An oxo-bridged dinuclear vanadium(V) complex of N,N'-bis(salicylidene)-1,5- diimino-3-azapentane: Synthesis and structure

Article abstract of DOI:10.1080/15533174.2012.680168

The reaction of vanadyl acetylacetonate with N,N'-bis (salicylidene)-1,5- diimino-3-azapentane (H₂SDA) affords an oxo-bridged dinuclear Schiff base vanadium(V) complex, [VO₂(HSDA)]₂. The structure of the complex was charac

Full text of DOI:10.1080/15533174.2012.680168

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An Oxo-Bridged Dinuclear Vanadium(V) Complex of
N,N′-bis(salicylidene)-1,5-diimino-3-azapentane:
Synthesis and Structure
a
Fu-Ming Wang
a
Department of Chemistry, Dezhou University , Dezhou Shandong , P. R. China
Accepted author version posted online: 01 Aug 2012.Published online: 05 Oct 2012.
To cite this article: Fu-Ming Wang (2012) An Oxo-Bridged Dinuclear Vanadium(V) Complex of N,N′-bis(salicylidene)-1,5-
diimino-3-azapentane: Synthesis and Structure, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 42:10, 1386-1389, DOI: 10.1080/15533174.2012.680168
To link to this article: http://dx.doi.org/10.1080/15533174.2012.680168
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1386–1389, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.680168
An Oxo-Bridged Dinuclear Vanadium(V) Complex of
ꢀ
N,N -bis(salicylidene)-1,5-diimino-3-azapentane: Synthesis
and Structure
Fu-Ming Wang
Department of Chemistry, Dezhou University, Dezhou Shandong, P. R. China
reaction of salicylaldehyde and primary amines have also been
ꢀ
[11–13]
The reaction of vanadyl acetylacetonate with N,N -bis prepared previously.
salicylidene)-1,5-diimino-3-azapentane (H
oxo-bridged dinuclear Schiff base vanadium(V) complex,
VO (HSDA)] . The structure of the complex was characterized
In this article we report the synthesis
(
2
SDA) affords an and structure of a new oxo-bridged dinuclear vanadium complex
ꢁ
of the Schiff base ligand N,N -bis(salicylidene)-1,5-diimino-3-
[
2
2
azapentane (H2SDA).
by elemental analysis, infrared spectroscopy, and single-crystal
X-ray diffraction. The complex crystallizes as monoclinic space
group P2
1
/n, with a = 6.619(2), b = 32.592(3), c = 8.715(2) Å, β =
EXPERIMENTAL
◦
3
1
1
04.001(3) , V = 1824.2(7) Å , Z = 4, R = 0.0637, wR = 0.1228 for
1
2
989 observed data. The complex exhibits a distorted octahedral Materials and Physical Measurement
geometry, involving in the equatorial plane the phenolate, imine,
and amine donors of the Schiff base ligand and the bridging oxo
O group and in the axial positions two other oxo O groups. The
intramolecular V···V distance is 3.226(1) Å.
Salicylaldehyde and diethylenetriamine werepurchased from
Aldrich Chemical Co. (USA) and used as received. All other
chemicals and solvents were of analytical grade and used as re-
ceived. Infrared spectrum was recorded on a Perkin-Elmer 783
spectrometer (Dezhou University, China) as KBr pellet. Micro-
analytical (C, H, N) data were obtained from a Perkin-Elmer
Keywords crystal structure, dinuclear complex, Schiff base,
vanadium complex
240C elemental analyzer (Dezhou University, China). Solution
electrical conductivity was measured with the DDS-11a conduc-
tivity meter (INESA Scientific Instrument Co., Dezhou Univer-
INTRODUCTION
There is considerable interest in the biological chemistry of sity, China). UV-vis spectrum was recorded on a Perkin-Elmer
vanadium due to the recent discovery of two types of vanadium- Lambda 9 instrument.
dependent enzymes. One has a nitrogenase activity, catalyz-
ing the reduction of dinitrogen to ammonia,[1] and the other
has bromoperoxidase activity, catalyzing the peroxidedepen-
dent halogenation of organic compounds in the presence of
2 2
Preparation of the Complex [VO (HSDA)]
Salicylaldehyde (0.30 g, 2 mmol) and diethylenetriamine
0.10 g, 1 mmol) were added to 30 mL methanol and allowed
(
[
2,3]
to react for 1 h. Vanadyl acetylacetonate (0.26 g, 1 mmol),
dissolved in 20 mL of methanol, was added to the solution. The
final mixture was further stirred for 2 h at room temperature to
obtain a clear yellow solution. X-ray quality single crystals were
obtained by slow evaporation of the solution in air for a week.
