Syntheses, characterizations and crystal structures of monomeric or macrocyclic compounds of di- or triorganotin (IV) moieties with 4,4′-thiodibenzenethiol

Article abstract of DOI:10.1016/j.poly.2007.09.033

Six organotin compounds with 4,4′-thiodibenzenethiol (LH₂) of the type R_nSnL_4-nSnR_n (n = 3: R = Me 1, Ph 2, PhCH₂ 3, n = 2: R = Me 4, Ph 5, PhCH₂ 6) have been synthesized. All compounds wer

Full text of DOI:10.1016/j.poly.2007.09.033

Available online at www.sciencedirect.com
Polyhedron 27 (2008) 420–428
www.elsevier.com/locate/poly
Syntheses, characterizations and crystal structures of monomeric
or macrocyclic compounds of di- or triorganotin (IV) moieties
with 4,40-thiodibenzenethiol
a,b,
a
a
Chun-Lin Ma
*, Zhi-Fo Guo , Ru-Fen Zhang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 17 September 2007; accepted 28 September 2007
Available online 19 November 2007
Abstract
Six organotin compounds with 4,40-thiodibenzenethiol (LH2) of the type RnSnL4ꢀnSnRn (n = 3: R = Me 1, Ph 2, PhCH2 3, n = 2:
R = Me 4, Ph 5, PhCH2 6) have been synthesized. All compounds were characterized by elemental analysis, IR and NMR (1H, 13C,
and 119Sn) spectra. The structures of compounds 1, 2, 4, 5 and 6 were also determined by X-ray diffraction analysis, which revealed that
compounds 1 and 2 were monomeric structures, compounds 4, 5 and 6 were centrosymmetric dinuclear macrocyclic structures, and all
the tin(IV) atoms are four-coordinated. Furthermore, supramolecular structures were also found in compounds 1, 2, 4, 5 and 6, which
exhibit one-dimensional chains, two-dimensional networks or three-dimensional structures through intermolecular C–Hꢁ ꢁ ꢁS weak hydro-
gen bonds (WHBs), non-bonded Snꢁ ꢁ ꢁS interactions or C–Hꢁ ꢁ ꢁp interactions.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: S ligand; Macrocyclic compounds; Crystal structure; Tin
1. Introduction
often complicated, architectures and topologies [3], and
also for their potential industrial applications and biologi-
cal activities [4]. More recently, flexible multidentate
ligands have been employed in order to gain access to
topologies not available from logical combinations of rigid
building blocks. de Sousa, for example, has reported a ser-
ies of diorganotin compounds based on the flexible 2,6-
diacetylpyridine ligand [5], Silva et al. have reported some
five- and six-membered chelate organotin mercaptide com-
pounds [6], and in particular Baul and co-workers have
reported a cyclic dinuclear organotin compound [7]. In
our previous work, we have reported several novel organo-
tin mercaptide compounds which were obtained from flex-
ible multidentate ligands, such as pentacoordinated
compounds with 2,5-dithiobiurea [8], tetranuclear or dinu-
clear monomers or three-dimensional polymers with meso-
2,3-dimercaptosuccinic acid [9]. To continue our research
on organotin(IV) complexes in this field, we choose
another interesting ligand: 4,40-thiodibenzenethiol.
Recently, developments in coordination chemistry have
produced numerous macrocyclic compounds through the
appropriate coordination geometry of organometallic com-
pounds and certain organic ligands [1]. Furthermore, non-
covalent weak molecular forces (such as hydrogen bonds,
van der Waals forces, non-bonded contacts and C–Hꢁ ꢁ ꢁp
interactions), capable of connecting these metallic subunits
into looser and more intriguing supramolecular infrastruc-
tures, have been widely investigated in structural biology,
structural chemistry and the pharmaceutical sciences [2].
Among them organotin compounds are attracting more
and more attention mainly due to their intriguing, and
*
Corresponding author. Address: Department of Chemistry, Liaocheng
University, Liaocheng 252059, PR China. Tel.: +86 635 8230660; fax: +86
538 6715521.
E-mail address: macl@lcu.edu.cn (C.-L. Ma).
0277-5387/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.09.033

C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
421
This ligand was chosen for the following reasons: first, it
has two thiol groups so it should form strong covalent
bonds with an organotin moiety; second, the conforma-
tional flexibility of this ligand will allow for the formation
of various and interesting molecular and supramolecular
structures; third, 4,40-thiodibenzenethiol can bond to more
than one organotin moiety in one discrete molecule, which
will increase the opportunities for supramolecular assembly
from these compounds through intermolecular weak inter-
actions. Here, we report the syntheses and character-
izations of six organotin compounds constructed from
4,40-thiodibenzenethiol (LH2). With a 1:2:2 molar ratio of
LH2:R3SnCl:EtONa three dinuclear monomeric com-
pounds (1–3) of the type R3SnLSnR3 [R = Me 1, Ph 2,
PhCH2 3] were obtained, and with a 1:1:2 molar ratio of
LH2:R2SnCl2:EtONa three dinuclear macrocyclic com-
pounds (4–6) of the type (R2SnL)2 [R = Me 4, Ph 5, PhCH2
6] were obtained.
