Synthesis, crystal structure, and DNA-binding studies of transition metal complexes with 2′-(4-dimethylaminobenzylidene)-2-hydroxybenzoylhydrazide

Article abstract of DOI:10.1080/15533174.2011.618479

A series of transition metal complexes of the general formula M(HL) ₂ (where H₂L=2-(4-dimethylaminobenzylidene)-2- hydroxybenzoylhydrazide, M=Ni, Cu, Zn, Cd) were prepared and characterized by elemental analysis, spectroscopic (IR, UV-vis) and the Ni(HL)₂ was structurally characterized by X-ray crystallography. Single-crystal X-ray diffraction results suggest that Ni(II) central atom situated in a distorted square planar geometry is four-coordinated. The DNA-binding properties of these complexes with calf thymus DNA were also investigated by electronic absorption titration (UV spectroscopy) and fluorescence emission titration. The results showed that these complexes bind to DNA mainly via intercalative mode.

Full text of DOI:10.1080/15533174.2011.618479

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Synthesis, Crystal Structure, and DNA-
Binding Studies of Transition Metal Complexes
with 2′-(4-Dimethylaminobenzylidene)-2-
hydroxybenzoylhydrazide
Hui-Lin Guo a , Liu-Jie Wang a , Feng-Ying Chen b , Heng-Xin Li a & Shui-Yang He a
a College of Chemistry & Materials Science , Northwest University, Key Laboratory of
Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shaanxi Key
Laboratory of Physico-Inorganic Chemistry , Xi’an , P. R. China
b Department of Chemistry & Chemical Engineering , Shangluo University , Shaanxi
Shangluo , P. R. China
Accepted author version posted online: 18 Apr 2012.Published online: 11 Jul 2012.
To cite this article: Hui-Lin Guo , Liu-Jie Wang , Feng-Ying Chen , Heng-Xin Li & Shui-Yang He (2012) Synthesis,
Crystal Structure, and DNA-Binding Studies of Transition Metal Complexes with 2′-(4-Dimethylaminobenzylidene)-2-
hydroxybenzoylhydrazide, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:6, 843-849
To link to this article: http://dx.doi.org/10.1080/15533174.2011.618479
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:843–849, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.618479
Synthesis, Crystal Structure, and DNA-Binding Studies of
Transition Metal Complexes with 2ꢀ-(4-Dimethylaminobe
nzylidene)-2-hydroxybenzoylhydrazide
Hui-Lin Guo,1 Liu-Jie Wang,1 Feng-Ying Chen,2 Heng-Xin Li,1 and Shui-Yang He1
1College of Chemistry & Materials Science, Northwest University, Key Laboratory of Synthetic and
Natural Functional Molecule Chemistry (Ministry of Education), Shaanxi Key Laboratory of
Physico-Inorganic Chemistry, Xi’an, P. R. China
2Department of Chemistry & Chemical Engineering, Shangluo University, Shaanxi Shangluo, P. R. China
rials,[2] catalysts,[3] luminescent probes,[4] molecular sensors,[5]
A series of transition metal complexes of the general for-
mula M(HL)2 (where H2L=2ꢀ-(4-dimethylaminobenzylidene)-2-
hydroxybenzoylhydrazide, M=Ni, Cu, Zn, Cd) were prepared and
characterized by elemental analysis, spectroscopic (IR, UV–vis)
and the Ni(HL)2 was structurally characterized by X-ray crys-
tallography. Single-crystal X-ray diffraction results suggest that
Ni(II) central atom situated in a distorted square planar geometry
is four-coordinated. The DNA-binding properties of these com-
plexes with calf thymus DNA were also investigated by electronic
