Self-assembly of organotin(IV) moieties with the Schiff-base ligands pyruvic acid isonicotinyl hydrazone and pyruvic acid salicylhydrazone: Synthesis, characterization, and crystal structures of monomeric or polymeric complexes

Article abstract of DOI:10.1002/ejic.200500412

A series of organotin(IV) complexes of the type [R₂SnLY] ₂ or [R₂SnL(R₃SnOH)]₂ [L = 4-NC ₅H₄CON₂C(CH₃)CO₂ or 2-HOC₆H₄CON

Full text of DOI:10.1002/ejic.200500412

FULL PAPER
Self-Assembly of Organotin(IV) Moieties with the Schiff-Base Ligands Pyruvic
Acid Isonicotinyl Hydrazone and Pyruvic Acid Salicylhydrazone: Synthesis,
Characterization, and Crystal Structures of Monomeric or Polymeric
Complexes
Handong Yin,*[a] Min Hong,[a] Haolong Xu,[a] Zhongjun Gao,[a] Gang Li,[a] and
Daqi Wang[a]
Keywords: N,O ligands / Self-assembly / Schiff bases / Tin
A series of organotin(IV) complexes of the type [R2SnLY]2 or
[R2SnL(R3SnOH)]2 [L 4-NC5H4CON2C(CH3)CO2 or 2-
coordinate in distorted pentagonal bipyramid geometries, of
which only complex 1 exhibits an asymmetric structure con-
taining two different types of tin atoms. The crystal structure
of 7 exhibits a dimeric structure containing distannoxane
units with two types of tin atoms, in which one tin atom ap-
pears to be seven-coordinate with a distorted pentagonal bi-
pyramid geometry and the other is four-coordinate with a
distorted tetrahedral geometry. A comparison of the IR spec-
tra of the ligands with those of the corresponding complexes
=
HOC6H4CON2C(CH3)CO2, and Y = H2O or CH3OH] have
been synthesized by the condensation reaction of R2SnO (R
= Ph 1, nC8H17 2) or R3SnCl (R = o-ClBz 3, o-FBz 4, p-FBz 5,
p-CNBz 6) with the Schiff-base ligand pyruvic acid isonicoti-
nyl hydrazone in a 1:1 molar ratio or (R3Sn)2O (R = nBu 7, Bz
8, p-CNBz 9) or R3SnCl (R = o-ClBz 10, p-ClBz 11, p-CNBz
12) with the Schiff-base ligand pyruvic acid salicylhydrazone
in a 1:1 molar ratio. All complexes were characterized by ele- reveals that the ligands coordinate to tin in the enol form due
mental analysis and IR, 1H, and 119Sn NMR spectroscopy.
The crystal structures of complexes 1, 2, 3, 7, and 10 have
been determined by X-ray single crystal diffraction analyses,
which show that the tin atoms of 1, 2, 3, and 10 are all seven-
to the disappearance of the bands assigned to the carbonyl
group.
(© Wiley-VCH Verlag GmbH and Co. KGaA, 69451
Weinheim, Germany, 2005)
utilizing their preference for different coordination geome-
try, choice of suitable ligands, and intermolecular interac-
tions such as hydrogen bonding. The details of the struc-
tural and spectroscopic characterization of complexes 1–12
are reported herein. Five of the complexes have been
studied by X-ray diffraction, and reveal that there exist five
different types of coordinated tin atoms (shown in
Scheme 1).
