Synthesis, characterization and antimicrobial activity of m-toluenesulfonamide, N,N′-1,2-ethanediylbis (mtsen) and [Cu(II)(phenanthroline)2]mtsen complex

Article abstract of DOI:10.1016/j.molstruc.2012.06.046

M-toluenesulfonamide, N,N′-1,2-ethanediylbis (a disulfonamide compound, mtsen) and [Cu(II)(phenanthroline)₂]mtsen compounds were newly synthesized. The molecular structure of mtsen was investigated by using elemental analyses, liquid chromatogr

Full text of DOI:10.1016/j.molstruc.2012.06.046

Journal of Molecular Structure 1028 (2012) 116–125
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, characterization and antimicrobial activity of m-toluenesulfonamide,
N,N0-1,2-ethanediylbis (mtsen) and [Cu(II)(phenanthroline)2]mtsen complex
c
d
e
f
Hamit Alyar a, Saliha Alyar b, , Arslan Ünal , Neslihan Özbek , Ertan Sßahin , Nurcan Karacan
⇑
a Department of Chemistry, Science Faculty, Çankırı Karatekin University, 18100 Çankırı, Turkey
b Department of Physics, Science Faculty, Çankırı Karatekin University, 18100 Çankırı, Turkey
c Department of Physics, Science and Art Faculty, Bilecik University, 11210 Bilecik, Turkey
d Department of Primary Education, Faculty of Education, Ahi Evran University, 40100 Kırßsehir, Turkey
e Department of Chemistry, Faculty of Science and Art, Atatürk University, TR-25240 Erzurum, Turkey
f Department of Chemistry, Science and Art Faculty, Gazi University, 06500 Ankara, Turkey
h i g h l i g h t s
"
"
"
"
"
M-toluenesulfonamide, N,N0-1,2-ethanediylbis (mtsen) and [Cu(II)(phenanthroline)2]mtsen compounds were synthesized.
The structure of msen was proved by single-crystal X-ray diffraction, spectral analyses and DFT.
The structure of complex was investigated magnetic susceptibility, conductivity measurement and FT-IR.
The complete assignments of mtsen were performed on the basis of the PED.
The in-vitro antibacterial activities of compounds were also tested.
a r t i c l e i n f o
a b s t r a c t
M-toluenesulfonamide, N,N0-1,2-ethanediylbis (a disulfonamide compound, mtsen) and [Cu(II)(phenan-
throline)2]mtsen compounds were newly synthesized. The molecular structure of mtsen was investigated
by using elemental analyses, liquid chromatography–mass spectrometry (LC–MS), X-ray diffraction,
Fourier transform infrared spectroscopy (FT-IR), dispersive Raman spectroscopy, 1H, 13C, heteronuclear
chemical-shift correlation (HETCOR) and correlation spectroscopy (COSY) NMR spectroscopies. The
FT-IR, dispersive Raman and far-infrared spectra of mtsen were recorded at room-temperature and dis-
cussed assisted with B3LYP/6-311G(d,p) level of theory along with scaled quantum mechanics force field
(SQM-FF) method. Furthermore, 1H and 13C NMR analyses were performed at B3LYP/6-311++G(d,p)
theory level using gauge including atomic orbital (GIAO) method and compared with the experimental
findings. Further analyses were also made for [Cu(II)(phenanthroline)2]mtsen complex by using elemen-
tal analysis, LC–MS, magnetic susceptibility; conductivity measurement and FT-IR. The antibacterial
activities of synthesized compounds were studied against some Gram-positive and Gram-negative bac-
teria by using the microdilution and disk diffusion method. The biological activity screening showed that
complex have more activity than ligand against the tested bacteria.
Article history:
Received 23 February 2012
Received in revised form 22 June 2012
Accepted 22 June 2012
Available online 29 June 2012
Keywords:
Disulfonamides
X-ray
DFT
SQM-FF
FT-IR and Raman
Antibacterial activity
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
and for urinary and gastrointestinal infections [3,4]. Multidrug
resistance remains as a significant problem for microbial infection
Sulfa drugs are the oldest chemically synthesized antimicrobial
agents and are still widely used today for the treatment of various
bacterial, protozoal and fungal infections [1,2]. After the introduc-
tion of the penicillin and other antibiotics the popularity of
sulfonamides decreased. However they are still used as sulfa drugs
such as sulfadiazine, sulfathiazole and sulfamerazine in certain
therapeutic fields especially in the case of ophthalmic infections
treatments [5–8]. Additionally the threat of bioterrorism using
agents such as weaponized Bacillus anthracis and Yersinia pestis
highlight the need for continuing research in infectious diseases
and the search for new therapeutic agents [9]. Due to their signif-
icant pharmacology applications and widespread use in medicine,
these compounds have gained attention in bio-inorganic and
metal-based drug chemistry.
Some metal sulfonamide complexes have attracted much atten-
tion due to the fact that showing greater biological activity than
the sulfonamide ligands or the metallic salts. For instance,
⇑
Corresponding author. Tel.: +90 0376 2132626.
E-mail address: saliha@karatekin.edu.tr (S. Alyar).
0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.06.046

H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
117
Ag(I)-sulfadiazine [10], Ce(III)-sulfadiazine [11], Ni(II)-sulfadime-
thoxine [12] and Cu(II)-sulfacetamide [13] have shown higher
antimicrobial activity than free ligands.
(60F254, Merck). All NMR spectra were recorded on a Bruker
WM-400 spectrometer at ambient probe temperature using
dimethyl sulfoxide-d6 (DMSO-d6) solutions with tetramethylsilane
as internal reference. The FT-IR (4000–400 cmꢀ1) spectra between
KBr pellet technique or KBr windows as Nujol or hexachloro-1,3-
butadiene mulls and far-infrared (400–30 cmꢀ1) spectra between
polyethylene pellet technique of the sample were recorded by
using a Bruker Optics IFS66v/s FTIR spectrometer with 2 cmꢀ1 res-
olution in vacuum. The dispersive Raman spectra were recorded
using a Bruker Senterra Dispersive Raman microscope spectrome-
ter at 532 nm excitation from a doubled Nd/YAG laser having
3 cmꢀ1 resolution between 4000 and 100 cmꢀ1 spectral region.
The molar magnetic susceptibilities at room temperature were
performed using a Sherwood Scientific Magway MSB MK1 model
magnetic balance by the Gouy method using Hg[Co(SCN)4] as the
calibrant measurement. The molar conductance measurements
were carried out using a Siemens WPA CM 35 conductometer.
