A supramolecular assembly of organotin complexes: Syntheses, characterization and crystal structures of organotin complexes with meso-2,3-dimercaptosuccinic acid

Article abstract of DOI:10.1002/ejic.200600169

A series of two types of organotin complexes, namely [(R ₃Sn)₄(dmsa)] (R = Ph 1, PhCH₂ 2, CH₃ 3, nBu 4; H₄dmsa = meso-2,3-dimercaptosuccinic acid) and [(R ₂Sn)₂(dmsa)(Y)]·L (R =

Full text of DOI:10.1002/ejic.200600169

FULL PAPER
DOI: 10.1002/ejic.200600169
A Supramolecular Assembly of Organotin Complexes: Syntheses,
Characterization and Crystal Structures of Organotin Complexes with
meso-2,3-Dimercaptosuccinic Acid
Chunlin Ma*[a,b] and Qingfu Zhang[a]
Keywords: S ligands / Self-assembly / Supramolecular chemistry / Tin
A series of two types of organotin complexes, namely [(R3Sn)4- with a metal-organic framework structure. The supramolec-
(dmsa)] (R = Ph 1, PhCH2 2, CH3 3, nBu 4; H4dmsa = meso-
2,3-dimercaptosuccinic acid) and [(R2Sn)2(dmsa)(Y)]·L (R =
Ph, Y = 2H2O, L = H2O, Et2O 5; R = PhCH2 6; R = CH3 7; R
= nBu 8; R = nBu, Y = 0.5MeOH 9) have been synthesized.
All complexes were characterized by elemental analysis and
FT-IR and NMR (1H, 13C and 119Sn) spectroscopy. Among
them, the strucrtures of complexes 1, 3, 5, and 9 were also
determined by X-ray crystallography. The structural analyses
show that complexes 1 and 3 are tetranuclear triorganotin
monomers, complex 5 is a dinuclear diphenyltin monomer,
and complex 9 is a 3D di-n-butyltin coordination polymer
ular structure analyses reveal that the type of organic substit-
uent attached to the tin atoms can apparently affect the
supramolecular assembly: when the substituents attached to
the tin atom are aromatic groups (1 and 5) the supramolec-
ular structures are dominated by intermolecular π–π (C–H···π)
weak interactions, whereas when the substituents attached
to the tin atom are alkyl groups (3 and 9) the supramolecular
structures are dominated by intermolecular SnǟX (X = S, O)
coordination interactions.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
tallic complexes[6–9] because the supramolecular structures
of such complexes can be more rationally controlled by tail-
oring the type and number of organic substituents attached
to the metal center. Among these complexes, organotin
complexes are attracting more and more attention due to
their wide industrial applications and antitumor activi-
ties,[10] as well as their interesting and varied supramolec-
ular structures.[7–9] In our previous work, we have also re-
ported several interesting supramolecular structures as-
sembled from organotin complexes.[9] To continue our re-
search in this area, we selected another interesting ligand −
meso-2,3-dimercaptosuccinic acid (H4dmsa). This ligand
was chosen based on the following considerations: first,
both the carboxy and thiol groups in this ligand can form
strong covalent bonds with the organotin moiety, thus pro-
viding sufficient thermodynamic stability for them to be
stable in the solid state, including toward corrosive sub-
stances such as oxygen and water; second, H4dmsa is a
polyfunctional chelate ligand with two carboxy and two
thiol groups, so it has a rich coordination chemistry and
can help to construct multidimensional coordination poly-
mers by acting as a multidentate bridging linker; third, the
conformational flexibility of this ligand will allow for the
formation of various and interesting molecular and supra-
molecular structures; fourth, H4dmsa can bond more than
one organotin moiety in one discrete molecule, which will
increase the opportunities for supramolecular assembly
from these complexes through intermolecular weak interac-
tions between substituents (such as π–π interactions); fifth,
Introduction
Recently, the design and self-assembly of metal com-
pounds into one-, two-, or three-dimensional supramolec-
ular architectures has been attracting considerable attention
due to their potential applications and intriguing architec-
tures.[1–9] Two main lines of study are adopted, based on
the different nature and bonding energy of the interactions
responsible for networking, namely (i) frameworks com-
prised of metal centers and di- or polydentate ligands con-
nected through chemical (covalent or coordination) bonds,
which have been widely studied in the crystal engineering
of microelectronic, nonlinear optical, ferromagnetic, and
catalytic materials,[2,3] (ii) networks derived by the assembly
of mono- or polynuclear metal complexes through intermo-
lecular weak interactions such as hydrogen bonds, π–π in-
teractions, electrostatic interactions, and so on, where it has
been found that these weak interactions play vital roles in
highly efficient and specific biological reactions and are es-
sential for molecular recognition and the self-organization
of molecules in supramolecular chemistry.[4,5]
Both systems mentioned above have recently been widely
investigated in the supramolecular chemistry of organome-
[a] Department of Chemistry, Liaocheng University,
Liaocheng 252059, People’s Republic of China
Fax: +86-538-671-5521
E-mail: macl@lctu.edu.cn
[b] Taishan University,
Taian 271021, People’s Republic of China
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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A Supramolecular Assembly of Organotin Complexes
FULL PAPER
H4dmsa is a simple linear ligand without a complicated in- nBu Y = 0.5MeOH 9). All complexes were characterized by
ner structure, which makes it easy to analyze the electronic elemental analysis and FT-IR and NMR (1H, 13C, and
and steric influence of the organic substituents attached to 119Sn) spectroscopy. The structures of complexes 1, 3, 5,
the tin atom on the supramolecular structure. In addition, and 9 were also determined by X-ray crystallography.
although H4dmsa is a mercapto-containing, water-soluble,
nontoxic, orally administered metal chelator that has been
used as an antidote to heavy metal (lead, mercury, arsenic,
Results and Discussion
and cadmium) toxicity for more than 50 years,[11] few metal
complexes with this ligand have been determined by X-ray
Syntheses
crystallography so far.[12] Recently, we began to treat
H4dmsa with organotin compounds with the hope of ob-
Complexes 1–4 were obtained by reaction of H4dmsa/
taining interesting supramolecular structures by assembly EtONa/R3SnCl in a 1:4:4 molar ratio in toluene/methanol
of this polyfunctional ligand with different organotin com- (5:1) at 40 °C, while complexes 5–8 were obtained by reac-
pounds. Here we report the detailed syntheses of eight new tion of H4dmsa/R2SnO in a 1:2 molar ratio in toluene/
organotin complexes of meso-2,3-dimercaptosuccinic acid methanol (5:1) at reflux. Crystals of complex 9 were ob-
of two types: [(R3Sn)4(dmsa)] (R = Ph 1, PhCH2 2, CH3 3, tained by solvothermal reaction of H4dmsa/KOH/R3SnCl
nBu 4) and [(R2Sn)2(dmsa)(Y)]·L (R = Ph Y = 2H2O L = in a 1:4:4 molar ratio in methanol/water (2:1) at 150 °C.
