Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-membered cyclic dithiocarbamates

Article abstract of DOI:10.1080/10426507.2020.1723018

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin ent

Full text of DOI:10.1080/10426507.2020.1723018

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Organotin(IV) azepane dithiocarbamates:
Synthesis and characterization of the first
organotin(IV) complexes with seven-membered
cyclic dithiocarbamates
Ave María Cotero-Villegas, María del Carmen Pérez-Redondo, Marcela López-
Cardoso, Alfredo Toscano & Raymundo Cea-Olivares
To cite this article: Ave María Cotero-Villegas, María del Carmen Pérez-Redondo, Marcela
López-Cardoso, Alfredo Toscano & Raymundo Cea-Olivares (2020): Organotin(IV) azepane
dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-
membered cyclic dithiocarbamates, Phosphorus, Sulfur, and Silicon and the Related Elements,
DOI: 10.1080/10426507.2020.1723018
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1723018
Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the
first organotin(IV) complexes with seven-membered cyclic dithiocarbamates
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Ave Marıa Cotero-Villegas , Marıa del Carmen Perez-Redondo , Marcela Lopez-Cardoso , Alfredo Toscano , and
Raymundo Cea-Olivaresc
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b
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Facultad de Ciencias Quımicas e Ingenierıas, Universidad Autonoma del Estado de Morelos, Cuernavaca, Morelos, Mexico; Centro de
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Ciencias Quımicas, Universidad Autonoma del Estado de Morelos, Cuernavaca, Morelos, Mexico; Instituto de Quımica, Universidad Nacional
Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico, D.F., Mexico
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ABSTRACT
ARTICLE HISTORY
Received 28 October 2019
Accepted 24 January 2020
We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes
with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and
the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and
tri-cyclohexyltin: [(C4H9)2SnfS2CN(CH2)6g2] (3), [(C6H11)3SnfS2CN(CH2)6g] (4), and [(C6H11)3Sng2
(l-S2CN(C5H10)NCS2)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, and
were characterized by elemental analyses, IR, FABþ–MS, and multinuclear NMR (1H, 13C, and 119Sn)
spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray
diffraction studies. The geometrical arrangement around the tin atom can be described as dis-
torted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode
for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithio-
carbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while
(3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally
neighboring molecule, giving rise to a zig-zag polymeric structure.
KEYWORDS
Tin dithiocarbamates;
organotin complexes;
azepane; azepane-
1-carbodithioate; seven-
membered rings
GRAPHICAL ABSTRACT
Introduction
derived from dithiocarbamates are known with virtually all
metal cations, including main group[2] and the transition d
metals[3] as well as lanthanoids[4] and actinoids.[5]
Dithiocarbamates are included into the series of the 1,1-
dithiolate ligands and are by far the best known of the series.
Other relevant 1,2-dithiolate ligands include dithioxanthates,
From a structural point of view, such complexes exhibit a
dithiophosphonates, dithiophosphates, and dithiophosphinates; great diversity of coordination forms, including the classical
however, dithiocarbamate complexes manifest important monodentate, symmetric bidentate, and asymmetric biden-
peculiarities and are quite different from the other complexes tate modes as well as acting as a bridging ligand, binding to
derived from 1,1-dithiolate ligands.[1] This situation is mainly more than one metal atom.[1] As a consequence of this,
due to their wide structural diversity and the important appli- multiple bibliographical reviews have been written, both in
cations in industrial fields and in particular, for their bio- particular and general aspects.[2,3,6] In this regard, organotin
logical activity as fungicides or pesticides and for the (IV) dithiocarbamates are especially interesting due to their
important pharmacological implications. The metal complexes stereochemistry and their usefulness in biological and
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Facultad de Ciencias Quımicas e Ingenierıas, Universidad Autonoma del Estado de Morelos,
CONTACT Ave Marıa Cotero-Villegas
avecotero@uaem.mx
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Instituto de Quımica, Universidad
Avenida Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, Mexico; Raymundo Cea-Olivares
Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Mexico 04510, D.F., Mexico.
cea@unam.mx
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ß 2020 Taylor & Francis Group, LLC

2
A. M. COTERO-VILLEGAS ET AL.
Scheme 1. Preparation of seven-membered organotin(IV) dithiocarbamates (3–5).
technological fields, including recently their use as precur- example of a tin complex bearing a azepane-dithiocarbamate
sors of tin sulfide nanoparticles.[7]
ligand, specifically Sn(II), has been reported to date.[16] In add-
The properties of organotin(IV) entities with the presence ition, only a handful of examples of organometallic complexes
of a ligand with the possibility to be bounded by two sulfur bearing azepane-dithiocarbamates are known, which include
atoms to the metal center, are responsible for the chemical, with the main group elements antimony and tellurium com-
plexes[17] and in the case of transition d metals, anionic sys-
structural, and biological activity as antibacterial, antifungal,
tems with Ti and Zr.[18] The coordination chemistry of the
and anticancer agents of the organotin(IV) dithiocarbamates,
seven-membered, homopiperazine dithiocarbamate ligand is
virtually unknown and to the best of our knowledge only one
example with CpRu has been reported to date.[19]
and given the relevance of this type of complexes they have
been extensively studied and reviewed bibliographically.[8]
The studies of some organotin (IV) dithiocarbamates regard-
ing their potential anticancer activity are very encouraging,
and in some cases, showed a higher activity than that of cis-
platin.[9] It is well known that a large proportion of bio-
logically active molecular compounds contain heterocyclic
rings such as tetrazoles, thiophenes, and benzoxazoles.