The crystals were filtered, washed with methanol and finally
dried in vacuum over phosphorus pentoxide. Yield: 73%. Found
halide ion.
The latter is thought to contain a vanadium(V)
active site.[ Vanadium has also attained increasing interest in
4]
the past few years because of its application in medicine es-
[
5–7]
pecially for its insulin-mimetic behaviour.
The importance
of vanadium in biological and medicinal chemistry has stimu-
lated our interest in the coordination and reaction chemistry of
this element. In the last years, a variety of vanadium complexes
have been introduced as structural and/or functional models for
(%): C, 54.8; H, 5.2; N, 10.7. Anal. Calcd. for C18H20N3O4V
−1
[
8–10]
(%): C, 55.0; H, 5.1; N, 10.7. IR frequencies in cm : 3448,
biologically active vanadium compounds.
A few examples
3
1
9
227, 1642, 1628, 1597, 1550, 1497, 1471, 1452, 1417, 1406,
344, 1303, 1280, 1208, 1150, 1123, 1190, 1040, 1011, 975,
31, 894, 857, 803, 763, 623, 576, 551, 462, 443.
of oxovanadium complexes of Schiff bases derived from the
Received 20 December 2011; accepted 1 January 2012.
The Department of Chemistry of Dezhou University is acknowl-
edged for financial support.
Address correspondence to Fu-Ming Wang, Department of Chem-
istry, Dezhou University, Dezhou Shandong 253023, P. R. China.
E-mail: wfm99999@126.com
X-Ray Crystallography
A suitable single crystal of the complex was mounted on
a thin glass fiber without protection. Cell dimensions were
determined at 298 K from the setting angles of a Bruker
1386

AN OXO-BRIDGED DINUCLEAR VANADIUM(V) COMPLEX
1387
SMART 1000 CCD diffractometer (Dezhou University, China)
TABLE 1
using a graphite monochromated Mo Kα (λ = 0.71073 Å)
radiation source. Data collection was completed using the
ω/2θ scan techniques. Pertinent cell parameters, data collection
conditions, and refinement details are provided in Table 1.
The structure was solved by direct methods, developed by
Crystal data and structure refinement for the complex
Formula weight
C18H20N3O4V
298(2)
0.71073
Monoclinic
P21/n
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
2
successive difference Fourier synthesis and refined on F by
a full-matrix least-squares procedure using the SHELXL-97
program (Bruker AXS, Lanzhou University, China).[ The po-
sitions of all non-hydrogen atoms were refined with anisotropic
displacement factors. The amino hydrogen atom was located
from a difference map, and with N–H distance restrained to
14]
6.619(2)
32.592(3)
8.715(2)
104.001(3)
1824.2(7)
4
b (Å)
c (Å)
◦
β ( )
Volume (Å )
0.90(1) Å. The remaining hydrogen atoms were geometrically
3
calculated and isotropically fixed at positions recalculated after
Z
each cycle of refinement [d(C-H) = 0.93–0.97 Å, d(O-H) =
−
3
Dcalc (g cm )
1.432
0
.82 Å, with the isotropic thermal parameter of Uiso(H) = 1.2
Absorption coefficient
0.572
Uiso(C) and 1.5 Uiso(O)]. In all the cases, absorption corrections
−
1
(
mm )
based on multiscan using SADABS software (Bruker AXS,
[
15]
F(000)
816
Lanzhou University, China)
were applied. Data reduction
Crystal size (mm)
Limiting indices
0.30 × 0.28 × 0.27
was accomplished using the SAINT plus software (Bruker
[
16]
–8 < h < 8, –41 < k < 41, –11
AXS, Lanzhou University, China).
The crystal data and
<
h < 11
Reflections collected/unique 14878/3972
refinement details are listed in Table 1.