H2O, Et2O 5; R = PhCH2 6; R = CH3 7; R = nBu 8; R = The synthetic procedures are shown in Scheme 1.
Scheme 1.
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C. Ma, Q. Zhang
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Spectroscopic Studies
IR
from the ligand to the metal atom. Although at least two
different types of carboxy groups are present, only one sin-
gle resonance is observed for the CO2 group in the 13C spec-
tra. A possible reason for this is that either accidental mag-
netic equivalence of the carbonyl carbon atoms occurs or
the separation between the sets of resonance is too small to
be resolved.
The main feature in the IR spectra of complexes 1–9 is
the absence of bands in the region 3120–2980 and 2560–
2410 cm–1, which appear in the free ligand as CO2H and SH
stretching vibrations, thus indicating metal–ligand bonding
through these sites. The typical absorptions for Sn–C, Sn–
O, and Sn–S vibrations in complexes 1–9 are all located in
the normal range of similar organotin complexes.[13,14]
IR spectroscopy can provide useful information concern-
ing the coordination of the carboxyl groups in organotin
carboxylates.[15,16] When the carboxylic group coordinates
the tin atom in a monodentate manner (mode I), the differ-
The 119Sn NMR spectroscopic data show two signals for
complexes 1–4 (δ = –95.1, –125.5 ppm for 1; δ = –93.5,
–118.8 ppm for 2; δ = –96.4, –121.6 ppm for 3; δ = –98.2,
–126.1 ppm for 4) and both of them are in the normal range
for four-coordinate tin complexes,[17] thus indicating the
existence of two different coordination environments
around the tin atoms for complexes 1–4 in solution, which
is similar to that found in the complexes [(Ph3Sn)2(p-
mpspa)] and [(Ph3Sn)2(cpa)].[18] The 119Sn NMR spectro-
scopic data of complexes 5–8 (δ = –150.2, –165.8, –175.7,
and –173.8 ppm for 5–8, respectively) show signals in the
normal range for five-coordinate tin complexes.[17] How-
ever, complex 9 shows two signals at δ = –126.8 and
–170.5 ppm, which are in the range corresponding to the
coordination number 5 (δ = –90 to –190 ppm),[17] thus it
can reasonably be assumed that there are also two different
coordination environments around the tin atoms of com-
plex 9 in solution.
ence between the wavenumbers of the asymmetric and sym-
–
metric carboxylic stretching bonds, ∆ν [∆ν = ν(ν CO ) –
˜
˜
˜
as
2
–
ν(ν CO )], is larger than that observed for ionic complexes.
˜
s
2
When the ligand chelates (mode II), ∆ν is considerably
˜
smaller than that for ionic complexes, while in the asymmet-
ric bidentate coordination mode the value is in the range
characteristic of monodentate coordination. The character-
istic wavenumber difference for mode III is larger than that
for chelating groups and nearly the same as that observed
for ionic complexes (Scheme 2).
Crystal Structures
X-ray Crystallographic Study of 1 and 3
Crystals of 1 suitable for an X-ray crystallography study
were grown from dichloromethane, while crystals of 3 were
grown from diethyl ether. The most relevant crystallo-
graphic data for 1 and 3 are summarized in the Experimen-
tal Section. Selected bond lengths and bond angles for 1
and 3 are given in Tables 1 and 2, respectively.
Scheme 2. Different coordination modes of the carboxylate group.
Based on the above results, it was possible to distinguish
–
the coordination mode of the CO2 group. The magnitude
of ∆ν (about 242–268 cm–1) for 1–6, compared with that for
˜
the corresponding sodium salts, reveals that the carboxylate
ligands are monodentate, while the value of about 200 cm–1
for 7–9 suggests a bidentate coordination mode. The con-
clusions drawn from the IR data are consistent with the X-
ray crystallography study.
Table 1. Selected bond lengths and angles for complex 1.
Bond lengths [Å]
Sn1–C3
Sn1–C15
Sn1–O1
Sn2–C21
Sn2–C33
Sn2–O2
C1–O2
2.122(5)
2.114(4)
2.071(3)
2.152(4)
2.130(5)
2.849(3)
1.224(5)
Sn1–C9
Sn1–S1
Sn1–O2
Sn2–C27
Sn2–S1
C1–O1
C2–S1
2.135(5)
2.4373(13)
2.838(3)
2.154(5)
2.4373(13)
1.294(5)
1.820(4)
NMR
The 1H NMR spectra show the expected integration and
peak multiplicities. In the spectra of the free ligand, the res-
onances observed at δ Ϸ 10.50 and 1.65 ppm, which are
absent in the spectra of the complexes, indicate removal of
the CO2H and SH protons and formation of Sn–O and Sn–
S bonds. This conclusion accords well with the IR data.
