Synthesis and Characterization of Diimine Adducts of BIS(N-Alkyl-N-Furfuryldithiocarbamato-S,S′)Cadmium(II): Crystal Structure of BIS(N-Furfuryl-N-Propyldithiocarbamato-S,S′)(1,10-Phenanthroline)Cadmium(II)

Article abstract of DOI:10.1080/10426507.2013.865126

A series of homoleptic and heteroleptic complexes: [Cd(fprdtc)₂] (1), [Cd(fprdtc)₂(1,10-phen)] (2), [Cd(fprdtc)₂(2,2′-bipy)] (3), [Cd(bufdtc)₂] (4), [Cd(bufdtc)₂(1,10-phen)] (5), and [Cd(bufdtc)₂(2,2′-bipy)] (6)(where fprdtc = N-furfuryl-N-propyldithiocarbamate; bufdtc = N-butyl-N-furfuryldithiocarbamate) have been prepared and characterized. A single crystal X-ray structural analysis was carried out for 2. Reduction in C-N (thioureide) for the heteroleptic complexes (2, 3, 5, and 6) compared to that of homoleptic complexes (1 and 4) is attributed to the change in coordination number from four to six and steric effect exerted by 1,10-phenanthroline and 2,2′-bipyridine. The downfield shift of N¹³CS₂ carbon signal for heteroleptic complexes from the chemical shift value of homoleptic complexes is also attributed to the increase in coordination number. Single crystal X-ray structure of 2 indicates that the mononuclear structure of 2 shows symmetric coordination of the dithiocarbamate ligands and a distorted octahedral geometry for cadmium, defined by an N₂S₄ donor set, results. In this crystal structure, most significant π-π interaction is also observed.

Full text of DOI:10.1080/10426507.2013.865126

This article was downloaded by: [Erciyes University]
On: 29 December 2014, At: 04:46
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
Synthesis and Characterization
of Diimine Adducts of BIS(N-
Alkyl-N-Furfuryldithiocarbamato-
S,S′)Cadmium(II): Crystal Structure of
BIS(N-Furfuryl-N-Propyldithiocarbamato-
S,S′)(1,10-Phenanthroline)Cadmium(II)
a
a
b
Palanisamy Jamuna Rani , Subbiah Thirumaran , Vivek K. Gupta &
Click for updates
b
Rajni Kant
a
Department of Chemistry, Annamalai University, Annamalainagar,
6
08 002, India
b
X-Ray Crystallography Laboratory, Post-Graduate Department of
Physics & Electronics, University of Jammu, Jammu Tawi, 180 006,
India
Accepted author version posted online: 13 Mar 2014.Published
online: 21 Aug 2014.
To cite this article: Palanisamy Jamuna Rani, Subbiah Thirumaran, Vivek K. Gupta & Rajni Kant
2014) Synthesis and Characterization of Diimine Adducts of BIS(N-Alkyl-N-Furfuryldithiocarbamato-
(
S,S′)Cadmium(II): Crystal Structure of BIS(N-Furfuryl-N-Propyldithiocarbamato-S,S′)(1,10-
Phenanthroline)Cadmium(II), Phosphorus, Sulfur, and Silicon and the Related Elements, 189:9,
1405-1416, DOI: 10.1080/10426507.2013.865126
To link to this article: http://dx.doi.org/10.1080/10426507.2013.865126
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“
Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or

howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 189:1405–1416, 2014
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2013.865126
SYNTHESIS AND CHARACTERIZATION OF DIIMINE
ADDUCTS OF BIS(N-ALKYL-N-
ꢀ
FURFURYLDITHIOCARBAMATO-S,S )CADMIUM(II):
CRYSTAL STRUCTURE
OF BIS(N-FURFURYL-N-PROPYLDITHIOCARBAMATO-
ꢀ
S,S )(1,10-PHENANTHROLINE)CADMIUM(II)
1
1
Palanisamy Jamuna Rani, Subbiah Thirumaran,
2
2
Vivek K. Gupta, and Rajni Kant
Department of Chemistry, Annamalai University, Annamalainagar 608 002, India
X-Ray Crystallography Laboratory, Post-Graduate Department of Physics &
1
2
Electronics, University of Jammu, Jammu Tawi 180 006, India
GRAPHICAL ABSTRACT
Abstract A series of homoleptic and heteroleptic complexes: [Cd(fprdtc)2] (1),
ꢁ
ꢁ
[
[
Cd(fprdtc)2(1,10-phen)]
(2),
[Cd(fprdtc)2(2,2 -bipy)]
(3),
[Cd(bufdtc)2]
(4),
Cd(bufdtc)2(1,10-phen)] (5), and [Cd(bufdtc)2(2,2 -bipy)] (6)(where fprdtc = N-furfuryl-
N-propyldithiocarbamate; bufdtc = N-butyl-N-furfuryldithiocarbamate) have been prepared
and characterized. A single crystal X-ray structural analysis was carried out for 2. Reduction
in νC–N (thioureide) for the heteroleptic complexes (2, 3, 5, and 6) compared to that of
homoleptic complexes (1 and 4) is attributed to the change in coordination number from four to
ꢁ
six and steric effect exerted by 1,10-phenanthroline and 2,2 -bipyridine. The downfield shift of
13
N
CS2 carbon signal for heteroleptic complexes from the chemical shift value of homoleptic
complexes is also attributed to the increase in coordination number. Single crystal X-ray
Received 6 September 2013; accepted 6 November 2013.
Address correspondence to Subbiah Thirumaran, M.Sc., M.Phil., PhD, Department of Chemistry, Annamalai
University, Annamalainagar 608 002, India. E-mail: sthirumaran@yahoo.com
1
405