The spectra were acquired at 298 K; 13C spectra are
broadband proton decoupled. The chemical shifts are
reported in ppm with respect to the references and
are stated relative to external tetramethylsilane (TMS)
for 1H and 13C NMR, and neat tetramethyltin for
119Sn NMR. Elemental analyses were performed with a
PE-2400II apparatus.
2.2. X-ray crystallography
Crystals were mounted in Lindemann capillaries under
nitrogen. All X-ray crystallographic data were collected
on a Bruker SMART CCD 1000 diffractometer with
graphite monochromated Mo Ka radiation (k =
˚
0.71073 A) at 298(2) K. A semi-empirical absorption cor-
rection was applied to the data. The structures were solved
by direct methods using SHELXS-97 and refined against F2
by full-matrix least squares using SHELXL-97. Hydrogen
atoms were placed in calculated positions. Crystal data
and experimental details of the structure determinations
are listed in Table 1.
2. Experimental
2.1. Materials and measurements
2.3. Syntheses of the complexes 1–6
Trimethyltin chloride, triphenyltin chloride, dimethyl-
tin dichloride, diphenyltin dichloride and 4,40-thiodiben-
zenethiol are commercially available, and they were
used without further purification. Dibenzyltin dichloride
and tribenzyltin chloride were prepared by a standard
method reported in the literature [10]. The melting points
were obtained with a Kofler micro-melting point appara-
tus and were uncorrected. Infrared-spectra were recorded
on a Nicolet-6700 spectrophotometer using KBr discs and
2.3.1. [(CH3)3 SnSC6H4]2S (1)
The reaction was carried out under a nitrogen atmo-
sphere. 4,40-Thiodibenzenethiol (0.250 g, 1 mmol) and
sodium ethoxide (0.136 g, 2 mmol) were added to benzene
(20 ml) in a Schlenk flask and stirred for 5 min. Trimethyl-
tin chloride (0.399 g, 2 mmol) was added to the reaction
mixture, which was then stirred for 12 h at 40 °C. After fil-
tration the solvent was gradually removed by evaporation
under vacuum until a solid product was obtained. The solid
was recrystallized from ether-petroleum and colorless crys-
tals were formed. Yield: 86%. M.p. 97–99 °C. Anal. Calc.
1
sodium chloride optics. H, 13C and 119Sn NMR spectra
were recorded on a Varian Mercury Plus 400 spectrome-
ter operating at 400, 100.6 and 149.2 MHz, respectively.
Table 1
Crystal, data collection and structure refinement parameters for compounds 1, 2, 4, 5 and 6
Compound
1
2
4
5
6
Empirical formula
M
C
18H26S3Sn2
C48H38S3Sn2
948.34
Triclinic
P1
9.829(4)
9.853(4)
12.685(5)
87.932(5)
76.041(5)
63.765(4)
1065.9(8)
1
C28H28S6Sn2
794.24
Monoclinic
P2ð1Þ=n
6.378(2)
14.684(5)
16.205(6)
90
92.584(6)
90
1516.0(9)
2
C48H36S6Sn2
1042.51
Triclinic
C52H44S6Sn2
1098.61
Monoclinic
P2ð1Þ=n
14.762(4)
11.832(3)
15.370(4)
90
117.664(3)
90
2377.6(11)
2
575.95
Monoclinic
P2ð1Þ=c
22.923(7)
7.341(2)
14.155(4)
90
97.828(5)
90
2359.7(13)
4
Crystal system
Space group
ꢀ
P1
˚
a (A)
9.051(3)
10.305(4)
13.480(5)
68.961(4)
71.938(4)
82.460(5)
1115.4(7)
1
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
l (mmꢀ1
)
2.380
1.350
2.078
1.433
1.349
Reflections collected
Independent reflections
Rint
11522
4075
5450
4426
7224
2667
5756
3836
12080
4198
0.0881
0.0672
0.1679
0.1554
0.2117
0.0213
0.0584
0.0701
0.1459
0.1556
0.0562
0.0423
0.0679
0.0945
0.1090
0.0361
0.0552
0.0933
0.0812
0.0906
0.0544
0.0443
0.0915
0.0900
0.1144
R1[I > 2r(I)]/R1
(all data)
wR1[I > 2r(I)]/wR1
(all data)

422
C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
for [(CH3)3SnSC6H4]2S: C, 37.53; H, 4.55. Found: C, 37.26;
tals were formed. Yield: 89%. M.p. 199–201 °C. Anal. Calc.
