Synthesis, spectroscopic investigations and crystal structures of organotin(IV) derivatives of 2-amino-1-cyclopentene-1-carbodithioic acid

Article abstract of DOI:10.1016/S0020-1693(01)00368-1

The organotin(IV) chlorides R_nSnCl_4-n (n=2, R=ⁿBu or Ph; and n=3, R=Ph) react with 2-amino-1-cyclopentene-1-carbodithioic acid (ACDA) to give [Ph₂SnCl(ACDA)] (1), [Ph₂Sn(ACDA)₂] (2), [Ph₃Sn(ACDA)] (3) and [Bu₂Sn(ACDA)₂] (4). The new complexes have been characterized by elemental analysis, UV-Vis, IR,¹H NMR, ¹¹⁹Sn NMR spectroscopy and mass spectrometry. On the basis of ¹¹⁹Sn NMR data the effective coordination number in solution is five. The structures of 1, 3 and 4 have been confirmed by X-ray crystallography. Crystals of 1 are monoclinic with space group P2₁/n. The tin environment is distorted trigonal bipyramid with Cl and sulfur atoms in apical positions. Crystals of 3 are orthorombic, P2₁2₁2₁, and the structure is distorted trigonal bipyramid with one sulfur and phenyl in the axial position. Complex 4 crystallizes in the triclinic space group, P1?, and the Sn atom shows extremely irregular octahedral coordination with four S atoms laying in the equatorial plane. In all complexes ACDA coordinates as an anisobidentate ligand and its orientation lends to form a NH···S intramolecular hydrogen bond. The packing is also stabilized by intermolecular hydrogen bonding.

Full text of DOI:10.1016/S0020-1693(01)00368-1

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Inorganica Chimica Acta 318 (2001) 15–22
Synthesis, spectroscopic investigations and crystal structures of
organotin(IV) derivatives of 2-amino-1-cyclopentene-1-carbodithioic
acid
Abbas Tarassoli a,*, Tahereh Sedaghat a, Bernhard Neumu¨ller b, Mitra Ghassemzadeh b
a Chemistry Department, College of Science, Shahid Chamran Uni6ersity, Ah6az, Iran
b Fachbereich Chemie der Uni6ersitaet Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
Received 11 August 2000; accepted 22 January 2001
Abstract
The organotin(IV) chlorides RnSnCl4−n (n=2, R=nBu or Ph; and n=3, R=Ph) react with 2-amino-1-cyclopentene-1-carbod-
ithioic acid (ACDA) to give [Ph2SnCl(ACDA)] (1), [Ph2Sn(ACDA)2] (2), [Ph3Sn(ACDA)] (3) and [Bu2Sn(ACDA)2] (4). The new
complexes have been characterized by elemental analysis, UV–Vis, IR,1H NMR, 119Sn NMR spectroscopy and mass spectrome-
try. On the basis of 119Sn NMR data the effective coordination number in solution is five. The structures of 1, 3 and 4 have been
confirmed by X-ray crystallography. Crystals of 1 are monoclinic with space group P21/n. The tin environment is distorted
trigonal bipyramid with Cl and sulfur atoms in apical positions. Crystals of 3 are orthorombic, P212121, and the structure is
distorted trigonal bipyramid with one sulfur and phenyl in the axial position. Complex 4 crystallizes in the triclinic space group,
(
P1, and the Sn atom shows extremely irregular octahedral coordination with four S atoms laying in the equatorial plane. In all
complexes ACDA coordinates as an anisobidentate ligand and its orientation lends to form a NH···S intramolecular hydrogen
bond. The packing is also stabilized by intermolecular hydrogen bonding. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Organotin complexes; Carbodithioiate complexes; Crystal structures
1. Introduction
and some of its derivatives have received considerable
attention both because they can mimic sulfur protein
compounds and because of their antifungal activity [6].
In view of the antifungal properties of organotin(IV)
compounds [7,8], it was considered interesting to syn-
thesize organotin(IV) derivatives of ACDA and exam-
ine the structural features as well as the biological
activities of these organotin(IV) complexes.
