Structural diversity of di and triorganotin complexes with 4-sulfanylbenzoic acid: Supramolecular structures involving intermolecular Sn?O, O-H?O or C-H?X (X = O or S) interactions

Article abstract of DOI:10.1016/j.jorganchem.2005.03.040

Twelve new organotin complexes with 4-sulfanylbenzoic acid of two types: R_nSn[S(C₆H₄COOH)]_4-n (I) (n = 3: R = Me 1, n-Bu 2, Ph 3; PhCH₂ 4; n = 2: R = Me 5; n-Bu 6, Ph 7, PhCH₂ 8) and R₃Sn(SC₆H₄COO)SnR ₃ ? mEtOH (II) (m = 0: R = Me 9, n-Bu 10, PhCH₂ 12; m = 2: R = Ph 11), along with the 4,4′-bipy adduct of 9, [Me ₃Sn(SC₆H₄COO)SnMe₃] ₂(4,4-bipy) 13, have been synthesized. The coordination behavior of 4-sulfanylbenzoic acid is monodentate in 1-8 by thiol S atom but not carboxylic oxygen atom. While, in 9-13 it behaves as multidenate by both thiol S atom and carboxylic oxygen atoms. The supramolecular structures of 6, 11 and 13 have been found to consist of 1D molecular chains built up by intermolecular O-H?O, C-H?O or C-H?S hydrogen bonds. The supramolecular aggregation of 7 is 2D network determined by two C-H?O hydrogen bonds. Extended intermolecular C-H?O interactions in the crystal lattice of 9 link the molecules into a 2D network.

Full text of DOI:10.1016/j.jorganchem.2005.03.040

Journal of Organometallic Chemistry 690 (2005) 3033–3043
www.elsevier.com/locate/jorganchem
Structural diversity of di and triorganotin complexes with
4-sulfanylbenzoic acid: Supramolecular structures
involving intermolecular Snꢀ ꢀ ꢀO, O–Hꢀ ꢀ ꢀO or C–Hꢀ ꢀ ꢀX
(X = O or S) interactions
a,b,
a
a
b
Chunlin Ma
*, Qingfu Zhang , Rufen Zhang , Linlin Qiu
a
Department of Chemistry, Liaocheng University, 34 Wenhua Road, Liaocheng 252059, Peopleꢀs Republic of China
b
Taishan University, Taian 271021, Peopleꢀs Republic of China
Received 23 February 2005; revised 16 March 2005; accepted 22 March 2005
Available online 5 May 2005
Abstract
Twelve new organotin complexes with 4-sulfanylbenzoic acid of two types: RnSn[S(C6H4COOH)]4ꢁn (I) (n = 3: R = Me 1, n-Bu 2,
Ph 3; PhCH2 4; n = 2: R = Me 5; n-Bu 6, Ph 7, PhCH2 8) and R3Sn(SC6H4COO)SnR3 Æ mEtOH (II) (m = 0: R = Me 9, n-Bu 10,
PhCH2 12; m = 2: R = Ph 11), along with the 4,40-bipy adduct of 9, [Me3Sn(SC6H4COO)SnMe3]2(4,4-bipy) 13, have been synthe-
sized. The coordination behavior of 4-sulfanylbenzoic acid is monodentate in 1–8 by thiol S atom but not carboxylic oxygen atom.
While, in 9–13 it behaves as multidenate by both thiol S atom and carboxylic oxygen atoms. The supramolecular structures of 6, 11
and 13 have been found to consist of 1D molecular chains built up by intermolecular O–Hꢀ ꢀ ꢀO, C–Hꢀ ꢀ ꢀO or C–Hꢀ ꢀ ꢀS hydrogen
bonds. The supramolecular aggregation of 7 is 2D network determined by two C–Hꢀ ꢀ ꢀO hydrogen bonds. Extended intermolecular
C–Hꢀ ꢀ ꢀO interactions in the crystal lattice of 9 link the molecules into a 2D network.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: 4-Sulfanylbenzoic acid; Organotin; Supramolecular structure
1. Introduction
ders and hexameric durms, etc. [7]. It has also been dem-
onstrated that other structural types are formed due to
the presence of additional coordinating sites (S, N or
O, etc.) along with a carboxylate moiety [5,6a,8].
In our previous work, we have reported several novel
molecular structures of organotin complexes with 2-
mercaptonicotinic acid [5a,9]. To continue our research,
we have been attracted by another interesting ligand, 4-
sulfanylbenzoic acid, recently. This ligand is interesting
because of its potential multiple molecular models in
organotin complexes. As exhibited in Scheme 1, at least
seven possible molecular models are conceivable
although nobody has investigated its actual molecular
structures until now.
Organotin complexes have attracted more and more
attention in recent years, partly owing to their determi-
nately or potentially pharmic value, where have been re-
ported many before [1–4], and also for the versatile
molecular structure and supramolecular architecture
exhibited by these complexes [5,6]. It is the latter which
forms the focus of this paper.
It is well known that the organotin carboxylates have
versatile molecular structures both in solid and solution,
such as monomers, dimers, tetramers, oligomeric lad-
*
Corresponding author. Tel.: +86 635 823 8121; fax: +86 538 671
Although the synthesis and characterization of some
transition metal complexes of 4-sulfanylbenzoic acid has
5521.