absorption titration (UV spectroscopy) and fluorescence emission
titration. The results showed that these complexes bind to DNA
mainly via intercalative mode.
and so on. In addition, the interaction of transition metal com-
plexes containing multidentate aromatic ligands with DNA has
gained much attention. This is due to their possible applica-
tion as new therapeutic agents and their photochemical prop-
erties which make them potential probes of DNA structure
and conformation.[6–10] The studies of interaction between hy-
drazones and their metal complexes with DNA are important
to further understand pharmacology of hydrazones.[11–15] The
modes of the DNA interaction with metal complex show in-
tercalative behavior, the electrostatic binding mode, and DNA
cleavage ability.[16,17] In our previous studies, a series of metal
complexes with N-(2-propionic acid)-salicyloyl hydrazone as
ligand have been investigated.[18–21] In order to continue to
study DNA-binding model of the benzoyl hydrazone transi-
tion metal complexes, in this article a series of transition metal
complexes of the general formula M(HL)2 were synthesized;
the DNA-binding properties of these complexes with calf thy-
mus DNA (CT-DNA) were investigated by electronic absorp-
tion titration (UV spectroscopy) and fluorescence emission
titration.
Keywords 2ꢁ-(4-dimethylaminobenzylidene)-2-hydroxybenzoylhy-
drazide, crystal structure, DNA-binding, transition metal
complex
INTRODUCTION
For years, hydrazones have been intensively investigated be-
cause of biological activity and pharmacological activity,[1] such
as antimicrobial, anticonvulsant, analgesic, anti-inflammatory,
antiplatelet, antitubercular, and antitumoral activities. Because
hydrazones have the structure of R1R2C=NNH2, these com-
pounds display a versatile behavior in metal coordination,
and their biological activity is often increased by bonding to
transition metals. Moreover, metal complexes of hydrazones
proved to have potential applications as nonlinear optical mate-
EXPERIMENTAL
General Information
Calf thymus DNA (CT-DNA) was purchased from Sigma
(USA) All chemicals used were of analytical grade. The C, H
and Nanalyses weretakenwithaPerkinElmer model 2400CHN
analyzer. The metal ion was determined by titration. The UV–vis
absorption spectra were obtained with an UV-1700 spectropho-
tometer (Pharmaspec, SHIMADZU Limited, Japan) at room
Received 6 April 2011; accepted 21 August 2011.
This work was supported by the important item ‘13115’ of tech-
nological plan of Shaanxi Province (No. ZDKG-268) and the Xi’an temperature. Fluorescence measurements were made on an F-
Science and Technology Bureau (NC09052).
4500 spectrophotometer (Hitachi Ltd., Tokyo, Japan). The in-
teraction of the complex with CT-DNA was studied in a doubly
Address correspondence to Shui-Yang He, College of Chemistry
& Materials Science, Northwest University, Key Laboratory of Syn-
distilled water buffer containing of Tris (hydroxymethyl) amino
thetic and Natural Functional Molecule Chemistry (Ministry of Educa-
methane (Tris) (5 mmol), 0.4% DMSO, and NaCl (5 mmol).
The system was adjusted to pH 7.1 with hydrochloric acid.
tion), Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Xi’an
710069, P. R. China. E-mail: xdchemistry411@126.com
843