A survey of literature reveals that a few attempts
have been made to synthesize metal complexes of these
ligands with non-transition elements [9–11], and only
some organotin derivatives of ACDA esters have been
synthesized [12,13]. In view of the interesting results
reported for organotin(IV) complexes, it has been con-
sidered worthwhile to synthesize their complexes with
ACDA and investigate the nature of bonding with tin.
Therefore as a part of our investigations on the organ-
otin(IV) compound [14], new complexes of organ-
otin(IV) with ACDA were synthesized and character-
ized. The results of this study are reported.
In view of the interesting role played by aminocar-
boxylic acid complexes in body systems and also be-
cause of the current interest in metal sulfur compounds
in biological molecules, delineation of the nature of
binding in metal chelates derived from the skeletal
NH2–CꢀC–C(S)S− warrants investigations. Among
these, 2-amino-1-cyclopentene-1-carbodithioic acid
(ACDA) has been found to be a good chelating agent.
This ligand is interesting because of its potential dual
bidentate coordinate possibilities, so that bonding takes
place either from the amino nitrogen and the deproto-
nated thiol sulfur or from the dithiocarboxylic moiety.
Up to now, considerable studies have been performed
on ACDA, its derivative and their complexes with
transition metal complexes [1–5]. Complexes of ACDA
* Corresponding author. Tel.: +98-611-360018; fax: +98-611-
337009.
E-mail address: tarasoli@ahvazuni.neda.net.ir (A. Tarassoli).
0020-1693/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0020-1693(01)00368-1

16
A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
2. Experimental
dropwise triethylamine (in the appropriate molar ratio).
The yellow needle crystals were formed gradually,
filtered and washed with methanol. Yield 80%; m.p.
(dec.) 182°C; umax (nm) (CH2Cl2): 259, 329, 392 (log m
3.66, 4.16, 4.54). Anal. Found: C, 56.5; H, 4.5; N, 2.7;
S, 12.7. Calc. for C24H23NS2Sn: C, 56.7; H, 4.5; N, 2.75;
S, 12.6%.
2.1. Materials and methods
All chemicals and solvents were purchased from
Merck chemical company. The ACDA ligand and its
ammonium salt (AACD) were prepared by the litera-
ture methods [15,16]. UV–Vis spectra of ligand and its
complexes were recorded on a Jasco model 7850 spec-
trophotometer. IR spectra were obtained using a Shi-
madzu 470 spectrophotometer in the 4000–400 cm−1
with the samples as KBr discs and a Pye Unicam
SP-2000 spectrophotometer in the 400–200 cm−1 re-
2.2.4. [Bu2Sn (ACDA)2] (4)
To a solution of Bu2SnCl2 (1.52 g, 5 mmol) in
methanol was added AgNO3 (1.70 g, 10 mmol). The
mixture was stirred for 1 h at room temperature (r.t.).
Silver nitrate assists the cleavage of the Sn–Cl bond
and accelerates the removal of chloride as AgCl precip-
itate. Then AgCl was filtered. To the filtrate a solution
of AACD (1.76 g, 10 mmol) in methanol was added
and after several minutes yellow crystals of product
were filtered and washed with methanol. Yield 80%;
m.p. (dec.) 190°C; umax (nm) (CH2Cl2): 344, 393 (log m
4.41, 4.90). Anal. Found: C, 44.0; H, 6.2; N, 5.2; S,
23.5. Calc. for C20H34N2S4Sn: C, 43.7; H, 6.2; N, 5.1; S,
23.3%.
1
gion. The H and 119Sn NMR spectra were recorded on
a Brucker Advance DPX-500 spectrometer (at 500.130
and 186.496 MHz, respectively) using TMS and SnMe4
as reference, respectively. The C, H, N and S analyses
were performed by the microanalytical service of the
N.I.O.C. Research Institute of Petroleum Industry.
Melting points were measured on a Mettler FP5
apparatus.