In our previous studies, some aliphatic or aromatic bis sulfon-
amide compounds were synthesized and their antimicrobial
activity were tested [14–17]. Furthermore, we have reported con-
formational analysis and vibrational spectroscopic investigation
of the methanesulfonic acid hydrazide [18], methanesulfonic acid
1-methylhydrazide [19], some methanesulfonyl hydrazone deriva-
tives [20–22]. We also reported the conformational behavior,
vibrational and NMR spectroscopic study of methanesulfonam-
ide-N,N0-1,2-ethanediylbis (msen) in our last study [23]. As a
continuation our studies, the aims of the current work is to inter-
pret the molecular structure, vibrational and NMR spectroscopic
properties of the mtsen from experimental and theoretical view-
points as a contribution to the understanding of the rational drug
design of sulfonamide derivatives. Furthermore, [Cu(phen)2]L
complex (where Cu(II)@Cu, phen = phenanthroline and L = mtsen)
was synthesized and characterized by using elemental analyses,
FT-IR, LC–MS, magnetic susceptibility and conductivity measure-
ments. Finally, the antibacterial activities of synthesized two
compounds were investigated by using disk diffusion and micro
dilution methods.
2.4. Computational details
The geometric parameters of mtsen were fully optimized with-
out any constraint with the help of standard gradient procedure
implemented within Gaussian 03 program [24]. All the parameters
were allowed to relax and all the calculations converged to an opti-
mized geometry which corresponds to a true energy minimum re-
vealed by the lack of imaginary values in the wave numbers
calculations. The vibrational wavenumbers were calculated with
B3LYP/6-311G(d,p) and then scaled by using the scaling factors
for primitive coordinates proposed by our previous study [23].
The scale factor values used in the SQM-FF methodology for inter-
nal coordinates are given Table S1 (Supporting information). The
each vibrational modes of the studied compound were character-
ized by their potential energy distributions (PED) which were
calculated by using SQM-FF program [25].
2. Experimental and theoretical part
2.1. Synthesis of ligand molecule
The nucleophilic substitution reaction of the 1,2 diaminopropane
with m-toluenesulfonyl chloride were carried out as follows: tetra-
hydrofuran solution of 1,2 diaminopropane (0.08 mol, 3.36 mL)
was added by slowly dropwise to the tetrahydrofuran solution of
m-toluenesulfonyl chloride (0.04 mol, 3.85 g), maintaining the tem-
perature between ꢀ5 and ꢀ10 °C. Then, the reaction mixture was
stirred for 24 h at room temperature (completion of the reaction
was monitored by thin layer chromatography). After the completion
of the reaction, the solvent was evaporated in vacuum. The solid res-
idue was purified by column chromatography. The white crystalline
solid was recrystallized from tetrahydrofuran/n-hexane mixture.
Product was dried in a vacuo and stored at tetrahydrofuran vapor.
Yield 72%; mp 158–161 °C MS (70 eV, APCl): 368.8 (M+), 369.8
(M1+), 370.8 (M2+), 214.7 (CH3C6H4SO2NHC2H4NH+), 167.6 (CH3C6H4
SO2NH)+ 154.6 (CH3C6H4SO2)+. Anal. Calc. for C16H20N2O4S2: C, 40.0;
H 8.0; N, 9.33; S, 21.3. Found: C, 40.23; H, 7.94; N, 9.10; S, 21.51.
The scaling factors were not applied to the infrared and Raman
intensities. The relative Raman intensity (IR), which simulates the
measured Raman spectrum, was calculated using the following
relation derived from the intensity theory of Raman scattering
[26,27];
4
fðm0
ꢀ
miÞ Si
IiR
¼
ð1Þ
mi½1 ꢀ expðꢀhc i=kTÞꢁ
m
where m0 is the exciting frequency (18798 cmꢀ1), mi is the vibra-
tional wavenumber of the ith normal mode (in cmꢀ1 units), Si is
the Raman scattering activity of the ith normal mode qi, h, c, k are
fundamental constants, T = 300°K and f (10ꢀ14) is a suitably chosen
common normalization factor for all peaks.
2.2. Synthesis of [Cu(phen)2]L complex
0.5 mmol of m-toluenesulfonamide, N,N0-1,2-ethanediylbis was
added to a solution of 0.5 mmol of Cu(II) acetate in 40 ml of
acetonitrile. The mixture was stirred for 3–4 h. Then, 1 mmol of
1,10-phenanthroline was added into the mixture. Product precipi-
tated slowly as a blue solid while the mixture was warmed. The
product was filtered off, dried, and recrystallized from dichloro-
methane/n-hexane. Data for [Cu(phen)2]L (phen: phenanthroline
and L:mtsen) complex (yield 70%). mp 338–340 °C MS (70 eV,
APCl): 790 [CuL(phen)2]+, 425.0 [Cu(phen)2]+ 243.9 [Cu(phen)]+,
368 [HL1]+. Anal. Calc. for C40H34N6O4S2Cu: C, 61.22; H, 4.51; N,
10.45; S, 7.97. Found: C, 58.99; H, 4.51; N, 12.58; S, 4.85.
NMR features of mtsen were calculated at B3LYP/6-311++G(d,p)
theory level using GIAO method [28,29] as implemented in Gauss-
ian 03W program package. Isotropic shielding tensors of 13C and 1H
were turned into chemical shifts using the linear relationship
equation as in Ref. [23].
2.5. Crystal structure of the mtsen
To get the molecular structural parameters of mtsen, the single-
crystal of the compound was used for data collection on a four-
circle Rigaku R-AXIS RAPID-S diffractometer (equipped with a
two-dimensional area IP detector). The graphite-monochromatized
2.3. Physical measurements
Mo K
with
tice parameters were determined by the least-squares methods on
the basis of all reflections with F2 > 2 (F2). Integration of the inten-
sities, correction for Lorentz and polarization effects and cell
refinement were performed using Crystal Clear (Rigaku/MSC Inc.,
a
radiation (k = 0.71073 Å) and oscillation scans technique
D
x = 5° for one image were used for data collection. The lat-
The elemental analyses (C, H, N and S) were performed by a
Fisons EA-108 type elemental analyzer. The mass spectrum was
recorded on Agilent 1100 LC/MS-APCI at 100 eV. Thin layer chro-
matography (TLC) was conducted on 0.25 mm silica gel plates
r

118
H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
Table 1
wells. Then, 100 lL from the serial dilutions was transferred into
Crystal data and structure refinement parameters for mtsen.
fourteen consecutive wells. The contents of the wells were mixed
and the microplates were incubated at 37 °C for 24 h. The
compounds were also tested against each microorganism twice.
