Synthesis and crystal structures of new complexes of di- andtribenzyltin N-ethyl and N-benzyl-2-amino cyclopent-1-ene-1-carbodithioates

Article abstract of DOI:10.1016/S0022-328X(01)01334-1

The dithiocarboxylato complexes of tin, Bz₂SnCl(EtACDA) (1a) Bz = benzyl, Bz₂Sn(EtACDA)₂ (1b), and Bz₃Sn(EtACDA) (1c) have been synthesized by the reaction of Bz₂SnCl₂ or Bz₃SnCl

Full text of DOI:10.1016/S0022-328X(01)01334-1

Journal of Organometallic Chemistry 645 (2002) 105–111
www.elsevier.com/locate/jorganchem
Synthesis and crystal structures of new complexes of di- and
tribenzyltin N-ethyl and N-benzyl-2-amino
cyclopent-1-ene-1-carbodithioates
Abbas Tarassoli a,*, Ashrafolmolouk Asadi a, Peter B. Hitchcock b
a Department of Chemistry, Faculty of Science, Ah6az Uni6ersity, Ah6az, Iran
b School of Chemistry, Physics and En6ironmental Science, Uni6ersity of Sussex, Brighton BN1 9QJ, UK
Received 10 July 2001; accepted 28 September 2001
Abstract
The dithiocarboxylato complexes of tin, Bz2SnCl(EtACDA) (1a) Bz=benzyl, Bz2Sn(EtACDA)2 (1b), and Bz3Sn(EtACDA) (1c)
have been synthesized by the reaction of Bz2SnCl2 or Bz3SnCl with 2-N-ethylamino-1-cyclopentene-1-carbodithioic acid (HEt-
ACDA). The reaction of 2-amino-1-cyclopente-1-carbodithioic acid (H2ACDA) with benzylamine, gave 2-N-benzylamino-1-cy-
clopente-1-carbodithioic acid (HBzACDA) (2), which reacts with Bz2SnCl2 or Bz3SnCl to give Bz2SnCl(BzACDA) (3a),
Bz2Sn(BzACDA)2 (3b) and Bz3Sn(BzACDA) (3c). The products were characterized by IR and NMR (1H, 13C and 119Sn)
spectroscopies and elemental analysis. The crystal structures of 1c, 2 and 3b have also been determined. In all the complexes Sn
is bound asymmetrically to the dithiocarboxylato ligand through two sulfur atoms. The orientation of the ligands is determined
by NH···S hydrogen bonds. © 2002 Published by Elsevier Science B.V.
Keywords: Tin complexes; Organotin(IV) compounds; Dithiocarboxylato ligands; Crystal structures
1. Introduction
We report here the synthesis of new organotin(IV)
complexes made by the reaction of Bz2SnCl2 or
Bz3SnCl with N-ethyl (HEtACDA) or N-benzyl
(HBzACDA) derivatives of H2ACDA, in which Sn is
bound to the ligand exclusively through two sulfur
atoms (Scheme 1b). Elemental analyses as well as IR
and NMR spectra confirm the structures of the prod-
ucts and the spectra show that the ligands bind to tin
through the sulfur atoms.
Organotin complexes are used as bactericides, fungi-
cides, acaricides and industrial biocides. Their antitu-
mor activity and their implications in antioncogenesis
have been investigated. Several organotin complexes
are effective antineoplastic (mainly antileukaemic) and
antivirial agents [1–4]. In view of antifungal properties
of 2-N-alkylamino-1-cyclopentene-1-carbodithioic acids
(HRACDA) [5] we considered it of interest to synthe-
size organotin compounds containing these ligands.
Crystallographic studies of organotin dithioate com-
plexes have revealed a variety of coordination ge-
ometries around the Sn atom. Remarkable diversity in
2-Amino-1-cyclopentene-1-carbodithioic
acid
(H2ACDA) contains the skeletal unit ꢀNHꢀCꢁCꢀ
C(ꢁS)SH and so it can be ambidentate. In many metal
ion complexes the N and S sites are involved in bond
formation (Scheme 1a) but with Co(II), Ni(II) and
some other metal ions disulfur chelation (Scheme 1b) is
common [5–11].