Bond angles [°]
C3–Sn1–C15
C15–Sn1–O1
C3–Sn1–C9
C9–Sn1–O1
C15–Sn1–O2
C21–Sn2–C33
C33–Sn2–S1
C21–Sn2–O2
S1–Sn2–O2
120.23(18)
107.00(15)
110.86(19)
101.51(15)
92.38(14)
114.72(18)
116.78(13)
84.33(14)
70.10(7)
C3–Sn1–O1
C9–Sn1–O2
C9–Sn1–C15
C3–Sn1–O2
O1–Sn2–O2
C21–Sn2–S1
C27–Sn2–O2
C33–Sn2–O2
C21–Sn2–C27
C27–Sn2–S1
108.67(15)
150.50(14)
106.90(18)
76.02(14)
50.53(10)
114.09(12)
164.38(14)
77.37(14)
108.08(18)
95.68(13)
1
Moreover, the H NMR spectroscopic data show that the
chemical shifts of the phenyl groups in complexes 1 and 5
(δ = 7.36–7.79 ppm), the methyl groups in complexes 3 and
7 (δ = 0.84–0.91 ppm), and the methylene groups connected
directly to the tin atom in complexes 2, 4, 6, 8, and 9 (δ =
1.25–3.26 ppm) undergo an upfield shift relative to those of
their precursors.
C27–Sn2–C33
104.74(18)
The 13C NMR spectra of all compounds show a signifi-
cant downfield shift of all carbon resonances compared
A perspective view of the molecular structure of complex
with the free ligand because of an electron-density transfer 1 is shown in Figure 1. Complex 1 is a tetranuclear tin moi-
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A Supramolecular Assembly of Organotin Complexes
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Table 2. Selected bond lengths and angles for complex 3.
Bond lengths [Å]
Sn1–C3
Sn1–C5
Sn1–O2
Sn2–C7
Sn2–S1
C1–O1
C2–S1
2.100(6)
2.114(6)
3.092(3)
2.130(6)
2.4384(13)
1.296(5)
1.834(4)
Sn1–C4
Sn1–O1
Sn2–C6
Sn2–C8
Sn2–O2
C1–O2
2.105(6)
2.095(3)
2.121(7)
2.125(7)
3.164(4)
1.212(5)
Bond angles [°]
C3–Sn1–C4
C4–Sn1–C5
C4–Sn1–O1
C6–Sn2–C7
C7 –Sn2–C8
C7–Sn2–S1
121.6(3)
115.1(3)
101.01(18)
116.0(3)
108.4(3)
111.30(19)
C3–Sn1–C5
C3–Sn1–O1
C5–Sn1–O1
C6–Sn2–C8
C6–Sn2–S1
C8–Sn2–S1
117.4(3)
100.3(2)
92.84(19)
109.8(3)
111.5(2)
98.3(2)
ety containing two symmetrical (Ph3Sn)2(SCHCO2) moie-
ties (inversion center: –x+2, –y+1, –z). Each tin atom in
complex 1 forms four primary bonds: three from the phenyl
C atoms and one from the O (for Sn1) or S (for Sn2) atom
of the bridging ligand. The bond angles around the Sn1
and Sn2 atoms range from 101.51(15) to 120.23(18)° and
Figure 1. Molecular structure of complex 1 (all hydrogen atoms
have been omitted for clarity).
from 95.68(13) to 116.78(13)°, respectively, suggesting ap- H8···Cg1 = 112.67°; C6···Cg2 = 3.752, H6···Cg2 = 2.867 Å,
parent distortion from an ideal tetrahedron. The Sn1–O1 C6–H6···Cg2 = 159.41°) are close to those found in bis(N-
(2.071 Å) and Sn2–S1 [2.4373(13) Å] distances are in the pyridoxy--amino acidato)cobalt(III) complexes,[23] thereby
normal range for Sn–O[19] and Sn–S[20] covalent bonds. suggesting they are strong enough to assemble these tetra-
There are also two weak intramolecular Sn···O interactions nuclear tin molecules into a 2D network in the solid state.
in complex
1
[Sn1–O2
=
2.838(3) and Sn2–O2
=
A perspective view of the molecular structure of 3 is
2.849(3) Å]. Although these distances are considerably shown in Figure 2. Complex 3 is also a tetranuclear tin moi-
longer than the normal Sn–O covalent bond, they lie in ety containing two symmetrical (Me3Sn)2(SCHCO2) moie-
the range of Sn···O distances of 2.61–3.02 Å that have been ties (inversion center: x, 1–y, –1/2+z). The molecular struc-
confidently reported for intramolecular bonds.[21] As the ture of 3 is similar to that of 1, so we will not deal with
oxygen atoms of the carboxylate groups in complex 1 are many structural details here. However, a comparison of the
involved in weak coordination interactions with the tin molecular conformations and configurations of complexes
atoms along one of the tetrahedral faces, the structural dis- 1 and 3 should be noted: first, the two intramolecular
tortion for the tin atoms in 1 is best described as a capped Sn···O weak interactions (Sn1···O2 = 3.092, Sn2···O2 =
tetrahedron.
3.165 Å) in complex 3 are weaker than in 1 and are out
Analysis of the supramolecular structure in the crystal of the range of typical intramolecular Sn–O bonds (2.61–
lattice of 1 reveals that weak intermolecular C–H···π inter- 3.02 Å).[21] Therefore, these distances are almost sufficient
actions play important roles in the supramolecular arrange- to make this oxygen atom stereochemically inactive around
ments. The C–H···π interaction can also be viewed as an the two Sn atoms; second, the Sn2 atom in complex 3 dis-
edge-to-face (as opposed to point-to-face or T-shaped) π–π plays a distorted tetrahedral coordination sphere, with six
interaction, and now is usually assigned to non-conven- angles ranging from 98.3(2) to 116.0(3)°. The bond angles
tional weak hydrogen bonds.[5c,5g] Although this interaction around Sn1 (from 92.84 to 121.6°) show a larger deviation
is much weaker than covalent and coordinative interactions, from the ideal value for a tetrahedron (109.5°), thereby indi-
and even than typical hydrogen bonds (such as O–H···O cating that there may be intermolecular contacts around
and N–H···O etc.), it clearly governs the supramolecular as- Sn1 in the crystal lattice (vide infra). Finally, all the Sn–C
sembly in many compounds.[5g,22] In complex 1, a series of and covalent Sn–O and Sn–S bonds around each tin atom
parallel molecular chains connected by weak intermolecular in complex 3 are unremarkable, as expected.