2.2. Synthesis of complexes
2.3. Crystal structure determination
2.2.1. [Ph2SnCl(ACDA)] (1)
A methanolic solution of ACDA (0.8 g, 5 mmol) or
its ammonium salt (0.88 g, 5 mmol) was added to a
methanolic solution of Ph2SnCl2(1.72 g, 5 mmol). Fine
needle crystals began to separate almost immediately,
after completion of crystallization the product was
filtered off and washed with methanol. Yield 85%; m.p.
(dec.) 207–209°C; umax (nm) (CH2Cl2): 260, 333, 390
(log m 3.61, 3.89, 4.56). Anal. Found: C, 46.3; H, 3.8; N,
3.4; S, 13.5. Calc. for C18H18ClNS2Sn: C, 46.3; H, 3.85;
N, 3.0; S, 13.7%.
For complexes 1 and 4, crystals suitable for X-ray
diffraction studies were obtained upon recrystallization
from CH2Cl2–MeOH and for 3 were selected from the
first batch of the synthesis in method B and no further
purification was necessary. Attempts at preparation of
suitable crystals from complex 2 was unsuccessful so no
crystallographic information for this compound has
been reported.
A needle crystal of complex 1 with dimensions
0.51×0.22×0.1 mm was used for crystal data collec-
tion. X-ray measurements were performed at 213 K on
an Enraf–Nonius CAD4 diffractometer using Cu Ka,
u=154.178 pm, radiation monochromated with a
highly oriented graphite crystal in the 2q range 4.45–
139.93°.
2.2.2. [Ph2Sn(ACDA)2] (2)
A methanolic solution of AACD (1.76 g, 10 mmol)
was added to a methanolic solution of Ph2SnCl2 (1.72
g, 5 mmol). The yellow product formed was filtered and
washed with methanol. Yield 75%; m.p. (dec.) 220°C;
umax (nm) (CH2Cl2): 340, 396 (log m 4.22, 4.75). Anal.
Found: C, 48.4; H, 4.4; N, 4.5; S, 21.8. Calc. for
C24H26N2S4Sn: C, 48.9; H, 4.4; N, 4.75; S, 21.7%.
For complex 3, a yellow needle crystal with dimen-
sions 0.39×0.13×0.03 mm was used. X-ray crystallo-
graphic measurements were carried out at 193 K using
an IPDS system (Stoe) diffractometer with graphite-
monochromated Mo Ka radiation (u=71.073 pm) in
the 2q range 2.54–51.9°.
2.2.3. [Ph3Sn(ACDA)] (3)
For complex 4 a yellow plate-shape crystal (0.36×
0.29×0.13 mm) was used for data collection in a
Siemens P4 diffractometer. Data were collected at 193
K using Mo Ka radiation (u=71.073 pm) monochrom-
atized with a graphite crystal in the 2q range 2.58–
50.0°.
The structures were solved by Patterson method and
were refined by a full-matrix least-squares calculations
with SHELXL-97. Hydrogen atoms were included in the
final refinements using a riding model (free refined
2.2.3.1. Method A. To a stirring methanolic solution of
Ph3SnCl (1.93 g, 5 mmol) was added a solution of the
AACD (0.88 g, 5 mmol) in methanol. The yellow
product was separated after a few minutes. The mixture
was stirred for another 30 min to ensure the completion
of the reaction. The product was filtered and washed
with methanol. Yield 80%; m.p. 182°C.
