Synthesis, crystal structure, and thermal property of [N′-(2-hydroxy- 3-methoxybenzylidene)-2-methoxybenzohydrazonato](methanol)(methoxy) oxovanadium(V)

Article abstract of DOI:10.1080/15533174.2013.799496

The aroylhydrazone Schiff base ligand N'-(2-hydroxy-3-methoxybenzylidene)- 2-methoxybenzohydrazide (H₂L) reacts with VO(acac)₂ in methanol gave the complex [N′-(2-hydroxy-3-methoxybenzylidene)-2- methoxybenzohydrazonato] (methanol) (

Full text of DOI:10.1080/15533174.2013.799496

This article was downloaded by: [Chulalongkorn University]
On: 05 January 2015, At: 10:01
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
Synthesis, Crystal Structure, and Thermal Property
of [N′-(2-hydroxy-3-methoxybenzylidene)-2-
methoxybenzohydrazonato](methanol)
(methoxy)oxovanadium(V)
Jun-Min Wanga, Hui-Min Liua, Dong-Nuan Zhanga, Peng-Lei Cuia & Jing-Jun Maa
a Hebei Key Laboratory of Bioinorganic Chemistry, College of Sciences, Agricultural
University of Hebei, Baoding, P. R. China
Accepted author version posted online: 17 Dec 2013.Published online: 17 Apr 2014.
Click for updates
To cite this article: Jun-Min Wang, Hui-Min Liu, Dong-Nuan Zhang, Peng-Lei Cui & Jing-Jun Ma (2014) Synthesis, Crystal
Structure, and Thermal Property of [N′-(2-hydroxy-3-methoxybenzylidene)-2-methoxybenzohydrazonato](methanol)
(methoxy)oxovanadium(V), Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:9, 1251-1254,
DOI: 10.1080/15533174.2013.799496
To link to this article: http://dx.doi.org/10.1080/15533174.2013.799496
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:1251–1254, 2014
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.799496
Synthesis, Crystal Structure, and Thermal Property
of [Nꢀ-(2-hydroxy-3-methoxybenzylidene)-2-
methoxybenzohydrazonato](methanol)(methoxy)oxovanadium(V)
Jun-Min Wang, Hui-Min Liu, Dong-Nuan Zhang, Peng-Lei Cui, and Jing-Jun Ma
Hebei Key Laboratory of Bioinorganic Chemistry, College of Sciences, Agricultural University of Hebei,
Baoding, P. R. China
and a 8-hydroxyquinoline coordinated vanadium complex
with an aroylhydrazone ligand.[17] As a further study on the
The aroylhydrazone Schiff base ligand N’-(2-hydroxy-3-
methoxybenzylidene)-2-methoxybenzohydrazide (H2L) reacts
with VO(acac)2 in methanol gave the complex [Nꢀ-(2-hydroxy-3-
methoxybenzylidene)-2-methoxybenzohydrazonato] (methanol)
(methoxy)oxovanadium(V), [VVOL(CH3OH)(CH3O)]. The struc-
ture of the complex was characterized by elemental analysis and
IR spectroscopic method in the solid state. Single-crystal X-ray
analysis was also performed, which indicates that the V atom
in the mononuclear complex is six-coordinated in an octahedral
geometry. VIV in VO(acac)2 was oxidized to VV by aerial oxygen in
the synthesis and crystallization. Thermal stability of the complex
was determined.
coordination of aroylhydrazone to vanadium ions, in this
paper, a new vanadium complex, [VVOL(CH3OH)(CH3O)],
[Nꢁ-(2-hydroxy-3-methoxybenzylidene)-2-methoxybenzohyd-
razonato](methanol)(methoxy)oxovanadium(V), was synthe-
sized and characterized.
EXPERIMENTAL
Materials and Methods
3-Methoxysalicylaldehyde, 2-methoxybenzohydrazide, and
vanadium(IV) oxide acetylacetonate ([VO(acac)2]) were pur-
chased from Merck and Fluka and used as received.
The aroylhydrazone Schiff base ligand Nꢁ-(2-hydroxy-3-
methoxybenzylidene)-2-methoxybenzohydrazide (H2L) was
prepared in a 93% yield by condensation reaction of 3-
methoxysalicylaldehyde with 2-methoxybenzohydrazide in
methanolic media, according to the literature method.[15,16] All
other chemicals and solvents used in this work were of an-
alytical grade available commercially and were used without
further purification. The elemental analyses (carbon, hydrogen,
and nitrogen) of the compounds were obtained from a Carlo
Erba Model EA 1108 analyzer. Infrared spectra were collected
by using KBr pellets on a Jasco-5300 FT-IR spectrophotometer.