E-mail address: macl@lctu.edu.cn (C. Ma).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.03.040

3034
C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
R
R
R
R
R
R
R
SnO2C
(B)
SH
S
Sn
HO2C
S
S
Sn
SnO2C
R
R
R
R
R
(C)
(A)
R
O2C
O2C
SH
R
R
HO2C
HO2C
R
Sn
O2C
S
S
CO2 Sn
R
Sn
Sn
R
SH
n
S
R
R
(F)
(E)
(D)
R
S
CO2
S
CO2
Sn
R
n
(G)
Scheme 1.
been carried out previously [10]. And to our knowledge,
no organotin derivatives of 4-sulfanylbenzoic acid have
been reported so far. Therefore, one of the aims of this
work is to investigate and characterize the structures of
new organotin derivatives of 4-sulfanylbenzoic acid.
Furthermore, supramolecular structure of organome-
talliccomplexes,especiallyaggregatedthroughintermolec-
ular soft hydrogen bonds [11], is of current interest and
importance, which is mainly due to their intriguing, often
complicated, architectures and topologies[12–15]. Ligands
such as 4-sulfanylbenzoic acid present a number of oppor-
tunities for creating supramolecular arrangements via
weak intermolecular metal–ligand interactions and/or H-
bonding from Lewis base sites (O or S). Thus, the other
aim of this work was to elucidate supramolecular struc-
turesoftheorganotinderivativesof4-sulfanylbenzoicacid.
R = Me 1, n-Bu 2, Ph 3; PhCH2 4; n = 2: R = Me 5;
n-Bu 6, Ph 7, PhCH2 8) and R3Sn(SC6H4COO)SnR3 Æ
mEtOH (II) (m = 0: R = Me 9, n-Bu 10, PhCH2 12;
m = 2: R = Ph 11), have been synthesized by reaction
of the 4-sulfanylbenzoic acid, sodium ethoxide and the
corresponding organotin chlorides (Eqs. (1) and (2)).
Further reaction of 9 with excess 4,40-bipy in dietheyl
ether results in the formation of a tetranuclear adduct,
[Me3Sn(SC6H4CO2)SnMe3]2 Æ(4,40-bipy) (13) (Eq. (3)).
The syntheses procedure is given in Scheme 2.
2.2. IR Spectra
The explicit feature in the IR spectra of the 13 com-
plexes 1–13 is the absence of the band in the region
2550–2420 cmꢁ1, which appears in the free ligand as
the -SH stretching vibration, thus indicating metal–
ligand bond formation through this site. In the far-IR
spectra, the absorption about 305–316 cmꢁ1 region for
all complexes 1–13, which is absent in the spectrum of
the ligand, is assigned to the Sn–S stretching mode of
the vibration and all the values are located within the
range for Sn–S vibration observed in common organotin
2. Results and discussion
2.1. Syntheses
Twelve new organotin complexes with 4-sulfanylben-
zoic acid of two types: RnSn[S(C6H4CO2H)]4ꢁn (n = 3:
derivatives of thiolate (300–400 cmꢁ1
)
[16,17].
(1)
(2)
(3)
Scheme 2.

C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
3035
Moreover, the broad absorption at 2900–3100 cmꢁ1 is
2.4. Structural chemistry
present in complexes 1–8, which is assigned to –CO2H
groups. While it is absent in complexes 9–13, indicating
the deprotonation and coordination of these carboxyl-
ate groups.
2.4.1. Ph3Sn[S(C6H4CO2H)] (3)
The molecular structure of complex 3 is shown in Fig.
1, selected bond lengths and angles are given in Table 1.
The central tin atom of complex 3 forms four primary
bonds: three to the phenyl groups and one to the sulfur
atom (model A). Thus, complex 3 displays a distorted
tetrahedral coordination sphere with six angles ranging
from 99.08(8) to 119.44(12)ꢁ. The Sn–C bond lengths
Furthermore, in organotin carboxylate complexes,
the IR spectroscopy can provide useful information con-
cerning the coordinate formation of the carboxylate [18].
When the carboxylate group coordinates the tin atom in
a monodentate manner (Scheme 3 mode I), the differ-
ence between the wavenumbers of the asymmetric and
symmetric carboxylate stretching bonds, Dm[m(COO)as–
m(COO)s], is larger than that observed for ionic
complexes. When the ligand chelates (mode II), Dm is
considerably smaller than that for ionic complexes
[19]. The characteristic wavenumber difference, Dm, for
mode III is larger than that for chelated ions and nearly
the same as observed for ionic complexes.
Based on the above mention, it was possible to distin-
guish the coordination mode of the –CO2 group. The Dm
values for complexes 9 and 10 (200 and 190 cmꢁ1) are
near to that in the sodium salt of the ligand
(205 cmꢁ1), which suggest that the coordinate formation
of these carboxylate groups is mode III. While the Dm
values for complexes 11, 12 and 13 (157, 150 and
165 cmꢁ1) are smaller than that in the sodium salt of
the ligand, which suggest that the coordinate formation
of these carboxylate groups is mode II. All the Dm values
of complexes 9–13, compared with those for the corre-
sponding sodium salts, reveal that the –CO2 group of
4-sulfanylbenzoic acid functions as bidentate under the
conditions employed [20,21]. This information is consis-
tent with the analysis of the related X-ray
crystallography.
˚
[2.123(3)–2.135(3) A] are in the range of that found in
˚
other triphenyltin thiolate (2.115–2.138 A) [22]. The
˚
Sn–S bond length [2.4272(13) A] is a little longer that
˚
has reported in methylthio-triphenyl-tin (2.390 A) [22]
and approaches the sum of the covalent radii of tin
˚
and sulfur (2.42 A) [23].