* Corresponding author. Tel.: +98-611-333-6116; fax: +98-611-
333-7009.
E-mail address: tarasoli@ahvazuni.neda.net.ir (A. Tarassoli).
Scheme 1.
0022-328X/02/$ - see front matter © 2002 Published by Elsevier Science B.V.
PII: S0022-328X(01)01334-1

106
A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
Scheme 2.
structure may be observed even when only small
changes in chemistry exist, so that for the diorganotin
bis(1,1-dithiolates) four structural motifs are found [12].
Therefore, it was considered interesting to study the
crystal structures especially for 3b. The coordination
geometry depends upon the bonding mode of the
dithioate, which acts as a mono- or bi-dentate ligand.
In this paper, we report the crystal structures of 1c and
3b in which the RACDA ligands are anisobidentate.
The crystal structure of 2 is also described.
symmetrically split for 1c and 3c indicating the uniden-
tate mode of chelation, but the appearance of asymmet-
rically split bands for 1a, 1b, 3a and 3b indicates the
unequal involvement of the two S atoms in the com-
plexation. Compounds 1a and 3a exhibit sharp and
weak bands at 289 and 282 cm−1, respectively,
assignable to w(SnꢀCl).
1
A comparison of H-NMR spectra of di- and triben-
zyltin(IV) complexes with those of the corresponding
ligands shows the disappearance of the signal for the
ꢀSH proton on the formation of the SnꢀS bond. In the
spectra of the complexes in CDCl3 solution, the ꢀNH
signals observed in the acids (HEtACDA and HBzA-
CDA) shift to upfield. This shift may be ascribed to the
weakening of the NH···SꢁC hydrogen bond on com-
plexation. The signals assigned to the protons of ethyl
or benzyl groups attached to nitrogen are not shifted
indicating that nitrogen atom is not involved in the
bonding to tin [9,13]. Likewise the position of signals
assigned to H(3), H(4) and H(5) do not change.
In the 13C-NMR spectra of the complexes, chemical
shifts are quite similar to those of the parent ligands.
Only a small shift in the position of C(6) is seen due to
the deshielding of this carbon upon deprotonation of
the thiol group and coordination through the other
sulfur atom.
2. Results and discussion
2.1. Synthesis
Bz2SnCl(EtACDA) (1a) was obtained from the reac-
tion of Bz2SnCl2 with HEtACDA in 1:1 molar ratio. In
the presence of triethylamine (TEA), treatment of
Bz2SnCl2 with two equivalents of HEtACDA gave
Bz2Sn(EtACDA)2 (1b). The reaction between Bz3SnCl
and HEtACDA in the presence of TEA gave a good
yield of Bz3Sn(EtACDA) (1c).
The benzyl derivative HBzACDA (2), which was
prepared from the reaction of benzylamine with
H2ACDA, did not react with Bz2SnCl2 or Bz3SnCl in
the absence of TEA, but in the presence of an appropri-
ate amount of TEA, Bz2SnCl(BzACDA) (3a) and
Bz2Sn(BzACDA)2 (3b) were obtained by reaction of
Bz2SnCl2 and 2 in 1:1 and 1:2 molar ratios, respectively.
The reaction between 2, Bz3SnCl and TEA in 1:1:1
molar ratio produced Bz3Sn(BzACDA) (3c) (See
Scheme 2).