The MIC values were determined from visual examinations as the
lowest concentration of the extracts in the wells with no bacterial
growth [32].
CCDC number
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
861029
C16H20N2O4S2
368.4
293(2) K
0.71073 Å
Monoclinic
P21/c
Unit cell dimensions
a = 9.1034(2) Å
b = 10.2851(2) Å
c = 10.1651(2) Å
866.69(3) Å3
2
a
= 90°
b = 114.41(3)°
= 90°
2.7. Disk diffusion method
c
Volume
Z
Bacterial susceptibility testing was performed by the disk diffu-
sion method according to the guidelines of Clinical and Laboratory
Standards Institute [33]. The sterilized (autoclaved at 120 °C for
30 min), liquefied Mueller Hinton agar (40–50 °C) was inoculated
with the suspension of the microorganism (matched to 0.5 McFar-
land) and poured into a Petri dish to give a depth of 3–4 mm. The
Density (calculated)
Absorption coefficient
F(000)
h-range for data collection
Index ranges
1.42 g/cm3
0.330 mmꢀ1
388
2.5–30.7°
ꢀ13 ꢃ h ꢃ 13, ꢀ14 ꢃ k ꢃ
14, ꢀ14 ꢃ l ꢃ 13
25110
paper disks impregnated with the test compounds (50
lg, 100 lg
Reflections collected
Independent reflections
Completeness to h = 30.7°
Refinement method
and 250 g) were placed on the solidified medium. Disks were
l
2654 [Rint = 0.044]
99.7%
placed on agar plates and the cultures were incubated at 37 °C
for 24 h for bacteria. Inhibition zones formed on the medium were
evaluated in mm. ciprofloxacin (5 lg/disk) was chosen as a stan-
dard in antibacterial activity measurements (positive control).
Full-matrix least-squares on F2
Data/restraints/parameters 2524/0/112
Goodness-of-fit on F2
Final R indices [F2 > 2
R indices (all data)
1.143
r
(F2)] R1 = 0.040, wR2 = 0.119
R1 = 0.043, wR2 = 0.124
0.080
DMSO poured disk was also used as negative control.
Extinction coefficient
Largest diff. peak and hole 0.268 and ꢀ0.267 e Åꢀ3
3. Results and discussion
3.1. The characterization of compounds
2005) software [30]. The structures were also solved by direct
methods using SHELXS-97 and refined by a full-matrix least-
squares procedure using the program SHELXL-97 [31]. All hydro-
gen atoms attached to carbon atoms were fixed geometrically
and treated as riding with CAH = 0.97 Å (methylene) or 0.96 Å
(methyl) with Uiso(H) = 1.2Ueq(methylene) and 1.5Ueq(methyl) of
the parent atom. The nitrogen protons were located in Fourier dif-
ference maps and constrained as riding atoms with N(1)AH(1 N)
set to 0.950 Å. The final difference Fourier maps showed no peaks
of chemical significance. Crystal data and structure refinement
parameters of compound mtsen were tabulated in Table 1.
Crystallographic data were deposited in CSD under CCDC
registration number 861029. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
An X-ray diffraction analysis was undertaken to understanding
the molecular structure of mtsen. The ORTEP diagram of mtsen is
presented in Fig. 1. The compound crystallizes in the monoclinic
space group P21/c, with two molecules in the unit cell. The structure
has a ‘partially extended’ conformation in which the terminal
m-toluenesulfonamide fragments fold back towards the diaminoe-
thane unit. The molecule possesses crystallographically imposed
centrosymmetry (Fig. 1). The crystal structure consists of layers
where the sulfonamide atoms are involved in hydrogen bonding
networks. As shown in Fig. 2, the sulfonamide group is involved
in two hydrogen bonds (between O atoms of sulfonamide and nitro-
gen atoms) with symmetry-related molecules, building a two
dimensional network parallel to the bc-plane [N1ꢂꢂꢂO1i = 3.034(2),
N1—HꢂꢂꢂO1i = 177°, Symmetry codes: (i) x,1/2 ꢀ y,1/2 + z]. NAHꢂꢂꢂO
hydrogen bonding networks are the characteristic feature of other
structural studies of the sulfonamides [34,35]. The methyl group
was also allowed to rotate about its local threefold axis. One noticed
that S@O of the sulfonyl unit bond lengths are a bit longer and also
SAN and SAC bond lengths are shorter than in our previous struc-
ture [22].
2.6. Micro-dilution assays
Staphylococcus aureus ATCC 25923, Bacillus cereus RSKK 709,
Bacillus subtilis ATCC 6633, Escherichia coli ATCC 35218, Pseudomo-
nas aeruginosa ATCC 27853 and Yersinia enterocolitica O:3 cultures
were obtained from the Department of Biology at Gazi University
or the Refik Saydam Hygiene Center Culture Collection. Bacterial
strains were cultured overnight at 37 °C in Nutrient Broth. These
stock cultures were stored in the dark at 4 °C during the survey.
All tests were performed in a Nutrient Broth supplemented with
DMSO to a final concentration of 10% (v/v) to enhance their solubil-
ity. Test strains were suspended in the Nutrient Broth by adjusting
to the 0.5 McFarland standards. The compounds to be tested were
dissolved in DMSO to give the highest concentration (450
Before offering an explanation for the molecular structure of
[Cu(phen)2]L complex, the magnetic susceptibility and conductiv-
ity measurement were examined. The effective magnetic moment
of the complex (as Bohr Magneton: B.M.) was measured at room
l
g mLꢀ1), and serial dilutions thereafter in sterile 10 mL test tubes
containing nutrient broth to give sample concentrations of the
range 45–450
g mLꢀ1. The minimum inhibitory concentration
l
(MIC) values of compounds were determined using a modification
of the micro-well dilution assay method. 96 well plates were
prepared by dispensing 95
inoculums into each well. 100
prepared at 450
g mLꢀ1 concentration were added into the first
l
L of nutrient broth and 5
lL of the
Fig. 1. The molecular structure of mtsen with the atom-numbering scheme;
displacement ellipsoids are drawn at 40% probability level. The pairs of atoms C1/
C1i etc. are related by the crystallographic inversion center.
lL from test compounds initially
l

H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
119
Fig. 2. Unit-cell packing diagram of mtsen.
Fig. 3. The molecular structure of [Cu(phen)2]L.
temperature. The magnetic moment of the complex (2.06 B.M.) is
close to the spin value 1 for one unpaired electron and within
the general range for Cu(II) complexes [36].
