Investigation of complexation behavior of the dithiocarbamates of N1,Nn-dicinnamylalkane-1,n-diamines with metals

Article abstract of DOI:10.1016/j.molstruc.2018.11.102

Synthesis and characterization of metal dithiocarbamate complexes of N¹,N³-dicinnamylpropane-1,3-diamine, N¹,N⁴-dicinnamylbutane-1,4-diamine and N¹,N⁶-dicinnamylhexane-1,6-diamine are reported. The ligands are prepared using cinnamaldehyde and primary diamines to provide the corresponding diimines, followed by reduction with NaBH₄ to afford the corresponding secondary diamines. Diamines react with carbon disulfide in basic medium to furnish the corresponding bis(dithiocarbamate) salts, which underwent complexation with metals. The prepared complexes were characterized by IR, ¹H and ¹³C NMR, TGA and elemental analyses. Although the dinuclear metal dithiocarbamate macrocyclic complexes were obtained from N¹,N⁶-dicinnamylhexane-1,6-diamine, the propane and butane diamines afforded the corresponding polymers. The synthesized complexes do not show any crystalline phase even in long lasting terms. Electron microscopy obviously shows that the material is amorphous, and X-ray diffraction technique is employed to investigate atom-atom distances in the molecule via the Fourier transform analysis of XRD data collected from powder sample.

Full text of DOI:10.1016/j.molstruc.2018.11.102

Accepted Manuscript
1
n
Investigation of complexation behavior of the dithiocarbamates of N ,N -
dicinnamylalkane-1,n-diamines with metals
Azim Ziyaei Halimehjani, Farzaneh Soleymani Movahed, Mohammad B. Fathi, Rasoul
Daliri Asbforoushani, Mohammad R. Saidi
PII:
S0022-2860(18)31415-7
DOI:
https://doi.org/10.1016/j.molstruc.2018.11.102
MOLSTR 25931
Reference:
To appear in: Journal of Molecular Structure
Received Date: 8 May 2018
Revised Date: 17 November 2018
Accepted Date: 28 November 2018
Please cite this article as: A.Z. Halimehjani, F.S. Movahed, M.B. Fathi, R.D. Asbforoushani, M.R. Saidi,
1
n
Investigation of complexation behavior of the dithiocarbamates of N ,N -dicinnamylalkane-1,n-diamines
with metals, Journal of Molecular Structure (2018), doi: https://doi.org/10.1016/j.molstruc.2018.11.102.
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ACCEPTED MANUSCRIPT
N
n
N
N
n
N
2
CS /NaOH
H
H
MeOH
S
S
-
S
S
-
Na+
Na+
4
a-c
Metal salt/methanol
rt
for n=1,2
Metal salt/methanol
rt
for n=4
S
M
N
n
N
M
N
N
N
S
n
S
M
S
S
S
S
S
S
S
S
S
M
N
(
polymer)
n
M= Zn, Ni, Pd, Hg, Pb
M= Zn, Ni, Pd, Hg, Pb

ACCEPTED MANUSCRIPT
Investigation of complexation behavior of the dithiocarbamates of
1
n
N ,N -dicinnamylalkane-1,n-diamines with metals
a,*
b
c
Azim Ziyaei Halimehjani, Farzaneh Soleymani Movahed, Mohammad B. Fathi, Rasoul
d
b,٭
Daliri Asbforoushani, Mohammad R. Saidi
a
Faculty of Chemistry, Kharazmi University, 49 Mofateh St., Tehran, Iran. E-mail:
ziyaei@khu.ac.ir
b
c
Department of Chemistry, Sharif University of Technology, PO Box 11465-9516, Tehran, Iran.
Email: saidi@sharif.edu
Solid State Department, Faculty of Physics, Kharazmi University, 49 Mofateh St., Tehran, Iran
d
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA
Abstract
Synthesis and characterization of metal dithiocarbamate complexes of N ,N -dicinnamylpropane-
1
3
1
4
1
6
1
,3-diamine, N ,N -dicinnamylbutane-1,4-diamine and N ,N -dicinnamylhexane-1,6-diamine are
reported. The ligands are prepared using cinnamaldehyde and primary diamines to provide the
corresponding diimines, followed by reduction with NaBH to afford the corresponding
4
secondary diamines. Diamines react with carbon disulfide in basic medium to furnish the
corresponding bis(dithiocarbamate) salts, which underwent complexation with metals. The
1
13
prepared complexes were characterized by IR, H and C NMR, TGA and elemental analyses.
1
6
Although the dinuclear metal dithiocarbamate macrocyclic complexes were obtained from N ,N -
dicinnamylhexane-1,6-diamine, the propane and butane diamines afforded the corresponding
polymers. The synthesized complexes do not show any crystalline phase even in long lasting
terms. Electron microscopy obviously shows that the material is amorphous, and X-ray
diffraction technique is employed to investigate atom-atom distances in the molecule via the
Fourier transform analysis of XRD data collected from powder sample.
Keywords: Dithiocarbamate, Transition metals, cinnamaldehyde, diamine, radial distribution
function, X-ray diffraction