Complexes 2, 3, and 10 are coordinated in mode A, and
each reveals a highly centrosymmetric dimeric structure
containings a distannoxane unit. This is the more usual
structure adopted by this class of complexes.[15,16] It is
worthwhile to note that crystals containing an n-octyl
group were obtained by the reaction of pyruvic acid isonic-
otinyl hydrazone with di-n-octyltin oxide and recrystallized
from acetone, as structural information for complexes con-
taining n-octyl groups was lacking until now. Meanwhile,
to our surprise, we obtained an unusual asymmetric linear
chain polymer complex 1 containing two different types of
tin atom from the reaction of Schiff-base ligand pyruvic
acid isonicotinyl hydrazone with diphenyltin oxide. These
two types of tin atom contain ligands in mode B. One of
the two types is coordinated by tridentate formation of the
Schiff base, while the other is not in the same way due to
Introduction
Schiff bases still play an important role as ligands in me-
tal coordination chemistry even after almost a century since
their discovery.[1–4] Organotin() complexes with Schiff
bases have received increasing attention owing to their anti-
tumor activities and potential applications in biotechnol-
ogy.[5–11] In addition, Schiff base organotin() complexes
are of interest for structural reasons. The coordination
chemistry of some tridentate ONO- and ONS-donor Schiff
bases has been described,[12,13] and we have recently re-
ported some organotin() complexes with the potentially
ONO tridentate Schiff-base ligands salicylideneamino acids
and pyruvic acid isonicotinyl hydrazone.[14,15] As part of
our ongoing project dealing with the study of the interac-
tion of tin() and organotin() species with O-donor and
N-donor ligands, we have now synthesized twelve new or-
ganotin() complexes of pyruvic acid isonicotinyl hydra-
zone and salicylhydrazone by self-assembly of metal ions,
[a] Department of Chemistry, Liaocheng University,
Liaocheng 252059, China
E-mail: handongyin@lctu.edu.cn
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
4572
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200500412
Eur. J. Inorg. Chem. 2005, 4572–4581

Self-Assembly of Organotin() Moieties with Schiff-Base Ligands
FULL PAPER
1595–1608 cm–1 in the spectra of these complexes indicate
the presence of C=N and C=N–N=C groups.[17] The
stretching frequencies of interest are those associated with
the acid COO and the Sn–O and Sn–N groups. The spectra
of all complexes have some common features. The explicit
feature in the infrared spectra of all complexes is the strong
absorption at about 700 cm–1 in the spectra of the com-
plexes, which is absent in the free ligands, which is assigned
to the Sn–O stretching mode of vibration. The weak- or
medium-intensity band in the region 476–486 cm–1 can be
assigned to the Sn–N stretching vibration. All these values
are consistent with those detected in a number of organoti-
n() derivatives.[18,19]
The IR spectra of organotin carboxylate complexes can
provide useful information concerning the coordination be-
havior of the carboxyl groups. The IR spectrum of complex
1 shows that the νas and νas bands are assigned to the re-
gions 1603, 1505 cm–1 and 1366, 1312 cm–1, respectively.
The magnitude of ∆ν [νas(COO) – νs(COO)] is 237 and
193 cm–1, and therefore indicates the presence of mono- and
didentate carboxyl groups.[20] Moreover, the magnitude of
∆ν (231–285 cm–1) for complexes 2–12 indicates that the
carboxylate ligand functions as a monodentate ligand in
these complexes.[20] These conclusions are supported by the
results of X-ray diffraction studies.
NMR Spectra
1
In H NMR spectra of the free ligands, the single reso-
nance for the proton of the -NHN= group is observed at
either δ = 3.75 or 3.89 ppm, and is absent in the spectra of
the complexes, thus indicating deprotonation of the
-NHN= group and confirming that the ligand coordinate
to the tin in the enol form. For complexes 1–6, the spectra
show that the chemical shifts of the protons on the pyridine
ring exhibit two sets of signal in the ranges δ = 7.57–
8.89 ppm, as a doublet, and δ = 7.22–8.13 ppm, also as a
doublet. The coupling constant is equal to 4.80–8.40 Hz.
The Ar-OH resonance appears in the region δ = 10.87–
11.43 ppm, as a singlet, for the complexes 7–12, which
strongly suggests that the phenolic oxygen atoms do not
participate in coordination to the tin atoms; this is quite
different to the four complexes we have reported pre-
viously.[14]
Scheme 1.
coordination between tin and two oxygen atoms derived
from the carboxyl group of the adjacent ligand.
Interestingly, we also succeeded in preparing a novel tet-
ranuclear organotin() complex [(nBu)2Sn{2-HOC6H4-
CON2C(CH3)CO2}{(nBu)3SnOH}]2 (7) by treatment of
[(nBu)3Sn]2O with the Schiff-base ligand pyruvic acid sal-
icylhydrazone in a 1:1 molar ratio, which exhibits a dimeric
structure containing distannoxane units with two types of
tin atoms, of which one tin atom appears to be seven-coor-
dinate with a distorted pentagonal bipyramid geometry and
the other is four-coordinate with a distorted tetrahedral ge-
ometry (mode C).
