I. Sheikhshoaie et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 (2014) 548–555
549
[
1,2]. They have a good potential for biochemical processes and are
Yield: 72%. m.p.: 183 °C. Anal. Calc. for
15 14 2 2
C H N O
ꢁ1
used as antimicrobial [3], anti-diabetic [4], antimalarial [5], anti-
cancer and potentially DNA damaging and mutagenic agents
[
structural properties of hydrazones have made them a good
candidate for new drug development [8] and opto-electronic
applications [9]. In addition the interest to these ligands are due
to the fact that aromatic ring in them is a constituent of many
biological system [10].
(254.28 g mol ): C, 70.85; H, 5.55; N, 11.02. Found: C, 69.93; H,
ꢁ1
4.92; N, 11.95%. FT-IR (KBr), cm
(C@O) 1652, (C@N) 1608, (NAN) 1131,
(400 MHz, DMSO-d , ppm): 13.37 (s, 1H, OH); 11.34 (s, 1H, NH),
6.87–7.94 (m, 9H, rings), 2.48 (s, 3H, CH
DMSO-d , ppm): 164.88, 159.24, 158.58, 133.43, 132.43, 131.73,
:
m
(NH) 3445,
m(OH) 3222,
1
6,7]. Also presence of fragment such as azomethine and other
m
m
m
m(CAO) 1253. H NMR
6
1
3
3
). C NMR (400 MHz,
6
131.51, 128.97, 128.87, 128.75, 128.59, 127.41, 119.85, 118.97,
14.51.
Furthermore, hydrazones react with transition metal ions in
living systems that their mode of chelation had been of significant
interest in last decades [11]. They can form wide variety of
coordination compounds with different metal ions and many
applications such as catalytic and biological activities have been
reported for them [12,13].
Computational methods
The geometry of the synthesized compound was fully optimized
without any symmetry constraints using density functional theory
(DFT), B3LYP exchange correlation functional and 6-31+G(d,p)
[15,16] with Gaussian 03 program package [17]. The starting
atomic coordinated were taken from X-ray structure (Fig. 1). The
optimized structures were characterized by frequency calculations
as true minima. Vibrational frequencies were scaled by 0.963 [18].
The density functional theory has been used to calculate the dipole
Based upon, we have synthesized hydrazone derivative
compound, 2-hydroxyacetophenone benzoylhydrazone (HL), and
1
13
characterized using FT-IR, H NMR, C NMR and electronic spectra.
DFT calculations have been performed to investigate detailed
experimental spectroscopic data, NLO properties and chemical
reactivity of synthesized compound. These calculations are valu-
able for providing insight into molecular properties of hydrazone
derivative compounds. Also, the biological activity of the title
compound as antimicrobial especially against Gram-positive and
Gram-negative bacteria was investigated.
moment (l), mean polarizability (a) and the total first static
hyperpolarizability (b) for HL in terms of x, y, z components and
are given by following equations [19].
1
=2
2
2
2
l
a
¼ ð
l
1
¼ ð
3
þ
þ
l
þ
yy
lz
Þ
x
y
a
xx
a
þ
a
zz
Þ
h
i
1
=2
2
2
2
Experimental
btot ¼ ðb þbxyy þbxzzÞ þðb þbyzz þbyxxÞ þðb þbzyy þbzxx
Þ
xxx
yyy
zzz
Reagents and physical measurements
The polarizability and hyperpolarizability tensors (
xx
xy yy
a , a , a ,
a
xz
,
a
yz
,
a
zz and bxxx, bxxy, bxyy, byyy, bxxz, bxyz, byyz, bxzz, byzz, bzzz)
All the chemicals were purchased from Merck Co. and used
without further purification. The UV–Vis spectrum of the HL was
run in methanol solution on a Perkin Elmer Lambda25 in the range
can be obtained by a frequency job output file of Gaussian.
However, and b values of Gaussian output are in atomic units
a.u.) so they have been converted into electrostatic units (esu)
a
(
(
2
00–800 nm. The FT-IR spectrum was recorded on a Nicolet-
ꢁ24
ꢁ33
a
; 1 a. u. = 0.1482 ꢂ 10
esu, b; 1 a.u. = 8.6393 ꢂ 10
esu).
ꢁ1
Impact 400D spectrometer (4000–400 cm ) in KBr pellets. NMR
spectra were acquired on a Bruker DRX400 spectrometer operating
at 400 MHz for H NMR and C NMR in DMSO-d as a solvent.
6
The GIAO method was used for calculating H NMR and 13C
1
NMR chemical shifts at the B3LYP/6-31+G(d,p) and HF/6-31+
G(d,p) levels. Solvent (DMSO) was considered as a uniform
dielectric constant 46.7 and Polarized Continuum Model (PCM).
In addition, electronic transitions were calculated at DFT level, as
implemented in the Amsterdam density functional package
(ADF2009.01) [20]. The tautomer structures were fully optimized
via generalized-gradient approximation (GGA) employing the Per-
dew–Wang exchange and correlation functionals (PW91) with DZP
basis set [21]. The excitation energies were estimated by Time
Dependent Density Functional Theory (TDDFT) [22]. This method-
ology is based on the linear response formalism within the
iterative Davison procedure implemented in the ADF2009.01 code.
The calculations performed by first-principles method let to obtain
accurate excitation energies and oscillator strengths for the
1
13
Carbon, hydrogen and nitrogen analyses were carried out using a
Thermo Finnigan Flash Elemental Analyzer 1112EA instrument.
2-hydroxyacetophenone benzoylhydrazone (HL)
The HL have been prepared according to a previous report [14].
A mixture of benzohydrazide (0.14 g, 1 mmol) and 2-hydroxyace-
tophenone (0.12 mL, 1 mmol) was refluxed in 10 ml methanol.
After 4 h, the precipitate was filtered, washed with cold ethanol
and dried in vacuum over silica gel. Colorless Crystals suitable for
crystallography were obtained in mother liquor after 3 days at
room temperature.
Fig. 1. ORTEP diagram of HL.