Synthesis, characterization and crystal structures of vanadium(V) complexes derived from halido-substituted tridentate hydrazone compounds with antimicrobial activity

Article abstract of DOI:10.1016/j.poly.2018.09.017

Three new chlorido-substituted hydrazone compounds N′-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide (H₂L¹), N′-(3,5-dichloro-2-hydroxybenzylidene)-4-fluorobenzohydrazide (H₂L²) and N′-(2-hydroxy-3-methylbenz

Full text of DOI:10.1016/j.poly.2018.09.017

Accepted Manuscript
Synthesis, characterization and crystal structures of vanadium(V) complexes
derived from halido-substituted tridentate hydrazone compounds with antimi-
crobial activity
Ling-Yan He, Xiao-Yang Qiu, Jun-Yan Cheng, Shu-Juan Liu, Su-Min Wu
PII:
S0277-5387(18)30569-2
https://doi.org/10.1016/j.poly.2018.09.017
POLY 13416
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
11 May 2018
6 September 2018
7 September 2018
Please cite this article as: L-Y. He, X-Y. Qiu, J-Y. Cheng, S-J. Liu, S-M. Wu, Synthesis, characterization and crystal
structures of vanadium(V) complexes derived from halido-substituted tridentate hydrazone compounds with
antimicrobial activity, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.09.017
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Synthesis, characterization and crystal structures of vanadium(V) complexes derived
from halido-substituted tridentate hydrazone compounds with antimicrobial activity
Ling-Yan Hea, Xiao-Yang Qiua,*, Jun-Yan Chengb, Shu-Juan Liua, Su-Min Wua
a College of Science & Technology, Ningbo University, Ningbo 315212, P.R. China
b
College of Chemistry, Chemical Engineering and Material Science, Shandong
Normal University, Jinan 250014, P.R. China
* e-mail: xiaoyang_qiu@126.com
Abstract
Three
new
chlorido-substituted
hydrazone
compounds
(H2L1),
and
N'-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide
N'-(3,5-dichloro-2-hydroxybenzylidene)-4-fluorobenzohydrazide (H2L2)
N'-(2-hydroxy-3-methylbenzylidene)-4-trifluoromethylbenzohydrazide (H2L3), were
1
prepared and characterized by IR, UV-Vis and H NMR spectra. Based on the
hydrazone
compounds,
three
new
vanadium(V)
complexes,
[VOL1(OEt)(EtOH)]·[VOL1(OEt)(MeOH)] (1), [VOL2(OEt)(EtOH)] (2) and
[VOL3(OEt)(EtOH)] (3), were prepared and characterized by IR and UV-Vis spectra,
as well as single crystal X-ray diffraction. X-ray analysis indicates that the complexes
are mononuclear vanadium(V) species, with the V atoms coordinated in octahedral
geometry. The hydrazone compounds and their vanadium complexes were evaluated
against the bacteria Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and
Pseudomonas fluorescence, and the fungi Candida albicans and Aspergillus niger.
The existence of the fluoro groups in the hydrazone ligands can improve the
1

antibacterial activities.
Keywords: Hydrazone; Vanadium complex; Mononuclear complex; Crystal structure;
Antimicrobial activity
1. Introduction
Hydrazones with the typical functional group -CH=N-NH-C(O)- are a kind of
biological active compound. The compounds have attracted remarkable attention for
their wide range of biological activities, such as antibacterial [1-3], antifungal [4,5],
and antitumor [6,7]. It was reported that compounds bearing electron-withdrawing
groups can improve their antimicrobial activities [8,9]. Rai and co-workers reported a
series of fluoro, chloro, bromo, and iodo-substituted compounds, and found that they
have significant antimicrobial activities [10]. Vanadium complexes with Schiff bases
and hydrazones have been reported to have interesting antibacterial activities [11-14].
As a continuation of work on the exploration of novel complex based antimicrobial
agents, in this paper, chloro and fluoro groups are incorporated in hydrazone
compounds, and then coordinate with vanadium, to form three new halido-substituted
hydrazone
compounds
N'-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide
(H2L1), N'-(3,5-dichloro-2-hydroxybenzylidene)-4-fluorobenzohydrazide (H2L2) and
N'-(2-hydroxy-3-methylbenzylidene)-4-trifluoromethylbenzohydrazide (H2L3), and
three new vanadium(V) complexes, [VOL1(OEt)(EtOH)] (1), [VOL2(OEt)(EtOH)] (2)
and [VOL3(OEt)(EtOH)] (3), and studied their antimicrobial activities.
2

