Synthesis and crystal structure of a dioxovanadium(V) complex with Schiff base derived from 2-[1-(2-aminocyclohexylimino)ethyl]phenol

Article abstract of DOI:10.1080/15533174.2010.509294

A new dioxovanadium(V) complex, [VO2L]22CH3OH, where L is the deprotonated form of 2-[1-(2-aminocyclohexylimino) ethyl]phenol, has been synthesized and characterized by I.R. spectra and single crystal X-ray diffraction. The compound consists of a centrosymmetric dinuclear dioxovanadium complex molecule and two methanol molecules of crystallization. Each V atom in the complex is six-coordinated through three bonds to oxo groups and through bonds to the tridentate Schiff base ligand, forming an octahedral geometry. The Vm·V distance is 3.188(2) . In the crystal structure, the dioxovanadium complex molecules are linked with the methanol molecules through intermolecular N Hm·O and O-Hm·O hydrogen bonds, forming chains running along the b axis. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2010.509294

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Synthesis and Crystal Structure of a
Dioxovanadium(V) Complex with Schiff Base Derived
from 2-[1-(2-Aminocyclohexylimino)ethyl]phenol
Yu-Ping Ma a & Zhong-Lu You a
a Department of Chemistry and Chemical Engineering , Liaoning Normal University ,
Dalian, P. R. China
Published online: 23 Oct 2010.
To cite this article: Yu-Ping Ma & Zhong-Lu You (2010) Synthesis and Crystal Structure of a Dioxovanadium(V) Complex
with Schiff Base Derived from 2-[1-(2-Aminocyclohexylimino)ethyl]phenol, Synthesis and Reactivity in Inorganic, Metal-
Organic, and Nano-Metal Chemistry, 40:9, 581-584
To link to this article: http://dx.doi.org/10.1080/15533174.2010.509294
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:581–584, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2010.509294
Synthesis and Crystal Structure of a Dioxovanadium(V)
Complex with Schiff Base Derived from
2-[1-(2-Aminocyclohexylimino)ethyl]phenol
Yu-Ping Ma and Zhong-Lu You
Department of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, P. R. China
A new dioxovanadium(V) complex, [VO2L]2·2CH3OH, where
L is the deprotonated form of 2-[1-(2-aminocyclohexylimino)
N
ethyl]phenol, has been synthesized and characterized by I.R. spec-
tra and single crystal X-ray diffraction. The compound consists
of a centrosymmetric dinuclear dioxovanadium complex molecule
and two methanol molecules of crystallization. Each V atom in
the complex is six-coordinated through three bonds to oxo groups
and through bonds to the tridentate Schiff base ligand, forming
NH2
OH
HL
. . .
˚
an octahedral geometry. The V V distance is 3.188(2) A. In the
crystal structure, the dioxovanadium complex molecules are linked
. . .
EXPERIMENTAL
Materials and Measurements
with the methanol molecules through intermolecular N−H O and
. . .
O−H O hydrogen bonds, forming chains running along the b
axis.
All chemicals used were commercially available with AR
grade. The I.R. spectra were recorded on a Nicolet AVATAR
360 spectrometer as KBr pellets in the 4000–400 cm region.
Keywords crystal structure, Schiff base, synthesis, vanadium
–1
complex
Synthesis of the Schiff Base HL
INTRODUCTION
A methanol solution (50 mL) of 1-(2-hydroxyphenyl)
ethanone (1.0 mmol, 136.2 mg) was added dropwise to a
stirred methanol solution (50 mL) of cyclohexane-1,2-diamine
(1.0 mmol, 114.2 mg). The mixture was stirred for 30 minutes
to give an amount of yellow precipitate. The precipitate was
filtered out, washed three times with cold methanol, and dried
in a vacuum over anhydrous CaCl2. Yield: 93%. Selected I.R.
data (KBr, cm–1): 3207 (νN−H), 1639 (νC=N).
Schiff bases and their metal complexes have received
much attention in coordination chemistry and biological
chemistry.[1–3] In recent years, the vanadium complexes have
been reported to have interesting biological activities such
as normalizing the high blood glucose levels and acting as
models of haloperoxidases.[4–6] In order to investigate the
synthesis and self-assembly of the vanadium complexes with
Schiff bases, in this work, a new dioxovanadium(V) complex,
[VO2L]2·2CH3OH, where L is the deprotonated form of 2-[1-
(2-aminocyclohexylimino)ethyl]phenol (HL), has been synthe-
sized and structurally characterized. It is notable that no com-
plexes with HL have been reported previously.
Synthesis of [VO2L]2·2CH3OH
A methanol solution (5 mL) of VO(acac)2(0.1 mmol,
26.5 mg) was added to a methanol solution (10 mL) of HL
(0.1 mmol, 23.2 mg) with stirring. The mixture was stirred at
room temperature for 30 min to give a yellow solution. The
resulting solution was allowed to stand in air for a few days.
Yellow block-shaped crystals suitable for X-ray single crystal
diffraction were formed at the bottom of the vessel. The isolated
product was washed three times with cold methanol, and dried
in air. Yield: 67%. Selected I.R. data (KBr, cm–1): 3413 (νO−H),
3205 (νN−H), 1627 (νC=N), 930, 845 (νV=O).
Received 16 January 2010; accepted 17 May 2010.
This work was financially supported by the National Science Foun-
dation of China (Project No. 20901036).
Address correspondence to Zhong-Lu You, Department of Chem-
istry and Chemical Engineering, Liaoning Normal University, Dalian
116029, P. R. China. E-mail: youzhonglu@yahoo.com.cn.
581