The 119Sn-NMR data for the tin complexes shown in
Table 1 suggest that the geometries in solution are
similar to those in the crystal. Although the shifts are
dependent on the nature of the substituents at the tin
atom, the values obtained for 1c and 3c are consistent
with the presence of four-coordinate organotin(IV)
dithioate species for which a range of 144 to −120
The IR spectra of HEtACDA and HBzACDA ex-
Table 1
hibit weak intensity bands at 2430 and 2546 cm−1
,
119Sn chemical shifts for di- and tribenzyltin(IV) chlorides and their
dithiocarboxylate complexes in CDCl3
respectively, due to the ꢀSH group. This band is absent
in the spectra of the corresponding complexes, but a
new band in the 350–370 cm−1 range may be assigned
to w(SnꢀS). The strong bands observed at 1605–1580,
1490–1480, 1345–1315 and 1290–1270 cm−1 in the
spectra of the ligands and their complexes may be
assigned to the combination bands of w(NH2+CꢁC),
w(CH2+CꢁC), w(CꢁN+CꢁS) and w(CꢁS+CꢁN), re-
spectively [9]. The band due to wasym CSS at :900
cm−1 of the ligand spectra is diagnostic in deciding the
mode of sulfur attachment to the tin center. It is
Species
l(119Sn)
Bz2SnCl2 (in CH2Cl2)
Bz3SnCl
−35
−52
Bz2SnCl(EtACDA)
Bz2SnCl(BzACDA)
Bz2Sn(EtACDA)2
Bz2Sn(BzACDA)2
Bz3Sn(EtACDA)
Bz3Sn(BzACDA)
−168
−166
−222
−221
−38
−36

A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
107
Table 2
tin(IV) compounds, suggesting that the coordination is
asymmetrical, with two S atoms held more weakly than
the other two.
,
Selected bond lengths (A) and bond angles (°) for 1c
Bond lengths
SnꢀC(14)
SnꢀC(21)
Sn···S(2)
S(2)ꢀC(1)
NꢀC(28)
C(2)ꢀC(6)
2.160(3)
2.171(3)
3.1001(10)
1.699(4)
1.469(6)
1.401(5)
SnꢀC(7)
SnꢀS(1)
S(1)ꢀC(1)
NꢀC(6)
C(1)ꢀC(2)
C(7)ꢀC(8)
2.166(3)
2.4577(8)
1.767(4)
1.294(6)
1.394(5)
1.504(5)
2.2. Description of the crystal structures
2.2.1. Bz3Sn(EtACDA) (1c)
In the unit cell of this compound, there are two
crystallographically independent molecules that show
only minor differences. Selected bond lengths and bond
angles for one of the molecules are given in Table 2 and
its view is shown in Fig. 1. The molecules contain
essentially the four-coordinate tin, but with distortion
from the normal tetrahedral environment. However, the
Bond angles
C(14)ꢀSnꢀC(7) 115.87(14)
C(7)ꢀSnꢀC(21) 107.53(15)
C(7)ꢀSnꢀS(1)
C(1)ꢀS(1)ꢀSn
C(8)ꢀC(7)ꢀSn
C(14)ꢀSnꢀC(21)
C(14)ꢀSnꢀS(1)
C(21)ꢀSnꢀS(1)
S(2)ꢀC(1)ꢀS(1)
C(15)ꢀC(14)ꢀSn
106.66(13)
116.87(10)
96.31(10)
118.5(2)
111.18(10)
98.82(12)
110.9(2)
114.3(2)
C(22)ꢀC(21)ꢀSn 112.8(2)
,
long Sn···S(2) interactions (3.1001(10) A) can be re-
garded as weak coordinate bonds corresponding to an
anisobidentate ligand [15]. The tin atom is also coordi-
nated to the other sulfur atom and to the one carbon
atom of each of the three benzyl groups. The SnꢀS(1)
bond length lies toward the middle of the range re-
Estimated standard deviations in parentheses.
,
ported for triphenyl thiolates (2.405–2.481 A) close to
,
the sum of the covalent radii of tin and sulfur (2.42 A)
[15,16]. Around the tin, the angles C(14)ꢀSnꢀC(7),
C(14)ꢀSnꢀS(1) and C(7)ꢀSnꢀS(1) are wider and
C(14)ꢀSnꢀC(21),
C(7)ꢀSnꢀC(21)
and
especially
C(21)ꢀSnꢀS(1) are narrower than the ideal tetrahedral
angle. This might suggest the description of the tin
environment as cis-trigonal bipyramid with S(2) and
C(21) in the apical positions and S(1), C(7) and C(14)
in the equatorial positions, but this bipyramid is ex-
tremely distorted: the sum of the equatorial angles is
only 344° and the axial SnꢀC bond lengths are very
similar to the equatorial ones. Thus, the environment of
tin is best described as distorted tetrahedral. [16,17].
Fig. 1. Crystal structure of Bz3Sn(EtACDA) (1c).