C8–H8···Cg1 interactions (Cg1 is the centroid of the phenyl
To our surprise, the common intermolecular C=OǞSn
ring C9–C14) is found along the horizontal direction. Inter- interactions that can give rise to either polymeric or cyclo-
estingly, these parallel molecular chains are further inter- oligomeric structures in trimethyltin compounds[24] are not
linked by weak intermolecular C6–H6···Cg2 interactions found in complex 3. In fact, the supramolecular structure
(Cg2 is the centroid of phenyl ring C27–C32) to form a 2D of complex 3 is a 2D network linked by weak intermo-
network structure in the defined plane (see Figure S1 in the lecular SnǟS coordination interactions. As shown in Fig-
Supporting Information). These C–H···π interactions in ure 3, the asymmetric unit of complex 3 is linked by weak
complex 1 (C8···Cg1 = 3.270, H8···Cg1 = 3.860 Å, C8– intermolecular Sn1···S1 coordination interactions along the
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C. Ma, Q. Zhang
FULL PAPER
methyltin.[25] If the weak Sn···S interaction is also consid-
ered, the coordination environment around the Sn1 atom
in complex 3 can best be described as a distorted trigonal
bipyramid.
X-ray Crystallographic Study of 5 and 9
Crystals of 5 suitable for an X-ray crystallography study
were grown from dichloromethane/diethyl ether, while crys-
tals of 9 were obtained from the mother liquor of the solvo-
thermal reaction. The most relevant crystallographic data
for 5 and 9 are summarized in the Experimental Section.
Selected bond lengths and bond angles for 5 and 9 are given
in Tables 3 and 4, respectively.
Table 3. Selected bond lengths and angles for complex 5.
Bond lengths [Å]
Figure 2. Molecular structure of complex 3.
Sn1–C11
Sn1–O1
Sn1–O5
Sn2–C17
Sn2–O6
2.11(2)
2.37(1)
2.443(6)
2.16(2)
2.406(7)
Sn1–C5
Sn1–S1
Sn2–C23
Sn2–O3
Sn2–S2
2.13(2)
2.416(4)
2.130(9)
2.36(1)
b and c axes to form a 2D layer with a 24-membered cavity
in the bc plane. Although the loose cavities provided by
these intermolecular Sn–S weak coordination interactions
are large enough (7.525×11.265 Å) and are not completely
filled by the methyl groups on the tin atoms that protrude
into the interior, there are no solvent molecules in these
cavities. This is not surprising in view of the fact that pack-
ing of such layers along the a axis produces a genuine no-
cavity structure in the crystal lattice of complex 3 (see Fig-
ure S2 in the Supporting Information). Although the weak
intermolecular Sn···S coordination distance in complex 3 is
2.413(4)
Bond angles [°]
C5–Sn1–C11
C5–Sn1–S1
C17–Sn2–C23
C17–Sn2–S2
121.7(7)
116.8(5)
118.7(6)
116.5(6)
C11–Sn1–S1
O1–Sn1–O5
C23–Sn2–S2
O3–Sn2–O6
118.4(6)
167.2(3)
122.2(3)
167.3(3)
A perspective view of the molecular structure of 5 is
3.286 Å, it still falls in the range proposed for secondary shown in Figure 4. The [(Ph2Sn)2(dmsa)·2H2O] asymmetric
Sn···S coordination bonds (2.79–3.81 Å)[6] and is even close unit is a dinuclear tin moiety with two coordinated water
to the C=S···Sn distance [3.2274(8) Å] found in (5- molecules. The [(Ph2Sn)2(dmsa)] moiety contains two five-
mercapto-3-phenyl-1,3,4-thiadiazoline-2-thionato)tri- membered SnSCCO chelate metallacycles with an envelope
Figure 3. Supramolecular structure of complex 3 showing the 2D network linked by intermolecular Sn1···S1 coordination interactions
(dotted line).
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Table 4. Selected bond lengths and angles for complex 9.[a]
Bond lengths [Å]
Sn1–C9
Sn1–O1
Sn1–S1
Sn2–C21
Sn2–O8B
Sn3–C25
Sn3–O5
Sn3–S3
2.125(18)
2.156(13)
2.394(5)
2.08(2)
2.186(9)
2.081(18)
2.183(10)
2.389(4)
2.138(18)
2.241(9)
Sn1–C13
Sn1–O9
Sn2–C17
Sn2–O3
Sn2–S2
Sn3–C29
Sn3–O4
Sn4–C33
Sn4–O2A
Sn4–S4
2.12(2)
2.264(15)
2.104(182)
2.234(10)
2.408(4)
2.138(19)
2.259(9)
2.09(2)
Sn4–C37
Sn4–O7
2.239(11)
2.402(4)
Bond angles [°]
C9–Sn1–C13
C13–Sn1–S1
C17–Sn2–C21
C21–Sn2–S2
C25–Sn3–C29
C29–Sn3–S3
C33–Sn4–C37
C37–Sn4–S4
125.0(10)
C9–Sn1–S1
O1–Sn1–O9
C17–Sn2–S2
119.5(6)
167.3(5)
114.5(6)
115.2(8)
125.4(8)
119.2(5)
123.5(9)
117.0(7)
118.1(9)
127.4(6)
O3–Sn2–O8A 164.4(4)
C25–Sn3–S3
O4–Sn3–O5
C33–Sn4–S4
O7–Sn4–O2B
119.3(6)
162.5(4)
114.4(7)
163.6(4)
Figure 4. Molecular structure of complex 5.
[a] Symmetry codes: A: x–1/2, –y+1/2, z–1/2; B: x, –y, z+1/2.