for [(CH3)2Sn(SC6H4)2S]2: C, 42.34; H, 3.55. Found: C,
42.10; H, 3.32%. IR (KBr, cmꢀ1): m(Sn–C), 575; m(Sn–S),
H, 4.30%. IR (KBr, cmꢀ1): m(Sn–C), 557; m(Sn–S), 312. 1H
2
NMR (CDCl3, ppm): d 0.34 (s, 9H, JSnH = 27.2 Hz), 7.06
(d, 2H), 7.23 (d, 2H). 13C NMR (CDCl3, ppm): d 29.6
(1J(119Sn–13C) = 390.4 Hz), 131, 131.6, 133.3, 134, 135,
135.2. 119Sn NMR (CDCl3, ppm): 100.4.
319. H NMR (CDCl3, ppm): d 0.6 (s, 6H), 7.1 (d, 2H),
1
7.3 (d, 4H), 7.4 (d, 2H). 13C NMR (CDCl3, ppm): d 30.0
(1J(119Sn–13C) = 502.2 Hz), 128.2, 128.6, 130.5, 132.4,
132.5. 119Sn NMR (CDCl3, ppm): 86.4.
2.3.2. [Ph3 SnSC6H4]2S (2)
Compound 2 was prepared in the same way as that for
compound 1. Yield: 92%. M.p. 153–155 °C. Anal. Calc. for
[Ph3SnSC6H4]2S: C, 60.79; H, 4.04. Found: C, 60.50; H,
2.3.5. [(Ph)2Sn(SC6H4)2S]2 (5)
Compound 5 was prepared in the same way as that for
compound 4. Yield: 81%. M.p. 160–162 °C. Anal. Calc. for
[(Ph)2Sn(SC6H4)2S]2: C, 55.30; H, 3.48. Found: C, 55.05;
H, 3.20%. IR (KBr, cmꢀ1): m(Sn–C), 558; m(Sn–S), 305.
1H NMR (CDCl3, ppm): d 6.8–7.5 (m, 18H). 13C NMR
(CDCl3, ppm): d 128.8 (1 J(119Sn–13C) = 503.3 Hz), 129.1,
129.4, 130.2, 131.1, 131.8, 133.8, 135.8, 136.0, 136.7,
136.9, 137.5. 119Sn NMR (CDCl3, ppm): ꢀ61.2.
1
3.90%. IR (KBr, cmꢀ1): m(Sn–C), 546; m(Sn–S), 309. H
NMR (CDCl3, ppm): d 6.8 (d, 2H), 7.2 (d, 2H), 7.2–7.7
(m, 15H). 13C NMR (CDCl3, ppm):
d
124.9
(1J(119Sn–13C) = 402.8 Hz), 128.7–129.2, 129.9–130.9,
131.67, 133.7, 135.4–135.7, 136.2–137.0, 137.3, 137.4.
119Sn NMR (CDCl3, ppm): ꢀ60.5.
2.3.3. [(PhCH2)3 SnSC6H4]2S (3)
2.3.6. [(PhCH2)2Sn(SC6H4)2S]2 (6)
Compound 3 was prepared in the same way as that for
compound 1. Yield: 80%. M.p. 100–102 °C. Anal. Calc. for
[(PhCH2)3SnSC6H4]2S: C, 62.81; H, 4.88. Found: C, 62.96;
H, 4.74%. IR (KBr, cmꢀ1): m(Sn–C), 551; m(Sn–S), 322. 1H
NMR (CDCl3, ppm): d 2.4 (s, 6H), 6.7–7.4 (m, 19H). 13C
NMR (CDCl3, ppm): d 22.7 (1J(119Sn–13C) = 440.3 Hz),
124.7, 124.8, 127.9–128.1, 128.7–129.1, 130.9–131.5,
132.4, 134, 135.8–135.9, 139.4. 119Sn NMR (CDCl3,
ppm): 37.7.
Compound 6 was prepared in the same way as that for
compound 4. Yield: 79%. M.p. 143–145 °C. Anal. Calc. for
[(PhCH2)2Sn(SC6H4)2S]2: C, 56.84; H, 4.04. Found: C,
56.62; H, 3.81%. IR (KBr, cmꢀ1): m(Sn–C), 530; m(Sn–S),
1
320. H NMR (CDCl3, ppm): d 2.5 (s, 4H), 6.7–7.4 (m,
18H).
13C
NMR
(CDCl3,
ppm):
d
26.0
(1J(119Sn–13C) = 443.8 Hz), 27.9, 125.4, 128.0–128.4,
128.8–128.9, 130.7–131.4, 134.9, 135.8, 136.4, 136.5,
137.2. 119Sn NMR (CDCl3, ppm): 23.0.