2.2.2. HBzACDA (2)
The molecular structure of 2 is shown in Fig. 2 and
selected bond lengths and bond angles are given in
Table 3. The bond lengths and bond angles within this
ligand are insignificantly different from those in 3b
described below. In 2 there are intramolecular hydrogen
Table 3
,
Selected bond lengths (A) and bond angles (°) for 2
Bond lengths
S(1)ꢀC(1)
N(1)ꢀC(6)
C(1)ꢀC(2)
S(1)ꢀHS
1.753(7)
1.318(7)
1.411(9)
1.23
S(2)ꢀC(1)
N(1)ꢀC(7)
C(2)ꢀC(6)
S(2)···HS
S(2)···HN
1.694(7)
1.468(9)
1.397(9)
2.99
Fig. 2. Crystal structure of BzACDA (2).
N(1)ꢀHN
0.92
2.24
Bond angles
C(6)ꢀN(1)ꢀC(7)
C(2)ꢀC(1)ꢀS(1)
C(6)ꢀC(2)ꢀC(1)
S(1)ꢀHS···S(2)
123.5(6)
114.6(5)
127.3(5)
123
C(2)ꢀC(1)ꢀS(2)
S(2)ꢀC(1)ꢀS(1)
N(1)ꢀC(6)ꢀC(2)
N(1)ꢀHꢀS(2)
125.5(5)
119.9(5)
126.4(6)
145
ppm was reported earlier [14]. Chemical shifts of 1a and
3a are in the expected range of −150 to −250, for the
five-coordinated tin(IV) species [13]. The chemical shifts
for 1b and 3b are somewhat different from the values,
−300 to −500 ppm, expected for the six coordinated
Estimated standard deviations in parentheses.

108
A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
Fig. 3. Crystal structure of Bz2Sn(BzACDA)2 (3b).
bonds between N(1)H···S(2) and intermolecular bonds
between S(1)H and S(2) [−x+1.5, y−0.5, −z+1.5].
Based on the NMR data Singh et al. showed that
among the possible tautomeric forms for H2ACDA,
form I exists exclusively [5]. This is confirmed by the
crystal structure of 2.
The longer CꢀS bond is associated with the shorter
SnꢀS bond, and the shorter CꢀS% bond is associated
with the longer SnꢀS% bond. The long SnꢀS distances
are significantly shorter than the sum of the van der
,
Waals radii (4.0 A) and the coordination number of Sn
is effectively six [22].
The bond distances and bond angles within the five-
member rings and benzyl groups are unexceptional.
Intramolecular hydrogen bonds between S and the ad-
jacent amine groups are observed. The distances be-
(1)
,
tween S and H atoms are 2.33 and 2.38 A for S(2)ꢀH(1)
and S(4)ꢀH(2), respectively.
2.2.3. Bz2Sn(BzACDA)2 (3b)
The molecular structure and the numbering scheme
are shown in Fig. 3 and selected bond lengths and bond
angles are listed in Table 4.
Table 4
,
Selected bond lengths (A) and bond angles (°) for 3b
Bond lengths
The tin atom has a highly distorted octahedral envi-
ronment in which the four S atoms lie in the equatorial
plane. The atoms C(27) and C(34) of the benzyl groups
define a CꢀSnꢀC angle of 129.22(16)° which is interme-
diate between those for cis- and trans-substitution [18].
The deviation from the regular octahedral geometry
may result from steric effects and differences in the
electronegativities of the ligands attached to the tin
atom [19]. The SꢀSnꢀS bond angles range from 79° in
the chelate ring to 154° for the angle between the
ligands.
The BzACDA ligands are anisobidentately chelated
to Sn, with one longer and one shorter SnꢀS bond
[19,20]. The much smaller differences between SnꢀS
distances in cis-Cl2Sn(S2CNEt2)2 was attributed to
packing forces and coordination geometry [21]. The
SnꢀSꢀCꢀS% bonding system in 3b is easy to discern [13].