ACCEPTED MANUSCRIPT
1
. Introduction
Dithiocarbamates (DTCs) are one of the key components in the field of chemistry science. These
compounds have myriad applications that range over a variety of scientific subjects, such as
medicine, agriculture, organic synthesis, biochemistry, rubber industry, etc. [1-5]. The function
of DTCs is not limited to these fields, and in fact, their full potential is yet to be discovered. In
recent years, these compounds have also been utilized as beneficial intermediates for the
synthesis of electron donor polymers in plastic solar cells [6-8].
The very existence of two sulfur atoms in a DTC group has bestowed an extraordinary feature
upon these materials which provides the possibility to stabilize a panoramic variety of metal
ions. Due to the fact that these compounds have a considerable sturdy complexion ability, DTCs
are known as bidentate ligands, whose high yields and complex diversities with various metals
have been well documented [9].
Besides their complexation behavior, they were applied in many fields, such as producing
chemical drugs [10], functioning as intermediates in organic synthesis [11], and protecting
groups in peptide synthesis [12]. Being particularly beneficial forerunners for the development of
metal nanoparticles, dithiocarbamate complexes have shown diverse applications in the realm of
nanoscience [13-16]. These complexes are also applied as catalysts in the chemoselective
reduction of azides [17]. In fact, with several important applications for DTC complexes, it
seems that any progress in this field has been utterly vindicated by the fact that these complexes
are effective agents to metal-extraction studies [18-19]. Interestingly, they have a particular
capability to react with NO that makes them ideal NO-trapping agents [20-21].
In addition to the mentioned applications, DTC ligand has proved to be an efficient and robust
motif for the formation of extremely useful structures, such as macrocycles, cages, catenanes,
and nano-dimensional assemblies. Dinuclear macrocyclic complexes of DTCs can be simply
formed by coordination of transition metals with appropriate bis(dithiocarbamate) salts. Such
cyclic complexes with tunable internal dimensions can be applied as host for cationic, anionic,
and neutral guest species [22]. Recently, dinuclear diorganotin (IV) dithiocarbamate macrocycles
have been synthesized from R SnCl and the bis(dithiocarbamate) derivative of N,N´-
2
2
dibenzylhexamethylene-1,6-diamine [23]. In addition, pioneering works in this field by Paul D.
Beer research group are noteworthy [24].

ACCEPTED MANUSCRIPT
In continuation of our research on the chemistry of dithiocarbamates [25], in the present work,
1
n
the complexation behavior of the DTCs of N ,N -dicinnamylalkane-1,n-diamines with transition
1
3
metals is investigated. We report the complexation reaction of dithiocarbamates of N ,N -
1
4
1
6
dicinnamylpropane-1,3-diamine,
N ,N -dicinnamylbutane-1,4-diamine
and
N ,N -
dicinnamylhexane-1,6-diamine with various metal ions at room temperature. To the best of our
knowledge, there has been no report for complexation reaction of these ligands with metal ions
1
13
up to now. At last, the structures of the complexes are verified by IR, H NMR, C NMR, CHN,
and TGA analyses. The electron microscopy is utilized to investigate the probable formation of
crystalline phase with a clear look at the topography of powder. The powder sample is analyzed
by X-ray diffraction and the Radial Distribution Function (RDF) analysis of the specimen shows
quantitative real space typical lengths formed in the molecule.
2
2
. Experimental Section
.1. General
The solvents and reagents were of analytical grade. The NMR spectra were recorded on a Bruker
00 MHz spectrometer. FT-IR spectra were recorded on ABB Bomem, MB 100 spectrometer.
5
Elemental analyses were conducted with a Perkin-Elmer 2004 (II) CHN analyzer.
Thermogravimetric analysis (TGA) was performed using Agilent Technology (HP) Quadrupole
Analyzer (Netzsch - TGA 209 F1) on samples (6.80 mg for 7a, 6.08 mg for 8a and 5.74 mg for
-1
8
b by weight) at a heating rate of 20°C min between room temperature and 600 °C under a flow
of nitrogen. FESEM elecron microscopy is utilized to investigate probable formation of any
crystalline phase. The results show obviously that no crystalline phases are present in the sample
and the material is grown in completely amorphous form. This result is justified by XRD
experiments showing the diffuse peaks in the diffracted data, too.
2
.2.
General procedure for synthesis of diimines
Cinnamaldehyde (2 mmol) was dissolved in 0.5 mL of dry ethanol and diamine (1mmol) was
added to the reaction flask. The mixture of the reaction was refluxed for 2 hours at 80 °C. The
product was simply achieved by evaporation of the solvent as a yellow solid. The yield of the
reaction was 79% for 1,3-propane diamine, 82% for 1,4-butane diamine and 75% for 1,6-hexane
diamine.

