Syntheses and crystal structures of oxovanadium(V) complexes derived from N'-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide and 2-hydroxy-N'-[1 -(2-hydroxynaphthyl)ethylidene]benzohydrazide

Article abstract of DOI:10.1134/S1070328412070111

Reactions of bis(acetylacetonato)oxovanadium(IV) with N'-[1-(2- hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide (H₂HNB) and 2-hydroxy-N'-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide (H₂HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]₂ (I) and [VO(OMe)(HHB)] (II). The complexes I and II have been characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P21/n, a = 8.208(2), b = 14.528(3), c = 16.418(3) A, ss = 97.887(3)°, V = 1939.3(7) A³, Z = 2. The crystal of II is triclinic: space group P1, a = 8.334(2), b = 10.236(2), c = 11.337(2) A, a = 80.91(3)°, ss = 75.41(3)°, y = 75.63(3)°, V = 902.0(3) A³, Z = 2. Complex I is a methoxide-bridged dimeric oxovanadium(V) complex, and complex II is a mononuclear oxovanadium(V) complex. The V atom in I is in an octahedral coordination, and that in II is in a square pyramidal coordination.

Full text of DOI:10.1134/S1070328412070111

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2012, Vol. 38, No. 8, pp. 583–588. © Pleiades Publishing, Ltd., 2012.
Syntheses and Crystal Structures of Oxovanadium(V) Complexes
Derived from N'ꢀ[1ꢀ(2ꢀHydroxynaphthyl)Ethylidene]ꢀ4ꢀ
Nitrobenzohydrazide and 2ꢀHydroxyꢀN'ꢀ[1 ꢀ(2ꢀ
Hydroxynaphthyl)Ethylidene]Benzohydrazide1
C. L. Yuan
Key Laboratory For Phytochemistry of Shaanxi Province, Department of Chemistry and Chemical Engineering,
Baoji University of Arts and Sciences, Baoji, Shaanxi, 721013 P.R. China
eꢀmail: chunlanyuan@163.com
Received May 10, 2011
Abstract—Reactions of bis(acetylacetonato)oxovanadium(IV) with N'ꢀ[1ꢀ(2ꢀhydroxynaphthyl)ethylidene]ꢀ
4ꢀnitrobenzohydrazide (H2HNB) and 2ꢀhydroxyꢀN'ꢀ[1ꢀ(2ꢀhydroxynaphthyl)ethylidene]benzohydrazide
(H2HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]2 (
[VO(OMe)(HHB)] (II). The complexes and II have been characterized by elemental analysis, IR spectra,
and single crystal Xꢀray diffraction. The crystal of is monoclinic: space group 21/ = 8.208(2),
14.528(3), = 16.418(3) Å, = 97.887(3) = 2. The crystal of II is triclinic: space group
= 1939.3(7) Å3,
= 8.334(2), = 10.236(2), = 11.337(2) Å, = 80.91(3) = 75.41(3) = 75.63(3)
= 902.0(3) Å3,
= 2. Complex is a methoxideꢀbridged dimeric oxovanadium(V) complex, and complex II is a mononuꢀ
I) and
I
I
P
n
,
a
b =
c
β
°
,
V
Z
P
Z
1,
a
b
I
c
α
°,
β
°,
γ
°, V
clear oxovanadium(V) complex. The V atom in
I
is in an octahedral coordination, and that in II is in a square
pyramidal coordination.
DOI: 10.1134/S1070328412070111
1
INTRODUCTION
NO2
H
Oxovanadium complexes, especially with biꢀ and triꢀ
N
N
dentate chelating ligands bearing pharmacological activꢀ
ity, have being extensively investigated in recent years
with respect to their remarkable efficiency as insulin
mimetic compounds [1–3]. In the last few years, the Oꢀ,
Nꢀ, and Sꢀcontaining hydrazone compounds have been
proved to possess versatile biological activity [4–7]. Study
on the structures of the oxovanadium complexes with
hydrazones is very important in both coordination chemꢀ
istry and medicinal chemistry. In this paper, the author
reports the synthesis, characterization, and crystal strucꢀ
tures of two new oxovanadium(V) complexes,
O
OH
(H HNB)
2
HO
H
N
N
O
OH
(H HHB)
2
[VO(OMe)(HNB)]2 (
I) and [VO(OMe)(HHB)] (II),
where HNB and HHB are the deprotonated form of
N'ꢀ[1ꢀ(2ꢀhydroxynaphthyl)ethylidene]ꢀ4ꢀnitrobenzoꢀ
hydrazide (H2HNB) and 2ꢀhydroxyꢀN'ꢀ[1ꢀ(2ꢀhydroxyꢀ
EXPERIMENTAL
Materials and methods. 2ꢀAcetylꢀ1ꢀnaphthol,
4ꢀnitrobenzohydrazide, and 2ꢀhydroxybenzohyꢀ
drazide were purchased from Lancaster Chemical Co.
The remaining reagents and solvents were purchased
from local sources and were used as received. C, H,
naphthyl)ethylidene]benzoꢀhydrazide
respectively:
(H2HHB),
1
The article is published in the original.
583

