Effect of weak sulfur...C(π) interactions, and hydrogen bonds in supramolecular association of chlorodiphenyltin(IV) dithiocarbamate complexes: Study of their stability in solution

Article abstract of DOI:10.1016/j.poly.2011.11.022

Five new chlorodiorganotin(IV) complexes derived from dithiocarbamate ligands have been prepared and structurally characterized. The complexes 1-5 with the general formula {(Ph₂SnCl)dtc} (dtc = R₁R ₂NCS₂^-

Full text of DOI:10.1016/j.poly.2011.11.022

Polyhedron 33 (2012) 223–234
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Effect of weak sulfur. . .C(p) interactions, and hydrogen bonds in supramolecular
association of chlorodiphenyltin(IV) dithiocarbamate complexes: Study of their
stability in solution
⇑
⇑
Adrian Tlahuext-Aca, Felipe Medrano, Hugo Tlahuext , Perla Román-Bravo, Carolina Godoy-Alcántar
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa, C.P. 62209, Cuernavaca, Morelos, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 July 2011
Accepted 16 November 2011
Available online 25 November 2011
Five new chlorodiorganotin(IV) complexes derived from dithiocarbamate ligands have been prepared and
ꢀ
structurally characterized. The complexes 1–5 with the general formula {(Ph2SnCl)dtc} (dtc = R1R2NCS2
;
1, R1 = Bn, R2 = 9-anthrylmethyl; 2, R1 = Bn, R2 = 9-phenanthrylmethyl; 3, R1 = Bn, R2 = 1-pyrenylmethyl;
4, R1 = 1-naphthylmethyl, R2 = 1-pyrenylmethyl; 5, R1 = R2 = 1-pyrenylmethyl) have been obtained from
Ph2SnCl2 and the sodium dithiocarbamate salts of benzyl(9-anthrylmethyl)amine, benzyl(9-phenanth-
rylmethyl)amine, benzyl(1-pyrenylmethyl)amine, 1-naphthylmethyl(1-pyrenylmethyl)amine and di(1-
pyrenylmethyl)amine. Compounds 1–5 have been analyzed as far as possible by elemental analysis,
FAB+ mass spectrometry, IR, UV–Vis, fluorescence and NMR (1H, 13C, 119Sn) spectroscopy, and single-
crystal X-ray diffraction analysis (1–3). The solid-state and solution studies showed that the dtc ligands
are coordinated to the tin atoms in the anisobidentate manner. In all cases the metal centers are
five-coordinate. The coordination geometry is intermediate between square-pyramidal and trigonal-
Keywords:
Organotin complexes
Dithiocarbamate
Supramolecular chemistry
Ligand-exchange
Anion binding
bipyramidal coordination polyhedra with
s
-values in the range of 0.49–0.55. The crystal structures show
and Sꢁꢁꢁ contacts. The stability of the (Ph2SnCl)dtc
the presence of C–HꢁꢁꢁCl, C–HꢁꢁꢁS, C–Hꢁꢁꢁ , offset
p
p
–
p
p
complexes in the presence of the acetate anion has been examined in acetonitrile solutions. For all of
these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dtc) by
the acetate anion was observed. The lability, as well as their intrinsic fluorescent properties of the
polyaromatic moieties in these (Ph2SnCl)dtc compounds make them interesting candidates to detect
the presence of O-donor anions at very low concentrations by displacement of the metal-coordinated dtc.
Published by Elsevier Ltd.
1. Introduction
engineering [6], conformational isomerism [7] and the properties
of ionic liquids [8].
Non-covalent interactions are fundamental for supramolecular
chemistry, drug design, protein folding, crystal engineering and
other areas of molecular science [1]. The non-covalent intermolec-
ular interactions that lead to crystal formation can typically be di-
vided into strong, moderate and weak interactions, although the
demarcations between them are not sharp. Hydrogen bonding is
a classical example of a strong or moderate, but generally specific
and highly directional intermolecular interaction. However,
So far, little is known about supramolecular assemblies derived
from organometallic building blocks. Indeed, there are only few
useful candidates for this purpose and among these are organotin
systems that have shown to be particularly interesting [9]. Com-
pounds containing tin(IV) as electrodeficient center have been pre-
viously examined for ion recognition including macrocycles,
cryptand-like and calixarene shaped receptors [10]. Tin continues
to attract significant attention, owing to its many and varied appli-
cations in fields such as agriculture, biology, catalysis, organic syn-
thesis, etc. [11]. An important class of compounds are mono-, di-,
and triorganotin dithiocarbamates, which have been studied in
solution and by single-crystal X-ray diffraction analysis [12]. The
uses and potential utility of these compounds have been reviewed
by Tiekink [13].
weaker interactions such as C–HꢁꢁꢁX, C–Hꢁꢁꢁ
p,
p
ꢁꢁꢁ , XꢁꢁꢁX and XꢁꢁꢁY
p
(X = O, N, S, F, Cl, Br, I) contacts are also of considerable importance
for the stabilization of molecular solids [2]. C–HꢁꢁꢁX hydrogen
bonds have been shown to be of great importance for molecular
recognition processes [3], the reactivity and structure of biomolec-
ular species [4], the stabilization of inclusion complexes [5], crystal
Recently, we reported on the spectroscopic and structural char-
acterization of dinuclear diorganotin(IV) dithiocarbamate macro-
cycles, as well as trinuclear diorganotin cavitands and capsules,
which have been prepared from bis- and tris-dithiocarbamate
ligands and diorganotin(IV) dichlorides [14a–e]. A further study
⇑
Corresponding authors. Tel./fax: +52 777 3297997 (H. Tlahuext).