ACCEPTED MANUSCRIPT
1
3
[
(0E,4E)-N ,N -bis((E)-3-phenylallylidene)propane-1,3-diamine] (3a): IR (KBr) ν 689,
-
1 1
7
2
49, 1164, 1620, 1639, 3028 cm ; H NMR (500 MHz, CDCl ) δ 8.08 (dd, 2H, J= 1 and 7 Hz,
3
CH=N), 7.36-7.52 (m, 10H, 2C H ), 6.96-6.97 (m, 4H, C H -CH=CH*2), 3.63 (t, 4H, J= 6.7
6
5
6
5
1
3
Hz, 2NCH ), 2.08 (m, 2H, NCH CH ) ppm; C NMR (125 MHz, CDCl ) δ 163.4, 141.9, 136.2,
2
2
2
3
1
29.5, 129.2, 128.6, 127.6, 59.5, 32.4 ppm.
1
4
[
(9E,14E)-N ,N -bis((E)-3-phenylallylidene)butane-1,4-diamine] (3b): IR (KBr) ν 689,
-
1 1
7
2
6
1
49, 1184, 1620, 1639, 3028 cm ; H NMR (500 MHz, CDCl
3
) δ 8.07 (dd, 2H, J= 1 and 7 Hz,
CH=N), 7.30-7.51 (m, 10H, 2C H ), 6.94-6.96 (m, 4H, C H -CH=CH*2), 3.60-3.63 (t, 4H, J=
6
5
6
5
1
3
.7 Hz, 2NCH ), 1.78-1.79 (m, 4H, 2NCH CH ) ppm; C NMR (125 MHz, CDCl ) δ 163.1,
2
2
2
3
41.8, 136.2, 129.5, 129.2, 128.6, 127.6, 61.8, 29.1 ppm.
1
6
[
(9E,16E)-N ,N -bis((E)-3-phenylallylidene)hexane-1,6-diamine] (3c): IR (KBr) ν 689, 745,
-
1
1
1
2
6
176, 1620, 1635, 3052 cm ; H NMR (500 MHz, CDCl ) δ 8.05 (dd, 2H, J = 1 and 7 Hz,
3
CH=N), 7.30-7.52 (m, 10H, 2C H ), 6.94-6.96 (m, 4H, C H -CH=CH*2), 3.54-3.57 (t, 4H, J=
6
5
6
5
1
3
2 2 2 2 2 2
.7 Hz, 2NCH ), 1.71-1.74 (m, 4H, 2NCH CH ), 1.43-1.45 (m, 4H, 2NCH CH CH ) ppm; C
NMR (125 MHz, CDCl ) δ 162.8, 141.6, 136.2, 129.4, 129.2, 128.7, 127.6, 61.9, 31.3, 27.6 ppm.
3
2
.3.
General procedure for synthesis of diamines
Diimine (1 mmol) was dissolved in methanol and sodium borohydride (4 mmol) was added
to the reaction in 0°C. The mixture was stirred overnight at room temperature. In completion,
water (10 mL) was added and the product was extracted by dichloromethane (10 mL). The
2 4
organic layer was dried over Na SO and the pure diamine was produced after evaporating the
solvent as a yellow viscous liquid in 95% for 1,3-propane diamine (4a), 87% for 1,4-butane
diamine (4b) and 90% for 1,6-hexane diamine (4c).
1
3
-
N ,N -dicinnamylpropane-1,3-diamine (4a): IR (KBr) ν 693, 741, 967, 1120, 1635, 3422 cm
1
1
;
H NMR (500 MHz, CDCl ) δ 7.20-7.36 (m, 10H, 2C H ), 6.50 (d, 2H, J= 16 Hz, C H -
3 6 5 6 5
CH=CH), 6.28 (dt, 2H, J= 6.5 and 16 Hz, C
6
H
5
-CH=CH), 3.39-3.42 (m, 4H, 2NCH
2
), 2.70-2.76
1
3
(
t, J= 6.5 Hz, 4H, 2NCH ), 1.72-1.74 (m, 2H, NCH CH ) ppm; C NMR (125 MHz, CDCl ) δ
2
2
2
3
1
37.6, 131.6, 128.9, 127.8, 127.7, 126.7, 52.4, 48.4, 30.8 ppm.
1
4
-1
N ,N -dicinnamylbutane-1,4-diamine (4b): IR (KBr) ν 693, 741, 971, 1124, 1647, 3471 cm ;
6 5
H NMR (500 MHz, CDCl ) δ 7.26-7.43 (m, 10H, 2C ), 6.55 (d, 2H, J=16 Hz, 2C H -
1
3
6
H
5