2.3.4. [(CH3)2Sn(SC6H4)2S]2 (4)
3. Results and discussion
The reaction was carried out under a nitrogen atmo-
sphere. 4,40-Thiodibenzenethiol (0.250 g, 1 mmol) and
sodium ethoxide (0.136 g, 2 mmol) were added to benzene
(20 ml) in a Schlenk flask and stirred for 5 min. Dimethyl-
tin dichloride (0.219 g, 1 mmol) was added to the reaction
mixture, which was then stirred for 12 h at 40 °C. After fil-
tration, the solvent was gradually removed by evaporation
under vacuum until a solid product was obtained. The solid
was recrystallized from ether–petroleum and colorless crys-
3.1. Syntheses
The reactions of triorganotin(IV) chloride with 4,40-thi-
odibenzenethiol in a 2:1 stoichiometry and diorganotin(IV)
dichloride with 4,40-thiodibenzenethiol in a 1:1 stoichiome-
try, depending on the nature of the starting acceptor and
reaction conditions, afforded air-stable compounds. The
syntheses procedures are shown in Scheme 1.
C6H6
EtONa
2R3SnCl
HS
S
SH
R3SnS
+
S
SSnR3
R=Me1, Ph 2, PhCH2
3
S
R
S
S
R
S
S
C6H6
EtONa
R2SnCl2
HS
S
SH
+
Sn
R
Sn
R
S
R=Me 4, Ph 5, PhCH2
6
Scheme 1.

C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
423
3.2. IR spectra
The IR spectra show that the strong absorption at
2560 cmꢀ1 in the free ligand due to the –SH group is absent
in the spectra of all the compounds 1–6, and at the same
time a new absorption appears in the region 305–
322 cmꢀ1. All these values are located within the range
for Sn–S vibrations observed in common organotin thio-
late derivatives (300–400 cmꢀ1) [11], consequently, they
can be assigned to m(Sn–S).
Fig. 1. Molecular structure of compound 1; ellipsoids at 30% probability;
3.3. NMR spectra
hydrogen atoms have been removed for clarity.
The 1H NMR data show that the signal of the –SH pro-
ton in the spectrum of the ligand is absent in all of the com-
pounds, indicating the removal of the –SH proton and the
2
formation of Sn–S bonds. The JSnH values of compounds
1 and 4 are 27.2 Hz and 83.2 Hz, which are similar to those
previously reported for four-coordinated tetrahedral
tin(IV) adducts [12]. The 13C NMR spectra of all the com-
pounds show a significant downfield shift of all carbon res-
onances, compared with the free ligand.
The 119Sn NMR data show that compounds 1–6 have
only one signal (100.4, ꢀ60.5, 37.7, 86.4, ꢀ61.2 and
23 ppm, respectively), they are all well in accordance with
values that have been reported in the literature which lie
in the range from +200 to ꢀ60 ppm [13].
3.4. X-ray crystallographic studies
3.4.1. Crystal structures of 1 and 2
The molecular structures of compounds 1 and 2 are
illustrated in Figs. 1 and 3, respectively. Selected bond
Fig. 2. Two-dimensional network of compound 1 connected through C–
Hꢁ ꢁ ꢁS WHBs, unattached hydrogen atoms have been removed for clarity.
˚
lengths (A) and angles (°) are listed in Table 2.
X-ray crystal structure analysis reveals that compounds
1 and 2 are monomeric with one ligand bonding to two tin
atoms through Sn–S bonds. Each of the tin atoms is four-
coordinated. Distortion from strict tetrahedral coordina-
tion is partly because of the bonding variance. The four
primary bonds to Sn are three methyl groups and one sul-
fur atom for 1 and three phenyl groups and one sulfur
atom for 2. The Sn–C bond lengths are consistent with
those reported in other triorganotin derivatives [14]. The
Fig. 3. Molecular structure of compound 2; hydrogen atoms have been removed for clarity.

