Fourier Transform Infrared and Raman spectra, DFT: B3LYP/6-311G(d, p) calculations and structural properties of bis(diethyldithiocarbamate)copper(II)

Article abstract of DOI:10.1016/j.saa.2012.11.053

Theoretical and experimental bands have been assigned for the Fourier Transform Infrared (FT-IR) and FT-Raman spectra of the bis(diethydithiocarbamate)Cu(II) complex, [Cu(DDTC)₂]. The calculations and spectra interpretation have been based on the DFT/B3LYP method, infrared and Raman second derivative spectra, and band deconvolution analysis. To better assign the metal-ligand normal modes in the spectral region of low energy, the deviation percentage of the geometrical parameters was used, with values from the interpretation of the normal modes of L matrix. Results indicate a planar structure around the Cu(II) cation. The calculated infrared and Raman spectra, based on the proposed geometrical structure of the bis(diethyldithiocarbamate)copper(II) complex, agreed with the experimental spectra.

Full text of DOI:10.1016/j.saa.2012.11.053

Accepted Manuscript
Fourier Transform Infrared and Raman Spectra, DFT: B3LYP/6-311G(d, p)
Calculations and Structural Properties of bis(diethyldithiocarbamate)-Cop‐
per(II)
A.C. Costa, J.M. Ramos, C.A. Téllez Soto, A.A. Martin, L. Raniero, G.F. Ondar,
O. Versiane, L.S. Moraes
PII:
S1386-1425(12)01149-3
http://dx.doi.org/10.1016/j.saa.2012.11.053
SAA 9991
DOI:
Reference:
To appear in:
Spectrochimica Acta Part A: Molecular and Biomo‐
lecular Spectroscopy
Received Date:
Revised Date:
Accepted Date:
22 August 2012
12 November 2012
18 November 2012
Please cite this article as: A.C. Costa, J.M. Ramos, C.A. Téllez Soto, A.A. Martin, L. Raniero, G.F. Ondar, O.
Versiane, L.S. Moraes, Fourier Transform Infrared and Raman Spectra, DFT: B3LYP/6-311G(d, p) Calculations
and Structural Properties of bis(diethyldithiocarbamate)-Copper(II), Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy (2012), doi: http://dx.doi.org/10.1016/j.saa.2012.11.053
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

FOURIER TRANSFORM INFRARED AND RAMAN SPECTRA, DFT:
B3LYP/6-311G(d, p) CALCULATIONS AND STRUCTURAL PROPERTIES OF
BIS(DIETHYLDITHIOCARBAMATE)-COPPER(II).
3
,4
2
1
1
1
4
A. C. Costa Jr. , J. M. Ramos C. A. Téllez Soto *, A. A. Martin , L. Raniero , G. F. Ondar ,
,
4
2
O.Versiane , L.S. Moraes .
1
Laboratory of Biomedical Vibrational Spectroscopy, IP&D, Research and Development Institute – Universidade do
Vale do Paraiba (UNIVAP), Av.Shishima Hifumi, 2911, Urbanova, 12.224-000, São José dos Campos, SP. Brazil.
2
Instituto de Química, Departamento de Química Inorgânica. Universidade Federal do Rio de Janeiro,
CEP 21941909 Rio de Janeiro, RJ, Brazil
3
Departamento de Química Inorgânica, Instituto de Química, Universidade Federal Fluminense (UFF), Morro do
Valonguinho s/n, Niterói-Centro CEP 24210-150, RJ, Brazil.
4
Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro (IFRJ), Unidade de Rio de Janeiro, Rio de
Janeiro, RJ, Brazil.
ABSTRACT
Theoretical and experimental bands have been assigned for the Fourier Transform Infrared (FT-
IR) and FT-Raman spectra of the bis(diethydithiocarbamate)Cu(II) complex, [Cu(DDTC) ]. The
2
calculations and spectra interpretation have been based on the DFT/B3LYP method, infrared
and Raman second derivative spectra, and band deconvolution analysis. To better assign the
metal-ligand normal modes in the spectral region of low energy, the deviation percentage of the
geometrical parameters was used, with values from the interpretation of the normal modes of L
matrix. Results indicate a planar structure around the Cu(II) cation. The calculated infrared and
Raman
spectra,
based
on
the
proposed
geometrical
structure
of
the
bis(diethyldithiocarbamate)coppert(II) complex, agreed with the experimental spectra.
Keywords: bis(diethyldithiocarbamate)copper (II) complex, FT-Infrared and FT-Raman
spectra, DFT method.
(
*) Corresponding author: tellez@vm.uff.br