ACCEPTED MANUSCRIPT
CH=CH), 6.31 (dt, 2H, J= 16 and 6.5 Hz, 2C
6 5
H -CH=CH), 3.45-3.46 (dd, 4H, J= 6.4 and 1.5 Hz,
1
3
2
NCH ), 2.71-2.74 (t, 4H, J= 6.5 Hz, 2NCH ), 1.61-1.63 (m, 4H, 2NCH CH ) ppm; C NMR
2
2
2
2
(
125 MHz, CDCl ) δ 137.5, 131.6, 128.9, 128.5, 127.7, 126.6, 52.3, 49.7, 28.4 ppm.
3
1
6
-1
N ,N -dicinnamylhexane-1,6-diamine (4c): IR (KBr) ν 697, 745, 967, 1128, 1651, 3426 cm ;
H NMR (500 MHz, CDCl ) δ 7.24-7.42 (m, 10H, 2C H ), 6.54-6.58 (d, 2H, J=16 Hz, 2C H -
1
3
6
5
6
5
CH=CH), 6.31-6.37 (dt, 2H, J= 16.0 and 6.5 Hz, 2C
6
H
5
-CH=CH), 3.43-3.45 (d, 4H, J=6.5 Hz,
2
2
5
NCH ), 2.67-2.7 (t, 4H, J= 6.5 Hz, 2NCH ), 1.55-1.58 (m, 4H, 2NCH CH ), 1.4-1.41 (m, 4H,
2
2
2
2
13
NCH
2
2 2 3
CH CH ) ppm; C NMR (125 MHz, CDCl ) δ 137.6, 131.6, 129.0, 128.9, 127.7, 126.7,
2.4, 49.9, 30.6, 27.8 ppm.
2
.4. General procedure for synthesis of DTC complexes
Diamine (1 mmol) was dissolved in 2 mL methanol and sodium hydroxide (2 mmol) was
added to the reaction container. After 10 minutes, CS (3 mmol) was added to the flask and the
2
reaction was continued for 4-5 hours to complete the sodium bis(dithiocarbamate) salt formation.
Finally, the ultimate complexes were produced with the in situ addition of metal salts solutions
(1 mmol in appropriate solvent in Tab. 1). The complexes were readily filtered and washed with
methanol and water for several times to remove any unreacted starting materials and dried in
vacuum at 70 °C for 24h to provide the complexes as stable solids in high yields of 73-92%.
-1
(
6a): IR (KBr) ν 693, 749, 967, 1220, 1422, 1490, 1655 cm ; Anal. Calcd for C H N S Zn:
23 24 2 4
C, 52.91; H, 4.63; N, 5.37. Found: C, 50.36; H, 4.83; 5.94.
-1
(
6b): IR (KBr) ν 696, 745, 962, 1220, 1429, 1496, 1601 cm ; Anal. Calcd for C H N S Ni:
23 24 2 4
C, 53.60; H, 4.69; N, 5.44. Found: C, 52.15; H, 5.27; N, 6.50.
-1
(
6c): IR (KBr) ν 693, 741, 963, 1220, 1418, 1486, 1623 cm ; Anal. Calcd for C H N S Pd:
23 24 2 4
C, 49.06; H, 4.30; N, 4.97. Found: C, 46.65; H, 4.50; N, 5.38.
-1
(
6d): IR (KBr) ν 698, 747, 965, 1204, 1417, 1492, 1625 cm ; Anal. Calcd for C23
24 2 4
H N S Hg:
C, 42.03; H, 3.68; N, 4.26. Found: C, 41.80; H, 3.70; N, 5.01.
-1
(
6e): IR (KBr) ν 605, 737, 967, 1212, 1406, 1474, 1643 cm ; Anal. Calcd for C23
24 2 4
H N S Pb:
C, 41.61; H, 3.64; N, 4.22. Found: C, 40.8; H, 3.66; N, 4.98.