424
C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
Table 2
Compounds 1 and 2 exhibit interesting intermolecular
interactions as shown in Figs. 2, 4 and 5: the molecules
of 1 are connected through C(15)–H(15)ꢁ ꢁ ꢁS(2) (Cꢁ ꢁ ꢁS,
˚
Selected bond lengths (A) and bond angles (°) for compounds 1 and 2
[(CH3)3SnSC6H4]2S (1)
Sn(1)–C(14)
Sn(1)–C(15)
Sn(1)–C(13)
Sn(1)–S(2)
C(14)–Sn(1)–C(15)
C(14)–Sn(1)–C(13)
C(15)–Sn(1)–C(13)
C(14)–Sn(1)–S(2)
C(15)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
2.10(15)
2.11(15)
2.12(13)
2.44(4)
Sn(2)–C(16)
Sn(2)–C(17)
Sn(2)–C(18)
Sn(2)–S(3)
C(16)–Sn(2)–C(17)
C(16)–Sn(2)–C(18)
C(17)–Sn(2)–C(18)
C(16)–Sn(2)–S(3)
C(17)–Sn(2)–S(3)
C(18)–Sn(2)–S(3)
2.07(19)
2.08(2)
2.11(2)
2.43(6)
˚
˚
3.85 A; Hꢁ ꢁ ꢁS, 2.94 A; C–Hꢁ ꢁ ꢁS, 158.5°) and C(3)–
˚
˚
H(3)ꢁ ꢁ ꢁS(1) WHBs (Cꢁ ꢁ ꢁS, 3.91 A; Hꢁ ꢁ ꢁS, 2.99 A; C–
Hꢁ ꢁ ꢁS, 175.9°) into a two-dimensional network in the bc
plane. In compound 2, there are two loose two-dimensional
networks through different WHBs in different directions:
one that consists of discrete molecules connected through
114.7(6)
109.8(8)
113.1(6)
112.3(6)
103.5(4)
106.3(4)
105.8(4)
108.4(8)
119.2(9)
107.5(6)
107.4(6)
103.8(6)
˚
˚
C(24)–H(24)ꢁ ꢁ ꢁS(3) (Cꢁ ꢁ ꢁS, 3.70 A; Hꢁ ꢁ ꢁS, 2.98 A; C–
˚
Hꢁ ꢁ ꢁS, 135.1°) and C(28)–H(28)ꢁ ꢁ ꢁS(2) (Cꢁ ꢁ ꢁS, 3.80 A;
˚
Hꢁ ꢁ ꢁS, 2.99A; C–Hꢁ ꢁ ꢁS, 146.3°) WHBs (Fig. 4) in the bc
[Ph3SnSC6H4]2S (2)
Sn(1)–C(25)
Sn(1)–C(13)
Sn(1)–C(19)
Sn(1)–S(1)
plane, and another that is connected through C(30)–
2.12(15)
Sn(2)–C(31)
Sn(2)–C(43)
Sn(2)–C(37)
Sn(2)–S(2)
2.10(17)
˚
H(30)ꢁ ꢁ ꢁp (37–42) [Hꢁ ꢁ ꢁp (centroid), 3.51 A; C–Hꢁ ꢁ ꢁp (cen-
2.15(16)
2.17(14)
2.43(4)
2.13(12)
2.15(13)
2.42(3)
troid), 122.0°] and C(46)–H(46)ꢁ ꢁ ꢁp (37–42) [Hꢁ ꢁ ꢁp (cen-
˚
troid), 3.38 A; C–Hꢁ ꢁ ꢁp (centroid), 138.1°] interactions
ꢀ
ꢀ
(Fig. 5) along the ½111ꢂ and ½110ꢂ directions.
C(25)–Sn(1)–C(13)
C(25)–Sn(1)–C(19)
C(13)–Sn(1)–C(19)
C(25)–Sn(1)–S(1)
C(13)–Sn(1)–S(1)
C(19)–Sn(1)–S(1)
111.4(6)
C(31)–Sn(2)–C(43)
C(31)–Sn(2)–C(37)
C(43)–Sn(2)–C(37)
C(31)–Sn(2)–S(2)
C(43)–Sn(2)–S(2)
C(37)–Sn(2)–S(2)
112.6(6)
110.4(6)
112.9(6)
107.6(4)
105.7(5)
108.5(4)
112.8(6)
112.5(5)
106.8(4)
104.5(3)
107.0(4)
The values for the C–Hꢁ ꢁ ꢁS WHB are longer than an
intramolecular C–Hꢁ ꢁ ꢁS WHB in (r-2, c-4)-3-benzyl-
˚
2,4,5,5-tetraphenyl-1,3-thiazolidine
(Cꢁ ꢁ ꢁS,
3.04 A;
˚
Hꢁ ꢁ ꢁS, 2.55 A and C–Hꢁ ꢁ ꢁS, 110°) [16], but they are clo-
sely in agreement with values that have been reported in
the literature [15,17], whilst the parameters for the C–
Hꢁ ꢁ ꢁp interactions in the compound are in agreement
with those that have been reported in the literature
[17,18].
Sn–S bonds lengths [the Sn–S bond lengths are between
2.43(6) and 2.44(4) A] are slightly less than the sum of
the covalent radii of Sn and S (2.44 A) [15].
˚
˚
Fig. 4. Two-dimensional network of compound 2 by C–Hꢁ ꢁ ꢁS WHBs along the bc plane, unattached hydrogen atoms have been removed for clarity.
ꢀ
ꢀ
Fig. 5. Two-dimensional network of compound 2 connected through C–Hꢁ ꢁ ꢁp interactions along the ½111ꢂ and ½110ꢂ directions, unattached hydrogen
atoms have been removed for clarity.

C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
425
3.4.2. Crystal structure of 4, 5 and 6
Perspective view of the molecular structures of com-
pounds 4, 5 and 6 are illustrated in Figs. 6, 8 and 10,
respectively. Selected bond lengths (A) and angles (°) are
listed in Table 3.