1406
P. J. RANI ET AL.
structure of 2 indicates that the mononuclear structure of 2 shows symmetric coordination
of the dithiocarbamate ligands and a distorted octahedral geometry for cadmium, defined by
an N2S4 donor set, results. In this crystal structure, most significant π–π interaction is also
observed.
Keywords Dithiocarbamate; cadmium(II); spectroscopic characterization; single-crystal
X-ray analysis; VBS analysis
INTRODUCTION
Dithiocarbamates and metal dithiocarbamate complexes are valuable compounds due
to their interesting chemistry and wide utilities and applications such as nitrogen-oxygen
1
2
3
4
trapping agents, as antioxidants, in organic synthesis , and medicine. The affinity
of 1,1-dithiolate ligands for metals such as zinc and cadmium was indicated by the
fact that the ligands themselves can be employed as scavengers for these elements in
5
biological media. All cadmium dithiocarbamate complexes have binuclear molecular
6,7
structures, (Scheme 1) in which the mononuclear moieties [Cd(S2CNR2)2] are combined
by two additional Cd–S bonds. Binuclear molecules involve two pairs of dithiocarbamate
ligands with terminal chelating and tridentate bridging structure functions. The former
ꢁ
dithiocarbamate ligands are S,S -bidentately coordinated to cadmium and form planar
four-membered chelate rings [CdS2C], where as the latter combine neighboring metal
atoms into centrosymmetric dimers, forming an extended eight-membered tricyclic
moiety [Cd2S4C2], which usually adopts a chair conformation. The only exception is
ꢁ
the bis(dibutyldithiocarbamato-S,S )cadmium(II), for which a boat conformation (with a
twofold axis ) has been established.8
Scheme 1 Structure of cadmium bis(dithiocarbamate) complex.
The treatment of cadmium dithiocarbamate complexes with nitrogen donor ligands
generally results9 in the monometallic compounds of general formula [Cd(S2CNR2)2(N-
–11
ꢁ
donor)x] (x = 1 or 2). The 1,10-phenanthroline and 2,2 -bipyridine are well known and
ꢁ
frequently used ligands. The presence of added 1,10-phenanthroline and 2,2 -bipyridine
12
in the coordination sphere increases the electron density on cadmium. The heteroleptic
complexes of metal dithiocarbamates with nitrogen heterocycles are of interest not only for
expanding the scope of objects in coordination chemistry, but also in view of their potential
applications. For example, the heteroleptic complexes of cadmium(II) dithiocarbamates
with nitrogen donor ligands (pyridine, 1,10-phenanthroline, and 2,2 -bipyridine) are used as
single source precursors for the preparation of CdS nanoparticles.
ꢁ
1
3–16
The dithiocarbamate
complex core M–S2CNR2 could prove to be great synthetic utility, since a wide variety of
organic substituents can be incorporated in this stable bidentate system. It gives rise to the

DIIMINE ADDUCTS OF CADMIUM DITHIOCARBAMATES
1407
chemical “fine tuning” of the properties of the complex by variation of the substituent R in
17
M–S2CNR2. The furan has a very peculiar chemical behavior which is often not closely
related to that of its homologous thiophene and pyrrole. The other reason for choosing the
ligand containing a furyl ring is the presence of an extra oxygen atom which can possibly
be utilized for coordination with another metal salt as shown in Scheme 2. The aim of
the present work was to prepare Cd(II) complexes of two dithiocarbamate ligands and the
ꢁ
reactivity of these complexes toward nitrogen donor ligands (1,10-phenanthroline, 2,2 -
bipyridine). In this paper, we report the synthesis, spectral studies of complexes 1–6 along
with the single crystal X-ray structure of 2.
Scheme 2 Possible bonding modes of ligands involving the furyl ring.
RESULTS AND DISCUSSION
Homoleptic and heteroleptic complexes were prepared according to the synthetic
procedure shown in Scheme 3. Furfuraldehyde was condensed with propylamine and
butylamine to form the imine. Sodium borohydride reduction of imine in methanol-
dichloromethane afforded secondary amine as yellow oil. Complexes 1 and 4 were prepared
from N-furfuryl-N-propylamine and N-butyl-N-furfurylamine, respectively, in EtOH by
reaction with carbon disulfide and Cd(CH3COO)2 in water. The reaction of complexes 1
ꢁ
and 4 with nitrogen donor ligands (1,10-phen, 2,2 -bipy) yielded heteroleptic complexes
(
2, 3, 5, and 6). The complexes are quite stable at ambient conditions. They are soluble in
water, methanol, dichloromethane, and insoluble in acetonitrile.
2.1. IR Spectra
Important absorptions in the dithiocarbamate complexes are due to νC–N and νC–S
stretching modes.1
8,19
The νC–N band has been used as a measure of the contribution
of the thioureide form to the structure of the dithiocarbamate. For the complexes 1–6,
−
1
strong bands appeared around 1470 and 1010 cm due to νC–N (thioureide) and νC–S
vibrations, respectively. The shift in νC–N values to lower wave numbers for heteroleptic
complexes compared to the parent complexes 1 and 4 is due to the change in geometry
from tetrahedral to octahedral. The reduction in νC–N (thioureide) for similar adducts such
−
1
ꢁ
1
as [Cd(2-mpipdtc)2(1,10-phen)] (1420 cm ), [Cd(2-mpipdtc)2(2,2 -bipy)] (1421 cm ),
− ꢁ −1
1
[
[
[
Cd(4-mpipdtc)2(1,10-phen)] (1427 cm ), [Cd(4-mpipdtc)2(2,2 -bipy)] (1420 cm ), and
ꢁ
−1
−1
9,10
Cd(S2CN(Me)(Cy)2(2,2 -bipy)] (1471 cm ) compared to [Cd(2-mpipdtc)2](1429 cm ),
−1
−1
Cd(4-mpipdtc)2](1445 cm ), and [(Cd(S2CN(Me)(Cy))2] (1482 cm ) are reported.
The νC–S band appear around 1010 cm without any splitting supporting the bidentate
−1