E-mail addresses: tlahuext@ciq.uaem.mx (H. Tlahuext), cga@uaem.mx
(C. Godoy-Alcántar).
0277-5387/$ - see front matter Published by Elsevier Ltd.
doi:10.1016/j.poly.2011.11.022

224
A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
2.2. Preparation of the diorganotin complexes
2.2.1. Ph2SnCl-dtc (1)
To a solution of benzyl(9-anthracenylmethyl)amine (0.6575 g,
2.21 mmol) and sodium hydroxide (0.114 g, 2.85 mmol) in tetrahy-
drofuran (3 mL)/methanol (25 mL) carbon disulfide was added
(2.0 mL, 33.25 mmol), and the mixture was stirred at 20 °C for
12 h. After addition of (Ph)2SnCl2 (0.92 g, 2.56 mmol) dissolved in
methanol (10 mL) the solution was stirred at 20 °C for 5 h. The
white precipitate was collected by filtration. Crystals suitable for
X-ray crystallography were grown from a solution of 1 in chloro-
form–methanol (1:1). Yield: 0.4687 g (31.1%). Mp: 201–208 °C. IR
(KBr): mmax = 994 (CS2), 1474 (C–NCS2) cmꢀ1 1H NMR (200 MHz,
.
~
CDCl3, Me4Si): d 4.57 (2H, s, NCH2Ph), 6.03 (2H, s, NCH2), 6.63–
8.50 (24H, m, aromatic hydrogens) ppm. 13C NMR (50 MHz, CDCl3,
Me4Si): d 51.62, 56.12 (NCH2), 123.43, 123.80, 125.48, 126.96,
127.46, 128.01, 128.72, 129.17, 129.51, 130.18, 130.53, 131.33,
131.48, 133.64, 136.00, 142.30 (aromatic carbons), 198.46
(CS2) ppm. 119Sn NMR (74.5 MHz, CDCl3, Me4Sn): d ꢀ313.19 ppm.
MS (FAB+): m/z (%) 646 (MꢀCl, 3.2). Anal. Calc. for C35H28ClNS2Sn
(680.88 g/mol): C, 61.74; H, 4.14; N, 2.06. Found: C, 61.57; H,
4.19; N, 2.57%.
Scheme 1. Chemical structures of the chlorodiphenyltin(IV) dithiocarbamate
complexes investigated herein.
has shown that diorganotin dithiocarbamates might be interesting
candidates for anion recognition [14f]. In this contribution we
present the synthesis, heteronuclear NMR and X-ray crystallo-
graphic studies of five chlorodiphenyltin(IV) dithiocarbamate
complexes, which were derived from benzyl(9-anthrylmeth-
yl)amine, benzyl(9-phenanthrylmethyl)amine, benzyl(1-pyre-
nylmethyl)amine, 1-naphthylmethyl(1-pyrenylmethyl)amine and
di(1-pyrenylmethyl)amine (Scheme 1). For the intrinsic Lewis acid
properties of the tin atom, as well as the fluorescent properties of
the anthryl, phenanthryl, pyrenyl and naphthyl moieties in these
chlorodiphenyltin(IV) complexes, they are interesting candidates
for anion recognition [14f,15].
2.2.2. Ph2SnCl-dtc (2)
Complex 2 was prepared following the protocol given for com-
pound 1. The white precipitate was collected by filtration. Crystals
suitable for X-ray crystallography were grown from a solution of 2
in dichloromethane–ethyl acetate (1:1). Yield: 72.8%. Mp: 102.6–
106.5 °C. IR (KBr): mmax = 996 (CS2), 1478 (C–NCS2) cmꢀ1 1H NMR
.
~
(200 MHz, CDCl3, Me4Si): d 4.98 (2H, s, NCH2), 5.46 (2H, s, NCH2),
7.19–8.79 (24H, m, aromatic hydrogens) ppm. 13C NMR (50 MHz,
CDCl3, Me4Si): d 56.53, 57.92 (NCH2), 122.78, 123.54, 123.73,
127.33, 127.49, 127.57, 127.73, 127.88, 127.97, 128.79, 128.99,
129.12, 129.25, 130.49, 133.58, 134.43, 135.91, 142.15 (aromatic
carbons), 199.63 (CS2) ppm. 119Sn NMR (74.5 MHz, CDCl3, Me4Sn):
d ꢀ316.51 ppm. MS (FAB+): m/z (%) 646 (MꢀCl, 13.5). Anal. Calc. for
2. Experimental
C35H28ClNS2Sn (680.88 g/mol): C, 61.74; H, 4.14; N, 2.06. Found: C,
2.1. General procedures and methods
60.70; H, 4.16; N, 2.46%.
Commercial starting materials and solvents have been used.
Ph2SnCl2 was commercially available and was used without
further purification. The synthesis of benzyl(9-anthrylmeth-
yl)amine, benzyl(9-phenanthrylmethyl)amine and benzyl(1-
pyrenylmethyl)amine were carried out by condensation of
9-anthracenecarboxaldehyde, 9-phenanthrenecarboxaldehyde
and 1-pyrenecarboxaldehyde with benzylamine by heating under
reflux in ethanol followed by Schiff bases reduction with NaBH4
in 88–97% yields. The secondary amines 1-naphthylmethyl(1-
pyrenylmethyl)amine and di(1-pyrenylmethyl)amine were carried
out by condensation of pyrenecarboxaldehyde, with 1-naphthylm-
ethylamine and 1-pyrenylmethylamine by heating under reflux in
ethanol followed by Schiff bases reduction with NaBH4 in 94% yield
[16a]. The sodium dithiocarbamate salts were prepared by treating
of the secondary amines with carbon disulfide and sodium hydrox-
ide in methanol [16b].