Azepanes which are seven-membered rings, are an example
of such compounds. The seven membered ring is highly
flexible, allowing that the functional groups attached to it
adopt a wide variety of positions, which increases the possi-
bility of forming hydrogen bonds and other types of interac-
tions, situation that is less possible with smaller rings as the
five or six-membered and such possibility can lead to
important implications in the biological and pharmaceutical
activity.[10] The azepane ring is present in many synthetic
and natural products and is part of more than 20 FDA-
approved compounds for different pharmaceutical.[11] The
azepane moiety has been considered among the 100 most
commonly used cyclic systems in drugs composed of small
molecules, out of a total of 351 listed by the FDA.[12]
It is highly surprising that, given the relevance of dithiocar-
bamates complexes, particularly of the organotin(IV) dithiocar-
bamates, as well as the importance of the azepane system,
particularly in their biological implications as therapeutic agents,
the dithiocarbamates of organotin(IV) containing the azepane
scaffold remain unknown. Consequently, we believe that
although there are many reports regarding organotin(IV) dithio-
carbamates, which deal with several points of view, including
their synthetic and structural traits, as well as in their applica-
tions, it is relevant to promote the study of organotin(IV)
dithiocarbamates bearing the azepane scaffold. Thus, contribu-
ting to the applied research on such type of compounds as well
as, enhancing their synthetic and structural knowledge.
Results and discussion
The reaction between the organotin(IV) chlorides, di-n-butyltin
dichloride and tricyclohexyltin chloride, with the sodium salts
of azepane-1-carbodithioate (1) and homopiperazine-1,4-bis-
carbodithioate (2) carried out in chloroform, gave the corre-
sponding organotin derivatives: [(C4H9)2SnfS2CN(CH2)6g2]
The coordination chemistry of azepane-dithiocarbamate is
relatively known, with some examples of complexes with tran-
sition d cations,[13] lanthanoids (III),[14] as well as with main (3), [(C6H11)3SnfS2CN(CH2)6g] (4), and [f(C6H11)3Sng2(l-
group cations, including Sb, Bi, Tl.[15] However, only one S2CN(C5H10)NCS2)] (5) (Scheme 1), with yields ranging from

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Figure 3. Molecular structure of [f(C6H11)3Sng2 (l-S2CN(C5H10)NCS2)] (5).
The FABþ mass spectrum of (4) shows the [M þ] at m/z
544, however, the spectra of (3) and (5) do not exhibit the
molecular ion, but fragments corresponding to [M–R]þ at
m/z 526 and 906, respectively. The presence of a fragment
[M–R]þ is common to many organotin compounds, while
(3) and (4) show a peak at m/z 294 related to [SnLigand]þ
and (3) exhibits the base peak at m/z 408.
Figure 1. Molecular structure of [(C4H9)2SnfS2CN(CH2)6g2] (3).
1
The H NMR spectra show the expected proton resonan-
ces related to the ligand backbone: azepane-1-carbodithioate
and homopiperazine-1,4-bis-carbodithioate, as well as those
for the organotin entities, with the splitting patterns and
intensities consistent with the proposed structures for (3–5).
In general, the chemical shifts are very similar in (3)
and (4).
The 13C NMR spectra of (3–5) show the expected pat-
terns, with only one signal due to the CS2 groups in the
range of 198–200 ppm, that is shifted upfield with respect to
the starting sodium salts of the ligands, and in the case of
(3) it is consistent with the equivalence, in solution, of the
two ligands. The signals due to the carbon atoms of the
organotin groups do not present a significative variation in
relation to the chloride starting compounds. However, (4)
exhibits four signals which suggest that these carbons are
disposed of symmetrical manner, while (5) shows six signals,
which suggest, in solution, a distorted conformation. The 119Sn
NMR shows only one signal at –336.3, –31.1, and –20.2 ppm
for (3–5), respectively, with an upfield shift, in relation to the
corresponding starting chlorinated organotin(IV) compounds
(126.0 and 72.2 ppm for (n-Bu)2SnCl2 and (C6H11)3SnCl,
respectively), in agreement with the reported values for other
dithiocarbamate complexes.[22] Moreover, for organotin(IV)
compounds, upfield shifts in their 119Sn values correspond to
an increase in the coordination number of the metal center,[23]
and according to Otera,[24] an upfield change of 60–150 ppm
corresponds to a change in the coordination number of the tin
atom from four to five, as is seen in (4) and (5), while (3)
would present a hexacoordinated species.
Figure 2. Molecular structure of [(C6H11)3SnfS2CN(CH2)6g] (4), showing the two
crystallographic independent molecules.
41 to 98%. They present an acceptable range of melting-points
(melting intervals of less than 3 ꢀC) as well as satisfactory elem-
ental analyses, in agreement with their proposed formulas.
Compounds (3–5) are white solids, soluble in common
organic solvents such as chloroform, dichloromethane, and
acetone, but insoluble in ethanol or hexane. They are stable
toward atmospheric oxygen and moisture.
