Synthesis and structural characterization of diorganotin dithiocarbamates from 4-(ethylaminomethyl)pyridine

Article abstract of DOI:10.1002/hc.21032

Three 4-(ethylaminodithiocarbamate) methylpyridine diorganotin derivatives were prepared using a one-pot synthetic procedure from 4-(ethylaminomethyl) pyridine, carbon disulfide, KOH as a base, and the corresponding diorganotin dichloride (R = Me, nBu, Ph). All three compounds were successfully characterized in solution (¹H, ¹³C, and ¹¹⁹Sn NMR) as well as in the solid state (IR, mass spectrometry, and X-ray diffraction). In all three cases, an anisobidentate coordination mode was observed for the dithiocarbamate moiety to the tin atom, evidenced mainly by the different Sn-S bond distances obtained from the X-ray diffraction analysis. The organic groups attached to the tin atom have no influence on the reaction course, leading in each case to the formation of mononuclear complexes with the metal center in a hexacoordinated environment. Interestingly, in the solid state the methyl-tin derivative showed Pyn and SSn intermolecular interactions, which were not observed in the two other complexes. Copyright

Full text of DOI:10.1002/hc.21032

Heteroatom Chemistry
Volume 00, Number 0, 2012
Synthesis and Structural Characterization of
Diorganotin Dithiocarbamates from
4-(Ethylaminomethyl)pyridine
Victor Barba, Bonifacio Arenaza, Jorge Guerrero, and Reyna Reyes
Centro de Investigaciones Qu´ımicas, Universidad Auto´noma del Estado de Morelos, Av.
Universidad 1001, C. P. 62209 Cuernavaca, Morelos, Me´xico
Received 20 December 2011; revised 30 April 2012
INTRODUCTION
ABSTRACT: Three 4-(ethylaminodithiocarbamate)
methylpyridine diorganotin derivatives were pre-
pared using a one-pot synthetic procedure from 4-
(ethylaminomethyl)pyridine, carbon disulfide, KOH
as a base, and the corresponding diorganotin dichlo-
ride (R = Me, nBu, Ph). All three compounds were
successfully characterized in solution (1H, 13C, and
119Sn NMR) as well as in the solid state (IR, mass
spectrometry, and X-ray diffraction). In all three cases,
an anisobidentate coordination mode was observed
for the dithiocarbamate moiety to the tin atom, evi-
denced mainly by the different Sn S bond distances
obtained from the X-ray diffraction analysis. The or-
ganic groups attached to the tin atom have no in-
fluence on the reaction course, leading in each case
to the formation of mononuclear complexes with the
metal center in a hexacoordinated environment. In-
terestingly, in the solid state the methyl-tin deriva-
tive showed Py· · ·Sn and S· · ·Sn intermolecular in-
teractions, which were not observed in the two other
The chemistry of dithiocarbamate ligands is well
known [1–3] and it has been shown that they are air
and moisture stable when derived from secondary
amines but unstable when prepared from primary
amines owing to decomposition of the correspond-
ing isothiocyanates [1]. Although most studies have
been focused on complexes with transition metals
[2], tin dithiocarbamates derivatives have attracted
much attention because of their increasing poten-
tial applications [3–7]. In general, the main topic for
a considerable number of papers is the preparation
and structural analysis of tin(IV) dithiocarbamates
[8–13]. Thus, structural characteristics such as lig-
and rigidity, type and disposition of donor atoms,
and the metal geometry are the principal factors
that determine the binding features of the result-
ing complexes. Therefore, significant structural vari-
ations can be mainly associated with bulky effects on
the amine moiety or the presence of secondary inter-
actions. For instance, in diorganotin(IV) complexes
[R2Sn(S2CNR2)2], the tin atoms generally adopt a
six coordination number having a skewed trapezoid
bipyramidal geometry, wherein the dithiocarbamate
ligand is linked in an anisobidentate manner. The
two organic alkyl groups attached to the tin atom
generally occupy the trans positions, and the sul-
fur atoms occupy the equatorial positions; neverthe-
less, when two aryl groups are present, they can be
frequently related to a cis disposition [8]. Usually,
for compounds having the dithiocarbamate group
linked to the metal center in an anisobidentate mode,
ꢀ
C
complexes.