H2L1
H2L2
H2L3
2. Experimental
2.1. Materials and methods
3,5-Dichlorosalicylaldehyde,
benzohydrazide,
4-fluorobenzohydrazide,
4-trifluoromethylbenzohydrazide, and VO(acac)2 were purchased from Sigma-Aldrich
and used as received. All other reagents were of analytical reagent grade. Elemental
analyses of C, H and N were carried out in a Perkin-Elmer automated model 2400
Series II CHNS/O analyzer. FT-IR spectra were obtained on a Perkin-Elmer 377
FT-IR spectrometer with samples prepared as KBr pellets. UV-Vis spectra were
1
obtained on a Lambda 35 spectrometer. H NMR data were recorded on Bruker 300
MHz spectrometer. X-ray diffraction was carried out on a Bruker APEX II CCD
diffractometer.
2.2. Synthesis of the hydrazones
To the ethanolic solution (30 mL) of 3,5-dichlorosalicylaldehyde (0.01 mol, 1.91 g)
was added an ethanolic solution (20 mL) of benzohydrazide (0.01 mol, 1.36 g),
4-fluorobenzohydrazide (0.01 mol, 1.54 g) or 4-trifluoromethylbenzohydrazide (0.01
mol, 2.04 g) with stirring. The mixtures were stirred for 30 min at room temperature,
and left to slowly evaporate to give colorless crystalline product, which were
recrystallized from ethanol and dried in vacuum containing anhydrous CaCl2.
For H2L1: Yield 92%. IR data (cm–1): 3454, 3190, 1643, 1596. UV-Vis data
(MeOH, λmax, nm): 290, 303, 332, 400. Anal. Calc. for C14H10Cl2N2O2: C, 54.4; H, 3.3;
N, 9.1. Found: C, 54.6; H, 3.2; N, 9.0%. 1H NMR (300 MHz, d6-DMSO): δ 12.52 (s,
1H, OH), 11.18 (s, 1H, NH), 8.58 (s, 1H, CH=N), 7.97 (d, 2H, ArH), 7.63 (m, 1H,
ArH), 7.57 (d, 2H, ArH), 7.37 (m, 2H, ArH). For H2L2: Yield 95%. IR data (cm–1):
3

3451, 3212, 1648, 1597. UV-Vis data (MeOH, λmax, nm): 240, 290, 330, 400. Anal.
Calc. for C14H9Cl2FN2O2: C, 51.4; H, 2.8; N, 8.6. Found: C, 51.3; H, 2.8; N, 8.5%. 1H
NMR (300 MHz, d6-DMSO): δ 12.50 (s, 1H, OH), 11.26 (s, 1H, NH), 8.57 (s, 1H,
CH=N), 8.03 (d, 2H, ArH), 7.65 (d, 2H, ArH), 7.37 (m, 2H, ArH). For H2L3: Yield
93%. IR data (cm–1): 3445, 3182, 1645, 1598. UV-Vis data (MeOH, λmax, nm): 290,
301, 332, 400. Anal. Calc. for C15H9Cl2F3N2O2: C, 47.8; H, 2.4; N, 7.4. Found: C,
47.6; H, 2.5; N, 7.5%. 1H NMR (300 MHz, d6-DMSO): δ 12.46 (s, 1H, OH), 11.20 (s,
1H, NH), 8.57 (s, 1H, CH=N), 8.17 (d, 2H, ArH), 8.14 (d, 2H, ArH), 7.37 (m, 2H,
ArH).
2.3. Synthesis of the complexes
The hydrazone compounds (0.1 mmol each) dissolved in ethanol were mixed with
VO(acac)2 (0.1 mmol, 26.5 mg) dissolved in methanol (10 mL). The mixtures were
refluxed for 1 h and then cooled to room temperature. Single crystals of the
complexes, suitable for X-ray diffraction, were grown from the solution upon slowly
evaporation within a few days. The crystals were isolated by filtration, washed with
ethanol and dried in vacuum containing anhydrous CaCl2.
For 1: Yield 51%. IR data (cm–1): 3432 (w), 1607 (s), 972 (m). UV-Vis data
(CH3CN, λmax, nm): 255, 303, 405, 435. Anal. calc. for C18H18Cl2FN2O5V: C, 44.7; H,
3.8; N, 5.8; found: C, 44.7; H, 3.7; N, 5.9%. For 2: Yield 43%. IR data (cm–1): 3437
(w), 1610 (s), 975 (m). UV-Vis data (CH3CN, λmax, nm): 262, 305, 410, 438. Anal.
calc. for C18H18Cl2FN2O5V: C, 44.7; H, 3.8; N, 5.8; found: C, 44.9; H, 3.6; N, 5.8%.
For 3: Yield 38%. IR data (cm–1): 3421 (w), 1610 (s), 973 (m). UV-Vis data (CH3CN,
λmax, nm): 257, 300, 406, 435. Anal. calc. for C19H18Cl2F3N2O5V: C, 42.8; H, 3.4; N,
5.3; found: C, 42.9; H, 3.5; N, 5.1%.
2.4. X-ray crystallography
4