The 119Sn NMR resonance at around δ = –450 ppm is
characteristic[21] of the seven-coordinate tin atom observed
in the crystalline state for all the complexes. As reported in
Results
the literature,[22–24] values of δ
in the ranges δ = –210
119Sn
to –400, –90 to –190, and 200 to –60 ppm have been associ-
ated with six-, five-, and four-coordinate tin centers, respec-
IR Spectra
119Sn
A remarkable difference between the IR spectra of the tively. On this basis we can conclude that the δ
value
ligands and those of the corresponding complexes is that for the other type of tin atom in 1 is δ = –226.9 ppm in
the stretching vibration bands of the carbonyl group disap- solution, which suggests that the intermolecular Sn–N in-
pear from the spectra of all the complexes. The absence of teraction probably does not survive in solution and that a
the bands assigned to the carbonyls unambiguously con- six-coordinate species is formed. Therefore, it can reason-
firms that the ligands coordinated to the tin are in their ably be assumed that the structure of complex 1 in solution
enol form. The characteristic absorptions at 1622–1640 and is different from that observed in the solid state. For com-
Eur. J. Inorg. Chem. 2005, 4572–4581
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4573

H.-D. Yin, M. Hong, H.-L. Xu, Z.-J. Gao, G. Li, D.-Q. Wang
FULL PAPER
plexes 7–9, the 119Sn chemical shifts (δ = 102.3–111.7 ppm) Table 1. Selected bond lengths [Å] and bond angles [°] for complex
1.
in CDCl3 indicate that there is also a type of four-coordi-
nate tetrahedral tin atom in these complexes.
Sn1–C19
Sn1–C25
Sn1–O3
Sn1–N1
Sn1–O7
Sn1–O1
Sn1–N6#1
C19–Sn1–C25
C19–Sn1–O3
C25–Sn1–N1
C25–Sn1–O7
C19–Sn1–O1
C25–Sn1–O1
N1–Sn1–O1
C19–Sn1–N6#1
O3–Sn1–N6#1
O1–Sn1–N6#1
2.089(15)
2.135(13)
2.221(11)
2.327(11)
2.370(10)
2.387(7)
2.394(9)
176.8(6)
91.5(4)
90.5(5)
87.0(5)
89.5(4)
90.3(5)
Sn2–C31
Sn2–C37
Sn2–O4
Sn2–O6
Sn2–N4
Sn2–O2
Sn2–O1
C31–Sn2–C37
C31–Sn2–O4
C37–Sn2–O6
C37–Sn2–N4
C31–Sn2–O2
C37–Sn2–O2
O6–Sn2–O2
C31–Sn2–O1
O4–Sn2–O1
O2–Sn2–O1
2.116(18)
2.136(14)
2.207(9)
2.210(7)
2.249(12)
2.388(10)
2.594(8)
169.9(6)
93.1(5)
90.1(5)
94.3(5)
83.8(6)
86.2(5)
Description of the Structures
Crystal Structure of {Ph2Sn[4-NC5H4CON2C(CH3)CO2]-
(H2O)}2 (1)
The molecular structure of complex 1 is shown in Fig-
ure 1. Figure 2 shows a particular one-dimensional linear
chain polymeric structure. Selected bond lengths and angles
are listed in Table 1. The crystal structure of complex 1 re-
veals a dinuclear complex containing two types of tin atom
(mode B), where a one-dimensional chain polymeric struc-
ture forms through an interaction between the N atoms of
the pyridine ring and the tin atoms of an adjacent molecule.