2012 Wiley Periodicals, Inc. Heteroatom
Chem 00:1–7, 2012; View this article online at wileyon-
linelibrary.com. DOI 10.1002/hc.21032
Correspondence to: Victor Barba; e-mail: vbarba@ciq.uaem.mx.
Contract grant sponsor: Consejo Nacional de Ciencia y Tec-
nolog´ıa (CONACyT).
Contract grant number: SEP-2004-C01-47347.
2012 Wiley Periodicals, Inc.
c
ꢀ
1

2
Barba et al.
6
(1) 2KOH
(2) 2CS2
R
Sn
R
5
S
S
S
S
7
(3) R2SnCl2
2H2O
2KCl
N
N
NH
+
2
r.t. MeOH
4
3
2
1
1: R = Me
2: R = nBu
3: R = Ph
N
N
N
SCHEME 1 Synthesis of diorganotin dithiocarbamates derived from 4-(ethylaminomethyl)pyridine.
the two Sn S bond distances are different: The first
RESULTS AND DISCUSSION
˚
˚
is approximately 2.5 A, and the other is ca. 3.0 A. The
˚
C N bond distance varies from 1.32 to 1.43 A, and
The secondary amine, 4-(ethylaminomethyl) pyri-
dine, was used as a starting material for the forma-
tion of diorganotin complexes in a one-pot synthetic
procedure (Scheme 1). The mixture containing the
secondary amine, carbon disulfide, potassium hy-
droxide, and the corresponding diorganotin dichlo-
ride (R2SnCl2, R = Me, nBu, and Ph) was stirred at
room temperature in methanol to give, after workup,
compounds 1, 2 and 3. All products were obtained
with moderate yields (54%, 75%, and 99%, respec-
tively) and are air-stable and soluble in common or-
ganic solvents.
The composition of the resulting products was
established as far as possible by mass spectrometry,
IR, UV vis, NMR spectroscopy (1H, 13C, and 119Sn),
and X-ray single crystal crystallography. The forma-
tion of the dtc ligand was evidenced first from the
IR, 13C, and 119Sn NMR analysis. The IR spectra
of these derivatives exhibit strong bands in the re-
gion of 1482–1485 cm−1, which can be attributed to
the vibration of the N-CS2 group. Also, strong bands
at 955–959 cm−1 due to (CS2) vibration suggest the
chelating character of the dithiocarbamate ligand in
all cases. UV vis spectra were recorded in methanol;
for all three compounds, two absorption bands were
observed at 240–248 and 277–281 nm. The two bands
can be assigned to π–π∗ and n–π∗ transitions of dith-
icarbamate groups characteristic of tin complexes
[24].
the S C S angle ranges from 117◦ to 129◦ [8–13].
Dithiocarbamate moieties have also been used as
building blocks for crystal engineering in the prepa-
ration of macrocycles [14–17], capsules [18–20],
catenanes [21], and multimetallic assemblies [22].
Furthermore, their importance has increased be-
cause of their ability to encapsulate ions and neutral
molecules [18,23]. A molecular receptor analysis re-
vealed that dithiocarbamate moieties are labile and
being replaced by monoanions such as acetate, hy-
drogen sulfate and fluoride; giving evidence of their
potential use as chromogenic sensors of anion bind-
ing [24].
In addition, dithiocarbamate ligands and their
derivatives have shown important biological prop-
erties [8]. For example, organotin dithiocarbamates
exhibited potential as anticancer agents when they
were evaluated against a number of human can-
cer cell lines [25]. Antifungal test activity experi-
ments revealed that tin dithiocarbamates are effec-
tive against Candida albicans (ATCC 18804) and C.
tropicalis (ATCC 750) [26]. Also, triorganotin dithio-
carbamates have insecticidal activity against some
mosquito larval species [27].
The interest in tin dithiocarbamates continues
to attract significant attention owing to their many
and various applications in fields as diverse as biol-
ogy, chemistry, organic synthesis, and supramolec-
ular chemistry. Herein, we explored the potential
of 4-(ethylaminomethyl)pyridine as a functionalized
dithiocoordinated (dtc) ligand. The presence of the
pyridine arm within the dtc ligand allows us to an-
alyze the possible formation of N Sn coordinative
bonds to give large oligomeric or polymeric chains
supported by intermolecular interactions.
