84
G. Elmacı et al. / Journal of Molecular Structure 1099 (2015) 83e91
Scheme 1. Synthetic pathway of BMH.
ꢁ
several days. Yield: 3.2 g (89%) m.p.: 174e176 C. HRMS (ESI,
the vibrational spectra was carried out with the aid of SQM
program.
CH3CN) (C21
H
15
N
3
O
3
) [MþH]þ calcd.: 358.1113; found: 358.1186.
2
. Experimental
2.3. X-ray diffraction analysis
2
.1. Materials and methods
For the crystal structure determination, the single-crystals of
the title compound used for data collection on a four-circle Rigaku
R-AXIS RAPID-S diffractometer (equipped with a two-dimensional
The chemical used in the synthesis of all dyes were obtained
from Aldrich Chemical Company (USA) and were used without
further purification. All solvent used were of analytical grade. Sol-
vents were dried according to standard procedures. All reactions
were magnetically stirred and monitored by thin layer chroma-
tography (TLC) using Merck silica gel (60 F254) plates (0.25 mm) and
area IP detector). The graphite-monochromatized Mo K radiation
a
ꢁ
(
l
¼ 0.71073 Å) and oscillation scans technique with Du ¼ 5 for
one image were used for data collection. The lattice parameters
were determined by the least-squares methods on the basis of all
reflections with F > 2s(F ). Integration of the intensities, correc-
2
2
1
13
visualized with ultraviolet light. H NMR and C spectra were
recorded on a Bruker 400 MHz NMR spectrometer (Hacettepe
tion for Lorentz and polarization effects and cell refinement were
performed using Crystal Clear (Rigaku/MSC Inc., 2005) software
[11]. The structures were solved by direct methods using SHELXS-
97 [12] and refined by a full-matrix least-squares procedure using
the program SHELXL-97 [12]. H atoms were positioned geomet-
rically and refined using a riding model. The final difference
Fourier maps showed no peaks of chemical significance. Crystal
data: C21H15N O ; crystal system, space group: triclinic, P-1; unit
University Department of Chemistry, Turkey) in DMSO-d
cal shifts are expressed in units (ppm) with tetramethylsilane
TMS) as the internal reference. Coupling constant (J) are given in
6
. Chemi-
d
(
hertz (Hz). Signals are abbreviated as follows: singlet, s; doublet, d;
doubletedoublet, dd; triplet, t; multiplet, m. Ultravioletevisible
(
UVevis) absorption spectra were recorded on an Analytikjena
3
3
Specord 200 Spectrophotometer (Gazi University Department of
cell dimensions: a ¼ 8.7014(2), b ¼ 11.6025(4), c ¼ 18.8789(5)Å,
ꢁ
Chemistry, Turkey) at the wavelength of maximum absorption
a
¼ 73.444(4),
b
¼ 79.002(5),
g
¼ 80.544(6) ; volume: 1781.12(10)
o
3
0
ꢀ3
(lmax, in nm). All melting points were uncorrected and in
C
Å ; Z ¼ 2; calculated density: 1.333 g cm ; absorption coeffi-
ꢀ1
(
Electrothermal 9200 melting point apparatus). Mass spectra was
cient: 0.091 mm ; F(000): 744; q range for data collection
2.4e26.4 ; refinement method: full-matrix least-square on F ;
data/parameters: 7295/490; goodness-of-fit on F : 0.999; final R
ꢁ
2
recorded using a Waters LCT Premier XE (TOF MS) (Gazi University
Laboratories, Department of Pharmacological Sciences) mass
2
ꢀ1
spectrometer. FT-MIR spectrum between 4000 and 400 cm and
indices [I > 2
s
(I)]: R ¼ 0.067, wR ¼ 0.142; R indices (all data):
1
2
ꢀ
1
FT-FIR spectrum between 400 and 30 cm of the compound were
recorded using Bruker Optics IFS66 v/S FT-IR spectrometer with
R1 ¼ 0.171, wR ¼ 0.194; largest diff. peak and hole: 0.174
2
and ꢀ0.146 e Å 3.
ꢀ
ꢀ1
mull technique using nujol with the resolution of 2 cm (Bruker,
Germany). The Raman spectrum was obtained using a Bruker
Senterra Dispersive Raman microscope spectrometer with 532 nm
2.4. Computational details
ꢀ
1
excitation from a 3B diode laser having 3 cm resolution in the
The compound was optimized at the DFT level of theory with
the hybrid of Becke's non-local three parameter exchange and
correlated functional with the Lee-Yang-Parr correlation functional
ꢀ1
spectral region of 3700e200 cm (Bruker, Germany). The X-ray
data were recorded in the Department of Chemistry, Atatürk Uni-
versity, Erzurum, Turkey.
(
B3-LYP) [13,14] supplemented with the 6-311þG(d,p) basis set.
Analytic frequency calculations were done to confirm that the
1
13
2
2
.2. Synthesis
optimized structure was of minimum energy. H and C NMR
chemical shifts were calculated with the gauge independent atomic
orbital GIAO approach [15] by applying B3LYP method with the
.2.1. Synthesis of benzil monohydrazone
Benzil monohydrazone was synthesized according to literature
B3LYP/6-311þG(d,p),
B3LYP/6-311þG(2d,p)
and
B3LYP/6-
method [10].
.2.2. Synthesis of (Z)-2-((E)-4-nitrobenzylidene)hydrazone)-1,2-
3
11þþG(2d,p) basis sets. Absorption spectra were computed as
vertical electronic excitations from the ground-state minima by
using the time-dependent density functional theory (TD-DFT). The
DFT calculations were carried out with the Gaussian 03 program
package [16].
2
diphenylethan-1-one
The compound was synthesized by mixing 2.24 g (0.1 mol) of
benzil monohydrazone and 1.51 g (0.1 mol) of 4-nitrobenzaldehyde
in 50 mL ethanol and two drops of acetic acid. The mixture was
refluxed for 1 h and then cooled, filtered and the solid was washed
with methanol. The compound was recrystallized using ethanol.
The appropriate single crystals were obtained as yellow within
Vibrational frequencies, infrared intensities and Raman activ-
ities were calculated based on the B3LYP/6-311þG(d,p) optimised
geometry. The total energy distribution (TED) was calculated by
using the scaled quantum mechanics (SQM) program [17]. The
fundamental vibrational modes were characterised by their TED.