2.2.3. Ph2SnCl-dtc (3)
Complex 3 was prepared following the protocol given for com-
pound 1. The white precipitate was collected by filtration. Crystals
suitable for X-ray crystallography were grown from a solution of 3
in dichloromethane–diethyl ether (1:1). Yield: 83.2%. Mp: 204.4–
208.6 °C. IR (KBr): mmax = 992 (CS2), 1477 (C–NCS2) cmꢀ1 1H NMR
.
~
(200 MHz, CDCl3, Me4Si): d 4.87 (2H, s, NCH2), 5. 96 (2H, s,
NCH2), 7.26–8.41 (24H, m, aromatic hydrogens) ppm. 13C NMR
(50 MHz, CDCl3, Me4Si): d 55.98, 57.33 (NCH2), 122.02, 124.67,
125.06, 125.18, 125.92, 126.09, 126.14, 126.50, 126.53, 127.40,
127.95, 128.33, 128.75, 129.03, 129.12, 129.25, 129.40, 130.50,
130.70, 131.36, 131.95, 133.47, 135.94, 142.17 (aromatic carbons),
199.09 (CS2) ppm. 119Sn NMR (74.5 MHz, CDCl3, Me4Sn):
d
ꢀ316.52 ppm. MS (FAB+): m/z (%) 670 (MꢀCl, 2.8). Anal. Calc. for
NMR studies were carried out with Varian Gemini 200 and
Varian Inova 400 instruments. Chemical shifts (dH, dC and dSn
)
Table 1
Selected 1H, 13C and 119Sn NMR spectroscopic data for compounds 1–5.a
and J values are given in ppm and Hz, respectively. Standard refer-
ences were used: TMS (dH = 0 and dC = 0) and SnMe4 (d119Sn = 0). IR
spectra have been recorded on a Bruker Vector 22 FT spectropho-
tometer. Mass spectra were obtained on a Jeol JMS 700 equipment.
Elemental analysis has been carried out on an Elementar Vario ELIII
instrument. The electronic absorption spectra were recorded at
25 °C on a Hewlet–Packard 8452A diode array spectrophotometer,
and emission spectra were recorded on a Perkin-Elmer LS55 spec-
trofluorimeter at 25 °C.
Compound
1H NMR
13C NMR
13C NMR
119Sn NMR
d(CH2NCS2)
d(CH2NCS2)
d(CS2)
1
2
3
4
5
4.57, 6.03
4.98, 5.46
4.87, 5.96
5.44, 5.72
5.71
51.6, 56.1
56.5, 57.9
56.0, 57.3
55.6, 55.9
55.8
198.4
199.6
199.1
199.8
199.9
ꢀ313
ꢀ316
ꢀ316
ꢀ314
ꢀ314
a
In CDCl3.

A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
225
Table 2
Crystallographic data for compounds 1–3.
Crystal dataa
1
2
3
Formula
C
35H28ClNS2Sn C35H28ClNS2Sn
C37H28ClNS2Sn
704.86
P1
MW (g molꢀ1
Space group
T (K)
)
680.84
P1
100(2)
680.84
P2(1)/n
294(2)
ꢀ
ꢀ
294(2)
Cell parameters
a (Å)
b (Å)
9.8876(11)
11.6148(13)
14.6837(17)
79.624(2)
80.144(2)
67.042(2)
1517.8(3)
2
9.2915(11)
20.083(2)
16.1261(19)
90.0
96.603(2)
90.0
2989.1(6)
4
1.110
10.5312(12)
12.1468(14)
12.4570(14)
78.878(2)
88.827(2)
84.601(2)
1556.6(3)
2
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
l
q
(mmꢀ1
)
1.093
1.490
1.068
1.504
calc.(g cmꢀ3
)
1.513
Data collection
h limits (°)
hkl limits
1.42 < h < 25
ꢀ11,11;
ꢀ13,13;
ꢀ17,17
1.63 < h < 25.00 1.67 < h < 25
ꢀ11,11;
ꢀ23,23;
ꢀ19,19
28437
ꢀ12,12;
ꢀ14,14; ꢀ14,
14
Number of reflections
collected
13105
15035
Number of independent 5323 (0.0439)
reflections (Rint
5261 (0.0304)
5086
5468 (0.0430)
4690
)
Number of observed
reflections
Refinement
Rb,c
4800
0.0417
0.1002
361
1.088
ꢀ0.639
1.168
0.0241
0.0583
361
1.139
ꢀ0.462
0.555
0.0473
0.1292
379
1.064
ꢀ0.607
1.676
d,e
Rw
Number of variables
Goodness-of-fit
D
D
qmin (e Åꢀ3
)
qmax (e Åꢀ3
)
a
b
c
kMo
I > 2
R =
All data.
= 0.71073 Å.
a
K
r
R
> (I).
2
2
(F0 ꢀ Fc2)/
RF0 .
d
e
w(F0 ꢀ Fc2)2/
R .
w(F02)2]1/2
2
Rw = [
R
Table 3
Geometric parameter
s
, selected bond lengths (Å), bond angles (°) and torsion angles
(°) for compounds 1–3.