66.2(3)
87.8(4)
72.7(4)
151.2(3)
87.8(3)
86.5(5)
77.6(3)
52.2(2)
Both of the tin atoms Sn1 and Sn2 have a seven-coordinate group from an adjacent molecule. The tin atom is sur-
geometry in a distorted pentagonal bipyramidal arrange- rounded by one water molecule, one tridentate pyruvic acid
ment.
isonicotinyl hydrazone ligand, two trans phenyl groups, and
The Sn1 atom is rendered seven-coordinate by coordina- nitrogen atom N6#1 (x – 1/2, –y + 3/2, z). Thus, the atoms
tion of the nitrogen atom N6#1 of the 4-pyridinecarbonyl O1, N1, O3, N6#1, and O7 are coplanar within 0.0263 Å,
Figure 1. Molecular structure of complex 1; ellipsoids shown at the 30% probability level.
Figure 2. Perspective view of the one-dimensional chain of complex 1.
4574
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 4572–4581

Self-Assembly of Organotin() Moieties with Schiff-Base Ligands
FULL PAPER
and form the equatorial plane. While two trans phenyl car- held together by hydrogen bonds (O4···N6#3 and
bon atoms occupy the axial sites, the angle of the axial O8···N3#4). These hydrogen bonds contribute to the crystal
C25–Sn1–C19 is 176.8(6)°, which deviates from the linear stability and compactness and result in a one-dimensional
angle of 180°. These data indicate that the Sn1 atom is in a chain arrangement. It is worthwhile to note that, for or-
distorted pentagonal bipyramid geometry. The intermo- ganotin() complexes containing straight-chain alkyl
lecular Sn1–N6#1 distance of 2.394(9) Å is longer than the groups, there are plenty of n-butyl group complexes, while
sum of the covalent radii of Sn and N (2.15 Å), but con- complexes with n-octyl groups are lacking until now. This
siderably less than the sum of the van der Waals radii
(3.75 Å),[25] therefore it should be considered as a bonding
interaction. In this connection it is relevant to note the Sn–
N bond lengths found in other crystal structures of or-
ganotin complexes containing a pyridinecarboxylate li-
gand.[20,26] For instance, in the dicarboxylate tetraorgano-
stannoxane {[(nBu)2Sn(2-pic)]2O}2 the two Sn–N bond
lengths are 2.550(5) Å and 3.150(5) Å,[26] and in the linear
polymer [(PhCH2)3Sn(OO2CC5H4N-4)] the Sn–N distance
is 2.563 Å.[20]
The Sn2 atom is bonded to the carboxyl oxygens O1 and
O2, with Sn2–O1 and Sn2–O2 bond lengths of 2.594(8) and
2.388(10) Å, respectively. Thus, the Sn2 atom is surrounded
by C31 and C37 of the two trans phenyl groups along the
axial direction while O1, O2, O6, N4, and O4 form the
equatorial plane. The pentagonal bipyramid geometry of
Sn2 is distorted, as indicated by the bonding angles of
169.9(6)°, 93.1(5)°, 90.1(5)°, 142.5(4)°, 95.4(5)°, 83.8(6)°,
157.4(3)° and 86.4(4)° for C31–Sn2–C37, C31–Sn2–O4,
C37–Sn2–O6, O4–Sn2–O6, C31–Sn2–N4, C31–Sn2–O2,
N4–Sn2–O2, and C37–Sn2–O1, respectively.
Crystal Structure of [(nC8H17)2Sn{4-NC5H4CON2C-
(CH3)CO2}(H2O)]2 (2)
Figure 3. Molecular structure of complex 2; ellipsoids shown at the
30% probability level.
The molecular structure of compolex 2 is shown in Fig-
ure 3. Figure S2 shows the packing of the molecule in the
unit cell as seen in projection on the plane. Selected bond
lengths and angles are listed in Table 2. In this complex, the
Sn atom exists in a seven-coordinate environment in which
one water molecule, two tridentate pyruvic acid isonicotinyl
Table 2. Selected bond lengths [Å] and bond angles [°] for com-
plexes 2 and 3.