For the conductivity measurement of complex, the molar con-
ductivity (Km) of 10ꢀ3 M solution in DMSO of the complex was
measured at 25 °C. The complex appears to be air stable, soluble
in DMSO and slightly soluble in acetonitrile. The experimental
conductivity value falls in the range of a 1:1 electrolyte [36,37]. An-
ionic ligand (L2ꢀ) is bonded out of the coordination sphere as
counter ion.
A lot number of Cu(II) complexes of related N-substituted
sulfonamides have been reported [36–43]. Also, structural infor-
mation about the deprotonated sulfonamide group conformation
has been obtained too. The consequence of these studies offers that
the copper atom is located on a twofold axis and is tetracoordinat-
ed by the four nitrogen atoms of two bidentate 1,10-phenanthro-
line molecules in [Cu(phen)2]++ cationic complex. Unusually, the
sulfonamidate anions are not coordinated to Cu(II). Ligand does
not interact with the metal ion and behaves as a counterion in
complex.
From the results of related references, elemental analysis, mass
spectrum, magnetic susceptibility, conductivity measurement as
well as infrared spectrum (the interpretation is given after the
vibrational spectral analysis of ligand), the molecular structure of
[Cu(phen)2]L is presented in Fig. 3.
Table 2
The experimental bond lengths (Å), bond and torsion angles (°) together within the
calculated data for mtsen.
Bond lengths (Å)
Experimental
B3LYP/6-311G(d,p)
SAO(2)
SAO(1)
SAN(1)
SAC(6)
N(1)AC(8)
C(7)AC(6)
C(7)AC(2)
C(6)AC(5)
C(8)AC(8)
C(2)AC(3)
C(2)AC(1)
C(5)AC(4)
C(4)AC(3)
1.432 (2)
1.437(2)
1.623(2)
1.761(2)
1.470(2)
1.384(3)
1.390(3)
1.393(3)
1.509(3)
1.392(3)
1.500(4)
1.377(3)
1.377(3)
1.459
1.461
1.694
1.796
1.468
1.389
1.394
1.394
1.527
1.402
1.509
1.394
1.390
Bond angles (°)
O(2)ASAO(1)
O(2)ASAN(1)
O(2)ASAC(6)
O(1)ASAN(1)
O(1)ASAC(6)
SAN(1)AC(8)
SAN(1)AH(1 N)
C(8)AN(1)AH(1 N)
C(6)AC(7)AC(2)
SAC(6)AC(7)
119.2(1)
106.0(1)
109.1(1)
108.0(1)
106.5(1)
118.6(1)
115.4(1)
113.0(2)
119.9(2)
118.8(2)
119.6(2)
121.7(2)
109.6(2)
118.1(2)
120.0(2)
121.9(2)
118.1(2)
120.9(2)
120.6(2)
121.6(2)
121.2
104.3
109.5
110.6
107.4
117.6
107.0
114.1
119.9
118.8
119.2
121.9
109.0
118.2
120.9
120.7
118.2
121.7
120.3
121.4
SAC(6)AC(5)
3.2. Geometry optimization results
C(7)AC(6)AC(5)
N(1)AC(8)AC(8)
C(7)AC(2)AC(3)
C(7)AC(2)AC(1)
C(3)AC(2)AC(1)
C(6)AC(5)AC(4)
H(009)AC(5)AC(4)
C(5)AC(4)AC(3)
C(2)AC(3)AC(4)
The optimized geometric parameters (bond lengths, angles and
torsion angles) calculated at B3LYP/6-311G(d,p) are listed with
experimental findings form XRD results in Table 2. In general
calculated geometric parameters seem to an agreement with exper-
imental findings except SAN(1) bond length and SAN(1)AH(1 N)
bond angle. Except the mentioned geometric parameters due to
intermolecular hydrogen bonding between the NAhydrogen and
the one of the sulfonyl oxygen (NAHꢂꢂꢂO), the largest difference be-
tween experimental and theoretical values was found to be
0.027 Å for bond lengths and 2.6° for bond angles. Possible differ-
ences could be due to the fact that while experimental findings in
the solid phase were obtained at very low temperature and so the
molecular rotations were restricted, the theoretical results were ob-
tainedfor a singlemoleculein the gasphase withoutany intermolec-
ular interactions. As a result, the optimized geometric parameters
Torsion angles (°)
O(2)ASAN(1)AC(8)
O(2)ASAN(1)AH(1 N)
O(2)ASAC(6)AC(7)
O(2)ASAC(6)AC(5)
O(1)ASAC(6)AC(7)
N(1)ASAC(6)AC(7
N(1)ASAC(6)AC(5)
168.4
29.7
31.6
ꢀ150.5
161.5
ꢀ82.9
95.0
161.3
31.2
37.8
ꢀ141.4
171.2
ꢀ72.3
108.5

120
H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
obtained at B3LYP/6-311G(d,p) show excellent agreement with the
experimental values.
in-plane or out-of plane bending vibrations are masked by other
strong vibrational modes.
The CAH asymmetric stretching vibrations of the CH3 group are
seen between 2975 cmꢀ1 and 2936 cmꢀ1, while the Raman active
CAH symmetric band is located around 2928 cmꢀ1. The symmetric
alkyl CAH stretching band of the CH2 group is observed around
2888 cmꢀ1 with weak intensity. The other fundamental CH3 and
CH2 group vibrations which are asymmetric or symmetric CH3
bending, CH2 wagging, CH2 twisting, CH3 rocking and CH2 rocking
3.3. Vibrational spectral analysis
Mtsen consists of 44 atoms, so it has 126 normal vibrational
modes and it is belong to the point group C1 with only identity
(E) symmetry operation. It is difficult to offer an explanation for
the vibrational assignments of title compound in the observed
vibrational spectra due to its low symmetry. Hence, the assign-
ment of bands was made taking into consideration the literature
data for compounds containing appropriate structural fragments
[18–20,22,44–53]. All the experimental and theoretical vibrational
data are tabulated in Table 3; see also Table S2 (Supporting
information) for the description of all vibrational modes. The
experimental FT-IR, dispersive Raman spectra of mtsen and com-
parison with the calculated spectra are given in Figs. 4 and 5. The
far-infrared spectrum is also presented in Fig. 6.
appear in the expected wavenumber region of 1459–760 cmꢀ1
.
3.3.3. CAC vibrations
The aromatic carbon–carbon stretching vibration occurs in the
region 1625–1430 cmꢀ1. In general, the bands are of variable
intensity and observed at 1468–1583, 1625–1590, 1590–1575,
1540–1470, 1460–1430 and 1380–1280 cmꢀ1 from the wavenum-
ber ranges given by Varsanyi [56] for the five bands in the region.
