N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure, thermal behavior and computational studies

Article abstract of DOI:10.1016/j.molstruc.2019.127414

A new dithiocarbamate molecule, named as N-benzoyl-S-(undecyl)-dithiocarbamate (C₁₉H₂₉NOS₂), was synthesized and characterized by ¹HNMR, ¹³CNMR, FT-IR spectroscopic methods. X-ray analysis of the crystal structure of title compound showed the presence of triclinic space group with a = 4.2417 (8) ?, b = 20.010 (4) ?, c = 27.959 (6) ?, Z = 4, V = 2338.9 ?3. Detailed investigation of molecular packing of the molecule indicated the presence of intermolecular hydrogen bond between C1–H1?S4ⁱ and C24–H24?S2^v that generates R₂ ² (10) motifs, and intermolecular hydrogen bonds between N1–H111?S4ⁱⁱ and N2–H222?S2^iv atoms that forms R₂ ² (7) rings. Thermal properties of the title compound were investigated by thermogravimetric analysis (DTA/TG) and differential scanning calorimetry (DSC). Molecular electrostatic potential (MEP), the HOMO and LUMO energies and thermodynamic parameters of the title compound were calculated using density functional theory (DFT) with B3LYP/6-311G (d,p) level.

Full text of DOI:10.1016/j.molstruc.2019.127414

Journal of Molecular Structure xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization,
X-ray single crystal structure, thermal behavior and computational
studies
,
, **
Fatma Aydın a *, N. Burcu Arslan b, Kadir Aslan c
a Department of Chemistry, Faculty of Arts and Sciences, Çanakkale Onsekiz Mart University, 17100, Çanakkale, Turkey
b Department of Computer Education and Instructional Technology, Faculty of Education, Giresun University, 28200, Giresun, Turkey
c Morgan State University, School of Engineering, Department of Civil Engineering, 1700 East Cold Spring Lane, Baltimore, MD, 21251, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A new dithiocarbamate molecule, named as N-benzoyl-S-(undecyl)-dithiocarbamate (C19H29NOS2), was
synthesized and characterized by 1HNMR, 13CNMR, FT-IR spectroscopic methods. X-ray analysis of the
crystal structure of title compound showed the presence of triclinic space group with a ¼ 4.2417 (8) Å,
b ¼ 20.010 (4) Å, c ¼ 27.959 (6) Å, Z ¼ 4, V ¼ 2338.9 Å3. Detailed investigation of molecular packing of the
molecule indicated the presence of intermolecular hydrogen bond between C1eH1/S4i and C24
eH24/S2v that generates R22 (10) motifs, and intermolecular hydrogen bonds between N1eH111/S4ii
and N2eH222/S2iv atoms that forms R22 (7) rings. Thermal properties of the title compound were
investigated by thermogravimetric analysis (DTA/TG) and differential scanning calorimetry (DSC). Mo-
lecular electrostatic potential (MEP), the HOMO and LUMO energies and thermodynamic parameters of
the title compound were calculated using density functional theory (DFT) with B3LYP/6-311G (d,p) level.
© 2019 Published by Elsevier B.V.
Received 17 May 2019
Received in revised form
11 November 2019
Accepted 12 November 2019
Available online xxx
Keywords:
Dithiocarbamate
X-ray structure determination
HOMO and LUMO analysis
Molecular electrostatic potential
Thermal properties (DTA/TG/DSC)
1. Introduction
cadmium (II), and mercury (II) [16,17]. Furthermore, DTCs are
employed in medicinal chemistry in cancer therapy [18e21], as
Dithiocarbamate (DTC) derivatives are a class of pesticides, and
are widely used as agrochemicals, such as, ziram, thiram, ferbam,
maneb, zineb, mangozeb etc. for protecting crops against fungal
diseases [1e5]. DTCs are also used as organic intermediates in the
synthesis of thiazoles [6e8] and metal sulfide nanoparticles [9],
additives in rubber industry [10], vulcanization accelerators [11].