584
YUAN
and N elemental analyses were determined on a Carlo 1159 m, 1074 w, 1022 s, 987 s, 827 w, 750 s, 695 w,
671 w, 615 s, 603 s, 487 w, 430 w.
Erba MOD 1106 elemental analyzer. FTꢀIR spectra
were recorded in the range 4000–400 cm–1 on a Nicoꢀ
let Avatarꢀ360 spectrometer using a KBr pellet.
For C20H17N2O5V (II
)
anal. calcd., %
Found, %
C, 57.70;
C, 57.86;
H, 4.12;
H,4.15;
N, 6.73.
N, 6.60.
Synthesis of H2HNB and H2HHB. The hydrazone
compounds H2HNB and H2HHB were synthesized by
the condensation of equimolar quantities of 2ꢀacetylꢀ
1ꢀnaphthol with 4ꢀnitrobenzohydrazide and
2ꢀhydroxybenzohydrazide, respectively, in methanol,
according to the literature method [8]. The yields were
Xꢀray structure determination. Diffraction intensiꢀ
ties for the complexes were collected at 298(2) K on a
Bruker APEXꢀII CCD diffractometer equipped with a
graphiteꢀmonochromatized Mo
K
radiation (
λ
=
α
95% for H2HNB and 93% for H2HHB. IR (KBr; ,
ν
0.71073 Å). Absorption corrections were applied using
SADABS [9]. The structures were solved by direct
methods and refined with the fullꢀmatrix leastꢀsquares
technique using SHELXSꢀ97 and SHELXLꢀ97 proꢀ
grams [10]. All nonꢀhydrogen atoms were refined with
anisotropic thermal parameters. All hydrogen atoms
were added in ideal positions and were not refined.
Crystallographic data are listed in Table 1 and selected
bond distances and angles are given in Table 2.
cm–1): for H2HNB—3422 w, 3200 m, 1684 s, 1610 m,
1593 s, 1511 s, 1437 w, 1343 s, 1266 s, 1178 w, 1114 m,
1059 w, 864 w, 847 m, 822 w, 751 m, 689 w; for
H2HHB—3423 w, 3234 w, 1644 s, 1623 s, 1605 s, 1533
m, 1512 m, 1492 w, 1457 w, 1434 w, 1369 w, 1349 w,
1310 m, 1278 w, 1241 m, 1210 m, 1157 w, 953 w, 893 w,
818 m, 750 m.
Supplementary material has been deposited
with the Cambridge Crystallographic Data Centre
(nos. 792717 (I) and 792718 (II); deposit@ccdc.
cam.ac.uk or http://www.ccdc.cam.ac.uk).
For H2HNB (C19H16N2O3)
anal. calcd., % C, 65.32;
Found, % C, 65.09;
For H2HHB (C H16N2O3)
H, 4.33;
H, 4.37;
N, 12.03.
N, 12.15.
9
1
anal. calcd., % C, 71.24;
Found, % C, 71.10;
H, 5.03;
H, 5.11;
N, 8.74.
N, 8.87.
RESULTS AND DISCUSSION
The reaction of VO(Acac)2 with hydrazone comꢀ
pounds readily affords the oxovanadium(V) comꢀ
plexes. The vanadium in the VO(Acac)2 is in V(IV)
oxidation state, however, it appears to be V(V) in the
complexes, indicating that it was oxidized by oxygen
during the reaction and crystallization procedures.
Synthesis of complex I. A methanol solution
(20 mL) of H2HNB (0.175 g, 0.5 mmol) was added to
a stirred methanol solution (20 mL) of VO(Acac)2
(0.132 g, 0.5 mmol). The mixture was stirred for
30 min at room temperature. The deep red solution
was left to slow evaporation for a few days, yielding
dark red blockꢀshaped single crystals. The crystals
were isolated by filtration. The yield was 72%. IR
The IR spectra of the hydrazone compounds
exhibit two absorption bands in the regions 3200–
3234 and 1644–1684 cm–1 due to the
ν
(N–H) and
ν
(C=O) stretches. The absence of these bands in the
(KBr;
, cm–1): 1615 m, 1592 m, 1569 m, 1547 s, 1515
ν
spectra of the complexes is consistent with the enolisaꢀ
tion of the amide functionality and subsequent proton
replacement by the vanadium atom. The weak band
observed at 3455 cm–1 in the spectrum of II due to the
O–H stretch of the coordinated methanol molecule is
m, 1444 w, 1425 w, 1376 m, 1340 s, 1243 m, 1050 w,
1022 m, 982 m, 866 w, 824 w, 757 w, 710 m, 618 m, 593
m, 419 w.
absent in the spectrum of I. The new bands appearing
For C40H32N6O12V2 (I)
in the 1243–1246 cm–1 range are assigned to the
stretching vibration of the enolic groups. The bands at
anal. calcd., %
Found, %
C, 53.94;
C, 53.63;
H, 3.62;
H, 3.71;
N, 9.44.
N, 9.32.
1615 and 1619 cm–1 in complexes
I and II, respecꢀ
tively, are assigned to the conjugate C=N–N=C moiꢀ
eties [11]. The bands observed at 982 and 987 cm–1 in
Synthesis of complex II. A methanol solution
(20 mL) of H2HHB (0.160 g, 0.5 mmol) was added to
a stirred methanol solution (20 mL) of VO(Acac)2
(0.132 g, 0.5 mmol). The mixture was stirred for
30 min at room temperature. The deep red solution
was left to slow evaporation for a few days, yielding
dark red blockꢀshaped single crystals. The crystals
were isolated by filtration. The yield was 80%. IR
I
and II, respectively, are assigned to the V=O
stretches [12, 13].
The molecular structure of I is shown in Fig. 1. The
complex is a methoxideꢀbridged centrosymmetric
dinuclear oxovanadium(V) complex. The V⋅⋅⋅V disꢀ
tance is 3.360(2) Å. The dianionic tridentate ligand
HNB binds the V atom through the phenolateꢀO,
imineꢀN, and deprotonated amideꢀO atoms, forming
a sixꢀand a fiveꢀmembered chelate rings. Each V atom
(KBr;
, cm–1): 3455 w, 1619 m, 1595 s, 1535 s, 1508
ν
m, 1490 m, 1450 w, 1430 w, 1373 m, 1310 w, 1246 s, is in a distorted NO5 octahedral coordination, with the
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