The NMR analysis reveals molecular symmetry
because signals for only half of the molecules were
1
observed. A comparison of the H NMR spectra be-
tween 4-(ethylaminomethyl)pyridine and the result-
ing products showed significant displacements to
lower fields for the two NCH2 methylene groups (1:
ꢀδ = 1.16 and 1.12 ppm, 2: 1.46 and 1.16 ppm, 3:
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Structural Characterization of Diorganotin Dithiocarbamates from 4-(Ethylaminomethyl)pyridine
3
TABLE 1 Crystallographic Data for Compounds 1, 2, and 3
Crystallographic Data
1
2
3c
Empirical formula
Formula weight
Crystal size (mm3)
Crystal system
Space group
C20H28N4S4Sn
571.39
C26H40N4S4Sn
655.55
0.39 × 0.24 × 0.12
Monoclinic
C2
C30H32N4S4Sn
696.53
0.40 × 0.34 × 0.20
0.44 × 0.28 × 0.20
Triclinic
Monoclinic
P − 1
C2/c
Unit cell dimensions
˚
a (A)
10.366(6)
12.019(7)
20.576(12)
26.997(7)
7.3866(19)
7.758(2)
25.255(10)
7.226(3)
17.757(7)
˚
b (A)
˚
c (A)
˚
α (A)
89.059(10)
79.196(10)
90
95.226(4)
90
β (◦)
111.000(6)
˚
γ (A)
87.115(9)
2515(3)
4
1.509
1.362
16628
5317 (0.033)
531
90
1540.6(4)
2
1.413
1.122
7513
2715 (0.037)
161
90
3025(2)
4
1.527
1.148
8337
3
˚
Volume [A ]
Z
ρcalcd (g/cm3)
μ (mm−1
)
Collected reflections
Independent reflections (Rint
Parameters
)
1597 (0.035)
178
R1 [I > 2σ (I )]
wR2 (all data)
GOOF
0.031
0.069
1.050
0.036
0.077
1.088
0.024
0.058
1.167
1.15 and 1.06 ppm). For compound 1, the signal of
the Me-Sn group was observed at δ = 1.53 ppm with
a coupling constant 2 J(119Sn-1H) of 82 Hz, which,
in accordance with Lockhart’s equation [28], corre-
sponds to a C Sn C bond angle of 133◦, indicat-
ing an approximate trans disposition of the methyl
groups attached to the tin center.
served at m/z = 331 and 92, corresponding to ligand–
tin (1:1) and PyCH2 fragments, respectively.
The structural characterization was completed
by X-ray diffraction analysis. All three compounds
were crystallized by slow evaporation of saturated
chloroform solutions. Data were acquired at room
temperature for compounds 1 and 2, and at 100 K
for compound 3. The most relevant crystallographic
data are summarized in Table 1. A view of the molec-
ular structures for 1–3 is given in Figs. 1–3. Se-
lected bond lengths and bond angles are given in
The 13C NMR spectra also showed that the sig-
nals for the carbon atoms of the two NCH2 groups
are displaced to lower fields in comparison with the
starting material (1: ꢀδ = 6.0 and 3.5 ppm, 2: 5.9 and
3.5 ppm, 3: 7.1 and 4.6 ppm). In addition, the signal
for the carbon atom of the dithiocarbamate group
was observed at δ = 202.1, 202.9, and 201.7 ppm
for 1, 2, and 3 respectively, confirming the tin–dtc
complex formation.
The 119Sn NMR spectroscopic data established
the coordination number of the tin atoms. According
to the information reported in the literature [3–7],
the 119Sn NMR chemical shift for compounds 1 (δ
= −333), 2 (δ = −335), and 3 (δ = −448) indicates
that the tin atoms are hexacoordinated in solution,
showing that two dtc ligands are joined to the metal
center.
Further evidence for the complex formation was
obtained from the mass spectra (EI). In all three
cases, a fragment corresponding to the ion that has
lost the two organic groups of the tin atom [M 2R]+
was found (m/z = 542); nevertheless, the molecular
ion was not observed. Other common peaks were ob-
FIGURE 1 Molecular structure of 1; thermal ellipsoids are at
the 35% probability level.
Heteroatom Chemistry DOI 10.1002/hc

4
Barba et al.
FIGURE 2 Molecular structure of 2; thermal ellipsoids are at
the 35% probability level.