Observed reflections [I >
σ(I)]
1989
RESULTS AND DISCUSSION
2
The Schiff base H2SDA was used to prepare complexes with
Completeness to θ = (%)
99.5
Cu,[
17,18]
Gd, Tb, Nd, Sm, Pr,
[19–21]
Cd,
[22]
and Sn.
[23]
In the
Refinement method
Full-matrix least-squares on F2
reported complexes, the Schiff base ligands coordinate to the
metal atoms through all the five donor atoms. The vanadium
complexes with H2SDA have never been reported. In the present
work, it is interesting that we have prepared an oxo-bridged
dinuclear vanadium(V) complex, with three of the five donor
atoms of the Schiff base ligand coordinate to each V atom, and
with the other two forms an intramolecular O H···N hydrogen
Data/restraints/parameters
3972/1/239
1.031
0.0637
0.1228
0.386, –0.279
2
Goodness-of-fit on F
Final R indices [I > 2σ(I)]
R indices (all data)
Largest difference in peak
−
3
and hole (e Å )
−3
bond. The molar conductance of a ca 0.10 mmol dm solution
◦
−1
2
−1
24]
of the complex in acetonitrile at 25 C is 8.3 ꢀ cm mol .
The data indicate nonelectrolytic behavior in the solution.[ In Description of the Structure of the Complex
the absorption spectrum of the complex, two absorption bands at
An ORTEP diagram of the complex is illustrated in Fig-
32 and 527 nm were observed. Absorption bands at 232 nm can ure 1, and important bond lengths and angles are provided in
2
∗
be assigned to π→π transition based on the ligand. Absorption Table 2. X-ray single-crystal structure analysis reveals that the
bands at 527 nm can be assigned to a dxy→(dxz,dyz) transition.
complex possesses crystallographic inversion center symmetry,
FIG. 1. An ORTEP drawing of the crystal structure of the complex with the atomic numbering scheme. The hydrogen bonds are shown as dashed lines. Symmetry
atoms with the suffix A are related to the operation 2 – x, 1 – y, 2 – z.

1388
F.-M. WANG
TABLE 2
Selected bond lengths (Å) and bond angles ( )
◦
Bond lengths
V1-O1
V1-O4
1.914(3)
1.652(3)
2.152(3)
V1-O3
V1-O4A
V1-N2
1.614(3)
2.440(3)
2.155(3)
V1-N1
Bond angles
O3-V1-O4
O4-V1-O1
O4-V1-N1
O3-V1-N2
O1-V1-N2
O3-V1-O4A
O1-V1-O4A
N2-V1-O4A
107.33(14)
98.20(12)
151.27(13)
92.52(13)
158.99(13)
169.11(12)
86.91(11)
77.47(10)
O3-V1-O1
O3-V1-N1
O1-V1-N1
O4-V1-N2
N1-V1-N2
O4-V1-O4A
N1-V1-O4A
101.67(14)
99.88(13)
84.91(13)
92.17(13)
77.37(13)
77.67(12)
73.97(11)
with the inversion center located at the midpoint of the two
V atoms. There form two intermolecular N–H···O hydrogen
bonds between the two [VO2(HSDA)] units. The intramolecu-
lar V···V distance is 3.226(1) Å. Each V atom is six-coordinated
with two distinct oxo groups being apparent. The distance be-
tween V1 and the oxo O3 proves it a typical double bond. The
other oxo O4 group is involved in the bridge between V1 and
V1A. The O4 atom is strongly coordinated to V1 (1.652(3) Å)
and is weakly associated with V1A (2.440(3) Å). The remain-
ing three coordination sites are occupied by the phenolate O
FIG. 2. The molecular packing of the complex, viewed along the a-axis. H
atoms, except those related to hydrogen bonding, are omitted for clarity.
CONCLUSION
A novel centrosymmetric vanadium(V) complex with the
ꢁ
Schiff base N,N -bis(salicylidene)-1,5-diimino-3-azapentane
has been prepared and characterized. The V atom is six-
coordinated in an octahedral geometry. The Schiff base ligand
coordinates to the V atom through three of the five donor atoms,
with the other two generate an intramolecular O–H···N hydro-
gen bond.