X-ray diffraction was carried out at a Bruker APEX II CCD area diffractometer
equipped with MoKα radiation (λ = 0.71073 Å). The collected data were reduced with
SAINT [15], and multi-scan absorption correction was performed using SADABS
[16]. The structures of the complexes were solved by direct method, and refined
against F2 by full-matrix least-squares method using SHELXTL [17]. All of the
non-hydrogen atoms were refined anisotropically. The hydrogen atoms of the
methanol and ethanol ligands were located from electronic density maps and refined
isotropically. The remaining hydrogen atoms were placed in calculated positions and
constrained to ride on their parent atoms. The trifluoromethyl group of complex 3 was
disordered over two sites, with occupancies of 0.514(3) and 0.486(3), respectively.
The crystallographic data and refinement parameters for the complexes are listed in
Table 1. Selected bond lengths and angles are listed in Table 2.
2.5. Antimicrobial assay
The antibacterial activities of the hydrazone compounds and the vanadium complexes
were tested against B. subtilis, S. aureus, E. coli, and P. fluorescence using MH
(Mueller–Hinton) medium. The antifungal activities of the compounds were tested
against C. albicans and A. niger using RPMI-1640 medium. The MIC values of the
tested compounds were determined by a colorimetric method using the dye MTT [18].
A stock solution of the compound (150 μg·mL–1) in DMSO was prepared and graded
quantities (75 μg·mL–1, 37.5 μg·mL–1, 18.8 μg·mL–1, 9.4 μg·mL–1, 4.7 μg·mL–1, 2.3
μg·mL–1, 1.2 μg·mL–1, 0.59 μg·mL–1) were incorporated in specified quantity of the
corresponding sterilized liquid medium. A specified quantity of the medium
containing the compound was poured into micro-titration plates. Suspension of the
microorganism was prepared to contain approximately 1.0 × 105 cfu·mL–1 and applied
to microtitration plates with serially diluted compounds in DMSO to be tested and
5

incubated at 37 °C for 24 h and 48 h for bacteria and fungi, respectively. Then the
MIC values were visually determined on each of the microtitration plates, 50 μL of
PBS (phosphate buffered saline 0.01 mol·L–1, pH = 7.4) containing 2 mg of
MTT·mL–1 was added to each well. Incubation was continued at room temperature for
4–5 h. The content of each well was removed and 100 μL of isopropanol containing
5% 1 mol·L–1 HCl was added to extract the dye. After 12 h of incubation at room
temperature, the optical density was measured with a microplate reader at 550 nm.
3. Results and discussion
3.1. Synthesis and characterization
The hydrazone compounds H2L1, H2L2 and H2L3 were readily prepared by the
condensation reaction of a 1:1 molar ratio of 3,5-dichlorosalicylaldehyde with
benzohydrazide, 4-fluorobenzohydrazide and 4-trifluoromethylbenzohydrazide,
respectively in ethanol. The complexes were prepared by the reaction of the
hydrazone compounds with vanadyl acetylacetonate in a mixture of methanol and
ethanol, followed by recrystallization. Elemental analyses of the complexes are in
accordance with the molecular structures proposed by the X-ray analysis.
3.2. Spectroscopic studies
In the spectra of the hydrazone compounds and the complexes, the weak and broad
bands in the range 3300-3500 cm-1 are assigned to the vibration of O–H bonds. The
weak and sharp bands of the hydrazone compounds located at about 3200 cm-1 are
assigned to the vibration of N–H bonds. The intense bands at 1640-1650 cm-1 of the
hydrazone compounds are generated by ν(C=O) vibrations, whereas the bands at
1590-1600 cm-1 by the ν(C=N) ones. The non-observation of the ν(C=O) and ν(N–H)
bands, present in the spectra of the hydrazone compounds, indicates the enolization of
6