1
2
3
s
0.49
0.55
0.56
Bond lengths
Sn–S
2.4588(10)
2.7034(10)
2.4652(10)
2.4779(6)
2.6738(6)
2.4591(6)
2.4659(12)
2.7310(11)
2.4481(11)
SnꢁꢁꢁS
Sn–Cl
Bond angles
C–Sn–C
C–Sn–S
S–Sn–Cl
S–Sn–S
121.85(15)
125.51(11)
154.87(3)
69.53(3)
122.24(8)
120.38(6)
155.121(19)
69.61(2)
122.73(15)
124.26(11)
157.64(4)
68.93(4)
Torsion angles
C–N–C–C
C–N–C–C
133.0(4)
103.8(4)
133.2(2)
94.3(2)
ꢀ126.7(4)
ꢀ98.1(4)
C37H28ClNS2Sn (704.90 g/mol): C, 63.04; H, 4.00; N, 1.99. Found: C,
62.97; H, 4.39; N, 2.32%.
2.2.4. Ph2SnCl-dtc (4)
Complex 4 was prepared following the protocol given for
compound 1. The white precipitate was collected by filtration.
Fig. 1. Molecular structures of compounds 1–3. Displacements ellipsoids are shown
at the 50% probability level, and H atoms are shown as small spheres of arbitrary
radius.
~
Yield: 72.0%. Mp: 188.2–191.4 °C. IR (KBr): mmax = 991 (CS2), 1477
(C–NCS2) cmꢀ1 1H NMR (200 MHz, CDCl3, Me4Si): d 5.44 (2H, s,
.
NCH2), 5. 72 (2H, s, NCH2), 7.15–8.26 (26H, m, aromatic hydro-
(NCH2), 121.64, 122.08, 122.42, 122.78, 124.71, 124.96, 125.34,
125.53, 125.82, 126.13, 126.68, 127.18, 127.68, 127.96, 128.59,
gens) ppm. 13C NMR (50 MHz, CDCl3, Me4Si): d 55.63, 55.95

226
A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
128.91, 129.07, 129.36, 129.62, 130.29, 130.70, 131.07, 131.39,
131.78, 134.02, 135.75, 136.15, 142.19 (aromatic carbons),
CH2NCH2), 7.57–8.24 (28H, m, aromatic hydrogens) ppm.
13C NMR (50 MHz, CDCl3, Me4Si): d 55.78 (CH2NCH2), 121.83,
124.71, 125.23, 125.86, 126.05, 126.20, 126.53, 127.47, 128.29,
128.84, 129.26, 130.63, 131.45, 131.90, 136.12, 142.43, (aromatic
carbons), 199.86 (CS2) ppm. 119Sn NMR (74.5 MHz, CDCl3, Me4Sn):
d ꢀ314.12 ppm. MS (HR-FAB+): m/z (%) 795.1063 (MꢀCl, 90.3).
Error: ꢀ1.7 ppm.
199.81 (CS2) ppm. 119Sn NMR (74.5 MHz, CDCl3, Me4Sn):
d
ꢀ314.42 ppm. MS (FAB+): m/z (%) 720 (MꢀCl, 7.8). Anal. Calc. for
C41H30ClNS2Sn (754.96 g/mol): C, 63.95; H, 4.01; N, 1.86. Found:
C, 63.82; H, 3.89; N, 2.14%.
2.2.5. Ph2SnCl-dtc (5)
Complex 5 was prepared following the protocol given for
compound 1. The white precipitate was collected by filtration.
2.3. X-ray crystallography
~
Yield: 54.7%. Mp: 211.6–220 °C. IR (KBr): mmax = 992 (CS2), 1477
X-ray diffraction studies were carried out on a BRUKER-AXS APEX
(C–NCS2) cmꢀ1
.
1H NMR (200 MHz, CDCl3, Me4Si): d 5.71 (4H, s,
diffractometer with a CCD area detector (kMo K = 0.71073 Å,
a
Fig. 2. Perspective views of the dimers 1d–3d, showing the C@Sꢁꢁꢁ
p and edge-to-face C–Hꢁꢁꢁp contacts (dashed lines). For clarity, benzyl groups and hydrogen atoms not
involved in the hydrogen-bonding interactions were omitted.

A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
227
monochromator: graphite). Frames were collected at T = 100 K
(compounds, 1) and 294 K (compounds 2 and 3) via - and
3. Results and discussion
x
/-rotation (Dx = 0.3°) at 10 s per frame [17a]. The measured inten-
3.1. Preparation and spectroscopic characterization
sities were reduced to F2 and corrected for absorption with SADABS
[17b]. Structure solution, refinement and data output were carried
out with the SHELXTL-NT program package [17c,d]. Figures were
created with DIAMOND [18].
Non-hydrogen atoms were refined anisotropically, while C–H
hydrogen atoms were placed in geometrically calculated positions
using a riding model.