ACCEPTED MANUSCRIPT
-1 1
(
7a): IR (KBr) ν 697, 749, 967, 1212, 1422, 1490, 1636 cm ; H NMR (500 MHz, DMSO-
d ) δ 7.24-7.31 (m, 20H, 4C H ), 6.58-6.64 (d, 4H, J= 16.0 Hz, 4C H -CH=CH), 6.33 (m, 4H,
6
6
5
6
5
4
4
C H -CH=CH), 4.62 (m, 8H, 4NCH ), 3.84 (t, 8H, J= 6.5 Hz, 4NCH ), 1.75 (m, 8H,
6
5
2
2
NCH
2
CH
2
) ppm; Anal. Calcd for C24
H
26
N
2
S
4
Zn: C, 53.77; H, 4.89; N, 5.23. Found: C, 52.47;
H, 5.22; N, 6.0.
-1
(
7b): IR (KBr) ν 697, 745, 963, 1216, 1434, 1502, 1644 cm ; Anal. Calcd for
24 26 2 4
C H N S Ni: C, 54.45; H, 4.95; N, 5.29. Found: C, 51.4; H, 5.2; N, 5.48.
-1
(
7c): IR (KBr) ν 693, 745, 967, 1212, 1430, 1498, 1636 cm ; Anal. Calcd for C48
52 4 8 2
H N S Pd :
C, 49.94; H, 4.54; N, 4.85. Found: C, 50.17; H, 4.89; N, 5.33.
-1 1
(
8a): IR (KBr) ν 697, 745, 967, 1212, 1430, 1494, 1643 cm ; H NMR (500 MHz, CDCl ) δ
3
7
4
4
5
.35-7.45 (m, 20H, 4C
6 5 6 5
H ), 6.59-6.63 (d, 4H, J= 15.6 Hz, 4C H -CH=CH), 6.29-6.35 (m, 4H,
C H -CH=CH), 4.64-4.65 (brs, 8H, 4NCH ), 3.86 (brs, 8H, 4NCH ), 1.84 (brs, 8H,
6
5
2
2
1
3
NCH CH ), 1.43 (brs, 8H, 4NCH CH CH ) ppm; C NMR (125 MHz, CDCl ) δ 25.8, 26.2,
2
2
2
2
2
3
60 4 8 2
3.7, 56.6, 121.8, 126.6, 127.8, 128.6, 134.4, 135.9, 203.9 ppm; Anal. Calcd for C52H N S Zn :
C, 55.35; H, 5.36; N, 4.97. Found: C, 55.70; H, 5.36; N, 5.16.
-1 1
(
3
8b): IR (KBr) ν 693, 749, 967, 1220, 1434, 1498 cm ; H NMR (500 MHz, CDCl ) δ 7.26-
7
.61 (m, 20H, 4C H ), 6.54-6.59 (d, 4H, J= 16.0 Hz, 4C H -CH=CH), 6.11-6.12 (m, 4H, 4C H -
6
5
6
5
6
5
CH=CH), 4.33 (brs, 8H, 4NCH
2
), 3.49-3.53 (brs, 8H, 4NCH
2
), 1.43-1.64 (brs, 8H, 4NCH
2
2
CH ),
1
3
1
.22-1.31 (brs, 8H, NCH CH CH ) ppm; C NMR (125 MHz, CDCl ) δ 25.9, 26.7, 48.5, 51.0,
2 2 2 3
1
21.2, 126.6, 128.2, 128.7, 134.9, 135.8, 207.1 ppm; Anal. Calcd for C H N S Ni : C, 56.02;
52 60 4 8 2
H, 5.42; N, 5.02. Found: C, 57.45; H, 5.80; N, 5.24.
-1
1
(
8c): IR (KBr) ν 692, 745, 962, 1216, 1429, 1474 cm ; H NMR (500 MHz, CDCl ) δ 7.25-
3
7
.35 (m, 20H, 4C H ), 6.55-6.60 (d, 4H, J= 15.8 Hz, 4C H -CH=CH), 6.11-6.15 (m, 4H, 4C H -
6 5 6 5 6 5
CH=CH), 4.42 (brs, 8H, 4NCH
2
), 3.48-3.63 (brs, 8H, 4NCH
2
), 1.66 (brs, 8H, 4NCH
2 2
CH ), 1.25-
1
3
1
1
5
.32 (brs, 8H, 4NCH CH CH ) ppm; C NMR (125 MHz, CDCl ) δ 26.0, 26.7, 48.9, 51.3,
2
2
2
3
21.2, 126.6, 128.2, 128.9, 134.9, 135.7, 211.2 ppm; Anal. Calcd for C H N S Pd : C, 51.6; H,
5
2
60
4
8
2
.0; N, 4.63. Found: C, 52.65; H, 5.44; N, 4.88.
8d): IR (KBr) ν 689, 745, 959, 1200, 1414, 1486, 1679 cm ; H NMR (500 MHz, CDCl ) δ
-1 1
(
3
7
.35-7.45 (m, 20H, 4C H ), 6.59-6.62 (d, 4H, J= 15.5 Hz, 4C H -CH=CH), 6.33-6.39 (m, 4H,
6 5 6 5