the amide functionality upon coordination to the V-center. Instead strong bands at
1607-1610 cm-1 are observed, which can be attributed to the asymmetric stretching
vibration of the conjugated CH=N–N=C–O groups, characteristic for the coordination
of the enolate form of the compounds. The strong ν(V=O) bands at 972-975 cm-1 for
the complexes could be clearly identified for the complexes [19].
In the electronic spectra of the hydrazones and the complexes, the bands in the
range of 300-340 nm are attributed to the intra-ligand π→π* absorption. In the
electronic spectra of the complexes, the lowest energy transition bands are observed at
420-450 nm, which are attributed to LMCT transition as charge transfer from p-orbital
on the lone-pair of ligands’ oxygen atoms to the empty d-orbital of the vanadium
atoms. The other mainly LMCT and to some extent π→π* bands appear at 250-270
nm for the complexes are due to the oxygen donor atoms bound to vanadium(V) [19].
3.3. Structure description of the complexes
Molecular structures of the complexes are shown in Figures 1-3, respectively. The
asymmetric unit of complex 1 contains two vanadium complex molecules. One
molecule contains a methanol and ethoxy ligands, and the other molecule contains an
ethanol and ethoxy ligands. Complexes 2 and 3 contain ethanol and ethoxy ligands. In
the complexes, the coordination geometry around the vanadium atoms can be
described as distorted octahedral with the tridentate hydrazone ligand coordinated in
meridional fashion, forming five- and six-membered chelate rings with bite angles of
73.7-74.0° and 83.9-84.3°, respectively, typical for this type of ligand systems [20].
Each chelating hydrazone ligand lies in a plane with one hydroxylato ligand which
lies trans to the hydrazone imino N atom. One solvent O atom of the methanol or
ethanol ligand trans to the oxo group completes the distorted octahedral coordination
sphere at rather elongated distances of 2.3-2.4 Å, due to the trans influence of the oxo
7

group. This is accompanied by significant displacements of the vanadium atoms from
the planes defined by the four basal donor atoms toward the apical oxo oxygen atoms
by 0.28-0.32Å. As expected, the hydrazone compounds coordinate in their doubly
deprotonated enolate form which is consistent with the observed O2–C8 and N2–C8
bond lengths of about 1.30 Å. This agrees with reported vanadium complexes
containing the enolate form of this ligand type [20-22].
In the crystal packing structure of complex 1, the complex molecules are linked by
methanol and ethanol ligands through intermolecular hydrogen bonds of O–H···N
[O3–H3 = 0.85(1) Å, H3···N4i = 2.07(5) Å, O3···N4i = 2.88(1) Å, O3–H3···N4i =
158(12)º, symmetry code for i: –1 + x, y, z; O8–H8 = 0.85(1) Å, H8···N2 = 2.08(6) Å,
O8···N2 = 2.87(1) Å, O8–H8···N2 = 154(11)º], leading to the formation of chains
along the a-axis direction (Figure 4). In the crystal packing structure of complex 2, the
complex molecules are linked by ethanol ligands through intermolecular hydrogen
bonds of O–H···N [O3–H3 = 0.93 Å, H3···N2ii = 1.95 Å, O3···N2ii = 2.869(4) Å,
O3–H3···N2ii = 169(7)º, symmetry code for ii: – x, 1 – y, –1 – z], leading to the
formation of chains along the c-axis direction (Figure 5). In the crystal packing
structure of complex 3, the complex molecules are linked by ethanol ligands through
intermolecular hydrogen bonds of O–H···N [O3–H3 = 0.85(1) Å, H3···N2iii = 2.08(3)
Å, O3···N2iii = 2.900(6) Å, O3–H3···N2iii = 163(7)º, symmetry code for iii: 1 – x, 1 –
y, 1 – z], leading to the formation of chains along the b-axis direction (Figure 6).
3.4. Antimicrobial activity
The hydrazone compounds and the vanadium complexes were screened for
antibacterial activities against two Gram (+) bacterial strains (Bacillus subtilis and
Staphylococcus aureus) and two Gram (–) bacterial strains (Escherichia coli and
Pseudomonas fluorescence) by MTT method. The MIC (minimum inhibitory
8