2.4.2. (n-Bu)2Sn[S(C6H4CO2H)]2 (6) and
(Ph)2Sn[S(C6H4CO2H)]2 (7)
The molecular structure of complexes 6 and 7 are
shown in Figs. 2 and 3, selected bond lengths and angles
are given in Tables 2 and 3. The geometries at central Sn
atoms of both complexes 6 and 7 are also distorted tetra-
hedron but formed by two S atoms from 4-sulfanylben-
zoic acid and two C atoms form butyl groups or phenyl
groups (model D). The C–Sn–C angle [113.8(6)ꢁ for 6,
116.44(19)ꢁ for 7] is nearly to that found in similar diorg-
anotin dithiolate (116.43–126.72ꢁ) [24–26]. The S–Sn–S
1
2.3. H NMR spectra
1H NMR data showed that the signal of the –SH pro-
ton (1.65 ppm) in the spectrum of the ligand is absent in
all of the complexes, indicating the removal of the –SH
proton and the formation of Sn–S bonds. Moreover, the
sharp resonance appears at about 10.5 ppm in the spec-
tra of 1–8, which is assigned to CO2H. While it is absent
in 9–13, indicating the replacement of the carboxylic
acid proton by RnSn (n = 2 or 3) moiety. Signals for
the other groups appear at the same position as in the
ligand. All the information accords well with what the
IR data have revealed.
Fig. 1. Molecular structure of the complex 3 with thermal ellipsoids at
30% probability level.
Table 1
˚
Selected bond lengths (A) and angles (ꢁ) for 3
Sn
O
Sn
Sn
O
O
Sn1–C8
Sn1–C20
2.133(3)
2.123(3)
Sn1–C14
Sn1–S1
2.135(3)
2.4272(13)
Sn
R'
R'
R'
O
I
O
O
C200–Sn1–C8
C8–Sn1–C14
C8–Sn1–S1
109.37(12)
119.44(12)
108.52(9)
C20–Sn1–C14
C20–Sn1–S1
C14–Sn1–S1
110.11(12)
109.63(9)
99.08(8)
II
III
Scheme 3.

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C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
˚
the Sn–S bond lengths [2.414(8) and 2.429(7) A for 6,
˚
2.4104(16) and 2.4108(16) A for 7] are excellent agree-
ment with other previously known organotin thiolates
in the literatures [24–27].
2.4.3. Me3Sn(SC6H4CO2)Me3Sn (9) and
Ph3Sn(SC6H4CO2)Ph3SnÆ2EtOH (11)
The molecular structure of complexes 9 and 11 are
shown in Figs. 4 and 5, selected bond lengths and angles
are given in Tables 4 and 5. There are two types of inde-
pendent Sn atoms in both complexes 9 and 11: one is the
four-coordinated Sn atom connected by thiol S atom,
Fig. 2. Molecular structure of the complex 6 with thermal ellipsoids at
30% probability level.
Fig. 4. Molecular structure of the complex 9 with thermal ellipsoids at
30% probability level.
Fig. 3. Molecular structure of the complex 7 with thermal ellipsoids at
30% probability level.
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for 6
Sn1–C15
Sn1–S1
2.099(16)
2.429(7)
Sn1–C19
Sn1–S2
2.189(13)
2.414(8)
C15–Sn1–C19
C19–Sn1–S2
C19–Sn1–S1
113.8(6)
114.3(3)
108.2(4)
C15–Sn1–S2
C15–Sn1–S1
S2–Sn1–S1
102.7(4)
110.7(4)
106.91(17)
Fig. 5. Molecular structure of the complex 11 with thermal ellipsoids
at 30% probability level.
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for 7
Table 4
Sn1–C21
Sn1–S1
2.121(5)
2.4108(16)
Sn1–C15
Sn1–S2
2.127(5)
2.4104(16)
˚
Selected bond lengths (A) and angles (ꢁ) of 9
Sn1–C10
Sn1–C9
Sn1–O2A
Sn2–C12
Sn2–S1
2.110(7)
2.131(7)
2.504(5)
2.137(8)
2.451(2)
1.232(8)
Sn1–C8
Sn1–O1
Sn2–C13
Sn2–C11
O1–C1
2.121(7)
2.140(4)
2.126(9)
2.139(10)
1.278(8)
C21–Sn1–C15
C15–Sn1–S1
C15–Sn1–S2
116.44(19)
102.51(15)
103.66(15)
C21–Sn1–S1
C21–Sn1–S2
S1–Sn1–S2
110.89(15)
109.60(15)
113.55(6)
O2–C1
angle [113.55(6)ꢁ for 6 and 106.91(17)ꢁ for 7] is close to
that found in bis(benzenethiolato)-diphenyl-tin
C10–Sn1–C8
C8–Sn1–C9
116.0(4)
125.5(3)
97.4(3)
C10–Sn1–C9
C10–Sn1–O1
C9–Sn1–O1
117.1(3)
88.7(2)
95.2(2)
87.6(2)
112.2(5)
112.2(4)
106.9(3)
(110.79ꢁ) [27], and markedly larger than that found in
chelate diorganotin dithiolates (90.54–92.48ꢁ) [25,26].
The related C–Sn–S angles [102.7(4)–114.3(3)ꢁ for 6,
102.51(15)–110.89(15)ꢁ for 7] are nearly to the theoreti-
cal tetrahedral angle. Both the Sn–C [2.099(16) and
C8–Sn1–O1
C10–Sn1–O2A
O1–Sn1–O2A
C13–Sn2–C11
C13–Sn2–S1
C11–Sn2–S1
87.1(2)
C9–Sn1–O2A
C13–Sn2–C12
C12–Sn2–C11
C12–Sn2–S1
175.60(17)
113.5(4)
108.1(3)
103.3(3)
˚
˚
2.189(13) A for 6, 2.121(5) and 2.127(5) A for 7] and

C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
3037
Table 5
Selected bond lengths (A) and angles (ꢁ) for 11
˚
Sn1–C8
Sn1–C20
Sn1–O2
Sn2–C32
Sn2–S1
O2–C1
2.131(5)
2.118(5)
2.737(4)
2.128(6)
2.4227(17)
1.227(6)
Sn1–C14
Sn1–O1
Sn2–C26
Sn2–C38
O1–C1
2.118(5)
2.055(3)
2.117(5)
2.135(5)
1.312(6)
Fig. 6. Molecular structure of the complex 13 with thermal ellipsoids
at 30% probability level.
