Synthesis and crystal structure of a μ2-Oxo bridged dinuclear oxovanadium(V) complex derived from N′-(2-hydroxy-4- diethylaminobenzylidene)-3-methylbenzohydrazide

Article abstract of DOI:10.1080/15533174.2012.762680

A tridentate hydrazone ligand N′-(2-hydroxy-4-diethylamino benzylidene)-3-methylbenzohydrazide (H₂L), reacts with vanadyl sulfate in methanol to give a novel μ₂-oxo bridged dinuclear oxovanadium(V) complex, [V₂O₂(μ₂-O)L ₂]. The complex was characterized by physicochemical and spectroscopic methods. The crystal of the complex is triclinic with space group P-1, a = 11.349(2), b = 13.385(3), c = 13.644(2) A, α = 90.377(2)°, β = 93.772(2)°, γ = 109.239(2)°, V = 1951.8(6) A³, Z = 2. X-ray crystallography indicates that each V atom is in a distorted square pyramidal coordination. The two V atoms are bridged by one O atom, with a distance of 3.010(1) A. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2012.762680

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Synthesis and Crystal Structure of a µ 2-Oxo Bridged
Dinuclear Oxovanadium(V) Complex Derived From
N′-(2-Hydroxy-4-diethylaminobenzylidene)-3-
methylbenzohydrazide
San-Jun Peng a b , Dao-Xin Wu b , Hong Tian c , Zhong-Liang Xiao b & Dong Qian a
a College of Chemistry and Chemical Engineering , Central South University , Changsha ,
Hunan , P. R. China
b School of Chemistry and Biological Engineering , Changsha University of Science and
Technology , Changsha , Hunan , P. R. China
c School of Energy and Power Engineering , Changsha University of Science and Technology ,
Changsha , Hunan , P. R. China
Accepted author version posted online: 12 Mar 2013.Published online: 25 Aug 2013.
To cite this article: San-Jun Peng , Dao-Xin Wu , Hong Tian , Zhong-Liang Xiao & Dong Qian (2013) Synthesis and Crystal
Structure of a µ 2-Oxo Bridged Dinuclear Oxovanadium(V) Complex Derived From N′-(2-Hydroxy-4-diethylaminobenzylidene)-3-
methylbenzohydrazide, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:10, 1506-1509,
DOI: 10.1080/15533174.2012.762680
To link to this article: http://dx.doi.org/10.1080/15533174.2012.762680
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1506–1509, 2013
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.762680
Synthesis and Crystal Structure of a ␮2-Oxo Bridged
Dinuclear Oxovanadium(V) Complex Derived From
Nꢀ-(2-Hydroxy-4-diethylaminobenzylidene)-3-
methylbenzohydrazide
San-Jun Peng,1,2 Dao-Xin Wu,2 Hong Tian,3 Zhong-Liang Xiao,2 and Dong Qian1
1College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan, P. R.
China
2School of Chemistry and Biological Engineering, Changsha University of Science and Technology,
Changsha, Hunan, P. R. China
3School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha,
Hunan, P. R. China
A tridentate hydrazone ligand Nꢀ-(2-hydroxy-4-diethylamino
benzylidene)-3-methylbenzohydrazide (H2L), reacts with vanadyl
sulfate in methanol to give a novel μ2-oxo bridged dinuclear oxo-
vanadium(V) complex, [V2O2(μ2-O)L2]. The complex was charac-
terized by physicochemical and spectroscopic methods. The crystal
of the complex is triclinic with space group P–1, a = 11.349(2),
b = 13.385(3), c = 13.644(2) Å, α = 90.377(2)◦, β = 93.772(2)◦,
γ = 109.239(2)◦, V = 1951.8(6) Å3, Z = 2. X-ray crystallography
indicates that each V atom is in a distorted square pyramidal co-
ordination. The two V atoms are bridged by one O atom, with a
distance of 3.010(1) Å.
SCH. 1. The new ligand H2L.