Complexes (3–5) were characterized by elemental analyses,
IR, FABþ mass spectrometry, and multinuclear NMR (1H, 13C,
and 119Sn) spectroscopy, whose details are included in the
experimental section. The crystal and molecular structures of
(3–5) were determined by single crystal X-ray techniques.
The IR spectra of (3–5) show characteristics bands due to
the ꢀN–CS2 in the range of 1407–1487 cmꢁ1, suggesting a car-
Description of the structures of (3–5)
bon-nitrogen bond order between a single (1250–1360 cmꢁ1
)
and double (1640–1690 cmꢁ1) bond, typical of the thioureide
band (1460–1550 cmꢁ1).[20] Furthermore, the presence of two
bands of medium intensity with frequencies between
Single crystals of (3–5), suitable for X-ray diffraction studies
were obtained by slow evaporation of dichloromethane solu-
tions of the corresponding complexes. The molecular struc-
1007–1094 cmꢁ1 and 917–990 cmꢁ1 are assigned to the ꢀCS2 tures for (3–5) are shown in Figures 1–3, respectively.
vibration, suggesting an asymmetric bidentate behavior of the Crystallographic data and selected bond lengths and angles
dithiocarbamate ligand.[21]
are listed in Tables 1–4. Compounds (3) and (5) crystallize

4
A. M. COTERO-VILLEGAS ET AL.
Table 1. Crystallographic data for the structural analyses of compounds (3), (4), and (5).
3
4
5
Formula
C22H42N2S4Sn
581.50
Triclinic
C25H45NS2Sn
542.45
Monoclinic
C43H76N2S4Sn2
986.67
Mr (gꢂmol–1
)
Crystal system
Space group
T (K)
Triclinic
P-1
150
P-1
150
P21/c
150
k (Å)
0.71073
0.71073
0.71073
a (Å)
b (Å)
9.5718(16)
12.170(2)
13.096(2)
68.876(4)
72.181(5)
83.141(5)
1354.7(4)
2
21.2779(12)
7.6643(4)
33.2428(19)
90
11.4392(10)
11.4437(10)
18.8428(17)
72.709(2)
79.879(2)
82.183(2)
2309.3(4)
2
c (Å)
a (ꢀ)
b (ꢀ)
104.774(1)
c (ꢀ)
90
5242.0(5)
8
1.375
1.146
V (Å3)
Z
q calc. (gꢂcm–3
)
1.426
1.263
604
1.419
1.293
1024
l (mm–1
F(000)
)
2272
Crystal size (mm3)
h range (ꢀ)
0.08 ꢃ 0.30 ꢃ 0.46
2.4 to 27.9
31260
0.32 ꢃ 0.39 ꢃ 0.40
1.0 to 27.9
99664
0.03 ꢃ 0.07 ꢃ 0.27
1.9 to 26.4
33618
Reflections collected
Rint
0.040
0.080
0.143
Data/restr./parameters
6440, 264
1.04
0.0235, 0.0525, 1.04
0.0235, 0.0525
–0.33, 0.45
12484, 560
1.06
0.0362, 0.0724, 1.06
0.0362, 0.0724
–1.44, 0.88
9441, 632
1.02
0.0896, 0.1676, 1.02
0.0896, 0.1676
–1.66, 1.42
GoF on F2
R1,a wR2b [I > 2r(I)], S
b
R1,a wR2 (all data)
Residuals (eꢂÅ–3
)
P
P
aR1 ¼ jjFoj ꢁ jFcjj/ jFoj.
P
P
bwR2 ¼ [ w(Fo ꢁ Fc ) / (Fo2)2]1/2
.
2
2 2
Table 4. Selected bond lengths (Å) and angles (ꢀ) for (5).
Table 2. Selected bond lengths (Å) and angles (ꢀ) for (3).
Sn(1)-S(1)
Sn(1)-S(2)
Sn(1)-C(9)
Sn(1)-C(15)
Sn(1)-C(21)
S(1)-C(1)
S(2)-C(1)
N(1)-C(1)
2.417(6)
3.208
Sn(2)-S(3)
Sn(2)-S(4)
Sn(2)-C(27)
Sn(2)-C(33)
Sn(2)-C(39)
S(3)-C(8)
S(4)-C(8)
N(4)-C(3)
N(4)-C(5)
2.650(6)
3.235
Sn(1)-S(1)
Sn(1)-S(2)
Sn(1)-S(3)
Sn(1)-S(4)
Sn(1)-C(17)
Sn(1)-C(21)
S(1)-C(8)
S(2)-C(8)
S(1)-Sn(1)-S(2)
S(1)-Sn(1)-S(3)
S(1)-Sn(1)-S(4)
S(2)-Sn(1)-S(3)
S(2)-Sn(1)-S(4)
S(3)-Sn(1)-S(4)
S(1)-Sn(1)-C(17)
S(2)-Sn(1)-C(17)
S(3)-Sn(1)-C(17)
S(4)-Sn(1)-C(17)
S(1)-Sn(1)-C(21)
2.562(1)
2.901(1)
2.580(1)
2.913(1)
2.157(2)
2.152(1)
1.751(2)
1.701(2)
