Stabilization of [(nBu2SnCl)(μ-Cl)2(ClSnnBu2)] within the solid-state structure of a Chlorodi-n-butyltin(IV) dithiocarbamate

Article abstract of DOI:10.1016/j.jorganchem.2014.07.027

The combination of bis-dithiocarbamate ligands derived from N,N′-dibenzylcyclohexane-trans-1,4-diamine with dimethyl- and di-n-butyltin(IV) dichloride provided two discrete dinuclear complexes of the composition [(Me₂SnCl)₂(bis-dtc)]

Full text of DOI:10.1016/j.jorganchem.2014.07.027

Accepted Manuscript
Stabilization of [(nBu SnCl)(μ-Cl) (ClSnnBu )] within the solid-state structure of a
2
2
2
Chlorodi-n-butyltin(IV) dithiocarbamate
Ericka Santacruz-Juárez, Jorge Cruz-Huerta, Aaron Torres-Huerta, María G.
Hernández-Cruz, Victor Barba, Hugo Tlahuext-Romero, Herbert Höpfl
PII:
S0022-328X(14)00381-7
10.1016/j.jorganchem.2014.07.027
JOM 18675
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 16 May 2014
Revised Date: 28 July 2014
Accepted Date: 29 July 2014
Please cite this article as: E. Santacruz-Juárez, J. Cruz-Huerta, A. Torres-Huerta, M.G. Hernández-
Cruz, V. Barba, H. Tlahuext-Romero, H. Höpfl, Stabilization of [(nBu SnCl)(μ-Cl) (ClSnnBu )] within the
2
2
2
solid-state structure of a Chlorodi-n-butyltin(IV) dithiocarbamate, Journal of Organometallic Chemistry
(2014), doi: 10.1016/j.jorganchem.2014.07.027.
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ACCEPTED MANUSCRIPT
Stabilization of [(nBu2SnCl)(
µ-Cl)2(ClSnnBu2)] within the Solid-State
Structure of a Chlorodi-n-butyltin(IV) dithiocarbamate
Ericka Santacruz-Juárez, Jorge Cruz-Huerta, Aaron Torres-Huerta, María G.
Hernández-Cruz, Victor Barba, Hugo Tlahuext-Romero, Herbert Höpfl*
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001,
C.P. 62209, Cuernavaca, México. Tel., Fax: +52 777 3297997. E-mail: hhopfl@uaem.mx.
Abstract
The combination of bis-dithiocarbamate ligands derived from N,N’-
dibenzylcyclohexane-trans-1,4-diamine with dimethyl- and di-n-butyltin(IV) dichloride
provided two discrete dinuclear complexes of the composition [(Me2SnCl)2(bis-
dtc)]ꢀ2CHCl3 (1) and [(nBu2SnCl)2(bis-dtc)] (2) with bis-dtc = N,N´-dibenzylcyclohexane-
trans-1,4-diamine-bisdithiocarbamate. Additionally, single crystals of the composition
[(nBu2SnCl)(mono-dtc)]ꢀ[nBu2SnCl2]2 (3) with mono-dtc = N,N´-dibenzylcyclohexane-
trans-1,4-diamine-monodithiocarbamate were isolated. Within the crystal structures of the
three complexes, a varied number of common (C−HꢀꢀꢀS, C−HꢀꢀꢀCl and N−HꢀꢀꢀCl) and less
common (SꢀꢀꢀS, SꢀꢀꢀCl, ClꢀꢀꢀCl, ClꢀꢀꢀN and ClꢀꢀꢀSn) secondary interactions were observed and
analyzed. The supramolecular solid-state organization of [(Me2SnCl)2(bis-dtc)]ꢀ2CHCl3
revealed the presence of channels, which were filled with chloroform molecules. In the
crystal structure of [(nBu2SnCl)(mono-dtc)]ꢀ[nBu2SnCl2]2, the di-n-butyltin dichloride units
are arranged in form of a so far unknown dimeric aggregate of the composition
[(nBu2SnCl)(µ-Cl)2(ClSnnBu2)]. The latter assembly represents thus a rare example for a
two-component co-crystalline assembly, in which a relatively large non-solvent molecule
with unusual molecular structure is stored and stabilized.
Corresponding author. Fax: (+52) 777 329 79 97
E-mail address: hhopfl@uaem.mx
1

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Keywords:
Organotin
complex,
di-n-butyltin(IV)
chloride,
dithiocarbamate,
supramolecular chemistry, secondary intermolecular interactions, cocrystal.