concentration, μg·mL–1) values of the compounds against four bacteria are listed in
Table 3. Penicillin G was used as the standard drug. The hydrazone compound H2L1
shows weak activity against B. subtilis and S. aureus, and no activity against P.
fluorescence and E. coli. The hydrazone compound H2L2 shows effective activity
against B. subtilis, and medium activity against S. aureus and E. coli, and no activity
against P. fluorescence. The hydrazone compound H2L3 shows effective activity
against B. subtilis and S. aureus, and medium activity agaist E. coli, and no activity
against P. fluorescence. The vanadium complexes, in general, have stronger activities
against the bacteria than the free hydrazones. Moreover, complexes 2 and 3 have
stronger activities than complex 1. Complexes 2 and 3 have strong activities against B.
subtilis and S. aureus, which are more effective than Penicillin G. However, the
complexes have no activity against P. fluoresence and two fungal strains (Candida
albicans and Aspergillus niger). From the results, we can conclude that the existence
of the fluoro groups in the hydrazone ligands can improve the antibacterial activities.
Appendix A. Supplementary data
CCDC 1841526, 1841527 and 1841528 contains the supplementary crystallographic
data for complexes 1, 2 and 3, respectively. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgments
We thank the Educational Commission of Henan Province of China (Grant No.
14B150036) and the Natural Science Foundation of Henan Province of China (Grant
9

No. 142300410252) for supporting of this work.
References
[1] Z.A. Kaplancikli, M.D. Altintop, A. Ozdemir, G. Turan-Zitouni, G. Goger, F.
Demirci. Lett. Drug Des. Discov. 11 (2014) 355.
[2] R. Narisetty, K.B. Chandrasekhar, S. Mohanty, B. Balram. Lett. Drug Des. Discov.
10 (2013) 620.
[3] F. Zhi, N. Shao, Q. Wang, Y. Zhang, R. Wang, Y. Yang. J. Struct. Chem. 54 (2013)
148.
[4] A. Ozdemir, G. Turan-Zitouni, Z.A. Kaplancikli, F. Demirci, G. Iscan. J. Enzyme
Inhib. Med. Chem. 23 (2008) 470.
[5] C. Loncle, J.M. Brunel, N. Vidal, M. Dherbomez, Y. Letourneux. Eur. J. Med.
Chem. 39 (2004) 1067.
[6] Y.-C. Liu, H.-L. Wang, S.-F. Tang, Z.-F. Chen, H. Liang. Anticancer Res. 34
(2014) 6034.
[7] P. Krishnamoorthy, P. Sathyadevi, A.H. Cowley, R.R. Butorac, N. Dharmaraj. Eur.
J. Med. Chem. 46 (2011) 3376.
[8] M. Zhang, D.-M. Xian, H.-H. Li, J.-C. Zhang, Z.-L. You. Aust. J. Chem. 65 (2012)
343.
[9] L. Shi, H.-M. Ge, S.-H. Tan, H.-Q. Li, Y.-C. Song, H.-L. Zhu, R.-X. Tan. Eur. J.
Med. Chem. 42 (2007) 558.
[10]N.P. Rai, V.K. Narayanaswamy, T. Govender, B.K. Manuprasad, S. Shashikanth,
P.N. Arunachalam. Eur. J. Med. Chem. 45 (2010) 2677.
[11]S.S. Wazalwar, N.S. Bhave, A.G. Dikundwar, P. Ali. Synth. React. Inorg.
Met.-Org. Nano-Met. Chem. 41 (2011) 459.
10