ACCEPTED MANUSCRIPT
4
1
C
6
H
5
-CH=CH), 4.60-4.61 (d, 8H, J= 6.5 Hz, 4NCH
2 2
), 3.79-3.82 (t, 8H, J= 6.7 Hz, 4NCH ),
.87-1.89 (m, 8H, 4NCH CH ), 1.44-1.45 (m, 8H, 4NCH CH CH ) ppm; Anal. Calcd for
2
2
2
2
2
C H N S Hg : C, 44.65; H, 4.32; N, 4.01. Found: C, 44.40; H, 4.29; N, 4.50.
52
60
4
8
2
-1 1
(
8e): IR (KBr) ν 701, 741, 963, 1200, 1418, 1474 cm ; H NMR (500 MHz, CDCl ) δ 7.22-
3
7
.6 (m, 20H, 4C H ), 6.47-6.52 (d, 4H, J = 15.7 Hz, C H -CH=CH), 6.23-6.28 (m, 4H, C H -
6 5 6 5 6 5
CH=CH), 4.53 (brs, 8H, 4NCH ), 3.84-3.88 (brs, 8H, 4NCH ), 1.61-1.75 (brs, 8H, 4NCH CH ),
2
2
2
2
1
3
1
.25-1.36 (brs, 8H, NCH
2
CH
2
2 3
CH ) ppm; C NMR (125 MHz, CDCl ) δ 25.9, 26.5, 48.5, 51.0,
1
21.2, 126.6, 127.9, 128.6, 133.8, 136.2, 202.9 ppm; Anal. Calcd for C H N S Pb : C, 44.23;
52 60 4 8 2
H, 4.28; N, 3.97. Found: C, 45.24; H, 4.55; N, 4.52.
3
. Results and Discussion
3
.1. Synthesis of ligands and complexes
First, we focused on the synthesis of secondary diamines. For this purpose, three diverse primary
diamines including 1, 3-propane diamine, 1, 4-butane diamine, and 1, 6-hexane diamine are
surveyed. The diamines were reacted with cinnamaldehyde to provide the corresponding
diimines in high to excellent yields. The diimines then were reduced with NaBH to afford the
4
final secondary N,N’-dicinnamyl alkanediamines in excellent yields (Scheme 1).
1
n
Scheme 1. Synthesis of N ,N -dicinnamylalkane-1,n-diamines.
After characterization of the synthesized diamines and confirmation of their structures, these
diamines were applied in other reaction with carbon disulfide in alkaline medium in methanol as

ACCEPTED MANUSCRIPT
the solvent to provide the corresponding bis(dithiocarbamate) salts. The in situ prepared
2
+
2+
2+
dithiocarbamate salts then reacted with various transition metal salts including Zn , Ni , Pd ,
2
+
2+
Hg and Pb salts to provide the corresponding cage-like (macrocyclic) complexes (Scheme 2).
Finally, the ultimate products were simply filtered.
Scheme 2. Synthesis of ligands and complexes.
The resulting complexes 6 produced from N,N’-dicinnamyl propanediamine had no solubility
in common organic and NMR solvents. Although, the CHN data of complexes are in accord with
theoretical calculations, as a result of outcomes of solubility test, we suggest that these
compounds might have become polymerized. Due to the fact that the cage constructed from
sulfur atoms and the metal ions is not enough big to produce and the metals may have been
placed close to each other, polymerization might be a more plausible way for the molecules to be
arranged with one another. In the case of N,N’-dicinnamyl butanediamine, only the complex
1
with Zn had a little solubility in DMSO that enabled us to study its H NMR spectrum.
Literature survey revealed that all the dinuclear macrocyclic dithiocarbamate complexes
1
6
reported to date are synthesized using a N ,N -diamine [26]. As the next step, the chain size of
1
6
the initial diamine is increased by two more carbon atoms. We utilized N ,N -dicinnamylhexane-
,6-diamine to assure that the two metals didn’t trigger steric hindrance. The corresponding
1

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macrocyclic complexes 8a-e were obtained in excellent yields. By performing the solubility test,
it can be established that the ultimate complexes have sufficient solubility in chloroform.
1
13
3
.2. Characterization of DTC complexes by IR, H NMR, C NMR and TGA analyses
1
13
The structure of the synthesized complexes was verified by IR, H NMR, C NMR, CHN, and
TGA analyses.
3
.2.1. IR spectral studies
The characteristic band in IR spectra of DTC complexes can be assigned in the range of 940-
-1
1
050 cm , without any splitting, which is related to the symmetrical mode of DTC ligand acting
-1
in a bidentate mode [27]. In all of the synthesized complexes, a single band at 960 cm was
observed, which completely confirms a bidentate symmetrical behavior of the DTC moiety.
-1
Other characteristic bands for synthesized complexes were observed in ranges of 1450-1550 cm
-1
and 1620-1650 cm , which are attributed to the thioureide and the C=C double bond groups,
respectively.
3
.2.2. NMR spectral studies
1
H NMR spectra of the complexes show a doublet peak at 4.6 ppm and a broad peak at 3.8 ppm
for the methylene groups attached to the nitrogen. These protons in the diamine were assigned at
.4 and 2.7 ppm, respectively. The other protons of the complexes were observed at the similar
3
chemical shift in comparison to the diamine. The observed deshielding for the NCH2cinnamyl and
NCH2chain of the methylene protons (around 1 ppm) in the complexes indicates the formation of
the dithiocarbamate complexes which is related to the release of the electrons from the nitrogen
atoms of the DTC group towards the sulfur atoms (or the metal) via the thioureide π system. The
1
proton signals of the macrocyclic products appeared as broad in H NMR spectra which may be
attributed to the existence of dynamic processes in the solution. The presence of a peak at 203.9
1
3
ppm for 8a, 207.1 ppm for 8b and 211.2 ppm for 8c in C NMR spectra is assigned for the
1
3
N CS
2
carbon atoms in the complexes [26, 28].
3
.2.3. TGA analyses
The thermogravimetric analysis (TGA) was applied to evaluate the physical behavior of
bis(dithiocarbamate) complex of nickel prepared from 1,6-hexane diamine 8b (Figure 1). The