SYNTHESES AND CRYSTAL STRUCTURES OF OXOVANADIUM(V) COMPLEXES
585
Table 1. Crystallographic data and details of the experiment and refinement of structures I and II
Value
Parameter
I
II
Fw
890.60
416.30
Block/red
0.23 0.20
Triclinic
P⎯
Crystal shape/colour
Crystal size, mm
Crystal system
Space group
Block/red
0.30
Monoclinic
21/
×
0.27
×
0.27
×
×
0.20
P
n
1
a
b
, A
A
8.208(2)
14.528(3)
16.418(3)
90
8.3340(17)
10.236(2)
11.337(2)
80.91(3)
75.41(3)
75.63(3)
902.0(3)
1.533
c
, A
, deg
, deg
, deg
, Å3
α
β
97.887(3)
90
γ
V
1939.3(7)
1.525
ρcalcd, g/cm3
Z
2
2
μ
F
θ
(Mo
K
), mm–1
0.556
0.586
α
(000)
Range, deg
912
428
1.88–27.00
1.87–27.00
Index ranges
h
,
k,
l
⎯
10
≤
h
l
≤
10,
20
⎯
18
≤
k
≤
18,
–10
–14
≤
h
l
≤
10, –13
14
≤
k ≤ 13,
–20
≤
≤
≤
≤
Tmax
/
Tmin
0.8645/0.8510
4155
0.8918/0.8770
3746
Reflections
Independent reflections (Rint
)
3057(0.0397)
273
3268 (0.0205)
255
Parameters
Goodness of fit on F2
1.017
1.029
R1
,
,
wR2
(
I
≥
2
σ
(
I
))*
0.0507, 0.1159
0.0743, 0.1258
0.0393, 0.1027
0.0452, 0.1074
0.343 and –0.274
R1
wR2 (all data)*
Largest diff. peak and hole,
e
/Å3
0.388 and –0.199
1/2
2
2
*
R
=
Σ
||F
|–|F
||/
Σ
|F
|, wR =
2
[Σw(F2o – Fc2) /Σw(F2o) ]
.
1
o
c
o
three donor atoms of the hydrazone ligand, and one ide group lies trans to the imineꢀN atom. The dianꢀ
methoxide O atom defining the basal plane, and with ionic tridentate ligand HHB binds the V atom through
one oxo O and one symmetryꢀrelated methoxide
O atom occupying the axial positions. The mean deviꢀ
ation of the four equatorial donor atoms from the
leastꢀsquares plane is 0.014(3) Å. The displacement of
the Vatom towards the oxo group from the plane is
0.356(2) Å. The distances of V=O and other coordinaꢀ
tion bonds in the complex are comparable to those
observed in other similar oxovanadium(V) complexes
the phenolateꢀO, imineꢀN, and deprotonated amideꢀ
O atoms, forming a sixꢀ and a fiveꢀmembered chelate
rings. The V atom is in a distorted NO4 square pyramiꢀ
dal coordination, with the three donor atoms of the
hydrazone ligand, and one methoxide O atom definꢀ
ing the basal plane, and with one oxo O atom occupyꢀ
ing the apical position. The mean deviation of the four
basal donor atoms from the leastꢀsquares plane is
0.084(3) Å. The displacement of the V atom towards
the oxo group from the plane is 0.387(2) Å. The disꢀ
tances of V=O and other coordination bonds in the
[14, 15]. The molecules are stacked along the
with no obvious short contacts (Fig. 2).
x axis
The molecular structure of II is shown in Fig. 3.
There is an intramolecular O–H⋅⋅⋅N hydrogen bond complex are comparable with those observed in
stabilizing the molecular conformation. The methoxꢀ other similar oxovanadium(V) complexes [14, 16, 17].
I and
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2012