Solution electrical conductivity was measured with a DDS-11A
conductivity meter. Thermal analysis of the complexes was car-
ried out by heating at a rate of 10◦C/min on a Perkin Elmer
TGA-4000 thermo balance.
Keywords aroylhydrazone, crystal structure, thermal property, vana-
dium complex
INTRODUCTION
The presence of vanadium(IV) and vanadium(V) compounds
in many vanadium-dependent enzymes,[1–3] as well as insulin
mimicking,[4,5] have stimulated the search for structural and
functional models based on vanadium complexes. In addition,
oxovanadium complexes have been attracted much attention for
their versatile catalytic properties in organic preparation.[6–8]
In recent years, the remarkable biological activity of aroylhy-
drazones and the dependence of their mode of chelation with
transition metal ions in living systems have been of significant
interest.[9–14] In order to understand clearly the properties of
such complexes, detailed structures should be characterized.
Considering that single-crystal X-ray diffraction is the best
choice for the characterization of metal complexes, recently,
we have reported some aroylhydrazone compounds[15,16]
Synthesis of [VVOL(CH3OH)(CH3O)]
[VO(acac)2] (0.01 mmol, 2.65 g) dissolved in methanol
(30 mL) was added dropwise to a stirred methanolic solution
(30 mL) of H2L (0.01 mol, 3.00 g). The mixture was gently
refluxed for 2 h, then most of the solvent was evaporated by
distillation. After cooling, the resulting brown solid was filtered
off, washed with cold absolute methanol, and dried in a vac-
uum containing anhydrous CaCl2. Yield: 3.27 g (76%). IR data
(cm−1, KBr): 3443 (w), 3208 (m), 1607 (s), 1558 (m), 1523 (m),
1488 (m), 1471 (m), 1451 (w), 1436 (w), 1352 (w), 1340 (m),
Received 16 April 2013; accepted 22 April 2013.
Address correspondence to Jing-Jun Ma, Hebei Key Labo-
ratory of Bioinorganic Chemistry, College of Sciences, Agricul-
tural University of Hebei, Baoding 071001, P. R. China. E-mail:
majingjun71@aliyun.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
1251

1252
J.-M. WANG ET AL.
TABLE 1
Crystallographic data for the complex
N
H
N
N
O
O
N
MeOH
O
OMe
OMe
Chemical
formula
Formula
weight
C18H21N2O7V ρ (g cm−3
μ (mm−1
)
1.416
VO(acac)2
+
O
OMe
V
OH
OMe
H
OMe
OMe
428.31
)
0.535
SCH. 1. The synthesis of the complex.
Crystal system Monoclinic Tmin, Tmax
Space group P21/c
0.8868, 0.9005
11527
Reflections
collected
Reflections
unique
Reflections
observed [I >
2σ(I)]
RESULTS AND DISCUSSION
Synthesis and Characterization
Unit cell
dimensions
a (Å)
4361
3904
The reaction of VO(acac)2 with the tridentate aroylhydra-
zone Schiff base ligand Nꢁ-(2-hydroxy-3-methoxybenzylidene)-
2-methoxybenzohydrazide in methanol under aerobic condi-
tions afforded the neutral oxovanadium(V) complex (Scheme 1).
Most likely during the synthesis and crystallization of the com-
plex from oxovanadium(IV) starting material, the aerial oxygen
acts as the oxidizing agent. Elemental analyses of the complex
are consistent with the general molecular formula proposed by
single-crystal X-ray determination. The complex is soluble in
common organic solvents such as dimethylsulfoxide, dimethyl-
formamide, methanol, and ethanol. In absolute methanolic so-
lution, it is electrically nonconducting.
9.9882(5)
b (Å)
c (Å)
α (◦)
19.4232(10) Parameters
260
1
10.8912(6)
90
Restraints
R1, wR2 [I >
2σ(I)]
R1, wR2 (all
data)
0.0349, 0.0913
β (◦)
108.060(1)
90
0.0395, 0.0947
1.085
γ (◦)
Goodness-of-fit
on F2
V (Å3)
2008.8(2)
Largest
0.203, –0.453
difference in
peak and hole
IR Spectroscopic Characteristics
The infrared spectra of the free aroylhydrazone Schiff base
ligand and the complex gave information about the coordination.