1
. INTRODUCTION
Copper complexes have been strongly associated from their wide range of biological
activity, including their potential use as antimicrobial, antiviral, anti-inflammatory, antitumor
agents, enzyme inhibitors, or chemical nucleases [1]. The works of C. H. Stier et al [2]., W. E.
Antholine [3], and L. A. Saryan [4] studied the reactions of bis(thiosemicarbazonato)copper (II)
complexes with tumor cells and mitochondria; the inhibition of tumor cell transplantability by
iron and copper complexes of 5-substituted 2- formyl pyperidine thiosemicarbazones; and a
comparative cytotoxix and biochemical effects of alpha-N- heterocyclic carboxaldehyde
thiosemicarbazones, respectively. In these studies the mechanism of copper(II) complexes in
their antitumor action involve inhibition of the enzyme ribonucleotide reductase, and according
to M. Karon et al. [5], also involve creation of lesions in DNA strands.
Due to the pharmacological activity of the thiosemicarbazides and thiosemicarbazones
[
6, 7] as well as the antitumor response of thiosemicarbazones, in which the Cu(II) complexes
have the greatest activity [8, 9], the 2-methylthiosemicarbazide copper (II) nitrate was
synthesized and a further structural study was carried out by Valdés-Martínez et al. [10].
However, the work of Valdés-Martínez contains no information about the vibrational spectra. A
vibrational analysis on the Ni(II) thiosemicarbazide complexes and their deutero isotopomers
was reported by Geetharani and Sathyamarayana [11], who, to simplify the normal coordinate
treatment, considered only half the structure of the complex Ni(Htsc) Cl , where Htsc means
2
2
thiosemicarbazide.
Téllez et al., [12] to elucidate tentative assignments of metal–ligand modes of
thiosemicarbazide complexes, did a structural study and a assignment of the normal vibrations
of 2-ethylthiosemicarbazide copper(II) nitrate, [Cu(MeTSC) (NO ) ] through the ab initio DFT:
2
3 2
pBP86/DN** procedure, and through normal coordinate analysis (NCA). In the vibrational
calculations, the elongated Cu-ONO2 bonds of the nitrate groups were considered in the C=S
and C=N tautomers of the complex. DFT calculations revealed that the infrared spectra can be
well interpreted through the C=N tautomer. The observed combination bands at 1763.0 and
-1
1
754.0 cm were an indication that the –NO groups act as monodentate ligands. Calculations
3
confirmed the experimental assignment of the infrared spectrum.
Although the [Cu(DDTC) ] complex belongs to a very important class of coordination
2
compounds, no conclusive structural, vibrational, and electronic study have been carried out.
Due to this lack of information, we propose for this complex a synthesis route analysis, based
on graphical method and complete spectroscopy study. The structural studies of the solid
powder were carried out by means of FT-IR and FT-Raman vibrational spectra as well as
quantum mechanical theoretical calculations.

2
. EXPERIMENTAL
.1. General
Copper(II) nitrate, sodium diethyldithiocarbamate trihydrate salt and HNO were
2
3
purchased from Vetec Co. All solvents and reagents were used as received without further
purification. Elemental analysis (CHN) was carried out in a Sinc EA 1110 analyzer. The
-1
infrared spectra between 4000 and 370 cm were measured as a KBr pellet and polyethylene
pellet at room temperature, on a Perkin Elmer 2000 FT-IR spectrometer. Data was collected
-1
-1 -1
with a resolution of 4 cm . Scanning speed 0.2 cm s and 120 scans were used. The Raman
-1
spectra between 4000 and 100 cm were measured of a solid sample at room temperature, on a
FT-Raman Bruker model RFS 100/S spectrometer. Data was collected with a resolution of 4
-
1
-1
cm and 120 scans were used. Source setting: laser of 9394.75 cm ; 500mW. Aperture setting:
7.0mm. The percentage of copper was determined by atomic absorption spectrometry using a
+
Perkin Elmer AAnalyst 100 spectrophotometer. The pH O control during the synthesis of the
3
complex was carried out with the potentiometer Micronal B 375.
2
.2. Synthesis of bis-diethyldithiocarbamate Cu(II)
A solution of diethyldithiocarbamate (5 mmol) in 50 mL of deionized water was stirred by 20
+
+
-1
minutes obtaining a pH O = 10. The pH O was adjusted to 6.5 with HNO3 6 mol.L . Then
3
3
+
cooper(II) nitrate (0.914 g, 5 mmol) was added to this solution and the pH O was maintained
3
around 6.5. This control was done using a potentiometer and all the synthesis was carried out
while stirring at room temperature. The agitation was maintained for ten minutes until the
formation of a green solid precipitate, which was then filtered under reduced pressure and
washed for three times with deionized water. [Cu(DDTC) ] solid was kept under vacuum in a
2
desiccator with sulfuric acid. Elemental analysis (CHN) and atomic absorption, for
C10H20N2S4Cu: Found C, 33.25%; N, 7.56%; H, 5.57%; and Cu, 17.42%. Calculated: C,
33.35%; N, 7.78%; H, 5.60%; and Cu, 17.65%.
2
. 3. Calculations
The calculations were carried out for the neutral complex, [Cu(DDTC) ], considered it as no
2
interacting independent units. For geometry optimization, the density functional theory method
B3LYP was used in the Gaussian 03 program [13]. For all calculations, we used the 6-311G(d,
p) basis set for all atoms. All calculations have been optimized from several initial geometries,