65.8(1)
N(1)-C(8)
N(1)-C(2)
N(1)-C(7)
S(3)-C(16)
S(4)-C(16)
N(9)-C(10)
N(9)-C(15)
N(9)-C(16)
1.338(3)
1.470(3)
1.475(3)
1.746(2)
1.699(2)
1.470(3)
1.479(3)
1.335(2)
87.0(1)
2.189(12)
2.167(11)
2.140(11)
1.742(18)
1.648(19)
1.35(2)
1.499(18)
1.47(2)
61.82
157.32
2.137(12)
2.159(14)
2.207(17)
1.738(16)
1.69(2)
1.47(2)
1.477(19)
1.35(2)
59.99
158.00
100.2(4)
125.1(3)
100.9(5)
116.2(5)
112.9(5)
100.9(6)
116.8(12)
121.0(12)
122.2(12)
123.6(12)
114.1(12)
121.9(13)
N(1)-C(2)
N(1)-C(7)
S(2)-Sn(1)-C(21)
S(3)-Sn(1)-C(21)
S(4)-Sn(1)-C(21)
C(17)-Sn(1)-C(21)
S(1)-C(8)-S(2)
S(1)-C(8)-N(1)
S(2)-C(8)-N(1)
S(3)-C(16)-S(4)
S(3)-C(16)-N(9)
S(3)-C(16)-N(9)
N(4)-C(8)
83.0(1)
104.5(1)
82.0(1)
S(1)-Sn(1)-S(2)
S(2)-Sn(1)-C(9)
S(1)-Sn(1)-C(9)
S(1)-Sn(1)-C(15)
S(1)-Sn(1)-C(21)
C(9)-Sn(1)-C(15)
C (9)-Sn(1)-C(21)
C(15)-Sn(1)-C(21)
S(1)-C(1)-N(1)
S(1)-C(1)-S(2)
S(2)-C(1)-N(1)
C(1)-N(1)-C(2)
C(1)-N(1)-C(7)
C(2)-N(1)-C(7)
S(3)-Sn(2)-S(4)
S(4)-Sn(2)-C(39)
S(3)-Sn(2)-C(27)
S(3)-Sn(2)-C(33)
S(3)-Sn(2)-C(39)
C(27)-Sn(2)-C(33)
C (27)-Sn(2)-C(39)
C (33)-Sn(2)-C(39)
S(3)-C(8)-N(4)
S(3)-C(8)-S(4)
S(4)-C(8)-N(4)
C(3)-N(4)-C(8)
C(3)-N(4)-C(5)
C(5)-N(4)-C(8)
147.4(1)
148.4(1)
146.5(1)
65.1(1)
104.3(1)
83.2(1)
100.6(1)
88.6(1)
100.9(1)
146.3(1)
119.5(1)
118.4(1)
122.1(2)
118.9(1)
119.6(2)
121.5(2)
96.3(3)
109.1(3)
118.7(3)
104.6(4)
111.3(4)
114.5(4)
115.1(12)
122.2(10)
122.7(13)
122.8(13)
122.1(13)
114.6(12)
Table 3. Selected bond lengths (Å) and angles (ꢀ) for (4).
N(1)-S(1)
Sn(1)-S(2)
2.475(1)
3.173
Sn(2)-S(3)
Sn(2)-S(4)
2.464(1)
3.180
Sn(1)-C(8)
2.164(2)
2.166(3)
2.185(2)
1.758(2)
1.682(2)
1.336(3)
1.472(3)
1.474(3)
65.44
114.4(1)
116.2(1)
94.0(1)
111.4(1)
109.9(1)
109.6(1)
120.5(1)
116.1(2)
123.4(2)
Sn(2)-C(26)
Sn(2)-C(32)
Sn(2)-C(38)
S(3)-C(44)
S(4)-C(44)
N(2)-C(44)
N(2)-C(45)
N(2)-C(50)
S(3)-Sn(2)-S(4)
S(3)-Sn(2)-C(26)
S(3)-Sn(2)-C(32)
S(3)-Sn(2)-C(38)
C(26)-Sn(2)-C(38)
C(26)-Sn(2)-C(32)
S(3)-C(44)-S(4)
S(3)-C(44)-N(2)
S(4)-C(44)-N(2)
2.159(2)
2.183(2)
2.164(2)
1.761(2)
1.683(2)
1.335(3)
1.471(3)
1.473(3)
62.42
Sn(1)-C(14)
Sn(1)-C(20)
S(1)-C(1)
S(2)-C(1)
N(1)-C(1)
in the triclinic space group P1 with one molecule in the
asymmetric unit, whereas compound (4) crystallizes in the
monoclinic P21/c space group with two independent mole-
cules in the asymmetric unit. (3–5) crystallize in discrete
molecular units, and the geometry around the tin atom can
be described as octahedral in (3) and trigonal bipyramidal
in (4) and (5).
The Sn–C bond lengths correspond to 2.1574(2) and
2.152(2) Å for (3), 2.164(2), 2.166(3), and 2.185(2) Å for (4),
and 2.189(1), 2.167(1), and 2.140(1) Å for Sn1 and 2.137(1),
2.159(1), and 2.207(2) Å for Sn2 in (5), these values are
similar to those found in other organotin compounds such as
N(1)-C(2)
N(1)-C(7)
S(1)-Sn(1)-S(2)
S(1)-Sn(1)-C(8)
S(1)-Sn(1)-C(14)
S(1)-Sn(1)-C(20)
C(8)-Sn(1)-C(14)
C(8)-Sn(1)-C(20)
C(14)-Sn(1)-C(20)
S(1)-C(1)-S(2)
S(1)-C(1)-N(1)
S(2)-C(1)-N(1)
112.8(1)
94.8(1)
115.9(1)
116.2(1)
110.8(1)
120.3(1)
115.3(2)
124.3(2)

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Figure 4. Intermolecular interactions observed in compound (3).