582
Y.-P. MA AND Z.-L. YOU
TABLE 1
Crystal data for the complex
TABLE 2
◦
˚
Selected bond lengths (A) and bond angles ( ) for the complex
Formula
C30H46N4O8V2
V1-O1
1.899(3)
V1-O2
V1-O3i
1.617(3)
FW
692.6
V1-O3
V1-N1
2.395(3)
2.212(3)
1.661(3)
2.111(3)
Crystal shape/color
Crystal size/mm
Crystal system
Space group
block/yellow
0.23 × 0.21 × 0.21
Triclinic
P-1
8.816(2)
8.920(2)
11.114(3)
94.494(2)
96.906(2)
109.058(2)
813.6(3)
1
V1-N2
O2-V1-O3i
O3i-V1-O1
O3i-V1-N2
O2-V1-N1
O1-V1-N1
O2-V1-O3
O1-V1-O3
N1-V1-O3
106.56(13)
97.68(11)
92.90(11)
94.34(12)
83.59(11)
172.15(11)
81.14(10)
80.58(9)
O2-V1-O1
O2-V1-N2
O1-V1-N2
O3i-V1-N1
N2-V1-N1
O3-V1-O3i
N2-V1-O3
104.35(13)
96.31(12)
152.93(11)
157.92(11)
77.50(11)
77.87(11)
76.82(10)
˚
a /A
˚
b /A
˚
c /A
α /◦
β /◦
γ /◦
V /A
Symmetry code: (i) 1 – x, 1 – y, 1 – z.
3
˚
Z
T /K
Dc/g cm
298(2)
1.414
–3
F(000)
364
0.628
0.869
0.879
–1
µ/mm (Mo-Kα)
Tmin
Tmax
TABLE 3
◦
˚
Hydrogen-bond geometry (A, ) for the complex
. . . . . . . . . . . .
A
Reflections/parameters
Independent reflections
Restraints
3119/201
2241
0
D–H D–H
A
D–H
H
A
D
A
i
. . .
. . .
N2–H2A O4 0.90
2.23 3.045(5)
2.13 2.929(4)
2.00 2.775(4)
150
147
158
Goodness of fit on F2
R1, wR2 [I ≥ 2σ(I)]a
R1, wR2 (all data)a
ꢀ
1.021
i
N2–H2B O1 0.90
ii
. . .
0.0529 0.1093
0.0814 0.1226
ꢀ
O4–H4 O2
0.82
Symmetry codes: (i) 1 – x, 1 – y, 1 – z; (ii) x, 1 +y, z.
ꢀ
aR1
=
||Fo| – |Fc||/ |Fo|, wR2 = [ w(Fo2 – Fc2)2/
ꢀ
w(Fo2)2]1/2, w = [σ2Fo2+ (0.0467(Fo2+ 2Fc2)/3)2+ 0.5212(Fo2+
–1
2Fc2)/3]
.
Crystal Structure Determination
Diffraction intensities for the complex were collected at
298(2) K using a Bruker SMART 1000 CCD area-detector
˚
with MoKα radiation (λ = 0.71073 A). The collected data
were reduced using the SAINT program,[7] and empirical
absorption corrections were performed using the SADABS
program.[8] The structure was solved by direct methods and
refined against F2 by full-matrix least-squares methods using
the SHELXTL package.[9] All of the non-hydrogen atoms were
refined anisotropically. H atoms in the complex were placed
in calculated positions and constrained to ride on their parent
atoms. The crystallographic data for the complex are summa-
rized in Table 1. Selected bond lengths and angles are listed in
Table 2. Hydrogen bonds are listed in Table 3.
RESULTS AND DISCUSSION
Preparation of HL and the Complex
The Schiff base HL was prepared by the reaction of equimolar
quantities of 1-(2-hydroxyphenyl)ethanone and cyclohexane-
FIG. 1. Molecular structure of the complex at 30% probability displacement.