in order to guarantee the global minima energy structures in two symmetry groups, C and C ,
2
v
1
-3
with the complex with C1 symmetry being more stable by 2.6x10 Kcal/mol.
After this procedure, the vibrational calculations were performed. No imaginary mode was
observed. Characteristic normal stretching and bending modes from the –C H groups were
2
5
visualized using the graphical Chemcraft program [14]. The skeletal or framework normal
modes were determined using the percentage deviation of the geometrical parameters (PDPG),
from its equilibrium position.
3
3
. RESULTS
.1. General
Monosodium DDTC salt is easily prepared by treatment of carbon disulfide with
diethylamine in the presence of sodium hydroxide. This compound is a stable reagent in solid
state, but the most important property of this ion is its protonation in acid solution and
subsequent decomposition into carbon disulfide and protonated amine. The composition is
+
2+
favored when the pH O of the reactional mean is lower than pKa of the R’RNH ion. The pKa
3
of diethyldithiocarbamate acid derived from diethylamine is 3.95 in 19 °C [15]. Thus, the
+
synthesis must be performed in optimum pH O range between 5.0 and 7.5. This prevents the
3
decomposition of DDTC and the metal hydroxide formation. The definition of these optimal
+
conditions of synthesis was evaluated in different pH O conditions. These data were obtained
3
from the graphical method [16], presented in Figure 1S (supplementary material). The graph
+
shows the region of optimum pH O to perform the synthesis of the complex around 6.5. This
3
allowed us to obtain the complex with adequate yield and satisfactory purity.
The solid obtained after purification was characterized through typical bands of the ligand in the
-1
infrared region, as (C-H) stretching between 3000-2900 cm and (C=N) stretching between
-1
1
500-1400 cm , presented in Figure 1 for the IR and Raman spectra.
3
.2. Optimization of the geometrical parameters
Ab initio optimization of the geometrical parameters and the structural analysis of the
[
Cu(DDTC) ] complex were carried out employing the methods described above which are
2
similar to the works found in the literature [17-20]. The B3LYP theoretical values for the Cu-S,
C=N, and C-S bond lengths were of 2.36, 1.34, and 1.73 Å, without symmetry restrictions. The
bond angles S(8)-Cu-S(11) and S(9)-Cu-S(10) were 179.49° and 179.69°, respectively, which
deviated a little from the planar structure of the CuS framework. Calculated selected bond
4
lengths and bond angles for the C and C symmetries are given in Table 1. The complete
2v
1
structure of the [Cu(DDTC) ] complex is represented in Figure 2.
2

3
.3. Vibrational assignments
Vibrational assignments were carried out with support of Density Functional Theory
(
DFT) calculations using the B3LYP method with a 6-311-G(d, p) basis set having the structural
geometry obtained by the same method as the starting point. The calculated values for C and
2
v
C symmetry of the [Cu(DDTC) ] complex did not present imaginary frequencies and are
1
2
described in Table 2. The simulated IR and Raman spectra are found in Figure 2S
supplementary material).
For the discussion of the vibrational assignment, we took the DFT values corrected by
the scale factor of 0.9613 as a base for comparison [21] in all fundamental vibrational modes,
n-6 = 105. These adjusted data were associated with the second derivative spectrum and with
DBA of the infrared bands of the [Co(DDTC) ] complex. For an accurate description of the
(
3
2
normal modes in the metal-ligand spectral range, we use the percentage of deviation of the
geometrical parameters (PDGP) from the equilibrium position as described in others works [22-
25]. The PDGP can also be normalized to obtain the percentage of participation of each internal
vibrational coordinate that describes the framework vibrations, at all 26 coordinates (10
stretching and 16 bending).
Assuming C2v symmetry for the [Co(DDTC)
representation is vibrational = 28a + 25a + 25b + 27b
active in the infrared spectrum. Therefore, 105 vibrational modes are expected in the Raman
spectrum, from which 80 are infrared active (a , b and b ). The results with and without
2
] complex, the vibrational irreducible
1
2
1
2
, where a vibrational modes are not
2
1
1
2
symmetry were compatible with the experimental data. The intensity variations between
calculated and experimental FT-IR and FT-Raman results are related with the nature of the
experimental measure in the solid state and the calculations carried out in the vacuum,
neglecting molecular interactions.
3
.3.1. CH stretching
The [Cu(DDTC)2] complex has four –CH groups and four –CH groups totalizing 20
3
2
stretching (C-H) vibrational modes. The FT-IR spectrum of Figure 1(a) shows in the region
-1
between 3000 and 2800 cm-1 large bands with three peaks at 2982, 2931, and 2851 cm with
-1
shoulders at 2975, 2968, 2960, and 2871 cm . The Raman spectrum illustrated in Figure 1(b)
-1
has five well defined bands at 2974, 2966, 2934, 2892, and at 2872 cm . For both spectra, we
obtained the second derivative followed by DBA to achieve the maximum of observable bands.

Figure 3 shows eighteen fundamental bands in both spectra obtained by this procedure.
Calculated and experimental wave numbers of the –CH stretching are given in Table 2.
3
.3.2. C=N stretching
The C=N stretching bands were observed in the infrared and Raman spectra at 1510(IR,
-
1
R), 1506(IR), and 1504(R) cm , which were corroborated by the second derivative spectra, and
-1
DBA at 1510 (IR), 1514(R), 1506(IR), and 1504(R) cm (Figure 4). These bands were assigned
with aid of the calculated DFT vibrational spectrum. The comparison between calculated bands
without correction by scale factor and experimental values for the (C=N) stretching was
excellent. Calculations also showed that these modes are coupled modes among different
internal coordinates in which the scissoring mode (HCH)(CH ) participates in the normal mode
2
description.
3
.3.3. HCH bending
In general terms, the HCH bending vibrations are considered as characteristic
wavenumbers. In the infrared and Raman spectra, Figure 2 shows the region between 1492 and
-1
-1
1
069 cm , and two additional bands between 669 and 607 cm totalizing 30 bands with aid of
DBA; all of them are assigned to HCH bending and listed in Table 2. The rocking vibrations
-1
were found in the region between 1002 and 453 cm , also with the DBA support, and the
assignments are also presented in Table 2. A plot between bending and rocking experimental
vibrations versus the calculated modes give the following results: correlation coefficients R =
0
.9972, with SD = 24.56. The graphic representation between the calculated and experimental
bending vibrations obtaining with aid of the Origen 6 program [26] is depicted in Figure 5.
3
.3.4. Skeletal framework vibrations
The identification of the metal-ligand vibrations was not straightforward as we have
pointed out in other publications [22-25]. This is due to the higher mixture of the different
internal coordinates that take part in the description of the normal modes. Thus, we studied the
distorted geometry of each normal mode, observing the extension to which the equilibrium
configuration parameters are dislocated. This procedure helps us to assign the low-energy
bands, whose spectra are depicted in Figure 6.
In this approach, we used 10 stretching and 16 bending internal coordinates, which are inside of
the skeletal framework of the complex in the description of the normal modes. The results
presented below obey the following nomenclature: we wrote (exp.IR) in bold the experimental