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TGA curve shows three weight losses: in the temperatures range above 100 °C (mass loss
3
2
.25%) that may be assigned for the loss of moisture and solvent residue from the sample; 200–
80 °C (mass loss 30.54%) that may be assigned for the loss of two cinnamyl isothiocyanate
°
groups (calculated mass loss 33.9%) and 270-440 C (mass loss 46.38%) was attributed to the
loss of other organic parts (calculated mass loss 48.9%). The remaining residue (20%) may be
2
assigned for the values calculated (22%) for the mass percentage of two NiS . [25a, 29]. Similar
behavior was observed for the Zn complexes 7a and 8a with 1,4-butanediamine and 1,6-
hexanediamine, but the final remaining residue may be attributed to the formation of two ZnS
(see Supplementary material).[30]
Figure 1. TGA of complex 8b.
.3. Electron microscopy and X-ray diffraction studies
In order to have a valid picture of our final products, we attempted to make crystals suitable for
3
X-ray crystallography. To do so, we applied two common methods of crystallization: tank
crystallization and diffusion method. Inasmuch as the complexes of 1, 6-hexane diamine had
shown an appropriate solubility in chloroform, we chose this solvent as the “good” solvent. In
diffusion method, we employed a spectrum of volatile solvents as the anti-solvent: ethanol,
methanol, and ethyl acetate. Despite all these efforts, there were not any crystals in the
crystallization tanks. In addition, attempt to obtain HRMS analysis of complexes was
unsuccessful. Therefore, we tried to analyze the structure by X-ray diffraction intensity showing
diffuse peaks typical of amorphous materials (vide infra).

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3
.3.1. Establishment of the atomic configuration of the molecule 8a (C52
electron microscopy and X-ray diffraction
60 4 8 2
H N S Zn ) by
Characterization of amorphous materials can be performed by a variety of techniques. As the
experiments by electron microscopy and X-ray diffraction will show, any attempts to crystallize
the molecule led to any crystalline form. FESEM is employed to make maps of real space
geometry of the morphology of the material under question and to recognize whether the
probable crystalline phases of micro-molecule are formed or not. As the results of electron
microscopy will show, no crystallization is observable in the powder of the synthesized complex.
Furthermore, XRD experiments contain diffuse peaks typical of amorphous materials that
confirm the result obtained via electron microscopy (see below). Due to its ability for obtaining
the characteristic lengths in amorphous materials, X-ray diffraction is applied to confirm atom-
atom distances in the molecule via the Fourier transforming, and the XRD data collected by two
different lab source facilities.
3
.3.1.1. FESEM Data
Here, data collected from FESEM facility are reported. The sample is coated with a thin layer of
gold to produce the conductivity. Figure 2 shows a 2µm size image of the sample. As shown in
Figure 2, the amorphous nature of the specimen is obvious and no crystalline phases are seen in
the sample.

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Figure 2. Image of the sample (2µm size)
Figure 3 is 200nm size image of the sample and confirms that no crystalline phase is
present in the sample.
s
Figure 3. Image of the sample with 29.00kV high voltage (200nm size)

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Interestingly, the samples of sizes down to 12 nm show no crystallization phases (see
Supplementary material). Therefore, we employ the XRD technique in order to progress towards
quantitatively investigating the geometry of the molecule in the next subsection.
3
.3.1.2. Local structure in 8a (C H N S Zn ) from X-ray Radial Distribution Analysis
52 60 4 8 2
X-ray experimental intensity scattered by the specimen, Iexp(q), contains the maximum
information about the atomic configuration of asymmetric units. The groundwork of Debye for
the intensity analysis scattered by a non-crystalline array of atoms makes it possible to establish
the correct atomic configuration. This is well performed by comparing the computed theoretical
function for the predicted model with the experimental intensity function obtained in X-ray
diffraction experiment.
Debye scattering equation (DSE) for the intensity scattered by a collection of atoms with a
given arbitrary arrangement in electron unit is given by [31]
sin 2pqrij
I =
fi fj
åi å
j
2
pqrij
where, f and f are the atomic scattering factor of i and j, and r is the magnitude of the vector
i
j
ij
separating i and j. The integral has been taken over all orientations of atomic arrangement in
space, to include the effect of the specimen rotation. The comparing procedure of Debye function
analysis and the trial-and-error contained in this method can be bypassed by obtaining radial
distribution function (RDF) of the sample directly, which is the real-space interatomic distance
correlation function [32]. RDF is the main machinery for the study of non-crystalline materials
through Fourier transformation analysis of X-ray diffraction data.
Two experiments are done in two different laboratories which show close results for
atom-atom distances. As shown in Figures 5 and 7, the materials’ XRD patterns contain diffuse
peaks typical of amorphous materials. The data were collected with X-ray lab-sources having Cu
lamps, which lack large scattering wavenumbers. According to the results shown below, the
quantitative establishment of the typical distances in the molecule can be realized. The
polarization and geometry effects are subtracted from the experimental data in both experiments.