1408
P. J. RANI ET AL.
Scheme 3 Preparation of 1 and 4.
coordination of the dithiocarbamate ligands.1 The ring frequencies associated with 1,10-
8
ꢁ
−1
phenanthroline and 2,2 -bipyridine are observed in the range of 1600–1000 cm . In the
−1
present study, 2 and 5 show bands around 1620, 1590, and 1508 cm whereas 3 and 6 show
bands at 1593 and 1567 cm . Other bands are masked by those due to dithiocarbamate
ligand.
−1

DIIMINE ADDUCTS OF CADMIUM DITHIOCARBAMATES
1409
Figure 1 Structure and numbering of ligands: (fprdtc) 1a and (bufdtc) 1b.
1
2
.2. H NMR Spectra
Structure and numbering of ligands are given in Figure 1. NMR spectra were recorded
1
at room temperature using TMS as internal reference. CDCl3 was used as a solvent. H and
13
C NMR spectra of 1 and 4 are shown in Figures S1–S4 (Supplemental Materials).
For complexes 1–3, the signals due to methylene protons of propyl (NCH2) and
furfuryl groups appear around 3.80 and 5.15 ppm. In the case of complexes 4–6, a singlet
observed around 5.15 ppm is assigned to methylene protons of furfuryl group and NCH2
(butyl) protons appear as a triplet around 3.85 ppm. The other aliphatic protons of propyl
and butyl groups resonate in the region 0.84–3.89 ppm. The observed deshielding of
the methylene protons in all the complexes is attributed to the release of electrons on the
nitrogen of the dithiocarbamate toward the sulfur (or the metal) via the thioureide π-system.
The signals observed around 6.45, 6.35, and 7.35 ppm are assigned to the protons present
in the furfuryl ring. The signals observed in the higher frequency region 7.00–9.45 ppm
for 2 and 5 and 7.80–9.04 ppm for 3 and 6 are assigned to the protons present in the
ꢁ
1
,10-phenanthroline and 2,2 -bipyridine, respectively.
2
.3. 13C NMR Spectra
1
3
10
The δ (N CS2) appeared in the expected region (above 202 ppm) for d metal
dithiocarbamates.21 In all the complexes 1–6, these signals are observed in the region
04.9–208.4 ppm, which indicate the bidentate character of the dithiocarbamate ligands.
2
13
The N CS2 carbon sites of heteroleptic complexes are additionally deshielded compared
to the homoleptic parent complexes 1 and 4. Additional coordination of nitrogenous bases
to cadmium dithiocarbamates yields a decrease of nitrogen-carbon partial double bond
character and, as a result of that, the displacement of electron density from carbon and
nitrogen of dithiocarbamate. This explains the additional deshielding of carbon sites in
the N CS2 of heteroleptic complexes. This observation is supported by the lower νC–N
22
13
value observed in the IR spectra of heteroleptic complexes.
2.4. Single Crystal X-ray Structural Analysis
The structure of 2 was confirmed by a single crystal X-ray analysis. Details of the crys-
tal data and structure refinement parameters for 2 are summarized in Table 1. Selected bond
distances and angles are listed in Table 2. The ORTEP diagram is shown Figure 2. Com-
plex 2 is chelated by two symmetrically coordinating dithiocarbamate ligands [Cd–S2 =
2.6707(7), Cd–S3 = 2.6698(8), Cd–S4 = 2.6691(8), and Cd–S5 = 2.6631(8) Å] and also