Method B. To a solution of Ph3SnCl (1.93 g, 5 mmol)
and ACDA (0.8 g, 5 mmol) in methanol was added

A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
17
Table 1
Crystal data, data collection, structural solution and refinement of complexes [SnPh2Cl(ACDA)] (1), [SnPh3(ACDA)] (3) and [SnBu2(ACDA)2] (4)
[SnPh2Cl(ACDA)] (1)
[SnPh3(ACDA)] (3)
[SnBu2(ACDA)2] (4)
Formula
M (g mol−1
Color
Crystal size (mm)
Crystal system
Space group
Unit cell dimensions
a (pm)
C18H18ClNS2Sn
466.61
Colorless, needle
0.51×0.22×0.1
monoclinic
P21/n
C24H23NS2Sn
508.26
Yellow, needle
0.39×0.13×0.03
orthorhombic
P212121
C20H34N2S4Sn
549.43
Yellow, plates
0.36×0.29×0.13
triclinic
)
(
P1
1187.6(3)
949.0(2)
1674.5(4)
838.4(1)
1645.2(1)
3214.2(3)
1180.3(2)
1434.0(2)
1670.1(4)
b (pm)
c (pm)
h (°)
76.97(1)
i (°)
93.22
72.40(1)
k (°)
72.51(1)
V (pm3)
Z
1884.2(8)×106
4
1.645
141.3
928
154.178
213
4433.5(7)×106
8
1.523
13.5
2048
2541.5(8)×106
4
Dcalc (g cm−3
)
1.436
13.4
1128
71.073
v (cm−1
F(000)
u (pm)
T (K)
)
71.073
193
193
2q Range (°)
Scan method
Scan width
4.45–139.93
ꢀ-scan
0.41+0.29tgq
2.54–51.9
2.58–50.0
ꢀ-scan
1.2
Reflections collected
Unique reflections
Absorbance reflections [Fo\4|(Fo)]
Refinement
3639
26 414
8287 (Rint=0.0866)
4265
9347
3296 (Rint=0.0858)
2912
Full-matrix least-squares
8348 (Rint=0.0455)
5576
Full-matrix least-squares
Full-matrix least-squares
Number of parameters
R1
wR2
215
518
538
0.0629
0.1804
1.039
0.0345
0.0509
0.664
0.0464
0.1069
1.007
Goodness-of-fit
N–H positions in 4). Crystallographic data, details of
the data collection, structure solution and refinements
are summarized in Table 1.
3.1. X-ray structures
3.1.1. Description of the structure of [Ph2SnCl(ACDA)]
(1)
Although a number of penta-coordinated diorgan-
otin complexes of the type R2ClSnS2C have been re-
ported, examples of structural studies are limited
[17–20]. Fig. 1 shows the molecular structure of
[SnPh2Cl(ACDA)] and atomic numbering scheme used.
Fig. 2 shows the molecular packing diagram in unit
cell. Intramolecular bond distances and angles are given
in Table 2.
3. Results and discussion
The ligand was synthesized as reported earlier in the
literature [15,16]. Singh et al. suggested existence of
form I exclusively for ACDA [10].
Organotin(IV) complexes of ACDA were formed by
reaction of organotin(IV) chlorides with ACDA or its
ammonium salt. The composition of the compounds
has been confirmed by their analytical data. The nature
of bonding in the complexes was recognized by spectro-
scopic data and X-ray crystallography.
Fig. 1. Molecular structure of 1.

18
A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
Fig. 2. Molecular packing diagram in unit cell of 1.
,
From both Table 2 and Fig. 1 it can be seen that the
lent radii of tin and sulfur (2.42 A) [22]. While the other
Sn–S bond is considered as a weak coordinative bond
corresponding to an anisobidentate ligand (thin lines in
Fig. 3). This might suggest description of the tin envi-
ronment as a trigonal bipyramid with S(2) and C(13) in
the apical positions and S(1), C(7) and C(19) in the
equatorial positions, this bipyramid is distorted: The
sum of the equatorial angles is 350.2(7)° instead of the
ideal 360° and the tin atom lies out of the equatorial
plane.