In the present work, the wavenumbers observed in the FT-IR spec-
trum at 1603, 1563, 1470, 1223 cmꢀ1 and in the Raman spectrum
at 1598, 1580, 1222 cmꢀ1 were assigned to aromatic CAC stretch-
ing vibrations.
3.3.1. NAH vibrations
The NAH stretching vibration of secondary amine groups of
some aliphatic or aryl sulfonamides occurs in the region 3300–
3200 cmꢀ1 [15,44,45]. The strong bands at 3238 cmꢀ1 (FT-IR) and
3241 cmꢀ1 (Raman) are assigned to the NAH stretching mode of
mtsen. On the other hand, this strong mode is split in the Raman
spectrum of crystalline mtsen with weak intensity at 3294 cmꢀ1
3.3.4. S@O vibrations
The SO2 asymmetric and symmetric stretching vibrations ap-
pear in the range 1330 30 cmꢀ1 and 1160 30 cmꢀ1, both with
high intensity [57,58]. The most intense signals appearing at
1332 cmꢀ1 and 1326 cmꢀ1 (IR) and the weak intense signal at
1314 cmꢀ1 (Ra) are attributed to the SO2 asymmetric modes. The
and 3239 cmꢀ1
.
symmetric
The splitting of the
crystal or solid state effects [18,23,49].
m
SO2 stretching vibration is observed at 1151 cmꢀ1
SO2 asymmetric bands could be attributed
.
The NAH in-plane bending vibration is expected near
1400 cmꢀ1 [15,18,20,44,47–49]. This vibration is usually masked
by the strong intense band of CH3 asymmetric bending or SO2
asymmetric stretching. However, weak intense infrared active
bands at 1419 cmꢀ1 and 1379 cmꢀ1 are assigned to NAH in-plane
bending vibration due to having with more contribution according
to PED results of related modes.
m
The SO2 scissoring and wagging vibrations occur in the range
570 60 cmꢀ1 and 520 40 cmꢀ1 [57]. The corresponding bands
are observed 587 cmꢀ1 and 468 cmꢀ1 in the FT-IR spectrum,
respectively. The infrared active band at 230 cmꢀ1 and Raman ac-
tive band 229 cmꢀ1 are attributed to the SO2 twisting vibrations
from the PED results of modes 19 and 18.
The calculated PED contribution (cNAH; 27%) and infrared
intensity of mode 36 suggest that sole infrared active medium
band in Nujol at 644 cmꢀ1 is the fundamental band of out-of-plane
bending vibration of NAH. But this band is masked by CAS stretch-
ing vibration in the FT-IR spectrum of crystalline mtsen. This
fundamental band is also observed above 600 cmꢀ1 with respect
to relevant literature data [18,20,45,49]. Another NAH out-of-pane
bending mode, both infrared and Raman active, is observed
3.3.5. SAN and CAS vibrations
The SAN stretching vibration exhibits a moderate band in the
range 905 70 cmꢀ1 [57]. This vibration typically occurs a medium
band in the IR spectrum and a weak band in the Raman spectrum
[57,58]. The infrared studies of some methanesulfonamide [46],
arylsulfonamides [44] and n-(substituted phenyl)-methanesulf-
onamides derivatives [45] are also assigned in the region of
940–836 cmꢀ1, 924–906 cmꢀ1 and 926–833 cmꢀ1. The bands at
890 cmꢀ1 (IR), 889 cmꢀ1 (Raman) and the other at 799 cmꢀ1 (IR)
are attributed to SAN stretching modes.
between 523 cmꢀ1 and 527 cmꢀ1
.
The splitting wavenumber differences between experimental
NAH vibrational bands are around 40–129 cmꢀ1. These downward
shifts offer that there is intermolecular hydrogen bonding by the
NH moiety of mtsen.
The assignment of the band correspond to CAS stretching vibra-
3.3.2. CAH vibrations
tions in different compounds is difficult. However, mCS band of
The hetero aromatic structures show the presence of CAH
stretching vibrations in the region 3100–3000 cmꢀ1 which is the
characteristic region for the ready identification of CAH stretching
vibrations. In this region, the bands are not affected appreciably by
the nature of substituents [54–56]. The modes 123 and 119 are due
to CAH stretching of hydrogen bonded carbon atoms of phenyl
ring. These modes are pure CAH stretching vibrations contributing
nearly 100% from the PED results.
some methanesulfonamide [46] and n-(substituted phenyl)-
methanesulfonamides [45] derivatives in solid phase have been
recognized in the region 789–740 cmꢀ1. The calculations suggest
that this fundamental band is masked by CH2 rocking mode.
However, the PED result of mode 43, the medium intense infrared
active band observed at 664 cmꢀ1 is attributed to
mCS vibration.
3.3.6. CAN vibrations
The aromatic CAH in-plane bending modes of benzene and its
derivatives are observed in the region 1300–1000 cmꢀ1 with a
weak intensity in the vibrational spectra [54,56]. The CAH out-
of-plane bending vibrations occur in the range 1000–750 cmꢀ1 in
the aromatic compounds [54,56]. The sole infrared active bands
observed at 760 cmꢀ1 are assigned to aryl CAH out-of-plane
bending vibrations from the pure PED outcomes of modes 47.
The computations suggest that the expected other bands of CAH
The assignments of the CN stretching wavenumbers were made
straightforwardly from analogy with 1,2-diaminoethane [51–53].
The vibrational results from pertinent references, the bands be-
tween 878 and 1100 cmꢀ1 are commonly ascribed to the conform-
ers of 1,2-diaminoethane displaying a gauche orientation around
the NCCN dihedral angle [51,53]. However, Batista de Carvalho
et al. [53] are reported the band above 1100 cmꢀ1 in the Raman
spectrum of 1,2-diaminoethane (in solid phase) which confirms

H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
121
Table 3
The vibrational assignments of the mtsen molecule by normal mode analysis based on SQM force field calculations.
Mode Experimentala
Assignment
B3LYP/6-311G(d,p)
PED (potential energy distributions)e
Descriptions (%)
d
d
IR(Nujol) IR(Crystal) R(Solid) R(Crystal) mc
IIR
IR
126
125
NAH stretch
NAH stretch
2 ꢄ m103
no
3294 vw
3239 w
3155 vw
3258 21.93
3224 24.91
752
1624
m
m
(N1AH) (100)
(N1AH) (100)
3238 s
3241 s
3241 s
3155
vw
123
119
114
CAH stretch (aromatic)
CAH stretch (aromatic)
CAH3 stretch (asym.)
