Progress in Crystal Growth and Characterization of Materials

52 (2006) 142e149
www.elsevier.com/locate/pcrysgrow

Synthesis and characterization of some vanadium(IV)

and vanadium(V) complexes
R.C. Maurya*, S. Rajput
Coordination Chemistry Laboratory, Department of Post Graduate Studies and Research in Chemistry,
R.D. University, Jabalpur 482 001, India

Abstract

The present paper reports the synthesis and characterization of two series of vanadium compounds:
(a) oxovanadium(IV) complexes of the composition, [VO(L1)(L2)(H2O)] {L1H ¼ 4-benzoyl-3-methyl-
l-phenyl-2-pyrazoline-5-one (bmpph), L2H ¼ acetoacetanilide (aaH), o-acetoacetotoluidide (o-aatdH),
o-acetoacetanisidide (o-aansH), methylacetoacetate (macacH), ethylacetoacetate (eacacH) or dibenzoyl-
methane (dbmH), and (b) dioxovanadium(V) complexes with Schiff bases (aroylhydrazones) of the com-
position, [VO2(L)(H2O)]$H2O (LH ¼ Schiff base derived from isonicotinic acid hydrazide (inH) and
bmpph, 4-butyryl-3-methyl-l-phenyl-2-pyrazolin-5-one (bumpph), 4-acetyl-3-methyl-1-phenyl-2-pyrazo-
lin-5-one (ampph), 3-methyl-l-phenyl-4-propionyl-2-pyrazolin-5-one (pmpph) or 4-iso-butyryl-3-
methyl-l-phenyl-2-pyrazolin-5-one (iso-bumpph). The 3D-molecular modeling and analysis for bond
lengths and bond angles have also been carried out for one representative compound of each series.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Oxovanadium(IV) complexes; Dioxovanadium(V) complexes; O,O-donor environment; ONO-donor aroyl-

hydrazones; Insulin adjuvants; 3D-molecular modeling

1. Introduction

Biomaterial science has expanded rapidly in the past few decades, nurtured by bioengineers
in the field of basic and medical professionals. Coordination chemists are also contributing to
the development of biomaterials [1] and biomaterial science.

* Corresponding author. Fax: þ91 761 2692120.

E-mail address: rcmaurya@sancharnet.in (R.C. Maurya).

0960-8974/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pcrysgrow.2006.03.019
 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials 143
52 (2006) 142e149
Insulin is a signaling hormone which is essential both for carbohydrate and fat metabolism.
Diabetes mellitus is a chronic metabolic disorder characterized by either hypoinsulinemia
(Type I or insulin dependent diabetes mellitus, IDDM) or hyperinsulinemia (Type II or non-
insulin dependent diabetes mellitus, NIDDM). Both the cases lead to high blood glucose levels
(hyperglycemia), the hallmark of diabetes mellitus. Good diabetic control with available ther-
apies continues to be an elusive goal as they have several problems such as physical and mental
pain due to daily insulin injections, and defects involving side effects [2]. Thus, there is a need
to find effective, orally active biomaterials in the 21st century that mimic or enhance the prop-
erties of insulin without side effects.
The insulin-like effect of vanadium compounds is one of the most noteworthy findings [3].
This capacity [4] of vanadium compounds is usually related to their ability to lower the blood
glucose level by activating the glucose transport into the cells of peripheral tissues. There has
been great interest in the past two decades in the mechanism of the insulin-like function of
vanadium and in developing new vanadium compounds as potential insulin adjuvants [1] or
replacement in the treatment of diabetes, most notably when administered orally. Still, gastro-
intestinal absorption (by passive diffusion) of vanadium is usually poor and depends on the
chemical nature, solubility, and speciation of the metal ion complex. Great efforts have there-
fore been made to synthesize oxovanadium(IV) complexes of high biological activity and low
toxicity which are readily absorbed. Many oxovanadium(IV) complexes with various coordina-
tion modes [1] have been prepared, viz., VO(O4), VO(S2N2), VO(S4), VO(N3O), and
VO(N2O2), and the relationship between their structures and insulin-mimetic activities has
been examined by evaluating both in vivo and in vitro results. Among others, bis(maltolato)-
oxovanadium(IV) [VO(O4) type] proved to be potent orally available glucose and lipid lower-
ing insulin mimetics, whether administered acutely or chronically [5]. Although most known
insulin-like complexes contain (þIV) oxidation state, dioxovanadium(V) complexes have
recently been found to have insulin-like properties [6]. With the isolation and characterization
of (4-hydroxypyridine-2,6-dicarboxylato)dixovanadate(V) (6) as insulin-enhancing biomate-
rial, there is a great interest among coordination chemists to design dioxovanadium(V)
compounds with more favourable chemical and insulin-enhancing properties. In view of ex-
tending the search for more efficacious compounds, we present here the synthesis and
characterization of some oxovanadium(IV) complexes [VO(O4) type] and dioxovanadium(V)
complexes involving ONO-donor aroylhydrazones.