configuration about the tin atom is penta-coordinated
distorted trigonal bipyramid with atoms S(1), C(7) and
C(8) occupying equatorial positions. The sum of the
ligand–Sn–ligand angle in the trigonal girdle of the
compound is 359.5(7)°. So the tin atom shows no
significant deviation from the equatorial plane. The Cl
atom occupies one of the apical positions of the trigo-
nal bipyramid. Due to being part of a chelate the angle
S(1)–Sn–S(2) is not 90° but only 70.65(6)°, so the S(2)
cannot occupy exactly the corresponding trans axial
position of Cl1 and the angle Cl1–Sn(1)–S(2) being
157.10(6)°. The Sn(1)–S(2) bond is markedly elongated
As indicated by dashed lines in Fig. 3, an intramolec-
ular hydrogen bond is formed between one of the NH2
protons and the sulfur atom which is involved in the
weaker Sn–S bond (N(1)H(1)···S(2) and N(2)H(3)···S(4)
in Fig. 3). Also as shown in this Figure the neighboring
,
(2.649(2) A) compared to the Sn(1)–S(1) bond (2.439(2)
,
A). This makes the dithiolate coordination unsymmetri-
cal. As shown in Fig. 1, the orientation of the ACDA
enables it to form an intramolecular hydrogen bond
(N(2)–H(2)···S(2)). Also neighboring molecules are held
together by intermolecular Cl(1a)···H(1)–N(1) hydro-
gen bonds. These hydrogen bonds can lend the crystal
stability and compactness and result in a chain arrange-
ment from the intermolecular bonds (Fig. 2).
Table 2
,
Selected bond distances (A) and angles (°) for [Ph2SnCl(ACDA)] (1)
Sn(1)–Cl(1)
Sn(1)–S(2)
Sn(1)–C(8)
S(2)–C(1)
C(1)–C(2)
N(1)–H(1)
2.543(2)
2.649(2)
2.123(7)
1.720(7)
1.381(9)
0.85(9)
Sn(1)–S(1)
Sn(1)–C(7)
S(1)–C(1)
N(1)–C(3)
C(2)–C(3)
N(1)–H(2)
2.439(2)
2.118(7)
1.756(7)
1.32(1)
1.40(1)
0.85(3)
3.1.2. Description of the structure of [Ph3Sn(ACDA)]
(3)
A stereoview of the molecules and atomic numbering
are shown in Fig. 3. As shown, the crystal consists of
two molecules which both have the same ligand shell
but two different positions for the tin center. Table 3
lists one set of bonding parameters.
The crystal structure shows the tin atom is coordi-
nated to the two sulfur atoms of the ACDA ligand and
to the one carbon atom of each of the three phenyl
Cl(1)–Sn(1)–S(1)
Cl(1)–Sn(1)–C(7)
S(1)–Sn(1)–S(2)
S(1)–Sn(1)–C(8)
S(2)–Sn(1)–C(8)
Sn(1)–S(1)–C(1)
S(1)–C(1)–S(2))
S(2)–C(1)–C(2)
C(1)–C(2)–C(6)
N(1)–C(3)–C(2)
C(2)–C(3)–C(4)
86.57(6) Cl(1)–Sn(1)–S(2)
93.4(2) Cl(1)–Sn(1)–C(8)
70.65(6) S(1)–Sn(1)–C(7)
157.10(6)
96.8(2)
126.2(2)
98.0(2)
121.3(3)
83.5(2)
117.9(5)
127.2(6)
108.5(6)
120.2(7)
119.8(5)
120.5(6)
113.0(8)
122.0(9)
112.0(2)
94.1(2)
S(2)–Sn(1)–C(7)
C(7)–Sn(1)–C(8)
Sn(1)–S(2)–C(1)
S(1)–C(1)–C(2)
C(1)–C(2)–C(3)
C(3)–C(2)–C(6)
N(1)–C(3)–C(4)
Sn(1)–C(7)–C(75)
Sn(1)–C(8)–C(81)
C(3)–N(1)–H(2)
H(1)–N(1)–H(2)
89.4(2)
116.0(4)
126.1(5)
124.2(6)
129.0(7)
110.8(7)
Sn(1)–C(7)–C(71) 121.1(5)
Sn(1)–C(8)–C(85) 120.5(5)
C(3)–N(1)–H(1)
,
groups. One of the Sn–S bonds (2.462(2) A) lies in the
range recently reported for triphenyltin thiolates
125.0(6)
,
(2.405–2.481 A) [21,22], close to the sum of the cova-

A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
19
Fig. 3. Molecular structure of 3.
molecules are oriented in the way that an intermolecu-
3.1.3. Description of the structure of [Bu2Sn(ACDA)2]
(4)
lar hydrogen bond is formed between another NH2
proton and one sulfur atom of the neighboring
molecule (N(1)H(2)···S(4) in Fig. 3), so that this sulfur
atom is involved in one intra- and one inter-molecular
hydrogen bond. The structure is held in two-dimen-
sional space by these intermolecular hydrogen bonding
forces (Fig. 4).
