Three novel Cd(II) dithiocarbamate complexes: synthesis, structural diversity and fluorescence properties

Article abstract of DOI:10.1007/s13738-020-01965-4

Three new homoleptic cadmium (II) dithiocarbamate complexes having molecular formula [Cd(KL)₂], (KL1 = C₁₅H₁₃N₁F₁S₂) (1); (L2 = C₁₃H₁₁N₁F₁S₂) (2); (L3 = C₁₁H₁₄N₁O₁S₂) (3), have been synthesized and characterized by elemental analysis, spectroscopy (IR, ¹H and ¹³CNMR and UV–Vis). Single crystal X-ray studies confirm that the complex 1 crystallises in Orthorhombic with space group Pna21 and holding dimeric structure. In this complex Cd²⁺ having distorted octahedral geometry about the metal centre forms 1D coordination polymeric structures. The dimeric form of complex 2 and 3 crystallizes in triclinic crystal lattice with space group P-1.

Full text of DOI:10.1007/s13738-020-01965-4

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-020-01965-4
ORIGINAL PAPER
Three novel Cd(II) dithiocarbamate complexes: synthesis, structural
diversity and fuorescence properties
1
1
1
2
Ravi Pratap Singh · Vinay Kumar Maurya · Lal Bahadur Prasad · Kafeel Ahmad Siddiqui
Received: 9 August 2019 / Accepted: 29 May 2020
©
Iranian Chemical Society 2020
Abstract
Three new homoleptic cadmium (II) dithiocarbamate complexes having molecular formula [Cd(KL) ], (KL1=C H N F S )
2
15 13
1 1 2
(
1); (L2=C H N F S ) (2); (L3=C H N O S ) (3), have been synthesized and characterized by elemental analysis,
1
3
11
1
1
2
11 14
1
1 2
1 13
spectroscopy (IR, H and CNMR and UV–Vis). Single crystal X-ray studies conꢀrm that the complex 1 crystallises in
2
+
Orthorhombic with space group Pna21 and holding dimeric structure. In this complex Cd having distorted octahedral
geometry about the metal centre forms 1D coordination polymeric structures. The dimeric form of complex 2 and 3 crystal-
lizes in triclinic crystal lattice with space group P-1.
…
Keywords Cd–dithiocarbamate complexes · C–H S interactions · Fluorescence properties
Introduction
fruitful way in the treatment of abnormalities of AIDS and
neurodegenerative diseases as the dithiocarbamate have the
potential to block the activation of nuclear factor KB (NF-
KB), a transcription factor involved in inꢁammatory pro-
cesses and human immunodeꢀciency virus type 1 (HIV-1)
expression and signaling events regarding to type of cancer
(Scheme 1).
The coordination chemistry of dithiocarbamate ligands is of
peculiar interest, as it can form complexes with most of the
transition and main group metal ions [1–6]. The intermo-
lecular interactions of dithiocarbamate ligands with metals
2
−
form homoleptic [M(L) ] anions, in monodentate, biden-
2
tate (chelate or bridging), tridentate and even tetradentate
fashion, yielding exciting coordination properties and unu-
sual bonding behavior which are responsible for structural
diversity and properties of complexes. Such abilities bring
in several keystone features which can be implemented in
various ꢀelds like industry, agriculture and in biomedical
In contrast to a plethora of examples of Zn(II) dithiocar-
bamates [2,3b] showing structural diversity, the number
and structural types of cadmium dithiocarbamate com-
plexes reported to date are extremely limited [7–16]. Here
we have reported three new homoleptic Cd-complexes of
having formula [Cd(KL) ], (KL1 = C H N F S ) (1);
2
15 13
1 1 2
ꢀ
elds (cancer, neurogenerative diseases). Recently the dithi-
(L2 = C H N F S ) (2); (L3 = C H N O S ) (3), based
1
3
11
1
1
2
11 14
1
1 2
ocarbamate and iron chelators moieties can be considered as
on dithiocarbamate.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-020-01965-4) contains
supplementary material, which is available to authorized users.