Recently, DTCs have also been used as protection groups in peptide
synthesis [12], linkers for the formation of self-assembled mono-
layers [13] and in the synthesis of ionic liquids [14]. Dithiocarba-
mate ligands used in coordination chemistry has generated a large
collection of crystallographic data for metal-dithiocarbamato de-
rivatives and they have been used in wide range of applications
such as medicine, industry and agriculture [15]. DTC derivatives
containing sulfur (i.e. N, N0-dialkyldithiocarbamate) are used for
the selective removal of heavy metals, such as, copper (II), lead (II),
pesticides agrochemicals [22] and as reagents in analytical chem-
istry [23,24]. In the last decade, some gold (III)-dithiocarbamato
derivatives as potential anticancer agents have been designed and
tested by research groups [25]. New coumarin derivatives bearing
dithiocarbamate moiety has been synthesized and used as anti-
microbial agents [26].
In the present study, a new aroyl dithiocarbamate was synthe-
sized via the reaction of benzoyl isocyanate and 1-undecanethiol
(Scheme 1), and characterized by elemental analysis (CHNS), FT-
IR, UVevis, 1H NMR, 13C NMR measurements. Single crystal
structural property was studied by experimental X-ray diffraction
method. The thermal behavior of the title compound was investi-
gated by thermogravimetric and differential thermal (TG/DTA)
analysis and differential scanning calorimetric (DSC) analysis.
Theoretical calculations for the molecular electrostatic potential,
the HOMO and LUMO energies and thermodynamic parameters of
the title compound were carried out using DFT with B3LYP/6-311G
(d,p) level. The UVevisible spectra of title compound were used for
investigation of electronic transitions, and the optical band gaps
(Eg, eV) values for the title compound in different solvents were
calculated from electronic absorption spectra.
* Corresponding author.
** Corresponding author.
E-mail addresses: faydin@comu.edu.tr (F. Aydın), kadir.aslan@morgan.edu,
aslakad@iit.edu (K. Aslan).
https://doi.org/10.1016/j.molstruc.2019.127414
0022-2860/© 2019 Published by Elsevier B.V.
Please cite this article as: F. Aydın et al., N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure,
thermal behavior and computational studies, Journal of Molecular Structure, https://doi.org/10.1016/j.molstruc.2019.127414

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F. Aydın et al. / Journal of Molecular Structure xxx (xxxx) xxx
Scheme 1. Synthesis pathway of the title compound.
2. Experimental section
acetone (15 mL) was added dropwise to the benzoyl isothiocyanate
and refluxed with stirring for 2 h. When the reaction was
completed, the solution was poured into a beaker containing some
ice. The yellow oil product was separated and washed with distilled
water. After drying under vacuum, recrystallized from tetrahydro-
furan to give the product. Mp: 52e53 ꢁC, Yield 86%. Elemental
analysis for C19H29NOS2: calculated, (%): C: 64.91, H: 8.31, N: 3.98, S:
18.24, O: 4.55; Found, (%): C: 64.72, H: 8.32, N: 4.07, S: 18.35, O:
4.54.
2.1. Material and methods
Benzoyl chloride, potassium isocyanate, 1-undecanethiol,
acetone, tetrahydrofuran was purchased from Sigma-Aldrich,
Merck Chemical. All commercial reagents were used without
further purification. Melting point of the title compound was
determined on Electrothermal 9100® apparatus. Reactions during
the synthesis of the title compound were monitored by thin-layer
chromatography (TLC) on silica-gel 60 F254 plates (Merck) and an
UV lamp. Elemental analysis was conducted on a LECO-932 CHNS
analyzer. FT-IR analysis was performed by using a PerkinElmer
Spectrum 100FT-IR instrument with an ATR apparatus in the range
2.3. X-ray crystallography
A single crystal of title compound was grown by slow evapo-
ration of the solution of products in tetrahydrofuran. Diffraction
data of it was collected at Bruker APEX-II CCD diffractometer using
4000-650 cmꢀ1 1HNMR and 13CNMR spectra were recorded on a
.