The dithiocarbamate (dtc) ligands required for the preparation
of compounds 1–5 were obtained from the combination of ben-
zyl(9-anthrylmethyl)amine, benzyl(9-phenanthrylmethyl)amine,
benzyl(1-pyrenylmethyl)amine, (1-naphthylmethyl)(1-pyrenylm-
ethyl)amine and di(1-pyrenylmethyl)amine with carbon disulfide
in the presence of sodium hydroxide. Subsequent reaction with
diphenyltin dichloride in 1:1 ligand-to-diorganotin(IV) stoichiom-
etric ratios gave the chlorodiphenyltin dithiocarbamate complexes
R2SnCl-dtc 1–5 in yields ranging from 31% to 83%. The composition
of complexes 1–5 was established by elemental analysis, mass
spectrometry, IR and NMR (1H, 13C, 119Sn) spectroscopy, and sin-
gle-crystal X-ray diffraction analysis (1–3). The formation of the
chlorodiorganotin complexes could be evidenced straightforward
from the IR and NMR (1H, 13C, 119Sn) spectra. The IR spectra
showed bands in the range from 1474 to 1478 cmꢀ1 and 991 to
996 cmꢀ1 that are typical for the vibrations of the C–Ndtc bonds
and CS2 groups, respectively [14,22].
2.4. Spectrophotometic titrations
UV–Vis and fluorimetric titrations were measured at 25 °C in
acetonitrile. For UV–Vis titrations aliquots of tetrabutylammonium
acetate stock solution (1 ꢂ 10ꢀ2 M) were added to diorganotin(IV)
dithiocarbamate complex solution (6.67 ꢂ 10ꢀ5
M for 1 and
1.67 ꢂ 10ꢀ5 M for 3) and the absorbance spectrum was recorded
in the range of 200–400 nm after each addition. Final concentra-
tion of the acetate in the cuvette were within 8 ꢂ 10ꢀ6 to
5 ꢂ 10ꢀ4 M. In the case of fluorimetric titrations aliquots of tetra-
butylammonium acetate stock solution (1 ꢂ 10ꢀ2 M) were added
The chemical shifts in NMR of 1H, 13C and 119Sn for compound
1–5 agree well with previously reported data on tin-dtc complexes
[12,14]. The CH2Ndtc methylene groups in the 1H and 13C NMR
spectra range from dH 4.57 to 6.03 ppm and dC 51.62 to
57.92 ppm, respectively. The 13C NMR signals of the dtc carbon
atoms (NCS2) vary from dC 198.4 to 199.8 ppm. The 119Sn NMR
chemical shift values were found in the expected region for chloro-
diphenyltin dithiocarbamates (dSn = ꢀ313 to ꢀ316 ppm), indicat-
ing that in solution the tin atoms are five-coordinate (Table 1).
The mass spectra (FAB+) of compounds 1–5 support the
assumption that diphenyltin(IV) dithiocarbamate complexes have
been obtained. In all cases the molecular ions could not be de-
tected, but it was possible to detect peaks corresponding to the
[MꢀCl]+ fragment ion (see Section 2).
to dithiocarbamate complex solution (7.2 ꢂ 10ꢀ6
M
for 1,
8.33 ꢂ 10ꢀ6 M for 2 and 3, 4 ꢂ 10ꢀ6 M for 4 and 4.2 ꢂ 10ꢀ6 M for
5) the emission spectrum was recorded using kex = 369 nm for 1,
252 nm for 2, 318 nm for 3 and 346 nm for 4 and 5 after each addi-
tion. Final concentration of the acetate in the cuvette was within
8 ꢂ 10ꢀ6–1 ꢂ 10ꢀ5 M.
2.5. Computational details
The molecular structure of compounds 4 and 5 was calculated
by computational chemistry methods according to a protocol de-
scribed by Buntine et al. [19a], which has been successfully used
by other authors to calculate dtc organotin(IV) complexes and alkyl
tin compounds [19b]. Density functional theory (DFT) calculations
were done with Jaguar code [20a] using the well known Becke–
Lee–Yang–Parr three parameters (B3LYP) hybrid functional [20b]
with LANL effective core (ECP) for Sn and 6-311G⁄⁄ basis set for
other atoms implemented as pseudospectral LACV3P⁄⁄ in jaguar.
All the calculations were done in acetonitrile using a Poisson–
Boltzmann model [21] in which the solvent is represented as layer
of charges at the molecular surface (which serves as a dielectric
continuum).
3.2. Single-crystal X-ray diffraction analysis of compounds 1–3
Single crystals of compounds 1–3 could be grown at room tem-
perature by slow evaporation of 1:1 chloroform–methanol (1),
dichloromethane–ethyl acetate (2), and dichloromethane–diethyl
ether (3) solutions. The most relevant crystallographic data are
summarized in Table 2. Selected geometric parameters are given
Table 4
Sꢁꢁꢁp
,
p
ꢁꢁꢁp
interactions and hydrogen bond geometry (Å, °) for compounds 1–3.