1410
P. J. RANI ET AL.
Table 1 Crystal data, data collection, and refinement parameters for 2
Empirical formula
FW
C30H32N4O2S4Cd
721.24
Crystal dimensions (mm)
0.3 × 0.2 × 0.2
Crystal system
Space group
a/Å
Triclinic
P–1
9.6727(2)
b/Å
11.0445(3)
c/Å
15.3080(4)
84.829(2)
79.073(2)
87.203(2)
◦
α/
β/
γ /
◦
◦
3
V/Å
1598.33(7)
Z
2
−
◦
3
Dc/g cm
μ/cm
F(000)
λ /Å
θ Range/
1.499
0.978
736
−
1
MoKα (0.71073)
3.49–26.00
Index ranges
−11 ≤ h ≤ 11, −13 ≤ k ≤ 13, −18 ≤ l ≤ 18
Reflections collected/unique
Observed reflections [I > 2σ(I)]
Weighting scheme
29885/6265
5143
2
2
2
Calc. w = 1/(σ (Fo ) + (0.0302P) + 0.7152P),
2
2
where P = (Fo + 2Fc )/3
Number of parameters refined
372
2
2
R[F > 2σ(F )]
0.0319
0.0665
1.025
2
wR(F )
GOOF
symmetrically by one 1,10-phenanthroline ligand. The symmetric mode of coordination
of the dithiocarbamate ligands is reflected in the narrow range associated C· · · · ·S bond
distances, i.e., 1.707(3) to 1.727(3) Å, which are in fact experimentally equivalent. The
cadmium centre in 2 exists within an N2S4-donor set that defines a distorted octahedral
geometry. The greatest distortion from ideal octahedral geometry is manifested in the
◦
Table 2 Selected bond distances (Å) and bond angles ( ) for 2
◦
Bond distance (Å)
Bond angle ( )
Cd1–S2
Cd1–S3
Cd1–S4
Cd1–S5
N2–C1
N27–C26
Cd1–N23
Cd1–N12
C1–S2
2.6707(7)
2.6698(8)
2.6691(8)
2.6631(8)
1.340(3)
1.347(4)
2.402(2)
2.408(2)
1.727(3)
1.712(3)
1.707(3)
1.724(3)
S2–Cd1–S3
S4–Cd1–S5
S3–C1–S2
S4–C26–S5
N2–C1–S2
N2–C1–S3
S5–C26–N27
S4–C26–N27
S2–Cd1–S5
S3–Cd1–S4
67.44(2)
67.56(3)
119.07(16)
119.56(17)
120.9(2)
120.0(2)
119.8(2)
120.6(2)
111.77(3)
161.74(2)
C1–S3
C26–S5
C26–S4

DIIMINE ADDUCTS OF CADMIUM DITHIOCARBAMATES
1411
Figure 2 ORTEP diagram of the molecular structure of 2.
◦
N23–Cd–S2 angle of 145.60(6) , probably reflecting the influence of three tight chelate an-
◦
◦
gles in the structure [N23–Cd–N12 = 69.20(7) , S5–Cd–S4 = 67.56(3) , and S2–Cd–S3 =
◦
6
7.44(2) ]. The C–S distances are to a considerable extent shorter than the typical C–S sin-
gle bond distance 1.81 Å. Therefore, all the C–S bonds in the present structure are of partial
23–25
double bond character as observed in most of the dithiocarbamate complexes.
The
νC–N thioureide distance [1.344(4) Å] observed in the present compound is similar to other
dialkyldithiocarbamate complexes 23–25 which confirms a considerable double bond char-
acter in keeping with the infrared spectroscopic data. This reflects a significant contribution
26
made by the thioureide canonical form as discussed earlier. The 1,10-phenanthroline
ligand is almost planar. Molecular parameters associated with 1,10-phenanthroline are
normal.
The packing in 2 shows π-π stacking interactions involving the 1,10-phenanthroline
ring system. The shortest π-π ring-centroid separation of 3.691(2) Å involves the centroid
1
i
Cg of the C16–C25 ring and its inversion – generated partner Cg1 (symmetry code:
i = −x, 1−y,1−z (Figure S5, Table 3).
2.5. VBS Analysis
In the present study, the VBS method is applied to [Cd(fprdtc)2(1,10-phen)] (2) to
estimate the effective valence of the metal ion from the bond lengths reported from the
2
7,28
crystal structure, calculated by two procedures.
The values are 2.00 (OK/B) and 2.04
(B/OK), confirming the valency to be 2.0 as expected.

