Synthesis and crystal structures of N′-3,5-dibromo-2- hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide and its oxovanadium(V) complex [N′-(3,5-dibromo-2-oxidobenzylidene-κo)-2-hydroxy-3- methylbenzohydrazidato-κ 2 N′,O](methanol-κo) (methan

Article abstract of DOI:10.1007/s10870-011-0141-4

A new hydrazine ligand N′-3,5-dibromo-2-hydroxybenzylidene)-2- hydroxy-3-methylbenzohydrazide (1) and its oxovanadium(V) complex [N′-(3,5-dibromo-2-oxidobenzylidene-κO)-2-hydroxy-3- methylbenzohydrazidato-κ ² N′,O](methanol-κO) (methanolato-κO)

Full text of DOI:10.1007/s10870-011-0141-4

J Chem Crystallogr (2011) 41:1568–1572
DOI 10.1007/s10870-011-0141-4
ORIGINAL PAPER
Synthesis and Crystal Structures of N0-3,5-Dibromo-2-
Hydroxybenzylidene)-2-Hydroxy-3-Methylbenzohydrazide and its
Oxovanadium(V) Complex [N0-(3,5-Dibromo-2-Oxidobenzylidene-
jO)-2-Hydroxy-3-Methylbenzohydrazidato-j2N0,O]
(Methanol-jO)(Methanolato-jO)Oxidovanadium(V)
•
Zhi-Ping Li You-Ji Li Zhao-Xia Li
•
•
•
Hui Li Zhu-Ping Xiao
Received: 18 March 2011 / Accepted: 28 May 2011 / Published online: 10 June 2011
Ó Springer Science+Business Media, LLC 2011
Abstract A new hydrazine ligand N0-3,5-dibromo-2-
hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (1)
and its oxovanadium(V) complex [N0-(3,5-dibromo-2-oxido-
benzylidene-jO)-2-hydroxy-3-methylbenzohydrazidato-j2N0,O]
(methanol-jO)(methanolato-jO)oxidovanadium(V) (2), were
prepared and were structurally characterized by elemental
analysis, IR spectra and single-crystal X-ray diffraction.
Compound 1 crystallizes in the triclinic space group P-1,
Keywords Hydrazine ꢀ Oxovanadium complex ꢀ
Synthesis ꢀ Crystal structure
Introduction
The coordination chemistry of oxovanadium complexes with
multidentate ligands has attracted much interest both for their
structures and biological activities [1–5]. In the recent years, a
large number of oxovanadium complexes have been reported;
however, the oxovanadium complexes with hydrazine ligands
are relatively rare [6–8]. In this paper, a new hydrazine ligand
N0-3,5-dibromo-2-hydroxybenzylidene)-2-hydroxy-3-methy-
lbenzohydrazide (1, Scheme 1) was prepared. Based on the
ligand, a new oxovanadium(V) complex, [N0-(3,5-dibromo-2-
oxidobenzylidene-jO)-2-hydroxy-3-methylbenzohydrazid-
ato-j2N0,O](methanol-jO)(methanolato-jO)oxidovanadi-
um(V) (2), was successful prepared. The structures of the
hydrazine ligand and the complex were characterized by
elemental analysis, IR spectra, and single-crystal X-ray
diffraction.
˚
with unit cell dimensions a = 7.813(2) A, b = 8.748(2),
˚
c = 26.071(6) A, a = 85.763(2)°, b = 81.521(2)°, c =
3
˚
89.358(3)°, V = 1757.6(7) A , Z = 4, R1 = 0.0587, and
wR2 = 0.1054. Compound 2 crystallizes in the triclinic
˚
space group P-1, with unit cell dimensions a = 7.777(3) A,
˚
b = 11.594(3), c = 12.363(3) A, a = 107.965(3)°, b =
3
˚
103.190(2)°, c = 96.656(2)°, V = 1011.3(5) A , Z = 2,
R1 = 0.0634, and wR2 = 0.1480. The hydrazine ligand
coordinates to the V atom through the phenolic O, imino N,
and ethanolic O atoms. The V atom in the complex is in an
octahedral coordination, with the three donor atoms of the
hydrazine ligand and one methanolato O atom defining the
equatorial plane, and with one methanol O and one oxo O
atoms occupying the axial positions. The displacement of the
V atom from the equatorial plane towards the axial oxo O
˚
atom is 0.305(2) A.