H-bond
D–H (Å)
H. . .A (Å)
D. . .A (Å)
D–H. . .A (°)
Symmetry codes
Compound 1
C15–H15AꢁꢁꢁCg2(C5–C7–C12–14)
0.99
0.95
0.99
0.95
2.70
2.87
2.94
2.57
3.510
3.80
3.874
3.423(5)
3.42
139.0
169
157.8
149
147.11
144.85
1 ꢀ x, 2 ꢀ y, 1 ꢀ z
1 ꢀ x, 1 ꢀ y, ꢀz
ꢀx, 2 ꢀ y, 1 ꢀ z
ꢀx, 2 ꢀ y, ꢀz
C34–H34ꢁꢁꢁCl1
C16–H16BꢁꢁꢁS2
C27–H27ꢁꢁꢁCg3(C30–C35)
C23–S1ꢁꢁꢁC(8)
1 ꢀ x, 2 ꢀ y, 1 ꢀ z
ꢀx, 2 ꢀ y, 1 ꢀ z
S2. . .Cg2(C5–C7–C12–C14)
3.503
Compound 2
C32–H32ꢁꢁꢁS2
0.95
0.95
0.99
2.95
2.80
2.75
3.828
158
126
147
151.18
1 + x, y, z
C20–H20. . .Cg4(C30–C35)
C15–H15AꢁꢁꢁCg2(C1–C2–C7–C8–C13–C14)
C23–S1ꢁꢁꢁCg1(C2–C7)
3.437(3)
3.601(2)
3.325
ꢀ1/2 + x, ½ ꢀ y, ½ + z
1 ꢀ x, 1 ꢀ y, ꢀz
1 ꢀ x, 1 ꢀ y, ꢀz
ꢀx, 1 ꢀ y, ꢀz
Cg1(C2–C7)ꢁꢁꢁCg3(C8–C13)
3.734
Compound 3
C1–S2ꢁꢁꢁC14
3.40
3.923
3.61
4.82
4.89
146.66
110.42
149
–
1 ꢀ x, 1 ꢀ y, 2 ꢀ z
ꢀx, 1 ꢀ y, 1 ꢀ z
1 ꢀ x, 1 ꢀ y, 1 ꢀ z
ꢀx, 1 ꢀ y, 1 ꢀ z
1 ꢀ x, 1 ꢀ y, 1 ꢀ z
C29–H29. . .Cg3(C26–C31)
C28–H28ꢁꢁꢁCg2(C4–C7–C17–C18)
Cg3ꢁꢁꢁCg3’
0.93
0.93
–
3.501
2.78
–
Cg3ꢁꢁꢁCg2
–
–
–

228
A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
in Table 3. Fig. 1 shows the molecular structures of the compounds
1–3.
The tin atoms are five-coordinate, being chelated by an asym-
metrically coordinating dithiocarbamate ligand, the chlorine atom
and two organic substituents. The coordination geometry is inter-
mediate between square-pyramidal and trigonal-bipyramidal
polyhedra with s-values in the range of 0.49–0.56 (Table 3) [23].
These geometries are similar to those observed for previously
reported chlorodiorganotin dithiocarbamates [12–14].
1d–3d with crystallographic inversion symmetry. The shortest
sulfur–carbon distances are 3.42 (S1ꢁꢁꢁC8) for 1d, 3.40 (S2ꢁꢁꢁC14)
for 3d, and the distance between the sulfur atom and the ring
center Cg1 (C2–C7) is 3.32 Å for 2d, which are less than the
sum of the van der Waals radii for S and C(
gest that the C@Sꢁꢁꢁ interaction is stronger in 2d than in 1d and
3d [24]. The dimers 1d and 2d are stabilized by two additional
interactions between adjacent anthrace-
p) (3.5 Å). This sug-
p
edge-to-face C–Hꢁꢁꢁ
p
nylmethyl and phenanthrenylmethyl groups, respectively (Fig. 2
The covalent Sn–S bonds for compounds 1–3 are in the range of
2.459(1)–2.4779(6) Å, and the covalent-coordinate SnꢁꢁꢁS bond
distances vary from 2.6738(6) to 2.7310(11) Å. Because of the
chelating coordination of the dithiocarbamate groups (S–Sn–S =
68.93(2)–69.61(1)°) in compounds 1–3, the bond angle between
the axial substituents deviate significantly from the ideal value of
180° (ScoordꢁꢁꢁSn–Cl = 154.87(3)–157.64(4)°) (Table 3).
and Table 4).
In the crystal structure of compound 1 neighboring dimers
are interconnected by the hydrogen bonds C34–H34ꢁꢁꢁCl1,
C16–H16BꢁꢁꢁS2 and S2ꢁꢁꢁ
p contacts [24–26] [distance between the
S2 and the ring center Cg2(C5–C7–C12–C14) is 3.5 Å]; thus
generating an overall 2D hydrogen-bonded network (Fig. 3(a)
and Table 4). The cyclic motifs in this arrangement possess crystal-
lographic inversion symmetry, and belong to the graph sets R22ð12Þ
and R22ð10Þ [27]. The packing is stabilized further by two additional
In the crystal structures of 1–3, neighboring molecules are
linked by pairs of C@Sꢁꢁꢁ
p contacts, thus generating the dimers
Fig. 3. (a) View of two adjacent chains in the crystal structure of 1, showing the association by C–HꢁꢁꢁCl, C–HꢁꢁꢁS hydrogen bonds [motifs R22ð12Þ, R22ð10Þ] and Sꢁꢁꢁ
p. (b) View of
edge-to-face C–Hꢁꢁꢁ
p interactions between adjacent phenyl groups. For clarity, phenyl groups and hydrogen atoms not involved in the hydrogen-bonding interactions were
omitted for clarity.

A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
229
edge-to-face C–Hꢁꢁꢁ
p
interactions between adjacent phenyl groups
interactions, thus generating supramolecular network like ladders
giving an overall 3D network. The distance C27ꢁꢁꢁCg3 (C24–C29) is
3.423(5) Å and the distance between the ring centroids is
4.321(3) Å (Fig. 3(b)).
which are further interconnected through edge-to-face C–Hꢁꢁꢁ
p
interactions between adjacent benzyl and phenyl groups to give
an overall 3D hydrogen-bonded network. The distances Cg1(C2–
C7)ꢁꢁꢁCg3(C8–C13) and C20ꢁꢁꢁCg4 (C30–C35) are 3.734 and
3.437(3) Å, respectively (Fig. 4 and Table 4).