Keywords crystal structure, dinuclear complex, hydrazone, oxovana-
esting structures and biological properties. During the search of
literature, we have found that most of the polynuclear vanadium
complexes derived from hydrazone ligands are bridged by de-
protonated solvent molecules, such as methoxy and ethoxy,[5–8]
and others derived from Schiff base ligands are bridged by dou-
ble oxo O atoms.[9–12] The dinuclear oxovanadium complexes
derived from hydrazone ligands with single oxo O atom as bridg-
ing group are very rare.[13–16] In this study, a novel single μ2-oxo
bridged dinuclear oxovanadium(V) complex, [V2O2(μ2-O)L2],
derived from the new hydrazone ligand Nꢁ-(2-hydroxy-4-
diethylaminobenzylidene)-3-methylbenzohydrazide (abbr. as
H2L in Scheme 1), was prepared and characterized.
dium complex, synthesis
INTRODUCTION
Metal complexes containing Schiff bases and hydrazone lig-
ands containing the C N- functional groups have been widely
investigated due to their versatile structures and widely applica-
tions.[1–4] The vanadium complexes with Schiff bases or hydra-
zone ligands have been received much attention for their inter-
Received 17 April 2012; accepted 23 December 2012.
This work was financially supported by Postdoctoral Science Foun-
dation of Central South University (No. 20120248), National Nat-
ural Science Foundation of China (Nos. 21171174, 21071052), the
Projects of Hunan Provincial Science and Technology Department
(Nos. 2011GK3115, 2011GK3119), the Project of Changsha Municipal
Science and Technology Bureau (No. K1104023-21), and Scientifical
Research Foundation of Hunan Provincial Education Department (No.
10C0384).
EXPERIMENTAL
Materials and Measurements
All chemicals were obtained from commercial sources and
were used as received without further purification. Infrared spec-
trum was recorded in KBr pellets using a Nicolet 520 FT–IR
spectrophotometer. Elemental analyses (C, H, N) were per-
formed on a Perkin-Elmer 240C elemental analyzer.
Address correspondence to Dong Qian, College of Chemistry and
Chemical Engineering, Central South University, Changsha, Hunan
410083, P. R. China. E-mail: qiandong6@vip.sina.com
1506

A μ2-OXO BRIDGED DINUCLEAR OXOVANADIUM(V) COMPLEX
1507
TABLE 1
Crystallographic data for the complex
X-Ray Structure Determination
A high-quality crystal of the complex was selected and
mounted on the top of a glass fiber. The data was col-
lected on a Bruker SMART 1000 CCD area diffractometer at
298(2) K. Graphite-monochromatized Mo Kα radiation (λ =
0.71073 Å) and the ω scan technique was used to collect the
data sets. Absorption corrections were applied using SAD-
ABS.[17] The crystal structure was solved with direct method
and refined with a full-matrix least-squares technique using
SHELXTL.[18] Anisotropic thermal parameters were applied
to all non-hydrogen atoms. Hydrogen atoms were generated
geometrically. The crystallographic data as well as details of
the data collection and refinement for the complex are listed
in Table 1. Selected bond lengths and angles are given in
Table 2.
Formula
FW
C38H42N6O7V2
796.7
Block, brown
0.20 × 0.17 × 0.16
triclinic
Crystal shape, color
Crystal size, mm
Crystal system
Space group
P–1
a, Å
b, Å
11.349(2)
13.385(3)
13.644(2)
90.377(2)
93.772(2)
109.239(2)
1951.8(6)
2
c, Å
α, ◦
β, ◦
γ , ◦
V, Å3
Z
RESULTS AND DISCUSSION
λ (MoKα), Å
0.71073
The hydrazone ligand H2L was readily prepared
by the reaction of 4-diethylaminosalicylaldehyde and 3-
methylbenzohydrazide in methanol (Scheme 2). The dinuclear
oxovanadium(V) complex was prepared by the reaction of the
hydrazone ligand and vanadyl sulfate in methanol. The hydra-
zone ligand transferred to its deprotonated and enolic form dur-
ing coordination (Scheme 3).