Compounds 4, 5 and 6 all proved to be centrosymmetric
dinuclear macrocyclic compounds with 4,40-thiodibenze-
nethiol bridging the adjacent tin atoms with a twenty-four
member Sn2S6C16 ring, and the ring can be valued by the
˚
˚
transcyclic distances (Sn(1)–Sn(1)# = 12.51 A and C(2)–
Fig. 6. Molecular structure of compound 4; ellipsoids at 30% probability; hydrogen atoms have been removed for clarity.
Fig. 7. Two-dimensional network of compound 4 connected through C–Hꢁ ꢁ ꢁS WHBs and non-bonded Snꢁ ꢁ ꢁS contacts, unattached hydrogen atoms have
been removed for clarity.
Fig. 8. Molecular structure of compound 5; ellipsoids at 30% probability; hydrogen atoms have been removed for clarity.

426
C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
Fig. 9. One-dimensional chain of compound 5, unattached hydrogen atoms have been removed for clarity.
[(Ph)2SnL] and [(PhCH2)2SnL], respectively, in which the
primary bonds of the ligand to tin occur through the two
sulfur atoms. To the best of our knowledge, dinuclear mac-
rocyclic compounds in common organotin derivatives of
thionate have so far only rarely been reported [19].
Each of the tin atoms in compounds 4, 5 and 6 has a dis-
torted tetrahedral coordination. The four primary bonds to
Sn are two Sn–C and two Sn–S bonds. The Sn–C bond
lengths are consistent with those found in compounds 1
˚
and 2. The Sn–S bond lengths are 2.42(17) A [Sn(1)–
˚
S(2)], 2.45(2) A [Sn(1)–S(3)#1] (#1 = ꢀx + 2,ꢀy + 1,
˚
˚
˚
˚
ꢀz + 1) for 4; 2.42(19) A [Sn(1)–S(3)], 2.42(18) A [Sn(1)–
S(2)] for 5 and 2.41(18) A [Sn(1)–S(2)], 2.43(19) A [Sn(1)–
S(3)] for 6, similar to those found in compounds 1 and 2.
Distortion from a strict tetrahedral coordination is partly
because of the bonding variance. The deviation from
an ideal tetrahedron is manifested by the bond angles
(see Table 3), all of which deviate from the idea value of
109.5°.
Fig. 10. Molecular structure of compound 6; ellipsoids at 30% probabil-
ity; hydrogen atoms have been removed for clarity.
Table 3
˚
Selected bond lengths (A) and bond angles (°) for compounds 4, 5 and 6
Analyses of the supramolecular infrastructure of the
compounds 4, 5 and 6 reveal that weak intermolecular
non-bonded Snꢁ ꢁ ꢁS contacts, C–H. . .S and C–Hꢁ ꢁ ꢁp WHBs
play important roles in the supramolecular arrangements.
The C–Hꢁ ꢁ ꢁp interactions can also be viewed as an edge-
to face p–p interaction [18d].
[(CH3)2Sn(SC6H4)2S]2 (4)
Sn(1)–C(14)
Sn(1)–C(13)
2.12 (7)
2.12 (6)
Sn(1)–S(2)
Sn(1)–S(3)#1
C(14)–Sn(1)–S(3)#1
C(13)–Sn(1)–S(3)#1
S(2)–Sn(1)–S(3)#1
2.42 (17)
2.45(2)
107.6(2)
104.0(19)
108.7(6)
C(14)–Sn(1)–C(13)
C(14)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
120.8(3)
107.8(18)
107.5(19)
[(Ph)2Sn(SC6H4)2S]2 (5)
Sn(1)–C(13)
The supramolecular structure of compound 4 is a two-
dimensional network in the bc plane, as shown in Fig. 7,
in which the discrete molecules are connected through
2.12(6)
Sn(1)–S(3)
Sn(1)–S(2)
C(13)–Sn(1)–S(2)
C(19)–Sn(1)–S(2)
S(3)–Sn(1)–S(2)
2.42(19)
2.42(18)
107.8 (15)
101.1(16)
105.7(7)
Sn(1)–C(19)
2.13(5)
120.9(2)
112.2(17)
107.5(19)
C(13)–Sn(1)–C(19)
C(13)–Sn(1)–S(3)
C(19)–Sn(1)–S(3)
˚
intermolecular C–Hꢁ ꢁ ꢁS (Cꢁ ꢁ ꢁS, 3.62–3.75 A; Hꢁ ꢁ ꢁS,
˚
2.87–2.96 A; C–Hꢁ ꢁ ꢁS, 135.0–140.6°) WHBs. This loose
structure is further stabilized by non-bonded Sn(1)ꢁ ꢁ ꢁS(3)
[(PhCH2)2Sn(SC6H4)2S]2 (6)
Sn(1)–C(20)
˚
interactions. The Sn(1)ꢁ ꢁ ꢁS(3) distance (3.700 A) is
2.15(6)
2.15(6)
Sn(1)–S(2)
Sn(1)–S(3)
C(20)–Sn(1)–S(3)
C(13)–Sn(1)–S(3)
S(2)–Sn(1)–S(3)
2.41(18)
2.43(19)
114.4(16)
106.7(19)
99.4(7)
shorter than that in compounds (PhCH2)2Sn(SC5H5N2)2
and (PhCH2)2SnCl(SC5H5N2) [20], and also shorter than
Sn(1)–C(13)
C(20)–Sn(1)–C(13)
C(20)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
115.7(2)
108.0(17)
111.5(19)
˚
the sum of the Van der waals radii of Sn and S (4.0 A)
[21].