Table 2. For compound 1, there are two independent
molecules in the asymmetric unit. Herein, we in-
clude the structural description of both for compar-
ative purposes. In contrast, compounds 2 and 3 crys-
tallize in the C2 and C2/c space groups; therefore, it
was only necessary to solve half of the molecules.
The molecular structures for compounds 1–3
are depicted in Figs. 1–3, respectively. In all three
compounds, the two dtc moieties are coordinated
to the tin atom in an anisobidentate manner, which
is typical for this type of ligand [8–13]. The cova-
lent Sn S bond distances are in the range from
FIGURE 3 Molecular structure of 3; thermal ellipsoids are at
the 35% probability level.
nation interactions range from 2.943(5) to 3.033(3)
˚
A. As a result of the differences in the Sn S bond
distances, the coordination geometry can be de-
scribed as a skewed-trapezoidal bipyramid, as ob-
served for analogous complexes [3–7]. The aniso-
bidentate character can also be noticed from the
different C S bond distances: The shorter distances
˚
2.4794(11) to 2.5428(16) A, and the Sn· · ·S coordi-
◦
˚
TABLE 2 Selected Bond Distances (A) and Bond Angles ( ) for Compounds 1, 2, and 3
1a
2
3
˚
Bond distances (A)
Sn1 S1
Sn1 S2
Sn1 Cα
Sn1 Cα
C1 S1
C1 S2
C1 N1
2.943(5)/2.849(4)
2.5428(5)/2.579(4)
2.116(5)/2.113(4)
2.115(5)/2.104(4)
1.678(5)/1.695(4)
1.738(5)/1.730(4)
1.333(6)/1.323(5)
3.006(7)
2.5220(6)
2.134(5)
2.134(5)
1.704(6)
1.730(7)
1.331(8)
3.033(3)
2.4794(3)
2.123(3)
2.123(3)
1.688(4)
1.760(4)
1.325(4)
ꢁ
Bond angles (◦)
S1 Sn1 S2
S1 Sn1 S2Ab
S1 Sn1 S1Ac
S1 Sn1 Cα
64.73(13)/65.65(14)
147.52(14)/142.72(14)
147.48(14)/154.08(14)
83.76(15)/87.64(14)
85.45(15)/89.17(14)
82.96(6)/77.19(14)
147.56(4)/142.72(14)
106.03(15)/102.37(15)
100.97(13)/101.10(15)
143.02(14)/152.52(15)
119.90(3)/118.80(3)
117.1(4)/118.6(3)
64.29(12)
146.75(13)
148.95(13)
85.47(12)
85.47(12)
82.50(6)
146.75(13)
106.48(14)
106.49(14)
135.6(3)
64.29(3)
145.86(3)
149.84(4)
86.99(3)
79.37(4)
81.57(5)
145.86(3)
112.63(9)
107.75(10)
125.81(18)
118.9(2)
117.2(3)
122.7(3)
120.0(3)
ꢁ
S1 Sn1 Cα
S2 Sn1 S2Ab
S2-Sn1-S1Ac
S2 Sn1 Cα
ꢁ
S2 Sn1 Cα
Cα Sn1 Cα
S2 C1 S1
S2 C1 N1
C1 N1 C2
C1 N1 C4
ꢁ
119.7(4)
117.9(5)
122.6(5)
122.5(4)
121.6(5)/121.5(4)
122.7(4)/123.1(4)
aThere are two independent molecules in the asymmetric unit.
bFor compound 1 S2A = S4.
cFor compound 1 S1A = S3.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Structural Characterization of Diorganotin Dithiocarbamates from 4-(Ethylaminomethyl)pyridine
5
FIGURE 4 Perspective view of the fragment formed by N(py) · · ·Sn and Sn· · ·S interactions in compound 1.
˚
of a fragment in which four molecules are connected
(Fig. 4); however, no chain propagation throughout
the lattice was observed. It is important to remark
that this behavior was not observed for compounds
2 and 3 mainly because the presence of large bulk ef-
fects of the nBu and Ph groups bonded to Sn atoms.
range from 1.678(5) to 1.704(6) A, whereas the larger
˚
distances range from 1.730(7) to 1.760(4) A (Table 2).