3073 vw
sh
3057
mw
3073 vw
sh
3057 w
3066 3.71
3047 12.69
2976 16.31
2182
2768
1408
m
m
m
s(C4,5AH)R2 (99)
as(C3,4,5AH)R2 (98)
as(CH3)R1 (100)
3063 s
no
3064 m
2975 w
2966 w
2975
2975 vw
vwa
112
111
110
CAH3 stretch (asym.)
CAH3 stretch (asym.)
CAH3 stretch (sym.)
2966 m
2951 15.45
2951 14.91
2900 20.81
1747
1670
4175
m
m
m
as(CH3)R2 (100)
as(CH3)R1 (97)
s(CH3)R1 (100)
2936 wb
2927 w
shb
2936 w
2927 w sh
109
108
CAH3 stretch (sym.)
CAH2 stretch (sym.)
2926 s
2887 w
sh
2928 m
2889 w
sh
2898 20.31
2883 30.59
4545
1699
m
m
s(CH3)R2 (100)
s(C8AH2) (100)
2888 wb
2872 wb
2888 w
2872 w
107
CAH2 stretch (sym.) or
2851 35.18
1263
m
s(C8AH2) (97)
m97 + m93
105
103
100
97
96
93
C@C stretch
C@C stretch
C@C stretch
CAH3 bend (asym.)
CAH3 bend (asym.)
NAH bend (ip.)
1603 vw
1577 vw
1469 sb
1454 sb
1603 w
1563 w
1470 s
1454 s
1601 w
1578 w
1598 w
1580 w
1620 10.08
1596 0.47
1478 17.01
1450 17.44
1441 7.14
1418 25.89
1054
1153
227
302
738
m
m
m
(CC)R2 (78)
(CC)R2 (80)
(CC)R2 (49) + d(CH)R2 (37)
das(CH3)R2 (67) +
das(CH3)R2 (99)
m(C6AC7)R2 (6)
1458 w
1459 vw
1419 wb
1379 wb
1419 w
1379 w
266
d(N1AH) (33) +
(8) + das(CH3)R2 (7)
d(NH) (49) + (C8AH2) (22)
(CH2) (45) + d(N1AH) (15)
as(SAO2) (69)
as(SAO2) (61) +
mas(C3,6AC4,7)R2 (9) + mas(S1AO2)
91
90
87
84
80
79
NAH bend (ip.)
CH2 wag
SAO2 stretch (asym.)
SAO2 stretch (asym.)
CH3 bend (sym.)
CACH3 stretch
1403 75.72
1381 1.40
1342 7.31
1321 152.49 382
1277 90.09
1215 7.71
257
957
205
x
1377 m
1313 w
1378 w
1314 w
x
m
m
1332 vsb 1332 vs
1326 vsb 1326 vs
1304 vsb 1304 vs
m
(CC)R1 (23)
97
492
umb(CH3) (35) +
x
(CAH)methylene (25) + d(NH) (7)
1223 m
1223 m
m
as(C2ACH3) (32) + d(C3,7AH)R2
(15) + s(C3AC2AC7)R2 (12)
as(C2ACH3) (32) + s(C3AC2AC7)R1
m
78
CACH3 stretch
1222 m
1222 m
1214 4.88
1475
m
m
(16) + d(C3,7AH)R1 (15)
77
74
73
70
68
CAH2 twist
1176 m
1176 m sh 1172 m
1151 m
1151 vs
1171 w
1151 m
1195 3.76
1142 93.74
1133 233.37 229
1098 23.12
1081 45.01
263
1712
tw(CH2) (72) + d(NH) (11)
SAO2 stretch (sym.)
SAO2 stretch (sym.)
CAN stretch
m
m
m
m
s(SAO2) (81)
s(SAO2) (79)
s(CN) (72) + ds(CCN) (7)
s(CCC)ar (41) + d(C7AH)ar (13) + ms(SAO2)
1152 vs
1100 m
1088 s
1100 s
1088 s
1111 m
1110 w
419
374
C@C@C stretch (sym.)
(8) +
as(CN) (67) +
(CH3)R1 (68) +
(CH3)R2 (68) +
m
(C8AN1) (5)
66
62
61
56
52
CAN stretch
CAH3 rock
CAH3 rock
CAH bend (op./aromatic) 932 w
SAN stretch
1065 vs
997 w
1065 vs
996 m
1060 w
999 vs
891 m
857 w
1059 vw
999 vs
889 w
1069 118.56 1308
m
q
q
m
(CC)methylene (4)
994
991
923
883
5.67
2.57
0.33
67.91
2038
2920
100
m
m
s(C2AC3AC4)R1 (11)
s(C2AC3AC4)R2 (11)
933 w
890 s
c
m
(CH)R2 (90)
s(SN) (36) +
890 s
2529
m
(C2ACH3)R1 (7) +
m
(C6AS)
s(C3AC2AC7)R2 (12) +
s(CS) (16) + s(SN)
(7) +
m(CC)methylene (5)
51
50
CACH3 stretch
CACH3 stretch
860 w
852 w
859
842
56.37
9.77
720
487
m
s(C2ACH3)ar (23) +
m
mas(CS)
(16) +
m
m
(SAN1) (8)
834 vw
m
s(C2ACH3)ar (19) +
m
m
(13) +
s(C3AC2AC7)R2 (8)
(C8AH2) (12) +
(SAN1) (23)
49
48
47
45
43
41
40
39
36
SAN stretch
CAH2 rock
CAH bend (op./aromatic) 763 w
C@C@C bend (op.)
CAS stretch
NAH bend (op.)
SAO2 scissor
792 m
785 m
799 w sh
782 m
760 w
692 vs
664 m
644 m
587 vs
807
794
788
692
683
621
595
579
533
112.33 236
m
as(SN) (33) +
q
m
(C2ACH3)R1 (4)
(C2ACH3)R2 (5)
no
785 vw
695 m
89.10
31.44
38.24
25.92
57.20
1098
274
1209
224
q
(CH2) (56) + m
c
c
m
c
(C3,4,5AH)R2 (85)
(CCC)R2 (80)
(C6AS) (34) +
(N1AH) (27) + sci(SAO2) (19) + m(SAN1) (15)
693 s
656 m
no
694 s
c
(CCC)R2 (29) +
m
2507
585 s
593 w
574 w
523 m
595 w
575 w
525 w
342.74 619
sci(SAO2) (38) +
c
(N1AH) (23)
CASAN bend (op., asym.)
NAH bend (op.)