Bruker AVANCE DPX NMR spectrometer operating at 400 and
101.6 MHz, respectively, using TMS as an internal standard and
DMSO‑d6 as solvent. UVevisible measurements were carried out
with a PerkinElmer WinLab-25 series spectrophotometer in quartz
cells of 1 cm path length. SETERAM LABSYS evo 1600 was used for
DTA/TG analysis of the title compound.
MoKa radiation. The crystal structure was solved and refined by
SHELXS-97 and SHELXL-97 programs, respectively [27,28]. The
refinement was carried out by full-matrix least-squares method on
the positional and anisotropic temperature parameters of the non-
hydrogen atoms, or equivalently corresponding to 416 crystallo-
graphic parameters. All non-hydrogen atoms were refined aniso-
tropically, whereas hydrogen atoms were located geometrically and
refined as riding with respective CeH distances of 0.93 ꢁA, 0.96 ꢁA
and 0.97 ꢁA corresponding to the aromatic, methylene and methyl
CeH bonds. The atomic numbering scheme with displacement el-
lipsoids of the crystal structure drawing with ORTEP III was
depicted at the 30% probability level for clarity (Fig. 1).
2.2. The synthesis of the N-Benzoyl-S-(undecyl)-dithiocarbamate
Benzoyl chloride (0.700 g, 5 mmol) was added slowly to dry
acetone solution (20 mL) containing potassium thiocyanate
(0.485 g, 5 mmol). A mixture was refluxed with stirring for 30 min
After then, a solution of 1-undecanethiol (0.940 g, 5 mmol) in
Fig. 1. ORTEP III diagram of title compound.
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3
2.4. Computational studies
organic solvent (THF, CH3CN and DMSO) in the range of
300e600 nm (Fig. 2), where. two bands were observed. The high-
density bands at 340, 344 and 348 nm for THF, CH3CN and DMSO
The molecular structure of title compound was optimized using
DFT in the ground state by B3LYP [29] method with the 6-311G (d,p)
[30] basis sets included in Gaussian 09 program [31]. Molecular
structure of the title compound optimized by 6-311G (d,p) basis set
displayed frontier molecular orbitals, and electrostatic potential
were simulated. In addition, thermodynamic parameters (i.e., heat
capacity, enthalpy and entropy values) for the title molecule were
calculated.
solvents, respectively, are due to the transition
p /p * of the
nitrogen-carbon-sulfur (-N-C]S) group on dithiocarbamate moi-
ety conjugated with benzoyl. It also appears as a shoulder on the
transition n/p* localized on sulfur connected with undecyl moi-
ety observed at 408, 411 and 415 nm. Optical band gaps (Eg, eV)
value from the electronic absorption spectra of the title compound
in different solvents were calculated for these transitions and the
2
optical energy were determined from the (
energy (h
ah
y)
versus photon
is the ab-
y
) graph using Tauc equation [36], where
a
3. Results and discussion
sorption coefficient (Fig. 3). From the value of Tauc equation, for the
title compound in THF, CH3CN and DMSO, the band gaps corre-
3.1. FT-IR and NMR spectral studies
sponding to n-
respectively.
p* transitions were calculated 3.59, 3.55 and 3.51 eV,
The IR spectra of the title compound showed significant ab-
sorption of the carbonyl group at 1697 cmꢀ1 y (C]O) and the amide
DFT (B3LYP) calculations and energy levels of the HOMO-1,
HOMO and LUMO, LUMOþ1 orbitals was used for determine the
low-lying excited states of compound [37,38]. Energy difference
HOMO-1, HOMO and LUMO, LUMOþ1 were calculated as 6.5769,
6.2841 and 2.2201, 1.1649 eV, respectively (Fig. 4). Large HOMO-
LUMO gap energy value of 4.064 eV indicates that the title com-
pound is in steady state. Fig. 4 also showed that the electronic
density on the HOMO of the title compound was localized primarily
on dithiocarbamate skeleton and carbonyl group, whereas the
LUMO orbital of it was localized on dithiocarbamate skeleton along
the phenyl ring and its amide group due to intramolecular charge
transfer. Energy level of LUMO, which is related to the electron
affinity, implies that the title compound is susceptible to nucleo-
philic attacks [39].