Cy3SnfS2CNMe(2-methyl-1,3-dioxolane)g (2.159(4), 2.169(4) covalent radii [Rcov (Sn,S) ¼ 2.44 Å],[28] while the latter are
and 2.179(4) Å),[25] Cy3SnfS2CN(4-benzylpiperidine)2g significantly shorter than the sum of their van der Waals
(2.170(3) and 2.181(3) Å),[26] and n-Bu2SnfS2CN(4-benzylpi- radii [RvdW (Sn,S) ¼ 4.00 Å].[29] Taking in to account the
peridine) g (2.141(7) and 2.135(5) Å).[27] The C-Sn1-C and four coordinated atoms, the geometry around the tin atom
2 2
C-Sn2-C angles show values ranging from 109.6(1)–111.4(1)ꢀ, is an octahedron highly distorted in a nearly coplanar situ-
and from 103.6(1) to 116.2(1)ꢀ for (4), and in the case of (5), ation of the four sulfur atoms, with angles S1-Sn-S2
from 104.6(4) to 114.5(4)ꢀ and 100.9(6) to 116.2(5)ꢀ, these 65.8(1)ꢀ, S2-Sn-S4 146.5(1)ꢀ, S3-Sn-S4 65.1(1)ꢀ, and S3-Sn-
values are similar to those exhibited in SnCy3fS2CNMe(2- S1 83.0(1)ꢀ giving a sum of 360.4ꢀ. Additionally, (3) exhibits
methyl-1,3-dioxolane)g, which range from 109.1(2) to an intermolecular interaction between the tin atom with a
113.3(1)ꢀ,[25] and to those in Cy3fS2CN(4-benzylpiperidine)2 sulfur atom of the reciprocally neighboring molecule, giving
ranging from 106.3(1) to 115.11(1)ꢀ.[26]
rise to a zig-zag polymer, this interaction has a bond length
of 3.574 Å, (Figure 4). Taking into account this interaction,
In (3–5), the ligand is coordinated asymmetrically, with
different values of Sn–bond lengths. The terminal C ¼ S the sphere of coordination corresponds to a distorted pen-
bonds 1.701(2) and 1.699(2) Å for 3, 1.682(2) and 1.683(2)
Å for (4), and 1.648(19) and 1.69(2) Å in (5) are shorter
tagonal bipyramid geometry with bond angles S4-Sn-S4’ of
61.1ꢀ and S4’-Sn–S2 of 85.4ꢀ, adding these with the previous
than the S–C bonds 1.751(2) and 1.746(2) Å for 3, 1.758(2) angles give 360.4ꢀ. This approach forces the generation of
and 1.761(2) Å for (4), and 1.742(18) and 1.738(16) Å for other interactions with bond lengths H21’ꢂꢂꢂS4 2.969 Å,
(5). The bite angles and bond lengths involved in these S4ꢂꢂꢂS4’ 3.348 Å and the interaction of the second molecule
angles are close to those found in similar compounds.[25,26] with a third molecule, through the interaction S3’ꢂꢂꢂH10’’
The structure of (3) is similar to the structure of 1,1-dibu- with a length of 2.955 Å, such values are slightly lower than
tyl-1,1-bis[(4-methyl-1-piperidinyl)dithiocarbamato)]
the sum of the van der Waals radii of the correspond-
tin(IV),[27] with Sn-S short distances of 2.534(2) and 2- ing atoms.
The environment around the tin atom in (4) and (5) is
536(11) in comparison to 2.562(1) Å and 2.580(1) Å in the
case of (3), and very similar C-Sn-C angles 83.03(14)ꢀ and
83.0(1)ꢀ. The azepane and homopiperazine ligands adopt a
twisted chair conformation that is known to be the most
stable for a seven-membered cycloalkane ring.
somewhat similar; in both complexes the tin atom is five-
coordinated, bounded to three cyclohexyl groups and to the
two sulfur atoms of the azepane ligand in (4) and to the
homopiperazine ligand in (5) the coordination is asymmet-
The tin atom in (3) is coordinated by two n-butyl groups rical, with different bond lengths of 2.475(1) and 3.173 Å for
and two asymmetrically coordinated azepane-1-carbodi- (4) and 2.417(6), 2.650(6) Å, 3.208 and 3.235 Å for (5), In
thioate ligands, with Sn–S short bond lengths of 2.562(1) these cases, the length of the tin atom with the terminal sul-
and 2.580(1) Å and longer bond lengths of 2.901(1) and fur atom is longer than the present in (3), which is probably
2.913(1) Å, the former are 5% longer than the sum of their due to the steric effect of the more voluminous substituents.