O1–Sn1–C20
C20–Sn1–C14
C20–Sn1–C8
O1–Sn1–O2
C14-Sn1–O2
C26–Sn2–C32
C26–Sn2–S1
C38–Sn2–S1
108.98(16)
117.2(2)
111.3(2)
O1–Sn1–C14
O1–Sn1–C8
C14-Sn1–C8
C20–Sn1–O2
C8–Sn1–O2
C26–Sn2–C38
C32–Sn2–S1
111.77(17)
96.13(18)
109.5(2)
Table 6
52.55(13)
85.67(17)
113.4(2)
83.26(16)
148.68(18)
113.4(2)
˚
Selected bond lengths (A)and angles (ꢁ) for 13
Sn1–C10
Sn1–C8
Sn1–N1
Sn2–C13
Sn2–C11
2.117(5)
2.109(5)
2.631(4)
2.124(5)
2.114(6)
Sn1–C9
2.123(5)
2.137(3)
3.151(4)
2.127(6)
2.4338(15)
Sn1–O1
Sn1–O2
Sn2–C12
Sn(2)–S(1)
102.05(15)
109.76(14)
109.17(16)
C10–Sn1–C9
C9–Sn1–C8
C9–Sn1–O1
C10–Sn1–N1
C8–Sn1–N1
C9–Sn1–O2
C10–Sn1–O2
N1–Sn1–O2
C13–Sn2–C11
C13–Sn2–S1
C11–Sn2–S1
116.1(2)
124.6(2)
C10–Sn1–C8
C10–Sn1–O1
C8–Sn1–O1
C9–Sn1–N1
O1–Sn1–N1
C8–Sn1–O2
O1–Sn1–O2
C13–Sn2–C12
C12–Sn2–C11
C12–Sn2–S1
117.1(2)
the other is the five-coordinate Sn atom connected by
carboxyl O atoms (model C). The geometries of Sn2
atoms of complexes 9 and 11 are both distorted tetrahe-
dral, and these bond lengths and bond angles are similar
to those found in complex 3. Moreover, the geometry at
Sn1 atom of complex 9 is distorted trigonal bipyramidal
with three methyl groups occupying equatorial plane
90.45(17)
99.64(18)
86.22(18)
179.02(13)
71.61(16)
44.90(11)
112.2(3)
94.33(19)
90.03(17)
79.38(17)
82.46(19)
134.30(16)
134.46(11)
113.8(3)
113.1(3)
106.10(18)
and two
O atoms in axial sites [O1–Sn1–O2A,
104.4(2)
106.3(2)
175.60(17)ꢁ]. The geometry at Sn1 atom of complex 11
is also distorted trigonal bipyramidal but with two O
atoms of carboxyl groups and one C atom of phenyl
group occupying equatorial plane and two C atoms of
phenyl groups in axial sites [C20–Sn1–C14, 117.2(2)ꢁ].
Therefore, the geometries of Sn1 atoms of complexes 9
and 11 are not identical: trans-O2SnC3 type [28] for 9
and cis-O2SnC3 type [29] for 11. The Sn–C distances
of the 4,40-bipy ligand. The structure contains two
Me3Sn(SC6H4CO2)SnMe3 units associated through a
bridging 4,40-bipy moiety. The coordination environ-
ment around tin is trans-NOSnC3 with the axial
positions occupied by the carboxyl O atom of 4-
sulfanylbenzoic acid and the ring N atom of the neutral
bipyridyl donor. The O–Sn–N [179.02(13)ꢁ] and C–Sn–
C angles [116.1(2)–124.6(2)ꢁ] reflect this coordination
˚
˚
[2.110(7)–2.131(7) A for 9, 2.118(5)–2.131(5) A for 11]
are consistent with those reported in other triorganotin
˚
carboxylates [28,29]. The Sn1–O1 distance [2.140(4) A
˚
for 9, 2.055(3) A for 11] is a little shorter than that re-
˚
ported in [Me3Sn(O2CC4H3S)] (2.149 A) [30] and
˚
[Ph3Sn(O2CC6H5)] (2.073 A) [31] and approaches the
˚
geometry. The Sn–O bond length [2.137(3) A] is almost
˚
near to that of 9 [2.140(4) A] and at the longer end of the
range of Sn–O distances measured for triorganotin car-
˚
boxylate [28–31]. The Sn–N bond length [2.631(4) A],
˚
sum of the covalent radii of Sn and O (2.13 A) [32].
˚
˚
The Sn1–O2 distance [2.504(5) A for 9, 2.737(4) A for
11] is close to the distance between coordinated O atom
and central Sn atom in other organotin complexes
[30,31], but large shorter than the sum of the van der
closely to the Sn–N distance in [Me3Sn(PhN2C2S3)]2 Æ
0
˚
(4,4 -bipy) [2.613(2) A] [14], is longer than those found
˚
in organotin tetrazoles [2.27–2.43 A] [33] or the cationic
nþ
polymer ½Me3Snð4; 40-bipyÞꢂ [2.411, 2.420 A] [34]. Fur-
˚
n
˚
waals radii of Sn and O, 3.68 A [32].
thermore, it is noteworthy that a weak intramolecular
Snꢀ ꢀ ꢀO interaction is recognized between the Sn1 and
the O2 derived from the monodentate carboxyl group.