group at 3313 cmꢀ1
(
y
NeH), respectively. Vibration bands with the
wave numbers of 3055 and 3050 cmꢀ1
CeH, AreH) and 1553 and
1502 cmꢀ1
(y
(y C]C) were observed as the result of the vibration of
phenyl ring. The frequencies of 2955, 2918 and 2850 cmꢀ1 and
1250 cmꢀ1 were assigned to the stretching vibrations (CeH) and
(CeC) in undecyl moiety, respectively [32]. The dithiocarbamate
compounds exhibit a characteristic band in the range (1580-1450)
cm-1 assignable to the y
(CeN) [33]. Additional bands at 1431 cmꢀ1
(y
ꢀCOeN) and 1207 cmꢀ1 (NꢀCS) were observed. The band of
747 cmꢀ1
(y C]S) was attributed to thiocarbonyl group (C]S)
symmetric stretching vibration [34,35] (Fig. S1).
1H NMR and 13C NMR spectra for title compound are shown in
Figs. S2 and S3 (Supplemental Materials). 1H NMR spectra exhibits
all expected resonances for (ꢀCeOeNH) and (ꢀCeSeCH2ꢀ)
groups at 12.65 ppm and 3.20 ppm, respectively. The 1H NMR signal
for NeH proton of amide or thioureide moiety due to the resonance
with the carbonyl (C]O) and thiocarbonyl (C]S) groups shifted
downfield to about 12.65 ppm, while that NeH appeared at about
~8.00 ppm. Three signals were appeared at 7.53 (d, 2H), 7.66 (m,1H)
and 7.94 (d, 2H) for phenyl protons. In addition, the title compound
has an undecyl moiety and aliphatic protons were assigned at 1.68
(2H, m), 1.40 (2H, m) 1.25 (16 H, m) and 0.86 (3H, t) ppm.
In the 13C NMR spectra of the title compound, aromatic proton
signals were appeared in the region 133.0, 131.8, 128.7 and
128.4 ppm for phenyl moiety. Functional groups in the structure of
aroyl dithiocarbamate derivative were confirmed with at 204.6
d
(C]S), 165.3
d
(C]O), 35.9
d
(SeCH2ꢀ), 13.9 ppm
d
(ꢀCH3) and
(ꢀCH2)nꢀ) within range of
d (31.3e22.1) ppm for title compound,
respectively (Scheme 2).
3.2. Electronic spectral studies and HOMO-LUMO analysis
High chemical reactivity, more polarizability and the transfer of
charge within a molecule are associated with the frontier orbital
gap (i.e., energy gap between HOMO and LUMO). The UVeVis
spectra of the title compound were recorded in different polarity
Fig. 2. UVevis spectra of title compound in THF, CH3CN and DMSO solvents.
Scheme 2. 1H and 13C NMR chemical shifts of the title compound in DMSO‑d6.
Please cite this article as: F. Aydın et al., N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure,
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F. Aydın et al. / Journal of Molecular Structure xxx (xxxx) xxx
Fig. 5. Molecular electrostatic potential map calculated at B3LYP/6-311þþG (d,p)level
for title compound.
potential: red and blue represent the regions of the most negative
and positive electrostatic potential whereas green represent the
regions of zero potential. As seen in Fig. 5, the negative regions
(from red to yellow) are placed around the oxygen and sulfur atoms
and it is shown the polar head (hydrophilic) such as dithiocarba-
mate, carbonyl group. The less positive regions (greenish) are
placed around all aliphatic and aromatic carbon and hydrogen
atoms and it is shown the long nonpolar groups (hydrophobic) of
phenyl and undecyl moiety. These calculations predict that
hydrogen bonds are located on medium region of molecule.