17.49
88.20
307
886
c
as(C6ASAN1) (36) +
c
(CCC)R1 (3)
527 w
527 w
c
(N1AH) (29) +
x
(SAO2) (14) + c(CCC)R1
(8) +
m
(C2ACH3)R1 (3)
(C2ACH3)R1 (22)
(SO2) (38) + das(CCN) (12)
das(O1SN) (12) + (CC)R2 (8) + m(SAN1) (4)
d(CarACH3)R1 (33) + tw(SO2) (15)
d(CarACH3)R2 (26) + ds(O1SN) (10) + m(C6AS) (3)
34
33
30
27
26
24
C@C@C bend (ip., sym.)
SO2 wag
O@SAN bend (ip., asym.) 441 vw
Ring-CH3 bend (ip.)
Ring-CH3 bend (ip.)
Ring-CH3 bend (ip.)
515 vw
467 s
513 w
468 s
441 vw
414 w
490 vw
485 vw
510
488
447
392
385
318
49.09
21.76
29.93
0.94
12.16
0.91
1040 ds(CCC)R1 (50) + m
117
257
333
166
916
x
s
414 w
374 w
417 w
336 w
300 w
421 vw
331 w
300 w
d(CarACH3)R2 (24) +
(14) + (C8AN1) (12)
as(C6ASAN1) (34) +
tw(SAO2) (30) + (CCN) (12) +
s(CCN) (18) +
(CC)methylene (28) + (SAN1) (17)
(SO2-ring) (43) + (C8AN1AS1) (10)
m(C6AS1) (17) + ds(O2SC6)
s
23
19
18
15
11
CASAN bend (op., asym.) 309 m
SAO2 twist
SAO2 twist
CAC torsion
SO2–Ring torsion
309
244
212
168
131
0.94
2.77
1.29
0.60
2.23
1033
596
c
m
(C6AS) (21) + d(CarACH3)R2 (15)
(C6AS1) (6)
s(CN) (13) +
230 vw
x
m
229 vs
161 m
no
229 m
155 vw
133 w
1969 tw(SO2) (27) +
c
m
ms(SN) (13)
1498
4635
s
s
s
127 w
s
(continued on next page)

122
H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
Table 3 (continued)
Mode Experimentala
Assignment
B3LYP/6-311G(d,p)
PED (potential energy distributions)e
Descriptions (%)
d
d
IR(Nujol) IR(Crystal) R(Solid) R(Crystal) mc
IIR
IR
10
9
CANAS torsion
CANAS torsion
89 w
80 w sh
93
83
2.12
2.03
1507
1431
s
s
(CNS) (42) +
(C8AN1AS) (21) +
(CCN) (8)
(CCN) (56) + (CNS) (20)
(CH3)R2 (95)
s
(SO2-R1) (9) +
s
(CC) (4)
(C6ASAN1)
s
(SO2-R2) (16) + s
(11) +
s
s
s
8
6
CACAN torsion
CAH3 torsion
58 w
35 vw
64
31
4.51
0.35
493
2781
s
a
vs: very strong, s: strong, m: medium, w: weak, vw: very weak, sh: shoulder, br: broad, no: not observed, asym.: asymmetric, sym.: symmetric, ip.: in-plane, op.: out-of-
plane and IR: infrared and R: Raman.
b
The infrared active vibrational wavenumbers are obtained in hexachloro-1,3-butadiene.
Wavenumbers scaled by SQM FF methodology according to our scale factors (See the text).
I: intensity, IR: infrared and R: Raman. The relative intensities of the simulated spectra were obtained after using the pure Lorenzian band shapes with a band with
c
d
10 cmꢀ1
.
e
R1: ring1, R2: ring2, ar: aromatic,
m: bond stretching, d: in-plane angle bending, c: out-of-plane angle bending, umb: umbrella bending, sci: scissoring, tw: twisting, x:
wagging,
q
: rocking, : torsion, as: asymmetric and s: symmetric. PED less than 3% are not shown.
s
Fig. 5. The dispersive Raman spectra of mtsen: (a) non-crystalline, (b) single
crystalline and (c) calculated.
seen from Table 3, the computed wavenumbers are great agree-
ment with the experimental ones. This agreement tends to us make
more reliable vibrational assignment of title compound. The skele-
tal vibrations, such as OASAN asymmetric in-plane bending,
ring-CH3 in-plane bending, SO2 twist and torsional vibrations are
undoubtedly assigned.
Fig. 4. The FT-IR spectra of mtsen: (a) single crystalline, (b) in Nujol, (c) in
hexacholoro-1,3-butadiene and (d) calculated.
3.4. Comparison of the characteristic vibrations of the ligand and
complex
the trans skeletal arrangement around the CAC axe. Hence, in the
present investigation, the bands at 1100 and 1065 cmꢀ1 (IR), 1110
and 1059 cmꢀ1 (Ra) is assigned to the fundamental CAN stretching.
Infrared spectra support the structure of the [Cu(phen)2]L com-
plex by the determination of the coordination modes. The changes
in the characteristic vibrations of the ligand were compared with
complex. Before comparison, the experimental FT-IR spectrum of
[Cu(phen)2]L is given in Fig. 7.
3.3.7. Skeletal vibrations
The low wavenumber region generally gives more qualified
information about the conformational behaviors of the compounds
[23,26,53]. Computational wavenumbers in this region (below
600 cmꢀ1) are sensitive than high wavenumber region. As clearly
The strong intense
tNH band of free ligand was observed around
3238 cmꢀ1 in Nujol solution and 3241 cmꢀ1 in crystalline phase, but

H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
123
3.5. NMR spectra
The experimental13C and 1H NMR chemical shifts (ppm) together
within the calculated data for mtsen in DMSO-d6 are given in Table 4.
It is well-known that symmetric C and H atoms in the compounds
show the same chemical shift due to having same chemical environ-
ment. Considering the chemical environment, mtsen shows eight
different carbon atoms in 13C NMR spectrum (Fig. 8a). The two peaks
observed at 42.20 ppm and 20.80 ppm are attributed to protons of
H2AC8 and H3AC1, respectively. The other six peaks between
140.15 ppm and 123.53 ppm are assigned to aromatic carbon pro-
tons. In Fig. 8b, aromatic proton peaks were also observed at about
7.54–7.46 ppm. The experimental NAH protons shift (4.34 ppm)
showed poor correlation with the calculated proton shifts
(7.64 ppm). The reason of this correlation is the NAH protons have
intra- or intermolecular hydrogen bonding [23]. The Heteronuclear
Chemical-Shift Correlation (HETCOR) and Correlation Spectroscopy
(COSY) spectrum of mtsen in Fig. 8c and d were also confirmed the
1H NMR spectrum.