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Figure 4 shows experimental diffraction data from the powder specimen which is collected by
PANAlytic lab source in KEFA COMPANY.
Figure 4. Experimental X-ray diffraction data from the powder specimen
Corresponding RDF of experimental X-ray diffraction data is shown in Figure 5.
Figure 5. Corresponding RDF of experimental X-ray diffraction data

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A parallel data collected by a different lab source experiment (XRD-PM) is shown in
Figure 6.
Figure 6. Experimental X-ray diffraction data from the powder specimen
Experimental RDF of X-ray diffraction collected in XRD-PM laboratory is shown in
Figure 7.
Figure 7. Corresponding RDF of experimental X-ray diffraction data

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Lower distances corresponding to the peaks of RDF in two graphs are tabulated in Table
. These distances are plausibly attributed to atom-atom lengths in the molecule, which are also
1
reported in the Table 1.
Table 1. Plausible attributed atom-atom lengths in the molecule
Peak Number
1
2
3
4
5
6
7
Distance (
Å
) (XRD-
1.34
5.25
8.90
12.51
16.03
19.63
23.24
KEFA
)
Distance (
Å
) (XRD-
)
1.34
5.48
5
8.59
12.45
15.80
12
19.08
14
22.53
17
PM
Number of dC= C length
6
9
N-N
N-N
Plausible Bond
C=C Zn-Zn
---
---
---
(
longitudinal) (diagonal)
2
First we define firstly typical C=C bond length, which mediates between different atoms by sp
°
overlapping, as dC= C = cos 30 ´ 1.34 ; 1.16Å . The second peak can be attributed plausibly to M-
M length for the complex with 5 C=C bonds, since the distance can be calculated through
°
dM-M = 5 ´ cos 30 ´ 1.34 ; 5.80Å . The first peak contains different distances contributing to the
peak, for example, C=C bond and sulfur-nitrogen bonds and other similar-distant bonds may
overlap to yield a diffuse peak with relatively large height. The third peak is ascribed to
meandN-N ; four N atoms construct a simple tetragon rectangle whose width and length are
respectively 5 and 6 dC= C . The fourth peak is about 9 dC= C mediating length, so we attribute it to
the diagonal of the rectangle constructed by N atoms. Because the diffuse peaks in RDF contain
different contributing atom-atom lengths, other parts cannot be inferred clearly. Other parts can’t
be inferred clearly.
4
.
Conclusion

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Being able to stabilize transition metals with a variety of oxidation states, dithiocarbamate
DTC) complexes have attracted scientists’ attention. This article described the synthesis and
(
1
n
characterization of DTC complexes based on N ,N -dicinnamylalkane-1,n-diamines. For this
purpose, cinnamaldehyde was condensed with diamines (1, 3-diaminopropane, 1, 4-
diaminobutane, 1, 6-diaminohexane) in ethanol as the solvent in order to form the related
diimines. Sodium borohydride reduction of the diimines in methanol afforded the related
diamines as yellow viscous liquids. The final complexes were prepared via the in situ reaction of
the diamines, CS and related metal salts. Although macrocyclic compounds were proved for
2
,
1
,6-hexane diamine, polymerization can be assumed for the shorter chained diamines due to the
insolubility of the corresponding complexes in diverse organic solvents.
Electron microscopy clearly shows the formation of clusters of the molecule without having
any crystalline phase. XRD intensities collected by various lab source facilities, also, show
clearly diffuse peaks typical of amorphous materials. Therefore, we employed the Radial
Distribution Function (RDF) analysis of X-ray diffracted data and investigate the atomic local
structure of the molecular complex. Atom-atom distances are calculated via Fourier transform
analysis of XRD intensity to yield a real-space visualization of the structure of the molecule.
Acknowledgement
We are grateful the research council of Kharazmi University for supporting this work. We also
thank Sharif University of Technology for financial support.
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1
n
Dithiocarbamate complexes base on N ,N -dicinnamylalkane-1,n-diamine were prepared► The
structure of complexes were assigned as polymer or macrocyclic complexes ► Complexes were
1
13
characterized by IR, H and C NMR, TGA and elemental analyses► Complexes do not show
any crystalline phase even in long lasting terms► X-ray diffraction technique is employed to
investigate atom-atom distances►