[(nC8H17)2Sn{4-NC5H4CON2C(CH3)CO2}(H2O)]2 (2)
Sn1–C18
Sn1–C10
Sn1–O3
Sn1–N1
C18–Sn1–C10
C10–Sn1–O3
C18–Sn1–N1
O3–Sn1–N1
C10–Sn1–O1
O3–Sn1–O1
N1–Sn1–O1
C18–Sn1–O4
2.06(3)
2.09(3)
2.219(9)
2.283(16)
164.4(10)
94.2(7)
98.5(8)
70.0(5)
90.1(7)
138.6(4)
68.6(4)
80.8(9)
Sn1–O1
Sn1–O4
Sn1–O5#1
2.340(10)
2.354(13)
2.715(10)
hydrazone ligands, and two trans n-octyl groups coordinate
to each Sn center (mode A). The atoms O1, O5, O4, O3,
and N1 are coplanar within 0.0244 Å, and form the equa-
torial plane. Furthermore, the angle of the axial C18–Sn1–
C10 is 164.4(10)°, which deviates from the linear angle of
180°. These data indicate that the tin atom of this complex
is in a distorted pentagonal bipyramid geometry. The O1
atom of the carboxylate residue also binds the other tin
atom, Sn2, generating an Sn2O2 four-membered ring. The
Sn2–O1#2 (x, y + 1, z) distance [2.745(10) Å] is longer than
that of Sn1–O1 [2.340(10) Å], but is comparable with those
found in related seven-coordinate diorganotin systems.[20,23]
The structure of this complex can therefore be described as
a dimer, and the coordination geometry of tin can be also
described as a trans-C2SnO4N pentagonal bipyramid with
the two n-octyl groups occupying trans positions [C18–Sn1–
C10 = 164.4(10)° and C35–Sn2–C43 = 165.1(8)°]. It also
has intradimer hydrogen bonds [O4···O6 = 2.642 Å and
O3–Sn1–O4
N1–Sn1–O4
O1–Sn1–O4
C10–Sn1–O5#1
O3–Sn1–O5#1
N1–Sn1–O5#1
O1–Sn1–O5#1
O4–Sn1–O5#1
77.4(4)
147.4(4)
143.9(4)
83.9(7)
154.8(4)
135.1(4)
66.6(3)
77.4(3)
[(oClBz)2Sn{4-NC5H4CON2C(CH3)CO2}(H2O)]2 (3)
Sn1–C17
Sn1–C10
Sn1–O3
2.145(9)
2.166(8)
2.180(5)
2.614(5)
165.0(3)
96.2(3)
94.8(3)
70.6(2)
87.3(3)
76.9(2)
Sn1–N1
Sn1–O4
Sn1–O1
2.275(6)
2.323(6)
2.400(5)
Sn1–O1#1
C17–Sn1–C10
C17–Sn1–O3
C10–Sn1–N1
O3–Sn1–N1
C17–Sn1–O4
O3–Sn1–O4
N1–Sn1–O4
C10–Sn1–O1
O3–Sn1–O1
N1–Sn1–O1
C17–Sn1–O1#1
O3–Sn1–O1#1
N1–Sn1–O1#1
O1–Sn1–O1#1
88.1(3)
139.10(18)
68.53(18)
83.0(3)
155.71(15)
133.69(17)
65.19(19)
O8···O2
= 2.661 Å] and interdimer hydrogen bonds
[O4···N6#3 (x – 1/2, –y + 1/2, z) = 2.718 Å and O8···N3#4
(x – 1/2, –y + 3/2, z) = 2.756 Å]. Neighboring molecules are
147.43(19)
Eur. J. Inorg. Chem. 2005, 4572–4581
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4575

H.-D. Yin, M. Hong, H.-L. Xu, Z.-J. Gao, G. Li, D.-Q. Wang
FULL PAPER
Figure 4. Molecular structure of complex 3; ellipsoids shown at the 30% probability level.
is possibly because the n-octyl group chain is so long that groups, and the O5 atom coordinate to each Sn center. The
crystals with it are not easy to form.
Although we abtained complex [(oClBz)2Sn{4- nal plane is 378.16°, so O3, O5, N(1), O1, and O1#1 (–x +
NC5H4CON2C(CH3)CO2}(H2O)]2 (3) by different 2, –y + 2, –z) lie almost in the same plane, with the Sn atom
sum of the angles subtended at the tin atom in the pentago-
a
method, the structure of 3 (Figure 4) is very similar to com- only 0.0062 Å away from the equatorial plane, while the two
plex 2 (mode A), and complex 3 also contains a one-dimen-
sional chain polymer (Figure S2) due to intermolecular hy-
drogen bonds (O–H···N).