(1.914(3) Å), imine N (2.152(3) Å), and amine N (2.155(3) Å)
atoms of the Schiff base ligand. Thus, the coordination spheres
of the vanadium atoms are best described as distorted octa-
hedral geometry. The distortion of the octahedral coordination
can also be observed form the coordinate bond angles. The
cis angles surrounded at the V1 atom are range from 74.0(1)
◦
to 107.3(1) , and the trans angles are range from 151.3(1) SUPPLEMENTARY MATERIALS
◦
to 169.1(1) . The coordinate bond lengths are within normal
Supplementary crystallographic data are available from the
CCDC, Union Road, Cambridge CB2 1EZ, UK on request quot-
values.[
25,26]
In the crystal of the complex, the [VO2(HSDA)]2 complex ing the deposition number CCDC 859119 (fax: +44 1223 336
molecules are stack along the a-axis by weak π···π interactions, 033; e-mail: deposit@ccdc.cam.ac.uk).
as shown in Figure 2.
REFERENCES
1
. Robson, R. L.; Eady, R. R.; Richardson, T. H.; Miller, R. W.; Hawkins, M.;
Postgate, J. R. The alternative nitrogenase of azotobacter-chroococcum is
a vanadium enzyme. Nature 1986, 322, 388–390.
IR Spectra
In the IR spectrum of the complex, the dioxo nature of the
complex is confirmed by the presence of two V O bands at
2
3
. Vilter, H. Peroxidases from phaeophyceae: a vanadium(V)-dependent per-
oxidase from ascophyllum-nodosum. Phytochem. 1984, 23, 1387–1390.
. de Boer, E.; van Kooyk, Y.; Tromp, M. G. M.; Plat, H.; Wever, R. Bromoper-
oxidase from ascophyllum-nodosum: a novel class of enzymes containing
vanadium as a prosthetic group. Biochim. Biophys. Acta 1986, 869, 48–53.
−1
9
31 and 894 cm . The νC N in the complex are found at 1642
−1
and 1628 cm . The former can be assigned to the free C12
N3 bond, and the later can be assigned to the coordinated C7
N1 bond. The IR spectrum of the complex shows a single sharp
band at 3227 cm designated to the N-H stretching mode of
the coordinated secondary amino group. The weak and broad
4. de Boer, E.; Tromp, M. G. M.; Plat, H.; Krenn, G. E.; Wever, R. Vana-
dium(V) as an essential element for haloperoxidase activity in marine
brown-algae: purification and characterization of a vanadium(V)-containing
bromoperoxidase from laminaria-saccharina. Biochim. Biophys. Acta 1986,
−1
−1
absorption centered at 3448 cm is attributed to the O-H bond,
which participates in the formation of intramolecular O–H···N
hydrogen bond.
8
72, 104–115.
5. Crans, D. C.; Trujillo, A. M.; Pharazyn, P. S.; Cohen, M. D. How environ-
ment affects drug activity: localization, compartmentalization and reactions

AN OXO-BRIDGED DINUCLEAR VANADIUM(V) COMPLEX
1389
of a vanadium insulin-enhancing compound, dipicolinatooxovanadium(V). 17. McKenzie, E. D.; Selvey, S. J. Copper(II) compounds with the potentially
Coord. Chem. Rev. 2011, 255, 2178–2192.
quinquedentate ligand N,N’-bissalicylidene-1,5-diimino-3-azapentane, in-
cluding an X-ray structure-analysis of [Cu2(C18H19N3O2)2]·2C3H6O. In-
org. Chim. Acta 1985, 101, 127–133.
6
. Islam, M. N.; Kumbhar, A. A.; Kumbhar, A. S.; Zeller, M.; Butcher,
R. J.; Dusane, M. B.; Joshi, B. N. Bis(maltolato)vanadium(III)-polypyridyl
complexes: synthesis, characterization, DNA cleavage, and insulin mimetic
activity. Inorg. Chem. 2010, 49, 8237–8246.
. Mendes, I. C.; Botion, L. M.; Ferreira, A. V. M.; Castellano, E. E.; Beraldo,
H. Vanadium complexes with 2-pyridineformamide thiosemicarbazones: in
18. Quintero-Tellez, G.; Alvarez, C. M. G.; Bernes, S.; Alcantara-Flores,
ꢁ
J. L.; Reyes-Ortega, Y. Bis{µ-2,2 -[(3-azapentane-1,5-diyl)bis(nitrilo
7
methylidyne)]diphenolato} dicopper(II) dimethyl sulfoxide disolvate. Acta
Crystallogr. 2008, E64, m631.
vitro studies of insulin-like activity. Inorg. Chim. Acta 2009, 362, 414–420. 19. Howell, R. C.; Spence, K. V. N.; Kahwa, I. A.; White, A. J. P.; Williams,
8
. Guilherme, L. R.; Massabni, A. C.; Cuin, A.; Oliveira, L. A. A.; Castellano,
E. E.; Heinrich, T. A.; Costa-Neto, C. M. Synthesis, characterization, crystal
structure, and biological studies of vanadium complexes with glycolic acid.
