
Crystal system
463.3
493.4
493.4
Brown; block
Brown; block
Brown; block
0.22
×
0.21
×
0.17
0.20
Monoclinic
21/
×
0.17
×
0.17
0.32
Monoclinic
21/
×
0.27 0.26
×
Orthorhombic
Space group
Pbca
P
n
P
c
Unit cell parameters:
a
, Å
, Å
13.071(1)
14.476(1)
22.918(2)
90
15.805(1)
8.157(1)
18.084(2)
100.512(2)
2292.2(3)
4
8.006(1)
31.065(3)
9.341(1)
106.217(2)
2230.6(3)
4
b
c
, Å
β
V
Z
, deg
, Å3
4336.4(5)
8
ρcalcd, g cm–3
1.419
298(2)
0.494
1904
1.430
1.469
Temperature, K
298(2)
0.475
298(2)
0.488
μ
, mm–1
F
(000)
1016
1016
Number of unique data
Number of observed data (
Number of parameters
3857
4082
3979
I
> 2
σ
(I
))
2269
2414
2895
290
309
309
Final
R
indices (
I
> 2σ(I
))
R
1 = 0.0763,
wR2 = 0.1307
1 = 0.1404,
R
1 = 0.0621,
R
1 = 0.056,
wR2 = 0.1188
1 = 0.0868,
wR2 = 0.1139
R
indices (all data)
R
R
1 = 0.1319,
R
wR2 = 0.1592
1.104
wR2 = 0.1387
1.042
wR2 = 0.1308
1.071
Goodness of fit on F2
Highest peak and deepest hole,
e
Å–3
0.441, –0.320
0.503, –0.338
0.469, –0.286
times with cold methanol and dried in air. The yields
were 65 ( ), 73 (II), 77% (III).
Xꢀray crystallography. Diffraction intensities for
the complexes were collected at 298(2) K using a
Bruker D8 VENTURE PHOTON diffractometer with
I
For C24H18N3O4V (
anal. calcd., %: C, 62.21;
Found, %: C, 62.38;
I)
Mo
K
radiation ( = 0.71073 Å). The collected data
λ
α
H, 3.92; N, 9.07.
H, 4.03; N, 8.92.
were reduced using the SAINT program [16], and
multiꢀscan absorption corrections were performed
using the SADABS program [17]. The structures were
solved by direct methods and refined against F2 by
fullꢀmatrix leastꢀsquares methods using the
SHELXTL [18]. All of the nonꢀhydrogen atoms were
refined anisotropically. Hydrogen atoms were placed
For C25H20N3O5V (II) and (III
)
anal. calcd., %: C, 60.86;
H, 4.09; N, 8.52.
Found, %:
Found, %:
C, 60.77;
C, 60.72;
H, 4.20; N, 8.41 (II).
H, 4.14; N, 8.65 (III).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
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2014

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950
QIAN et al.
Table 2. Selected bond distances and angles for the complexes
Bond
d
, Å
Bond
d, Å
I
V(1)–O(1)
V(1)–O(3)
V(1)–N(1)
1.839(4)
1.838(4)
2.074(5)
V(1)–O(2)
V(1)–O(4)
V(1)–N(3)
1.924(4)
1.580(4)
2.344(4)
II
V(1)–O(1)
V(1)–O(4)
V(1)–N(1)
1.848(3)
1.838(2)
2.071(3)
V(1)–O(2)
V(1)–O(5)
V(1)–N(3)
1.933(2)
1.587(3)
2.359(3)
III
V(1)–O(1)
V(1)–O(4)
V(1)–N(1)
1.849(2)
1.847(2)
2.076(3)
V(1)–O(2)
V(1)–O(5)
V(1)–N(3)
1.936(2)
1.578(2)
2.380(3)
Angle
ω
, deg
Angle
ω
, deg
I
O(4)V(1)O(3)
O(3)V(1)O(1)
O(3)V(1)O(2)
O(4)V(1)N(1)
O(1)V(1)N(1)
O(4)V(1)N(3)
O(1)V(1)N(3)
N(1)V(1)N(3)
101.8(2)
103.5(2)
90.3(2)
97.6(2)
84.3(2)
176.8(2)
83.6(2)
83.5(2)
O(4)V(1)O(1)
O(4)V(1)O(2)
O(1)V(1)O(2)
O(3)V(1)N(1)
O(2)V(1)N(1)
O(3)V(1)N(3)
O(2)V(1)N(3)
99.5(2)
99.0(2)
154.0(2)
157.5(2)
75.3(2)
76.5(2)
78.3(2)
II
O(5)V(1)O(4)
O(4)V(1)O(1)
O(4)V(1)O(2)
O(5)V(1)N(1)
O(1)V(1)N(1)
O(5)V(1)N(3)
O(1)V(1)N(3)
N(1)V(1)N(3)
98.7(1)
104.3(1)
91.1(1)
100.0(1)
84.0(1)
174.5(1)
82.0(1)
85.4(1)
O(5)V(1)O(1)
O(5)V(1)O(2)
O(1)V(1)O(2)
O(4)V(1)N(1)
O(2)V(1)N(1)
O(4)V(1)N(3)
O(2)V(1)N(3)
99.7(1)
97.4(1)
154.8(1)
157.9(1)
75.0(1)
75.7(1)
82.7(1)
III
O(5)V(1)O(4)
O(4)V(1)O(1)
O(4)V(1)O(2)
O(5)V(1)N(1)
O(1)V(1)N(1)
O(5)V(1)N(3)
O(1)V(1)N(3)
N(1)V(1)N(3)
99.2(1)
105.2(1)
90.2(1)
96.8(1)
83.8(1)
174.5(1)
82.3(1)
88.3(1)
O(5)V(1)O(1)
O(5)V(1)O(2)
O(1)V(1)O(2)
O(4)V(1)N(1)
O(2)V(1)N(1)
O(4)V(1)N(3)
O(2)V(1)N(3)
100.2(1)
100.7(1)
151.5(1)
159.8(1)
74.7(1)
75.4(1)
78.6(1)
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SYNTHESIS, CHARACTERIZATION, AND XꢀRAY CRYSTAL STRUCTURES
951
in idealized positions and constrained to ride on their
parent atoms. The crystallographic data for the comꢀ
(а)
plexes I–III are summarized in Table 1. Selected bond
C(10)
C(15)
C(11)
C(5)
C(6)
C(1)
lengths and angles are given in Table 2.