T, K
298(2)
0.534
0.9008
0.9195
μ, mm–1 (MoKα)
Tmin
Tmax
No. of measured reflections
No. of unique reflections and Rint
No. of observed reflections
Data/restraints/parameters
F(000)
13582
7079 and 0.0314
4677
7079/51/483
828
1.046
0.0693, 0.1933
0.1033, 0.2273
IR Spectrum
Goodness of fit on F2
R1, wR2 [I ≥ 2σ(I)]
R1, wR2 (all data)
In the IR spectrum of the complex, the shifting of νC
N
of H2L to lower wavenumber in the complex (1610 cm–1) in-
dicates the coordination of the azomethine N atom to the V
atom.[19,20] A new band appearing at 1243 cm–1 in the complex
TABLE 2
Coordinate bond lengths (Å) and angles (◦) for the complex
Synthesis of H2L
A mixture of 4-diethylaminosalicylaldehyde (0.193 g,
1.0 mmol) and 3-methylbenzohydrazide (0.150 g, 1.0 mmol)
in 50 mL methanol was stirred at room temperature for 1 h to
give a clear colorless solution. The solution was evaporated by
distillation and cooled to room temperature, yielding colorless
solid product, which was recrystallized from methanol. Yield:
87%. Anal. Calcd. for C19H23N3O2: C, 70.1; H, 7.1; N, 12.9%.
Found: C, 70.3; H, 7.2; N, 12.8%.
Bond distances
V1–O1
V1–O5
V1–N1
V2–O3
V2–O5
V2–N3
Bond angles
O6–V1–O5
O5–V1–O1
O5–V1–O2
O6–V1–N1
O1–V1–N1
O7–V2–O5
O5–V2–O3
O5–V2–O4
O7–V2–N3
O3–V2–N3
1.814(3)
1.801(3)
2.058(4)
1.825(3)
1.797(3)
2.069(4)
V1–O2
V1–O6
V1–V2
V2–O4
V2–O7
1.946(3)
1.579(4)
3.0097(12)
1.935(3)
1.582(4)
107.77(18)
101.40(15)
85.92(13)
100.04(19)
84.01(15)
107.43(19)
100.92(14)
87.34(13)
99.9(2)
O6–V1–O1
O6–V1–O2
O1–V1–O2
O5–V1–N1
O2–V1–N1
O7–V2–O3
O7–V2–O4
O3–V2–O4
O5–V2–N3
O4–V2–N3
104.25(18)
103.84(17)
147.10(15)
149.16(15)
74.52(14)
104.16(18)
103.00(17)
147.62(15)
150.04(15)
74.57(14)
Synthesis of the Complex
A methanol solution (10 mL) of vanadyl sulfate (0.082 g,
0.5 mmol) was added dropwise to the methanol solution (20 mL)
of H2L (0.163 g, 0.5 mmol) with stirring. The mixture was stirred
at reflux for 30 min and then cooled to room temperature. Brown
block-shaped single crystals were formed after slow evaporation
of the solution in air for a few days. Crystals were filtered out
and air-dried. Yield: 45%. Anal. Calcd. for C38H42N6O7V2: C,
57.3; H, 5.3; N, 10.5%. Found: C, 57.2; H, 5.4; N, 10.7%.
83.66(14)

1508
S.-J. PENG ET AL.
SCH. 2. The synthesis of the ligand H2L.
SCH. 3. The synthesis of the oxovanadium(V) complex.
is attributed to the νC–O(enolic) mode. The weak bands in the re- minal oxo O atom. The V O and V N bond lengths are agree
gion 400–650 cm–1 can be attributed to the stretching vibrations well with the corresponding values reported in similar oxovana-
of the V–O and V–N coordinate bonds. The weak and broad dium(V) complexes.[13–16,23] The V1 and V2 atoms are displaced
band (3435 cm–1) indicative of the O–H vibration is absent in 0.465(2) and 0.455(2) Å, respectively, from the least-squares
the complex, indicating the deprotonation of the phenol group planes defined by the corresponding four basal donor atoms,
when complexation. The spectrum of the complex exhibits a toward the apical positions. The obvious distortion from an
typical band at 993 cm–1, which can be assigned to the V O ideal square pyramidal geometry for the V atoms could be a re-
stretching.[21,22]
sult of the five-membered chelate rings V1 N1 N2 C8 O2
and V2 N3 N4 C27 O4. The greatest distortion of the co-
ordination from the ideal square pyramidal geometry can be
observed from the coordinate bond angles. The angles in the
basal planes of the square pyramidal geometries are in the range
74.5(1)–149.2(2)◦ for V1 and 74.6(1)–150.0(2)◦ for V2. The an-
gles among the apical and the basal donor atoms are in the range
100.0(2)–107.8(2)◦ for V1 and 99.9(2)–107.4(2)◦ for V2. The
relatively short C8 N2 and C27 N4 bond lengths of 1.289(6)
and 1.295(6) Å, and the relatively long N1 N2 and N3 N4
bond lengths of 1.393(5) and 1.399(5) Å, indicate that there
are conjugation effects along the backbones of the hydrazone
ligands.