6
A. M. COTERO-VILLEGAS ET AL.
The length of this intramolecular interaction is less than the high anisotropic ADP of this entities. Just one of them
sum of van der Waals radii, so considering it, then the
geometry around the tin atom is a highly distorted trigonal
bipyramidal in which the axial positions are occupied by S2
and C20 with an angle of 156.15ꢀ, while the equatorial
positions are occupied by S1, C8, and C14 with angles of
C8-Sn1-C14 of 111.4(1)ꢀ, C14-Sn1-S1 of 116.1(1)ꢀ, and S1-
Sn1-C8 of 114.4(1)ꢀ for (4). A similar situation is found in
(5) with apical angles of C9-Sn1-S2 of 157.3ꢀ and S4-Sn2-
C39 of 158ꢀ, while the angles presented by the atoms at the
equatorial positions are C15-Sn1-S1 of 109.1(3)ꢀ, C15-Sn1-
C21 of 114.5(4)ꢀ, and S1-Sn1-C21 of 118.7(3)ꢀ for Sn1 and
S3-Sn2-C33 of 125.1(3)ꢀ, C27-Sn2-C33 of 116.2(5)ꢀ, and S3-
Sn2-C27 of 100.2(4)ꢀ for Sn2. All these angles indicate devi-
ations with respect to the regular geometry, situation that
may be due to the large volume of cyclohexyl groups, that
prevent the sulfur atom from getting closer to the tin atom
as well as to achieve the coplanarity of the carbons and the
sulfur atom occupying the equatorial positions, in the same
way, impeding that they present intermolecular interactions.
On the other hand, if we omit in the sphere of coordin-
ation, the interaction of Sn-S and consider the angles C-Sn1-C
and C-Sn2-C that show values ranging from 109.6(1) to
111.4(1), and from 103.6(1) to 116.2(1) for (4), and in the case
of (5), from 104.6(4) to 114.5(4) and 100.9(6) to 116.2(5),
slightly deviated from a regular geometry (109.5ꢀ), we could
alternatively propose for the tin atoms that are four coordi-
nated and a slightly distorted tetrahedral geometry for both.
C30–C44 was also modeled into two sites and their popula-
tions paired to those of the dithiocarbamate moiety.
For compound (5) one of the azepane rings (N1-C7) dis-
plays a conformational disorder with unequal occupancies
[0.702(5):0.298(5)]. For both compounds geometric and
ADP restrains were applied by using SADI, SIMU, and
DELU SHELXL commands.
Crystallographic data for (3–5) have been deposited at
the Cambridge Crystallographic Data Centre under CCDC
1958916-1958918.
Synthesis of the starting compounds
All reagents were of commercial grade and were used as
received. Sodium salts azepane-1-carbodithioate
1 and
homopiperazine-1,4-bis-carbodithioate 2, are known com-
pounds and their identity was only verified by comparison
and were prepared using a modification of the procedure
reported in the literature, as described below.[14b]
½NafS2CNðCH2Þ6g2ꢄ
(1)
To sodium hydroxide (2.00 g, 0.05 mol) dissolved in the
minimum amount of cold water, was added cold ethanol
(50 mL). The solution was stirred vigorously in an ice bath
and azepane (4.96 g, 0.05 mol) was added. Finally, carbon
disulfide (0.05 mol, 3.05 mL) was added slowly, dropwise to
form a precipitate. The reaction mixture was allowed to stir
in a cold bath for thirty minutes in order to complete the
reaction. The yellow solid was filtered and recrystallized
from a methanol/ether mixture giving the sodium salt of the
Experimental
General comments
azepane dithiocarbamate as a shiny microcrystalline white
ꢁ1
solid. Yield: 85%. M.p. 214–217 ꢀC. IR (KBr, cm ):v3380 s,
IR spectra were recorded in the region 4000–500 cmꢁ1 as KBr
~
1
pellets, using a Brucker Tensor 27 spectrometer. H, 13C, and
3178 m, 2935 m, 2852 w, (ꢀ C–H), 1625 m, 1485 s, (ꢀ C–N,
N–C–S), 1410 s, 1367 m, (d C–H and ꢀ C ¼ N), 1284,
1259 m, 1245 m, 1188 s, 1170 m, 1047 m, and 954 s (ꢀ CS2),
975 s, 905 m, 539 m, 492 m, 455 m. 1H NMR (200 MHz,
119Sn magnetic resonance spectra were obtained on a Varian
1
Mercury 200 MHz (199.973, 50.288, and 74.571 MHz for H
and 13C), Varian Inova 400 MHz, (399.747, 100.515, and
3
1
149.01 MHz for H, 13C, and 119Sn) at ambient temperature in
DMSO-d6, ppm): d 4.09 (t, 4 H, JH–H ¼ 5.8 Hz, CH2N), 1.66
(br s, 4 H, CH2CH2N), 1.41(br m, 4 H, CH2(CH2)2N). 13C
NMR (50 MHz, DMSO-d6, ppm): d 212.5 (CS2), 53.1
(CH2N), 27.1 (CH2CH2N), 26.4 (CH2(CH2)2N).
CDCl3, CD3OD, or DMSO-d6. Chemical shifts are relative to
internal Me4Si (1H, 13C) and tetramethyltin (119Sn) for the
indicated nuclei. Mass spectra were performed on a Hewlett-
Packard MS/GS 598 instrument.
½Na2ðS2CNÞ2ðC5H10Þꢄ
(2)
Single crystals of (3–5) suitable for X-ray diffraction, were
obtained by the slow evaporation of their dichloromethane sol-
utions. Crystallographic and structural solution data are sum-
marized in Tables 1–4. Data from X-ray diffraction of single
crystal were collected with a Bruker Smart Apex CCD diffract-
ometer with Mo-Ka radiation (k ¼ 0.7107 Å). The structures
were solved by direct methods (SHELXS-SHELXL) and refined
against all data by full-matrix least-squares on F2.[30] It was
apparent from an early stage in the refinement of compounds
(4) and (5) that the molecules were disordered in some extent.