2. Introduction
Diorganotin(IV) dichlorides, R2SnCl2, can be reacted selectively with either one or
two stoichiometric equivalents of dithiocarbamate (dtc) ligands to give the corresponding
(R2SnCl)(dtc) and R2Sn(dtc)2 complexes.1 Such mononuclear derivatives have been known
for many years, and intensively studied due to anti-fungal, anti-bacterial, insecticidal and
cytotoxic properties.2 In materials science they have proven useful for the preparation of tin
sulfide nanoparticles and thin films.3 However, it was only until recently that di-, tri- and
polynuclear derivatives have also emerged, which can be attributed to the following
reasons. First, organotin halides have potential for anion recognition, particularly for F-, Cl-
and RCOO- species.4-5 Secondly, bis-dtc complexes derived from di- and tritopic ligands
can generate macrocyclic and cage-type assemblies. In this context, Beer et al., our own
research groups and others have shown that metallosupramolecular assemblies based on
sulphur-containing ligands, in particular bis-dithiocarbamate ligands, are an excellent
alternative choice for the formation of new and complex supramolecular structures.6-8
Among others, supramolecular chemistry deals with the formation of chemical
aggregates through the combination of molecular sub-units (building blocks) by non-
covalent intermolecular interactions.9 These include πꢀꢀꢀπ, C−Hꢀꢀꢀπ, C−ΗꢀꢀꢀX, C−XꢀꢀꢀY, and
XꢀꢀꢀY contacts (with X = O, N, S, F, Cl, Br, I; Y = S, Cl, Br, I), which stabilize the
molecular organization in the solid state.10 Previous studies have shown that C−HꢀꢀꢀX
interactions are of singular importance in molecular recognition processes,11 in stabilizing
inclusion complexes,12 in crystal engineering,13 among others. Moreover, crystalline
assemblies of molecular compounds linked through such non-covalent interactions can
contain cavities or channels, in which additional molecules, frequently solvent, are
included.14 Occasionally, guest molecules included in the confined space of an organic or
metal-organic skeleton can present unusual structural properties.15
Previous reports in the literature have shown that the solid state structures of
diorganotin dithiocarbamates are significantly influenced by the steric effects originated
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from the organic substituents attached to the tin atoms and intermolecular interactions such
as C−HꢀꢀꢀCl, C−HꢀꢀꢀS, SꢀꢀꢀCl, SꢀꢀꢀS, ClꢀꢀꢀSn and C-Hꢀꢀꢀπ contacts.5c, 16
Herein, we report on the preparation and structural characterization of three
chlorodiorganotin(IV) mono- and bis-dithiocarbamate complexes derived from N,N´-
dibenzylcyclohexane-trans-1,4-diamine. The single-crystal X-ray diffraction analysis of the
solid state structures revealed a total of six different secondary interactions involving S and
Cl atoms. Additionally, one compound co-crystallized with nBu2SnCl2, which was included
within the solid state structure in the form of a so far unknown dimeric assembly of the
composition [(nBu2SnCl)(µ-Cl)2(ClSnnBu2)].
2. Experimental section
2.1. General procedures and methods
Commercial starting materials and solvents have been used. Me2SnCl2 and
nBu2SnCl2 were commercially available and were used without further purification. The
synthesis of the secondary amine N,N´-dibenzylcyclohexane-trans-1,4-diamine was
achieved in high yields by condensation of cyclohexane-trans-1,4-diamine with
benzaldehyde followed by reduction with NaBH4 in absolute ethanol.17
Elemental analyses of samples dried in an Abderhalden equipment have been carried
out on an Elementar Vario ELIII instrument. NMR studies were carried out with Varian
Gemini 200 and Varian Inova 400 equipments. Standard references were used: TMS (
δ
1H =
0; δ δ
13C = 0) and SnMe4 ( 119Sn = 0). For the correct assignment of the H and C NMR
1
13
spectra, COSY, DEPT and HSQC experiments have been carried out. IR spectra have been
recorded on a Bruker Vector 22 FT spectrophotometer. Mass spectra were obtained on a
Jeol JMS 700 equipment.
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2.2 Synthesis and spectroscopic characterization
2.2.1. Preparation of [(Me2SnCl)2(bis-dtc)] (1)
To a solution of N,N´-dibenzylcyclohexane-trans-1,4-diamine (0.250 g, 0.85 mmol)
in 20 mL of absolute ethanol were added two equivalents of potassium hydroxide (0.095 g,
1.70 mmol) and excess of carbon disulfide (1.30 g, 17 mmol). The mixture was stirred for 2
h at room temperature, whereupon dimethyltin dichloride (0.374 g, 1.70 mmol) dissolved in
30 mL of absolute ethanol was added dropwise. After stirring for 12 h at room temperature,
the colorless precipitate was collected by filtration and washed with hot hexane. Single-
crystals suitable for X-ray crystallography were grown from a 1:1 solvent mixture of
dichloromethane and ethanol. Yield: 65% (0.450 g). Mp 242-244 ºC. High-resolution MS
(FAB+) for C26H36ClN2S4Sn2 [M-Cl]+: m/z (%) = 778.9898 (61). Error: +51.9 ppm. IR
(KBr, cm-1): ṽmax = 2943 (w), 1463 ν(C-Ndtc) (s), 1423 (s), 1355 (m), 1243 (m), 1151 (m),
1079 (w), 1021 (m), 964 νas(CSS) (m), 906 (w), 787 (m), 736 (m), 695 (m), 554 (m), 457
1
(w). H NMR (200 MHz, CDCl3, TMS, ppm):
δ
= 1.31 (s, 12 H, Sn-CH3, 2JSn-H = 73 Hz),
1.43 (m, 4H, H2a, H3a), 1.95 (m, 4H, H2e, H3e), 4.59 (br, m, 2H, H1, H4), 4.98 (s, 4H,
NCH2), 7.17–7.38 (m, 10H, Ph). 13C NMR (50 MHz, CDCl3, TMS, ppm):
= 10.2 (Sn-
CH3), 29.2 (C2, C3), 53.2, 53.7 (N-CH2-Ph), 63.7 (C1, C4), 126.4 (Cm), 128.0 (Cp), 129.0
(Co), 134.7 (Ci), 199.6 (CSS). 119Sn NMR (149 MHz, CDCl3, SnMe4, ppm)
= -188.5.