Structure Description of the Complex
The complex is a μ2-oxo bridged dinuclear oxovanadium(V)
compound, as shown in Figure 1. The distance between the
two V atoms is 3.010(1) Å. The complex crystallizes in the tri-
clinic crystal system with space group P–1. Each V atom in the
complex is five-coordinated in a distorted square pyramidal ge-
ometry, in which the basal plane is defined by the phenolate O,
azomethine N, and enolic O atoms of the hydrazone ligand, and
the μ2-oxo O atom; the apical position is occupied by one ter-
In the crystal structure of the complex, molecules are stacked
along the a axis with weak π···π stacking interactions.
CONCLUSIONS
We have successfully synthesized the novel μ2-oxo bridged
dinuclear oxovanadium(V) complex with the tridentate hy-
drazone ligand Nꢁ-(2-hydroxy-4-diethylaminobenzylidene)-3-
methylbenzohydrazide. The elemental analyses, IR spectra, and
single-crystal X-ray diffraction support the dinuclear structure
of the complex.
SUPPLEMENTARY MATERIALS
CCDC-856606 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at http://www.ccdccam.ac.uk/const/retrieving.html or from the
FIG. 1. The structure of the complex with 30% probability level.

A μ2-OXO BRIDGED DINUCLEAR OXOVANADIUM(V) COMPLEX
1509
Cambridge Crystallographic Data Centre (CCDC), 12 Union
Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or
e-mail: deposit@ccdc.cam.ac.uk.
(aminomethyl)pyrrolidine and aromatic o-hydroxycarbonyl compounds:
synthesis, characterization and structure. Polyhedron 2006, 25, 2809–2814.
11. Rayati, S.; Wojtczak, A.; Kozakiewicz, A. One step preparation of [(VO(μ-
O)L)]2: A 2D supramolecular network directed by intermolecular interac-
tion. Inorg. Chim. Acta 2008, 361, 1530–1533.
12. You, Z.-L.; Sun, H.; Ding, B.-W.; Ma, Y.-P.; Zhang, M.; Xian, D.-M. Prepa-
ration and structural characterization of oxovanadium(V) complexes with
Schiff bases and their inhibition studies on Helicobacter pylori urease. J.
Coord. Chem. 2011, 64, 3510–3520.
REFERENCES
1. Shahabadi, N.; Kashanian, S.; Darabi, F. DNA binding and DNA cleavage
studies of a water soluble cobalt(II) complex containing dinitrogen Schiff
base ligand: the effect of metal on the mode of binding. Eur. J. Med. Chem.
2010, 45, 4239–4245.
13. Sangeetha, N. R.; Pal, S. A family of dinuclear vanadium(V) complexes
4+
containing the {OV(μ-O)VO} core: Syntheses, structures, and proper-
2. Chen, Z.; Morimoto, H.; Matsunaga, S.; Shibasaki, M. A bench-stable
homodinuclear Ni2-Schiff base complex for catalytic asymmetric synthesis
of α-tetrasubstituted anti-α,β-diamino acid surrogates. J. Am. Chem. Soc.
2008, 130, 2170–2171.
3. Lin, P.-H.; Burchell, T. J.; Clerac, R.; Murugesu, M. Dinuclear dyspro-
sium(III) single-molecule magnets with a large anisotropic barrier. Angew
Chem. Int. Ed. 2008, 47, 8848–8851.
4. Gordon, R. J.; Campbell, J.; Henderson, D. K.; Henry, D. C.R.; Swart, R.
M.; Tasker, P. A.; White, F. J.; Wood, J. L.; Yellowlees, L. J. Polyacidic
multiloading metal extractants. Chem. Commun. 2008, 4801–4803.