844
H.-L. GUO ET AL.
TABLE 1
Interaction with Calf Thymus DNA
Crystal data and structure refinement for Ni(HL)2
In order to eliminate the absorbance of nucleic acid itself, an
equal amount of CT-DNA was added to the sample and refer-
ence cells. Spectrometric titrations were performed according to
Wang et al.[23] K4[Fe(CN)6] emission quenching was performed
according to the Liu et al.[19]
Crystal data
Ni(HL)2
Formula
Formula weight
Temp. (K)
Crystal system
space group
a (Å)
C32 H32 N6 Ni O4
623.36
293(2) K
Monoclinic
P2(1)/c
13.580(6)
5.848(2)
18.550(7)
90
X-Ray Crystallography
Single-crystal X-ray diffraction was carried out with Bruker
Smart 1000 CCD X-ray diffractometer (Siemens). Intensities of
reflections were measured at 298 K using graphite monochro-
matized Mo Kα radiation (λ = 0.710 73 Å) with ω scan mode.
Empirical absorption correction was applied using SABADS
b (Å)
c (Å)
α (◦)
β (◦)
101.772(8)
90
1442.2(10)
2
1440
0.722
program (University of Gottingen, Gottingen, Germany). The
crystal structures were solved by direct methods and Fourier-
difference syntheses. All the non-hydrogen atoms were refined
anisotropically. Full-matrix least-squares refinement on F2 was
performed by the SHELXL-97 program package (Bruker AXS
Inc., Madison, WI, USA). Crystal data, data collection, and re-
finement details are given in Table 1. The final R1, wR2, and
other refinement parameters are also presented in Table 1.
¨
¨
γ (◦)
V (Å3)
Z
Dc(mg m−3
)
Abs coeff. (mm−1
F(000)
)
656
Reflns collected
Unique reflns
Params
6774
2543
202
0.821
RESULTS AND DISCUSSION
GOF on F2
Composition of the Complexes
Element Analysis
The results of element analysis for all the complexes are listed
in Table 2 along with their formulae. From the table, it can be
seen that the found values are in agreement with the calculated
ones. These complexes are quite stable at room temperature and
do not show any decomposition after a long period of standing.
R1, wR [I > 2σ(I)]
R1, wR (all data)
Largest diff. peak and hole(Å−3
0.0459, 0.0533
0.1451, 0.0600
0.250 and –0.432
)
Synthesis of M(HL)2 (M = Ni, Cu, Zn, Cd)
IR Spectra
The synthesis route and physical-chemical property of ligand
2ꢁ-(4-dimethylaminobenzylidene)-2-hydroxybenzoylhydrazide
The main IR frequencies of the ligand and its complexes
(H2L) was reported in the literature.[22] A mount of ligand H2L along with their relative assignments are recorded in Table 3. IR
(0.1483 g, 0.5 mmol) was added to a DMF-ethanol mixture spectra of the complexes and the (H2L) are identified according
(v/v = 5:1, 40 mL). Then a solution of these metal nitrates to theliterature.[24] The bands appearing inthe infraredspectraof
(0.25 mmol) in water (20 mL) was added dropwise to the the free ligand (H2L) at 3435, 1635, and 1605 cm−1 are assigned
system. After being stirred at 75◦C for 5 h, there is some to vN-H, vC O, and vC N, respectively. Compared with the ligand,
precipitate that was isolated by filtration. Resulting solution the C O vibration bands at 1624–1631 cm−1 show a little shift
was allowed to evaporate slowly at the room temperature, and to short wavenumbers, which can explain that the C O (O
the red single crystals suitable for X-ray analysis of Ni(HL)2 atom) was coordinated; all complexes show a strong band in
were obtained.
1590–1602 cm−1 assigned to ν(C N) vibration, which indicates
TABLE 2
Element analysis data for the complexes
H%
Complexes
C%
N%
RE%
Ni(HL)2
Zn(HL)2
Cu(HL)2
Cd(HL)2
61.38 (61.65)
60.87 (61.00)
60.98 (61.18)
56.55 (56.76)
4.78 (5.17)
5.12 (5.11)
4.82 (5.13)
4.48 (4.76)
13.26 (13.48)
12.91 (13.33)
13.16 (13.37)
12.35 (12.41)
9.32 (9.41)
10.30 (10.38)
9.89 (10.11)
16.50 (16.60)