The crystal consists of relatively isolated molecules
that differ in conformation of the butyl group. Fig. 5
shows a view of two crystallographically independent
molecules (A, B) and also gives the atom-numbering
scheme. Corresponding bond distances and angles of
the two crystallographic molecules are slightly different.
Selected bond distances and angles for molecule A are
given in Table 4.
The Sn atoms show extremely irregular octahedral
coordination. The four S atoms lie in the equatorial
plane. The C(1) and C(5) atoms of the butyl groups
define C–Sn–C angles 134.2(3)° (molecule A) and
136.9(3)° (molecule B) is intermediate between cis and
trans. The ACDA ligand is anisobidentately chelated to
Table 3
,
Selected bond distances (A) and angles (°) for [Ph3Sn(ACDA)] (3)
Sn(1)–S(1)
Sn(1)–C(13)
S(1)–C(1)
N(1)–C(3)
C(2)–C(3)
N(2)–H(2)
2.462(2)
2.132(9)
1.766(9)
1.323(9)
1.41(1)
Sn(1)–C(7)
Sn(1)–C(19)
S(2)–C(1)
C(1)–C(2)
N(1)–H(1)
2.120(8)
2.115(8)
1.665(9)
1.44(1)
0.95(7)
0.86(7)
S(1)–Sn(1)–C(7)
S(1)–Sn(1)–C(19)
C(7)–Sn(1)–C(19)
Sn(1)–S(1)–C(1)
S(1)–C(1)–C(2)
C(1)–C(2)–C(3)
C(3)–C(2)–C(6)
N(1)–C(3)–C(4)
Sn(1)–C(7)–C(12)
Sn(1)–C(13)–C(18)
Sn(1)–C(19)–C(24)
C(3)–N(1)–H(2)
H(1)–N(1)–H(2)
121.7(2)
111.2(2)
116.6(3)
95.8(3)
115.0(7)
125.6(7)
108.4(6)
122.3(7)
127.5(6)
124.1(6)
122.8(6)
109.0(4)
135.0(6)
S(1)–Sn(1)–C(13)
C(7)–Sn(1)–C(13)
C(13)–Sn(1)–C(19)
S(1)–C(1)–S(2)
94.8(3)
101.4(3)
105.4(3)
118.8(5)
126.1(7)
126.0(7)
126.5(7)
111.1(6)
117.7(6)
122.0(6)
120.5(7)
112.0(4)
S(2)–C(1)–C(2)
C(1)–C(2)–C(6)
N(1)–C(3)–C(2)
C(2)–C(3)–C(4)
Sn(1)–C(7)–C(8)
Sn(1)–C(13)–C(14)
Sn(1)–C(19)–C(20)
C(3)–N(1)–H(1)
Fig. 4.

20
A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
Sn, with one longer and one shorter Sn–S bond (Figure
5). From X-ray studies the dithiolate ligands act as
anisobidentate in most of the diorganotin(IV) dithiolate
complexes [23,24]. As indicated in Figure 5 by dashed
lines, there are intramolecular hydrogen bonds between
N(1)H(2)···S(2) and N(2)H(4)···S(4) similar to previous
described molecules.
3.2. Vibrational spectra
The explicit feature in the spectra of all complexes is
absence of the band in the region 2550–2430 cm−1
,
which appears in the free-ligand as the w(S–H) vibra-
tion, thus indicating metal–ligand bond formation
through this site. The N–H stretching frequencies in
the complexes remain approximately the same or in-
crease slightly in complexes, comparing uncomplexed
ligand, attesting to no participation of nitrogen in
coordination to the metal center. The bands attributed
to w(N–H) usually shift their position rather signifi-
cantly to lower energy upon coordination to a metal
[25]. The complexes of Ph2SnCl2 and Ph3SnCl also
show the IR bands typical of phenyltin complexes at
around 1070, 1020, 1000, 730, 690, 450 cm−1 as re-
ported earlier [26]. In the far-infrared spectra of the
complexes, strong absorption at 340–365 cm−1, which
is absent in the spectrum of the ligand, is assigned to
Sn–S stretching mode of vibration.