Experimental
Materials and methods
*
Lal Bahadur Prasad
lbprasad@bhu.ac.in
All the chemicals like acetaldehyde, benzaldehyde, 2-thio-
phenecarboxaldehyde, 4-methoxybenzylamine, 4-ꢁouroben-
*
Kafeel Ahmad Siddiqui
kasiddiqui.chy@nitrr.ac.in
zylamine, CS and NaOH were purchased from Sigma
2
Aldrich and used as such.
1
2
Department of Chemistry, Institute of Science, Banaras
Hindu University, Varanasi 221005, India
Department of Chemistry, National Institute of Technology
Raipur, G. E. Road, Raipur, Chhattisgarh 492010, India
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
Synthesis of complexes
R2
R2
R2
R2
S
S
S
S
S
S
S
N
N
N
The homoleptic complexes 1–3 are prepared by known pro-
cess [20–25] in good yield by the reaction of cadmium metal
and their corresponding ligand in 1:2 molar ratios in metha-
nolic solution (Scheme 3). The complexes are air-stable and
melt in the 142–210 °C temperature range. The complexes
have been characterized by elemental analyses and spectros-
N
R1
S
R1
R1
(III)
R1
(II)
(IV)
(I)
Scheme 1 Delocalization of electron in dithiocarbamate ligands
1
13
copy (IR, H and CNMR, UV–Vis). Single crystal X-ray
++
studies show that all complexes are having Cd with diꢂer-
ent molecular geometry and space group (Scheme 4).
F
F
OMe
Results and discussion
S
S
S
S
S
S
N
K
N
N
K
K
Synthesis
S
The complexes 1–3 were synthesized by the reaction of
Cd(CH COO) with their corresponding ligand in 1:2 molar
3
2
ratio in the methanolic solution. All the complexes are sta-
ble at room temperature and soluble in organic solvent like
KL1
KL2
KL3
CHCl , DMSO and DMF. The C, H, N analysis of com-
3
Scheme 2 Structure of ligands used in this work
plexes is, Found (calcd.) for C H CdF N S (1): C, 51.83
3
0
26
2
2 4
(
51.80); H, 4.06 (3.91); N, 4.03 (3.96) (yield: 0.51 g, 73%);
Synthesis of dithiocarbamate ligands
C H CdF N S (2): C, 44.15 (44.11); H, 3.42 (3.27); N,
5
2
44
4
4 12
3
.96 (3.91) (yield: 0.49 g, 69%); C H CdN S (3): C, 44.89
20
24
2 4
Potassium salt of the dithiocarbamate ligands viz.
(KL1 = C H N F S (N-Ethyl-N-4-ꢁourobenzyl dithi-
(44.80); H, 4.90 (4.81); N, 5.25 (5.18) (yield: 0.54 g, 72%).
[
1
5
13
1 1 2
ocarbamate); KL2 = C H N F S (N-4-flourobenzyl-
NMR spectra
1
3
11
1 1 2
N-thiophene dithiocarbamate); KL3 = C H N O S
1
1
14
1
1 2
1
3
(
N-ethyl-N-4-methoxybenzyl dithiocarbamate)] were pre-
The CNMRof complexes 1–3 showed a low ꢀeld reso-
pared according to literature procedures [17–19] by the
reaction of the appropriate secondary amine with KOH in
nance associated with the NCS carbons of the dithiocar-
2
bamates moieties in the range δ = 203–208 ppm due to
+
2−
CS (Scheme 2).