CRYSTAL STRUCTURE AND DNA-BINDING OF NI(HL)2
845
TABLE 3
The main spectral data for the ligand and complexes (cm−1
TABLE 4
)
Selected bond length (Å) and angle (◦) of Ni(HL)2
ω, ◦
Samples
vN-H
vC
vC
Bond
d, Å
Angle
O
N
H2L
3435(s)
3435(s)
3435(s),
3437(s)
3431(s)
1635(s)
1626(s)
1627(s)
1624(s)
1631(s)
1605(s)
1591(s)
1601(s)
1602(s)
1602(s)
Ni(II)-O(1A) 1.831 (3) O(1A)-Ni(II)-N(2)
95.50 (14)
84.50 (15)
180.0 (3)
179.997 (1)
84.50 (15)
95.50 (14)
Ni(HL)2
Zn(HL)2:
Cu(HL)2
Cd(HL)2
Ni(II)-N(2)
Ni(II)-O(1)
1.869 (3) O(1A)-Ni(II)-N(2A)
1.831 (3) N(2)-Ni(II)-N(2A)
Ni(II)-N(2A) 1.869 (3) O(1A)-Ni(II)-O(1)
O(1)-Ni(II)-N(2)
O(1)-Ni(II)-N(2A)
about 1.44 and 1.20 Å, respectively, which suggests that (HL−)
coordinates with central Ni in keto-form. The dihedral angle
of parallelogram and hydroxybenzoyl plane is 4.67◦, the other
dihedral angle of parallelogram and dimethylaminobenzylidene
plane is 10.67◦. These indicate that the molecular structure of
the Ni(HL)2 is nearly coplanar.
that the C N (N atom) was coordinated. The intensities of
the adsorption bands at 3431–3437 cm−1 in all complexes are
without evident changes. This indicates that proton is not put
off from the N-H bond.
Description of crystal structure of Ni(HL)2
The molecular structure of the Ni(HL)2 along with the atomic
numbering scheme is shown in Figure 1. Selected bond lengths
and angles are given in Table 4.
The Studies of Complex Interaction with CT-DNA
Electronic absorption spectra
In Ni(HL)2, the Ni(II) ion is four-coordinated by two depro-
Electronic absorption spectroscopy is one of the most useful
tonated 2ꢁ-(4-dimethylaminobenzylidene)-2-hydroxybenzoy- techniques for DNA-binding studies of metal complex. The ab-
lhydrazide ligands in a bidentate fashion through the acyl sorption spectra of these complexes M(HL)2 (M = Ni, Cu, Zn,
oxygen and imido nitrogen (Figure 1). Thus, two five-member Cd) in the absence or presence of CT-DNA are given in Fig-
rings sharing Ni(II) ion are formed by the two ligands. At ure 2. In the presence of CT-DNA, the absorption bands of Ni
the same time, the atoms O1, N2, O1A, and N2A are copla- complex at 373 nm exhibited hypochromism of about 33% and
nar approximately [angles N(2)-Ni(II)-N(2A) = 180.0(3)◦, and bathochromism of about 3 nm, and the absorption bands of Cd
O(1A)-Ni(II)-O(1) = 179.997(1)◦], and form a parallelogram. complex at 369 nm exhibited hypochromism of about 37% and
The angle of the clamp O1-Ni-N2 is 84.50◦ and the angle of bathochromism of about 4 nm. These results suggest an intimate
the clamp O1-Ni-N2A is 95.50◦, so the coordination polyhe- interaction of the Ni(HL)2 and Cd(HL)2 with CT-DNA and the
dron around Ni(II) was described as a square planar geometry. interaction is also likely that complexes bind to the helix via in-
The bond lengths of O(1)-C(1) and O(1A)-C(1A) are 1.255 Å, tercalation.[25] After the compounds intercalate to the base pairs
so they show double-bond character between the C(1) atom of DNA, the π∗ orbit of the intercalated ligands on the com-
and O(1) atom in (HL-) (bond lengths of C–O and C = O are pounds could couple with orbits of the base pairs, thus decreas-
ing the π-π∗ transition energies. On the other hand, the coupling
π∗ orbits are partially filled by electrons, thus, decreasing the
transition probabilities. Therefore, these interactions resulted in
the observed hypochromism and bathochromism.[26] So, the pre-
vious phenomena imply that these Ni(II) and Cd(II) complexes
interact with CT-DNA quite probably by intercalating the ligand
into the base pairs, but the kind of Cu(II) and Zn(II) complexes
interact with CT-DNA need more experiment to determine.
Fluorescence spectra
The enhancements in the emission intensity of these com-
plexes M(HL)2 (M = Ni, Cu, Zn, Cd) with increasing CT-DNA
concentrations are shown in Figure 3. In the absence of DNA,
these complexes emit weak luminescence in Tris buffer at am-
bient temperature, with a maximum appearing at 475–477 nm.
When DNA is present, the intensity of the emission for these
complexes all increase along with increasing DNA concentra-
tion. The results of the emission titrations suggest that these
complexes are protected from solvent water molecules by the
FIG. 1. ORTEP drawing of Ni(HL)2 with hydrogen atoms omitted for clarity
(30% thermal ellipsoids probability) (color figure available online).

