Structural, antimicrobial and computational characterization of 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea

Article abstract of DOI:10.1016/j.saa.2012.08.020

A new thiourea derivative, 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea (bcht) has been synthesized from the reaction of 2-amino-4-chlorophenol with benzoyl isothiocyanate. The title compound has been characterized by elemental analyses, FT-IR, ^13<

Full text of DOI:10.1016/j.saa.2012.08.020

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
Contents lists available at SciVerse ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Structural, antimicrobial and computational characterization
of 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea
b
b
c
b
Murat Atißs a, , Fatma Karipcin , Bahtiyar Sarıbog˘a , Murat Taßs , Hasan Çelik
⇑
a Department of Physics, Sciences and Arts Faculty, Nevsehir University, 50300 Nevsehir, Turkey
b Department of Chemistry, Sciences and Arts Faculty, Nevsehir University, 50300 Nevsehir, Turkey
c Department of Chemistry, Sciences and Arts Faculty, Giresun University, 28100 Giresun, Turkey
g r a p h i c a l a b s t r a c t
h i g h l i g h t s
The synthesized new thiourea derivative, 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea character-
ized by elemental analyses, X-ray, FT-IR, 13C, 1H NMR, UV spectroscopy and calculated by using B3LYP
method with the standard 6-311++G(d,p) basis sets; and also exhibited antimicrobial activity against, Lis-
teria monocytogenes and Staphylococcus aureus.
"
"
"
"
"
The 1-benzoyl-3-(5-chloro-2-
hydroxyphenyl)thiourea
synthesized.
The FT-IR, 13C, 1H NMR, UV
spectroscopy and X-ray used for
characterization.
The B3LYP method with the standard
6-311++G(d,p) basis sets used to
calculation.
Theoretical calculations are in good
agreement with experimental
results.
Bcht exhibited antimicrobial activity
against, Listeria monocytogenes and
Staphylococcus aureus.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 21 May 2012
Received in revised form 3 August 2012
Accepted 12 August 2012
Available online 20 August 2012
A new thiourea derivative, 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea (bcht) has been synthe-
sized from the reaction of 2-amino-4-chlorophenol with benzoyl isothiocyanate. The title compound
has been characterized by elemental analyses, FT-IR, 13C, 1H NMR spectroscopy and the single crystal
X-ray diffraction analysis. The structure of bcht derived from X-ray diffraction of a single crystal has been
presented. The structural and spectroscopic data of the molecule in the ground state were calculated by
using density functional method using 6-311++G(d,p) basis set. The complete assignments of all vibra-
tional modes were performed on the basis of the total energy distributions (TED). Isotropic chemical
shifts (13C NMR and 1H NMR) were calculated using the gauge-invariant atomic orbital (GIAO) method.
Theoretical calculations of bond parameters, harmonic vibration frequencies and nuclear magnetic reso-
nance are in good agreement with experimental results. The UV absorption spectra of the compound that
dissolved in ACN and MeOH were recorded. Bcht was also screened for antimicrobial activity against
pathogenic bacteria and fungi.
Keywords:
Thiourea
Spectroscopy
Crystal structure
Hydrogen bonds
DFT
Antimicrobial activity
Ó 2012 Elsevier B.V. All rights reserved.
Introduction
clic compounds [1–4]. Thioureas are potentially very versatile
ligands, as they are able to coordinate to a range of metal centers
Thiourea derivatives are very useful building blocks for the syn-
thesis of a wide range of aliphatic macromolecular and heterocy-
as either neutral ligands, monoanions, or dianions [5–11]. In addi-
tion, the oxygen, nitrogen and sulfur donors provide a multitude of
bonding possibilities. Thiourea derivatives display a wide range of
biological activity including antibacterial, anti-fungal, antitubercu-
lar, antithyroid, antihelmintic, rodenticidal, insecticidal, herbicidal,
⇑
Corresponding author. Tel.: +90 384 228 1100; fax: +90 384 215 3948.
E-mail addresses: atis@nevsehir.edu.tr, atismurat@gmail.com (M. Atisß).
1386-1425/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2012.08.020

M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
291
and plant growth regulator properties [12–18]. Moreover, the
Experimental
hydrogen-bonding ability of the thiourea moiety has extensively
been used in the construction of anion receptors [19–22] and in
the thiourea-based metal complexes [7–11] and organocatalysts
[23–25]. In particular, aroylthioureas have been successfully used
in environmental control, as ionophores in ion selective electrodes
[18,26,27].
Materials
All chemicals used for the preparation of the compound were
analytically reagent grade. Acetone was dried before use.
The structure and intra-molecular and intermolecular hydrogen
bonding behavior of many N-benzoyl-N0-arylthioureas have been
thoroughly investigated [28–33]. In addition, the conformational
changes in these molecules are analogous to those arising in folded
proteins, and a full understanding of these effects requires under-
standing the effects of intermolecular hydrogen bonding interac-
tions and hydrophobic interactions. The title compound can
exhibit thione-thiol tautomerism because it contains a thioamide
–NH–C@S functional group, and a carbonyl group, which can ac-
cept hydrogen bonding donor groups and then come into anion
receptor [32].
The molecular structural study of bcht is important for struc-
ture-activity relationship which is useful for rational design strat-
egy. In this present study, we have synthesized a new thiourea
derivative and investigated by using FT-IR, 1H NMR, 13C NMR, UV
spectra and X-ray crystallographic techniques in order to reveal
the hydrogen bonding and tautomeric equilibrium (Scheme 1).
We also report the results of calculated structure and spectra (IR,
UV and NMR) of the bcht molecule, the calculations being on the
basis of density functional theory (DFT) approximations. All spec-
troscopic properties which examined by the experimental tech-
niques were supported by the computed results. In the ground
state theoretical geometric parameters, IR, NMR and UV spectra
and HOMO and LUMO energies of title molecule were calculated
by using Gaussian 09 suite of quantum chemistry codes [34]. For
bcht, the tautomeric thioketo-amine form is observed with C7–
S1 distance of 1.660(2) Å. Strong intramolecular hydrogen bonds
are found between the N1–H1ꢀ ꢀ ꢀO2 atoms with an N1–H1 and
N1–O2 distances of 0.86 and 2.600(2) Å.