conformation, which is similar to the anion of the dior-
A perspective view of the molecular structure of 9 is
ganotin carboxylate [(nPr)3NH][Me2Sn(µ2-SCH2COO)C- shown in Figure 5; for clarity, the somewhat disordered β,
l].[26] Each tin atom in complex 5 is a five-coordinate trigo- γ and δ carbon atoms of the butyl groups have been omit-
nal bipyramid, with two phenyl groups and the sulfur atom ted. The structure analysis for 9 reveals that it is a 3D
of dmsa occupying the equatorial plane and one of the car- metal-organic framework constructed by the S-shaped
boxyl oxygen atoms (O1 or O3) and one coordinated water building block [(nBu2Sn)2(dmsa)]2·MeOH. The S-shaped
molecule (O5 or O6) in axial positions. Because there is a asymmetric unit consists of two [(nBu2Sn)2(dmsa)] moieties
strong (O,S) chelate effect (O1–Sn1–S1 = 78.64°, O3–Sn2– and one coordinated MeOH molecule. Interestingly, every
S2 = 78.75°), the corresponding axial–Sn–axial angles two five-membered SnSCCO chelate metallacycles in the
(167.20° for Sn1 and 167.24° for Sn2) and equatorial angles asymmetric unit that are connected by the same dmsa li-
(116.80°, 118.40°, 121.69° for Sn1 and 116.51°, 118.67°, gand, such as pSn1 and pSn2, pSn3 and pSn4,[28] are not
122.15° for Sn2) suggest the geometries of both tin atoms coplanar (dihedral angles between pSn1 and pSn2 and pSn3
in complex 5 are distorted trigonal pyramids. The two coor- and pSn4 are 71.51° and 60.69°, respectively), while pSn2,
dinative Sn–OH2 bonds (Sn1–O5 = 2.443, Sn2–O6 = pSn3, and the bridging O4 atom are almost in the same
2.406 Å) are slightly longer than the corresponding covalent plane (largest deviation: 0.071 Å; mean deviation: 0.035 Å).
Sn–O bonds (Sn1–O1 = 2.367, Sn2–O2 = 2.360 Å) and are Each [(nBu2Sn)2(dmsa)] moiety in complex 9 also contains
in the range of known Sn–OH2 bonds [2.14(3)– two five-membered SnSCCO chelate metallacycles, similar
2.47(2) Å].[27] Both Sn–O (Sn1–O1 = 2.367, Sn2–O2 = to those found in complex 5. The coordination environment
2.360 Å) and Sn–S (Sn1–S1 = 2.415, Sn2–S3 = 2.413 Å) around each tin atom in complex 9 is also distorted trigo-
bond lengths are close to those found in diorganotin car- nal-bipyramidal, with the equatorial positions occupied by
boxylates and thiolates.[9a] In addition, there are co-crys- two n-butyl groups and one thiol sulfur atom from the
tallized water and diethyl ether molecules in complex 5.
dmsa ligand and the axial positions shared by one coordi-
The supramolecular structure of complex 5 is dominated nated oxygen atom from the dmsa ligand and an additional
by a 1D helical molecular chain along the c axis linked by Lewis base, which may be a solvent molecule (for Sn1) or
intermolecular C–H···π (C3–H3···Cg3, Cg3 is the centroid an intermolecular C=OǞSn bond (for Sn2, Sn3, and Sn4).
of phenyl C5–C10) weak hydrogen-bonding interactions The corresponding axial–Sn–axial skeletons are bent (rang-
(see Figure S3 in the Supporting Information); the pitch of ing from 162.51° to 167.51°; av. 164.53°) due to the strong
this helix (13.337 Å) is longer than that found in (Ph3Sn)2- chelate effect of the O and S atoms (O–Sn–S chelate angles
(SC6H4CO2) (9.991 Å).[20b] The corresponding C3···Cg3, ranging from 80.31° to 82.68°; av. 81.36°), which is similar
H3···Cg3, and C3–H3···Cg3 values (3.866 Å, 3.019 Å, and to that found in complex 5. All the Sn–S and Sn–O dis-
145.31°) in complex 5 are close to the C–H···π values in the tances lie in the range 2.389(4)–2.408(4) and 2.156(13)–
CH4/C6H6 system[5g] but larger than that found in complex 2.259(9) Å, respectively, except for Sn1–O9, which is consis-
1, which is in good agreement with theoretical calculations tent with the situation reported in other organotin com-
that predict that C–H···π interactions in aliphatic/aromatic pounds.[9a,29] Moreover, the solvent-coordinated Sn–O
systems are weaker than in aromatic/aromatic systems.[5g]
bond (Sn1–O9) is only 2.264(15) Å, which is close to the
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C. Ma, Q. Zhang
FULL PAPER
corresponding covalent Sn–O bond [Sn1–O1 = 2.156(13) Å]
formed with carboxylate groups (the difference between
these two Sn–O bonds is only 0.108 Å) and shorter than
that found in [(Me3Sn)(TMA)]·2MeOH (2.462 and
2.586 Å),[9b] thus showing the strong coordinative interac-
tions between guest methanol molecules and the host
framework.
The supramolecular structure of complex 9 is a 3D
metal-organic framework built by {[(nBu2Sn)2(dmsa)]2·
MeOH} units. As shown in Figure 6a, each {[(nBu2Sn)2-
(dmsa)]2·MeOH} unit is linked by intermolecular C=OǞSn
¯
coordination interactions along the 110 and 011 directions,
thus forming a 2D layer with 53-membered organotin rings
in the defined plane. Furthermore, these layers are linked
to form a 3D framework along the 010 direction to give 56-
membered rhombic channels (Figure 6b). The size of the
53-membered ring channel is 26.83×11.50 Å (transannular
Sn4···Sn4Ј and Sn2···Sn3), while the 56-membered ring
rhombic channels are only 13.551×9.658 Å in size (trans-
annular Sn4···Sn4ЈЈ and Sn2Ј···Sn3Ј). The solvent methanol
molecules reside in the 53-membered ring channels because
Figure 5. Molecular structure of complex 9 (the β, γ, and δ carbon
atoms of the butyl groups on the tin atom have been omitted for
clarity).
they are strongly coordinated to the framework Sn1 atoms. work are believed to be responsible for the formation of
A strong H-bonding interaction is also found between the the framework structure. It is worth mentioning here that,
methanol molecule and the framework oxygen atom O9 although the channels in this complex are ostensibly large
(O9···O6 = 2.525 Å). These coordinating and H-bonding in- enough to capture the guest methanol molecules, they con-
teractions between the methanol molecules and the frame- stitute only 4.3% of the crystal volume and are almost com-
Figure 6. a) 2D “wall-like” layer and b) 3D metal-organic framework of complex 9. The O–H···O hydrogen bonds between guest methanol
molecules and the host organotin framework are shown with a broken line (the n-butyl groups on the tin atoms have been omitted for
clarity).