observations in the infrared spectrum and (exp.R) the Raman spectrum. The Deconvolution
Band Analysis was written concisely as (DBA/IR; R). The abbreviation corr., means that the
calculated wave number by the DFT:B3LYP/6-311G (d, p) procedure was scaled by 0.9613.
The percentage (%) indicates the percentage variation of the bond lengths and bond angle.
Stretching, bending, and torsion internal coordinates are represented by the Greek letters , ,
and , respectively.




 corr. (a ), 451 corr. (a), 453(exp.IR), 454 (DBA/IR): (CS) 41.3% + (SCN)
2
39.9% + (CuSC) 15.5%.
430 corr.(a , a), 442 (exp.IR): (CuSC) 26.3% + (CS) 22.36% + (SCuS) 21.4% +
1
(SCN) 11.1% + (CuS) 8.8 % or (SC-SCu).
427 corr. (b , a), 435 (exp. IR): (CuSC) 28.9% + (CS) 17.0% + (SCuS) 12.7% +
2
(SCS) 10.9% + (CuS) 9.7% + (SCN) 9.6% or (CN-CS).
421corr. (a ), 420 corr.(a), 426 (exp. IR), 424 (exp. R), 424 (DBA/R): (SCuS) 27.2% +
1
(CuSC) 26.1% + (CS) 21.9% + (SCN) 9.0% + (SCS) 8.7 % or (CN-CS) ou (HC-
NC).






417 corr. (b ), 416 corr. (a), 419 (exp. IR), 419 (DBA/IR): (CuSC) 27.3% + (CS)
2
22.6% + (SCuS) 16.7%
351 corr. (a , a), 363 (DBA/IR), 364( exp. R; DBA/R): (CuSC) 27.5% + (CuS)
1
24.2% + (SCS) 19.6% + (SCN) 18.3%.
347 corr. (b , a), 357 (DBA/IR), 353( exp. R): (CuS) 31.6% + δ(CuSC) 20.7% +
2
as
(SCS) 18.2% + (SCN) 17.2 %.
310 corr. (b , a), 323 (DBA/IR), 329( exp. R; DBA/R): (CuS) 31.2% + (SCN) 27.7%
1
+
(CuSC) 22.9% + (CS) 9.8%.
298 corr. (a , a), 297( exp. R), 298( DBA/R): (SCN) 51.9% + (CS) 25.8% + (CuS)
2
16.2%.
293 corr. (b , a), 287 (DBA/IR): (CuS) 32.8% + (CuSC) 32.7% + (SCuS) 15.5% +
1

(CS) 9.6%.


280 corr. (a , a), 281 (DBA/IR): (SCN) 38% + (CuS) 25.8% + (CuSC) 26.3%.
2
244 corr. (b , a), 256 (exp.IR; DBA/IR), 251 (exp. R): (CuSC) 28.2% + (CuS)
2
25.8% + (SCuS) 22.6%.

227 corr. (b , a), 237 (R), 242 (DBA/R): (CuS) 30.4% + (CuSC) 26.5% + (SCuS)
1
19.7% + (SCN) 11.5% + (SCuS)linear 10.0%.

In the [Cu(DDTC) ] complex, we expected 4 main contributions of the Cu-S stretching
2
internal coordinates in the normal modes, and the above assignment shows that the principal
-1
-1
contributions of the (CuS) appears as  (CuS) at 353 (R) cm and at 323 (IR)/329(R) cm ,
as
-1
-1
and as  (CuS) at 287 (DBA/IR) cm and at 227 (DBA/R) cm . Figure 7 shows the
s
displacement vectors in the framework of the [Cu(DDTC) ] complex of these 4 vibrational
2
modes.
3.3.5. Torsional vibrations
The characterization of these torsional modes using the DFT results of the normal
modes was rather complicated. To obtain an approximate assignment of these normal modes,
we used the 3D computerized visualization. Eighteen torsional internal coordinates were defined
in [Co(DDTC) ]. From the infrared and Raman spectra, we were able to associate 16 bands of
2
weak intensity. All the torsional modes present coupling with other stretching and bending
internal coordinates whose descriptions are given in Table 2.
4
. CONCLUSIONS
Synthesis, elementary CHN analysis, infrared and Raman spectra of the [Cu(DDTC)2]
complex were presented. Theoretical calculations concerning structural analysis show a pseudo
planar framework structure for the CuS4 chromosphere. Vibrational assignments of bands in the
infrared spectrum of the [Cu(DDTC) ] complex have been done based on the DFT: B3LYP/6-
2
311G(d,p) quantum mechanical calculation. The most probable assignment for the skeletal
vibrations was based on the interpretation of the distorted geometry of the normal modes,
having as focus the study of the percentage of deviation of the geometrical parameters. The
results suggest the structure depicted in Figure 2 as the most probable, and the full assignment
for the complex is presented in Table 2.
Acknowledgments
We are grateful to the Brazilian agencies CAPES (PNPD) for financial support. Prof.
Téllez thanks the FAPESP for the grant of Visiting Professor at Laboratory of Biomedical
Vibrational Spectroscopy, IP&D, Research and Development Institute – UNIVAP. We also
acknowledge to Jefferson Robson Amorin da Silva and CSAAT team from IFRJ for the support
of this work.