dominant contribution of R N =CS resonance form in
2 2
2
the dithiocarbamate complexes as compare to free ligand
Scheme 3 Schematic represen-
tation of synthesis of complexes
1
3

Journal of the Iranian Chemical Society
F
F
F
F
S
S
S
S
S
S
S
S
S
S
S
S
N
N
N
N
Cd
Cd
N
N
Cd
S
S
2
3
1
Scheme 4 Schematic representation of complexes 1–3
Table 1 NMR data (δ, ppm) of ligands (1–3)
Compound
C H N F S (KL1)
Nucleus –C H
–CH C H F –CH C H
–OCH3 CS2
–C H S
–CH3
6
4
2
6
4
2
6
5
4
3
−
1
H
C
6.93–7.34(m) 3.82(s)
114–138 53.30
6.79–7.18(m) 3.68(s)
3.80(s)
52.55
–
–
–
–
–
–
–
–
–
–
–
15
13
1 1 2
1
1
1
1
1
3
216.32
–
−
C H N F S (KL2)
H
6.72–7.18(d,s)
1
3
11
1 1 2
3
C
114–135
6.80–7.30(m)
113–129
55.35
–
–
216.38
–
210.31
158–159
–
−
C H N O S (KL3)
H
–
–
3.87(s)
56.30
3.69(s)
53.24
1.18(t)
20.06
1
1
14
1
1 2
3
C
Table 2 NMR chemical shifts
δ, ppm) of Complexes (1–3)
Compound
Nucleus –C H
–CH C H F CH C H
5
CS2
–CH2
–CH3
6
4
2
6
4
2
6
(
1
C H N CdF S (1)
H
C
6.91–7.30(m) 3.66(s)
111–134 56.94
6.56–7.20(m) 3.66(s)
3.58(s)
57.73
–
–
207
–
–
–
–
–
–
–
–
–
3
0
26
2
2 4
1
1
1
1
1
3
C H N CdF S (2)
H
2
6
22
2
2 4
3
C
H
C
114–129
6.80–7.20(m)
105–137
54.91
–
205.18
–
203.01 40.05
C H CdN S (3)
–
–
3.69(s)
51.41
2.34(q) 1.16(t)
12.19
2
0
24
2 4
3
1
(
δ = 209–219 ppm). In H NMR spectra of the complexes
1
–3, shows characteristic of the ligand functionalities and
participate well to the corresponding hydrogen atoms. There
is no perceptible shift in the proton NMR spectra of the
complexes in comparison to potassium salt of the ligands
(
Tables 1, 2).
FTIR Spectra
In the IR spectra of complexes 1–3 the strong υ(C–N)
−
1
bands was observed in the range of 1426–1477 cm . This
stretching vibration may be ascribed to an increase in the
carbon–nitrogen double bond character due to delocalization
of electron towards the metal atoms in each of the dithiocar-
bamate complexes [26–28].In the dithiocarbamate ligands
two types of υ(C–S) bands, the υ(CS )
and υ(CS )
2 sym
2
asym.
−
1
−1
are appear at around 1020 cm and 975 cm , respectively.
Fig. 1 UV–Vis spectra of 1–3 in CH Cl solution
2
2
1
3

Journal of the Iranian Chemical Society
ligand charge transfer (ILCT) and metal perturbed intra
ligand charge transfer (ILCT) transitions, respectively. The
excitation of 270 nm for complex 1, 265 nm for complex 2
and 267 nm for complex 3 we observed the emission peaks
at 332 nm, 334 nm and 351 nm, respectively, for complexes
1
, 2 and 3. The stokes shift of 62 nm, 69 nm and 84 nm
10
was observed for these complexes. The closed shell d
cadmium(II) compounds are very important because of
their luminescence properties. When excited at 270 nm in
the liquid state a strong broad bands at 315–320 nm arises
from the metal perturbed intra ligands charge transfer state
(
Figs. 1, 2).
Crystal structures
Single crystals of complexes 1–3 were grown by
slow evaporation of solutions of the compounds in
CH Cl -methanol [31–34] and the molecular structures
Fig. 2 Emission spectra of 1–3 in CH Cl solution
2
2
2
2
of complexes are determined by X-ray crystallography.
Crystal data and refinement details are listed Table 3
and selected bond lengths and bond angles are given in
These absorption are replaced by a strong singlet at approxi-
−
1
2+
mately 1000 cm in all the complexes, indicates a sym-
metrical coordination of the dithiocarbamate moiety to the
metal ions [29, 30].