Besides, it should be noted that the component
Ph3Sn(SC6H4CO2)Ph3Sn crystallizes with two solvent
molecules of EtOH, but it has not been found the obvi-
ous interactions between the Ph3Sn(SC6H4CO2)Ph3Sn
moiety and the solvent molecules.
˚
The Sn1ꢀ ꢀ ꢀO2 distance [3.151(4) A], which is longer than
˚
that of 11 [2.737(4) A], is considerably less than the sum
˚
of the van der waals radii (3.68 A) [32]. Thus, if the weak
Sn1ꢀ ꢀ ꢀO2 interaction is considered, the geometry of Sn1
2.4.4. [Me3Sn(SC6H4COO)Me3Sn]2 Æ(4,40-bipy) (13)
The molecular structure of complex 13 is shown in
Fig. 6, selected bond lengths and angles are given in Ta-
ble 6. The asymmetric unit of 13 was found to consist of
one-half of the tetranuclear molecule, the remainder
being generated by an inversion center at the midpoint
is best described as distorted octahedron.
2.5. Supramolecular structures
As shown in Fig. 7, a pair of intermolecular O–Hꢀ ꢀ ꢀO
hydrogen bonds are recognized, which associate the

3038
C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
dimers of compelx 6 are further linked by intermolecu-
lar C–Hꢀ ꢀ ꢀO hydrogen bonds. As shown in Fig. 8(b),
the C18 atom acts as a hydrogen-bond donor via
H18C atom to carboxyl O3B atom, and the C18B atom
also acts as a hydrogen-bond donor via H18B atom to
carboxyl O3, so forming a centrosymmetric macrocycle
with a head-to-tail arrangement [35]. The Cꢀ ꢀ ꢀO and
Hꢀ ꢀ ꢀO distances and the C–Hꢀ ꢀ ꢀO angle are 3.608 and
˚
2.677 A and 163.57ꢁ, which is consistent with that
Fig. 7. Dimer structure of the complex 3, showing intermolecular
O–Hꢀ ꢀ ꢀO hydrogen bonding.
reported in 2-nitrophenoxyacetanilide (Cꢀ ꢀ ꢀO =
˚
˚
3.5006(15) A, HÆO = 2.55 A, C–Hꢀ ꢀ ꢀO = 162ꢁ) [36]. De-
spite these weak C–Hꢀ ꢀ ꢀO interactions often being ne-
glected, they clearly govern these self-assembly of the
molecules into 1D chain (Fig. 8(b)).
discrete molecule into a dimer. This is similar to that
found in Au(Et3P)(4-SC6H4CO2H) [10]. The Oꢀ ꢀ ꢀO
and Hꢀ ꢀ ꢀO distance and the O–Hꢀ ꢀ ꢀO angle are 2.644
The two molecules of complex 7 also form a macro-
cyclic dimer (Fig. 9(a)), which is similar to that found
in complex 6. The dimers of complex 7 are linked by
two intermolecular C–Hꢀ ꢀ ꢀO hydrogen bonds, one a lit-
tle weaker than the other. The stronger one
˚
and 1.829 A and 171.99ꢁ, respectively.
As shown in Fig. 8(a), through the dimerization of
the two molecules of complex 6, the two benzoic acid
units become stacked on top of each other, however,
the phenylene rings are not coplanar and have a distance
˚
˚
(C25Aꢀ ꢀ ꢀO1C = 3.276 A,
H25Aꢀ ꢀ ꢀO1C = 2.568 A,
˚
between their centers of 3.9575 A, which is a little short-
er than that found in Au(Ph3P)(4-SC6H4CO2H)
C25A–H25Aꢀ ꢀ ꢀO1C = 133.30ꢁ) forms a chain of rings
(Fig. 9(b)), which is similar to that found in complex
6. Besides, these dimers of complex 7 are linked by the
˚
(4.041 A) [10]. The carboxylic acid end groups are able
˚
to engage in parallel paired hydrogen bonding with an-
other molecular unit. The distance between the stacked
˚
hydrogen-bonded systems is 3.8705 A, and thus a little
shorter than the distance between the stacked phenylene
units. In total, the complex 6 forms dimer through a
large elongated macrocycle comprising two tin atoms
and two pairs of 4-sulfanylbenzoic acid groups. These
longer one [C22Aꢀ ꢀ ꢀO4C = 3.423 A, H22Aꢀ ꢀ ꢀO4C =
˚
2.636 A, C22A–H22Aꢀ ꢀ ꢀO4C = 142.77ꢁ], also forming
a chain of rings [Fig. 9(c)]. Therefore, a 2D network
(Fig. 9(d)) has been found in complex 7.
The intermolecular C@O ! Sn coordination in 9
leads to infinite zigzag chains containing the metal cen-
ters and carboxyl groups (Fig. 10(a)), which is similar to
Fig. 8. The supramolecular structure of the complex 6, showing (a) macrocyclic dimer and (b) 1D chain of rings connected by intermolecular
O–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀO hydrogen bonding.

C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
3039
Fig. 10. Suparmolecular structure of complex 9, showing (a) polymer
propagation via O!Sn coordination and (b) additional inter-chain
C–Hꢀ ꢀ ꢀO hydrogen bonding.
Fig. 9. Supramolecular structure of complex 7, showing (a) macrocy-
clic dimer, (b) 1D chain of rings along a axis, (c) 1D chain of rings
along b axis and (d) a 2D network in ab plane.
another organotin that has been reported [28]. Further-
more, the O atoms of the carboxyl groups and the C
˚
atoms of methyl groups interconnect at 3.499 A, so
forming intermolecular C–Hꢀ ꢀ ꢀO hydrogen bonds
˚
˚
(C11ꢀ ꢀ ꢀO1 = 3.499 A,
H11ꢀ ꢀ ꢀO1 = 2.706 A,
C11–
H11ꢀ ꢀ ꢀO1 = 140.24ꢁ). This structural feature leads to
an expansion of the supramolecular structure of 9 to a
2D network (Fig. 10(b)).