Supporting Information Available:
Species distribution diagram for the [Cu(DDTC) ] synthesis, calculated infrared and
2
Raman spectra and band deconvolution analysis are available as supplementary material as a
PDF file at http://…
REFERENCES
1. I. Iakovidis, I. Delimaris, S. M. Piperakis, SAGE-Hindawi Access to Research Molecular
Biology International Volume 2011, Article ID 594529, 13 pages, doi:
10.4061/2911/504529.
2
3
4
. C. H. Chan-Stier, D. T. Minkel, D. H. Petering, Bioinorganic Chem. 6 (1976) 203-217.
. W. F. Antholine, J. M. Knight, D. H. Petering, J. Med. Chem. 19 (1976) 336-341.
. L. A. Saryan, E. Ankel, C. Krishanamurti, D. H. Petering, H. Elford, J. Med. Chem. 22
(
1979) 1218-1221.
5
6
7
. M. Karon, W. F. Benedict, Science 62 (1972) 178.
. S. Padhye, G, B, Kauffman, Coord. Chem. Ver. 63 (1985) 127.
. D. X. West, A. E. Liberta, S. D. Padhye, R. C. Chikate, P. B. Sonawane, A. S. kumbhar, R.
G. Yeraude, Coord. Chem. Rev, 123 (1993) 49.
8
9
1
1
1
. H. G. Petering, H. H. Burskirk, J. A, Crim, Cancer Res. 27 (1967) 1115.
. L. Tripathi, P. Kumar, A. K. Singhai, Indian Journal of Cancer, 44(2) (2007) 62-71.
0. J. Valdéz-Martínez, R. A. Toscano, J. Ramírez-Ortíz, Polyhedron 14(5) (1995) 579.
1. K. Geetharani, D. N. Sathyamarayana, Aust. J. Chem. 30 (1977) 1617.
2. J. M. Ramos, R. M. Viana, C. A. Téllez S., W. C. Pereira, A. O. Izolani, Spectrochim. Acta
Part A 65 (2006) 433-43.
13. Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.
Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N.
Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B.
Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B.
Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.
Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A.
Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D.
Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J.

B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox,
T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M.
W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople,
Gaussian, Inc., Wallingford CT, 2004.
1
1
1
4. Chemcraft
5. R. Zahradnik and P. Zuman. Collection Czech. Chem. Commun., 24 (1959) 1132.
6. H. Freiser, Q. Fernando. Ionic Equilibrium in Analytical Chemistry, John Wiley & Sons,
Inc., New York, 1963.
1
1
1
2
7. C. A. Téllez Soto, J. M. Ramos, R. S. Rianelli, M. C. B. V. Souza, V. F. Ferreira,
Spectrochim. Acta Part A 67 (2007) 1080-1087.
8. J. M. Ramos, O. Versiane, C. A. Téllez Soto, Spectrochim. Acta Part A 67 (2007) 1046-
1
054.
9. O. Versiane, B. L. Rodrígues, J. M. Ramos, C. A. Téllez Soto, Spectrochim. Acta Part A 65
2006) 1112-1119.
0. J. M. Ramos, G. F. Ondar, O. Versiane, C. A. Téllez Soto, Spectrochim. Acta Part A 71
2008) 1364-1370.
(
(
2
2
1. L. Radom, A. P. Scott, J. Phys. Chem. 100 (1996) 16502.
2. B. A. Almeida, J. M. Ramos, O. Versiane, M. Souza, C. A. Téllez Soto, A. L. R. Mercê, A.
S. Mangrich, Polyhedron 27 (2008) 3662-3668.
2
2
2
2
3. J. M. Ramos, O. Versiane, M. T. M. Cruz, A. C. Costa Jr., O. Versiane, C. A. Téllez Soto,
ScienceAsia 37 (2011) 247-255.
4. J. M. Ramos, O. Versiane, C. A. Téllez Soto, Spectrochim. Acta Part A 68 (2007) 1370-
1
378.
5. J. M. Ramos, O. Versiane, C. A. Téllez Soto, Spectrochim. Acta Part A 72 (2009) 182-
89.
6. Origen 6
1

FIGURE CAPTIONS
Figure 1. FT-IR and FT-Raman spectra of [Cu(DDTC) ] complex.
2
Figure 2. DFT:B3LYP/6-311G (d, p) calculated structure for the [Cu(DDTC)2] complex.
Cu(1), S(8, 9, 10, 11), C(2, 12), N(3, 13); C(4, 5, 6 ,7 ; 14, 15, 16, 17).
Figure 3. Band deconvolution analysis in the FT-IR and FT-Raman spectra in the region of the

(C-H) stretching.
-1
Figure 4. Infrared and Raman BDA in the region of 1550 – 1480 cm for the [Cu(DDTC) ]
2
complex.
Figure 5. Plot between calculated and experimental FT-IR and FT-Raman bending vibrations of
the –CH CH groups of the [Cu(DDTC) ] complex.
2
3
2
-1
Figure 6. FT-Raman and FT-infrared spectra in the region of 450 – 180 cm .
Figure 7. Skeletal normal modes in which the (CuS) stretching has principal contributions.