Table 4. The Cd ions shows no stereo-chemical prefer-
ences arising from ligand ꢀeld stabilization eꢂects due to
this reason it can show diversity of coordination numbers,
viz. 4, 5 and 6, and geometries.
Absorption and emission spectra
Complex 1 crystallizes in orthorhombic crystal sys-
tem with space group Pna21 and holding dimeric struc-
2
+
The absorption and emission spectra of dithiocarbamate
complexes are measure in CH Cl solution and predicted
ture. In this complex, Cd is having distorted octahedral
geometry and forms 1D coordination polymeric struc-
tures (Figs. 3, 4) in which sulphur atoms S13, S43 are
2
2
in Figs. 1 and 2. The absorptions in the range between 200
and 800 nm all the complexes due to ligand centered intra
2
+
bridging with two Cd atoms. The bond length between
Table 3 Crystallographic
Compound
1
2
3
parameters for complexes 1–3
Formula
C
H
Cd F N S
C
H
Cd F N S
C
H
Cd N S4
3
0
26
2
2
4
52 44
2
4
4
12
20 24
2
Formula weight
Crystal system
Space group
a (Å)
693.17
1410.43
Triclinic
P -1
533.05
Triclinic
P -1
Orthorhombic
Pna21
8.1758(4)
11.5717(5)
29.699(18)
90
9.8027(4)
11.9846(4)
12.1569(4)
74.478(1)
81.903(1)
88.069(1)
1362.39(8)
1
8.664(3)
b (Å)
11.4196(4)
11.7088(4)
74.932(1)
87.279(1)
77.417(1)
1091.71(7)
2
c (Å)
α (Å)
β (Å)
90
δ (Å)
90
3
V (Å )
2809.8(3)
4
Z
ƿ
calc (g cm-3)
1.639
1.719
1.622
T (K)
150(2)
1.112
100(2)
100(2)
μ (Mo Kα) (mm−1)
F (000)
1.296
1.391
1400
708
540
Independent reꢁns
7585
6764
4061
Reꢁections with I>2 (I)
6553
5844
3817
σ
a
b
Final indices [I>2 s(I)] R1 , wR
0.0526
0.0636,0.1311
1.007
0.0403
0.0737
2
a
b
R1 , wR2 [all data]
0.0510, 0.0896
1.085
0.0255, 0.0737
1.226
Goodness of Fit
a
R =∑||Fo| − |Fc||/∑|Fo|
2
1
b
2
2
2 2 1/2
2
2
2
2
2
R ={[∑w (F0 − Fc )/∑w (Fo ) ]} , w=1/ [σ (Fo )+(xP) ], where P=(Fo +2Fc )/3.
1
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Journal of the Iranian Chemical Society
Table 4 Table for selected bond lengths and bond angle of complexes
2.288 and 2.530 , respectively (Fig. 5), and the bond length
1
–3
…
…
of F(28)–H(56) is 2.486 Å. In C–H S interaction the H S
…
distance is 2.579 Å and C–H S angle is 111.05°.
1
The dimeric form of complex 2 crystallizes in triclinic
Bond lengths (Å)
Cd(1)–S(11)
Cd(1)–S(13)
Cd(1)–S(41)
Cd(1)–S(43)
2
+
crystal lattice with space group P-1. In this complex Cd
2.549(2)
2.7524(13)
2.549(2)
2.7458(13)
1.34(7)
are in square pyramidal environments in whichS(002) atoms
are bridging with two Cd atoms. The bond length between
Cd(01)–S(003) and Cd(01)–S(005) are 2.608 Å 2.572 Å,
respectively (Figs. 6, 7, 8, 9).