Experimental
Materials and Measurements
3,5-Dibromosalicylaldehyde and 2-hydroxy-3-methylben-
zohydrazide were purchased from Aldrich. Other chemi-
cals and solvents were of reagent grade and were used as
obtained. Elemental analyses were performed on a Carlo-
Erba EA microanalyser. Infrared spectra were recorded as
KBr discs on a Bruker IFS-66V spectrometer. The 1H
NMR spectrum of the hydrazine ligand was recorded on a
Bruker 400 MHz spectrometer with CDCl3 as the solvent.
Z.-P. Li (&) ꢀ Y.-J. Li ꢀ Z.-X. Li ꢀ Z.-P. Xiao
College of Chemistry and Chemical Engineering, Jishou
University, Jishou Hunan 416000, People’s Republic of China
e-mail: lizhiping64@126.com
H. Li
College of Biology and Environmental Science, Jishou
University, Jishou Hunan 416000, People’s Republic of China
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J Chem Crystallogr (2011) 41:1568–1572
1569
program [10]. The structures of the compounds were
solved by direct method, which revealed the positions of all
non-hydrogen atoms. Both structures of the compounds
were refined on F2 by a full-matrix least-squares procedure
using anisotropic displacement parameters for all non-
hydrogen atoms. The amino H atoms in the hydrazine
ligand and the methanol H atom in the complex were
located from difference Fourier maps and refined isotrop-
ically, with N–H and O–H distances restrained to 0.90(1)
H
N
Br
N
O
OH
OH
Br
Scheme 1 N0-3,5-Dibromo-2-hydroxybenzylidene)-2-hydroxy-3-met-
hylbenzohydrazide
˚
and 0.85(1) A, respectively. The remaining hydrogen
Synthesis of N0-3,5-Dibromo-2-Hydroxybenzylidene)-
2-Hydroxy-3-Methylbenzohydrazide (1)
atoms were located in their calculated positions and refined
using a riding model. The crystals were weakly diffracting
so that the ratio of observed to unique reflections is low
(43% for 1 and 42% for 2). The details of the X-ray crystal
A methanolic solution (30 mL) of 3,5-dibromosalicylal-
dehyde (2.0 mmol, 560 mg) was added dropwise to a
stirred methanolic solution (20 mL) of 2-hydroxy-3-
methylbenzohydrazide (2.0 mmol, 332 mg). The mixture
was stirred at room temperature for 1 h to give clear col-
orless solution. The solution was slowly evaporated in air
to give colorless solid product of the hydrazine ligand.
Yield: 93%. Analysis calculated for C15H12Br2N2O3: C,
42.1; H, 2.8; N, 6.5%; found: C, 42.3; H, 2.8; N, 6.6%. 1H
NMR data (CDCl3, ppm): d = 2.15 (s, 3H), 6.92 (q, 1H),
7.31 (d, 1H), 7.66 (d, 1H), 7.73 (s, 1H), 7.81 (s, 1H), 8.15
(s, 1H), 8.73 (s, 1H), 10.3 (b, 2H). Single crystals of the
compound were obtained by recrystallization of the prod-
uct in methanol.
Table 1 Crystallographic data for 1 and 2
Compound
1
2
Empirical formula
Formula weight
Crystal shape/colour
Crystal size (mm)
Crystal system
C16H16Br2N2O4
460.1
C17H17Br2N2O6V
556.1
Block/colorless
Block/brown
0.23 9 0.20 9 0.20 0.27 9 0.23 9 0.23
Triclinic
P-1
Triclinic
P-1
Space group
˚
a (A)
7.813(2)
8.748(2)
26.071(6)
85.763(2)
81.521(2)
89.358(3)
1757.6(7)
4
7.777(3)
11.594(3)
12.363(3)
107.965(3)
103.190(2)
96.656(2)
1011.3(5)
2
˚
b (A)
˚
c (A)
Synthesis of [N0-(3,5-Dibromo-2-Oxidobenzylidene-
jO)-2-Hydroxy-3-Methylbenzohydrazidato-j2N0,O]
(Methanol-jO)(Methanolato-jO)
a (°)
b (°)
c (°)
Oxidovanadium(V) (2)
3
˚
V (A )
Z
To a stirred methanolic solution (5 mL) of the hydrazine
ligand (0.5 mmol, 214 mg) was added dropwise a metha-
nolic solution (5 mL) of VO(acac)2 (0.5 mmol, 132 mg).