Physical measurements
Carbon, hydrogen, nitrogen and sulfur were determined using a
LECO 932 CHNS analyzer. Infrared spectrum was recorded in the
4000–650 cmꢁ1 region using a Perkin Elmer Spectrum 100 FT-IR
spectrometer. 1H NMR and 13C NMR spectra were obtained on Bru-
ker 400 High Resolution Console in CDCl3. Proton chemical shifts
are reported in part per million (ppm) relative to an internal stan-
dard of Me4Si. The UV–Visible spectra were measured using a Per-
kin Elmer Lambda 25 UV/VIS Spectrometer. Melting point was
determined using an EZ-Melt melting point apparatus and were
uncorrected.
Synthesis
1-Benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea was pre-
pared by a procedure similar to that reported in the literature
[8–11,44,45]. A solution of benzoyl chloride (2.80 g, 20 mmol) in
dry acetone (10 mL) was added dropwise to a solution of NH4SCN
(1.52 g, 20 mmol) in dry acetone (30 mL) under stirring. After the
addition was completed, the mixture was kept at 40 °C for 1 h,
and then cooled to room temperature. The formed precipitate of
NH4Cl was filtered off. A solution of 2-amino-4-chlorophenol
(2.87 g, 20 mmol) in dry acetone (20 mL) was slowly added to
the resulting yellow solution, which then was stirred at ambient
temperature for 2 h. Afterwards the reaction mixture was poured
into ice-water mixture and stirred well. The solid product was sep-
arated and washed with deionized water, cold MeOH and diethyl-
ether and purified by recrystallization from methanol to give fine
crystals of the title compound, with an overall yield of 87%.
Pale yellow crystal. Mp: 213 °C. Calcd for C14H11ClN2O2S: C,
54.82; H, 3.61; N, 9.13; S, 10.45%. Found: C, 55.23; H, 3.65; N,
8.80; S, 10.61%. FT-IR (cmꢁ1):
(m, br), (C–H) 3000 (m, br),
(vs), 1486 (vs), 1426 (s), 1366 (vs), 1331 (s), 1290 (m),
m
m
(O–H) 3394 (m, br),
(C@O) 1655 (s), 1598 (vs), 1524
(C@S)
m(N–H) 3274
HO
O
m
m
+
N
C
S
H2N
C
1253 (vs), 1185 (vs), 1142 (vs), 1079 (s), 1025 (w), 1000 (w) 980
(w), 935 (m), 871 (vs), 833 (m), 808 (vs), 707 (s), 690 (m). 1H
NMR (CDCl3; d, ppm): 7.00 (d, J = 8.66 Hz, 1H, Ph), 7.16 (dd,
J1 = 8.65, J2 = 2.60 Hz, 1H, Ph), 7.57 (t, J = 7.88 Hz, 2H, Ph), 7.69 (t,
J = 7.41 Hz, 1H, Ph), 8.00 (d, J = 7.28 Hz, 2H, Ph), 8.86 (d, J = 2.56,
1H, Ph), 10.80 (s, 1H, OH), 11.64 (s, 1H, CONH), 13.16 (s, 1H, CSNH);
13C NMR (CDCl3; d, ppm): 116.2, 121.6, 122.0, 125.8, 127.2, 128.5,
128.8, 132.0, 133.3, 147.7 (Ph), 168.4 (C@O), 177.7 (C@S).
Cl
HO
O
S
C
C
Thioketo-amine
N
NH
H
X-ray crystallographic analysis
Cl
The crystal data were collected using
an Agilent SuperNova, (Single source at offset and Eos CCD detec-
tor) diffractometer with SuperNova (Mo) X-ray Source (Mo-K
k = 0.71073 Å). The CrysAlisPro software program was used for
data collection, cell refinement and data reduction. Using Olex2
[35], the structure was solved by the ShelXS [36] structure solution
program using direct methods and refined with the ShelXL [37]
refinement package using least squares minimization. To prepare
material for publication Mercury 3.0 were used. All H atoms were
refined using a riding model.
x–2h scan techniques on
a,
HO
O
C
SH
C
Thiol-imine
N
N
H
Cl
Scheme 1. Synthesis route and chemical structures of the title compound (bcht).

292
M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
Computational details
DMSO, ACN and acetone. The analytical and spectroscopic data
are consistent with the structures given in Fig. 1.
All calculations were performed at density functional theory
(DFT/B3LYP) at the 6-311++G(d,p) basis set level by using Gaussian
09 program [34]. Optimized structural parameters were used by in
vibrational wave numbers, isotropic chemical shifts and electronic
transitions calculations. The total energy distribution (TED) was
calculated by using VEDA 4 [38] program. For NMR calculations,
after optimization, 1H and 13C NMR chemical shifts (dH and dC)
were calculated using the gauge-invariant atomic orbital (GIAO)
method [39,40] in chloroform-d (CDCl3) solvent. The GIAO method
is one of the most common approaches for calculating nuclear
magnetic shielding tensors. The GIAO approach allows the compu-
tation of the absolute chemical shielding due to the electronic
environment of the individual nuclei and this method is often more
accurate than those calculated with other approaches for the same
basis set size. The chemical shifts were reported in ppm relative to
tetramethylsilane (TMS) for 1H and 13C NMR spectra.
Description of the crystal structure
The structure of 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thio-
urea was confirmed by the result of a single crystal X-ray structure
determination. Fig. 1 shows the molecular structure of bcht. Exper-
imental details for data collection and structure refinement are
summarized in Table 1. The selected bond lengths and angles are
presented in Table
interactions).