δ
δ
Anal. calcd. (%) for C26H36Cl2N2S4Sn2 (813.16 gmol-1): C, 38.40; H, 4.46; N, 3.44. Found:
C, 38.60; H, 4.48; N, 3.68.
2.2.2. Preparation of [(nBu2SnCl)2(bis-dtc)] (2)
Complex 2 was prepared following the protocol given for compound 1. Yield: 56%
(0.471 g). Mp 289-290 ºC (dec). High resolution MS (FAB+) for C38H60ClN2S4Sn2 [M-Cl]+:
m/z (%) 947.1329 (100). Error: -4.6 ppm. IR (KBr, cm-1): ṽmax = 2953 (m), 2925 (w), 2860
(m), 1631 (m), 1461 ν(C-Ndtc) (s), 1408 (m), 1236 (w), 1156 (m), 1021 (w), 964 νas(CSS)
1
(w), 870 (w), 734 (w), 694. H NMR (200 MHz, CDCl3, TMS, ppm):
δ = 0.96 (t, 12H, δ-
CH3), 1.39-1.55 (m, 12H, H2a, H3a, γ-CH2), 1.67-2.10 (m, 20H, H2a, H3a, α-CH2, β-CH2),
4.62 (br, m, 2H, H1, H4), 4.99 (s, 4H, NCH2), 7.16–7.38 (m, 10H, Ph). 13C NMR (50 MHz,
CDCl3, TMS, ppm):
δ
= 13.8 (δ−CH3), 26.4 (γ−CH2), 28.0, 29.2 (C2, C3, α-CH2, β−CH2),
4

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53.1 (N-CH2-Ph), 63.6 (C1, C4), 126.4 (Cm), 128.0 (Cp), 129.0 (Co), 134.9 (Ci), 200.5
(CSS). 119Sn NMR (149 MHz, CDCl3, SnMe4, ppm):
δ = -188.0. Anal. calcd. (%) for
C38H60Cl2N2S4Sn2 (981.48 gmol-1): C, 46.50; H, 6.16. Found: C, 46.37; H, 5.69.
2.2.4. X-ray Crystallography
X-ray diffraction studies were carried out on a BRUKER-AXS APEX diffractometer
equipped with a CCD area detector (λMοKα = 0.71073 Å, monochromator: graphite).
Frames were collected at T = 150(2) K (compound 1) and T = 173(2) K (compounds 2 and
3) via ω/φ-rotation (∆ω = 0.3º) at 10 s per frame. The measured intensities were reduced to
F2 and corrected for absorption with SADABS. Corrections were made for Lorentz and
polarization effects. Structure solution, refinement and data output were carried out with
the SHELXTL-NT program package.18 Non-hydrogen atoms were refined anisotropically,
while C–H hydrogen atoms were placed in geometrically calculated positions using a
riding model. For compound 3, N–H hydrogen atoms have been located from iterative
examination of difference Fourier maps following least squares refinements of the previous
models with dN−H = 0.86 Å and Uiso(H) = 1.5Ueq(N). Figures were created with
DIAMOND.19 In compound 1, the N-benzyl groups and the chloroform solvent molecules
were disordered, in the first case over two positions (occupancy factors = 0.49 and 0.51)
and in the second case over three positions (occupancy factors = 0.46, 0.48 and 0.06). For
the refinement, EADP, DFIX, SIMU, DELU and SAME instructions have been employed.
Crystallographic data for the three crystal structures have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publications no. CCDC-
1002259-1002261. Copies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk, www: http://www.ccdc.cam.ac.uk).
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3. Results and Discussion
3.1. Preparation and Spectroscopic Characterization
Reaction of trans-1,4-cyclohexanediamine with benzaldehyde followed by reduction
with NaBH4 in absolute ethanol resulted in the secondary amine N,N´-
dibenzylcyclohexane-trans-1,4-diamine in high yields (> 95%). For the formation of the
coordinating dtc ligands, the N,N´-disubstituted diamine was then combined with two
equivalents of potassium hydroxide and an excess of carbon disulfide (10-fold). After
stirring for two hours, either dimethyl- or di-n-butyltin dichloride dissolved in 20 mL of
absolute ethanol was added dropwise. After 12 hours, a white precipitate had formed,
which was filtered and washed with hot n-hexane (Scheme 1). Compound 3 was obtained
in a small amount as crystalline by-product during the preparation of compound 2. The
chlorodiorganotin bis-dithiocarbamate complexes 1-2 were characterized by elemental
analysis, IR spectroscopy, NMR (1H, 13C, 119Sn) spectroscopy, FAB+ mass spectrometry
and single-crystal X-ray diffraction analysis. Selected spectroscopic and mass spectrometric
data are summarized in Table 1.
m
m
o
o
i
p
Cl
p
R
i
H
H
4
H
4
Ph
R
Sn
S
1) 2 KOH, CS2
2) R2SnCl2
S
NH
N
S
N
2
3
3
2
S
S
+
1
1
HN
N
HN
S
EtOH, stirring
R
nBu
Ph
Sn
Sn
H
H
H
R
Cl
Cl
nBu
.
2 nBuSnCl2
1 R= Me
γ
β
α
δ
3
2 R= -CH2-CH2-CH2-CH3
Scheme 1. Preparation of the chlorodiorganotin (IV) dithiocarbamate complexes 1-3.
Table 1. Selected IR (cm-1) and NMR (ppm) spectroscopic data for compounds 1-2
.