In the crystal structure of compound 2, neighboring dimers are
linked by weak C32–H32ꢁꢁꢁS2 hydrogen bonds and offset
pꢁꢁꢁp
Fig. 4. (a) View of the supramolecular network like ladder running along axis a; (b) View of additional edge-to-face interactions between adjacent benzyl and phenyl
moieties. For clarity, phenyl groups and hydrogen atoms not involved in the hydrogen-bonding interactions were omitted.

230
A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
Fig. 5. View of the supramolecular 2D network for compound 3, showing the association by edge-to-face C–Hꢁꢁꢁ
p, offset pꢁꢁꢁp, and Sꢁꢁꢁp interactions. For clarity, phenyl and
benzyl groups, as well as hydrogen atoms not involved in the hydrogen-bonding interactions were omitted.
In the crystal structure of 3, neighboring dimers are linked
through edge-to-face C–Hꢁꢁꢁ
p
interactions and offset
p p interac-
ꢁꢁꢁ
tions, thus generating an overall 2D hydrogen-bonded network.
The distances between the ring centers are 4.82 for Cg3ꢁꢁꢁCg30
and 4.89 Å for Cg3ꢁꢁꢁCg2, and the shortest carbon-carbon distances
are 3.35 and 3.75 Å in each case (Fig. 5 and Table 4) [28].
3.3. Calculated molecular structures of compounds 4 and 5
The calculated molecular structures of compounds 4 and 5 are
presented in Fig. 6. In both cases the tin atom is five-coordinated
with one bidentate dtc ligand, one chlorine and two organic groups.
The calculated Sn–S and SnꢁꢁꢁS distances are 2.521, 2.742 Å for 4
and 2.516, 2.741 Å for 5, which are larger than the observed values
by X-ray diffraction (compounds 1–3). Other authors reported that
DFT/B3LYP/ECP geometry calculations for dithiocarbamate organo-
tin complexes giving Sn–S distances larger than X-ray determinat-
ed. The difference was attributed to the compression effect that
solid state packing induced on the complex geometry [19]. In the
other hand, structure of compound 5 has two pyrene moieties that
form an intramolecular slipped face to face
p p interaction. The
ꢀ
shortest carbon-carbon distance is 3.729 Å. In the emission spectra
of this compound a long wavelength band corresponding to an
intramolecular excimer was observed even at very dilute solutions
(vide infra). The
p p interaction justify the observation of an exci-
ꢀ
mer band in the fluorescence spectrum of compound 5. In the case
of compound 4 only bands corresponding to the monomeric aro-
matic moieties were observed. In the calculated structure aromatic
rings are far form each other and do not form any interaction.
3.4. UV–Vis spectroscopy
In order to obtain information about the interactions occurring
in solution, UV–Vis spectra for compounds 1–5 have been recorded
at 25 °C in acetonitrile (Fig. 7). The wavelengths of the absorption
Fig. 6. Geometry optimized structures for compounds 4 (a) and 5 (b) in acetonitrile.
The calculations where done with DFT (B3LYP) and Poisson–Boltzmann (PB) to
model the solvent.
maxima and their corresponding extinction coefficients (loge) are
summarized in Table 5. All dithiocarbamate complexes show six
bands in the 200–400 nm region. Bands I–V can be assigned to
the
p
?
p⁄ transitions of the aromatic groups, while band VI corre-
The UV spectrum of complex 1 shows a bathochromic shift of its
five bands.
sponds to the n ? p⁄ transition of the dithiocarbamate groups [29].

A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
231
Fig. 7. Absorption spectra of 1–5 complexes: 1, 3 (1.7 ꢂ 10ꢀ5 M), 4 (1.8 ꢂ 10ꢀ5 M), and 2, 5 (3.3 ꢂ 10ꢀ5 M) in acetonitrile at 25 °C.
Table 5
Wavelengths of the absorption maxima and approximate absorptivities (log
e
) for complexes 1–5 (in acetonitrile).
k/nm (loge)
Compound
Band I
Band II
Band III
Band IV
Band V
Band VI
1
2
3
4
5
–
288 (3.91)
246 (4.72)
266 (4.53)
243 (4.85)
266 (4.30)
337 (3.65)
254 (4.78)
277 (4.59)
277 (4.64)
277 (4.41)
353 (3.88)
278 (4.24)
315 (4.95)
315 (4.14)
316 (3.98)
371 (4.05)
287 (4.15)
329 (4.50)
329 (4.48)
329 (4.31)
391 (4.02)
297 (4.08)
345 (4.51)
345 (4.53)
346 (4.42)
223 (4.66)
243 (4.75)
223 (4.98)
243 (4.68)
As been shown previously [14f], the stability of chlorodiphenyl-
tin(IV) dithiocarbamate complexes in the presence of acetate anion
cause the displacement of the coordinated ligands (i.e., chloride
and dithiocarbamate) from the organotin(IV) moiety. The same
phenomenon occurs with these new polyaromatic dithiocarbamate
complexes and was explored with compounds 1 and 3. As can be
observed in the UV–Vis titrations for 1 and 3, a new absorption
band appears at 300 nm upon the acetate addition (Fig. 8). This
band correspond to the free dithiocarbamate anion as was con-
firmed by independent measurement of the absorption spectrum
of dtc sodium salt. In the case of complex 1 the free dithiocarba-
mate band rises separate of anthracenyl band while in complex 3
this band is overlapped with one of pyrenyl bands.
excimer emission bands observed for complex 5. The emission
intensity of the complexes is lower than intensity of the corre-
sponding dtc sodium salts.