2 (includes intra and inter molecular
In bcht, the bond lengths and angles are generally normal in the
N-alkyl-N0-benzoylthiourea compounds [4,31–33,43,44]. The bond
lengths of the carbonyl (C8–O2 = 1.230(2) Å) and thiocarbonyl
(C7–S1 = 1.660(2) Å) groups of bcht have typical double-bond
character [31–33,43,44]. However, the C–N bond lengths for the
investigated compound are all shorter than the average single C–
N
bond length of 1.472(5) Å, being C7–N2 = 1.403(2) Å, C8–
Antimicrobial studies
N2 = 1.368(2) Å, C6–N1 = 1.402(2) Å, C7–N1 = 1.327(2) Å thus
showing varying degrees of single bond character [4,31–
33,43,44]. Bond characters of the structure are presumed as a re-
sult of the intra-molecular H-bond ‘‘locking’’ the molecule into a
planar six-numbered ring structure. These results are in agreement
with the expected delocalization in bcht and confirmed by C8–N2–
C7 = 128.52(17)o and C7–N1–C6 = 132.58(17)o angles showing a
sp2 hybridization on the N1 and N2 atoms. As presented in Fig. 1,
the molecule maintains its cis–trans configuration with respect to
the position of the phenyl and 2-hydroxo-5-chlorophenyl groups
relative to the thiocarbonyl sulfur atom across the N2–C8 and
N1–C7 bonds, respectively [43,44]. The conformation of the mole-
cule with respect to the thiocarbonyl and carbonyl moieties is
twisted, as reflected by the torsion angles C7–N2–C8–O2, C8–
N2–C7–N1 and C8–N2–C7–S1 ꢁ4.1(3), 3.5(3) and ꢁ175.80(17),
respectively.
The phenyl rings are nearly planar and the angle between the
two phenyl ring planes is found as 18.25°. The angles between
the planes forming by C8–N2–C7–N1–S1–O2 atoms are calculated
as 2.92° and 20.04° for 2-hydroxy-4-chlorophenyl ring plane and
for the other phenyl ring plane, respectively. These results indi-
cated that the phenyl rings were twisted around the non-aromatic
part of the compound and this may attribute to the intra molecular
hydrogen bond between the the C5 atom of 2-hydroxy-4-chloro-
phenyl part and ticketing part.
Bcht was screened for their antimicrobial activity against bacte-
ria Streptococcus pneumoniae (ATCC 29212), Staphylococcus aureus
(ATCC 6538), Methicillin Resistant Staphylococcus aureus MRSA
(ATCC 43300), Bacillus cereus (ATCC 7064), Entrococcus faecalis
(ATCC 29212), Listeria monocytogenes (ATCC 19114) and Salmonella
typhi (CCM 5445), and yeast. Candida albicans (ATCC 10231) in vitro
using the microdilution method. The antibacterial activity assays
of all compounds were performed according to the Clinical and
Laboratory Standards Institute (CLSI) protocols [41]. The antifungal
activities of all compounds were evaluated according to the Na-
tional Committee for Clinical Laboratory Standards (NCLS) [42].
All determinations were performed in triplicate and confirmed
by three separate experiments. The MIC (l
g mLꢁ1) was defined
as the lowest concentration of compound inhibiting the growth
of each strain. Vancomycine (Himedia) and Ciprofloxcacin (Sigma)
for bacterial strains and Amphotericin B (Sigma) for fungal strains
were used as a positive control.
Results and discussion
The synthesis of the compound involves the reaction of a ben-
zoyl chloride with ammonium thiocyanate in dry acetone followed
by condensation of the benzoyl isothiocyanate with 2-amino-4-
chlorophenol. The compound was purified by recrystallisation
from methanol and characterized by elemental analysis, 1H, 13C
NMR, UV, IR spectroscopy and the single crystal X-ray diffraction
analysis. Bcht is insoluble in water, ether, and hexane but slightly
soluble in chloroform, methanol, and ethanol and soluble in DMF,
As presented in Table 2 and Fig. 1, the N1 atom formed bifur-
cated intramolecular hydrogen bonds with the carbonyl oxygen
(O2) and hydroxyl oxygen (O1). The C5 atom of a phenyl group
formed an intramolecular hydrogen bond with sulfur atom of the
compound.
Fig. 1. The intramolecular H-bonds and the structure diagram with 50% probability ellipsoids of the compound with atomic numbering scheme.

M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
293
Table 1
The calculated bond parameters are also listed in Table 2. The
optimized structural parameters of title compound were calculated
at B3LYP/6-311++G(d,p) basis set level. The correlation between
the experimental and calculated geometric parameters obtained
by the DFT methods is given in Table 2. The bond lengths are well
correlated by cross 0.9879 with observed data. The differences be-
tween calculated and observed bond lengths of hydrogen (X–H) are
higher than bond non-contain hydrogen. For example, the correla-
tion values between calculated and experimental are 0.9895,
0.9914 and 0.9965 for CC, NC and CO, respectively. However, they
are 0.8584, 0.8444 and 0.8524 for CH, NH and OH, respectively. Ar-
slan et al. [45] reported that DFT method correlates (r = 0.9952)
well for the bond length compared with the HF method. Also, their
[45] largest difference between experimental and calculated DFT
bond length is about 0.047 Å while it is 0.154 for X–H and
0.019 Å for X–X bonds in the present study, respectively. As a re-
sult, the optimized bond lengths obtained by DFT-B3LYP/6-
311++G (d,p) method shows the best agreement with the experi-
mental values. The difference between experimental and calcu-
lated geometric parameters comes from the environment of the
compound. It is clear that the experimental results belong to solid
phase and theoretical calculations belong to a gaseous phase.
Crystal data and structure refinement for bcht.
Identification code
H1_5
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
C
14H11ClN2O2S
306.76
293 (2)
Monoclinic
P21/n
11.1594 (6)
4.7461 (3)
25.8628 (13)
90.00
98.484 (5)
90.00
1354.80 (13)
4
1.504
0.438
632.0
b/Å
c/Å
a
/°
b/°
/°
c
Volume/Å3
Z
q
calcmg/mm3
m/mm-1
F(000)
Crystal size/mm3
0.128 ꢂ 0.143 ꢂ 0.218
2H range of data collection
6.46 to 74.84°
Index ranges
ꢁ17 6 h 6 18, ꢁ3 6 k 6 8, ꢁ43 6 l 6 27
11552
6738[R(int) = 0.0467]
6738/0/182
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
1.019
Final R indexes [I> = 2
r
(I)]
R1 = 0.0662, wR2 = 0.1184
R1 = 0.1736, wR2 = 0.1661
0.27/ꢁ0.35
Final R indexes [all data]
Largest diff. peak/hole/e Åꢁ3
FT-IR spectrum
The experimental and theoretical Infrared spectra of bcht are
shown in Fig. 5, where calculated intensity is plotted against the
wave numbers. The observed and calculated wave numbers along
with their relative intensities and probability assignments with
TED of title molecule are given in Table 3. The theoretical calcula-
tions were made for a free molecule of vacuum, while the experi-
ments were performed for the solid sample. Therefore, there are
The molecules extended by the intermolecular hydrogen bonds
are given in Table 2 and showing in Fig. 2 to form two dimensional
networks along the b and c axes. The interactions presenting in
Fig. 3 extend the molecules along the axis. So, the molecules form
three dimensional networks of intermolecular hydrogen bond and
C–Oꢀ ꢀ ꢀ
p interactions (Fig. 4).