[12]J.-L. Liu, M.-H. Sun, J.-J. Ma. Synth. React. Inorg. Met.-Org. Nano-Met. Chem.
45 (2015) 117.
[13]Z.H. Chohan, S.H. Sumrra, M.H. Youssoufi, T.B. Hadda. Eur. J. Med. Chem. 45
(2010) 2739.
[14]O. Taheri, M. Behzad, A. Ghaffari, M. Kubicki, G. Dutkiewicz, A. Bezaatpour, H.
Nazari, A. Khaleghian, A. Mohammadi, M. Salehi. Transition Met. Chem. 39
(2014) 253.
[15]Bruker, SMART (Version 5.625) and SAINT (Version 6.01). Bruker AXS Inc.,
Madison, Wisconsin, USA (2007).
[16]G.M. Sheldrick. SADABS. Program for Empirical Absorption Correction of Area
Detector, University of Göttingen, Germany (1996).
[17]G.M. Sheldrick. SHELXTL V5.1 Software Reference Manual, Bruker AXS, Inc.,
Madison, Wisconsin, USA (1997).
[18]J. Meletiadis, J.F.G.M. Meis, J.W. Mouton, J.P. Donnelly, P.E. Verweij. J. Clin.
Microbiol. 38 (2000) 2949.
[19]A. Sarkar, S. Pal. Polyhedron 26 (2007) 1205.
[20]H.H. Monfared, S. Alavi, R. Bikas, M. Vahedpour, P. Mayer. Polyhedron 29
(2010) 3355.
[21]X.-T. Zhang, X.-P. Zhan, D.-M. Wu, Q.-Z. Zhang, S.-M. Chen, Y.-Q. Yu, C.-Z. Lu.
Chinese J. Struct. Chem. 21 (2002) 629.
[22]H.H. Monfared, S. Alavi, R. Bikas, M. Vahedpour, P. Mayer. Polyhedron 29
(2010) 3355.
11

Table 1. Crystallographic and refinement data for the complexes
Complex
1
2
3
Formula
C35H36Cl4N4O10V2 C18H18Cl2FN2O5V C19H18Cl2F3N2O5V
Formula weight
916.36
483.18
533.19
Crystal shape/color Block/brown
Block/brown
298(2)
Block/brown
298(2)
T (K)
298(2)
Crystal dimensions
(mm3)
0.22  0.20  0.19
0.27  0.27  0.23
0.32  0.27  0.26
Crystal system
Space group
a (Å)
Triclinic
P1
Monoclinic
Cc
Triclinic
P-1
7.556(2)
12.401(2)
12.462(2)
70.346(2)
73.392(2)
19.681(2)
15.091(2)
7.620(1)
90
7.991(2)
12.383(1)
13.232(1)
64.818(2)
76.265(2)
b (Å)
c (Å)
α (º)
109.147(2)
 (º)
76.727(2)
1042.1(3)
1
90
78.859(2)
1144.7(3)
2
 (º)
V (Å3)
2137.9(5)
4
Z
Dcalc (g cm–3)
 (Mo K) (mm–1)
F(000)
1.460
1.501
0.754
1.547
0.762
0.724
468
984
540
Measured
reflections
5912
6234
6741
Unique reflections 4796
Observed 3232
3516
2838
4228
2948
12

reflections (I
2(I))

Min. and max. 0.8503 and 0.8688 0.8224 and 0.8458 0.8014 and 0.8342
transmission
Parameters
Restraints
505
6
264
2
321
68
Goodness of fit on 1.073
1.034
1.109
F2
R1, wR2 [I  2(I)]a
0.0675, 0.1534
0.0414, 0.0922
0.0765, 0.2009
0.1082, 0.2214
R1, wR2 (all data)a 0.1079, 0.1923
0.0569, 0.1048
2
2 2 1/2
a R1 = Fo – Fc/Fo, wR2 = [ w(Fo – Fc2)/ w(Fo ) ]
13

Table 2. Selected bond distances (Å) for the complexes
1
V1-O5
1.572(8)
1.850(8)
2.141(9)
1.572(8)
1.873(8)
2.140(8)
103.0(4)
100.6(4)
95.8(3)
94.3(4)
83.5(3)
174.8(3)
80.0(4)
80.5(3)
99.9(4)
98.7(4)
152.2(3)
159.8(3)
73.9(3)
81.6(3)
80.1(3)
V1-O4
1.747(7)
1.930(7)
2.391(8)
1.766(7)
1.919(7)
2.374(7)
99.4(4)
98.8(4)
152.0(3)
161.3(3)
74.0(3)
82.2(3)
79.9(3)
103.8(4)
101.1(3)
94.3(3)
94.4(3)
84.2(3)
174.6(3)
79.4(3)
80.2(3)
V1-O1
V1-O2
V1-N1
V1-O3
V2-O10
V2-O9
V2-O6
V2-O7
V2-N3
V2-O8
O5-V1-O4
O4-V1-O1
O4-V1-O2
O5-V1-N1
O1-V1-N1
O5-V1-O3
O1-V1-O3
N1-V1-O3
O10-V2-O6
O10-V2-O7
O6-V2-O7
O9-V2-N3
O7-V2-N3
O9-V2-O8
O7-V2-O8
2
O5-V1-O1
O5-V1-O2
O1-V1-O2
O4-V1-N1
O2-V1-N1
O4-V1-O3
O2-V1-O3
O10-V2-O9
O9-V2-O6
O9-V2-O7
O10-V2-N3
O6-V2-N3
O10-V2-O8
O6-V2-O8
N3-V2-O8
V1-O5
1.555(3)
V1-O4
1.752(3)
14