The supramolecular structure of 11 is dominated by
one-dimensional helical polymer (Fig. 11) along the b
Fig. 11. Supramolecular structure of complex 11, showing a hical
chain along c connected by intermolecular C–Hꢀ ꢀ ꢀS hydrogen bonds.

3040
C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
Fig. 12. Supramolecular structure of complex 13, showing 1D chain of rings connected by intermolecular C–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀS hydrogen bonding.
aixs linked by intermolecular hydrogen bonds C–Hꢀ ꢀ ꢀS
3.2. Syntheses
˚
˚
(C11Aꢀ ꢀ ꢀS1 = 3.821 A, H11Aꢀ ꢀ ꢀS1 = 2.957 A, C11A–
H11Aꢀ ꢀ ꢀS1 = 155.18ꢁ). The ꢁpitchꢀ of the helix
3.2.1. Me3Sn[S(C6H4CO2H)] (1)
˚
(9.991 A) is large shorter than that found in 4-[2-(trieth-
The reaction was carried out under nitrogen atmo-
sphere. The 4-sulfanylbenzoic acid (0.154 g, 1 mmol)
was added to the solution of benzene 20 ml with sodium
ethoxide (0.068 g, 1 mmol), and the mixture was stirred
for 10 min, then added Me3SnCl (0.199 g, 1 mmol) to
the mixture, continuing the reaction for 12 h at 40 ꢁC.
After cooling down to the room temperature, the solu-
tion was filtered. The solvent of the filtrate was gradu-
ally removed by evaporation under vacuum until solid
product was obtained. The solid was then recrystallized
from ether. Colorless crystal was formed. Yield: 85%.
m.p. 98–100 ꢁC. Anal. Calc. for C10H14O2SSn: C,
˚
ylstannyl)tetrazol-5-yl] pyridine (40 A) [37], which is
possibly due to the different molecular conformation
and bonding mode between the two complexes.
The salient feature of the supramolecular structure of
complex 13 is that of a 1D polymer linked by intermolec-
ular C–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀS hydrogen bonds. As shown in
Fig. 12, a 14-membered ring is formed by two intermolec-
˚
ular C–Hꢀ ꢀ ꢀO (C14Aꢀ ꢀ ꢀO2C = 3.195 A, H14Aꢀ ꢀ ꢀO2C =
˚
2.469 A, C14A–H14Aꢀ ꢀ ꢀO2C = 134.95ꢁ) hydrogen
bonds with a head-to-tail arrangement. Besides, the
˚
adjacent intermolecular C–Hꢀ ꢀ ꢀS (C18ꢀ ꢀ ꢀS1C = 3.755 A,
1
˚
H18ꢀ ꢀ ꢀS1C = 2.959 A, C18–H18ꢀ ꢀ ꢀS1C =144.62ꢁ) hydro-
37.89; H, 4.45. Found: C, 37.80; H, 4.38%. H NMR
gen bonds also form similar 32-membered ring. Thus,
intermolecular quadruplex hydrongen bonds have been
found in complex 13, which help the construction of con-
centric annular structure. To our knowledge, this similar
structure has not been reported so far.
(CDCl3, ppm): d 10.55 (s, 1H) 7.23–7.38 (m, 4H), 0.75
(s, 9H). IR (KBr, cmꢁ1): 2980, 1725, 545, 520, 312.
3.2.2. (n-Bu)3Sn[S(C6H4CO2H)] (2)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.068 g, 1 mmol) and (n-Bu)3SnCl (0.326 g, 1 mmol),
reaction time 12 h, temperature 40 ꢁC. Recrystallized
from ether–petroleum. Colorless crystal was formed.
Yield: 78%. m.p. 70–72 ꢁC. Anal. Calc. for
C19H32O2SSn: C, 51.49; H, 7.28. Found: C, 51.50; H,
3. Experimental
3.1. Materials and measurements
1
Trimethyltin chloride, tri-n-butyltin chloride, triphe-
nyltin chloride, dimethyltin dichloride, di-n-butyltin
dichloride, diphenyltin dichloride and 4-sulfanylbenzoic
acid were commercially available, and they were used
without further purification. Tribenzyltin chloride and
dibenzyltin dichloride were prepared by a standard
method reported in the literature [38]. The melting
points were obtained with Kofler micro melting point
apparatus and are uncorrected. Infrared spectra were
recorded on a Nicolet-460 spectrophotometer using
KBr discs and sodium chloride optics. 1H NMR spectra
were obtained on a JEOL-FX-90Q spectrometer, chem-
ical shifts were given in ppm relative to Me4Si in CDCl3
solvent. Elemental analyses were performed with a PE-
2400II apparatus.
7.32%. H NMR (CDCl3, ppm): d 10.48 (s, 1H) 7.25–
7.38 (m, 4H), 0.84–1.71 (m, 27H). IR (KBr, cmꢁ1):
3100, 1720, 548, 526, 308.
3.2.3. Ph3Sn[S(C6H4CO2H)] (3)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.068 g, 1 mmol) and Ph3SnCl (0.385 g, 1 mmol), reac-
tion time 12 h, temperature 40 ꢁC. Recrystallized from
hexane-dichloromethane. Colorless crystal was formed.