The effect of acetate addition on the fluorescence spectrum was
investigated by titration of complex solutions in acetonitrile. In all
cases examined herein, addition of two acetate equivalents to a
solution of the metal complex caused an instantaneous reduction
in the fluorescence intensity. However, if the solutions were left
to stand for ca. 60 min, the fluorescence intensity was recovered.
These findings were investigated in more detail with complex 3
(Fig. 11), for which the fluorescence emission intensity 3 was
recorded in function of time. Addition of one equivalent of acetate
caused a rapid and moderate increase of the fluorescence intensity.
Addition of a second acetate equivalent reduced the fluorescence
intensity immediately, but slow recovery of the bands was
observed. The initial intensity was reached after approx. 60 min.
Subsequent observations showed that the fluorescence intensity
increased until reaching the value of a solution of the correspond-
ing dtc sodium salt. A similar titration was carried out using
UV–Vis absorption spectroscopy (Fig. 12). In this case, addition of
acetate generated a new absorption band at 300 nm (assigned to
the free dithiocarbamate [14f]), but no evidence for the dynamic
process observed by fluorescence was found.
Fig. 9 shows a plot of the changes of molar absorptivity coeffi-
cient (De) of the free dtc band versus the acetate/dtc molar ratio
during the titration. At low ratios, less than 1, both curves are al-
most overlapped. At more than 5 acetate/dtc ratio both curves
show saturation. The saturation
D
e
correspond with those of the
dithiocarbamate salt band (sodium salt of 1 dithiocarbamate
e
e
305 = 18,510 cmꢀ1 Mꢀ1 and sodium salt of 3 dithiocarbamate
303 = 14,335 cmꢀ1 Mꢀ1
.
3.5. Fluorescence
The above observations can be explained by a displacement of
the chloride and dithiocarbamate ligands by acetate as is illus-
trated in Scheme 2. In a first step, chloride is rapidly displaced from
the metal center by an acetate anion. Addition of the second ace-
tate equivalent slowly displaced the dithiocarbamate group. In this
step one dtc sulfur atom is displaced by one oxygen atom from the
acetate anion forming an intermediate six-coordinate intermediate
The organotin(IV) complexes reported in this work have polycy-
clic aromatic groups, which are well known for their excellent
photophysical properties. All complexes had emission bands in
the 300–450 nm wavelength range (Fig. 10) with spectral charac-
teristics in good agreement with the emission spectra of the
corresponding aromatic hydrocarbons [30], including the pyrene

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A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
Fig. 10. Emision spectra of 1–5 complexes: 1 (3.60 ꢂ 10ꢀ7 M, kexc = 369 nm), 2
(4.17 ꢂ 10ꢀ7 M, kexc = 252 nm),
3
(8.33 ꢂ 10ꢀ6 M, kexc = 318 nm),
4
(4 ꢂ 10ꢀ6 M,
kexc = 346 nm) and 5 (2.09 ꢂ 10ꢀ6 M, kexc = 346 nm) in acetonitrile at 25 °C.
4. Conclusions
This contribution has shown that the dithiocarbamate ligands
in the chlorodiorganotin complexes examined herein are
coordinated to the tin atoms in the anisobidentate manner. The
metal centers are five-coordinate, showing that the coordination
geometry is intermediate between square-pyramidal and trigo-
nal-bipyramidal coordination polyhedra. In the solid state, the
packing is modulated by cooperative intermolecular interactions
such as C–HꢁꢁꢁCl and C–HꢁꢁꢁS hydrogen bonds, Sꢁꢁꢁ
p, edge-to-face
and offset interactions. Intrinsic fluorescent properties of
pꢁꢁꢁ
p
(7 ꢂ 10ꢀ5 M) (a) and
3
M
the anthryl, phenanthryl, pyrenyl and naphthyl moieties in these
chlorodiphenyltin(IV) dithiocarbamate compounds makes these
compounds interesting candidates to detect the presence of
O-donor anions at very low concentrations by displacement of
the metal-coordinated dithiocarbamate. A dynamic process of ace-
tate addition was detected by emission spectroscopy and a mech-
anism is proposed.
Fig. 8. Absorption spectra during the titration of
1
(2 ꢂ 10ꢀ5 M) (b) with different quantities of acetate in the range 0–5.12 ꢂ 10ꢀ4
and 0–3.8 ꢂ 10ꢀ4 M, respectively.
structure [31]. This mechanism was previously reported for other
organotin(IV) dithiocarbamates [14f].
Fig. 9. Changes of absorption coefficient at 302 and 303 nm during the titration of 1 (7 ꢂ 10ꢀ5 M) and 3 (2 ꢂ 10ꢀ5 M), respectively, with different quantities of acetate in the
range 0–5.12 ꢂ 10ꢀ4 M for 1 and 0–3.8 ꢂ 10ꢀ4 M for 3.

A. Tlahuext-Aca et al. / Polyhedron 33 (2012) 223–234
233
Acknowledgments
The authors thank CONACyT for financial support through pro-
jects SEP-2004-C01-47347and CB2010-158098. C.G.A. thanks
CONACyT project 60747.
Appendix A. Supplementary data
CCDC 796384–796386 contains the supplementary crystallo-
graphic data for 1–3. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
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