Figure 1
IR
Raman

Figure 2

Figure 3
Infrared
Raman

Figure 4
Infrared
Raman

Figure 5
1
1
1
1
600
400
200
000
8
6
4
00
00
00
4
00
600
800
1000
1200
1400
1600
Experimental FT-IR and FT-Raman bending and rocking
vibrations from -CH CH groups
2
3

Figure 6
Infrared

Table(s)
Table 1. Calculated parameters with B3LYP using 6-311G (d, p) base set for [Co(DDTC)
complex of C and C (in italic characters) symmetries.
2]
1
2v
Atoms
i,j
Bond
Lengths
Å)
Atoms
i,j, k
Bond angles
(°)
Atoms
i,j, k
Bond angles
(°)
(
R(1-8)
R(1-9)
R(1-10)
R(1-11)
R(2-3)
R(2-8)
R(2-9)
R(10-12)
R(11-12)
R(12-13)
2.36
2.36
2.36
2.36
1.34
1.73
1.73
1.73
1.73
1.34
A(8-1-9)
76.87/76.85
103.12/103.15 A(1-11-12)
179.49/179.48 A(3-2-8)
83.86/83.87
179.69/179.48 A(8-2-9)
103.13/103.15 A(10-12-11) 115.35/115.36
83.87/83.87
76.87/76.85
A(1-10-12)
83.86/83.87
83.86/83.87
122.32/122.32
122.32/122.32
115.35/115.36
A(8-1-10)
A(8-1-11)
A(1-8-2)
A(9-1-10)
A(9-1-11)
A(1-9-2)
A(3-2-9)
A(10-12-13) 122.32/122.32
A(11-12-13) 122.32/122.32
A(10-1-11)

-1
Table 2. Experimental FT-IR and DFT:B3LYP/6-311G (d, p) calculated spectra for [Cu(DDTC) ] complex (wavenumber in cm ).
2
Wncalc
Wncor
Wncalc
Wncor
(C
3007
112.0330 3007
WnExp
(%T)
DBA
(IR)
WnExp
DBA
Assigment
(*)
(*)
IIR
Symm
IIR
B3LYP (C )
(C2v
)
B3LYP (C1)
)
1
(R.Int.) (Raman)
(InternalCoordinate)
2v
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
128
128
123
123
108
108
105
105
099
099
093
093
061
061
054
054
041
041
038
0.0152
3007
a1
b2
a2
b1
a1
b2
b1
a2
a1
b2
a2
b1
a1
b2
a2
b1
a1
b2
b1
3128
3128
3123
3123
3108
3108
3105
3105
3099
3099
3093
3093
3061
3061
3054
3054
3041
3041
3038
0.0388




 (CH)(CH ) +  (CH)(CH )
as
3
as
2
112.0973 3007
 (CH)(CH ) +  (CH)(CH )
as
3
as
2
0.0000
4.9356
3002
3002
2988
2988
2985
2985
2979
2979
2973
2973
2943
2943
2936
2936
2923
2923
2920
0.1018
4.8266
3002
3002
 (CH)(CH ) +  (CH)(CH )
as
3
as
2
 (CH)(CH ) +  (CH)(CH )
as
3
as
2
20.5408
3.8266
20.3630
3.9471
2988 2982 (60)
2988
2986
2982
2982
2975

 (CH)(CH ) +  (CH)(CH )
s
3
as
2

 (CH)(CH ) +  (CH)(CH )
s
3
as
2
57.7897
0.0000
34.8113
22.6174
11.0919
20.9490
0.8795
2985 2975 (69)
2985

 (CH)(CH ) +  (CH)(CH )
s
3
as
2

 (CH)(CH ) +  (CH)(CH )
s
3
as
2
11.0945
21.0257
0.0000
2979
2974
2968
2961
2949
2936
2928
2920
2909

 (CH)(CH ) +  (CH)(CH )
as
3
as
2
2979 2968 (75)
2973 2960 (82)
2973
2967
2935

 (CH)(CH ) +  (CH)(CH )
as
3
as
2

 (CH)(CH ) +  (CH)(CH )
as
3
as
2
18.6790
42.8952
58.5765
0.0000
18.1366
42.8823
58.7554
0.0004

 (CH)(CH ) +  (CH)(CH )
as
3
as
2
2943 2931 (74)
2943

 (CH)(CH )
s
2

 (CH)(CH )
s
2
2936



 (CH)(CH )
as
2
1.3752
1.3761
2936
 (CH)(CH )
as
2
26.1619
67.0326
19.1638
26.2180
66.7842
17.3150
2923
 (CH)(CH )
s
3
2923
2897
2871
2892
2872

 (CH)(CH )
as
3
2920 2871 (86)

 (CH)(CH )
as
3

3
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
038
531
528
507
506
502
502
500
500
490
490
481
481
469
467
417
416
410
410
400
399
384
0.0000
2920
1472
a2
a1
b2
a1
b2
b1
a2
a1
b2
a2
b1
a2
b1
a1
b2
a1
b2
a2
b1
a1
b2
b1
3038
1531
1528
1507
1506
1502
1502
1500
1500
1490
1490
1481
1481
1469
1467
1417
1416
1410
1410
1400
1400
1383
1.7336
2920 2851 (93)

 (CH)(CH )
as
3
18.6832
18.6685
1471
1510 sh
1506 (8)
1510
1504
1492
1510
1501

s(C=N) + (HCH)(CH )
2 sciss.
401.3761 1469
1.0352 1449
117.9015 1448
399.8950 1469
0.9652 1449
118.8667 1448

as(C=N) + (HCH)(CH )
2 sciss.