1412
P. J. RANI ET AL.
Table 3 Geometry of π−π interactions
◦
◦
CgI
CgJ
1(
Cgl···CgJ (Å)
Cgl···P (Å)
α ( )
β ( )
ꢀ (Å)
i)
1
1
3.691(2)
3.709(2)
3.374
3.356
0.00
2.06
23.93
25.58
1.496
1.568
(i)
2
Symmetry code: i = −x, 1−y, 1−z.
Cg represents the center of gravity of the rings N12–C25 and C16–C25, respectively, Cg1 ring A and Cg2
ring B. CgI···CgJ represents the distance between the ring centroids; CgI . . . P, the perpendicular distance of the
centroid of one ring from the plane of the other. α is the dihedral angle between the planes of rings I and J; β is
the angle between normal to the centroid of ring I and the line joining ring centroids; ꢀ is the displacement of
the centroid of ring J relative to the intersection point of the normal to the centroid of ring I and the least-squares
plane of ring J.
CONCLUSIONS
Six new complexes were prepared and characterized through elemental analysis
and spectroscopic studies. The spectral studies on complexes indicate that the additional
coordination of nitrogen donors decreases the nitrogen-carbon partial double bond character
of dithiocarbamate ligands. A single crystal X-ray structure of 2 shows that the cadmium
atom exists in a distorted octahedral geometry defined by an N2S4 donor set.
EXPERIMENTAL
All reagents and solvents were commercially available high-grade materials
(Merck/Sd fine/Himedia) and used as received. Elemental analysis was performed by
Perkin Elmer 2400 series (II) CHN analyzer. IR spectra were recorded on a THERMO
−1
NICOLET AVATAR 330 FT-IR spectrophotometer (range 4000–400 cm ) as KBr pellet.
The NMR spectra were recorded on Bruker NMR spectrometer operating at 400 MHz for
1
13
H NMR and 100.63 MHz for C NMR at room temperature in CDCl3, using TMS as
internal reference.
4.1. X-ray Crystallography
Diffraction data for 2 were recorded on an “Xcalibur, Sapphire 3” diffractometer
using graphite monochromated MoKα radiation (λ = 0.71069) at ambient temperature.
29
The structure was solved by SHELXS-97 and refined by full matrix least-squares method
29
in SHELXL-97. All the nonhydrogen atoms were refined anisotropically and the hydrogen
atoms were refined isotropically.
4.2. Preparation of Amines
N-Furfuryl-N-propylamine and N-butyl-N-furfurylamine were prepared by general
methods reported earlier.3 H and C NMR spectral data are given in supplemental
0 1
13
materials.
4.3. Preparation of [Cd(fprdtc)2] (1)
N-Furfuryl-N-propylamine (4.0 mmol, 0.55 g) in ethanol was mixed with car-
bon disulfide (4.0 mmol, 0.3 mL) under ice cold conditions. To the resultant yellow

DIIMINE ADDUCTS OF CADMIUM DITHIOCARBAMATES
1413
dithiocarbamic acid solution, an aqueous solution of Cd(CH3COO)2·2H2O (2.0 mmol,
.533 g) was added with constant stirring. The solid which precipitated was washed several
0
times with cold water and then dried (Scheme 3).
◦
−1
Yield 74%, mp 213–215 C. IR (KBr, cm ): ν = 2927 (νC–H(aliph.)), 1477 (νC–N),
1
1
014 (νC–S). H NMR (400 MHz, CDCl3, ppm): δ = 0.91 (t, 6H, J = 7.4 Hz,