δ 13C(CS2)
199.6
δ
119Sn
Compound υ(N-CSS) υas(CSS)
1463
1461
964
964
-188.5
-188.0
1
2
200.5
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The IR spectra of compounds 1 and 2 showed bands for the stretching vibration of the
N–CS2 bonds in the range of 1461-1463 cm-1, which are intermediate between the values
observed for C−N single and C=N double bonds. The asymmetric vibrations of the CS2
groups appeared at 964 cm-1, in agreement with the values reported previously for a series
of different organotin dithiocarbamates.7, 20
1
13
As previously established for related compounds, in the H and C NMR spectra of
1-2 (recorded in CDCl3) the signals of the NCH2Ph methylene and NCHR2 methine groups
1
are significantly low-field shifted when compared to the starting bis-amine.7-8 In the H
NMR spectra, the variations of the chemical shifts were approximately ∆
δ = 1.2 ppm for
the NCH2Ph functions and ∆ = 2.1 ppm for the NCHR2 hydrogen atoms of the
δ
cyclohexylene ring. Of these, the low-field shift of the axially oriented NCHR2 hydrogen
atoms is unusually large, but can be explained by the presence of a short intramolecular
C−HꢀꢀꢀS contact, as established by the single-crystal X-ray diffraction analyses (vide infra).
In the 13C NMR spectra, the variations were approximately ∆
functions and ∆
= 7 ppm for the NCHR2 carbon atoms. The 13C NMR spectra gave also
signals in the range from =199.6 to 200.5 ppm, which are characteristic for NCS2 groups
coordinated to tin atoms.7,21 119Sn NMR data were recorded in CDCl3 and the chemical
shifts for compounds 1 ( = -188.5 ppm) and 2 ( = -188.0 ppm) indicate that the tin atoms
δ = 2 ppm for the NCH2Ph
δ
δ
δ
δ
are embedded in five-coordinate coordination geometries.22 For the structurally related
complexes (nBu2SnCl)(S2CNEt2) and (Me2SnCl)(S2CNEt2) similar shift displacements
have been reported.23
The molecular structures of compounds 1-2 were finally established by high-
resolution mass spectrometry. The corresponding mass spectra gave peaks at m/z =
778.9898 and 947.1329, respectively, which correspond to the [M–Cl]+ fragments. In both
cases the experimental isotope pattern matches the simulated pattern (Figure S1). The loss
of the chlorine atoms from chlorodimethyl and chlorodi-n-butyltin dithiocarbamates is
commonly observed and has been previously reported.7c,7g, 16, 24
3.2. Single-crystal X-ray diffraction analysis
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Complexes 1-2 were also characterized by single-crystal X-ray diffraction analysis.
Additionally, during the recrystallization of compound 2 from a 1:1 (v/v) dichloromethane-
ethanol mixture a small portion of crystals having the composition [(Bu2SnCl)(mono-
dtc)][nBu2SnCl2]2 (3) were distinguished under the microscope due to their different color
(2, light yellow; 3, colorless). Crystals for compound 1 were grown from a 1:1 (v/v) solvent
mixture of chloroform and ethanol. Relevant crystallographic data are summarized in Table
2. Selected intra- and intermolecular geometric parameters for the corresponding crystal
structures are given in Tables 3-5.
Table 2. Selected crystallographic data for compounds 1-3
Crystal data[a]
1
2
3
Formula
C26H36Cl2N2 S4Sn2ꢀ2CHCl3
242-244
1051.82
C29H43ClN2S2Snꢀ2nBu2SnCl2
C38H60Cl2N2S4Sn2
289-290 (dec.)
981.40
Trigonal
P3221
M.p. (°C)
110-112
1245.54
Triclinic
P-1
MW (g mol−1)
Crystal system Monoclinic
Space group
Temp. (K)
a (Å)
b (Å)
c (Å)
C2/c
150(2)
173 (2)
173(2)
17.6156(14)
11.0285(9)
21.7555(18)
103.092(1)
4116.7(6)
4
1.959
1.697
0.0339
0.0859
16.7228(11)
16.7228(11)
14.2267(13)
90
3445.5(4)
3
1.412
1.419
0.0521
0.1239
9.7551(6)
15.4575(9)
19.3268(12)
101.600(1)
2831.1 (3)
2
1.652
1.461
0.0512
0.1392
β
(°)
V (Å3)
Z
µ
(mm−1)
ρ
calcd (g cm−3)
R[b, c]
[d, e]
Rw
GOF
1.043
1.031
1.074
[a]
2
2 2 ½
λ
= 0.71073 Å, [b] Fo > 4σ(Fo). [c] R = Σ||Fo|−|Fc||/Σ|Fo|. [d] All data. [e] Rw = [Σw(Fo −Fc2)2/Σw(Fo ) ] .