SnꢀC(34)
SnꢀS(3)
2.158(4)
2.5072(3)
3.1030(3)
1.755(4)
1.749(4)
1.328(5)
0.84
SnꢀC(27)
SnꢀS(1)
2.165(4)
2.5157(3)
2.9564(3)
1.702(4)
1.722(4)
1.459(5)
0.87
Sn···S(2)
Sn···S(4)
S(1)ꢀC(1)
S(3)ꢀC(14)
N(1)ꢀC(6)
N(1)ꢀH(1)
S(2)···H(1)
S(2)ꢀC(1)
S(4)ꢀC(14)
N(1)ꢀC(7)
N(2)ꢀH(2)
S(4)···H(2)
2.33
2.38
Bond angles
C(34)ꢀSnꢀC(27) 129.22(16)
C(34)ꢀSnꢀS(3)
C(34)ꢀSnꢀS(1)
S(3)ꢀSnꢀS(1)
C(1)ꢀS(1)ꢀSn
S(2)ꢀC(1)ꢀS(1)
C(28)ꢀC(27)ꢀSn
N(1)ꢀH(1)ꢀS(2)
116.94(12)
104.71(12)
79.574(9)
99.02(14)
117.7(2)
115.6(3)
138
C(27)ꢀSnꢀS(3)
C(27)ꢀSnꢀS(1)
S(2)···Sn···S(4)
C(14)ꢀS(3)ꢀSn
S(4)ꢀC(14)ꢀS(3) 116.3(2)
C(35)ꢀC(34)ꢀSn 116.2(3)
104.78(11)
110.37(11)
153.76(1)
95.77(13)
N(2)ꢀH(2)ꢀS(4)
134
Estimated standard deviations in parentheses.

A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
109
3. Experimental
Hz, p-C), 129.0 (3JSnC=44 Hz, o-C), 139.8 (i-C), 169.0
(C(2)), 198.0 (C(6)).
3.1. General procedure
3.4. Synthesis of Bz3Sn(EtACDA) (1c)
Starting materials were purchased from commercial
sources and used without further purification, except
for benzyl chloride and Et3N, which were distilled
before use. HEtACDA, Bz2SnCl2 and Bz3SnCl were
prepared using the literature methods [23 and 24, re-
spectively]. IR spectra were obtained in FT BOMEM
MB102 or SHIMADZU IR-470 infrared spectrometers
A solution of HEtACDA (0.500 g, 2.67 mmol) and
Et3N (0.37 cm3) in CH2Cl2 (10 cm3) was added to a
solution of Bz3SnCl (1.14 g, 2.67 mmol) in CH2Cl2 (10
cm3). The mixture was stirred for 2 h and then MeOH
(10 cm3) was added and the solution was kept at
−4 °C to give greenish-yellow plates, m.p. 95 °C.
Yield: 1.2 g (78%). Anal. Calc. for C29H33NS2Sn: C,
60.22; H, 5.74; N, 2.42. Found: C, 59.86, H, 5.75; N,
1
from KBr disks. H-, 13C- and 119Sn-NMR spectra were
recorded with
spectrometer.
a
Bruker DRX500 ADVANCE
2.47. 1H-NMR:
l
1.31 (3JHH=7.3 Hz, 3H, t,
CH2ꢀCH3), 1.81 (3JHH=7.4 Hz, 2H, tt, H(4)), 2.60
3.2. Synthesis of Bz2SnCl(EtACDA) (1a)
(2J119 =68 Hz, 6H, s, CH2ꢀPh), 2.65 (3JHH=7.6 Hz,
SnH
2H, t, H(3)), 2.86 (3JHH=7.5 Hz, 2H, t, H(5)), 3.37
(2H, m, CH2ꢀCH3), 6.77 (6H, d, o-H), 6.99 (3H, t,
p-H), 7.14 (6H, t, m-H), 11.52 (1H, s, ꢀNH). 13C-
A solution of HEtACDA (0.400 g, 2.14 mmol) in
warm MeOH (20 cm3) was added dropwise to a solu-
tion of Bz2SnCl2 (0.796 g, 2.14 mmol) in the same
solvent (10 cm3). A pale yellow precipitate was formed
almost immediately. This was filtered, washed with
MeOH and recrystallized from CH2Cl2–MeOH to give
pale yellow crystals, m.p. (dec) 157 °C. Yield: 0.93 g
(83%). Anal. Calc. for C22H26ClNS2Sn: C, 50.55; H,
5.01; N, 2.68. Found: C, 50.09; H, 5.02; N, 2.75%.