Table 2
Selected bond lengths (Å), Angels, Torsion angles (Å) and interactions for bcht.
Bond length
XRD
Calc.
Bond angle
XRD
Calc.
Dihedral angle
XRD
Calc.
S1–C7
Cl1–C4
N2–C7
N2–C8
O2–C8
N1–C6
N1–C7
O1–C1
C6–C5
C6–C1
C5–C4
C8–C9
C1–C2
C9–C14
C9–C10
1.660(2)
1.736(2)
1.403(2)
1.368(2)
1.230(2)
1.402(2)
1.327(2)
1.355(2)
1.378(3)
1.405(3)
1.383(3)
1.481(3)
1.374(3)
1.385(3)
1.391(3)
1.673
1.760
1.409
1.382
1.225
1.408
1.349
1.368
1.397
1.412
1.391
1.497
1.387
1.401
1.400
C10–C9–C8
C14–C9–C8
O2–C8–C9
N2–C8–C9
O2–C8–N2
C8–N2–C7
N1–C7–S1
N1–C7–N2
N1–C6–C1
N2–C7–S1
C5–C6–N1
C7–N1–C6
O1–C1–C6
O1–C1–C2
C5–C6–C1
116.78(19)
124.10(19)
120.48(18)
118.18(17)
121.33(19)
128.52(17)
127.53(16)
114.86(16)
113.45(18)
117.60(14)
127.08(17)
132.58(17)
115.87(18)
124.23(19)
119.47(19)
117.14
123.49
121.84
115.67
122.48
130.45
129.46
114.28
115.27
116.26
126.00
131.22
116.27
123.16
118.73
N1–C6–C1–C2
N1–C6–C1–O1
N1–C6–C5–C4
N2–C8–C9–C10
N2–C8–C9–C14
O2–C8–C9–C10
O2–C8–C9–C14
C6–N1–C7–N2
C6–N1–C7–S1
C7–N1–C6–C1
C7–N1–C6–C5
C7–N2–C8–C9
C7–N2–C8–O2
C8–N2–C7–N1
C8–N2–C7–S1
ꢁ179.48(19)
0.7(3)
ꢁ179.83(19)
ꢁ160.9(2)
17.7(3)
ꢁ179.24
0.81
ꢁ179.14
ꢁ159.05
22.44
17.8(3)
20.28
ꢁ163.6(2)
ꢁ178.58(19)
0.6(3)
ꢁ158.22
ꢁ178.70
1.53
176.9(2)
ꢁ3.0(4)
175.08
ꢁ5.76
174.61(18)
ꢁ4.1(3)
176.80
ꢁ3.87
3.5(3)
ꢁ0.81
ꢁ175.80(17)
ꢁ179.39
Hydrogen bond geometries
D–Hꢀ ꢀ ꢀA
D–H
0.86
0.86
0.93
0.86
0.93
0.82
0.93
0.93
0.93
0.93
Hꢀ ꢀ ꢀA
1.86
2.09
2.58
2.83
2.78
1.95
2.92
3.07
3.04
3.05
Dꢀ ꢀ ꢀA
D–Hꢀ ꢀ ꢀA
142.9
113.2
127.1
150.4
122.4
171.1
125.5
143.1
127.2
123.1
N1–H1ꢀ ꢀ ꢀO2
2.600(2)
2.555(2)
3.225(2)
3.6027(17)
3.368(2)
2.762(2)
3.543(3)
3.857(3)
3.675(3)
3.642(3)
N1–H1ꢀ ꢀ ꢀO1
C5–H5ꢀ ꢀ ꢀS1
N2–H2ꢀ ꢀ ꢀS1i
C14–H14ꢀ ꢀ ꢀS1i
O1–H1Aꢀ ꢀ ꢀO2ii
C2–H2Aꢀ ꢀ ꢀO2ii
C13–H13ꢀ ꢀ ꢀS1iii
C11–H11ꢀ ꢀ ꢀCl1iv
C11–H11ꢀ ꢀ ꢀCl1v
C–Oꢀ ꢀ ꢀ
p interactions geometries
C8–O2ꢀ ꢀ ꢀCg1vi
1.230(2)
1.230(2)
3.8924(18)
3.8309(18)
4.096(2)
3.721(2)
90.67(12)
75.59(11)
C8–O2ꢀ ꢀ ꢀCg2vii
i = ꢁx, 1ꢁy, ꢁzii = 1/2ꢁx, ꢁ1/2 + y, 1/2ꢁziii = ꢁx,2ꢁy, ꢁziv = 1 + x,1 + y,ziv = 1x,2 + y, zvi = x,1 + y, zvii = x, ꢁ1 + y, z
Cg refer to center of the rings Cg1 for C1–C2–
C3–C4–C5–C6 Cg2 for C9–C10–C11–C12–C13–
C14

294
M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
Fig. 2. Inter-molecular hydrogen bonds interactions.
Fig. 3. C–Oꢀ ꢀ ꢀ
p
interactions.
nonsignificant disagreements between them. The title compound
contains 31 atoms, and so they have 87 normal vibrational modes.
The optimized geometry was used for vibrational analysis calcula-
tion. Because there was no imaginary frequency for the stationary
points, the optimized structure accepted as real minimum. Vibra-
tional spectral assignments have been performed on the recorded
FT-IR spectrum based on theoretically predicted wavenumbers
and their TED.
prove the agreement with the experiment. In our study, we have
followed two different scaling factors, i.e. 0.983 up to 1700 cmꢁ1
and 0.958 for <1700 cmꢁ1 [46].