Yield: 80%. m.p. 178–180 ꢁC. Anal. Calc. for
C25H20O2SSn: C, 59.67; H, 4.01. Found: C, 59.71; H,
1
3.98%. H NMR (CDCl3, ppm): d 10.58 (s, 1H) 7.18–
7.37 (m, 4H), 7.46–7.79 (m, 15H). IR (KBr, cmꢁ1):
3000, 1718, 546, 519, 310.

C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
3041
3.2.4. (PhCH2)3Sn[S(C6H4CO2H)] (4)
from ether–petroleum. Colorless crystal was formed.
Yield: 83%. m.p. 128–130 ꢁC. Anal. Calc. for
C22H28O4S2Sn: C, 49.00; H, 5.23. Found: C, 48.95; H,
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.068 g, 1 mmol) and (PhCH2)3SnCl (0.427 g, 1 mmol),
reaction time 12 h, temperature 40 ꢁC. Recrystallized
from dichloromethane. Colorless crystal was formed.
Yield: 75%. m.p. 134–136 ꢁC. Anal. Calc. for
C28H26O2SSn: C, 61.67; H, 4.81. Found: C, 61.77; H,
1
5.25%. H NMR (CDCl3, ppm): d 10.46 (s, 2H) 7.20–
7.37 (m, 8H), 0.86–2.12 (m, 18H). IR (KBr, cmꢁ1):
2955, 1715, 550, 525, 315.
3.2.7. Ph2Sn[S(C6H4CO2H)]2 (7)
1
4.86%. H NMR (CDCl3, ppm): d 10.52 (s, 1H) 7.30
(m, 4H), 6.88–7.15 (m, 15H), 2.78 (s, 6H). IR (KBr,
The synthesis procedure was the same as 1. 4-Sulfanyl-
benzoic acid (0.308 g, 2 mmol), sodium ethoxide (0.136 g,
2 mmol) and Ph2SnCl2 (0.344 g, 1 mmol), reaction time
12 h, temperature 45 ꢁC. Recrystallized from ether–
petroleum. Colorless crystal was formed. Yield: 75%.
m.p. 168–170 ꢁC. Anal. Calc. for C26H20O4S2Sn: C,
cmꢁ1): 3015, 1722, 538, 513, 307.
3.2.5. Me2Sn[S(C6H4CO2H)]2 (5)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.308 g, 2 mmol), sodium ethoxide
(0.136 g, 2 mmol) and Me2SnCl2 (0.220 g, 1 mmol),
reaction time 12 h, temperature 40 ꢁC. Recrystallized
from ether–petroleum. Colorless crystal was formed.
Yield: 88%. m.p. 124–126 ꢁC. Anal. Calc. for
C16H18O4S2Sn: C, 34.74; H, 3.28; N, 20.26. Found: C,
1
53.91; H, 3.48. Found: C, 53.88; H, 3.54%. H NMR
(CDCl3, ppm): d 10.57 (s, 2H) 7.20–7.33 (m, 8H), 7.46–
7.79 (m, 10H). IR (KBr, cmꢁ1): 3005, 1724, 548, 529, 309.
3.2.8. (PhCH2)2Sn[S(C6H4CO2H)]2 (8)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.308 g, 2 mmol), sodium ethoxide
(0.136 g, 2 mmol) and (PhCH2)2SnCl2 (0.372 g,
1 mmol), reaction time 12 h, temperature 40 ꢁC. Recrys-
tallized from ether–petroleum. Colorless crystal was
formed. Yield: 80%. m.p. 102–104 ꢁC. Anal. Calc. for
C28H24O4S2Sn: C, 55.37; H, 3.98. Found: C, 55.35; H,
1
34.84; H, 3.23; N, 20.07%. H NMR (CDCl3, ppm): d
10.54 (s, 2H) 7.26–7.40 (m, 8H), 1.42 (s, 6H). IR
(KBr, cmꢁ1): 2900, 1710, 543, 517, 305.
3.2.6. (n-Bu)2Sn[S(C6H4CO2H)]2 (6)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.308 g, 2 mmol), sodium ethoxide
(0.136 g, 2 mmol) and (n-Bu)2SnCl2 (0.304 g, 1 mmol),
reaction time 12 h, temperature 40 ꢁC. Recrystallized
1
3.99%. H NMR (CDCl3, ppm): d 10.52 (s, 2H) 7.17–
7.42 (m, 8H), 6.82–7.05 (m, 10H), 3.52 (s, 4H). IR
(KBr, cmꢁ1): 3058, 1716, 548, 524, 310.