586
YUAN
and II
Table 2. Selected bond lengths (Å) and bond angles (deg) for
I
*
Bond
d
, Å
Bond
d, Å
I
V(1)–O(1)
V(1)–O(5)
V(1)–N(1)
1.8368(19)
1.580(2)
2.088(2)
V(1)–O(2)
V(1)–O(6)
V(1)–O(6A)
1.9351(18)
1.8283(18)
2.3588(18)
II
I
V(1)–O(2)
V(1)–O(4)
V(1)–N(2)
Angle
1.9327(15)
1.5759(17)
2.1081(19)
V(1)–O(3)
V(1)–O(5)
1.8856(14)
1.7669(15)
ω
, deg
Angle
ω
, deg
O(5)V(1)O(6)
O(6)V(1)O(1)
O(6)V(1)O(2)
O(5)V(1)N(1)
O(1)V(1)N(1)
O(5)V(1)O(6
O(1)V(1)O(6
N(1)V(1)O(6
102.81(9)
105.51(8)
89.39(7)
97.53(10)
81.71(8)
176.69(9)
79.60(7)
85.78(7)
O(5)V(1)O(1)
O(5)V(1)O(2)
O(1)V(1)O(2)
O(6)V(1)N(1)
O(2)V(1)N(1)
O(6)V( 1)O(6
O(2)V(1)O(6A)
100.77(10)
101.21(9)
149.85(8)
156.54(8)
75.18(7)
A
A
A
)
)
)
A
)
73.96(8)
79.64(7)
II
O(4)V(1)O(5)
O(5)V(1)O(3)
O(5)V(1)O(2)
O(4)V(1)N(2)
O(3)V(1)N(2)
102.53(8)
101.09(6)
94.01(7)
95.92(8)
80.94(6)
O(4)V(1)O(3)
O(4)V(1)O(2)
O(3)V(1)O(2)
O(5)V(1)N(2)
O(2)V(1)N(2)
101.57(8)
106.14(8)
144.60(7)
160.55(7)
74.75(7)
* Symmetry formation used to generate equivelant atoms: (Å) 2 –
x, 1 –
y, 2 –
z.
O(4)
N(3)
C(17)
C(18)
O(3)
C(16)
C(19)
C(14)
C(12)
C(8)
N(2)
C(15)
C(9)
C(11)
C(1)
C(13)
C(7)
O(2)
N(1)
O(5)
C(10)
V(1)
C(6)
C(2)
C(5)
C(4)
O(6A)
O(6)
O(1)
V(1A)
C(3)
C(20)
Fig. 1. Molecular structure of
I
with 30% thermal ellipsoids. Unlabelled atoms are related to the symmetry operation 2 –
x, 1 –
y, 2 –
z.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38 No. 8
2012