5. Sangeetha, N. R.; Kavita, V.; Wocadlo, S.; Powell, A. K.; Pal, S. Vana-
dium(V) complexes of O,N,O-donor tridentate ligands containing the
ties. Bull. Chem. Soc. Jpn. 2000, 73, 357–363.
14. Mondal, B.; Drew, M. G.B.; Ghosh, T. First report of structurally charac-
terized dimorph of an oxovanadium(V)-hydrazonato complex containing,
V2O34+ core. Indian J. Chem. A 2008, 47, 1204–1207.
15. Mondal, B.; Ghosh, T.; Sutradhar, M.; Mukherjee, G.; Drew, M. G.B.;
Ghosh, T. Synthesis, structure and solution chemistry of a family of din-
uclear hydrazonato-vanadium(V) complexes with [OV(μ-O)VO]4+ core.
Polyhedron 2008, 27, 2193–2201.
16. Dinda, R.; Sengupta, P.; Ghosh, S.; Mak, T. C.W. Valence delocalization in
a mixed-oxidation divanadium (IV, V) complex electrogenerated from its
structurally characterized divanadium (V) analogue with a tridentate (ONO)
ligand. Inorg. Chem. 2002, 41, 1684–1689.
2+
{V(v)O(OMe)} unit: Syntheses, structures and properties. J. Coord.
17. Sheldrick, G. M. SADABS. Program for Empirical Absorption Correction
Chem. 2000, 51, 55–66.
of Area Detector; University of Go¨ttingen, Germany. 1996.
18. Sheldrick, G. M. SHELXTL, Version 6.10, Software Reference Manual;
Bruker Instrumentation, Madison, WI, 2000.
6. Seena, E. B.; Mathew, N.; Kuriakose, M.; Kurup, M. R. P. Synthesis, spectral
and EPR studies of oxovanadium(IV) complexes incorporating tridentate
ONO donor hydrazone ligands: Structural study of one oxovanadium(V)
complex. Polyhedron 2008, 27, 1455–1462.
7. Mondal, B.; Drew, M. G. B.; Banerjee, R.; Ghosh, T. Chemistry of mixed-
ligand methoxy bonded oxidovanadium(V) complexes with a family of
hydrazone ligands containing VO3+ core and their substituent controlled
methoxy-bridged dimeric forms. Polyhedron 2008, 27, 3197–3206.
8. Yuan, C. L. Syntheses, characterization, and crystal structures of oxovana-
dium(V) complexes with similar tridentate hydrazones. Russ. J. Coord.
Chem. 2011, 37, 606–612.
9. Root, C. A.; Hoeschele, J. D.; Cornman, C. R.; Kampf, J. W.; Pecoraro,
V. L. Structural and spectroscopic characterization of dioxovanadium(v)
complexes with asymmetric Schiff-base ligands. Inorg. Chem. 1993, 32,
3855–3861.
10. Kwiatkowski, E.; Romanowski, G.; Nowicki, W.; Kwiatkowski, M.
Dioxovanadium(V) complexes of Schiff bases derived from S-(+)-2-
19. Nejo, A. A.; Kolawole, G. A.; Opoku, A. R.; Wolowska, J.; O’Brien, P.
Synthesis, characterization and preliminary insulin-enhancing studies of
symmetrical tetradentate Schiff base complexes of oxovanadium(IV). Inorg.
Chim. Acta 2009, 362, 3993–4001.
20. Nica, S.; Rudolph, M.; Go¨rls, H.; Plass, W. Structural characterization
and electrochemical behavior of oxovanadium(V) complexes with N-
salicylidene hydrazides. Inorg. Chim. Acta 2007, 360, 1743–1752.
21. Liu, S.-X.; Gao, S. Synthesis and characterization of two novel monoox-
ovanadium(V) complexes with bidentate benzohydroxamate ligand. Inorg.
Chim. Acta 1998, 282, 149–154.
22. Ghosh, T.; Roy, A.; Bhattacharya, S.; Banerjee, S. A family of mixed-ligand
oxovanadium(V) complexes incorporating tridentate ONO donor hydra-
zone ligands derived from acetylhydrazide and 2-hydroxybenzaldehyde/2-
hydroxyacetophenone. Transition Met. Chem. 2005, 30, 419–425.