MoKα
Analysis of the molecular geometries of 1-3
The X-ray crystallographic studies revealed that compound 1 had crystallized in form
of a chloroform solvate of the composition [(Me2SnCl)2(bis-dtc)]ꢀ2CHCl3. As expected, the
molecular structure corresponds to a discrete dinuclear molecule, in which according to the
τ
–parameter the coordination geometries around the tin atoms are intermediate between
ideal trigonal-bipyramidal and square-pyramidal coordination polyhedra (
τ
= 0.45).25 The
molecules possess crystallographic inversion symmetry which orients the benzyl groups
8

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anti with respect to the central cyclohexylene ring of the ligand (Figure 1a). Within the
coordination polyhedron of the metal center, the carbon atoms of the CH3-Sn groups and
one of the sulfur atoms (S1) from the dtc group occupy approximate equatorial positions,
giving bond angles around the tin center in the range of 115.10(19)° to 127.81(19)° (Table
2). The latter value corresponds to the C-Sn-C bond angle, which is in good agreement with
2
the bond angle calculated according to Lockhart’s equation26 from the J(119Sn-1H)
coupling constant in solution (123 °). The remaining sulfur atom (S2) and the chlorine
substituent occupy approximate axial positions; however, the S2-Sn-Cl bond angle of
155.07(3)° deviates significantly from the ideal value for a trigonal bipyramide, which can
be attributed to the formation of the four-membered CS2Sn chelate ring with a S1-Sn-S2
bond angle of only 69.74(3)°. According to Bent´s rule, the axial Sn-S2 bond is
significantly longer than the equatorial Sn-S1 bond, thus giving an anisobidentate
coordination mode with Sn-S bond distances of 2.4733(9) Å for Sn-S1 and 2.6530(10) Å
for Sn-S2, respectively. The bonding asymmetry of the dtc ligand is also reflected in the C-
S bond lengths, which are significantly different from each other, 1.745(4) Å for C1-S1 and
1.711(4) Å for C1-S2. Within the dtc function, the C-Ndtc bond length of 1.331(5) Å
1
indicates a substantial delocalization of π–electron density.27 In agreement with the H
NMR data, which showed an unusual low-field shift for the NCHR2 hydrogen atoms upon
the dtc-formation, there is a short intramolecular C−HꢀꢀꢀS contact formed between the
hydrogen and one of the dtc-sulphur atoms (H2ꢀꢀꢀS1, 2.49 Å; Σrvdw (H, S) = 3.00 Å).
Interestingly, this contact is observed in all three molecular structures examined herein (2,
H2ꢀꢀꢀS1, 2.42 Å; 3, H2ꢀꢀꢀS2, 2.45 Å; Table S1). A somewhat longer contact is also observed
for the NCH2Ph hydrogen atoms (1, H5BꢀꢀꢀS2, 2.55 Å; 2, H5BꢀꢀꢀS2, 2.58 Å; 3, H8AꢀꢀꢀS1,
2.55 Å; Table S1).
The crystal structure of compound 2 has the composition [(Bu2SnCl)2(bis-dtc)]. As
for the dimethyltin analogue 1, a discrete dinuclear molecular structure is observed with the
difference that the molecules possess now crystallographic C2-symmetry, in which the
benzyl groups as an overall entity are anti-oriented with respect to the central
cyclohexylene ring of the ligand, but, contrary to compound 1, the phenyl rings are syn-
oriented (Figure 1b). The
τ
-parameter indicates that the metal coordination polyhedron in
9

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this case approaches more the square-pyramidal than the trigonal-bipyramidal geometry (
τ
= 0.39). The Sn-S1 and Sn-S2 bond distances are 2.4626(15) and 2.7677(19) Å,
respectively, indicating a substantially longer Sn-S2 bond in comparison to 1, which is in
agreement with the presence of the more voluminous Sn-n-butyl groups. Accordingly, the
C-Sn-C bond angle increases from 127.81(19)° for 1 to 128.8(3)° for 2. The coordination
characteristics found for compounds 1 and 2 are common for chlorodiorganotin
dithiocarbamates and are comparable to those previously described for a series of
chlorodimethyltin,
chlorodiethyltin,
chlorodi-t-butyltin
and
chlorodiphenyltin
dithiocarbamates.1b,5b,5c,24
10

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Figure 1. Perspective views of the molecular structures of the chlorodiorganotin
dithiocarbamates 1-3: a) [(Me2SnCl)2(bis-dtc)]; b) [(nBu2SnCl)2(bis-dtc)]; c)
[(nBu2SnCl)(mono-dtc)].
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Table 3: Selected bond lengths [Å] and angles [°] for the molecular structures of
compounds 1-3.