The mixture was stirred for 1 h at room temperature to give
brown solution. Brown crystals of the complex, suitable for
X-ray diffraction, were obtained after one weak for slow
evaporation of the solution in air. Yield: 61%. Analysis
calculated for C17H17Br2N2O6V: C, 36.7; H, 3.1; N, 5.0%;
found: C, 36.5; H, 3.2; N, 5.1%.
Dcalc (g/cm3)
1.739
1.826
T (K)
l (mm-1
F(000)
298(2)
4.634
298(2)
)
4.477
912
548
Range of h, k, l
-9/9, -10/10,
-31/27
-9/9, -14/14,
-15/15
Max. and min.
transmission
0.415 and 0.458
0.378 and 0.426
Unique reflections
6442
2746
4290
1806
Observed reflections
I [ 2r(I)
X-ray Crystallography
Data/restraints/
parameters
Goodness-of-fit on F2
6442/4/451
4290/1/261
Each single crystal of the compounds was mounted on a
glass fiber. Intensity data were collected on a BRUKER
SMART 1000 CCD diffractometer. Intensities and lattice
parameters were obtained with graphite-monochromated
0.932
0.899
Rint
0.0662
0.0587
0.1054
0.1698
0.1404
0.0723
0.0634
0.1480
0.1694
0.2089
R1 [I C 2r(I)]
wR2 [I C 2r(I)]
R1 (all data)
˚
Mo Ka radiation (k = 0.71073 A). All data were corrected
for Lorentz and polarization effects. Empirical absorption
corrections were also applied for both crystal structures [9].
Complex scattering factors were taken from the SHELXTL
wR2 (all data)
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J Chem Crystallogr (2011) 41:1568–1572
˚
Structure of 1
Table 2 Selected bond lengths (A) and angles (°) for 1 and 2
1
The molecular structure of the hydrazine ligand is shown
in Fig. 1. The compound consists of two hydrazine mol-
ecules and two methanol molecules of crystallization. The
hydrazine molecules are approximately coplanar, with
mean deviation from the least squares planes defined by
Bond lengths
N1–C7
1.273(9)
1.265(9)
N1–N2
N3–N4
1.373(8)
1.378(8)
N3–C22
2
Bond lengths
N1–C7
˚
the non-hydrogen atoms of 0.062(1) and 0.039(1) A,
1.274(9)
1.865(6)
1.577(6)
1.746(5)
N1–N2
V1–O2
V1–O5
V1–N1
1.390(9)
1.955(6)
2.308(6)
2.134(6)
respectively. The dihedral angles between the two ben-
zene rings are 6.6(2) and 4.4(2)°. The intramolecular
O–H_N hydrogen bonds (Table 3) may contribute to the
formation of the planar geometry of the molecules. The
hydrazine molecule adopts a trans configuration about
the C7–N1 and C22–N3 bonds. The long C7–N1 and
C22–N3 bonds and the short N1–N2 and N3–N4 bonds
suggest the delocalization of the acetohydrazide moieties.
All the bond distances in the compound are within normal
ranges [14], and are comparable to those in the similar
compounds [15, 16].
V1–O1
V1–O4
V1–O6
Bond angles
O4–V1–O6
O6–V1–O1
O6–V1–O2
O4–V1–N1
O1–V1–N1
O4–V1–O5
O1–V1–O5
N1–V1–O5
102.5(3)
100.4(3)
97.1(2)
95.7(3)
81.9(2)
176.4(3)
81.6(2)
81.4(2)
O4–V1–O1
O4–V1–O2
O1–V1–O2
O6–V1–N1
O2–V1–N1
O6–V1–O5
O2–V1–O5
100.0(3)
97.5(3)
151.8(2)
161.0(3)
74.6(2)
80.3(2)
79.8(2)
In the crystal structure of the compound (Fig. 2), the
adjacent two hydrazine molecules are linked by two
methanol molecules through two intermolecular C31-
H31B_O2 hydrogen bonds (Table 3) and two intermo-
lecular O7-H7_O1 hydrogen bonds (Table 3), to form
dimers. There are no obvious short contacts among the
dimers.
data, and the structure solution and refinement for both
compounds are given in Table 1. Selected bond lengths and
angles are given in Table 2. Crystallographic data for both
compounds have been deposited in the Cambridge Crys-
tallographic Data Centre (CCDC 817824 and 817825).