C(42)–N(44)
The bond lengths of S(002)–Cd(01) is 2.787 Å con-
Bond angles (°)
S(11)–Cd(1)–S(13)
S(11)–Cd(1)–S(43)
S(13)–Cd(1)–S(43)
2
ꢀ
rming that S(002) is bonding with Cd(01) in S,S-chelat-
96.31(6)
100(5)
107.23(3)
ing-bridging as well as S,S-chelating manner. The bite
angle S(002)–Cd(01)–S(002) is 89.28°, while the angle
Cd(01)–S(002)–Cd(01) is 90.72°. The N(00B)–C(00D) and
N(00A)–C(00C) bond lengths are 1.332 and 1.337 Å indi-
cating the partial double bond character in the N–C bond of
the ligand. In complex 2 C–H⋯S, C–H⋯π, π⋯π and S⋯S
non-covalent interactions are observed in which C–H⋯S
interactions having C–H⋯S interaction distance of 2.918 Å
and angle of 92.19° (Figs. 10, 11, 12, 13).
Bond lengths (Å)
Cd(01)–S(002)
Cd(01)–S(003)
Cd(01)–S(004)
Cd(01)–S(005)
Bond angles (°)
S(002)–Cd(01)–S(002)
S(003)–Cd(01)–S(002)
S(004)–Cd(01)–S(002)
S(004)–Cd(01)– S(003)
3
2.6115(8)
2.6081(9)
2.5784(9)
2.5723(9)
The complex 3 crystallizes in triclinic with space group
89.28(3)
109.73(3)
105.77(3)
70.28(3)
2
+
P-1. In this complex Cd are in square pyramidal environ-
mentsabout the metal centre in which S(4) atoms are bridg-
ing with two Cd atoms. The bond length of Cd(1)–S(4)
2
.7867(6)Å is longer than other Cd–S bond length. The
C–H⋯π interaction in this complex having bond length
.334 Å and the length between H(9A)–H(9B) is 2.287 Å
Figs. 14, 15).
Bond lengths (Å)
Cd(1)–S(1)
Cd(1)–S(2)
Cd(1)–S(3)
Cd(1)–S(4)
3
2.5515(7)
2.6036(7)
2.5566(6)
2.5999(6)
(
3.6.Thermogravimetric analysis of complexes 1–3
Bond angles (°)
S(1)–Cd(1)–S(3)
S(1)–Cd(1)–S(4)
S(2)–Cd(1)–S(4)
S(3)–Cd(1)–S(2)
S(4)–Cd(1)–S(2)
Thermal decompositions of complexes have been investi-
gated in temperature range 30–800 °C with a ꢁow rate of
145.32(2)
103.443(19)
160.16(2)
105.79(2)
110.23(2)
1
0.00 °C/min under N atmosphere. The TGA graph shows
2
that all complexes begin to loss their weight in two steps
35–39]. In ꢀrst step all the dithiocarbamate complexes loss
[
their weight around 100 °C which corresponds to the loss of
water molecule present within the crystal lattice. The second
weight loss starts at around 270 °C and leads to the forma-
tion of CdS phases around 620 °C. In complexes 1 the higher
residual weights were obtained, which indicate the higher
percentage of oxygen and sulfur giving in decomposition
products. These products probably containing mixed metal
oxide-sulphides and CdS residue [40–43] (Fig. 16).
Cd(1)–S(41),Cd(1)–S(11) is 2.549(2)Å and the bond
lengths of S(13)–Cd(1), S(43)–Cd(1) are 2.7524 Å and
2
.8265(13) Å, respectively, conꢀrming that S(13), S(43)
are S,S-chelating-bridging as well as S,S-chelating fashion.
The bite angle S(43)–Cd(1)–(13) is 87.09°, while the angle
S(41)–Cd(1)–S(13) is 98.85°. The N44–C42 and N14–C12
bond lengths are 1.340 and 1.335 Å, respectively. These val-
ues are midway between C–N (1.47 Å) and C=N (1.28 Å)
indicating the partial double bond character in the N–C bond
of the ligand.