Compound
1
2
3
Bond lengths
Sn-C
2.115(4)
2.117(4)
2.4733(9)
2.6530(10) 2.7677(19) 2.7263(17)
2.5224(10) 2.493(2)
1.745(4)
1.711(4)
1.331(5)
2.125(10)
2.132(8)
2.4626(15) 2.4576(17)
2.106(8)
2.134(6)
Sn-S1
Sn-S2
Sn-Cl
C1-S1
C1-S2
C1-N1
2.4850(18)
1.751(6)
1.701(6)
1.328(8)
1.757(7)
1.701(6)
1.320(8)
Bond Angles
C-Sn-C
C-Sn-S(1)
127.81(19) 128.8(3)
115.10(12) 113.4(2)
116.67(14) 116.6(2)
126.8(3)
117.5(3)
114.21(19)
95.2(2)
99.08(19)
86.94(6)
95.5(3)
91.48(18)
69.07(5)
156.01(6)
C-Sn-Cl
94.31(12)
95.88(14)
85.34(3)
98.6(3)
96.9(3)
84.09(6)
93.3(3)
94.9(2)
68.31(5)
152.39(6)
S(1)-Sn-Cl
C-Sn-S(2)
95.88(12)
95.70(14)
S(1)-Sn-S(2) 69.74(3)
Cl-Sn-S(2) 155.07(3)
As already mentioned, the crystals isolated for compound 3 had the composition
[(nBu2SnCl)(mono-dtc)][nBu2SnCl2]2, indicating that the chlorodi-n-butyltin
dithiocarbamate co-crystallized with two equivalents of the starting nBu2SnCl2. The
molecular structure of [(nBu2SnCl)(mono-dtc)] showed the expected mononuclear
composition with a coordination geometry around the tin atom very similar to that observed
for the dinuclear analogue 2 (τ = 0.49, Figure 1c, Table 3). On the contrary, the molecular
structure of the di-n-butyltin dichloride entity embedded within the crystal structure of this
compound is rather different from that observed in neat nBu2SnCl2.28 Figure 2 shows that
the nBu2SnCl2 units are arranged in form of dimeric aggregates of the composition
[(nBu2SnCl)(µ-Cl)2(ClSnnBu2)] with Sn-Cl bond distances (Table 4) close to the sum of
the corresponding covalent radii (Sn, 1.39(4) Å; Cl, 1.02(4) Å). Some years ago, Tiekink et
al. performed a comprehensive analysis of SnꢀꢀꢀCl interactions in a series of diorganotin
dichlorides and found that this type of interaction is quite common for derivatives carrying
small to medium-sized organic substituents at the tin metal center.29 Nevertheless, in all
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structures analyzed in this report, the SnꢀꢀꢀCl distances were secondary interactions with
values varying from 3.308(1) to 3.976(3) Å, and, therefore, significantly larger than the Sn-
Cl bond lengths found for [nBu2SnCl2]2 in compound 3. Furthermore, and contrary to what
is expected, two of the bridging Sn-Cl bonds are significantly shorter (Sn2-Cl3, 2.4212(16);
Sn3-Cl3, 2.4197(16) Å) than the remaining terminal and bridging Sn-Cl bonds (Sn2-Cl2,
2.4744(16); Sn3-Cl4, 2.6588(16); Sn2-Cl5, 2.8777(18); Sn3-Cl5, 2.5961(18) Å).
Figure 2. Perspective view of the dimeric aggregate formed between the nBu2SnCl2
components in the crystal structure of [(nBu2SnCl)(mono-dtc)][nBu2SnCl2]2.
In the crystal structure of 3, the [nBu2SnCl2]2 dimers are asymmetric, but the
molecular structure approaches mirror plane symmetry. The coordination geometries of the
two tin centers are both distorted trigonal-bipyramidal with slight differences regarding
bond lengths and angles (Table 4). The corresponding τ-values are 0.71 for Sn2 and 0.79
for Sn3. The equatorial positions of the coordination polyhedra are occupied by the organic
substituents and the bridging chlorine atom having the shortest Sn-Cl bond (Cl3), with
bond angles ranging from 111.1(2) to 135.8(2) ° (Table 4). The axial positions are occupied
by the terminal and the remaining bridging chlorine atom Cl5 with bond angles close to
180° (Cl2-Sn2-Cl5, 178.62(5); Cl4-Sn3-Cl5, 177.75(5) °). Within the four-membered
Sn2Cl2 ring, the Cl-Sn-Cl and Sn-Cl-Sn bond angles are significantly different from each
other. Of these, the largest bond angle corresponds to the Sn-Cl-Sn bond formed with
chlorine Cl3, Sn2-Cl3-Sn3 = 99.41(6) °, that occupies one of the equatorial positions in the
coordination polyhedra surrounding Sn2 and Sn3. The Sn-Cl-Sn bond angle formed with
the axially oriented Cl5 bridge is smaller by approximately 15 °, Sn2-Cl5-Sn3 = 84.67(5) °.
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The values of the Cl-Sn-Cl bond angles are less different from each other, Cl3-Sn2-Cl5 =
83.72(5) and Cl3-Sn3-Cl5 = 90.11(5) °. In neat nBu2SnCl2, the molecular geometry of the
tin atom is distorted octahedral due to weak secondary SnꢀꢀꢀCl contacts with bond distances
of 3.514(5) and 3.544(5) Å, giving rise to 1D chains of the composition [(nBu2Sn(µ-
Cl)2]n.28
Table 4. Selected bond lengths [Å] and bond angles [°] for the molecular structure of
[(nBu2SnCl)( -Cl)2(ClSnnBu2)] embedded in the crystal structure of [(Bu2SnCl)(mono-
dtc)][nBu2SnCl2]2.