The shorter angle around the tin center corresponds
to the S1 Sn1 S2 bond angle, which is in the range
from 64.29◦(3) to 65.65◦ (14). In contrast, there
are three large angles, S1 Sn1 S2A, S1 Sn1 S1A,
and S2 Sn1 S2A,that range from 142.72◦(14) to
149.84◦(4). On the other hand, the organic group
attached to the tin atom has trans disposition be-
CONCLUSIONS
ꢁ
The formation of diorganotin complexes was con-
firmed in all three cases by spectroscopic techniques
showing that the organic moieties attached to the tin
atoms have no influence on the reaction course. As
expected, the dithiocarbamate ligand has a chelat-
ing coordination mode leading to a hexacoordinated
geometry for the tin atom. For the dimethyltin com-
plex, secondary Py· · ·Sn and S· · ·Sn intermolecu-
lar interactions have been observed, leading to the
formation of aggregates containing four molecular
units.
tween each other. As expected, the Cα-Sn-Cα bond
angle decreases in the following direction: Me > nBu
> Ph (143.0◦(2)/152.52◦(15)) for Me, 135.6◦(3) for
nBu, and 125.81◦(18) for Ph). The fact that the Me
ꢁ
derivative showed the largest Cα Sn Cα angle can
be attributed to the formation of secondary interac-
tions at the supramolecular level. For instance, there
are intermolecular N(Py) · · ·Sn interactions with a dis-
˚
tance of 2.978 A (Fig. 4), providing the tin atom with
a hepta-coordinated geometry. This additional inter-
action between N and S atoms in complex 1 could
also be associated with the smaller hindrance effect
on the methyl bond to the tin atom in comparison
with the bulkier R-groups in complex 2 and 3. In fact,
the N· · ·Sn distance observed is longer when com-
pared with the intermolecular N(py) Sn distances of
EXPERIMENTAL
All reagents and solvents used were obtained from
Aldrich (St. Louis, MO) and used without further pu-
1
rification. The H, 13C, and 119Sn NMR spectra were
˚
2.450 and 2.468 A reported for tin derivatives with
recorded at room temperature using a Varian VXR
400 spectrophotometer (Varian, Santa Clara, CA).
Standard references were used: TMS (internal, H,
the same geometry [29]. In addition, the formation
of four-membered rings Sn2S2 through intermolecu-
1
˚
lar Sn· · ·S (3.724 A) interactions was observed, lead-
δ = 0.00 ppm, 13C, δ = 0.0 ppm) and SnMe4 (exter-
nal, 119Sn, δ = 0.0 ppm). The 2D COSY and HET-
COR experiments were carried out for the unam-
biguous assignment of the 1H and 13C NMR spectra.
Infrared spectra were recorded on a Bruker Vector
22 FT-IR spectrophotometer (Michael Faraday Lab.,
DeKalb, IL). Mass spectra were obtained using a Jeol
ing to the dimerization of neighboring molecules.
The four-membered rings have been previously ob-
served for some dithiocarbamate derivatives [8] and
are related to the four-membered Sn2O2 rings found
in diorganotin ONO tridentate ligands [30–32]. The
presence of both Sn· · ·N and Sn· · ·S intermolecular
interactions in compound 1 leads to the formation
Heteroatom Chemistry DOI 10.1002/hc

6
Barba et al.
Mstation JMS 700 equipment (JEOL Ltd., Tokyo,
Japan). Melting points were determined with a
Bu¨chi B-540 digital apparatus (BUCHI Corp., New
Castle, DE). The electronic absorption spectra were
recorded at 25◦C on a HP 8452A diode-array spec-
trophotometer (Hewlett-Packard, Santa Clara, CA).