The band at 3394 cmꢁ1 should be attributed to the stretching
frequencies of the O–H group. Medium peak at 3274 cmꢁ1 is attrib-
uted to the stretching vibration of N–H groups. The appropriate
calculated frequencies of
mOH and mNH are positioned at 3688
and 3462 cmꢁ1
,
respectively when DFTB3LYP/6-311++G(d,p)
The vibrational wavenumbers were crossed with a uniform
scaling factor for agreement with experimental data well. The cal-
culated wavenumbers are usually higher than the corresponding
experimental quantities because of the combination of electron
correlation effects and basis set deficiencies. The observed slight
disagreement between theory and experiment could be a conse-
quence of the anharmonicity and the general tendency of the
quantum chemical methods to overestimate the force constants
at the exact equilibrium geometry. Therefore, it is customary to
scale down the calculated harmonic wavenumbers in order to im-
method was applied. The TED contribution of these stretching
modes indicates that these are pure stretching modes. The differ-
ence between experimental and calculated mOH and mNH are about
294 and 188 cmꢁ1, respectively. This striking discrepancy comes
from the formation of intermolecular hydrogen bonding with O–
H and N–H. Also, we note that the experimental results belong to
solid phase and theoretical calculations belong to a gaseous phase.
In aromatic compoundsthe
ing in the range of 3000–3100, 1000–1300 and 750–1000 cmꢁ1
respectively [47,48]. In this study, towards the end the last six
mCH, bCH and cCH modes are appear-
,

M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
295
Fig. 4. A view of packing diagram of the synthesized compound.
vibrations are assigned to C–H stretching, which correspond to
stretching modes C–H of ring units. All modes are nearly pure
stretching vibrations 100% TED terms. The experimental C–H
stretching vibrations appeared at 3000 cmꢁ1. The C–H in-plane
bending vibrations appeared in therange 1084–1333 cmꢁ1 and their
corresponding experimental wavenumbers, 980–1331 cmꢁ1 are
inconsistent with computed values. According to their TED, they
are described as mixed modes, generally with C–C stretching vibra-
tions. The assignments also find support from the literature [48–50].
intensity and are observed at 1625–1590, 1590–1575, 1540–1470,
1460–1430 and 1380–1280 cmꢁ1 from the wavenumber ranges re-
ported by Varsanyi [52] for the five bands in the region. In the pres-
ent work, the wavenumbers assigned in the FT-IR spectrum at
1598, 1426, 1331–1290, 1253 and 1185–1141 cmꢁ1 are assigned
to C–C stretching vibrations. The symmetric ring-breathing mode
was usually found to be near 1000 cmꢁ1 in the monosubstituted
benzene ring. The bands at 1025–871 cmꢁ1 should be attributed
to the vibration of ring-breathing. Shimanouchi et al. [53] reported
the wavenumber data of these vibrations in different benzene
derivatives through normal coordinate analysis. The band observed
at 689 cmꢁ1 in the FT-IR spectrum is assigned to C–C–C deforma-
tion of the phenyl ring. The same vibration appears in the theoret-
ical calculation at 682 cmꢁ1. The TED contribution of this mode
(17%) indicates that this is a pure mode.
The
mCH stretching vibrations of the phenyl ring were assigned
to a band observed at 3000 cmꢁ1 in the IR spectrum of bcht. The
difference between experimental and calculated
mCH is about
29 cmꢁ1. The bigger differences belong to stretching vibrations of
C–H bond forming intermolecular hydrogen bonding.
Stretching vibration of carbonyl group C@O can be observed as
a very strong band in both FT-IR at 1655 cmꢁ1. The carbonyl
stretching C@O vibration is expected to occur in the region
1715–1680 cmꢁ1 [48,51]. This is interpreted by the result of its
conjugated resonance with the phenyl ring and by the formation
of intra-molecular hydrogen bonding with N–H. The difference be-
The abnormally intense absorption peak at 1524 cmꢁ1 is re-
garded as the asymmetric stretching vibrations of N–C–N. It re-
veals that intra-molecular hydrogen bonding exists in the
compound.
The identification of other C–N vibration is a very difficult task,
since the mixing of several bands is possible in this region. How-
ever, with the help of theoretical calculation (DFT), the C–N
stretching vibrations are calculated. The C–N stretching vibration
coupled with scissoring of N–H and C–C is moderately to strongly
tween experimental (1655 cmꢁ1
C@O is about 6 cmꢁ1
The ring carbon-carbon stretching vibrations are appearing in
the range of 1625–1430 cmꢁ1. In general, the bands are of variable
) )
and calculated (1649 cmꢁ1
m
.

296
M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
shown in Table 4. The atom positions were numbered in Fig. 1.
0.5
0.4
0.3
0.2
0.1
0.0
a
The NMR spectrum is recognized that accurate predictions of
molecular geometries are essential for reliable calculations of mag-
netic properties. Therefore the molecular structure of title com-
pound was optimized before theoretical NMR calculation. Then,
gauge-including atomic orbital (GIAO) 13C NMR and 1H NMR
chemical shift calculations were carried out by using B3LYP func-
tional with 6-311++G(d,p) basis sets. The GIAO [39,40] method is
one of the most common approaches for defining isotropic nuclear
magnetic shielding tensors. For the same basis set size, the GIAO
method is often more accurate than other approaches [58]. The cal-
culations reported were performed in CDCl3 solution using the IEF-
PCM model, rather than in the gas phase, in agreement with exper-
imental chemical shifts obtained in CDCl3 solution. The isotropic
shielding values were used to calculate the isotropic chemical
shifts with respect to tetramethylsilane (TMS). As seen from Ta-
ble 4, experimental and theoretical results are generally in good
agreement. However, all of the theoretical 13C NMR values a bit
bigger from observed values. But in 1H NMR values, there is not
any systematic relation between experimental and calculated val-
ues. While some theoretical 1H NMR values have perfect agree-
ment (like as H1, H2A, H3, H14), some values are so different
(like as H2 and H1A), (Table 4).