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A Supramolecular Assembly of Organotin Complexes
FULL PAPER
pletely filled by the butyl groups on the tin atoms that pro- molecular aggregation in crystal engineering of organome-
trude into the interior (if nBu groups are omitted they con- tallic complexes.
stitute up to 69.7%; see Figure S4, Supporting Infor-
mation).[30] This is apparently different to ionic complexes
Experimental Section
with a 3D open-framework structure, such as [{Mn(dcbp)}·
2H2O]n (dcbp = 4,4Ј-dicarboxylato-2,2Ј-bipyridine)[31] and
Materials and Measurements: Commercially available starting ma-
terials and solvents were used. Tribenzyltin chloride,[33]dimethyltin
[Co(bix)2(H2O)2](SO4)·7H2O [bix = 1,4-bis(imidazol-1-yl-
oxide, and dibenzyltin oxide[34]were prepared by standard methods
methyl)benzene],[32] which all have a large pore aperture for
reported in the literature. The melting points were obtained with a
guest molecules (18.2% and 27%, respectively) and show
Kofler micro-melting point apparatus and are uncorrected. IR
spectra were recorded with a Nicolet-460 spectrophotometer using
reversible “desorption-adsorption” processes.
The TGA of 9 shows a continuous weight loss (found:
2.7%) from 77 to 135 °C, which is attributed to the loss of
guest methanol molecules (calcd. 2.5%); the host frame-
work is stable up to 280 °C, at which point decomposition
starts. However, during thermal treatment under vacuum
the crystal lattice collapses at relatively low temperatures
(Ͻ 100 °C). X-ray crystallography proved that the crystal-
line 3D framework is transformed into an amorphous mate-
rial, which is similar to that found in the organotin complex
[{(nBu)2Sn(2,5-pdc)(H2O)}3·3H2O·yEtOH]n.[8a] To evaluate
the porosity of this material, crystals of 1 were thermally
treated for a period of 1 h (100 °C at 10 Torr) and then ex-
posed to vapors of H2O, EtOH, MeOH, and NH3. In all
cases no solvent molecules were found by elemental analysis
KBr discs and sodium chloride optics. 1H, 13C, and 119Sn NMR
spectra were recorded with a Varian Mercury Plus 400 spectrome-
ter operating at 400, 100.6, and 149.2 MHz, respectively. The spec-
tra were acquired at room temperature (298 K) unless otherwise
specified; 13C NMR spectra were broadband-proton-decoupled.
The chemical shifts are reported in ppm with respect to the refer-
ences and are quoted relative to external tetramethylsilane (TMS)
1
for H and 13C NMR, and to neat tetramethyltin for 119Sn NMR
spectroscopy. Elemental analyses were performed with a PE-2400II
apparatus.
[(Ph3Sn)4(dmsa)] (1): This reaction was carried out under nitrogen.
meso-2,3-Dimercaptosuccnic acid (0.182 g, 1 mmol) and sodium
ethoxide (0.272 g, 4 mmol) were added to a mixed solution of tolu-
ene and methanol (5:1) in a Schlenk flask and stirred for 0.5 h.
After the addition of triphenyltin chloride (1.542 g, 4 mmol), the
mixture was stirred at 40 °C for 12 h and then filtered. The solvent
was gradually removed by evaporation under vacuum until a solid
product was obtained. This solid was then recrystallized from
dichloromethane to give colorless crystals of 1. Yield: 1.294 g
(82%). M.p. 212–214 °C. C76H62O4S2Sn4 (1578.1): calcd. C 57.84,
1
or integration of the H NMR spectrum in CD3COCD3,
thus showing the irreversibility of the removal of the en-
clathrated guest molecule within the host framework. This
is well in agreement with the crystal structure analysis.
H 3.96, S 4.06; found C 57.75, H 4.05, S 4.00. IR (KBr): ν =
˜
1594 cm–1 ν(COO)as, 1352 ν(COO)s, 560 ν(Sn–C), 447 ν(Sn–O), 320
Conclusions
1
ν(Sn–S). H NMR (CDCl3): δ = 4.25 (s, 2 H, CH), 7.46–7.79 (m,
60 H, C6H5) ppm. 13C NMR (CDCl3): δ = 53.1, 128.1, 129.3, 136.5,
148.6, 177.4 ppm. 119Sn NMR (CDCl3): δ = –95.1, –125.5 ppm.
In summary, a series of organotin complexes based on
meso-2,3-dimercaptosuccinic acid have been synthesized.
All complexes were characterized by elemental analysis and
FT-IR and NMR (1H, 13C and 119Sn) spectroscopy. The
structures of complexes 1, 3, 5, and 9 have also been deter-
mined by X-ray diffractomety. Both the spectra and crystal
structures show that when meso-2,3-dimercaptosuccinic
acid reacts with triorganotin compounds it can form tetra-
nuclear monomers, whereas when it reacts with diorganotin
compounds it can form dinuclear monomers or 3D poly-
mers with a metal-organic framework structure.
The supramolecular structures described in this paper
demonstrate that the type of substituent attached to the tin
atom has an influence on the supramolecular arrangement:
when the groups attached to the tin atom are aromatic
groups (1 and 5), the supramolecular structures are domi-
nated by intermolecular C–H···π weak interactions, whereas
when the groups attached to the tin atom are alkyl groups
(3 and 9), the supramolecular structures are dominated by
intermolecular SnǟX (X = S, O) coordination interactions.
In diorganotin complexes, it also shows that the number of
solvent molecules coordinated to the tin atom is crucial for
[{(PhCH2)3Sn}4(dmsa)] (2): Complex 2 was prepared in the same
way as compound 1, by adding tribenzyltin chloride (1.710 g,
4 mmol) to meso-2,3-dimercaptosuccinic acid (0.182 g, 1 mmol)
and sodium ethoxide (0.272 g, 4 mmol). The solvent was gradually
removed by evaporation under vacuum until a solid product was
obtained. Yield: 1.484 g (85%). M.p. 200–202 °C. C88H86O4S2Sn4
(1746.6): calcd. C 60.51, H 4.96, S 3.70; found C 60.55, H 5.00, S
3.75. IR (KBr): ν = 1595 cm–1 ν(COO)as, 1358 ν(COO)s, 575 ν(Sn–
˜
1
C), 438 ν(Sn–O), 335 ν(Sn–S). H NMR (CDCl3): δ = 3.24 (s, 24
H, CH2), δ = 4.25 (s, 2 H, CH), 7.25–8.05 (m, 60 H, C6H5) ppm.