Fig. 6. The far-infrared spectrum of mtsen.
3.6. Antibacterial bioassay
Mtsen and [Cu(phen)2]L compounds were screened in vitro for
their antibacterial activity against three Gram-negative (Esche-
richia coli, P. aeruginosa and Y. enterocolitica) and three Gram-posi-
tive species ( S. aureus, Bacillus subtilis and Bacillus cereus) of
bacterial strains by the microdilution and agar-disk diffusion
method. The antimicrobial activity of mtsen and [Cu(phen)2]L
compounds with dilution method are tabulated in Table 5. As seen
from the table, compounds showed overall a remarkable activity
against E. coli, Y. enterocolitica, B. cereus and S. aureus bacterial
strains. In addition, [Cu(phen)2]L compound shows higher antibac-
terial activity than ligand molecule. The highest activity with the
lowest MIC value of [Cu(phen)2]L compound is against the Gram
negative bacteria E. Coli and Y. enterocolitica.
Fig. 7. The FT-IR spectrum of [Cu(phen)2]L.
Table 4
The experimental 13C and 1H NMR chemical shifts (ppm) together within the
calculated data for mtsen in DMSO-d6.
Assignment
Experimentala
B3LYP/6311++G(d,p)b
C6
C2
C3
C4
C7
C5
C8
C1
HAC7
HAC5
HAC3
HAC4
HAN1
H2AC8
H3AC1
140.15
138.89
133.04
129.03
126.60
123.53
42.20
143.80
140.96
134.47
130.01
127.11
123.49
42.71
20.36
7.91
7.85
7.74
7.73
4.34
The inhibition zones formed by standard antibiotics (ciprofloxa-
cin, Penicillin and Ampicillin) against all bacteria are reported in
Table 6. The results were compared with those of the standard drugs.
All compounds exhibited significant activity than Penicillin and
Ampicillin for all Gram-negative and Gram-positive bacterial strains.
20.80
7.55 s
7.51 d
7.49 s
7.46 d
7.64 s
2.74 s
2.38 s
4. Conclusion
2.66
2.46
In the present work, we were performed experimental and the-
oretical vibrational, NMR and XRD analyses of msen, for the first
time. The molecular geometric parameters, vibrational wavenum-
bers, infrared and Raman intensities of the title molecule in the
ground state were calculated by using B3LYP method with
6-311G(d,p) basis set. A complete vibrational analysis was also
performed according to our frequency scale factors which were
firstly used in our last study within the SQM-FF method based on
the same theory level. The great match between experimental
and calculated vibrational wavenumbers and intensities of each
vibrational mode enables us to safely assign the fundamental
bands. Some fundamental bands in the vibrational spectra such
as NAH in-plane bending, SO2 asymmetric stretching, CAN stretch-
ing, SAN stretching and NAH out-of-plane bending bands are split,
which can be attributed to solid state effects or caused by the inter-
molecular hydrogen bonding between the NAhydrogen and the
one of the sulfonyl oxygen. To confirm the hydrogen bonding in
liquid state, 1H and 13C chemical shifts were calculated at B3LYP/
6-311++G(d,p) theory level and were compared with experimental
values. The observed and the calculated isotropic chemical shifts
are found to be in good agreement with the exception of NAH
protons shift. The reason of this discrepancy can be shown due
to the intermolecular hydrogen bonding.
a
s: Singlet and d: doublet.
b
r
Transform into d using equations given in Ref. [23]; d13C = 175.7–0.963 13C
r
and d1H = 31.0–0.970
r
1H.
it disappeared by the chelation through the amide nitrogen in the
complex. This observation indicates deprotonation of the amide
group. The asymmetric and symmetric SO2 bands did not show sig-
nificant shifts with respect to those of ligand, in spite of deprotona-
tion of the amide group [36–43]. In the FT-IR spectra of the complex
the vibration of the imine nitrogen bond (C@N) of the stretching
band of the phenanthroline rings shifts from 1644 cmꢀ1 to
1585 cmꢀ1 by the complexation which causes a great need for the
oscillation of the bonds in the ring. And as the electron clouds of
the CAN bonds flow to the phenanthroline rings, making the elec-
tron density around the CAN bonds decreased, the stretching vibra-
tion of the CAN bond in complex shifts to low wavenumber region.
And also, the CAH out-of-plane bending vibrations of the phenan-
throline ring were shifted in the 855 cmꢀ1 and 715 cmꢀ1 as com-
pared with coordination compound in the 863 cmꢀ1 and 723 cmꢀ1
because of due to take part in between ligand and Cu(II) [36,59].

124
H. Alyar et al. / Journal of Molecular Structure 1028 (2012) 116–125
Fig. 8. The NMR spectra of mtsen in DMSO-d6: (a) 13C, (b) 1H, (c) HETCOR and (d) COSY.
Table 5
Antimicrobial activity of mtsen and its Cu(II) complex with microdilution method.
Compound
MIC (lg/mL)
Escherichia coli ATCC
35218
P. aeruginosa ATCC
27853
Y. enterocolitica
O:3
Bacillus cereus RSKK
709
Bacillus subtilis ATCC
6633
S. aureus ATCC
25923
mtsen
[Cu(phen)2]L 60
80
120
100
80
60
80
80
240
120
100
80
Table 6
Result of the antimicrobial test of mtsen and its Cu(II) complex disk potency 70
l
g.
Compound
Diameter inhibition zone (mm, 70 lg/disk)
Escherichia coli ATCC
35218
P. aeruginosa ATCC
27853
Y. enterocolitica
:3
Bacillus cereus RSKK
709
Bacillus subtilis ATCC
6633
S. aureus ATCC
25923
mtsen
[Cu(phen)2]L 25
Ciprofloxacin 36
Penicillin
23
24
26
–
–
–
18
20
–
–
–
16
22
26
8
20
23
–
–
–
18
20
29
8
17
11
Ampicillin
13
14
<10: Weak; >10: moderate; >16: significant.
Further analyses were also made for [Cu(phen)2]L complex by
using elemental analysis, LC–MS, magnetic susceptibility; conduc-
tivity measurement and FT-IR. The comparison of the characteris-
tic experimental vibrations of the ligand and complex along with
the structural agreement from the magnetic susceptibility and
conductivity measurement data led us to understand the molecu-
lar structure and coordination about the complex. The structure
of complex is proposed as a tetragonal geometry.
The biological activity of two compounds screening indicated
that complex has more activity than ligand against the tested bac-
teria. However, two compounds exhibited significant activity than
standard antibiotic drugs Penicillin or Ampicillin.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.molstruc.2012.06. 046.
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