Table 3. Selected bond lengths [Å] and bond angles [°] for complex
7.
Sn1–C11
Sn1–C15
Sn1–O3
Sn1–O5
Sn1–O1
Sn1–N1
Sn1–O1#1
O3–C4
C11–Sn1–C15
C11–Sn1–O3
C11–Sn1–O5
O3–Sn1–O5
C11–Sn1–N1
O5–Sn1–O1#1
C11–Sn1–O1
C11–Sn1–O1#1
2.087(12)
2.095(12)
2.188(8)
2.259(9)
2.419(8)
2.324(11)
2.585(7)
1.274(15)
167.5(5)
95.5(4)
87.9(5)
79.7(3)
95.3(4)
77.6(3)
Sn2–O5
Sn2–C19
Sn2–C23
Sn2–C27
N1–C2
N1–N2
N2–C4
O2–O5#1
O5–Sn2–C19
O5–Sn2–C23
C19–Sn2–C23
O5–Sn2–C27
C19–Sn2–C27
C23–Sn2–C27
N1–Sn1–O1
O1–Sn1–O1#1
2.024(9)
2.073(17)
2.088(14)
2.116(17)
1.247(14)
1.345(12)
1.315(17)
2.545
101.6(6)
107.8(5)
113.9(7)
98.9(6)
Crystal Structure of [(nBu)2Sn{2-HOC6H4CON2C(CH3)-
CO2}{(nBu)3SnOH}]2 (7)
The molecular structure is illustrated in Figure 5 and se-
lected bond lengths and angles are listed in Table 3. The
molecular possesses a dimeric structure containing distan-
noxane units with two types of tin atoms (mode C).
The Sn1 atom lies in a distorted pentagonal bipyramidal
coordination environment [Sn1–C11 = 2.087(12) Å, Sn1–
C15 = 2.095(12) Å, Sn1–O3 = 2.188(8) Å, Sn1–O5 =
2.259(9) Å, Sn1–N1 = 2.324(11) Å, Sn1–O1 = 2.419(8) Å,
Sn1–O1#1 = 2.585(7) Å] in which one tridentate pyruvic
acid isonicotinyl hydrazone ligand, two trans n-butyl
116.7(8)
115.2(8)
67.0(3)
87.1(4)
83.3(4)
66.6(3)
Figure 5. Molecular structure of complex 7; ellipsoids shown at the 30% probability level.
4576 www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2005, 4572–4581

Self-Assembly of Organotin() Moieties with Schiff-Base Ligands
FULL PAPER
trans n-butyl carbon atoms take up the axial sites around torted pentagonal bipyramidal coordination environment in
the Sn1 atom; the angle of the axial C11–Sn1–C15 is which one methanol molecule, two tridentate pyruvic acid
167.5(5)°. The O1 atom of the carboxylate residue also salicylhydrazone ligands, and two trans o-chlorobenzyl
binds the other tin atom, Sn1#1, generating an Sn2O2 four- groups coordinate to each Sn center. The atoms O1, O1#1,
membered ring, therefore the structure of this complex can O5, O3, and N1 are coplanar within 0.0334 Å, and form
be described as a dimer.
the equatorial plane. Furthermore, the angles of the axial
The coordination at the tin atom Sn2 is distorted tetrahe- C18–Sn1–C11 is 163.8(4)°, which deviates from the linear
dral, as indicated by bonding angles of 101.6(6)°, 107.8(5)°, angle of 180°. The O1 atom of the carboxylate residue also
113.9(7)°, 98.9(6)°, 116.7(8)°, and 115.2(8)° for O5–Sn2– binds the other tin atom Sn1#1 (–x + 2, –y + 1, z), generat-
C19, O5–Sn2–C23, C19–Sn2–C23, O5–Sn2–C27, C19–Sn2– ing an Sn2O2 four-membered ring. Thereby the molecular
C27, and C23–Sn2–C27, respectively. In this complex, two structure of this compound can be described as a dimer,
different types of tin atom are connected through the bridg- and the coordination geometry of tin can be also described
ing O atom, and intramolecular hydrogen bonds O5– as a trans-C2SnO4N pentagonal bipyramid, with the two o-
H5···O2#1 [2.565(11) Å] and O4–H4···N2 [2.535(15) Å] are chlorobenzyl groups occupying trans positions. From these
also found. The phenolate oxygen atoms do not participate data we can see that the crystal structure of complex 10 is
in coordination to the tin atom.