µ
Bond lengths
Bond angles
Sn2-C34 2.127(6)
Sn2-C30 2.135(6)
C34-Sn2-C30 135.8(3)
C34-Sn2-Cl3 111.1(2)
Sn2-Cl3 2.4212(16) C30-Sn2-Cl3 111.6(2)
Sn2-Cl2 2.4744(16) C34-Sn2-Cl2 94.0(2)
Sn2-Cl5 2.8777(18) C30-Sn2-Cl2 93.6(2)
Cl3-Sn2-Cl2
94.95(6)
C34-Sn2-Cl5 86.8(2)
C30-Sn2-Cl5 86.6(2)
Cl3-Sn2-Cl5
Cl2-Sn2-Cl5
83.72(5)
178.62(5)
Sn3-C38 2.130(8)
Sn3-C42 2.163(9)
C38-Sn3-C42 130.3(4)
C38-Sn3-Cl3 114.8(2)
Sn3-Cl3 2.4197(16) C42-Sn3-Cl3 114.4(3)
Sn3-Cl5 2.5961(18) C38-Sn3-Cl5 93.7(2)
Sn3-Cl4 2.6588(16) C42-Sn3-Cl5 92.1(4)
Cl3-Sn3-Cl5
90.11(5)
C38-Sn3-Cl4 87.4(2)
C42-Sn3-Cl4 88.6(4)
Cl3-Sn3-Cl4
Cl5-Sn3-Cl4
87.65(5)
177.75(5)
Sn3-Cl3-Sn2 99.41(6)
Sn3-Cl5-Sn2 84.67(5)
Although arrangements with a central four-membered cyclic M2Cl2 core are quite
common in coordination chemistry, for organotin complexes they are unusual. A revision
of the Cambridge Structural Database (CSD version 5.35)30 reveals that there is no entry so
far for a double clorine-bridged five-coordinate organotin (IV) species, but there are four
entries for five-coordinate organotin complexes containing a single-bridged chlorine atom
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(FUJQEG, JAHQAK, SEJCEP and SEYFUX). There is a limited number of six-coordinate
diorganotin (IV) compounds containing a Sn2Cl2 ring (BENFOP, DERTUP, FUPTEP,
KUVGOX, VAXCON, WIGLIH, YATLIQ), and there are five entries for double
heteroatom-bridged structures with five-coordinate organotin atoms of the compositions
[(R2SnCl)(µ-Cl)(µ µ-Cl)(µ-
-S)(ClSnR2)]- (with R = Me and tBu)31 and [(Me2SnCl)(
PR2)(ClSnMe2)] (with R = iPr, tBu).32 On the contrary, diorganotin complexes containing
Sn2OCl rings are quite frequent, most of them being bis(tetraorganodistannoxane)
derivatives.33
R
R
R
Cl
R
-
R
Cl Sn
R
Me
Cl
S
Cl
P
R
Sn Cl
R
Me
Sn Cl
Me
Cl Sn
O
Sn
Cl Sn
R
Sn O Sn Cl
Me
R
Cl
R
R
R
R
R = Me, tBu
R = iPr, tBu
R = Me, Et, iPr, nBu, CH2Ph
Overall, this structural discussion shows that the formation of inclusion compounds
or co-crystals provides an interesting strategy for the stabilization and characterization of
unusual molecular and coordination geometries of metal complexes, providing in such a
way insight into the structural variations such complexes may suffer even in solution due to
solvent coordination or the formation of intermolecular aggregates. Reports in this direction
exist, but are still relatively scarce.15
Analysis of the supramolecular structures of 1-3
Within the crystal lattice of compound 1, two crystallographically independent
intermolecular interactions were observed, which are both involving the Sn−Cl chlorine
atom. First, a C−HꢀꢀꢀCl contact with a Carom−H hydrogen atom of the benzyl group and,
second, a SꢀꢀꢀCl type interaction with the S2 sulfur atom from the dtc group. As seen from
Table S1, the distances for both interactions are shorter than the corresponding sum of the
van der Waals radii [Σrvdw (H, Cl) = 2.95 Å; Σrvdw (S, Cl) = 3.55 Å] (Figure 3a). The
presence of these secondary interactions generates 2D layers parallel to the bc plane. In the
third dimension, these layers are stacked in such a way that channels are generated along c,
which house the disordered chloroform molecules. Within these channels, the solvent
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ACCEPTED MANUSCRIPT
molecules are linked through ClꢀꢀꢀCl contacts into infinite 1D chains (Figure 3b); however,
in this case the disorder prevents an accurate determination of the geometric parameters for
this interaction.
Figure 3. Fragments of the crystal structure of compound 1, showing a) the intermolecular
C−HꢀꢀꢀCl and SꢀꢀꢀCl interactions formed between the dinuclear complex molecules, and b) a
lateral perspective view of one of the channels containing 1D chains of the disordered
chloroform molecules. Note: Hydrogen atoms not involved in intermolecular interactions
have been omitted for clarity.
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In compound 2, the dominant supramolecular interactions are SꢀꢀꢀS and C−HꢀꢀꢀX (X=
Cl, S) contacts within the crystal lattice. Of these, the SꢀꢀꢀS interactions have a separation
distance of 3.261(2) Å [Σrvdw (S, S) = 3.60 Å] and generate 1D chains along c, which are
further linked by two crystallographically independent C−HꢀꢀꢀX (X= Cl, S) contacts to give
an overall 3D network (Figure 4).
Figure 4. Fragments of the crystal structure of compound 2, showing a) the 1D chains
formed through SꢀꢀꢀS contacts, and b) the intermolecular C−HꢀꢀꢀS and C−HꢀꢀꢀCl interactions
formed between the dinuclear complex molecules. Note: Parts of the n-butyl groups and
hydrogen atoms not involved in intermolecular contacts have been omitted for clarity.