13C NMR (CDCl3): δ = 34.8, 54.2, 126.6, 128.7, 129.7, 134.2, 135.0,
176.3 ppm. 119Sn NMR (CDCl3): δ = –93.5, –118.8 ppm.
[(Me3Sn)4(dmsa)] (3): Complex 3 was prepared in the same way as
compound 1, by adding trimethyltin chloride (0.800 g, 4 mmol) to
meso-2,3-dimercaptosuccinic acid (0.182 g, 1 mmol) and sodium
ethoxide (0.272 g, 4 mmol). The solvent was gradually removed by
evaporation under vacuum until a solid product had formed. The
solid was then recrystallized from ethanol to give colorless crystals
of 3. Yield: 0.733 g (88%). M.p. 108–110 °C. C16H38O4S2Sn4
(833.34): calcd. C 23.06, H 4.60, S 7.69; found C 23.10, H 4.65, S
7.65. IR (KBr): ν = 1598 cm–1 ν (COO), 1360 νs(COO), 583 ν(Sn–
˜
as
1
C), 476 ν(Sn–O), 357 ν(Sn–S). H NMR (CDCl3): δ = 0.84 (s, 36
the supramolecular assembly. This contribution adds se- H, CH3), 4.25 (s, 2 H, CH) ppm. 13C NMR (CDCl3): δ = –5.0, 2.5,
53.4, 175.5 ppm. 119Sn NMR (CDCl3): δ = –96.4, –121.6 ppm.
veral new features to the fast developing field of supramo-
lecular chemistry and aids the fundamental understanding
of molecular recognition and systematic rationalization of compound 1, by adding tri-n-butyltin chloride (1.302 g, 4 mmol)
[(nBu3Sn)4(dmsa)] (4): Complex 4 was prepared in the same way as
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3251

C. Ma, Q. Zhang
FULL PAPER
to meso-2,3-dimercaptosuccinic acid (0.182 g, 1 mmol) and sodium
ethoxide (0.272 g, 4 mmol). The solvent was gradually removed by
evaporation under vacuum until a solid product was obtained.
temperature, the solvent was removed under vacuum to give 7 as a
colorless solid. Yield: 0.418 g (88%). M.p. 221–223 °C.
C8H14O4S2Sn2 (475.74): calcd. C 20.20, H 2.97, S 13.48; found C
Yield: 1.137 g (85%). M.p. 152–154 °C. C52H110O4S2Sn4 (1338.4): 20.25, H 3.00 S 13.55. IR (KBr): ν = 1635 cm–1 νas(COO), 1326
˜
calcd. C 46.70, H 8.25, S 4.75; found C 46.66, H 8.28, S 4.79. IR
νs(COO), 543 ν(Sn–C), 480 ν(Sn–O), 345 ν(Sn–S). 1H NMR
(KBr): ν = 1590 cm–1 νas(COO), 1358 νs(COO), 575 ν(Sn–C), 450 (CDCl3): δ = 0.91 (s, 12 H), 4.27 (s, CH) ppm. 13C NMR (CDCl3):
˜
3
ν(Sn–O), 365 ν(Sn–S). 1H NMR (CDCl3): δ = 0.92 (t, JH,H
=
δ = –0.6, 54.8, 177.5 ppm. 119Sn NMR (CDCl3): δ = –175.7 ppm.
7.2 Hz, 36 H, CH3), 1.25–1.71 (m, 72 H, CH2CH2CH2), 4.27 (s, 2
H) ppm. 13C NMR (CDCl3): δ = 13.4, 25.8, 26.5, 27.0, 54.0,
177.2 ppm. 119Sn NMR (CDCl3): δ = –98.2, –126.1 ppm.
[(nBu)2Sn]2(dmsa) (8): Complex 8 was prepared in the same way as
complex 5, by refluxing (nBu)2SnO (0.498 g, 2 mmol) and meso-
2,3-dimercaptosuccinic acid (0.182 g, 1 mmol). After cooling to
room temperature, the solvent was removed under vacuum to give
8 as a colorless product. Yield: 0.515 g (80%). M.p. 310–312 °C.
C20H38O4S2Sn2 (644.1): calcd. C 37.30, H 5.95, S 9.96; found C
[(Ph2Sn)2(dmsa)(2H2O)]·H2O·Et2O (5): A mixture of meso-2,3-di-
mercaptosuccinic acid (0.182 g, 1 mmol) and Ph2SnO (0.580 g,
2 mmol) in toluene/methanol (5:1) was refluxed in a Dean–Stark
trap for 10 h. After cooling to room temperature, the solvent was
removed under vacuum to give 5 as a colorless solid. This solid
was then recrystallized from diethyl ether to give colorless crystals
37.32, H 5.80, S 10.00. IR (KBr): ν = 1632 cm–1 νas(COO), 1330
˜
νs(COO), 558 ν(Sn–C), 464 ν(Sn–O), 328 ν(Sn–S). 1H NMR
3
(CDCl3): δ = 0.80–0.93 (t, JH,H = 6.8 Hz, 12 H, CH3), 1.35–1.82
of 5. Yield: 0.732 g (86%). M.p. Ͼ 300°C (dec.). C32H38O8S2Sn2 (m, 24 H, CH2CH2CH2), 4.22 (s, 2 H, CH) ppm. 13C NMR
(852.1): calcd. C 45.10, H 4.50, S 7.55; found C 45.08, H 4.45, S
(CDCl3): δ = 13.5, 25.8, 26.3, 27.5, 52.0, 175.4 ppm. 119Sn NMR
(CDCl3): δ = –173.8 ppm.
7.60. IR (KBr): ν = 1585 cm–1 ν (COO), 1352 νs(COO), 558 ν(Sn–
˜
as
C), 460 ν(Sn–O), 375 ν(Sn–S). 1H NMR (CDCl3): δ = 7.68–7.36
(m, 20 H, C6H5), 4.26 (s, 2 H, CH) ppm. 13C NMR (CDCl3): δ =
51.8, 128.4, 128.8, 131.5, 150.8, 176.5 ppm. 119Sn NMR (CDCl3):
δ = –150.2 ppm.