X-ray diffraction studies were performed on
a Bruker-APEX diffractometer (Bruker AXS, Karl-
sruhe, Germany) with a CCD area detector, Mo Kα-
3.28 mmol) in methanol (20 mL), carbon disulfide
(0.25 g, 3.28 mmol) was added. The solution was
stirred at room temperature for 2 h, and then a solu-
tion of di-nbutyltin dichloride (0.500 g, 1.64 mmol)
in methanol (10 mL) was added, whereupon the so-
lution was stirred for two additional hours. After
filtration, the product was recovered by complete
evaporation. A colorless solid was obtained. Yield
75% (0.85 g). Crystals suitable for X-ray crystallog-
raphy were grown from slow evaporation of a chlo-
roform solution. mp 124–126◦C. 1H NMR (400 MHz,
CDCl3) δ (ppm): 8.48 (4H, d, J = 5.6 Hz, H1), 7.21
(4H, d, J = 5.6 Hz, H2), 5.26 (4H, s, H4), 3.82 (4H,
q, J = 6.5 Hz, H5), 1.15 (6H, t, J = 6.5 Hz, H6),
1.70–2.00 (m, 4H, α), 1.70–2.00 (m, 4H, β), 1.34 (sex,
4H, J = 7.2 Hz, γ ), 0.86 (t, 6H, J = 7.2 Hz, δ). 13C
NMR (100 MHz, CDCl3) δ (ppm): 202.9 (C7), 150.2
(C1), 122.0 (C2), 144.8 (C3), 56.0 (C4), 49.7 (C5), 12.2
(C6), 34.5 (Cα), 28.8 (Cβ), 26.6 (Cγ ), 14.1(Cδ). 119Sn
NMR (74.5 MHz, CDCl3) δ (ppm): −335. IR (KBr) v
(cm−1) = 1483 (N C, s), 1183 (CS2assym, m), and 959
(CS2sym, m). EI-MS m/z (%): 542 ([M 2Bu]+, 10), 445
([M C9H11N2S2]+, 87), 331 ([M C9H11N2S2-2Bu]+,
47), 92 ([C6H6N]+, 100). Elemental Anal. Calcd for
C26H40N4S4Sn: C 47.63, H 6.15, N 8.55. Found: C
47.18, H 5.96, N 8.19. UV vis in methanol λ nm (log
ε): 245 (4.26), 277 (2.17).
˚
radiation, λ = 0.71073 A, and graphite monochro-
mator. Frames were collected at T = 293 K for 1 and
2 and at 100 K for 3 by ω rotation (ꢀ/ω = O.3◦) at 10
s per frame. The measured intensities were reduced
to F2. Structure solution, refinement, and data out-
put were carried out with the SHELXTL program
package [33]. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in geo-
metrically calculated positions using a riding model.
4-(Ethylaminodithiocarbamate)methylpyridine
Dimethyltin(IV) 1
To a solution of 4-(ethylaminomethyl) pyridine
(0.619 g, 4.54 mmol) and potassium hydroxide (0.25
g, 4.45 mmol) in methanol (20 mL), carbon disul-
fide (0.346 g, 4.54 mmol) was added. The solution
was stirred at room temperature for 2 h, and then
a solution of dimethyltin dichloride (0.500 g, 2.27
mmol) in methanol (10 mL) was added, whereupon
the solution was stirred for two additional hours. Af-
ter filtration, the product was recovered by complete
evaporation. A colorless solid was obtained. Yield
54% (0.80 g). Crystals suitable for X-ray crystallog-
raphy were grown from slow evaporation of a chlo-
roform solution. mp 188–190◦C. 1H NMR (400 MHz,
CDCl3) δ (ppm): 8.52 (4H, d, J = 5.8 Hz, H1), 7.11
(4H, d, J = 5.8 Hz, H2), 5.04 (4H, s, H4), 3.78 (4H,
q, J = 7.2 Hz, H5), 1.21 (6H, t, J = 7.2 Hz, H6), 1.53
(6H, s, 2 J(119Sn-1H) = 82 Hz, H8). 13C NMR (100
MHz, CDCl3) δ (ppm): 202.1 (C7), 150.3 (C1), 122.1
(C2), 144.6 (C3), 56.0 (C4), 49.8 (C5), 12.1 (C6), 15.8
(C8). 119Sn NMR (74.5 MHz, CDCl3) δ (ppm): −333.
IR (KBr) v (cm−1) = 1482 (N C, s), 1181 (CS2assym, m)
and 955 (CS2sym, m). EI-MS m/z (%): 542 ([M 2Me]+,
15), 361 ([M C9H11N2S2]+, 100), 331 ([M C9H11N2S2-
2Me]+, 25), 92 ([C6H6N]+, 64). Elemental Anal. Calcd
for C20H28N4S4Sn: C 42.04, H 4.94, N 9.80. Found: C
41.78, H 4.76, N 9.67. UV vis in methanol λ nm (log
ε): 240 (4.41), 279 (2.21).