N CH2 CH2 CH3), 1.73–1.79 (m, 4H, N CH2 CH2 CH3), 3.84 (t, 4H, J = 8.0 Hz,
N CH2 CH2 CH3), 5.12 (s, 4H, NCH2 (furfuryl)), 6.45 (d, 2H, J = 3.2 Hz, H–3
13
(
(
5
furyl)), 6.37 (t, 2H, J = 1.6 Hz, H–4 (furyl)), 7.40 (b, 2H, H–5 (furyl)). C NMR
100 MHz, CDCl3, ppm): δ = 11.3 (N CH2 CH2 CH3), 20.0 (N CH2 CH2 CH3),
2.4 (N CH2 CH2 CH3), 57.7 (NCH2 (furfuryl)), 110.0, 110.7, 142.5, 148.9 (furyl ring
carbons), 205.2 (NCS2). Anal. calcd. for C18H24S4N2O2Cd (%): C, 39.96; H, 4.47; N,
.18. Found (%): C, 39.63; H, 4.36; N 5.09.
5
4.4. Preparation of [Cd(fprdtc)2(1,10-phen)] (2)
A hot solution of 1,10-phenanthroline (2.0 mmol, 0.40 g) in ethanol was added to a hot
solution of complex 1 (1.0 mmol, 0.541 g) in chloroform. The resulting solution was cooled
◦
and petroleum ether (boiling range: 40–60 C) was added (100 mL). An yellow precipitate of
the heteroleptic complex separated out, which was filtered and dried. Single crystals suitable
for X-ray structural analysis were obtained from dichloromethane-acetonitrile (2:1) solvent
mixture (Scheme 3).
◦
−1
Yield 64%; mp 271–273 C. IR (KBr, cm ): ν = 3045 (νC–H(arom.)), 2923
1
(
(
(
νC H(aliph.)), 1620, 1592, 1508 (1,10-phen), 1459 (νC N), 1010 (νC–S). H NMR
400 MHz, CDCl3, ppm): δ = 0.84 (t, 6H, J = 7.4 Hz, N–CH2 CH2 CH3), 1.60–1.74
m, 4H, N CH2 CH2 CH3), 3.82 (t, 4H, J = 8.0 Hz, N CH2 CH2 CH3), 5.17 (s, 4H,
NCH2 (furfuryl)), 6.37 (b, 2H, H–3 (furyl)), 6.29 (b, 2H, H–4 (furyl)), 7.31 (b, 2H, H–5
(
8
furyl)), 9.43 (b, 2H, H–2 (1,10-phen)), 7.80 (dd, 2H, J = 4.4, 4.8 Hz, H–3 (1,10-phen)),
13
.39 (d, 2H, J = 7.6 Hz, H–4 (1,10-phen)), 7.87 (s, 2H, H–5 (1,10-phen)). C NMR
(
100 MHz, CDCl3, ppm): δ = 11.2 (N CH2 CH2 CH3), 20.0 (N CH2 CH2 CH3),
1.8 (N CH2 CH2 CH3), 56.9 (NCH2 (furfuryl)), 109.2, 110.5, 142.0, 149.8 (furyl ring
carbons), 150.1 (C–2 (1,10-phen)), 124.6 (C–3 (1,10-phen)), 128.9 (C–4a (1,10-phen)),
37.8 (C–4 (1,10-phen)), 126.8 (C–5 (1,10-phen)), 208.4 (NCS2). Anal. calcd. for
5
1
C30H32S4N4O2Cd (%): C, 49.96; H, 4.47 ; N, 7.77. Found (%): C, 49.59; H, 4.39; N, 7.61.
ꢀ
4
.5. Preparation of [Cd(fprdtc)2(2,2 -bipy)] (3)
ꢁ
A hot solution of 2,2 -bipyridine (2.0 mmol, 0.31 g) in ethanol (20 mL) was added
to a hot solution of complex 1 (1.0 mmol, 0.541 g) in chloroform (25 mL). The resulting
◦
solution was cooled and petroleum ether (boiling range: 40–60 C) was added (100 mL).
The yellow precipitate of the heteroleptic complex separated out, which was filtered and
then dried (Scheme 2).
◦
−1
Yield 64%, mp 265–267 C. IR (KBr, cm ): ν = 3053 (νC H(arom.)), 2929
ꢁ
1
(
νC H(aliph.)), 1593, 1567 (2,2 -bipy), 1469 (νC N), 1009 (νC S). H NMR (400 MHz,
CDCl3, ppm): δ = 0.84 (t, 6H, J = 7.2 Hz, N CH2 CH2 CH3), 1.64–1.76 (m, 4H,
N CH2 CH2 CH3), 3.82 (t, 4H, J = 8.0 Hz, N CH2 CH2 CH3), 5.16 (s, 4H,
NCH2 (furfuryl)), 6.37 (b, 2H, H–3 (furyl)), 6.30 (b, 2H, H–4 (furyl)), 7.32 (b, 2H,
ꢁ
H–5 (furyl)), 9.04 (d, 2H, J = 4.4 Hz, H–3 (2,2 -bipy)), 7.46 (t, 2H, J = 6.2 Hz, H–4
ꢁ
ꢁ
(
2,2 -bipy)), 7.91 (t, 2H, J = 7.8 Hz, H–5 (2,2 -bipy)), 8.13 (d, 2H, J = 8.0 Hz, H–6