V1-O1
1.861(3)
V1-O2
1.920(3)
V1-N1
2.143(3)
V1-O3
2.345(3)
O5-V1-O4
O4-V1-O1
O4-V1-O2
O5-V1-N1
O1-V1-N1
O5-V1-O3
O1-V1-O3
N1-V1-O3
3
103.18(15)
101.63(14)
94.42(14)
95.53(16)
83.90(14)
175.35(14)
80.51(15)
79.88(13)
O5-V1-O1
O5-V1-O2
O1-V1-O2
O4-V1-N1
O2-V1-N1
O4-V1-O3
O2-V1-O3
98.31(18)
99.37(16)
152.67(13)
159.38(15)
73.80(14)
81.47(12)
80.18(13)
V1-O5
1.572(4)
1.858(4)
2.138(4)
101.7(2)
104.38(17)
92.90(17)
94.6(2)
V1-O4
1.757(4)
1.962(4)
2.330(4)
99.7(2)
V1-O1
V1-O2
V1-N1
V1-O3
O5-V1-O4
O4-V1-O1
O4-V1-O2
O5-V1-N1
O1-V1-N1
O5-V1-O3
O1-V1-O3
N1-V1-O3
O5-V1-O1
O5-V1-O2
O1-V1-O2
O4-V1-N1
O2-V1-N1
O4-V1-O3
O2-V1-O3
97.3(2)
152.64(18)
160.2(2)
73.77(16)
82.66(17)
79.81(17)
83.59(16)
174.95(18)
81.53(18)
80.61(16)
15

Table 3. Antimicrobial activities of the compounds with minimum inhibitory
concentrations (μg·mL–1)
Tested material B. subtilis
S. aureus
37.5
37.5
18.8
18.8
1.2
E. coli
> 150
75
P. fluorescence
> 150
H2L1
75
H2L1
18.8
9.4
18.8
2.3
1.2
2.3
> 150
H2L1
18.8
37.5
18.8
9.4
> 150
> 150
1
> 150
2
2.3
> 150
3
Penicillin G
4.7
>150
> 150
16

Figure 1. A perspective view of complex 1 with the atom labeling scheme. Thermal
ellipsoids are drawn at the 30% probability level.
17

Figure 2. A perspective view of complex 2 with the atom labeling scheme. Thermal
ellipsoids are drawn at the 30% probability level.
18

Figure 3. A perspective view of complex 3 with the atom labeling scheme. Thermal
ellipsoids are drawn at the 30% probability level.
19

Figure 4. Molecular packing structure of complex 1, with hydrogen bonds shown as
dotted lines.
20

Figure 5. Molecular packing structure of complex 2, with hydrogen bonds shown as
dotted lines.
21

Figure 6. Molecular packing structure of complex 3, with hydrogen bonds shown as
dotted lines.
22

23

Three
new
chlorido-substituted
hydrazone
compounds
(H2L1),
and
N'-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide
N'-(3,5-dichloro-2-hydroxybenzylidene)-4-fluorobenzohydrazide (H2L2)
N'-(2-hydroxy-3-methylbenzylidene)-4-trifluoromethylbenzohydrazide (H2L3), were
prepared and characterized. Based on the hydrazone compounds, three new
vanadium(V)
complexes,
[VOL1(OEt)(EtOH)]·[VOL1(OEt)(MeOH)]
(1),
[VOL2(OEt)(EtOH)] (2) and [VOL3(OEt)(EtOH)] (3), were prepared and
characterized. The hydrazone compounds and their vanadium complexes were
evaluated on their antimicrobial activities. The existence of the fluoro groups in the
hydrazone ligands can improve the activities.
24