N(2)
C(7)
N(1)
Supplementary material for structures
I–III has
C(4)
C(3)
C(8)
been deposited with the Cambridge Crystallographic
Data Centre (nos. 1004087 (
O(4)
I), 1004088 (II), and
C(12)
C(13)
C(9)
O(2)
C(23)
C(22)
1004089 (III); deposit@ccdc.cam.ac.uk or http://
C(2)
O(1)
www.ccdc.cam.ac.uk
C(14)
V(1)
O(3)
N(3)
C(24)
C(21)
RESULTS AND DISCUSSION
Replacement of two acetylacetonate ligands of
[VO(Acac)2] by hydrazone and 8ꢀhydroxyquinoline
ligands in methanol resulted in the formation of three
structurally similar complexes. The complexes are solꢀ
uble in DMF, DMSO, methanol, ethanol, and acetoꢀ
nitrile. Molar conductance of the complexes at
C(16)
C(20)
C(19)
C(17)
C(18)
the concentrations of 10–4 mol L–1 are in the range
(b)
C(11)
C(12)
C(13)
–1
20–50
Ω
cm2 mol–1, indicating they are nonꢀelecꢀ
C(6)
C(1)
N(2)
C(5)
C(10)
trolytes [19].
C(8)
The molecular structures and atom numbering
schemes of complexes I, II, and III are shown in
C(4)
O(5)
C(14)
C(15)
N(1)
O(3)
C(7)
C(9)
Fig. 1. The V atoms in the complexes are in octahedral
coordination, with the three donor atoms of
the hydrazone ligands and the hydroxy O atom of the
8ꢀhydroxyquinoline ligand defining the equatorial
plane, and with one oxo O atom and the pyridine N
atom of the 8ꢀhydroxyquinoline ligand occupying the
C(16)
O(2)
C(3)
C(2)
V(1)
C(24)
O(1)
N(3)
O(4)
C(17)
C(23)
C(25)
C(22)
axial positions. The distances V(1)–O(4) in
I and
C(21)
C(20)
V(1) O(5) in II and III are in the range 1.57–1.59 Å,
⎯
indicating they are typical V=O double bonds. The
V(1)–N(3) bonds in the complexes are significantly
longer than the other coordinate bonds, yet, it is not
uncommon for such complexes [20, 21]. The coordiꢀ
nate bond lengths in the complexes are comparable to
each other and also similar to those observed in the
mononuclear oxovanadium(V) complexes with octaꢀ
hedral coordination [20–23]. The angular distortion
in the octahedral environment around V comes from
the five– and sixmembered chelate rings taken by the
hydrazone ligands. For the same reason, the trans
angles significantly deviate from the ideal values of
C(18)
C(19)
(c)
C(16)
C(6)
C(2)
C(11)
C(1)
O(5)
C(5)
C(4)
C(8)
N(2)
C(10)
C(12)
N(1)
N(3)
C(13)
C(14)
C(9)
O(2)
C(3)
O(1)
C(15)
V(1)
O(3)
C(7)
180
observed from the coordinate bond angles, ranging
from 75.3(2) to 103.5(2) for the perpendicular
angles, and from 154.0(2) to 176.8(2) for the diagoꢀ
nal angles for , and from 75.0(1) to 104.3(1)
perpendicular angles, and from 154.8(1) to 174.5(1)
for the diagonal angles for II, and from 74.7(1)
°
. Distortion of the octahedral coordination can be
C(24)
C(25)
C(23)
C(22)
O(4)
C(17)
°
°
°
°
C(18)
C(19)
I
°
°
for the
°
°
C(21)
C(20)
°
to
105.2(1)
151.5(1)
°
for the perpendicular angles, and from
to 174.5(1) for the diagonal angles for III
Fig. 1. ORTEP plot of the crystal structures of I (a), II (b),
°
°
.
and III (c). Displacement ellipsoids of nonꢀhydrogen
atoms are drawn at the 30% probability level.
The displacement of the V atoms from the equatorial
plane are 0.319(1) Å for , 0.298(1) Å for II, and
0.309(1) Å for III. The dihedral angle between the
benzene rings of the hydrazone ligand are 7.7(5) for
24.7(4) for II, and 7.7(3) for III
The complexes exhibit typical V=O absorption
I
ν
(C=O) were absent in the complexes, but new C–O
stretches appeared at about 1230–1260 cm–1 for the
°
I,
°
°
.
complexes. This suggests occurrence of ketoꢀimine
bands at about 973 cm–1 [24]. The bands due to tautomerization of the ligands during complexation.
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2014