2. Experimental

4-Acyl-3-methyl-l-phenyl-2-pyrazoline-5-one (bmpph, bumpph, ampph, pmpph or iso-

bumpph) used in the present study was synthesized by the method reported elsewhere [7].
[VO(acac)2] (acacH ¼ acetylacetone) was prepared by the method of Patel [8].

2.1. Preparation of Schiff base ligands

Isonicotinic acid hydrazide (6.85 g, 0.05 mol) was dissolved in 25 mL ethanol. To this
13.90 g, 0.05 mol of bmpph, 12.20 g, 0.05 mol of bumpph, 10.75 g, 0.05 mol of ampph,
11.5 g, 0.05 mol of pmpph or 12.20 g, 0.05 mol of iso-bumpph dissolved in 25 mL of ethanol
was added and the reaction mixture was refluxed with stirring for 3 h. A bright orange coloured
precipitate was formed while refluxing. It was filtered and washed several times with ethanol
144 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials
52 (2006) 142e149
and dried in a desiccator over anhydrous CaCl2. The analytical data of these Schiff bases are
consistent with the formulation of these compounds.

2.2. Preparation of oxovanadium(IV) complexes

To a 1 mmol of bmpph (0.278 g) in 10 mL of ethanol was added 1 mmol of [aaH (0.177 g),
o-aatdH (0.191 g), o-aansH (0.207 g), macacH (0.11 mL), eacacH (0.13 mL) or dbmH
(0.224 g)] in 10 mL ethanol. The resulting mixture of the two appropriate ligands was added
slowly with constant stirring to the solution of 1 mmol of VOSO4$5H2O (0.253 g) in 10 mL
of water, when coloured solid precipitated immediately. After refluxing the mixture for approx-
imately 1 h, solid mass was suction filtered, repeatedly washed with 1:1 ethanolewater mixture
and dried in vacuo.

2.3. Synthesis of dioxovanadium(V) complexes

A hot methanolic solution (25 mL) of [VO(acac)2] (0.001 mol, 0.264 g) was added to the
methanolic solution of 25 mL of the respective Schiff base (0.001 mol). The resulting solution
was refluxed for 4 h. It was cooled and filtered. The filtrate was collected and the precipitate
was dissolved in ethanolemethanol mixture (1:10) and again filtered. The filtrate thus obtained
is again added to the above filtrate which is then kept for air oxidation at room temperature for
3e4 days, with occasional shaking. The resulting compound was collected and recrystallized
from methanol.
The vanadium content of the synthesized compounds was determined volumetrically [9].
The analytical data of the Schiff bases as well as vanadium compounds are consistent with
the formulation of these compounds. The 3D molecular modeling of one synthesized compound
was carried out on CS Chem 3D Ultra Molecular Modeling and Analysis Programme [10].