(HCH)(CH ) +  (C=N)
3
s
1481

(HCH)(CH ) +  (C=N)
3
as
12.8420
0.0000
1.8325
0.1700
0.0000
0.1864
0.0000
10.3571
12.4810
1444
1444
1442
1442
1432
1432
1424
1424
1412
12.8901
0.0090
1.8159
0.1515
0.0701
0.1032
0.0004
10.4484
12.4098
1444
1444

(HCH)(CH ),(CH )
3
2
1458
1450
1437
1434
1429
1428
1381
1378
1375
1372
1360
1356
1352
1348
1341
1337

(HCH)(CH ),(CH )
3
2
1442 1461 (64)
1442 1451 (61)
1432
1463
1455

(HCH)(CH ),(CH )
3
2

(HCH)(CH ),(CH )
3
2

(HCH)(CH ),(CH )
3
2
1432 1437 (28)
1424 1430 (38)
1424
1437
1380

(HCH)(CH ),(CH )
3
2

(HCH)(CH ),(CH )
3
2

(HCH)(CH ),(CH )
3
2
1412

(HCH)(CH ) +  (C=N)
2
s
398.3510 1410
397.5080 1410 1378 (68)

(HCH)(CH ) +  (C=N)
2
as
30.1968
41.5286
0.0000
1362
1361
1355
1355
1346
30.2496
40.5054
0.1185
1362
1373
1358

(HCH)(CH ),(CH )
3
2
1361 1356 (61)

(HCH)(CH ),(CH )
3
2
1355
1355
1346

(HCH)(CH ),(CH )
3
2
13.1824
0.2021
13.0440
0.2405

(HCH)(CH ),(CH )
3
2
1347



(HCH)(CH ),(CH ) +  (C=N)
3
2
s
162.9902 1345
5.0926 1330
163.2854 1346
5.0686 1329
(HCH)(CH ),(CH ) +  (C=N)
3
2
as
(HCH)(CH ),(CH )
3
2

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
384
342
342
315
312
234
232
173
171
110
109
108
108
084
083
016
016
003
0.0000
42.8793
0.0000
2.0372
1330
1290
1290
1264
a2
b1
a2
a1
b2
b1
a2
a1
b2
a1
b2
b1
a2
b1
a2
a1
b2
b1
a2
b1
a2
a1
1383
1341
1341
1314
1311
1233
1231
1172
1171
1110
1109
1108
1108
1083
1083
1015
1015
1002
993
0.0119
42.1155
0.0001
2.0482
1329 1302 (64)
1289
1302
1300
1275
1273
1303
1278

(HCH)(CH ),(CH )
3
2

 (HCH)(CH ),(CH )
as
3
2
1289 1274 (21)
1263

 (HCH)(CH ),(CH )
as
3
2

(HCH)(CH ),(CH ) +  (C=N)
3
2
s
436.6179 1261
435.7347 1260
1260
1206

(HCH)(CH ),(CH ) +  (C=N)
3
2
as
88.1560
0.0000
0.9863
1186
1184
1128
88.3111
0.0003
0.9812
1185 1210 (48)
1209

(CNC) + (HCH)(CH ),(CH )
3
2
1183

(CNC) + (HCH)(CH ),(CH )
3
2
1127 1150 (47)
1150
1144
1098
1078
1075
1069
1150
1077
1002

(HCH)(CH ),(CH ) +  (C=N)
3
2
s
156.9911 1126
157.6833 1126

(HCH)(CH ),(CH ) +  (C=N)
3
2
as
10.6327
52.9251
38.5431
0.0000
15.6421
0.0000
1.0331
7.4451
53.9140
0.0000
26.8289
0.0000
0.2392
1067
1066
1065
1065
1042
1041
977
10.6328
53.7144
38.6088
0.0149
16.6342
0.0001
1.0505
7.7750
52.9928
0.0001
27.0298
0.0001
0.2292
1067 1098 (74)

(HCH)(CH ),(CH )
3
2
1066 1077 (61)

(HCH)(CH ),(CH )
3
2
1065
1065
1041

(HCH)(CH ),(CH ) +  (CN)
3
2
as

(HCH)(CH ),(CH ) +  (CN)
3
2
as

(CH3)
(CH3)
(CH3)
(CH3)
1041
976
976
963
955
882
879
821
999 (59)
917 (74)
998
987


977
981
910

964
914

(NCS) + (CCS) + (CN)
s
9
93
17
14
54
955

(NCS) + (CCS) + (CN)
as
9
882
917
892
884



(CH3)
(CH3)
9
8
879
914
821
854
846 (64)
848
(CH ) + (CH )
3
2

8
7
7
53
84
84
54.4758
0.0000
4.0213
820
754
754
b2
a2
b1
853
784
784
54.3409
0.0002
4.0372
820
754
754
781 (83)
786
778
783
682


(CH ) + (CH )
3
2
(CH ) + (CH )
3
2

(CH ) + (CH )
3
2


(HCH)(CH3)wagging +
(HCH)(CH2)twisting
7
7
80
80
0.0335
750
750
a1
b2
780
780
0.0323
750
750
669 (96)
607 (95)
669
607




(HCH)(CH3)wagging
+
14.7467
14.6932
(HCH)(CH2)twisting
6
6
5
5
4
19
17
70
69
71
0.9758
1.3370
0.2985
12.9039
16.0580
595
593
548
547
453
a1
b2
a1
b2
b1
619
617
570
568
471
0.9733
1.4210
0.3072
12.9886
16.1496
595
593
548
546
453
595 (95)
573 (85)
500 (92)
470 (97)
459 (97)
595
572
500
478
466
595
574
500
488
463