very similar to those of 2 and 3. Obviously, the nature of
the alkyl group bonding to the Sn center does not exert a
great influence on the overall structural motif. The Sn1–O5
bond length is 2.394(7) Å, which is longer than those in
analogous complexes[20,27] due to the formation of intrad-
imeric hydrogen bonds (O2···O5#1 = 2.583 Å). There are
also strong intramolecular O–H···N hydrogen bonds
(O4···N2 = 2.537 Å) involving atom N2 and the phenolic
hydroxyl oxygen atom O4, which does not coordinate to the
Sn center. Undoubtedly, these hydrogen bonds contribute
to the compactness of the dimer.
Crystal Structure of [(oClBz)2Sn{2-HOC6H4CON2C-
(CH3)CO2}(CH3OH)]2 (10)
The crystal structure of complex 10 is shown in Figure 6.
All hydrogen atoms have been omitted for the purpose of
clarity. Table 4 lists selected bond lengths and angles.
Table 4. Selected bond lengths [Å] and bond angles [°] for complex
10.
Sn1–O3
Sn1–N1
Sn1–O1
Sn1–O5
Sn1–O1#1
C11–Sn1–C18
C11–Sn1–O3
O3–Sn1–N1
C11–Sn1–N1
O3–Sn1–O1
C18–Sn1–O1
N1–Sn1–O1
O3–Sn1–O5
2.138(7)
2.270(9)
2.331(7)
2.394(7)
2.647(7)
163.8(4)
92.9(4)
70.7(3)
95.5(4)
140.4(3)
90.2(4)
69.8(3)
77.5(3)
N1–C2
N1–N2
N2–C4
O1–C1
1.266(15)
1.377(12)
1.304(13)
1.297(12)
1.252(12)
82.6(4)
148.0(3)
142.1(3)
153.8(2)
85.3(3)
Discussion
O3–C4
C11–Sn1–O5
N1–Sn1–O5
O1–Sn1–O5
O3–Sn1–O1#1
C11–Sn1–O1#1
N1–Sn1–O1#1
O1–Sn1–O1#1
O5–Sn1–O1#1
The complexes [R2SnLY]2 and [R2SnL(R3SnOH)]2
(mode A, B, or C) are produced by the reaction between
pyruvic acid isonicotinyl hydrazone and dialkyltin oxide or
triaryltin chloride and pyruvic acid salicylhydrazone and
triaryltin chloride or bis(trialkyltin) oxide, in a 1:1 molar
ratio. It is clear that the presence of the enolic proton of
the ligands leads to the dealkylation of the trialkyltin car-
135.5(3)
65.7(3)
76.4(2)
The crystal structure of 10 is also very similar to that of boxylates [R3Sn{4-NC5H4C(O)NHN=C(CH3)CO2}] and
complex 2. In this complex, the Sn atom exists in a dis- [R3Sn{2-HOC6H4C(O)NHN=C(CH3)CO2}], which are the
Figure 6. Molecular structure of complex 10; ellipsoids shown at the 30% probability level.
Eur. J. Inorg. Chem. 2005, 4572–4581
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4577

H.-D. Yin, M. Hong, H.-L. Xu, Z.-J. Gao, G. Li, D.-Q. Wang
FULL PAPER
Scheme 2.
Scheme 3.
Scheme 4.
www.eurjic.org
4578
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2005, 4572–4581

Self-Assembly of Organotin() Moieties with Schiff-Base Ligands
FULL PAPER
v/v) solution (50 mL) of Ph2SnO (2.0 mmol). The mixture was
heated under reflux with stirring for 6 h. The clear solution thus
obtained was evaporated under vacuum to form a brown solid and
recrystallized from dichloromethane/hexane to give red crystals.
Yield: 78% (113.2 mg). M.p. 165–167 °C. C42H38N6O8Sn2 (992.16):
major products of the reaction of R3SnCl or (R3Sn)2O with
Schiff-base ligands. Seven-coordinate dimers are formed as
a result of steric or solvent effects in the recrystallization.