3. Results and discussion

The oxovanadium(IV) complexes were prepared according to reaction (1), while dioxovana-
dium(V) complexes were prepared as per reactions (2) and (3) given below:

Ethanol; H2 O
VOSO4 $5H2 O þ L1 H þ L2 H










!½VOðL1 ÞðL2 ÞðH2 OÞ þ H2 SO4 ð1Þ
Reflux

L1H ¼ bmpph, L2H ¼ (aaH) (1), o-aatdH (2), o-aansH (3), macacH (4), eacacH (5) or dbmH
(6).

Methanol
½VOðacacÞ2  þ LH










!½VOðLÞðacacÞ þ acacH ð2Þ
Reflux

Ethanolemethanolð1:10Þ
½VOðLÞðacacÞ










!½VO2 ðLÞðH2 OÞ$H2 O þ acac
ð3Þ
Aerial oxidation

LH ¼ bmppheinH (7), bumppheinH (8), amppheinH (9), pmppheinH (10) or iso-bumpphe

inH (11) and acacH ¼ acetylacetone.
The compounds obtained were characterized by different physico-chemical techniques.
 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials 145
52 (2006) 142e149
3.1. Oxovanadium(IV) complexes

In the present work, the n(V]O) is found at 979e1003 cm
1 which suggests the absence of
a eV]OeV]Oe chain structure [11]. bmppH exhibits two strong bands [7] at 1600 and
1645 cm
1 due to n(C]O) (cyclic) and n(C]O) (exocyclic) modes, respectively. The band
due to n(C]O) (cyclic) at 1600 cm
1 in all the complexes is absent, indicating the enolization
of the (C]O) (cyclic) group. Instead, a new band appears at 1230e1245 cm
1 due to n(CeO)
(enolic) [10]. The n(C]O) (exocyclic carbonyl group) observed at 1645 cm
1 in bmppH is
shifted to lower wave numbers and appears at 1625e1630 cm
1 in all these complexes, sug-
gesting the bonding of the exocyclic carbonyl oxygen [11] to vanadium. The two significant
absorption bands due to coordinated aaH, o-aatdH, o-aansH anions are n(C]O) (acetyl car-
bonyl) and n(C]O) (amide carbonyl) and these have been observed at 1560e1578 and
1600e1605 cm
1, respectively, in the complexes (l)e(3), in agreement with the reported re-
sults [12]. The characteristic absorption bands due to coordinated macacH, eacacH or dbmH
anions are n(C]O) (acetyl/benzoyl) and n(C]C) modes, and these have been observed in
the 1595e1605 and 1577e1580 cm
1 regions, respectively, in the complexes (4)e(6), in
agreement with reported results [13], for such compounds. A broad band centered at
3400e3450 cm
1 due to n(OH) in all the complexes may be due to the presence of coordinated
water in them.
The molar conductance values (12.5e20.3 ohm
1 cm2 mol
1) in 10
3 M DMF solutions of
these compounds are consistent with the non-electrolytic nature of the complexes. The ob-
served magnetic moments for the present complexes are in the range 1.77e1.85 B.M., as ex-
pected for mononuclear complexes. The X-band EPR (RT) spectra of two representative
compounds, (2) and (6), were recorded on powdered sample at 9.47 and 9.45 GHz, respectively.
Both spectra are similar to many other ESR spectra of powdered oxovanadium(IV) compounds.
The calculated g values for the compounds (2) and (6) are 1.975 and 1.973, respectively.
The electronic spectra of two representative compounds, namely, (2) and (3), were recorded
in 10
3 M DMF. Compound (2) displayed five spectral peaks at 291, 302, 334, 360 and 458 nm.
The first four peaks of relatively higher extinction coefficients are due to charge transfer tran-
sitions, while the fifth peak of lower extinction coefficient (3 ¼ 473 1 cm
1 mol
1) may be due
to b2 / a1* transition. Compound (3) exhibited seven spectral peaks at 285, 298, 334, 349,
360, 440 and 624 nm. The first five peaks may be assigned as charge transfer transitions, while
the sixth (3 ¼ 1000) and seventh (3 ¼ 83) peaks may be due to b2 / a1* and b2 / b1* transi-
tions, respectively.
The TG curve of a representative compound, [VO(bmpp)(dbm)(H2O)] (6), was recorded in
the temperature range 50e700  C. This shows a weight loss of 40.11% in the temperature
range 200e410  C (calcd. weight loss for 1 mol of H2O and 1 mol of dbm: 41.20%) corre-
sponding to the elimination of one molecule of coordinated water and one dbm group. The de-
composition continues with the gradual weight loss, and it ceases at about 560  C. This weight
loss in the temperature range 410e560  C (observed 75%) (calcd. 88%, assuming weight loss
for 1 mol of bmpp ligand) roughly corresponds to the removal of one coordinated bmpp group.
The final residue attaining a constant weight (observed 27.5%) over 650  C corresponds to
V2O5.
The cyclic voltammogram (1500 to
1000 mV) was recorded for two compounds, (2) and
(3), dissolved in CH3CN using [CH3(CH2)3]4NBF4 as a supporting electrolyte. The oxidations
and reductions of these complexes are achieved by waves with Er values in the range from 431
to 431.5 mV and from
622 to
713 mV against saturated Ag/AgCl electrode. These two
146 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials
52 (2006) 142e149
O CH3
O O
V O
O
O O