Fig. 3. A plot of (
and DMSO solvents,
a
h
y
)
2 versus photon energy (h
a: the absorption coefficient.
y) of the title compound in THF, CH3CN
3.3. Molecular electrostatic potential (MEP)
3.4. X-ray properties
Molecular electrostatic potential is used for relative reactivates
toward electrophilic attack and nucleophilic reactions, for a mole-
cule, plays an important role in determining the electron acceptor
and donor sites. MEP also shows the electron cloud distributions for
hydrophilic and hydrophobic groups of a molecule. MEP was
assessed using the B3LYP/6-311G (d,p) method to investigate the
reactive sites of title compound (Fig. 5). In MEP surface, different
colors are represented by different values of the electrostatic
N-Benzoyl-S-(undecyl)-dithiocarbamate is crystallized in the
triclinic form with space group P-1 by two symmetric molecules in
asymmetric unit with Z ¼ 4 in the unit cell. The title compound
consists of dithiocarbamate, carbonyl group, phenyl ring and its
amide group and contains an undecyl moiety as hydrophobic
group. Molecular packing diagrams of the title compound are dis-
placed along a-axis in Fig. 6. Because of the functional groups of the
Fig. 4. Frontier molecular orbitals diagram for the title compound.
Please cite this article as: F. Aydın et al., N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure,
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F. Aydın et al. / Journal of Molecular Structure xxx (xxxx) xxx
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Table 1
Crystal data, data collection and refinement parameters for the title compound.
Crystal data
Chemical formula
Mr
C19H28NOS2
350.54
Crystal system, space group
Temperature (K)
a, b, c (Å)
Triclinic, P-1
296
4.2417 (8), 20.010 (4), 27.959
(6)
a
,
b
,
g
(ꢁ)
82.422 (6), 86.478 (6), 84.577
(6)
2338.9 (8)
4
V (Å3)
Z
Radiation type
MoKa
No. of reflections for cell measurement
9907
3.0e28.1
0.23
q
range (ꢁ) for cell measurement
m
(mmꢀ1
)
Crystal shape
Block
Crystal size (mm)
0.19 ꢂ 0.17 ꢂ 0.14
Data collection
Diffractometer
Absorption correction
Tmin, Tmax
BrukerAPEX-II CCD
Multi-scan
0.676, 0.746
No. of measured, independent and observed
87167, 9171, 5101
[I > 2
Rint
(sin
s
(I)] reflections
0.070
0.617
q
/
l
)max (Åꢀ1
)
Refinement
R [F2 > 2 (F2)], wR (F2), S
No. of reflections
No. of parameters
H-atom treatment
s
0.156, 0.526, 1.31
9171
416
H-atom parameters
constrained
w ¼ 1/[ 2(Fo2) þ (0.1249P)
s
2 þ 30.6399P]
where P ¼ (Fo2 þ 2Fc2)/3
0.341
1.42, ꢀ0.43
(
D
/
s
)max
Drmax, Drmin (e Åꢀ3
)
Computer programs: BrukerAPEX2, BrukerSAINT, SHELXT 2014/4 (Sheldrick, 2014),
SHELXL2016/6 (Sheldrick, 2016).
3.5. Thermodynamic properties
The statistically thermodynamic parameters such as standard
heat capacity of constant pressure (Cp), enthalpy (H) and entropy
(S) were calculated using the B3LYP/6-311G (d,p) method in ground
state by increasing from 100 K to 900 K in gas phase. The results are
shown in Fig. 7 and Table S1. Fig. 7 shows that Cp, S and the H of the
title compound increase from 100 K to 900 K, which is caused by
the rise of molecular vibration intensity with the increasing tem-
perature [40]. Quadratic formulas were used to fit the correlation
equations between different parameters heat capacity, enthalpy,
entropy and temperature, R being the corresponding fitting factor
(R2) for these thermodynamic parameters. The corresponding
fitting equations for title compound are as presented below:
Fig. 6. A partial view of the crystal packing of title compound, showing the linear
arrangement built from (a) NeH …. S- and (b) CeH …. S- hydrogen bonds. The
hydrogen bonds are shown as dotted lines.
title compound, b-axis and c-axis (20.010 and 27.959 Å, respec-
tively) are larger than the a-axis (4.2417 Å) in the crystal di-
mensions. Crystallographic data and the details of X-ray diffraction
study of the title compound is shown in Table 1, whereas selected
bond lengths and bond angles is compiled in Table 2.