In compound 5, an intermolecular C(5)–H(5)ꢁ ꢁ ꢁS(3)
˚
˚
˚
˚
˚
˚
˚
(Cꢁ ꢁ ꢁS, 3.65A; Hꢁ ꢁ ꢁS, 2.97 A; C–Hꢁ ꢁ ꢁS, 130.3°) WHB con-
nects the discrete molecules into a linear chain, as shown in
Fig. 9.
C(2)# = 3.89 A for 4; Sn(1)–Sn(1)# = 10.42 A and C(8)–
C(8)# = 6.75 A for 5; Sn(1)–Sn(1)# = 11.42 A and C(2)–
C(2)# = 4.44 A for 6). The units are [(CH3)2SnL],

C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
427
Fig. 11. Two-dimensional network of compound 6 connected through C–Hꢁ ꢁ ꢁS WHBs and non-bonded Snꢁ ꢁ ꢁS contacts, unattached hydrogen atoms
have been removed for clarity.
Fig. 12. One dimensional chain of compound 6 connected through C–Hꢁ ꢁ ꢁp interactions along the [111] direction.
In compound 6, the two-dimensional network in the ac
plane (as shown in Fig. 11) is connected by C–Hꢁ ꢁ ꢁS WHBs
sional structures, in which the subunits are
organometallic compounds.
The current study also provides aids in the fundamental
understanding of molecular recognition, and insight into
the interpretation of supramolecular aggregation in crystal
engineering.
˚
˚
(Cꢁ ꢁ ꢁS, 3.81A; Hꢁ ꢁ ꢁS, 2.95 A; C–Hꢁ ꢁ ꢁS, 153.6°) and non-
bonded Snꢁ ꢁ ꢁS interactions, and the linear chain along
the [111] direction is connected by C–Hꢁ ꢁ ꢁp [Hꢁ ꢁ ꢁp (cen-
˚
troid), 3.36–3.51 A; C–Hꢁ ꢁ ꢁp (centroid), 131.5–136.3°]
interactions at the same time (as shown in Fig. 12), forming
a three-dimensional structure.
5. Supplementary material
CCDC 636269, 636268, 636266, 636267, 636265 con-
tains the supplementary crystallographic data for 1, 2, 4,
5 and 6. 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, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.
4. Conclusion
4,40-Thiobisbenzenethiol has been shown to be able to
form monomeric compounds with triorganotin moieties,
and also to form dinuclear macrocyclic compounds with
diorganotin moieties due to the flexibility of the ligand
and the nature of the starting acceptor. The supramolecu-
lar structures described in this paper demonstrate that
weak intermolecular interactions have enormous potential
for assembling discrete molecular systems into one-dimen-
sional chains, two-dimensional networks or three-dimen-
Acknowledgement
We thank the National Natural Science Foundation of
China (20271025) for financial support.

428
C.-L. Ma et al. / Polyhedron 27 (2008) 420–428
[7] T.S.B. Baul, K.S. Singh, A. Lycˇka, M. Holcˇapek, A. Linden, J.
References
Organomet. Chem. 690 (2005) 1581.
[8] R.F. Zhang, J.F. Sun, C.L. Ma, Heteroatom Chem. 17 (2006) 93.
[9] C.L. Ma, Q.F. Zhang, Eur. J. Inorg. Chem. (2006) 3244.
[10] K. Sisido, Y. Takeda, Z. Kinugawa, J. Am. Chem. Soc. 83 (1961)
538.
[11] J.R. May, W.R. Mc Whinnie, R.C. Poller, Spectrochim. Acta 27A
(1971) 969.
[12] T.P. Lockhart, W.F. Manders, Inorg. Chem. 25 (1986) 892.
[13] J. Holecek, M. Nadvornik, K. Handlir, A. Lycka, J. Organomet.
Chem. 315 (1986) 299.
[14] C.L. Ma, J.F. Sun, Y. Shi, R.F. Zhang, J. Organomet. Chem. 690
(2005) 1560.