4000 3500 3000 2500 2000 1500 1000
500
0
Wavenumber (cm-1)
500
b
400
300
200
100
0
Corresponding to the literature, the 1H NMR spectrum of bcht
indicates that the NH resonances appear at 13.16 and 11.64 ppm,
but these resonances vary with different parameters, such as the
substituted groups on the rings, which release and withdraw elec-
tron density in each ring, their positions and intra- and intermolec-
ular hydrogen bondings [32,57,59]. In most compounds with
aromatic substituent at N1, the hydrogen bonded proton N1–H1
has a higher d 1H value between 12 and 13 ppm. Acidic protons
N2–H2 show their d 1H values between 11 and 12 ppm. 1H NMR
studies in CDCl3 show that the proton of N1–H1 chemical shift is
found about d 13.16 ppm for the hydrogen bonded proton N1–
H1. The chemical shift of acidic proton of N2–H2 is about d
11.64 ppm. The chemical shift of proton of O1–H1A is about d
10.80 ppm. The protons at benzene ring resonance come out in
downfield at about d 7.0–8.86 ppm. This can be corroborated with
concrete examples: The protons H14–H10, d = 8.00 ppm (d, 2H,
J = 7.28 Hz), appear in downfield due to intra-molecular hydrogen
bonded reaction O2ꢀ ꢀ ꢀH14 and H10. The protons H13 and H11 ap-
pear at d = 7.57 ppm (t, 2H, J = 7.88 Hz), the proton H12 appears at
d = 7.69 ppm (t, 1H, J = 7.41 Hz), the protons H5, H3, H2A appear at
8.86 (d, 1H, J = 2.56 Hz), 7.16 (dd, 1H, J = 2.60, 8.65 Hz), 7.00 (d, 1H,
J = 8.66 Hz) ppm, respectively, in light of substituted group effect.
The most de-shielded 13C NMR signals correspond to C@O and
C@S groups. The carbon atom of thiocarbonyl group d 177.7 ppm
shows the highest values, due to the lower excitation energy n–
p⁄ [60]. The 13C NMR signals of carbonyl group appearing at d
168.4 ppm are more de-shielded in the NMR spectra, due to the
existence of the intra-molecular hydrogen bond related to the car-
bonyl oxygen atom. Meanwhile, the aromatic carbon resonances
can be found in between dC 116.2–147.7 ppm which is correspond-
ing to phenyl rings in the compound. This similar chemical shift
could be due to the isolated position of the thione group in these
compounds [32,43,57,61].
4000 3500 3000 2500 2000 1500 1000
500
0
-1
Wavenumber (cm )
Fig. 5. (a) Experimental and (b) Theoretical IR spectra of 1-benzoyl-3-(5-chloro-2-
hydroxyphenyl)thiourea.
active in the region 1275 55 cmꢁ1 [51]. In the present investiga-
tion C–N stretching frequencies are observed at 1079, 1185, 1253,
1331 and 1366 cmꢁ1 by FT-IR and their corresponding calculated
wavenumbers appeared in the range of 1146–1361 cmꢁ1. These
experimental values of C–N stretching mode show good agreement
with theoretical values. The mCN stretching vibration normally ap-
pears around 1300 cmꢁ1 [48,51].
The band at 1253 cmꢁ1 might be attributed to
m(C–O). The re-
corded four peaks by Klots et al. [54] which are 608.8, 753.5,
839.5, and 872.8 cmꢁ1 are assigned to C–S stretching by Singh
et al. [55] according to the potential energy distribution (PED) ob-
tained from DFT calculations. In this study, we have assigned five
bands due to the C–S stretching based on the TED calculations,
and obtained a single band at 773 cmꢁ1 (mode 35) which the ob-
served value is 707 cmꢁ1. In this study, two in-planes bending of
S–C–N calculated at 222 and 233 cmꢁ1 and an out-plane-bending
of S–N–N–C calculated at 598 cmꢁ1 based on TED calculation.
The IR spectrum of the compound does not display the S–H mode
at about 2600 cmꢁ1 indicating that in the solid state this com-
pound remains in the thioketo-amine form [32,33,56,57]. The
non-discussed modes details are given in Table 3. The majority of
the experimental FT-IR values show good agreement with theoret-
ical values.
HOMO, LUMO analysis
The highest occupied molecular orbital (HOMO) energy and the
lowest unoccupied molecular orbital (LUMO) energy and the en-
ergy gap of HOMO and LUMO for bcht calculated at the B3LYP/6-
311++G(d,p) level is shown in Table 5. Both HOMO and LUMO play
an important role in the electrical and optical properties, as well as
in UV–Vis spectra and chemical reactions [62–64]. The bioactivity
and chemical activity of the molecule depends on the eigenvalue of
NMR spectra
The NMR spectrum was recorded in CDCl3 at room temperature
at 400.00 MHz on a Bruker 400 instrument. The two most de-
shielded signals were assigned to NH protons. The NMR data are

M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
297
Table 3
Comparison of the theoretical and experimental vibrational spectra and proposal assignment.a
No
IRExp
IRCalc
Unsc.
TED (P10%)
Sc.