Cꢁp;m ¼ ꢀ 11; 3366 þ 0; 3045 T ꢀ 1; 4282x10ꢀ5 T2ðR2
ꢀ
The benzamide moiety of the title compound has a closely
planar configuration and the maximum deviation from the mean-
plane belongs to O1 oxygen atom with 0.267 Å. The undecyl
group twists slightly due to the consistent of dithiocarbamate
group. The torsion angle values about this twist are ꢀ4.4ꢁ on C7/N1/
C8/S1 atom group and 178.7ꢁ on N1/C8/S1/C9 atom group.
Detailed investigation of molecular packing of the molecule
indicates the intermolecular hydrogen bond C1eH1/S4i and
C24eH24/S2v generates R22 (10) motifs. In addition, intermolecular
¼ 0; 9973
ꢀ
Sꢁm ¼ 56; 5472 þ 0; 2633 T ꢀ 5; 5547x10ꢀ5 T2ðR2 ¼ 0; 9991
D
H0m ¼ ꢀ 3; 95915 þ 0; 0309 T þ 6; 2975x10ꢀ5T2ðR2
ꢀ
¼ 0; 9978
hydrogen
bonds
occur
between
N1eH111/S4ii
and
The thermogravimetric measurements and calculations clearly
N2eH222/S2iv atoms to form R22 (7) rings.
show that the high temperature phase of title compound is
Please cite this article as: F. Aydın et al., N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure,
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F. Aydın et al. / Journal of Molecular Structure xxx (xxxx) xxx
Table 2
Hydrogen-bond geometry (Å, ꢁ).
DdH$$$A
DdH
H$$$A
D$$$A
DdH$$$A
C1eH1/S4i
0.93
0.86
0.96
0.86
0.93
0.96
2.89
2.70
2.77
2.72
2.91
2.81
3.777 (14)
3.534 (9)
3.647 (18)
3.546 (9)
3.792 (14)
3.665 (19)
160.5
162.6
151.5
162.5
158.9
148.3
N1eH111/S4ii
C19eH19A$$$O2iii
N2eH222/S2iv
C24eH24/S2v
C38eH38A$$$O1vi
Symmetrycodes: (i) xþ1, y, z; (ii) xþ2, y, z; (iii) x, yꢀ1, z; (iv) xꢀ2, y, z; (v) xꢀ1, y, z;
(vi) x, yþ1, z.
Fig. 8. Thermo analytical (TG/DTA) curves of title compound.
Fig. 7. Correlation graph of calculated thermodynamic properties and temperatures
for the title compound.
thermally unstable and final decomposition stars at about 200 ꢁC
for compound [41,42]. All the theoretical parameters can be helpful
information for the new synthesis of like title compound or thio-
carbamate derivatives.
Fig. 9. Differential scanning calorimetric graphs of title compound.
is thermally stable up to 184.08 ꢁC [43].
3.6. Thermal analysis
4. Conclusions
Fig. 8 shows the TG and DTA curves of obtained crystal of the
title compound. The DTA curve showed three endothermal peaks.
The first sharp peak at 53.2 ꢁC is a significant endothermic peak
corresponding to the melting of the crystal. At the melting point no
weight loss was observed in the TG curve. The first decomposition
step of the compound was observed in the temperature range
198.1e228.0 ꢁC and the approximate weight loss was 17.53%. Above
this temperature, a second weight loss of 71.02% (Calc. 70.14%)
occurred in the range 292e331 ꢁC which indicates elimination of
Synthesis, experimental and theoretical characterization of a
new dithiocarbamate molecule, called N-benzoyl-S-(undecyl)-
dithiocarbamate was reported. X-ray analysis revealed that the title
compound crystallizes in the triclinic space group P-1, with cell
parameters a ¼ 4.2417 (8) Å, b ¼ 20.010 (4) Å, c ¼ 27.959 (6) Å,
a
¼ 82.422 (6) ꢁ,
b
¼ 86.478 (6) ꢁ,
g
¼ 84.577 (6) ꢁ and V ¼ 2338.9 Å3.