[15] L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell
University Press, Ithaca, 1960, pp. 64.
[16] M. Domagala, S.J. Grabowskia, K. Urbaniakb, G. Mloston, J. Mol.
Struct. 690 (2004) 69.
[17] C.L. Ma, Q.F. Zhang, R.F. Zhang, D.Q. Wang, Chem. Eur. J. 12
(2006) 420.
[18] (a) P.K.C. Paul, Cryst. Eng. 5 (2002) 3;
[1] (a) M. Eshel, A. Bino, Inorg. Chim. Acta 320 (2001) 127;
(b) E. Kiss, K. Petrohan, D. Sanna, E. Garribba, G. Micera, T. Kiss,
Polyhedron 19 (2000) 55;
(c) D. Dakternieks, A. Duthie, B. Zobel, Organometallics 21 (2002) 647;
(d) M. Verdenelli, S. Parola, L.G. Hubert-Pfalzgraf, S. Lecocq,
Polyhedron 19 (2000) 2069;
(e) T.P. Lockhart, Organometallics 7 (1988) 1438;
(f) Ok-Sang Tung, Y.S. Sohn, J.A. Ibers, Inorg. Chem. 25 (1986)
2273.
[2] (a) For recent reviews see: T. Steiner, W. Saenger, J. Am. Chem. Soc.
114 (1992) 10146;
(b) K.N. Houk, S. Menzer, S.P. Newton, F.M. Raymo, J.F. Stoddart,
D.J. Williams, J. Am. Chem. Soc. 121 (1999) 1479;
(c) G.R. Desiraju, Acc. Chem. Res. 29 (1996) 441;
(d) M. Iwaoka, S. Tomoda, J. Am. Chem. Soc. 116 (1994) 4463;
(e) R. Boese, M.T. Kirchner, W.E. Billups, L.R. Norman, Angew.
Chem. 115 (2003) 1921. Angew. Chem., Int. Ed., 42 (2003) 1961;
(f) G.R. Desiraju, Acc. Chem. Res. 29 (1996) 441;
(g) T. Steiner, Crystallogr. Rev. 6 (1996) 1;
(b) J.G. Planas, C. Masalles, R. Sillanpa¨a¨, R. Kiveka¨s, F. Teixidor, C.
Vinas, Cryst. Eng. 8 (2005) 75;
˜
(h) T. Steiner, Chem. Commun. (1997) 727;
(c) H.W. Roesky, M. Andruh, Coord. Chem. Rev. 236 (2003) 91;
(d) M. Nishio, CrystEngComm. 6 (2004) 130.
[19] (a) K. Jurkschat, W. Uhlig, C. Mugge, A. Tzschach, B. Schmidt, M.
Drager, Z. Anorg. Allg. Chem. 556 (1988) 161;
(b) H. Preut, K. Gratz, F. Huber, Acta. Crystallogr., Sect. C 40 (1984)
941;
(i) M.C.T. Fyfe, J.F. Stoddart, Coord. Chem. Rev. 183 (1999) 139.
[3] (a) M. Hill, M.F. Mahon, K.C. Molloy, J. Chem. Soc., Dalton Trans.
(1996) 1857;
(b) S. Bhandari, C.G. Frost, E. Hague, M.F. Mahon, K.C. Molloy, J.
Chem. Soc., Dalton Trans. (2000) 663;
(c) V. Berceanc, C. Crainic, I. Haiduc, M.F. Mahon, K.C. Molloy,
M.M. Venter, P.J. Wilson, J. Chem. Soc., Dalton Trans. (2002) 1036;
(c) Ok-Sang Jung, Youn Soo Sohn, J.A. Ibers, Inorg. Chem. 25 (1986)
2273;
(d) F.E. Hahn, A. Dittler-Klingemann, T. Lugger, Z. Naturforsch.,
Teil. B 58 (2003) 1030.
´
(d) R. Garcıa-zarracino, J. Ramos-Quinones, H. Hopfl, Inorg. Chem.
˜
42 (2003) 3835.
[4] S.K. Duboy, U. Roy, Appl. Organomet. Chem. 17 (2003) 3.
[5] G.F. de Sousa, V.M. Deflon, M.T. do P. Gambardella, R.H.P.
Francisco, J.D. Ardisson, E. Niquet, Inorg. Chem. 45 (2006) 4518.
[6] A.P.G. de Sousa, R.M. Silva, A. Cesar, J.L. Wardell, J.C. Huffman,
A. Abras, J. Organomet. Chem. 605 (2000) 82.
[20] C.L. Ma, J.H. Zhang, G.R. Tian, R.F. Zhang, J. Organomet. Chem.
690 (2005) 519.
´
´
[21] J.S. Casas, A. Castineiras, E.G. Martinez, A.S. Gonzalez, A. Sanchez,
J. Sordo, Polyhedron 16 (1997) 795.