The supramolecular arrangement of compound 3 is particularly interesting, mainly for
two reasons. First, the diversity of secondary interactions generates cavities in the crystal
lattice, and, second, this crystal structure is an unusual example of a two-component solid
state structure, in which large non-solvent molecules are included. This arrangement can be
attributed to the presence of only one dithiocarbamate group, generating an asymmetric
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ACCEPTED MANUSCRIPT
molecule that maintains an amine group and enables N−HꢀꢀꢀCl interactions with
neighboring molecules. Interestingly, in this case the diorganotin dithiocarbamates are
linked to each other only through relatively weak C−HꢀꢀꢀS and C−Hꢀꢀꢀπ contacts (C8-
H8AꢀꢀꢀS1 and C22-H22BꢀꢀꢀC14, Table S1), while a larger number of interactions of the
N−HꢀꢀꢀCl, C−HꢀꢀꢀCl and NꢀꢀꢀCl type are formed with the second component of the crystal
structure (Figure 5a, Table S1). This indicates that [(nBu2SnCl)(mono-dtc)][nBu2SnCl2]2 is
rather a co-crystal than an inclusion complex. This is an important observation when
considering that the global organization of the molecular components within the crystal
lattice seems to indicate the presence of the latter structure type with channels along a
(Figure 5b). However, the four [(nBu2SnCl)(mono-dtc)] molecules that surround a total of
four di-n-butyltin dichloride molecules are not directly connected to each other. As already
mentioned, the di-n-butyltin dichloride molecules are arranged in form of dimeric entities
of the composition [(nBu2SnCl)(µ-Cl)2(ClSnnBu2)]. Interestingly, within the cavities
formed by each four [(Bu2SnCl)(mono-dtc)] units, the [nBu2SnCl2]2 dimers are located
close to each other thus resembling a bis(tetraorganodistannoxane) type arrangement;
however, the SnꢀꢀꢀCl distances of 3.7476(19) Å approach the upper limit established for
SnꢀꢀꢀCl interactions (4.0 Å).29 Therefore, it is suggested that the approximation is indeed
induced by two C-HꢀꢀꢀCl contacts (Figure 5a).
Figure 5. Fragments of the crystal structure of compound 3, showing a) the intermolecular
N−HꢀꢀꢀCl and C−HꢀꢀꢀCl interactions formed between the molecular components, and b) a
perspective view of the supramolecular organization along a. Note: Parts of the n-butyl
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groups and hydrogen atoms not involved in intermolecular contacts have been omitted for
clarity.
4. Conclusions
This work described discrete mono- and dinuclear dimethyl- and dibutyltin chloride
complexes derived from mono- and bis-dithiocarbamate ligands and analyzed the
supramolecular arrangements generated by C−HꢀꢀꢀCl, C−HꢀꢀꢀS, N−HꢀꢀꢀCl and SꢀꢀꢀS, SꢀꢀꢀCl,
ClꢀꢀꢀCl, ClꢀꢀꢀN and ClꢀꢀꢀSn intermolecular interactions. Interestingly, one compound co-
crystallized with di-n-butyltin dichloride molecules giving a so far unknown dimeric
aggregate with a central Sn2Cl2 core, in which the Sn-Cl distances are close to the sum of
the covalent radii of tin and chlorine. Thus, the results presented in this article contribute to
the understanding of the factors responsible for the supramolecular organization of
organotin derivatives in the solid state. It should also be noticed that the non-covalent
interactions described in this contribution are of relevance not only in chemistry, but also in
related fields such as biochemistry, pharmaceutical chemistry, medicine and materials
science.
Supplementary Material
High resolution FAB+ mass spectra for compounds 1 and 2 (Figure S1) and geometric
parameters for relevant intra- and intermolecular interactions in the crystal structures of
compounds 1-3 (Table S1).
Acknowledgements
Financial support from Consejo Nacional de Ciencia y Tecnologia (CONACyT) is
gratefully acknowledged (Project No. CB2010-158098 and postdoctoral fellowships for
ESJ and MGH). The authors gratefully acknowledge for awarding them access to the X-ray
facilities in the Chemical Research Center at the Autonomous State University of Morelos
(CIQ-UAEM).
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Synopsis and Graphical Abstract
The single-crystal X-ray diffraction analysis of three chlorodiorganotin dithiocarbamates
revealed the presence of a variety of intermolecular interactions including C−HꢀꢀꢀS,
C−HꢀꢀꢀCl, N−HꢀꢀꢀCl, SꢀꢀꢀS, SꢀꢀꢀCl, ClꢀꢀꢀCl, ClꢀꢀꢀN and ClꢀꢀꢀSn contacts, which can stabilize
supramolecular co-crystalline assemblies containing unusual molecular aggregates such as
the [nBu2SnCl2] dimer.
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Highlights
1. Chlorodiorganotin dithiocarbamates have been prepared.
2. SꢀꢀꢀS, SꢀꢀꢀCl, ClꢀꢀꢀCl, ClꢀꢀꢀN and ClꢀꢀꢀSn contacts were found in the solid state.
3. Unusual dimers of the composition [(nBu2SnCl)(µ-Cl)2(ClSnnBu2)] are described.
4. The latter are stored in form of a co-crystalline assembly.
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Supplementary Material
Stabilization of [(nBu2SnCl)(
µ-Cl)2(ClSnnBu2)] within the Solid-State
Structure of a Chlorodi-n-butyltin(IV) dithiocarbamate
Ericka Santacruz-Juárez, Jorge Cruz-Huerta, Aaron Torres-Huerta, María G.
Hernández-Cruz, Victor Barba, Hugo Tlahuext-Romero, Herbert Höpfl*
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001,
C.P. 62209, Cuernavaca, México. Tel., Fax: +52 777 3297997. E-mail: hhopfl@uaem.mx.
Figure S1. High resolution FAB+ mass spectra for compounds a) 1 and b) 2, indicating the
presence of the corresponding [M–Cl]+ fragment. For comparison, the
simulated isotope patterns are also given.
Table S1. Geometric parameters for relevant intra- and intermolecular interactions in the
crystal structures of compounds 1-3.
Corresponding author. Fax: (+52) 777 329 79 97
E-mail address: hhopfl@uaem.mx

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Figure S1. High resolution FAB+ mass spectra for compounds a) 1 and b) 2, indicating the
presence of the corresponding [M–Cl]+ fragment. For comparison, the simulated isotope
patterns are also given.