1414
P. J. RANI ET AL.
ꢁ
13
(
(
1
(
2,2 -bipy)). C NMR (100 MHz, CDCl3, ppm): δ = 11.2 (N CH2 CH2 CH3), 20.0
N CH2 CH2 CH3), 51.9 (N CH2 CH2 CH3), 57.0 (NCH2 (furfuryl)), 109.3, 110.5,
ꢁ ꢁ
42.1, 149.7 (furyl ring carbons), 150.5 (C–1 (2,2 -bipy)), 150.0 (C–3 (2,2 -bipy)), 125.5
ꢁ
ꢁ
ꢁ
C–4 (2,2 -bipy)), 138.8 (C–5 (2,2 -bipy)), 121.3 (C–6 (2,2 -bipy)), 207.9 (NCS2). Anal.
calcd. for C28H32O2S4N4Cd (%): C, 48.23; H, 4.63; N, 8.04. Found (%): C, 48.01; H, 4.51;
N, 7.88.
4.6. Preparation of [Cd(bufdtc)2] (4)
A method similar to that described for the synthesis of 1 was adopted; however
N-furfuryl-N- butylamine was used instead of N-furfuryl-N-propylamine.
◦
−1
Yield 67%, mp 230–232 C. IR (KBr, cm ): ν = 2955 (νC H(aliph.)), 1481
1
(
νC N), 1011 (νC S). H NMR (400 MHz, CDCl3, ppm): δ = 0.91 (t, 6H, J = 7.4 Hz,
N CH2 CH2 CH2 CH3), 1.28–1.34 (m, 4H, N CH2 CH2 CH2 CH3), 1.69–1.73
(
5
m, 4H, N CH2 CH2 CH2 CH3), 3.89 (t, 4H, J = 8.0 Hz, N CH2 CH2 CH2 CH3),
.14 (s, 4H, NCH2 (furfuryl)), 6.45 (d, 2H, J = 2.8 Hz, H–3 (furyl)), 6.35 (b, 2H,
13
H–4 (furyl)), 7.39 (b, 2H, H–5 (furyl)). C NMR (100 MHz, CDCl3, ppm):
= 13.8 (N CH2 CH2 CH2 CH3), 20.1 (N CH2 CH2 CH2 CH3), 28.5
N CH2 CH2 CH2 CH3), 52.4 (N CH2 CH2 CH2 CH3), 56.0 (NCH2 (fur-
δ
(
furyl)), 110.3, 110.7, 142.5, 149.0 (furyl ring carbons), 204.9 (NCS2). Anal. calcd. for
C20H26S4O2N2Cd (%): C, 42.21; H, 4.96; N, 4.92. Found (%): C, 41.97; H, 4.83; N, 4.80.
4.7. Preparation of [Cd(bufdtc)2(1,10-phen)] (5)
A method similar to that described for the synthesis of 2 was adopted; however
complex 4 was used instead of complex 1.
◦
−1
Yield 61%, mp 243–245 C. IR (KBr, cm ): ν = 3049 (νC H(arom.)), 2927
1
(
νC H(aliph.)), 1619, 1590, 1507 (1,10-phen), 1468 (νC N), 1013 (νC S). H NMR (400 MHz,
CDCl3, ppm): δ = 0.87 (t, 6H, J = 7.4 Hz, N CH2 CH2 CH2 CH3), 1.21–1.30 (m,
4
4
2
3
8
H, N CH2 CH2 CH2 CH3); 1.60–1.71 (m, 4H, N CH2 CH2 CH2 CH3), 3.86 (t,
H, J = 7.6 Hz, N CH2 CH2 CH2 CH3), 5.17 (s, 4H, NCH2 (furfuryl)), 6.37 (b,
H, H–3 (furyl)), 6.30 (b, 2H, H–4 (furyl)), 7.31 (b, 2H, H–5 (furyl)), 9.45 (d, 2H, J =
.2 Hz, H–2 (1,10-phen)), 7.81 (dd, J = 4.4, 4.8 Hz, H–3 (1,10-phen)), 8.40 (d, 2H, J =
13
.0 Hz, H–4 (1,10-phen)), 7.88 (s, 2H, H–5 (1,10-phen)). C NMR (100 MHz, CDCl3,
ppm): δ = 13.8 (N CH2 CH2 CH2 CH3), 20.1 (N CH2 CH2 CH2 CH3), 28.5
N CH2 CH2 CH2 CH3), 51.7 (N CH2 CH2 CH2 CH3), 55.1 (NCH2 (furfuryl)),
09.2, 110.5, 141.7, 149.8 (furyl ring carbons), 150.1 (C–2 (1,10-phen)), 124.6 (C–3 (1,10-
phen)), 137.8 (C–4 (1,10-phen)), 128.9 (C–4a (1,10-phen)), 126.8 (C–5 (1,10-phen)), 208.2
NCS2). Anal. calcd. for C32H34N4O2S4Cd (%): C, 51.29; H, 4.84; N, 7.48. Found (%): C,
0.86; H, 4.76; N, 7.32.
(
1
(
5
ꢀ
4
.8. Preparation of [Cd(bufdtc)2(2,2 -bipy)] (6)
A method similar to that described for the synthesis of 3 was adopted; however
complex 4 was used instead of complex 1.
◦
−1
Yield 60%, mp 216–218 C. IR (KBr, cm ): ν = 3047 (νC–H(arom.)), 2927
ꢁ
1
(
νC H(aliph.)), 1592, 1567 (2,2 -bipy), 1470 (νC N), 1011 (νC S). H NMR (400 MHz,
CDCl3, ppm): δ = 0.89 (t, 6H, J = 7.2 Hz, N CH2 CH2 CH2 CH3), 1.24–1.30 (m,