CH3

Fig. 1. Structure of bis(maltolato)oxovanadium(IV).

complexes showed redox couples with peak-to-peak separation values (DEp) ranging from 82 to
87 mV, indicating a single step one electron transfer process [14]. The positive Er values
(431e431.5 mV) may be assigned to the metal centered oxidation [14] of V(IV) to V(V) while
the negative Er potentials (
622 to
713 mV) may be assigned to the conversion [15] of V(IV)
to V(III). Besides establishing (þIV) oxidation state, these observations conclude that the li-
gand environments present in these two complexes facilitate electron transfer reaction.
In view of the X-ray characterized crystal structure [15] of bis(maltolato)oxovanadium(IV)
(Fig. 1) [involving a monoprotic bidentate (O,O-donor) maltol ligand, similar to monoprotic
(O,O-donor) L1H and L2H ligands in the present investigation], the molecular modeling [16]
of the proposed compound [VO(bmpp)(aa)(H2O)] (1) is based on its octahedral structure
(Fig. 2) with axial oxo group and water molecule trans to O (oxo), and O,O-donor L1H and
L2H at the equatorial positions in cis-arrangement. In all, 191 bond lengths, plus the bond an-
gles are found. In most of the cases, the actual bond lengths and bond angles are close to the
optimal value, and thus the proposed structure (Fig. 2) of the compound (1) (and also others) is
acceptable.

3.2. Dioxovanadium(V) complexes

The IR spectra of Schiff bases exhibit a weak broad band centered at 3400e3550 cm
1 for
n(OH), a medium band at 1632e1640 cm
1 for n(C]O) (pyrazolone skeleton) and a strong
band due to n(C]N) (azomethine) at 1590e1614 cm
1. Moreover, the absence of n(NH)
and n(C]O) due to isonicotinic acid hydrazide part of the ligand was observed in the IR spec-
tra of all the ligands. These observations suggest that the Schiff bases exist in the enol form in
the solid state (Fig. 3).

X
O R' R' = CH3, R =N
H
H3C O O
and X = H (1), X = o-CH3 (2)
V CH
X = o-OCH3 (3)
O O R = CH3 (4), R = C2H5 (5)
N R = R' = C6H5(6)
N R
OH2

Fig. 2. Proposed structures of oxovanadium(IV) complexes.

 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials 147
52 (2006) 142e149
X OH
N
N
H3C

N O
N N

Fig. 3. Enol form of the Schiff bases.