The free ligand displays a broad band centered at 3415 cm−1
and a weak and sharp band at 3223 cm−1. These bands are
possibly due to the O–H and N–H stretches. However, the sharp
band is absence in the spectrum of the complex. The absence
of the ν(C O) band, presents in H2L at 1651 cm−1, indicates
the enolization of the amide functionality upon coordination to
the V atom. Strong band observed at 1607 cm−1 for the complex
can be attributed to the stretching vibrations of the azomethine
(e Å−3
)
Z
4
1291 (m), 1256 (s), 1222 (w), 1106 (w), 973 (s), 917 (w), 870
(w), 752 (m), 700 (w), 682 (w), 601 (m), 435 (w). Dark brown
block-like single crystals of the complex, suitable for single
crystal X-ray diffraction, were obtained by slow evaporation of
a methanol solution containing the complex. Anal. Calcd. for
C18H21N2O7V (%): C, 50.48; H, 4.94; N, 6.54. Found: C, 50.30;
H, 5.05; N, 6.36.
group, νC
.
[19] The spectrum of the complex displays typical
N
and intense band at 973 cm−1, which can be assigned to the
stretch of the V O bonds.[20]
Description of the Crystal Structure of the Complex
X-Ray Crystallography
The molecular structure and the atom numbering scheme
for the complex is depicted in Figure 1. Selected bond lengths
and angles are given in Table 2. The complex is a neutral
mononuclear oxovanadium compound. The coordination geom-
etry around the vanadium atom can be described as a distorted
octahedral with the tridentate aroylhydrazone ligand coordi-
nated in a meridional fashion, forming five- and six-membered
chelate rings with bite angles of 74.49(5)◦ (N1–V1–O2) and
83.48(5)◦ (N1–V1–O1), typical for this type of ligand sys-
tem.[17,21,22] The aroylhydrazone Schiff base ligand coordinates
in its dianionic enolate form, which is consistent with the ob-
served C8–O2 and C8–N2 bond lengths of 1.298(2) and 1.300(2)
Å. The three donor atoms of the aroylhydrazone ligands and O6
atom of the deprotonated methanol ligand define the equatorial
A suitable X-ray quality crystal of the complex was placed
under a microscope and investigated in a diffraction experi-
ment at 298(2) K on a Bruker Apex II diffractometer with
monochromated Mo Kα radiation (λ = 0.71073 Å) obtained
from a graded multilayer X-ray optics. The structure was solved
by direct methods with SHELXS-97,[18] and refined with full-
matrix least-squares techniques on F2 with SHELXL-97.[18]
The C-bonded hydrogen atoms were calculated in an idealized
geometry, riding on their parent atoms, with distances restrained
to 0.93–0.96 Å. H5A atom attached to O5 in the complex was
located from a difference Fourier map and refined isotropically,
with O–H distance restrained to 0.85(1) Å. The crystal data and
refinement parameters are listed in Table 1.

SYNTHESIS, CRYSTAL STRUCTURE, AND THERMAL PROPERTY
1253
TABLE 2
Selected bond lengths (Å) and angles (◦) for the complex
Bond lengths (Å)
V1–O1
V1–O5
V1–O7
1.8475(12)
2.3071(13)
1.5857(14)
V1–O2
V1–O6
V1–N1
1.9596(12)
1.7778(12)
2.1309(14)
Bond angles (◦)
O7–V1–O6
O6–V1–O1
O6–V1–O2
O7–V1–N1
O1–V1–N1
O7–V1–O5
O1–V1–O5
N1–V1–O5
102.09(7)
101.91(6)
94.50(5)
94.45(7)
83.48(5)
174.99(6)
79.73(5)
80.57(5)
O7–V1–O1
O7–V1–O2
O1–V1–O2
O6–V1–N1
O2–V1–N1
O6–V1–O5
O2–V1–O5
100.37(7)
97.29(7)
152.69(6)
161.26(6)
74.49(5)
82.75(6)
80.88(5)
FIG. 2. Molecular packing diagram of the complex, viewed down the a axis.
Hydrogen bonds are drawn as dashed lines.
plane of the octahedral coordination. The two axial positions of
the octahedral coordination are occupied by the O5 atom of the
methanol ligand, and one oxo group. The O5 atom coordinates
to the V atoms at rather elongated distance of 2.307(1) Å, due
to the trans influence of the oxo groups. This is accompanied
by a significant displacement of the V atom from the equatorial
plane towards the oxo group by 0.296(2) Å.