846
H.-L. GUO ET AL.
FIG. 2. Electronic spectra of these complexes (10 µM) in the presence of increasing amounts of CT-DNA, c DNA = 0, 5, 10, 15, 20, 25, and 30 µM. The arrow
indicates the absorbance changes upon increasing DNA concentration.
FIG. 3. The emission enhancement spectra of these complexes (10 µM) in the presence of 0, 5, 10, 15, 20, 25, and 30 µM CT-DNA. The arrow indicates the
emission intensity changes upon increasing DNA concentration.

CRYSTAL STRUCTURE AND DNA-BINDING OF NI(HL)2
847
FIG. 4. The emission spectra of DNA- EB system (10 µM DNA and 0.32 µM EB) in the presence of 0, 5, 10, 15, 20, 25, and 30 µM these complexes. The arrow
indicates the emission intensity changes upon increasing complex concentration.
hydrophobic environment inside the DNA helix. This suggests tem, leading to the decreased emission of the DNA-EB system.
that these complexes penetrate into the hydrophobic environ- The results were caused by EB being expelled from the hy-
ment inside the DNA, thereby avoiding the quenching effect of drophobic environment into the water solution.[28] Since these
solvent water molecules. Since the hydrophobic environment changes indicate only one kind of quenching process, it may be
inside the DNA helix reduces the accessibility of the solvent concluded that these complexes bind to CT-DNA via the same
water molecules into these complexes, these complexes are re- mode (intercalation mode) and this result agrees with those ob-
stricted at the binding site, decreasing the vibrational mode. The served for the UV spectra and emission spectra.
binding of these complexes to DNA leads to a marked increase
The emission quenching spectra of these complexes in the
in the emission intensity, this phenomenon for Ni(II) and Cd(II) absence and presence of DNA are shown in Figure 5. With
complexes agree with those observed for the UV spectra, while the increase of the K4[Fe(CN)6] quencher concentrations, the
the phenomenon for Cu(II) and Zn(II) complexes suggest that emission intensity of these complexes and complex-DNA is
the two complexes have an interaction with the CT-DNA. The obviously reduced. The only difference is that the emission
binding of these complexes to DNA leads to a marked increase intensity of these complexes in the absence of DNA are less
in the emission intensity, which also agrees with those observed than that in the presence of DNA under the same concentra-
for other intercalations.[27]
tion of the K4[Fe(CN)6] quencher. This result represents that
In order to test if the complexes could bind to DNA by inter- these complexes can interact with DNA and be protected by
calation, ethidium bromide (EB) was employed, as EB interacts DNA efficiently, since the hydrophobic environment inside the
with DNA as a typical indicator of intercalation. As shown in DNA helix reduces the accessibility of the quenching of the
Figure 4, the emission intensity of the DNA-EB system (λem K4[Fe(CN)6] quench to the complexes. The spectral character-
= 592 nm) decreased along with the concentration of these istic suggests these complexes possibly are bound to CT-DNA
complexes increased. An isobathic point appeared at 550 nm, mainly by intercalation and agree with those observed for the
which indicated the formation of a complex-DNA system. These UV spectra, fluorescence emission spectra, and DNA-EB sys-
changes show that complex replaced EB from the DNA-EB sys- tem fluorescence spectra.

848
H.-L. GUO ET AL.
FIG. 5. Emission quenching spectra of these complexes and complex-DNA, with increasing of the concentration of the K4[Fe(CN)6] quencher. c M(HL)2 = 1.0
× 10−4 mol/L; c K4[Fe(CN)6] = 0, 0.5, 1, 1.5, 2, 2.5, and 3 × 10−3 mol/L, and c DNA = 40 × 10−6 mol/L.

CRYSTAL STRUCTURE AND DNA-BINDING OF NI(HL)2
849
CONCLUSIONS
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A
series of single-ligand transition metal com-
plexes of the general formula M(HL)2 (H2L=2ꢁ-(4-
dimethylaminobenzylidene)-2-hydroxybenzoylhydrazide, M =
Ni, Cu, Zn, Cd) have been prepared and characterized. The
Ni(HL)2 crystal structure indicates the ligand functions as a
keto-form and the molecular structure of the complex is nearly
coplanar. The DNA-binding properties of these complexes were
investigated. The results support the fact that these complexes
bind to CT-DNA via intercalation.
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SUPPLEMENTARY MATERIALS
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Centre,
CCDC No. 800679 for Ni(HL)2. Copies of this information may
be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge, CB21EZ (Fax: +44 1223 336 033; E-mail:
deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
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