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F. Karipcin et al. / Journal of Molecular Structure 1048 (2013) 69–77
N-benzoyl-N0-arylthioureas have been thoroughly investigated
used for data collection, cell refinement and data reduction. Using
Olex2 [42], the structure was solved by the ShelXS [43] structure
solution program by direct methods and refined with the ShelXL
[44] refinement package using least-squares minimization. To pre-
pare material for publication Mercury 3.0 were used. All H atoms
were refined using a riding model. The details of the X-ray data col-
lection, structure solution and structure refinement are given in
Table 1. Selected bond distances and angles are listed in Table 2.
in connection with the formation of intramolecular hydrogen
bonding [29–31]. Bifunctionality of amine–thiourea compounds
carries the possibility of intra- and intermolecular interactions
via hydrogen bonding. In effect, it was found that the intramolec-
ular hydrogen bond between the oxygen atom in the C@O group
and the hydrogen atom of the thiourea group is favored [30,31].
The intramolecular H-bond observed in these compounds is in
agreement with Etter’s hydrogen bond rules, which indicate that
if six-membered ring intramolecular hydrogen bonds can form,
they will usually do so in preference to forming intermolecular
hydrogen bonds [32]. Another rule states that the best proton do-
nors and acceptors remaining after intramolecular hydrogen bond
formation form intermolecular hydrogen bonds to one another
[33]. Moreover, the hydrogen-bonding ability of the thiourea moi-
ety has extensively been used in the construction of anion recep-
tors [31,33] and in the thiourea-based metal complexes [25–28]
and organocatalysts [3–5].
By means of increasing development of computational chemis-
try in the past decade, the research on theoretical modeling of drug
design, functional material design, etc., has become much more
mature than ever. Many important chemical and physical proper-
ties of biological and chemical systems can be predicted from the
first principles of various computational techniques [34]. With
the development of computer hardware, software, and computa-
tional methods, it is possible to correctly describe the physico-
chemical properties of relatively small molecules from the first
principles [34–36]. In conjunction with the development of tech-
nology, among the computational methods calculating the elec-
tronic structure of molecular systems, Density Functional Theory
(DFT) has been used extensively to calculate a wide variety of
molecular properties such as equilibrium structure, charge distri-
bution, UV–visible, FTIR and NMR spectra, and provided reliable re-
sults which are in accordance with experimental data [37–39]. The
literature survey revealed that the DFT has a great accuracy in
reproducing the experimental values in terms of geometry, dipole
moment, vibration frequency, and so on [38–41].
2.1.1. Synthesis
1-Benzoyl-3-furan-2-ylmethyl-thiourea was prepared by a pro-
cedure similar to that reported in the literature [26,33,45]. A solu-
tion of benzoyl chloride (20 mmol; 2.80 g) in dry acetone (10 mL)
was added dropwise to a solution of ammonium thiocyanate
(20 mmol; 1.52 g) in dry acetone (30 mL) under stirring. The reac-
tion mixture was heated (40 °C) under reflux for 1 h, and then
cooled to room temperature. The formed precipitate of NH4Cl
was filtered off. A solution of furfurylamine (22 mmol; 2.14 g) in
dry acetone (20 mL) was slowly added to the resulting solution,
which then was stirred for 2 h. Afterwards the mixture was filtered
into a beaker containing some ice. The resulting white precipitate
was washed with distilled water followed by MeOH and diethyl-
ether (yield 63%). Re-crystallization from methanol yielded color-
less crystals suitable for X-ray analysis.
Colorless crystals. Yield: 63%. Mp: 117 °C. Anal. Calcd. for C13-
H12N2O2S: C 59.98; H 4.64; N 10.76; S 12.32. Found: C 60.19; H
4.71; N 10.46; S 12.24%. FT-IR (cmꢁ1):
t
(NAH) 3223 (m, br),
(C@O) 1663(vs), 1600(w),
(C@S) 1259(s), 1166(s), 1107(m),
3161(w), 3118(w),
t(CAH) 3035(w), t
1505(vs), 1449(m), 1323 (m),
t
1084(w), 1070(m), 1019(s), 1000(w), 974(w), 918(m), 901(w),
884(m), 818(m), 791(m), 730(m), 688(s). 1H NMR (d-acetone; d,
ppm): 11.18 (s, 1H, CSNH), 10.17 (s, 1H, CONH), 7.98 (d,
J = 7.21 Hz, 2 H, Ph), 7.64 (t, J = 7.45 Hz, 1 H, Ph), 7.54 (d,
J = 1.02 Hz, 1H, furane ring), 7.52 (t, J = 8.02 Hz, 2H, Ph), 6.45–
6.41 (m, 2H, furane ring), 4.94 (d, J = 5.29 Hz, 2H, CH2). 13C NMR
(d-acetone; d, ppm): 207.3 (C@S), 182.4 (C@O), 169.4, 151.8,
144.3, 134.9, 133.9, 130.4, 129.8, 112.2, 110.0 (Ph and furane ring),
43.6 (CH2).
Concerning with the above mentioned phenomena, we present
here the synthesis, crystallographic, spectroscopic studies of the
newly synthesized thiourea derivative ligand, 1-benzoyl-3-furan-
2-ylmethyl-thiourea, as well as the theoretical studies on it by
using DFT/6-311++G(d,p) method. Additionally, the ground state
theoretical geometrical parameters of title molecule were calcu-
lated. Moreover, the dipole moment, nonlinear optical (NLO) prop-
erties has also been studied. We also make comparisons between
experiments and calculations.
Table 1
Crystal data and structure refinement for bftu.
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C13H12N2O2S
260.31
293.0
Monoclinic
P21/c
9.434(5)
2. Experimental
b (Å)
11.822(5)
2.1. Materials and physical measurements
c (Å)
12.378(5)
90.000(5)
109.010(5)
90.000(5)
1305.2(10)
4
1.325
0.243
a
(°)
b (°)
(°)
All reagents used in this study were reagent grade and used
without further purification. Acetone was dried and used freshly
distilled prior to use.
c
Volume (Å3)
Z
qcalc (mg/mm3)
The room temperature attenuated total reflection Fourier trans-
form infrared (FT-IR ATR) spectrum of the compound was regis-
tered using a Perkin Elmer Spectrum 100 FT-IR spectrometer
(4000–650 cmꢁ1). 1H NMR and 13C NMR spectra were recorded
on a Bruker 400 High Resolution Console, using d-acetone as the
solvent and TMS as an internal standard. C, H, N and S analyses
were carried out on a LECO 932 CHNS analyzer. Melting point
was determined using an EZ-Melt melting point apparatus and
was uncorrected.
m/mmꢁ1
F(000)
544.0
Crystal size/mm3
0.078 ꢂ 0.095 ꢂ 0.208
2H range for data collection
6.9–61°
Index ranges
ꢁ12 6 h 6 13, ꢁ11 6 k 6 16, ꢁ17 6 l 6 16
6985
3897[R(int) = 0.0535]
3897/0/139
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
1.014
Final R indexes [I P 2
r
(I)]
R1 = 0.1040, wR2 = 0.2686
R1 = 0.2413, wR2 = 0.3939
1.05/ꢁ0.48
Final R indexes [all data]
Single crystal X-ray data were collected on an Agilent
SuperNova diffractometer with an Eos CCD detector using Mo K
Largest diff. peak/hole (e Åꢁ3
)
a
radiation (k = 0.71073 Å). The CrysAlisPro software program was