J. Coord. Chem. 2009, 62, 1561–1571.
D. J. The preparation and crystal and molecular structures of new lumi-
nescent Schiff-base complexes featuring coupled lanthanide(III) cations. J.
Chem. Soc., Dalton Trans. 1996, 6, 961–968.
20. Chakraborty, J.; Ray, A.; Pilet, G.; Chastanet, G.; Luneau, D.; Ziessel,
R. F.; Charbonniere, L. J.; Carrella, L.; Rentschler, E.; El Fallah, M. S.;
Mitra, S. Dalton Trans. 2009, 46, 10263–10272.
21. Chakraborty, J.; Pilet, G.; El Fallah, M. S.; Ribas, J.; Mitra, S. Syn-
thesis, characterization and cryomagnetic studies of a novel homonu-
clear Nd(III) Schiff base dimmer. Inorg. Chem. Commun. 2007, 10, 489–
493.
9
. Crans, D. C.; Smee, J. J.; Gaidamauskas, E.; Yang, L. Q. The chemistry and
biochemistry of vanadium and the biological activities exerted by vanadium
compounds. Chem. Rev. 2004, 104, 849–902.
1
1
1
1
0. Ashiq, U.; Ara, R.; Mahroof-Tahir, M.; Maqsood, Z. T.; Khan, K. M.; Khan,
S. N.; Siddiqui, H.; Choudhary, M. I. Synthesis, spectroscopy, and biolog-
ical properties of vanadium(IV)–hydrazide complexes. Chem. Biodivers.
2
008, 5, 82–92.
22. Chakraborty, J.; Thakurta, S.; Samanta, B.; Ray, A.; Pilet, G.; Batten,
S. R.; Jensen, P.; Mitra, S. Synthesis, characterisation and crystal structures
of three trinuclear cadmium(II) complexes with multidentate Schiff base
ligands. Polyhedron 2007, 26, 5139–5149.
23. Luna-Garcia, R.; Damian-Murillo, B. M.; Barba, V.; Hopfl, H.; Beltran,
H. I.; Zamudio-Rivera, L. S. Structural relationship between a host included
chain of spirocyclic water hexamers and bulk water: the role of water
clusters in self assembly and crystallization processes. Chem. Commun.
2005, 44, 5527–5529.
24. Geary, W. J. The use of conductivity measurements in organic solvents for
the characterisation of coordination compounds. Coord. Chem. Rev. 1971,
7, 81–122.
25. 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.
1. Khatri, P. K.; Singh, B.; Jain, S. L.; Sain, B.; Sinha, A. K. Cyclotriphosp-
hazene grafted silica: a novel support for immobilizing the oxo-vanadium
Schiff base moieties for hydroxylation of benzene. Chem. Commun. 2011,
4
7, 1610–1612.
2. 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.
3. Wazalwar, S. S.; Bhave, N. S.; Dikundwar, A. G.; Ali, P. Microwave assisted
synthesis and antimicrobial study of Schiff base vanadium(IV) complexes
of phenyl esters of amino acids. Synth. React. Inorg. Met.-Org. Nano-Met.
Chem. 2011, 41, 459–464.
1
1
1
4. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. 2008, A64,
1
12–122.
5. Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction
of Area Detector Data; University of G o¨ ttingen, G o¨ ttingen, Germany, 1996. 26. Rayati, S.; Wojtczak, A.; Kozakiewicz, A. One step preparation of [(VO(µ-
6. Bruker. SAINT-Plus, Software Users Guide, Version 6.0; Madison, WI:
Bruker Analytical X-ray Systems, 1999.
O)L)]2: a 2D supramolecular network directed by intermolecular interac-
tion. Inorg. Chim. Acta 2008, 361, 1530–1533.