IRint
0.07
1.26
0.25
1
2
3
10
27
40
10
27
39
s
s
s
CCNC(70), CNCN(17)
CCNC(10), NCCC(21), CNCC(40), CNCN(16)
NCCC(51), CNCC(16)
4
57
56
1.21
bNCN(14), NCC(16), CNC(36)
5
6
7
8
84
110
83
0.00
6.75
0.02
0.95
2.91
7.87
54.66
45.96
2.47
0.97
12.06
1.34
11.24
0.62
0.25
0.06
10.06
5.91
4.26
41.64
6.58
s
s
s
CCCN(19), NCNC(29), CNCN(14)
CCCN(10), NCNC(34), CNCN(12)
CCCC(54) + cClCCC(25)
109
122
122
141
188
222
233
258
281
290
347
367
374
403
410
434
452
489
555
577
598
620
625
635
649
682
689
704
714
773
790
794
821
838
843
876
884
909
931
964
978
996
999
1029
1070
1084
1091
1104
1146
1157
1166
1188
1213
1237
1271
1281
1313
1322
1333
1361
1424
1452
1492
1499
1524
1570
1591
1612
124
124
144
191
226
237
263
286
295
353
373
380
bCCN(23), CNC(11), ClCC(13)
bNCN(21)
sCCCC(20) + cCCCC(18)
bSCN(21) +
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
sHOCC(44)
bSCN(21) +
sHOCC(42)
sCCCN(14), CNCN(18) + cClCCC(18)
bCNC(11), CCC(17), ClCC(24)
bOCC(15), CCC(21), ClCC(23)
sCCCC(33), CCCN(10) +
cClCCC(17), OCCC(23)
bOCN(21), NCN(14), CNC(19)
m
s
m
ClC(39) + bCCC(15)
HCCC(11), CCCC(49)
410
417
441
460
497
565
587
608
631
636
646
661
694
701
716
727
786
803
CC(15) + bCCC(14) +
CCCC(14) +
HCCC(20), CCCC(35) +
bNCC(11), OCC(21)
bCCC(12), NCC(16), OCC(14)
s
CCCC(10)
CCCC(12)
OCCC(28)
bOCC(12) +
s
s
c
c
s
s
HCCC(11), CCCN(38) +
HNCC(11) + SNNC(69)
HNCC(10)
HNCC(15)
cClCCC(22)
9.17
4.36
c
bCCC(67) +
bCNC(10) +
s
s
12.89
43.78
38.65
11.26
18.37
55.76
1.07
sHNCC(53)
bCCC(17)
bCCC(17)
689
689
689
707
707
707
777
793
808
808
808
822
822
833
833
871
s
s
s
m
s
s
CCCC(68)
HCCC(24) +
HCCC(12), CCCC(54) +
SC(36)
HCCC(76) +
HCCC(12), CCCC(10) +
OC(13) + bCCC(34)
cONCC(32)
cOCCC(15)
8.61
38.50
13.66
9.59
50.71
0.95
46.09
11.38
3.47
0.96
10.91
1.18
0.31
5.43
cOCCC(16)
808
cONCC(27), CCCC(17)
835
852
858
892
900
m
s
s
HNCN(84)
HCCC(98)
bOCN(18), CNC(11)
s
s
s
HCCC(70)
HCCC(85), CCCC(11)
HCCC(80)
924
947
981
995
1013
1016
1047
1089
1103
1109
1123
1165
1177
1186
1208
1234
1259
1293
1303
1335
1345
1356
1384
1449
1477
1518
1525
1551
1598
1619
1640
bCCC(33), NCN(11)
s
s
HCCC(89)
HCCC(80)
871
871
881
935
m
m
m
m
m
m
m
m
m
m
m
m
m
CC(21) + bCCC(62)
CC(41) + bCCC(11)
CC(10), NC(30)
CC(39) + bHCC(16)
CC(25) + bHCC(28)
CC(12) + bCCC(11), HOC(17), HCC(11)
NC(40) + bHNC(10)
CC(13) + bHOC(29), HCC(41)
CC(10) + bHCC(74)
CC(12) + bHCC(64)
NC(31) + bCCC(10)
CC(21) + bHNC(14)
CC(15), OC(26) + bHCC(20)
8.95
13.57
13.15
23.93
63.89
306.38
32.00
0.97
32.33
32.12
193.69
26.98
21.79
13.91
238.52
5.18
511.06
56.00
4.74
247.57
71.03
342.36
546.39
14.59
30.55
980
1000
1025
1079
1141
1167
1185
1185
1253
1253
1271
1290
1331
1331
1366
1426
1445
1486
1497
1524
1598
1598
1598
bHCC(44)
m
m
m
m
m
CC(41)
CC(24), NC(11) + bHOC(12)
CC(11) + bHCC(61)
NC(25)
CC(53) + bHCC(15)
bHCC(53)
bHNC(11), HCC(12)
bHCC(30)
m
m
m
m
NC(13) + bHNC(44)
CC(14) + bHNC(35)
CC(41)
CC(39)
(continued on next page)

298
M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
Table 3 (continued)
No
IRExp
IRCalc
Unsc.
TED (P10%)
Sc.
IRint
74
75
76
77
78
79
80
81
82
83
84
85
86
87
1598
1598
1655
3000
3000
3000
3000
3000
3000
3000
3000
3274
3274
3394
1640
1643
1721
3161
3165
3172
3183
3194
3204
3208
3238
3317
3614
3850
1612
1616
1649
3029
3032
3039
3050
3059
3070
3073
3102
3178
3462
3688
110.28
224.35
129.23
11.12
3.71
m
m
m
m
m
m
m
m
m
m
m
m
m
m
CC(39)
CC(12) + bHNC(24)
OC(70) + bHNC(10)
CH(97)
CH(96)
CH(96)
CH(86)
CH(81)
CH(97)
CH(97)
CH(99)
NH(99)
NH(100)
OH(100)
1.82
12.63
11.83
5.39
0.55
24.00
348.00
38.21
99.91
a
Unsc. – Unscaled, Sc. – Scaled, IRint – IR intensity (Kmmolꢁ1),
m
-streching; b-in-plane-bending;
c
-out-of-plane bending; s-torsion. TED P 10% are shown.
HOMO energyðB3LYPÞ ¼ ꢁ6:147eV
Table 4
The experimental and predicted 13C and 1H isotropic chemical shifts (with respect to
TMS, all values in ppm) for 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea.
LUMO energyðB3LYPÞ ¼ ꢁ2:294eV
Atom
Exp.
B3LYP
Atom
Exp.
B3LYP
HOMO ꢁ LUMOenergy gapðB3LYPÞ ¼ ꢁ3:853eV
C7
C8
C1
C12
C4
177.8
168.4
147.7
133.3
132.0
127.2
128.5
128.8
128.8
125.8
128.5
122.0
121.6
116.2
186.34
171.62
152.05
140.85
139.82
139.15
137.31
135.95
135.32
134.09
132.06
131.45
125.64
118.67
H1
H5
H2
H10
H14
H12
H11
H13
H3
13.16
8.86
11.64
8.00
8.00
7.69
7.57
7.57
7.16
7.00
10.80
–
13.12
10.21
8.88
8.59
8.04
7.91
7.89
7.85
7.19
6.94
4.83
–
The calculated self-consistent field (SCF) energy of bcht is
ꢁ1658.757 a.u. The HOMO and LUMO energy gap explains the
eventual charge transfer interactions taking place within the mol-
ecule. The smaller band gap energy increases the stability of the
molecule [64].