DIIMINE ADDUCTS OF CADMIUM DITHIOCARBAMATES
1415
4
(
2
H, N CH2 CH2 CH2 CH3), 1.63–1.71 (m, 4H, N CH2 CH2 CH2 CH3), 3.86
t, 4H, J = 8.0 Hz, N CH2 CH2 CH2 CH3), 5.15 (s, 2H, NCH2 (furfuryl)), 6.39 (d,
H, J = 2.8 Hz, H–3 (furyl)), 6.32 (b, 2H, H–4 (furyl)), 7.34 (b, 2H, H–5 (furyl)), 9.05
ꢁ
ꢁ
(
b, 2H, H–3 (2,2 -bipy)), 7.48 (t, 2H, J = 5.8 Hz, H–4 (2,2 -bipy)), 7.94 (t, 2H, J = 7.6 Hz,
ꢁ
ꢁ
13
H–5 (2,2 -bipy)), 8.17 (d, 2H, J = 8.0 Hz, H–6 (2,2 -bipy)). C NMR (100 MHz, CDCl3,
ppm): δ = 13.8 (N CH2 CH2 CH2 CH3), 20.1 (N CH2 CH2 CH2 CH3), 28.5
(
N CH2 CH2 CH2 CH3), 51.8 (N CH2 CH2 CH2 CH3), 55.2 (NCH2 (furfuryl)),
ꢁ
109.4, 110.5, 142.1, 149.7, 149.9 (furyl ring carbons), 160.0 (C–2 (2,2 -bipy)), 151.2 (C–3
ꢁ
ꢁ
ꢁ
ꢁ
(
2
(
2,2 -bipy)), 125.3 (C–4 (2,2 -bipy)), 138.6 (C–5 (2,2 -bipy)), 121.2 (C–6 (2,2 -bipy)),
07.6 (NCS2). Anal. calcd. for C30H34O2N4S4Cd (%): C, 49.68; H, 5.00; N, 7.72. Found
%): C, 49.45; H, 4.87; N, 7.33.
SUPPLEMENTAL MATERIAL
Supplementary data for this article can be accessed on the publisher’s website,
www.tandfonline.com/gpss
Crystallographic data have been deposited with the Cambridge Crystallographic
Centre: Deposition number CCDC-955354 for 2. Copies of the data can be obtained free
of charge on application to CCDC, 12 Union Road, Cambridge, CBZ, IEZ, UK.
REFERENCES
1. Siqqidi, K. S.; Nami, S. A. A.; Chebude, L. J. Brazil. Chem. Soc. 2006, 17, 107-112.
2. Kateva, J.; Ivanov, S. K. J. Polym. Sci.: Polym. Chem. Ed. 1979, 17, 2707-2718.
3. Henckens, A.; Colladet, K.; Fourier, S.; Celij, T. J.; Lutsen, L.; Gelan, J.; Vanderzande, D.
Macromolecules 2005, 38, 19-26.
4
. Jarrett, P. S.; Dhubhghaill, O. M. N.; Sadler, P. J. J. Chem. Soc. Dalton Trans. 1993,
1863-1870.
5
6
7
8
. Manohar, A.; Karpagavel, K.; Thillai Arasu, P. Int. J. Chem. Tech. Res. 2013, 5, 1486-1494.
. Hogarth, G. Prog. Inorg. Chem. 2005, 53, 71-585.
. Tiekink, E. R. T. Cryst. Eng. Comm. 2003, 5, 101-113.
. Casas, J. S.; Sanchez, A.; Bravo, J.; Garcia-Fontan, S.; Castellano, E. E.; Jons, M. M. Inorg.
Chim. Acta 1989, 158, 119-126.
9. Suba, P. V.; Valarmathi, P.; Srinivasan, N.; Thirumaran, S.; Saminathan, K. Polyhedron 2010, 29,
1078-1082.
1
1
0. Srinivasan, N.; Jamuna Rani, P.; Thirumaran, S. J. Coord. Chem. 2008, 62, 1271-1277.
1. Valarmathi, P.; Thirumaran, S.; Kapoor, K.; Gupta, V. K.; Kant, R. Acta Crystallogr. E 2012,
68, m89.
1
1
1
1
1
1
2. Thirumaran, S.; Ramalingam, K.; Bocelli, B.; Righi, L. Polyhedron 2009, 28, 263-268
3. Srinivasan, N.; Thirumaran, S.; Ciattini, S. J. Mol. Struct. 2012, 1026, 102-107.
4. Srinivasan, N.; Thirumaran, S. Superlattices Microst. 2012, 51, 912-920.
5. Ajibade, P. A.; Ejelonu, B. C. Spectrochim. Acta A 2013, 113, 408-414.
6. Onwudiwe, D. C.; Strydom, C. A.; Hosten, E. C. Inorg. Chim. Acta 2013, 401, 1-10.
7. Dilworth, J. R.; Griffiths, D. V.; Parrott, S. J.; Zheng, Y. J. Chem. Soc. Dalton Trans. 1997,
2931-2936.
1
1
2
2
8. Bradley, D. C.; Gitlitz, M. H. J. Chem. Soc. A 1969, 1152-1156.
9. Hill, J. O.; Magee, R. J. Rev. Inorg. Chem. 1981, 3, 141-197.
0. Bonati, F.; Ugo, R. J. Organomet. Chem. 1967, 10, 257-268.
1. Van Gaal, H. L. M.; Diesveld, J. W.; Pijpers, F. W.; Van der Linden, J. G. M. Inorg. Chem. 1979,
18, 3251-3260.

1416
P. J. RANI ET AL.
22. Arul Prakasam, B.; Ramalingam, K.; Bocelli, G.; Cantoni, A. Polyhedron 2007, 26,
4489-4493.
2
2
2
2
2
2
2
3
3. Coucouvanis, D. Prog. Inorg. Chem. 1970, 11, 233-371.
4. Coucouvanis, D. Prog. Inorg. Chem. 1979, 22, 301-469.
5. Heard, P. J. Prog. Inorg. Chem. 2005, 53, 1-69.
6. Chatt, J.; Duncanson, L. A.; Venanzi, L. M. Suom. Kemistil. B 1956, 29, 75-82.
7. Keeffe, M. O.; Brese, N. E. J. Am. Chem. Soc. 1991, 113, 3226-3229.
8. Rese, N. E.; Keeffe, M. O. Acta Crystallogr. B 1991, 47, 192-197.
9. Sheldrick, G. M. Acta Crystallogr. A 2008, 64, 112-122.
0. Nabipour, H.; Ghammamy, S.; Ashuri, S.; Aghbolagh, Z. S. Org. Chem. J. 2010, 2, 75-80.