For compound (4) the bis-dithiocarbamate moiety presents dis-
order which was modeled over two sets of atomic sites having
nearly equal occupancies (0.527(3):0.473(3)]. It looks like mol-
ecule B has been rotated by 180ꢀ along the axis passing
through the nitrogen atoms N1 and N4, affecting in some
A similar procedure as for 1 was used for the sodium
homopiperazine-1,4-bis-carbodithioate (2), using sodium
hydroxide (4.00 g, 0.10 mol), homopiperazine (5.00 g,
0.05 mol), and carbon disulfide (0.10 mol, 6.10 mL) in cold
ethanol, (50 mL). The obtained yellow solid was filtered and
recrystallized from a methanol/ether mixture giving homopi-
perazine ligand a bright-yellow solid. Yield 88%. M.p. 270 ꢀC
(dec). IR (KBr, cmꢁ1): v3323 s, 2959 w, 2920 w, 2015 w (ꢀ
~
C–H), 1622 s, 1480 s, 1445 w (ꢀ C–N, N–C–S), 1408 s,
1357 m, 1332 m (d C–H, ꢀ C ¼ N), 1292 s, 1257 m, 1210 s,
1167 s, 1075 m, 977 s (ꢀasym CS2), 917 m, 875 m, 751 w,
657 m,(ꢀsym C-S), 544 m and 421 m (ꢀ S–Sn). 1H NMR
(400 MHz, CD3OD): d 4.50 (s, 4 H, NCH2CH2N), 4.16 (t,
2
3
4 H, CH2N, JH–H ¼ 12.8, JH–H ¼ 6.4 Hz), 2.34 (q, 2 H,
2
3
extent the cyclohexyl tin substituents as judging by the rather CH2CH2N, JH–H ¼ 12.8, JH–H ¼ 6.0 and 6.4 Hz) . 13C NMR

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
7
(100 MHz, CD3OD, ppm): d 213.5 (CS2), 56.6 (NCH2CH2N), l-NaS2CN(C5H10)NCS2Na (2) (0.30 g, 1.01 mmol) in chloro-
form (30 mL). White solid. M.p. 225–228 ꢀC. Yield: 98%
(0.98 g, 0.10 mmol). Anal. calc. for C43H76Sn2S4N2: C, 52.33;
H, 7.76; S, 12.99; N, 2.83. Found: C, 52.56; H, 7.91; S, 9.70;
N, 2.39. FABþ-MS (70 eV) m/z 906(20) [M-C6H11]þ,
740(10) [M-(C6H11)3]þ, 460(22) [NCS2Sn(C6H11)3]þ,
53.8 (CH2N), 23.8 (CH2CH2N).
Synthetic procedure for the preparation the
organotin(IV)) of complexes (3–5)
ꢀ
ꢁ
369(38) [Sn(C6H11)3]þ. IR (KBr, cmꢁ1): v2918 s (ꢀas C–H),
~
ðC4H9Þ2SnfS2CNðCH2Þ6g2 :
(3)
2844s (ꢀs C–H), 1477 m, 1442 m, 1407 m (ꢀs N–C ¼ S), 1329
A chloroform solution of di-n-butyltin dichloride (0.23 g,
0.76 mmol) was added slowly to sodium azepane-1-carbodi-
thioate (1) (0.30 g, 1.52 mmol) in chloroform (30 mL). The
reaction mixture was stirred at ambient temperature for
24 h. After which the precipitated was filtered off and the
solution was evaporated at low pressure using a rotary evap-
orator, giving a pale-yellow oil. Upon standing in an ice
bath, a solid was formed and washed with hexane, and iso-
lated as a white solid. M.p. 135–138 ꢀC. Yield: 41% (0.183 g,
0.31 mmol). Anal. Calc. for C22H42SnS4N2: C, 45.43; H, 7.27;
S, 22.05; N, 4.81. Found: C, 45.41; H, 7.28; S, 21.58; N, 5.27.
FABþ-MS (70 eV) m/z 526(5) [M-C4H9]þ, 408(100) [M-
S2CN(CH2)6]þ, 294(30) [SnS2CN(CH2)6]þ. IR (KBr, cmꢁ1):
w (d CH2), 1208 m, 1169 m (ꢀ CS2), 1079 w, 990 m, 917 w,
1
877 w, 841 w and 656 w(ꢀ CSS). H NMR (400 MHz, CDCl3,
3
ppm): d 4.32 (s, 4 H, NCH2CH2N), 4.02 (t, JH–H ¼ 6.4 Hz,
3
2
4 H, NCH2CH2CH2N), 2.39 (q, JH–H ¼ 6.0 y 6.4 Hz, JH–H
¼
12.4 Hz, 2 H, NCH2CH2CH2N), 1.96 (m, 18H, CHaxCHSn),
1.68 (br m, 30H, CHecCHSn and CHaxCHaxCH2CHSn) , 1.31
(m, 18H, CHecCHecCH2CHSn). 13C NMR (100 MHz, CDCl3,
ppm): d 200.3 (CS2), 56.4 (NCH2CH2N), 53.9 (NCH2CH2
CH2N), 34.9 (1JSn-C ¼ 165.5 Hz, CHSn), 32.3, 31.3 (2JSn-C
¼
8.45 Hz, 7.65Hz, CH2CHSn), 29.5, 29.0 (3JSn-C ¼ 33Hz,
32.2 Hz, CH2CH2CHSn), 27.2 (CH2CH2CH2CHSn), 22.2
(NCH2CH2CH2N). 119Sn NMR (148.96MHz, CDCl3, ppm):
d –20.1.