1H-NMR: l 1.32 (3JHH=7.3 Hz, 3H, t, CH2ꢀCH3),
1.85 (3JHH=7.5 Hz, 2H, tt, H(4)), 2.70 (4H, m, H(3)
NMR: l 15.1 (CH2ꢀCH3), 19.7 (C(4)), 25.2 (2J119
=
301 Hz, CH2ꢀPh), 33.2 (C(3)), 35.3 (C(5)), Sn4C0.6
(CH2ꢀCH3), 120.4 (C(1)), 123.8 (4JSnC=21 Hz, m-C),
127.6 (5JSnC=30 Hz, p-C), 128.4 (3JSnC=17 Hz, o-C),
141.0 (2JSnC=43 Hz, i-C), 170.1 (C(2)), 195.0 (C(6)).
3.5. Synthesis of BzACDA (2)
A solution of H2ACDA (2.000 g, 12.58 mmol) and
benzylamine (1.350 g, 12.58 mmol) in MeOH (40 cm3)
was stirred at room temperature (r.t.) for 24 h. Water
(80 cm3) was added to the solution and the mixture was
filtered. The filtrate was cooled to 0 °C and neutralized
with 2 N HCl to give crystalline orange precipitate,
which was filtered, washed with MeOH and dried over
CaCl2. The dry product was then recrystallized from
MeOH to give orange needles, m.p. 98 °C. Yield: 2.3 g
(73%). Anal. Calc. for C13H15NS2: C, 62.61; H, 6.06; N,
and H(5)), 3.14 (2J119 =86 Hz, 4H, s, CH2ꢀPh), 3.43
SnH
(2H, m, CH2ꢀCH3), 7.04–7.21 (10H, m, aromatic-H),
9.56 (1H, s, ꢀNH). 13C-NMR: l 15.0 (CH2ꢀCH3), 19.7
(C(4)), 33.6 (C(3)), 34.5 (C(5)), 36.1 (CH2ꢀPh), 41.6
(CH2ꢀCH3), 120.1 (C(1)), 124.9 (m-C), 128.3 (p-C),
128.4 (o-C), 138.3 (i-C), 172.3 (C(2)), 190.7(C(6)).
3.3. Synthesis of Bz2Sn(EtACDA)2 (1b)
Triethylamine (0.52 cm3) was added to a suspension
of HEtACDA (0.7 g, 3.74 mmol) in MeOH (10 cm3).
The clear solution was then added to a solution of
Bz2SnCl2 (0.69 g, 1.85 mmol) in MeOH (10 cm3).
Formation of a yellow crystalline precipitate was ob-
served after a few minutes. Stirring was continued
overnight and then the product was filtered, washed
with MeOH and recrystallized from MeOH–CH2Cl2 to
give yellow crystals, m.p. 178–180 °C. Yield: 0.71 g
(57%). Anal. Calc. for C30H38N2S4Sn: C, 53.49; H, 5.69;
5.62. Found: C, 62.85; H, 6.08; N, 5.67%. H-NMR: l
1
1.86 (3JHH=7.5 Hz, 2H, tt, H(4)), 2.70 (3JHH=7.7 Hz,
2H, t, H(3)), 2.76 (3JHH=7.5 Hz, 2H, t, H(5)), 4.57
(3JHH=6.2 Hz, 2H, d, NꢀCH2), 4.89 (1H, s, ꢀSH),
7.27–7.38 (5H, m, aromatic-H), 12.72 (1H, s, ꢀNH).
13C-NMR: l 20.1 (C(4)), 33.3 (C(3)), 34.1 (C(5)), 49.3
(NꢀCH2), 119.0 (C(1)), 127.0 (m-C), 127.9 (p-C), 129.0
(o-C), 136.1 (i-C), 171.3 (C(2)), 191.0 (C(6)).