C9
C10
C11
C13
C6
C14
C3
In the ground state, the charge density is mainly accumulated
on the 5-chloro-2-hydroxyphenyl ring and C@S parts in the case
of HOMO. The charge densities move to benzoyl group in case of
LUMO. The charge density of the HOMO orbitals allows to visually
considering the most probable sites for an interaction with nucle-
ophilic species. In this case, the nitrogen and sulfur atoms are sur-
rounded by a greater surface of negative charge, becoming these
sites potentially more favorable for a possible coordination point.
On the other hand, it was found that there are other effects such
as the formation of a hydrogen bridge that could be playing in fa-
vor of the six member heterocyclic ring formation, making impos-
sible the simultaneous coordination with the sulfur and an oxygen
atom of the carbonyl group [66].
H2A
H1A
C5
C2
–
–
–
–
Table 5
Calculated energy values of 1-benzoyl-3-(5-
chloro-2-hydroxyphenyl)thiourea in its ground
state with singlet symmetry and dipole moment
at DFT method in the gas phase.
TD-DFT/B3LYP/6–311++G (d, p)
Another electronic effect that accentuates the nucleophilic reg-
ioselectivity through the sulfur atom, is the formation of resonant
bonds in the 6 member ring, specifically the (O)C–N- and (S)C–N
bonds, corroborated with the bond length, which is shorter than
in a normal C–N bond, about 1.47 Å [4,31–33,43,44]. In this type
of bonds, it does not occur any rotation in the molecule at the same
level due to the rigidity provided by the electronic distribution of
Energy (eV)
GAS
HOMO
LUMO
ꢁ6.147
ꢁ2.294
ꢁ3.853
ꢁ6.294
ꢁ1.339
ꢁ4.954
ꢁ6.147
C1
HOMO–LUMO gap, (dE)
HOMOꢁ1
LUMO + 1
HOMO–LUMO gap, (dE)
Dipole moment,
Symmetry
l(D)
nature
p bond [66].
Electronic spectra
HOMO, LUMO and energy gap. The HOMO represents the ability to
donate an electron, LUMO as an electron acceptor represents the
ability to obtain an electron. This electronic absorption corre-
sponds to the transition from the ground to the first excited state
and is mainly described by one electron excitation from the HOMO
to the LUMO. The smaller the energy gap of LUMO and HOMO, the
easier it is for the electrons of HOMO to be excited. The higher the
energies of HOMO, the easier it is for HOMO to donate electrons;
the lower the energies of LUMO, the easier it is for LUMO to accept
electrons [64,65]. From the molecular orbital analysis the energy
difference between the HOMO and LUMO is about ꢁ3.853 eV.
The frontier molecular orbital of bcht (HOMO–LUMO) is shown
in Fig. 6.
Electronic absorption spectra of bcht were recorded in the
200–400 nm range in ACN and methanol. Absorption bands in
ACN were observed at 239, 266 and 328 nm in UV region of the
intraligand charge transfer transitions
p–
p⁄(phenyl nucleus) and
n–p⁄, (C@N/(C@S and C@O). In order to explain the electronic
transition and to compare with the experimental spectrum, TD-
DFT method was applied to obtain a prediction of the electronic
spectrum based on the B3LYP/6-311++G(d,p) level optimized
structure. The solvent effect of the theoretical electronic transi-
tions was studied with the PCM (polarized continuum model)
in ACN. The experimental and computed electronic values, such
as absorption wavelength, excitation energies, and oscillator

M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
299
LUMO+1
E=-1.339
LUMO
(First excited state)
E=-2.294
ΔE=-3.853
ΔE=-4.954
HOMO
(Groundstate)
E=-6.147
HOMO-1
E=-6.294
Fig. 6. The atomic orbital compositions of the frontier molecular orbital of 1-benzoyl-3-(5-chloro-2-hydroxyphenyl)thiourea (energies given in eV).
Table 6
1.2
The Experimental and theoretical electronic absorption spectra values of bcht.
TD-DFT/B3LYP/6-311++G(d,p)
1.0
0.8
0.6
0.4
0.2
0.0
Solvent
Wavelengths
Excitation
energies (eV)
Oscillator
strengths
(f)
Log
e
k (nm)
Exp. Theo.
Acetonitrile 239 278.08 4.459
(73,75,78?80;78?81)
280.84 4.415 (76?80,79?81)
328 352.23 3.520 (79?80)
0.13
4.36
266
0.61
0.21
0.13
4.26
3.95
4.26
Methanol
240
279.23 4.440 (76,77?80;
79?81)
263
280.74 4.416 (76?80; 79?81)
0.61
0.21
4.20
3.90
331 352.13 3.521 (79?80)
240
260
280
300
320
340
360
380
400
strengths are tabulated in Table 6. Experimental UV–Vis spectrum
in ACN solvent is shown in Fig. 7. For ACN solvent, the three in-
tense calculated electronic transitions at kmax = 278.08 nm,
f = 0.13; kmax = 280.84 nm, f = 0.61 and kmax = 352.23 nm, f = 0.21
have been obtained which corresponds to the experimental kmax
values at 239, 266 and 328 nm, respectively. For methanol sol-
vent, the theoretical and experimental values nearly same with
ACN solvent. Table 6 indicates that the theoretical transition
peaks for bcht in both solvent are red-shifted compared with
the experimental data. However, the agreement between theoret-
ical and experimental data is acceptable.
Wavelength, nm
Fig. 7. The experimental UV spectrum of study compound (in ACN).
Antimicrobial activities
The in vitro antimicrobial properties against Gram positive and
Gram negative bacteria, and yeast of bcht are presented in Table 7,
respectively. Bcht showed different degrees of antimicrobial activ-
ity in relation to the tested species. Among the tested microorgan-
isms, L. monocytogenes and S. aureus appears to be the most

300
M. Atißs et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 98 (2012) 290–301
Table 7
MIC values (l
g mLꢁ1) of the bcht against the tested bacterias.
S. aureus
MRSA
S. pneumoniae
B. cereus
E. faecalis
L. monocytogenes
S. typhi
C. albicans
Bcht
128
2
–
>1024
>1024
>1024
>1024
128
2
4
>1024
–
<0.25
–
>1024
–
–
Vancomycine
Ciprofloxcacin
Amphotericin B
2
–
–
2
–
–
4
–
–
4
–
–
–
–
0.25
sensitive strains MIC values of 128 l
g mLꢁ1. However, bcht were
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