The band due to n(C]O) (hydrazide moiety) at w1670 cm
1 is absent in all the complexes
indicating the enolization of the carbonyl group. Instead, a new band appears at
1106e1163 cm
1 due to the coordination of n(CeO enolic) [17]. The n(C]O) mode of the
cyclic carbonyl group observed at 1632e1640 cm
1 in the ligands is shifted to lower wave
numbers and appears at 1560e1576 cm
1 in these complexes. This suggests the bonding of
the cyclic carbonyl oxygen [11] to vanadium. The Schiff bases display a sharp and strong
band due to n(C]N) (azomethine) at 1590e1614 cm
1. The observed low energy shift of
this band in the complexes at 1576e1592 cm
1 suggests the coordination of the azomethine
nitrogen to vanadium. This is further supported by the shifting [17] of n(NeN) from 1002e
1046 cm
1 to 1020e1061 cm
1 in the complexes. The overall IR spectral studies conclude
that the Schiff bases used in the present study behave as monobasic tridentate ONO-ligands.
The metal complexes also show two medium bands or one broad band (w3400 cm
1) due
to n(OH) because of the presence of lattice/coordinated water in them. The observed molar con-
ductances (12.5e20 ohm
1 cm2 mol
1) in 10
3 M DMF solutions of these complexes are con-
sistent with the non-electrolytic nature of the complexes.
The 51V NMR spectra of two representative compounds (7) and (8) were recorded in
DMSO-d6. The complexes exhibit a strong resonance at calcd.
508.81 and
508.96, respec-
tively, as expected for the dioxovanadium(V) complexes having a mixed O/N donor set [18].
Proton NMR spectrum of one representative compound, [VO2(bumpphein)(H2O)]$H2O (8),
was recorded in CDCl3. The absence of the enolic (eOH) proton signals at w12 ppm and
the hydrazone (eNH) proton signal at w11 ppm in the complex indicates the coordination
of enolic oxygen to the metal ion after deprotonation. The proton signals due to aromatic pro-
tons of the ligand in the compound appeared at 7.2e7.9 ppm. The two proton signals at
1.5e1.6 ppm and 2.4 ppm may be due to butyryl and methyl group, respectively, present in
the ligand. The mass spectrum of one representative compound, [VO2(bumpphein)-
(H2O)]$H2O (8), was recorded. The appearance of a molecular ion peak at 446.1634 m/z is
consistent with the molecular mass of the present compound excluding two water molecules
present therein, which are supposed to be lost before ionization. The electronic spectra of
four compounds, namely, (8)e(11) were recorded in 10
4 M DMF solution. Dioxovana-
dium(V) complexes have a 3d0 configuration, and hence ded bands are not expected. Com-
pound (8) displayed one medium intensity peak at 229 nm (3 ¼ 7390) while compounds
(9)e(11) displayed two medium intensity peaks one at 228e229 nm (3 ¼ 7730e8020) and
other at 254e256 nm (3 ¼ 9460e9910). These peaks are due to intraligand charge transfer.
Rest of the very high intensity peaks at 218e365 nm in all the complexes is due to ligand to
metal charge transfer transitions. These results are comparable to the data reported elsewhere
148 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials
52 (2006) 142e149

X = -C6H5
-C3H7
N N O
O O -CH3
H3C V -C2H5
N OH2 O -iso-C3H7
X
N

Fig. 4. Proposed structures of dioxovanadium(V) complexes.

[19], for dioxovanadium(V) compounds. The TG curve of compound (2), [VO2(bumpphein)-