~
v2925 s (ꢀas C–H), 2853 m (ꢀs C–H), 1487 s, 1421 s (ꢀs
N–C ¼ S), 1368 m (d CH2), 1265 s, 1194 s (ꢀ CS2), 1094 w,
1
1071 w, 1046 w and 1007 w(ꢀ CSS). H NMR (400 MHz,
Conclusions
3
CDCl3, ppm): d 3.99 (t, JH–H ¼ 6 Hz, 8 H, CH2N), 2.06 (m,
The synthesis and characterization of the first organotin(IV)
complexes with seven-membered dithiocarbamates ligands is
presented. In the three new complexes, when considering an
asymmetric bidentate coordination it is possible to describe
a geometry around the tin atom, octahedral in 3, and tri-
gonal-bipyramidal for 4 and 5. However, omitting the long
S-Sn bonds, we propose a monodentate coordination for 4
and 5, together with the slightly distorted bond angles with
respect to regular geometry, a slightly tetrahedral geometry
could be considered alternately in both complexes. The fac-
tors that may contribute to the remarkable structural diver-
sity include the electronic properties and steric factors of the
4 H, CH2CH2Sn), 1.93 (m, 4 H, CH2CH2Sn), 1.85 (br s, 8 H,
CH2CH2N), 1.58 (br q, 8 H, CH2(CH2)2N), 1.44 (sext, 4 H,
CH2CH2CH2Sn), 0.92 (t, 6 H, CH3CH2CH2CH2Sn). 13C
NMR (100 MHz, CDCl3, ppm): d 200.1 (CS2), 55.0 (CH2N),
34.4 (CH2Sn), 28.7 (CH2CH2Sn), 27.0 (CH2CH2N), 26.8
(CH2(CH2)2N), 26.6 (CH2CH2CH2Sn), 14.0 (CH3CH2CH2
CH2Sn). 119Sn NMR (149.0 MHz, CDCl3, ppm): d –336.3.
½ðC6H11Þ3SnfS2CNðCH2Þ6gꢄ:
(4)
A similar procedure as for (3) was used for (4), starting
from (C6H11)3SnCl (0.51 g, 1.27 mmol) and (CH2)6NCS2Na
(0.25 g, 1.27 mmol) in chloroform (30 mL). White solid. M.p.
134–137 ꢀC. Yield: 83% (0.57 g, 1.10 mmol). Anal. Calc. for diorgano or triorganotin centers and/or dithiocarbamate
C25H45SnS2N: C, 55.35; H, 8.36; S, 11.82; N, 2.58. Found: C,
55.02; H, 8.39; S, 9.89; N, 2.44. FABþ-MS (70 eV) m/z 544(5)
[Mþ], 460(83) [(C6H11)3SnS2CN]þ, 446(10) [(C6H11)3SnS2C]þ,
401(10) [(C6H11)3SnS]þ, 370(10) [(C6H11)3Sn]þ, 319(25)
[(C6H11)2SnS]þ, 294(35) [SnS2CN(CH2)6]þ. IR (KBr, cmꢁ1):
ligands and less tangibly, crystal packing effects.
Acknowledgments
The spectroscopic analyses (IR, EI-MS, and multinuclear NMR 1H,
13C, and 119Sn) were performed at the Centro de Investigaciones
~
v2916 s (ꢀas C–H), 2843 s (ꢀs C–H), 1484 m, 1420 m (ꢀs
ꢀ
Quımicas, UAEM and single-crystal X-ray diffraction at the Instituto
N–C¼ S), 1360 w (d CH2), 1267m, 1170m (ꢀ CS2), 1082 w,
ꢀ
de Quımica, UNAM. The authors are grateful to the staff for this ser-
986 m, 903 w, 657 w (ꢀ CS). 1H NMR (400 MHz, CDCl3,
ꢀ
vice. We acknowledge to Prof. Bryan Sowerby and Prof. Monica Moya-
Cabrera for their helpful commentaries, and Dr. Perla -Bravo for her
technical assistance.
2
ppm): d 4.05 (t, JH–H ¼ 11.8Hz, 4H, CH2N), 1.95 (m, 9 H,
CHaxCHSn), 1.84 (br s, 4 H, CH2CH2N), 1.69 (m, 18 H,
CH2CHecCHSn), 1.58 (br s, 4 H, CH2(CH2)2N), 1.31 (m, 6 H,
CH2CH2CH2CHSn). 13C NMR (100 MHz, CDCl3, ppm): d
198.5 (CS2), 56.1 (CH2N), 34.9 (CHSn), 32.2 (CH2CHSn), 31.2
(CH2CH2CHSn), 29.6 (CH2CH2CH2CHSn), 27.2 (CH2CH2N),
26.9 (CH2(CH2)2N). 119Sn NMR (149.0 MHz, CDCl3, ppm): d
–31.13.
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