3.6. Synthesis of Bz2SnCl(BzACDA) (3a)
1
N, 4.16. Found: C, 53.36; H, 5.70; N, 4.25%. H-NMR:
l 1.33 (3JHH=7.3 Hz, 6H, t, CH2ꢀCH3), 1.79 (3JHH
=
A solution of HBzACDA (0.350 g, 1.41 mmol) and
Et3N (0.142 g, 1.41 mmol) in MeOH (15 cm3) was
added dropwise to a solution of Bz2SnCl2 (0.522 g,
0.141 mmol) in the same solvent (10 cm3). The mixture
was stirred for 3 h during which a pale yellow precipi-
tate was formed. This was filtered, washed with MeOH
and recrystallized from CH3OH–CH2Cl2 to give pale
yellow crystals, m.p. 121–123 °C. Yield: 0.65 g (79%).
7.5 Hz, 4H, tt, H(4)), 2.67 (3JHH=7.7 Hz, 4H, t, H(3)),
2.76 (3JHH=7.5 Hz, 4H, t, H(5)), 3.36 (2J119
=
83 Hz, 4H, s, CH2ꢀPh), 3.40 (4H, m, CH2ꢀCH3), S6n.H99–
7.29 (10H, m, aromatic-H), 10.85 (1H, s, ꢀNH).
13C-NMR: l 15.3 (CH2ꢀCH3), 19.7 (C(4)), 33.4 (C(3)),
35.0 (C(5)), 37.9 (CH2ꢀPh), 40.6 (CH2ꢀCH3), 119.8
(C(1)), 124.2 (4JSnC=31 Hz, m-C), 127.4 (5JSnC=25

110
A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
Table 5
Crystal data and structure refinement parameters for 1c, 2 and 3b
Bz3Sn(EtACDA) (1c)
Bz2Sn(BzACDA)2 (3b)
BzACDA (2)
Empirical formula
Formula weight
C29H33NS2Sn
578.37
C40H42N2S4Sn
797.69
C13H15NS2
249.38
,
Wavelength (A)
0.71073
Triclinic
0.71073
Triclinic
0.71073
Monoclinic
P21/n (no. 14)
Crystal system
Space group
(
(
P1 (no. 2)
P1 (no. 2)
Unit cell dimensions
,
a (A)
13.1380(4)
13.7351(6)
16.4793(6)
91.907(2)
95.123(2)
110.975(2)
4
11.1332(8)
11.4042(7)
15.3036(11)
80.960(4)
87.516(3)
72.395(4)
2
8.708(2)
7.571(3)
19.448(5)
90
94.223(15)
90
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Z
4
3
,
V (A )
2758.8(2)
1.094
1829.0(2)
0.96
1278.7(6)
0.39
v (mm−1
)
Reflections collected
22 004
12 668
3940
Independent reflections
Reflections observed [I\2|(I)]
Final R indices [I\2|(I)]
13 035 (Rint=0.063)
10 529
R1=0.046, wR2=0.098
6398 (Rint=0.059)
5288
R1=0.045, wR2=0.105
1481 (Rint=0.166)
880
R1=0.069,
wR2=0.109
R1=0.137,
wR2=0.130
R indices (all data)
R1=0.062, wR2=0.107
R1=0.059, wR2=0.113
Anal. Calc. for C27H28ClNS2Sn: C, 55.45; H, 4.83; N,
3.8. Synthesis of Bz3Sn(BzACDA) (3c)
1
2.40. Found: C, 54.96; H, 4.83; N, 2.45%. H-NMR: l
1.81 (3JHH=7.5 Hz, 2H, tt, H(4)), 2.68 (3JHH=7.7 Hz,
2H, t, H(3)), 2.70 (3JHH=7.4 Hz, 2H, t, H(5)), 3.14
A solution of HBzACDA (0.300 g, 1.2 mmol) and
Et3N (0.121 g, 1.2 mmol) in MeOH (10 cm3) was added
to a solution of Bz3SnCl (0.515 g, 1.2 mmol) in CH2Cl2
(10 cm3). The mixture was stirred for 5 h and then the
solvent was removed under vacuum to give a gummy
solid, which gave an orange powder when treated with
acetone. The powder was filtered and recrystallized
from CH2Cl2–MeOH (2:1) to give orange plates, m.p.