{[(nBu)2Sn]4(dmsa)2(MeOH)}n (9): A mixture of meso-2,3-dimer-
captosuccinic acid (0.091 g, 0.5 mmol), KOH (0.112 g, 2 mmol), tri-
n-butyltin chloride (0.651 g, 2 mmol), CH3OH (10 mL) and H2O
(5 mL) was heated in a Teflon-lined autoclave at 150 °C for 3 d.
After cooling to room temperature, colorless crystals of 9 were col-
lected and washed with hexane. Yield: 0.280 g (85%). M.p. 298°C
(dec.). C41H81O9S4Sn4 (1320.5): calcd. C 37.30, H 6.11, S 9.72;
[{(PhCH2)2Sn}2(dmsa)] (6): Complex 6 was prepared in the same
way as complex 5, by refluxing (PhCH2)2SnO (0.634 g, 2 mmol)
and meso-2,3-dimercaptosuccinic acid (0.182 g, 1 mmol). After
cooling to room temperature, the solvent was removed under vac-
uum to give 6 as a colorless solid. Yield: 0.647 g (83%). M.p. 205–
207 °C. C32H30O4S2Sn2 (780.13): calcd. C 49.27, H 3.88, S 8.22;
found C 37.25, H 6.20, S 9.70. IR (KBr): ν = 3195 cm–1 νas(OH),
˜
1625, 1555 νas(COO), 1532, 1326 νs(COO), 556 ν(Sn–C) 470 ν(Sn–
1
O), 330 ν(Sn–S). H NMR (CD3COCD3, D2O): δ = 0.82–0.96 (t,
found C 49.30, H 3.85, S 8.20. IR (KBr): ν = 1578 cm–1 νas(COO),
3JH,H = 7.0 Hz, 24 H, CH3), 1.33–1.85 (m, 48 H, CH2CH2CH2),
4.25 (s, 4 H, CH) ppm. 13C NMR (CD3COCD3): δ = 13.8, 25.5,
˜
1
1310 νs(COO), 552 ν(Sn–C), 460 ν(Sn–O), 336 ν(Sn–S). H NMR
(CDCl3): δ = 3.26 (s, 8 H, CH2), 4.27 (s, 2 H, CH), 7.24–7.58 (m, 26.2, 27.1, 52.4, 176.8 ppm. 119Sn NMR (CD3COCD3): δ = –126.8,
20 H, C6H5) ppm. 13C NMR (CDCl3): δ = 56.3, 125.8, 128.7, 129.3, –170.5 ppm.
143.7, 177.1 ppm. 119Sn NMR (CDCl3): δ = –165.8 ppm.
X-ray Crystallography: Crystals were mounted in Lindemann capil-
[(Me2Sn)2(dmsa)] (7): Complex 7 was prepared in the same way as
complex 5, by refluxing Me2SnO (0.330 g, 2 mmol) and meso-2,3-
dimercaptosuccinic acid (0.182 g, 1 mmol). After cooling to room
laries under nitrogen. All X-ray crystallographic data were collected
with a Bruker SMART CCD 1000 diffractometer with graphite-
monochromated Mo-Kα radiation (λ = 0.71073 Å) at 298(2) K. A
Table 5. Crystallographic data for complexes 1, 3, 5, and 9.
Complexes
1
3
5
9
Empirical formula
Formula mass
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C76H62O4S2Sn4
1578.14
C16H38O4S2Sn4
833.34
monoclinic
C2/c
18.556(3)
13.3144(14)
13.0162(14)
90
105.2910(15)
90
C32H38O8S2Sn2
852.12
triclinic
Pna2(1)
9.431(2)
37.063(10)
13.337(4)
90
90
90
C41H80O9S4Sn4
1320.05
monoclinic
Cc
23.733(9)
13.087(5)
18.598(7)
90
102.383(6)
90
triclinic
¯
P1
11.027(2)
12.329(3)
12.733(3)
80.690(3)
86.406(3)
77.944(3)
1669.7(6)
1
α [°]
β [°]
γ [°]
Volume [Å3]
Z
3103.7(7)
4
3.330
4662(2)
4
1.196
5642(4)
4
1.941
Absorption coefficient [mm–1] 1.590
Crystal size [mm]
0.42×0.35×0.19
1.569
0.51×0.43×0.17
1.809
0.31×0.27×0.12
1.214
0.19×0.15×0.12
1.554
Dcalcd. [gcm–3]
θ range for data collection [°] 1.62–25.03
1.91–25.03
7895
2.23–25.01
23091
1.76–25.03
14550
Reflections collected
Unique reflections
Data/restraints/parameters
8855
5842 (Rint = 0.0196)
5842/0/338
2742 (Rint = 0.0306)
2742/0/118
R1 = 0.0286,
wR2 = 0.0669
R1 = 0.0416,
wR2 = 0.0768
8071 (Rint = 0.0794)
8071/610/394
R1 = 0.0882,
wR2 = 0.2255
R1 = 0.1448,
wR2 = 0.2683
7029 (Rint = 0.0553)
7029/141/516
R1 = 0.0525,
wR2 = 0.1159
R1 = 0.1007,
wR2 = 0.1408
R1 = 0.0326,
wR2 = 0.0733
R1 = 0.0560,
wR2 = 0.0886
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
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A Supramolecular Assembly of Organotin Complexes
FULL PAPER
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semiempirical absorption correction 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.
Non-hydrogen atoms were refined anisotropically, while hydrogen
atoms were placed in geometrically calculated positions using a ri-
ding model. Crystal data and experimental details of the structure
determinations are listed in Table 5. The molecular and supramo-
lecular structures in this paper were created with the X-Seed soft-
ware package.[35] CCDC-238964 (1), -254168 (3), -254166 (5), and
-254171 (9) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/
data_request/cif.
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Supporting Information (see footnote on the first page of this arti-
cle): Supromolecular structures of complexes 1, 3, 5, and 9 (Fig-
ures S1–S4).
Acknowledgments
The authors thank the National Natural Science Foundation of
China (20271025) for financial support.
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