In the crystal structure of the complex, molecules are
linked through intermolecular O5–H5A···N2 hydrogen bonds
[O5–H5A = 0.85(1) Å, H5A···N2i = 1.955(11) Å, O5···N2i =
2.791(2) Å, O5–H5A···N2i = 172(3)◦; symmetry code for i: x,
1/2 – y, –1/2 + z], forming 1D chains along the c axis (Figure 2).
following degradation schemes (Figure 3). The complex is sta-
ble up to 87◦C. Above this temperature, the TG curve show four
steps of weigh losses. The first step of decomposition in the
temperature range 87–132◦C involved the removal of methanol
ligand. The second step of decomposition in the temperature
range 132–190◦C involved the removal of the deprotonated
methanol ligand. The third step of decomposition in the temper-
ature range 190–400◦C involved the removal of two methoxy
groups of the aroylhydrazone Schiff base ligand. With further
elevation in temperature, a rapid weigh loss in the temperature
range 400–520◦C was observed. The decomposition of the final
stage weight loss may be ascribed to the dissociation of the re-
maining part of the aroylhydrazone Schiff base ligand, and the
formation of the final product V2O5.
Thermal Property
Thermogravimetric analysis of the complex was carried out
in the temperature range 50–1000◦C at a heating rate of 10◦C
min−1. The TG and DTA curves of the complex are given
40
100
20
80
0
60
40
20
DT
-20
-40
-60
TGA
600
200
400
800
1000
Temperature (oC)
FIG. 1. Structure of the complex with atom labeling scheme. All non-hydrogen
atoms are represented at 30% probability thermal ellipsoids.
FIG. 3. DT-TGA curves of the complex.

1254
J.-M. WANG ET AL.
10. Zhang, M.; Xian, D.-M.; Li, H.-H.; Zhang, J.-C.; You, Z.-L. Synthesis and
FUNDING
structures of halo-substituted aroylhydrazones with antimicrobial activity.
Aust. J. Chem. 2012, 65, 343–350.
The authors are grateful to Hebei Key Laboratory of Bioinor-
ganic Chemistry and College of Sciences of Agricultural Uni-
versity of Hebei for financial support.
11. Horiuchi, T.; Takeda, Y.; Haginoya, N.; Miyazaki, M.; Nagata, M.;
Kitagawa, M.; Akahane, K.; Uoto, K. Discovery of novel thieno[2,3-
d]pyrimidin-4-yl hydrazone-based cyclin-dependent kinase 4 inhibitors:
Synthesis, biological evaluation and structure-activity relationships. Chem.
Pharm. Bull. 2011, 59, 991–1002.
SUPPLEMENTAL MATERIAL
CCDC 906159 contains the supplementary crystallographic
data for the complex. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223–336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
12. Kaplancikli, Z.A.; Altintop, M.D.; Ozdemir, A.; Turan-Zitouni, G.; Khan,
S.I.; Tabanca, N. Synthesis and biological evaluation of some hydrazone
derivatives as anti-inflammatory agents. Lett. Drug Des. Discov. 2012, 9,
310–315.
13. Zhang, J.-C.; Li, H.-H.; Xian, D.-M.; Zhang, M.; Zhen, M.-M.; Zhao, Y.;
You, Z.-L. Synthesis, structures, and Helicobacter Pylori urease inhibition
of oxovanadium(V) complexes with hydrazones. Chin. J. Inorg. Chem.
2012, 28, 1959–1966.
14. You, Z.-L.; Shi, D.-H.; Zhang, J.-C.; Ma, Y.-P.; Wang, C.; Li,
K. Synthesis, structures, and urease inhibitory activities of oxovana-
dium(V) complexes with Schiff bases. Inorg. Chim. Acta 2012, 384,
54–61.
15. Liu, W.-H.; Song, S.-J.; Ma, J.-J. Nꢁ-(5-Bromo-2-hydroxybenzylidene)-4-
nitrobenzohydrazide methanol monosolvate. Acta Crystallogr. 2011, E67,
o2198.
REFERENCES
1. Hu, Y.-L.; Lee, C. C.; Ribbe, M. W. Extending the carbon chain: Hydrocar-
bon formation catalyzed by vanadium/molybdenum nitrogenases. Science
2011, 333, 753–755.
2. Hu, Y.-L.; Lee, C.C.; Ribbe, M.W. Vanadium nitrogenase: A two-hit won-
der? Dalton Trans. 2012, 41, 1118–1127.