Conclusion
We have successfully synthesized homoleptic Cd(II)
complexes based on [(KL1 = C H N F S (N-ethyl-N-
Complex 1 is stabilized by several non-covalent interac-
15 13
1 1 2
…
4-flourobenzyl dithiocarbamate); KL2 = C H N F S
tions in which C–H F interaction form a six member ring
13 11 1 1 2
(
N-4-flourobenzyl-N-thiophene dithiocarbamate);
having F(58)–H21(B) and F(58)–H(23) bond lengths are
KL3 = C N O (N-ethyl-N-4-methoxybenzyl
H
1
1
14
1
12
1
3

Journal of the Iranian Chemical Society
Fig. 3 ORTEP diagram of a
complex 1
dithiocarbamate)] ligands. Complex 1 crystallises in
Orthorhombic with space group Pna21 and holding dimeric
2
+
structure. In this complex Cd having distorted octahedral
geometry about the metal centre forms 1D coordination
polymeric structures. The dimeric form of complex 2 and
3
crystallizes in triclinic crystal lattice with space group
P-1. The TGA analysis of the complexes begin to loss their
weight in two steps leads to the formation of CdS phases
around 620 °C. In complexes 1 the higher residual weights
probably containing mixed metal oxide-sulphides and CdS
residue.
Fig. 4 Polymeric structure of complex 1
1
3

Journal of the Iranian Chemical Society
…
Fig. 5 C–H F interaction with
six-member ring in complex 1
…
…
Fig. 7 C–H S and C–H π interaction of complex 1
…
Fig. 6 C–H F interaction of complex 1
Fig. 8 Flower like structure of complex 1
1
3

Journal of the Iranian Chemical Society
…
Fig. 12 π π interaction in complex 2
Fig. 9 Crystal structure of complex 2
…
Fig. 10 C–H S interaction of complex 2
…
Fig. 13 S S interaction in complex 2
…
Fig. 14 C–H π interaction of complex 3
…
Fig. 11 C–H π chelate in complex 2
1
3

Journal of the Iranian Chemical Society
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Fig. 15 C–H S and H H interaction of complex 3
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Bahadur, N. Singh, Chem. Eur. J. 16, 4307 (2010)
3. D.C. Onwudiwe, T. Arꢀn, C.A. Strydom, Electrochim. Acta
1
16, 217 (2014)
4. J. Zukerman-Schpector, A. Otero-de-la-Roza, V. Luaña, E.R.T.
Tiekink, Supramolecular architectures based on As (lone pair)⋯
π (aryl) interactions. Chem. Commun. 47(27), 7608 (2011)
5. I. Caracelli, J. Zukerman-Schpector, E.R.T. Tiekink, Supra-
molecular synthons based on gold… π (arene) interactions.
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Fig. 16 TGA plot of complexes
2
Acknowledgements We gratefully acknowledge the Council of Scien-
tiꢀc and Industrial Research (CSIR), New Delhi for ꢀnancial assistance
in the form of Senior Research Fellowship (SRF). Authors are also
thankful to Department of Chemistry, Institute of Science, Banaras
Hindu University, Varanasi, for the Instrumental facilities. Dr. Kaf-
eel Ahmad Siddiqui is thankful to Council of Scientiꢀc and Industrial
Research (CSIR), New Delhi India for award of a project under EMR-
II Sanction order No. 01 (2962/18/EMR-II) to support his “Crystal
Engineering Research”
26. A. Kumar, M. Figge, W.S. Sheldrick, N. Singh, Synthesis, struc-
ture, conductivity, and calculated nonlinear optical properties of
two novel bis(triphenylphosphane)copper(I) dithiocarbamates.
Eur. J. Inorg. Chem. 18, 2720 (2009)
27. A. Husain, S.A. Nami, S.P. Singh, M. Oves, K.S. Siddiqi, Ana-
gostic interactions, revisiting the crystal structure of nickel
dithiocarbamate complex and its antibacterial and antifungal
studies. Polyhedron 30(1), 33 (2011)
2
8. T.S. Thakur, G.R. Desiraju, Theoretical investigation of C–H⋯
M interactions in organometallic complexes: a natural bond
orbital (NBO) study. J. Mol. Struct. (Thoechem) 810(1–3), 143
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