(CH ) + (CH ) + (CN)
3
2

(CH ) + (CH ) + (CN)
3
2

(CH ) + (CH )
3
2


(CH ) + (CH )
3
2
(CH ) + (CH )
3
2

(CS) 41.3% + (SCN) 39.9% +
(CuSC) 15.5%
(CuSC) 26.3% + (CS) 22.36% +
(SCuS) 21.4% + (SCN) 11.1% +
(CuS) 8.8 % or (SC-SCu)
(CuSC) 28.9% + (CS) 17.0% +
(SCuS) 12.7% + (SCS) 10.9% +
(CuS) 9.7% + (SCN) 9.6% or
(CN-CS)
(SCuS) 27.2% + (CuSC) 26.1% +
(CS) 21.9% + (SCN) 9.0% +
(SCS) 8.7 % or (CN-CS) ou
(HC-NC)
(CuSC) 27.3% + (CS) 22.6% +
(SCuS) 16.7%
4
4
70
47
0.0000
6.0590
452
430
a2
a1
469
447
0.0000
6.0727
451
430
453 (97)
454



442 (98)




4
44
1.2436
427
b2
444
1.2611
427
435 (98)






4
4
38
34
0.7386
0.6636
421
417
a1
b2
437
433
0.7527
0.5976
420
416
426 (98)
419 (97)
424
424


419




(CuSC) 27.5% + (CuS) 24.2% +
(SCS) 19.6% + (SCN) 18.3%
as(CuS) 31.6% + δ(CuSC) 20.7%
(SCS) 18.2% + (SCN) 17.2 %
(CuS) 31.2% + (SCN) 27.7% +
3
3
3
3
3
2
2
65
61
22
10
05
91
54
0.3700
121.1294
0.8205
351
347
310
298
293
280
244
a1
b2
b1
a2
b1
a2
b2
365
361
322
310
305
291
254
0.3705
120.9731
0.7921
351
347
310
298
293
280
244
363
357
323
364
353
329
297



+




(CuSC) 22.9% + (CS) 9.8%
(SCN) 51.9% + (CS) 25.8% +
(CuS) 16.2%
(CuS) 32.8% + (CuSC) 32.7% +
(SCuS) 15.5% + (CS) 9.6%
(SCN) 38% + (CuS) 25.8% +
(CuSC) 26.3%
(CuSC) 28.2% + (CuS) 25.8% +
(SCuS) 22.6%
(CuS) 30.4% + (CuSC) 26.5% +

0.0000
0.0000



7.1899
7.2158
287
281
256





0.0000
0.0000



20.3990
20.4486
256
241
251
237

2
36
4.1630
227
b1
236
4.1880
227

(SCuS) 19.7% + (SCN) 11.5% +
(SCuS)linear 10.0%
2
2
2
1
1
27
25
04
83
75
0.0040
0.1923
0.0000
0.8548
1.6301
218
216
196
176
168
a1
b2
a2
b1
a1
227
225
203
183
175
0.0044
0.2080
0.0000
0.8614
1.6222
218
216
195
176
168
228
215
202
183
160
228
215
202
183
160

(CH)
210
156

(CH)

(CH)


(CH)
(CN) (o.o.p)
(CN)(o.o.p)
(SCuS) 31.4% + (SCuS)linear
9.3% + (CuSC) 26.8%
(-CH CH ) in which (CuS) 25.3%
1
1
53
46
0.0262
4.0199
147
140
b2
a1
153
146
0.0219
3.9761
147
140



2

2
3
1
30
4.1654
125
a1
130
4.2284
125
131

+ (SCuS)linear 24.7% + (SCuS)
6.9% + (CuSC) 15.5%
1


(-CH CH ) in which (CuS) 40.6%
2
3
1
17
0.0000
0.1452
112
94
a2
b2
117
99
0.0001
0.1460
112
95
107


+
(CuSC) 33.4%

(-CH CH ) in which (CuSC)
2
3
9
8
6
29.4% + (CS) 23.8% + (SCS)
7.6% + (SCN) 16.6%
(-CH CH ) in which (SCuS)
1

2
3
8
0.0385
83
a1
87
0.0365
84

23.4% + (CuSC) 21.3% + (CuS)
2
1.8%
8
8
5
5
1
4
0.2956
0.0000
1.8800
82
78
52
b1
a2
b1
85
82
54
0.2971
0.0000
1.8796
82
79
52


(CuS-CN)
(SCu-SC)
76
(-CH CH ) + (ring)
2
3
4
4
3
2
0
4
0.0010
0.0000
0.3353
40
38
33
b2
a2
b1
42
40
34
0.0010
0.0000
0.3394
40
38
33



ring(CSCuS) wagging
(-CH CH )
2
3
(-CH CH )
2
3

(-CH CH ) + (SCuS)linear 30.6%
2
3
1
1
7
5
0.0000
3.1595
16
14
a2
a1
19
15
0.0074
3.1559
18
14


+ (CuSC) 15.3% + (SCuS) 12.9%
(CS) 19%
(-CH CH )
+
2
3

FT-IR
spectrum
FT-Raman
spectrum
[
Cu(DDTC)2]




Synthesis of bis-diethyldithiocarbamate Cu (II) was carried out.
The FT-IR and Raman spectra of [Cu(DDTC) ] were carried out.
2
The calculations and spectra interpretation have been based on the DFT/B3LYP
method, infrared and Raman second derivative spectra, and band deconvolution
analysis.