124–126 °C. Yield: 0.47 g (61%). Anal. Calc. for
C34H35NS2Sn: C, 63.76; H, 5.51; N, 2.19. Found: C,
(2J119 =86 Hz, 4H, s, SnꢀCH2), 4.54 (3JHH=6.2 Hz,
SnH
2H, d, NꢀCH2), 7.03–7.42 (15H, m, aromatic-H), 9.92
(1H, s, ꢀNH). 13C-NMR: l 19.6 (C(4)), 33.9 (C(3)), 34.6
(C(5)), 36.0 (SnꢀCH2), 50.2 (NꢀCH2), 120.5 (C(1)),
124.8–138.1 (aromatic-C), 172.5 (C(2)), 192.8 (C(6)).
3.7. Synthesis of Bz2Sn(BzACDA)2 (3b)
1
A solution of HBzACDA (0.400 g, 1.6 mmol) and
Et3N (0.162 g, 1.6 mmol) in MeOH (20 cm3) was added
to a solution of Bz2SnCl2 (0.299 g, 0.8 mmol) in the
same solvent (5 cm3). The mixture was stirred
overnight. The resultant orange precipitate was filtered,
washed with MeOH and dissolved in CH2Cl2 (10 cm3).
Methanol (5 cm3) was added and the solution then was
kept at −4 °C to give orange needles, m.p. (dec.)
177–199 °C. Yield: 0.46 g (72%). Anal. Calc. for
C40H44N2S4Sn: C, 60.07; H, 5.54; N, 3.50. Found: C,
63.36; H, 5.62; N, 2.25%. H-NMR: l 1.80 (3JHH=7.4
Hz, 2H, tt, H(4)), 2.61 (2J119SnH=67 Hz, 6H, s,
SnꢀCH2), 2.67 (3JHH=7.9 Hz, 2H, t, H(3)), 2.89
(3JHH=7.5 Hz, 2H, t, H(5)), 4.54 (3JHH=6.2 Hz, 2H,
d, NꢀCH2), 6.76–7.38 (20H, m, aromatic-H), 11.88
(1H, s, ꢀNH). 13C-NMR: l 19.7 (C(4)), 25.2 (1JSnC
=
280 Hz, SnꢀCH2), 33.6 (C(3)), 35.5 (C(5)), 49.5
(NꢀCH2), 120.9 (C(1)), 123.8–141.0 (aromatic-C),
170.0 (C(2)), 197.6 (C(6)).
1
59.38; H, 5.30; N, 3.58%. H-NMR: l 1.78 (3JHH=7.4
3.9. X-ray structure analysis of 1c, 2 and 3b
Hz, 4H, tt, H(4)), 2.67 (3JHH=7.7 Hz, 4H, t, H(3)),
2.79 (3JHH=7.6 Hz, 4H, t, H(5)), 3.38 (2J119
=
Data were collected in Kappa CDD diffractometer at
173 K by using Mo–K radiation and the structures
were solved by direct methods. Further details are given
in Table 5. Full matrix least-squares against F2
SnH
88 Hz, 4H, s, SnꢀCH2), 4.58 (3JHH=6.3 Hz, 4H, s,
NꢀCH2), 6.97–7.41 (20H, m, aromatic-H), 11.23 (2H, s,
ꢀNH). 13C-NMR: l 19.7 (C(4)), 33.7 (C(3)), 35.2 (C(5)),
38.0 (SnꢀCH2), 49.4 (NꢀCH2), 120.4 (C(1)), 124.3–
139.7 (aromatic-C), 168.9 (C(2)), 200.6 (C(6)).
(SHELXL-97) was used for refinement with non-H atoms
anisotropic and H atoms in riding mode anisotropic.

A. Tarassoli et al. / Journal of Organometallic Chemistry 645 (2002) 105–111
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Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 165159, 165161 and 165160
for compounds 1c, 2 and 3b, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
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Acknowledgements
The authors thank Professor Colin Eaborn and Dr J.
David Smith for helpful discussions. Support of this
work by the National Research Council of Iran (Project
No. 1956) and School of Chemistry, Physics and Envi-
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