3. Mba, M.; Pontini, M.; Lovat, S.; Zonta, C.; Bernardinelli, G.; Kundig,
P. E.; Licini, G. C3 vanadium(V) amine triphenolate complexes: Vanadium
haloperoxidase structural and functional models. Inorg. Chem. 2008, 47,
8616–8618.
4. Mukherjee, T.; Pessoa, J.C.; Kumar, A.; Sarkar, A.R. Synthesis, spectro-
scopic characterization, insulin-enhancment, and competitive DNA binding
activity of a new Zn(II) complex with a vitamin B-6 derivative-a new fluo-
rescence probe for Zn(II). Dalton Trans. 2012, 47, 5260–5271.
5. Crans, D.C.; Trujillo, A.M.; Pharazyn, P.S.; Cohen, M.D. How
environment affects drug activity: Localization, compartmentalization and
reactions of a vanadium insulin-enhancing compound, dipicolinatooxo-
vanadium(V). Coord. Chem. Rev. 2011, 255, 2178–2192.
6. Grivani, G.; Khalaji, A.D.; Tahmasebi, V.; Gotoh, K.; Ishida, H. Synthesis,
characterization and crystal structures of new bidentate Schiff base ligand
and its vanadium(IV) complex: The catalytic activity of vanadyl complex
in epoxidation of alkenes. Polyhedron 2012, 31, 265–271.
7. Romanowski, G.; Wera, M. Mononuclear and dinuclear chiral vana-
dium(V) complexes with tridentate Schiff bases derived from R(-)-1,2-
diaminopropane: Synthesis, structure, characterization and catalytic prop-
erties. Polyhedron 2010, 29, 2747–2754.
8. Orabi, A.S.; Ayad, M.I.; Ramadan, A.E.M. Synthesis, characterization and
oxidase catalytic activity of vanadium(IV) and oxovanadium(IV) com-
plexes with Schiff base ligands derived from beta-diketones. Transition
Met. Chem. 1998, 23, 391–396.
16. Zhou, X.; Ma, J.-J. Synthesis, characterization and crystal structures
of 2-cyano-Nꢁ-(2-chlorobenzylidene)acetohydrazide and 2-cyano-N’-(4-
dimethylaminobenzylidene)acetohydrazide. J. Chem. Crystallogr. 2012,
42, 1138–1141.
17. Liu, H.-M.; Zhang, L.-H.; Cui, P.-L.; Zhang, D.-N.; Ma, J.-J. [Nꢁ-(2-
Hydroxy-3-methoxybenzylidene)-2-methoxybenzohydrazonato](quinolin-
8-olato)oxovanadium(V): Synthesis, crystal structure and thermal
property. Synth. React. Inorg. Met.-Org. Nano-Met. Chem. 2013, 43, 873–
876.
18. Sheldrick, G.M. A short history of SHELX. Acta Crystallogr. 2008, A64,
112–122.
19. Sarkar, A.; Pal, S. Some ternary complexes of oxovanadium(IV) with acety-
lacetone and N-(2-pyridyl)-Nꢁ-(salicylidene)hydrazine and its derivatives.
Polyhedron 2006, 25, 1689–1694.
20. Sarkar, A.; Pal, S. Complexes of oxomethoxovanadium(V) with triden-
tate thiobenzhydrazide based Schiff bases. Inorg. Chim. Acta 2008, 361,
2296–2304.
21. Li, Z.-P.; Li, Y.-J.; Li, Z.-X.; Li, H.; Xiao, Z.-P. Synthesis and crystal
structures
of
Nꢁ-3,5-dibromo-2-hydroxybenzylidene)-2-hydroxy-3-
methylbenzohydrazide and its oxovanadium(V) complex [N’-(3,5-
dibromo-2-oxidobenzylidene-κO)-2-hydroxy-3-methylbenzohydrazidato-
κ2N’,O](methanol-κO)(methanolato-κO)oxidovanadium(V). J. Chem.
Crystallogr. 2011, 41, 1568–1572.
22. Lalami, N.A.; Monfared, H.H.; Noei, H.; Mayer, P. Binuclear vanadium(V)
complexes of bis(aryl)adipohydrazone: Synthesis, spectroscopic studies,
crystal structure and catalytic activity. Transition Met. Chem. 2011, 36,
669–677.
9. Blanot, D.; Lee, J.; Girardin, S.E. Synthesis and biological evaluation of
biotinyl hydrazone derivatives of muramyl peptides. Chem. Biol. Drug Des.
2012, 79, 2–8.