Fig. 5. Molecular structure of 4.
3.3. NMR spectra
Table 4
,
Selected bond distances (A) and angles (°) for [Bu2Sn(ACDA)2] (4)
1H NMR data of ACDA and its corresponding
complexes are shown in Table 5. The signal of the –SH
proton in the spectrum of ACDA is absent in all of
adducts, indicating the removal of the SH proton and
Sn(1)–S(1)
Sn(1)–C(1)
S(1)–C(9)
2.492(2)
2.140(6)
1.750(6)
1.769(6)
1.309(9)
1.511(8)
1.51(1)
Sn(1)–S(3)
Sn(1)–C(5)
S(2)–C(9)
2.530(2)
2.135(6)
1.712(6)
1.693(7)
1.31(1)
1.549(9)
1.41(1)
1.28(1)
1.401(8)
1.43(1)
0.81(6)
0.85(5)
S(3)–C(15)
N(1)–C(11)
C(1)–C(2)
C(3)–C(4)
C(6)–C(7)
C(9)–C(10)
C(15)–C(16)
N(1)–H(1)
N(2)–H(3)
S(4)–C(15)
N(2)–C(17)
C(2)–C(3)
C(5)–C(6)
C(7)–C(8)
C(10)–C(11)
C(16)–C(17)
N(1)–H(2)
N(2)–H(4)
1
the formation of Sn–S bonds. In the H NMR spec-
trum of ACDA, two signals assigned to the –NH2
protons have appeared at l 6.1 and l 11.2 ppm,
showing the nonequivalence of the protons of the
amino group. This is attributed to the involvement of
one of the NH2 protons in hydrogen bonding through
the sulfur atom of the –CꢀS group in structure III of
the ACDA. In the spectra of tin complexes these two
bands are also observed with some changes in chemical
shifts. In all spectra, the signal observed at l 11.2 ppm
in the free ligand shifts upfield, this might be due to the
breaking of the hydrogen bond (N–H···Sꢀ) during the
complexation. However, the existence of two signals for
the –NH2 protons, instead of one signal in complexes,
indicates the probability of some interaction, between
one of the NH2 protons and the sulfur atom (–CꢀS) of
the dithiocarboxylate group resulting in magnetically
anisotropic NH2 protons (structure II). It is suggested
that the weaker metal sulfur bond (–CꢀS···Sn) and the
stronger hydrogen bonding (NH···Sꢀ) results.
1.67(1)
1.399(8)
1.411(8)
1.05(8)
0.98(8)
S(1)–Sn(1)–S(3)
S(1)–Sn(1)–C(5)
S(3)–Sn(1)–C(5)
Sn(1)–S(1)–C(9)
Sn(1)–C(1)–C(2)
C(2)–C(3)–C(4)
C(5)–C(6)–C(7)
S(1)–C(9)–S(2)
82.64(6)
106.2(2)
105.9(2)
96.3(2)
113.3(5)
113.4(7)
118.0(1)
117.4(4)
S(1)–Sn(1)–C(1)
S(3)–Sn(1)–C(1)
C(1)–Sn(1)–C(5)
Sn(1)–S(3)–C(15)
C(1)–C(2)–C(3)
Sn(1)–C(5)–C(6)
C(6)–C(7)–C(8)
S(2)–C(9)–C(10)
N(1)–C(11)–C(12)
S(3)–C(15)–C(16)
N(2)–C(17)–C(18)
C(11)–N(1)–H(2)
C(17)–N(2)–H(3)
H(3)–N(2)–H(4)
111.3(2)
104.2(2)
134.2(3)
100.3(2)
113.7(6)
115.0(7)
101.0(1)
126.6(5)
120.6(6)
115.0(5)
122.9(9)
118.0(4)
128.0(5)
117.0(*)
N(1)–C(11)–C(10) 128.4(7)
S(3)–C(15)–S(4)
S(4)–C(15)–C(16)
119.5(4)
125.5(5)
N(2)–C(17)–C(16) 128.0(8)
C(11)–N(1)–H(1)
H(1)–N(1)–H(2)
C(17)–N(2)–H(4)
121.0(5)
116.0(7)
115.0(8)

A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
21
from the hindered rotation of the amino group and the
presence of a positive formal charge over the nitrogen
leading to deshielding of –NH2 group protons.