The presence of intermolecular N…HS, N/HO, C/HO, and C/HN
hydrogen bond interactions was confirmed via experimental and
theoretical studies. Molecular electrostatic potential surface
parameter of the title compound was good agreement with the
predicted hydrogen bonds. The energy gap between the HOMO-
LUMO orbital for the title compound was calculated to be
4.064 eV. Electronic absorption spectra for the title compound was
predicted from DFT calculations and were compared to experi-
C
12H24NS2$. The second decomposition step, which also includes
the first-thermal degradation step is observed at Tmax ¼ 318.5 ꢁC for
the DTA peak. After this at around 458 ꢁC, decomposition was about
100% leaving no residue in the crucible. The DSC curve of the
compound was obtained at a heating rate of 10 ꢁC/min under argon
atmosphere (Fig. 9). The melting point of the compound as can be
seen in the DSC curve was observed as a sharp endothermic peak at
about 50.33 ꢁC and the positive enthalpy value of 105.14 J g-1 at
50.33 ꢁC can be attributed to the energy absorbed during the
(endothermic) melting process. The lower point and sharpness of
DSC curve indicated that the compound had good crystallinity and
high purity. The degradation of the compound related with the
endothermic peak in the DSC curve was observed at 200.45 ꢁC with
mental UVevisible spectrum, which showed the presence of n-
p*
and * bands. The low melting point of the title compound is
p- p
predicted to be related to the large unit cell and the weak inter-
molecular H-bonding in the crystal structure of the molecule. TG/
DTA and DSC curves showed that the compound melted at a low
temperature (53.2 and 50.33 ꢁC, respectively). DTA of the title
compound showed that the decomposition was taken place in two
steps. Calculated frontier molecular orbital energies were
DН ¼ 99.12 J g-1. The DSC curve clearly indicates that the compound
Please cite this article as: F. Aydın et al., N-Benzoyl-S-(undecyl)-dithiocarbamate: Synthesis, characterization, X-ray single crystal structure,
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F. Aydın et al. / Journal of Molecular Structure xxx (xxxx) xxx
materials, Dalton Trans. 4 (2009) 607e609.
7
compared with the optical band gaps (Eg, eV) value from electronic
absorption spectra. Hydrophilic and hydrophobic groups of the
compound were also predicted from the molecular electrostatic
potential.
We hope that the synthesis, crystallographic and spectroscopic
characterization and DFT studies of N-Benzoyl-S-(undecyl)-dithio-
carbamate will be helpful for the synthesis of new
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Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work “N-Benzoyl-S-(undecyl)-dithio-
carbamate: synthesis, characterization, X-ray single crystal struc-
ture, thermal behavior and computational studies” reported in this
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Appendix A. Supplementary data
Supplementary data associated with this article can be found in
the online version, at https://doi.org/10.1016/j.molstruc.2019.
127414. These data include MOL file and InChiKeys of the most
important compounds described in this article.
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Author contributions
Fatma AYDIN: Investigation;Conducting a research and investi-
gation process, specifically performing the experiments, or data/
evidence collection, Visualization; Preparation (Experimental sec-
tion), creation and presentation of the published work, specifically
visualization/ data presentation, Writing- Review & Editing; Prep-
aration, creation and presentation of the published work by those
from the original research group, commentary or revision e
including pre-or postpublication stages; N. Burcu ARSLAN: Using
Software Programming (DFT with B3LYP/6-311G(d,p) level), X-ray
analysis and molecular structure determination; Kadir ASLAN:
Review & Editing;Preparation, creation and presentation of the
published work, Resources; Provision of study materials, reagents,
materials, Funding acquisition;Acquisition of the financial support
for the project leading to this publication.
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