4-(Ethylaminodithiocarbamate)methylpyridine
Diphenyltin(IV) 3
To
a solution of 4-(ethylaminomethyl)pyridine
(0.396 g, 2.90 mmol) and potassium hydroxide
(0.162 g, 2.90 mmol) in methanol (20 mL), carbon
disulfide (0.221 g, 2.90 mmol) was added. The solu-
tion was stirred at room temperature for 2 h, and
then a solution of diphenyltin dichloride (0.500 g,
1.45 mmol) in methanol (10 mL) was added, where-
upon the solution was stirred for two additional
hours. After filtration, the product was recovered
by complete evaporation. A colorless solid was ob-
tained. Yield 99% (1.11 g). Crystals suitable for X-ray
crystallography were grown from slow evaporation
1
of a chloroform solution. mp 179–181◦C. H NMR
(400 MHz, CDCl3) δ (ppm): 8.45 (4H, d, J = 5.7 Hz,
H1), 7.04 (4H, d, J = 5.7 Hz, H2), 4.95 (4H, s, H4),
3.72 (4H, q, J = 7.0 Hz, H5), 1.19 (6H, t, J = 7.0
Hz, H6), 7.85 (4H, dd, J = 7.6, 1.6 Hz, o), 7.29–
7.36 (m, 6H, m, p). 13C NMR (100 MHz, CDCl3) δ
(ppm): 201.7 (C7), 150.5 (C1), 122.0 (C2), 144.1 (C3),
57.1 (C4), 50.9 (C5), 12.3 (C6), 150.3 (i), 134.3 (o),
128.5 (m), 128.9 (p). 119Sn NMR (74.5 MHz, CDCl3)
δ (ppm): −448. IR (KBr) v (cm−1) = 1485 (N C,
s), 1187 (CS2assym, m) and 957 (CS2sym, m). EI-MS
m/z (%): 542 ([M 2Ph]+, 20), 485 ([M C9H11N2S2]+,
4-(Ethylaminodithiocarbamate)methylpyridine
Di-nbutyltin(IV) 2
To a solution of 4-(ethylaminomethyl)pyridine (0.45
g, 3.30 mmol) and potassium hydroxide (0.184 g,
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Structural Characterization of Diorganotin Dithiocarbamates from 4-(Ethylaminomethyl)pyridine
7
31), 331 ([M C9H11N2S2-2Ph]+, 8), 92 ([C6H6N]+,
100). Elemental Anal. Calcd for C30H32N4S4Sn: C
51.80, H 4.64, N 8.05. Found: C 51.70, H 4.32, N
7.87. UV vis in methanol λ nm (log ε): 248 (4.37),
281 (2.11).
[14] Wong, W. W. H.; Curiel, D.; Lai, S. W.; Drew, G. B.;
Beer, P. D. Dalton Trans 2005, 774–781.
[15] Reyes-Mart´ınez, R.; Mejia-Huicochea, R.; Guerrero-
Alvarez, J. A.; Ho¨pfl, H.; Tlahuext, H. Arkivoc 2008,
19–30.
[16] Santacruz-Juarez, E.; Cruz-Huerta, J.; Herna´ndez-
Ahuactzi, I. F.; Reyes-Mart´ınez, R.; Tlahuext, H.;
Morales, H.; Ho¨pfl, H. Inorg Cherm 2008, 47, 9804–
9812.
SUPPLEMENTARY DATA
[17] Rojas-Leo´n, I.; Guerrero-Alvarez, J. A.; Herna´ndez-
Paredes, J.; Ho¨pfl, H. Chem Commun 2012, 48, 401–
403.
[18] Beer, P. D.; Berry, N. G.; Cowley, A. R.; Hayes, E. J.;
Oates, E. C.; Wong, W. W. H. Chem Commun 2003,
2408–2409.
[19] Reyes-Mart´ınez, R.; Garc´ıa y Garcı´a, P.; Lo´pez-
Cardoso, M.; Ho¨pfl, H.; Tlahuext, H. Dalton Trans
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2011, 696, 693–701.
CCDC Nos. 801196-801198 contain the supple-
mentary crystallographic data for compounds 1–
3, respectively. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
[21] Wong, W. W. H.; Cookson, J.; Evans, E. A. L.;
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Heteroatom Chemistry DOI 10.1002/hc