Structure of 2
The molecular structure of the oxovanadium(V) complex is
shown in Fig. 3. The dianionic hydrazine ligand coordi-
nates to the V atom through the phenolic O, imino N, and
enolic O atoms, forming a five-membered and a six-
membered chelate rings with bite angles of 74.6(2) and
81.9(2)°. The V atom in the complex is in an octahedral
coordination, with the three donor atoms of the hydrazine
ligand and one methanolato O atom defining the equatorial
plane, and with one methanol O and one oxo O atoms
occupying the axial positions. The displacement of the V
atom from the equatorial plane towards the axial oxo O
Results and Discussion
The hydrazine ligand and the oxovanadium(V) complex
are stable in air at room temperature. They are soluble in
methanol, ethanol and acetonitrile. The elemental analyses
are in good agreement with the chemical formulae pro-
posed for the compounds.
The hydrazine compound N0-3,5-dibromo-2-hydro-
xybenzylidene)-2-hydroxy-3-methylbenzohydrazide is a
flexible multidentate ligand, which coordinates to the metal
atoms through the phenolic O, imino N, and enolic O
atoms. The V atoms usually adopt octahedral and square-
pyramidal coordination [11–13]. The methanol was proved
to be a preferred solvent for the preparation of such
complexes.
˚
atom is 0.305(2) A. The coordinate bond lengths and
angles in the complex are similar to those reported else-
where [11–13]. The formation of the coordinate bonds with
the V atom for the hydrazine ligand, together with the
Fig. 1 Molecular structure of 1
with 30% probability ellipsoids.
Hydrogen bonds are shown as
dashed lines
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J Chem Crystallogr (2011) 41:1568–1572
1571
Table 3 Hydrogen geometries for 1 and 2
˚
˚
˚
D–H_A
d(D–H, A) d(H_A, A) d(D_A, A) Angle
(D–H_A, °)
1
O7–H7_O1#1
O6–H6_O5
N4–H4A_O8#2
O3–H3_O2
O1–H1_N1
N2–H2_O7#3
O4–H4C_N3
0.82
2.61
3.056(9)
2.545(8)
2.901(10)
2.547(8)
2.567(8)
2.878(9)
2.582(8)
3.423(8)
116
0.82
1.83
145
0.90(1)
0.82
2.17(5)
1.84
138(7)
143
0.85(1)
0.90(1)
0.85(1)
1.82(5)
2.02(3)
1.82(4)
2.50
146(8)
161(7)
148(8)
161(8)
C31–H31B_O2#4 0.96
2
Fig. 3 Molecular structure of 2 with 30% probability ellipsoids.
Hydrogen bonds are shown as dashed lines
O5–H5_O3#5
O3–H3_N2
C7–H7_O4#6
0.85(1)
1.90(2)
1.81
2.733(8)
2.536(9)
3.225(8)
166(8)
146
0.82
0.93
2.54
131(8)
Symmetry codes: #1: 1 - x, -y, 1 - z; #2: x, y, -1 ? z; #3: x, 1 ? y, z; #4:
-x, 1 - y, 1 - z; #5: 2 - x, 1 - y, 1 - z; #6: 1 - x, 1 - y, 1 - z
Fig. 2 Molecular packing diagram of 1. Hydrogen bonds are shown
as dashed lines
Fig. 4 Molecular packing diagram of 2. Hydrogen bonds are shown
as dashed lines
existence of the intramolecular O–H_N hydrogen bond
(Table 3), leads to the planarity of the hydrazine ligand.
The dihedral angle between the C1–C6 and C9–C14 ben-
zene rings is 5.6(2)°.
In the crystal structure of the complex (Fig. 4), the
adjacent two complex molecules are linked by two inter-
molecular C7-H7_O4 hydrogen bonds (Table 3), to form
a dimer. The adjacent dimers are further linked by two
methanol ligands through two intermolecular O5-H5_O3
hydrogen bonds (Table 3), to form chains along the a axis.
IR Spectra
The typical band centered at 3432 cm-1 of the hydrazine
ligand can be attributed to the phenolic O–H stretch. The
m(C=O) absorption band at 1653 cm-1 and the sharp m(NH)
band at 3223 cm-1 in the IR spectrum of the hydrazine
ligand are absent in the complex, indicating the enolisa-
tion of the amide functionality and subsequent proton
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J Chem Crystallogr (2011) 41:1568–1572
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