The spectrum of Ph2Sn(ACDA)2 is obtained in
DMSO-d6, because of low solubility of this compound
in CDCl3. This spectrum differs from others because
the signal of free –NH observed in the upfield of the
spectrum in the other adducts disappears and two
singlets with a small splitting (0.2 ppm) and equal
intensity appear in the downfield. It is apparent that the
NH2 protons are magnetically different. The position of
the chemical shifts and the observation of unequal
shifts for the two NH2 group protons show this system
is analogous in behavior to Ni(ACDA)2 in DMSO [30].
In this polar solvent, the ionic resonance from IV is
preferred and delocalization of the lone pair electrons
of nitrogen atom can bring forth a double bond charac-
ter in the N–C bond. Magnetic inequivalence of the
NH2 protons in the metal complexes can then arise
Table 5 shows 119Sn{H} NMR data for synthesized
complexes. 119Sn NMR was not reported for complex 4
because of its limited solubility in common organic
solvents. In each case the 119Sn spectrum shows only a
sharp singlet indicating the formation of a single spe-
cies, with the 119Sn resonance appearing at lower fre-
quency than that of its organotin chloride precursor. In
general 119Sn chemical shifts move to lower frequency
with increasing coordination number. Although the
shift ranges are somewhat dependent on the nature of
the substituents at the tin atom, the following ranges
have been proposed for some tin(IV) dithiocarbamato
Table 5
1H and 119Sn NMR data for complexes 1, 2, 3 and 4 (l in ppm and J in Hz) a
Compound
Solvent
Ph
CH2(3)
CH2(4)
CH2(5)
NHa
NHb
l(119Sn)
H2,6
H3,4,5
3J(119Sn,H)
b,c
ACDA
CDCl3
CDCl3
CDCl3
(CD3)2SO
2.66t
2.75t
2.60t
2.52t
1.88q
1.88q
1.70q
1.79q
2.76t
2.84t
2.70t
2.95t
6.1s
6.70
8.68
5.85
11.2s
8.86
d
SnPh2Cl2
7.70m
8.06
7.89
7.80
7.67
7.75
7.56m
7.45
7.35
7.62
7.47
7.40
81.7
82.5
114.9
101
60.4
63.6
−27
−257.98
1
d
SnPh2Cl2
2
8.94
SnPh3Cl d
CDCl3
CDCl3
−48
−154.97
3
10.01
Bu
Ha
Hb
Hg
Hd
e
SnBu2Cl2
4
CDCl3
CDCl3
1.8m
1.41m
1.93
1.4m
1.43ps
0.95t
0.92
122 f
−200.21
1.99m g
2.69
1.82
2.91
6.03
10.0
a s, singlet; t, triplet; q, quintet; ps, pseudo sixtet; m, multiplet.
b Numbering scheme:
c Ref. [12].
d Ref. [27].
e Ref. [28].
f Ref. [29].
g Satellites undetectable.

22
A. Tarassoli et al. / Inorganica Chimica Acta 318 (2001) 15–22
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4. Supplementary material
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
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147393 (4). Copies of this information may be obtained
free of charge from the Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
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Acknowledgements
Support of this work by Shahid Chamran University,
Ahvaz, Iran and Marburg University, Marburg, Ger-
many (for X-ray facilities) is gratefully acknowledged.
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