SYNTHESES AND CRYSTAL STRUCTURES OF OXOVANADIUM(V) COMPLEXES
587
x
z
0
y
Fig. 2. Molecular packing structure of
I
viewed along the x axis.
O(1)
C(2)
C(17)
C(9)
C(8)
C(3)
C(16)
C(18)
N(1)
C(19)
C(4)
C(10)
C(15)
N(2)
C(1)
C(7)
C(14)
C(13)
C(5)
C(6)
C(11)
C(12)
O(3)
O(2)
V(1)
O(4)
O(5)
C(21)
Fig. 3. Molecular structure of II with 30% thermal ellipsoids. Intramolecular O–H⋅⋅⋅N hydrogen bond is shown as a dashed line.
x
y
z
0
0
Fig. 4. The weak V⋅⋅⋅O linked dimeric structure of II
.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38 No. 8
2012

588
YUAN
7. Deep, A., Jain, S., Sharma, P.C., et al., Acta Pol.
Pharm., 2010, vol. 67, no. 3, p. 255.
It is notable that there exists weak V⋅⋅⋅Ophenolate interacꢀ
tions (V⋅⋅⋅O 2.359(2) Å) between the adjacent two
molecules (Fig. 4).
8. Deflon, V.M., Oliveira, D.M. de Sousa, G.F., et al.,
Z. Anorg. Allg. Chem., 2002, vol. 628, no. 5, p. 1140.
9. Sheldrick, G.M., SADABS, Program for Empirical
Absorption Correction of Area Detector, Göttingen (Gerꢀ
many): Univ. of Göttingen, 1996.
ACKNOWLEDGMENTS
I am grateful for the financial support from the
industrialization foster (no. 06JC25) of Shaanxi Provꢀ
ince and the main project (no. 04JS37) of the Key
Laboratory of Shaanxi Province, P.R. China.
10. Sheldrick, G.M., SHELXS, SHELXLꢀ97: Program for
the Refinement of Crystal Structure, Göttingen (Gerꢀ
many): Univ. of Göttingen, 1997.
11. ElꢀSayed, L. and Iskander, M.F., J. Inorg. Nucl. Chem.
1971, vol. 33, no. 2, p. 435.
,
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