(H2O)]$H2O (M.W. ¼ 480.942), shows a weight loss of 3.41% at 66  C corresponding to the
loss of one lattice water molecule (calcd. 3.74%), and shows another weight loss at 130  C
(3.63%) corresponding to coordinated water molecule (calcd. 3.89%). It shows a final weight
loss at 395e469  C leading to a constant weight corresponding to the residual mass of V2O5
of 40.68% at 580  C (calcd. 40.87%).
The analytical data coupled with the studies presented above suggest that the dioxovana-
dium(V) complexes are of composition [VO2(L)(H2O)]$H2O. Keeping in view the hexa-coor-
dination of all the complexes, and the well established octahedral structure [20] of
dioxovanadium(V) complexes, K[VO2(saleiNH)(H2O)] and K[VO2(ClsaleiNH)(H2O)] involv-
ing N-isonicotinamidosalicylaldimines ligand (similar to LH in the present investigation), the
molecular modeling of the proposed compound [VO2(ampphein)(H2O)]$H2O (9) is based on
its octahedral structure (Fig. 4) with cis-dioxo group. In all, 275 measurements of the bond
lengths, plus the bond angles are found. In most of the cases, the observed bond lengths and
bond angles are close to the optimal values, and thus the proposed structure of compound 9
(and also others) is acceptable.

Acknowledgements

Financial assistance from CSIR and DST, New Delhi is gratefully acknowledged. Thanks are
due to Dr. S.M. Paul Khurana, Vice-Chancellor of this University for encouragement.

References

[1] K.H. Thompson, C. Orvig, Coord. Chem. Rev. 219 (2001) 1053.
[2] H. Sakurai, Y. Kojima, Y. Yoshikawa, K. Kawabe, H. Yasui, Coord. Chem. Rev. 226 (2001) 187.
[3] K.H. Thompson, J.H. McNeill, C. Orvig, Chem. Rev. 99 (1999) 2561.
[4] M.M.C.A. Castro, F. Avecilla, C.F.G.C. Geraldes, B. de Castro, M. Rangel, Inorg. Chim. Acta 356 (2003) 142.
[5] K.H. Thompson, J. Chiles, V.G. Yuen, J. Tse, J.H. McNeill, C. Orvig, J. Inorg. Biochem. 98 (2004) 683.
[6] D.C. Crane, L. Yang, J.A. Alfano, L.H. Chi, W. Jin, M.M. Tahir, K. Robbins, M.M. Toloue, L.K. Chan, A.J. Plante,
R.Z. Grayson, G.R. Willsky, Coord. Chem. Rev. 237 (2003) 13.
[7] R.C. Maurya, V. Pillai, S. Rajput, Synth. React. Inorg. Met. -Org. Chem. 33 (2003) 699.
[8] K.S. Patel, J. Inorg. Nucl. Chem. 45 (1981) 887.
 R.C. Maurya, S. Rajput / Progress in Crystal Growth and Characterization of Materials 149
52 (2006) 142e149
[9] N.H. Furman, Standard Methods of Chemical Analysis, sixth ed., vol. I, D. Van Nostrand Company, Inc., New
Jersey, 1962, p. 1211.
[10] R.C. Maurya, H. Singh, A. Pandey, T. Singh, Indian J. Chem. 40A (2001) 1053.
[11] R.C. Maurya, D.D. Mishra, Indian J. Chem. 29A (1990) 1230.
[12] R.C. Maurya, D.D. Mishra, S. Pillai, Synth. React. Inorg. Met.-Org. Chem. 27 (1997) 1453.
[13] R.C. Maurya, D.D. Mishra, S. Mukherjee, P.K. Trivedi, Transition Met. Chem. 16 (1991) 524.
[14] J. Dai, H. Wang, M. Mikuriya, Polyhedron 15 (1996) 1806.
[15] Y. Sun, B.R. James, S.J. Retting, C. Orvig, Inorg. Chem. 35 (1996) 1667.
[16] CS Chem 3D Ultra Molecular Modeling and Analysis, Cambridge, <www.cambridgesoft.com>.
[17] R.C. Maurya, R. Verma, Synth. React. Inrog. Met.-Org. Chem. 33 (2003) 311.
[18] A. Butler, C.J. Carrano, Coord. Chem. Rev. 109 (1991) 61.
[19] M.R. Maurya, S. Khurana, W. Zhang, D. Rehder, J. Chem. Soc. Dalton Trans. (2002) 3015.
[20] M.R. Maurya, S. Khurana, Carola Schulzke, D. Reher, Eur. J. Inorg. Chem. (2001) 779.