A DIOXOVANADIUM(V) COMPLEX WITH SCHIFF BASE
583
NH2
N
O
V
MeOH
O
V
N
O
VO(acac)2
+
O
NH2
O
O
OH
N
H2N
SCH. 1.
1,2-diamine in methanol. To obtain HL with high purity, 1-(2-
hydroxyphenyl)ethanone was slowly added to the methanol
solution of cyclohexane-1,2-diamine. If the sequence was
reversed, an amount of the bis-Schiff base 2,2ꢀ-[(1,2-
cyclohexanediyl)bis(nitriloethylidyne)]bisphenol was obtained.
The complex was readily synthesized according to the stan-
dard procedure (Scheme 1), crystallized as yellow crystals,
which is stable in air at room temperature. The crystal of the
complex is soluble in DMSO, DMF, MeCN, MeOH and EtOH,
and insoluble in water.
O3 atom is involved in the bridge between V1 and V1A, strongly
˚
coordinated to V1A [1.661(2) A] and weakly coordinated to V1
˚
[2.395(2) A]. The coordinate bond lengths are comparable to
those observed in other similar vanadium complexes.[10−12] The
distortion of the octahedral coordination can be observed by the
coordinate bond angles, ranging from 76.8(2) to 106.6(2)◦ for
the perpendicular angles, and from 152.9(2) to 172.2(2)◦ for the
diagonal angles.
In the crystal structure, the dioxovanadium complex
molecules are linked with the methanol molecules through inter-
. . .
. . .
molecular N−H O and O−H O hydrogen bonds, forming
chains running along the b axis (Figure 2).
Structure Description of the Complex
The molecular structure of the complex is shown in Figure 1.
The compound consists of a centrosymmetric dinuclear diox-
ovanadium complex molecule and two methanol molecules of
SUPPLEMENTARY MATERIALS
. . .
˚
crystallization. The V V distance is 3.188(2) A. Each V atom
in the complex is six-coordinated through three bonds to oxo
groups and through bonds to the tridentate Schiff base ligand,
forming an octahedral geometry. The distance between atoms
Supplementary crystallographic data are available from
the CCDC, Union Road, Cambridge CB2 1EZ, UK on
request quoting the deposition number CCDC 761789
(fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.
uk).
˚
V1 and O2 is 1.617(2) A, indicating a typical V=O bond. The
FIG. 2. Molecular packing arrangement of the complex. Viewed along the c axis. Intermolecular hydrogen bonds are shown as dashed lines.

584
Y.-P. MA AND Z.-L. YOU
6. Messerschmidt, A., Prade, L., and Wever, R. Implications for the catalytic
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