Table 7
Crystal, data collection and structure refinement parameters for 3, 6, 7, 9, 11 and 13
Complex
3
6
7
9
11
13
Empirical formula
Formula weight
Crystal system
Space group
C
25H20O2SSn
C22H28O6S2Sn
539.25
C26H20O4S2Sn
579.23
C13H22O9SSn2
479.75
C47H46O4SSn2
944.28
C36H52N2O4S2Sn4
1115.68
Triclinic
503.16
Triclinic
P1
Triclinic
P1
Triclinic
P1
Monoclinic
C2/c
Monoclinic
P21/n
P1
Unit cell dimension
˚
a (A)
˚
9.814(5)
10.125(5)
12.241(6)
92.304(6)
111.864(6)
94.615(6)
2
8.76(3)
10.16(3)
14.33(4)
100.06(5)
99.63(6)
100.01(5)
2
8.868(2)
12.138(3)
12.318(3)
96.992(3)
100.824(2)
102.045(4)
2
12.820(5)
9.807(4)
29.454(11)
90
18.204(4)
9.991(2)
26.030(6)
90
7.4323(15)
10.086(2)
15.183(3)
99.911(3)
99.809(3)
95.607(3)
1
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
Z
90.503(4)
90
107.148(3)
90
8
2.804
2
1.189
Absorption coefficient
(mmꢁ1
1.249
1.252
1.215
2.385
)
Crystal size (mm)
Dc (g cmꢁ3
0.49 · 0.45 · 0.39 0.42 · 0.29 · 0.24 0.31 · 0.19 · 0.15 0.47 · 0.39 · 0.25 0.53 · 0.42 · 0.19 0.43 · 0.37 · 0.15
)
1.489
2.02–25.03
1.480
2.08–25.03
1.537
1.71–25.03
1.721
2.61–25.02
1.3 87
2.34–25.03
1.691
2.07–25.03
h range for data
collection (ꢁ)
Reflections collected
5843
3905 (0.0116)
5776
6661
9228
22,686
5772
Unique reflections (Rint
Data/restraints/parameters 3905/0/263
)
4053 (0.1090)
4053/10/262
R1 = 0.0776,
wR2 = 0.0997
R1 = 0.2626
wR2 = 0.1381
4383 (0.0214)
4383/0/298
R1 = 0.0385
wR2 = 0.1064
R1 = 0.0609
wR2 = 0.1223
3275 (0.0301)
3275/0/163
R1 = 0.0396
wR2 = 0.1177
R1 = 0.0489
wR2 = 0.1242
7929 (0.0361)
7929/25/490
R1 = 0.0411
wR2 = 0.0955
R1 = 0.0771
wR2 = 0.1148
3808 (0.0157)
3808/0/217
R1 = 0.0302
wR2 = 0.0661
R1 = 0.0458
wR2 = 0.0754
Final R indices
[I > 2r(I)]
R indices (all data)
R1 = 0.0278
wR2 = 0.0724
R1 = 0.0336,
wR2 = 0.0776

3042
C. Ma et al. / Journal of Organometallic Chemistry 690 (2005) 3033–3043
3.2.9. Me3Sn(SC6H4CO2)Me3Sn (9)
3.3. X-ray crystallography
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.136 g, 2 mmol) and Me3SnCl (0.398 g, 2 mmol), reac-
tion time 12 h, temperature 40 ꢁC. Recrystallized from
ether. Colorless crystal was formed. Yield: 80%. m.p.
128–130 ꢁC. Anal. Calc. for C13H22O2SSn2: C, 32.54;
Crystals were mounted in Lindemann capillaries un-
der nitrogen. All X-ray crystallographic data were col-
lected on a Bruker SMART CCD 1000 diffractometer
with graphite monochromated Mo Ka radiation
˚
(k = 0.71073 A) at 298(2) K. A semi-empirical absorp-
1
H, 4.62. Found: C, 32.55; H, 4.59%. H NMR (CDCl3,
tion correction was applied to the data. The structure
was solved by direct methods using SHELXL-97 and re-
fined 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 7.
ppm): d 7.15–7.40 (m, 4H), 0.70–0.75 (m, 18H). IR
(KBr, cmꢁ1): 1665, 1465, 547, 522, 313.
3.2.10. (n-Bu)3Sn(SC6H4CO2)(n-Bu)3Sn (10)
The synthesis procedure was the same as 1. 4-Sulfanyl-
benzoic acid (0.154 g, 1 mmol), sodium ethoxide (0.136 g,
2 mmol) and (n-Bu)3SnCl (0.652 g, 2 mmol), reaction
time 12 h, temperature 40 ꢁC. Recrystallized from
ether–petroleum. Colorless crystal was formed. Yield:
76%. m.p. 83–85 ꢁC. Anal. Calc. for C31H58O2SSn2: C,
4. Supplementary material
Crystallographic data (excluding structure factors)
for the structure analysis of the compounds have been
deposited with the Cambridge Crystallographic Data
Center, CCDC No. 260185 3, 260183 6, 260182 7,
260181 9, 260184 11 and 260186 13. Copies of these
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://www.ccdc.cam.ac.uk).
1
50.85; H, 7.98. Found: C, 50.90; H, 7.99%. H NMR
(CDCl3, ppm): d 7.15–7.28 (m, 4H), 0.83–1.61 (m, 54H).
IR (KBr, cmꢁ1): 1628, 1438, 557, 528, 316.
3.2.11. Ph3Sn(SC6H4CO2)Ph3SnÆ2EtOH (11)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.136 g, 2 mmol) and Ph3SnCl (0.770 g, 2 mmol), reac-
tion time 12 h, temperature 45 ꢁC. Recrystallized from
ether. Colorless crystal was formed. Yield: 85%. m.p.
186–188 ꢁC. Anal. Calc. for C47H46O4SSn2: C, 59.78;
Acknowledgment
1
H, 4.91. Found: C, 59.75; H, 4.99%. H NMR (CDCl,
We thank the National Natural Science Foundation
of China (20271025) and the Natural Science Founda-
tion of Shandong Province for financial support.
ppm): d 7.16–7.38 (m, 4H,C6H4), 7.44–7.69 (m, 30H).
IR (KBr, cmꢁ1): 1634, 1477, 562, 530, 310.
3.2.12. (PhCH2)3Sn(SC6H4CO2)(PhCH2)3 (12)
The synthesis procedure was the same as 1. 4-Sulfa-
nylbenzoic acid (0.154 g, 1 mmol), sodium ethoxide
(0.136 g, 2 mmol) and (PhCH2)3SnCl (0.854 g, 2 mmol),
reaction time 12 h, temperature 40 ꢁC. Recrystallized
from dichloromethane. Colorless crystal was formed.
Yield: 70%. m.p. 180–182 ꢁC. Anal. Calc. for
C49H46O2SSn2: C, 62.85; H, 4.95. Found: C, 62.77; H,
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7.28 (m, 8H), 6.85–7.13 (m, 36H), 0.68–0.77 (s, 36H).
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