The crystal-structure determinations show that the struc-
tures of complexes 1–3 are one-dimensional infinite chain
polymers due to intermolecular hydrogen-bond interactions
between the coordinated water molecule and the pyridine
nitrogen atom of the adjacent unit. Complexes 7 and 10,
which contain pyruvic acid salicylhydrazone, are mono-
mers. Their possible reaction mechanisms are shown in
Schemes 2, 3, and 4.
1
calcd. C 50.81, H 3.73, N 8.47; found C 50.73, H 3.69, N 8.52. H
NMR (CDCl3, 400 MHz): δ = 2.66 (s, 6 H, CH3), 5.31 (s, 4 H,
H2O), 7.44–7.79 (m, 20 H, Ph-H), 8.13 (d, J = 6.00 Hz, 4 H, 3,5-
pyridine-H), 8.84 (d, J = 5.20 Hz, 4 H, 2,6-pyridine-H) ppm. 119Sn
NMR (CDCl3): δ = –226.9, –451.0 ppm.
[(nC8H17)2Sn{4-NC5H4CON2C(CH3)CO2}(H2O)]2 (2): Complex 2
was prepared in the same way as complex 1 by adding di-n-octyltin
oxide (2.0 mmol) to pyruvic acid isonicotinyl hydrazone
(2.0 mmol). Unlike the analogous reaction mixtures with di-n-bu-
tyl-[15] or diphenyltin() oxide, crystallization from dichlorometh-
ane/hexane failed to generate the desired crystals of 2, which is the
di-n-octyltin analog of the di-n-butyltin complex.[15] However, when
acetone was used as crystallization solvent colorless crystals of 3
were obtained. Yield: 88% (121.0 mg). M.p. 77 °C. C25H43N3O4Sn
(568.31): calcd. C 52.73, H 7.57, N, 7.39; found C 52.81, H 7.42,
Conclusions
The pyruvic acid hydrazone ligands have been shown to
be able to form monomeric or polymeric complexes. The
nuclearity and stereochemistry are found to be dependent
on the nature of the starting acceptor and the reaction con-
ditions. The ligand chelates to tin atoms, bonding through
the oxygen of the carboxyl or enolic hydroxy group and the
nitrogen atoms. In the polymeric complex, the dimers are
connected through intermolecular hydrogen bonds or inter-
actions between the nitrogen atoms of the pyridine ring and
the tin atoms of an adjacent molecule. The monomeric
complexes possess a highly centrosymmetric dimeric struc-
ture containing a distannoxane unit. The reaction of [(nBu)3-
N 7.35. IR (KBr): ν = 2924 cm–1, 2854 (s, C–H), 1640 (s, C=N),
˜
1606 (s, C=N–N=C), 1619, 1334 (s, CO2), 1207 (s, C–O), 694 (s,
Sn–O), 541 (w, Sn–C), 476 (w, Sn–N). 1H NMR (CDCl3,
400 MHz): δ = 0.85 (t, J = 10.0 Hz, 6 H, CH3), 1.22–1.31 [m, 8 H,
Sn(CH2)2 (α,β)], 1.64–1.75 [m, 20 H, CH2 (ω)], 2.65 (s, 3 H, CH3),
7.99 (d, J = 5.60 Hz, 2 H, 3,5-pyridine-H), 8.77 (d, J = 5.20 Hz, 2
H, 2,6-pyridine-H) ppm. 119Sn NMR (CDCl3): δ = –460.6 ppm.
[(oClBz)2Sn{4-NC5H4CON2C(CH3)CO2}(H2O)]2 (3): Pyruvic acid
Sn]2O with pyruvic acid salicylhydrazone gives a novel tet- isonicotinyl hydrazone (2.0 mmol) and tri-o-chlorobenzyltin chlo-
ride (2.0 mmol) were added to a solution of absolute toluene
(30 mL) and heated under reflux with stirring for 1 h. After the
addition of triethylamine (2.0 mmol) to the reactor, the reaction
mixture was refluxed for 1 h more. The clear solution thus obtained
was evaporated under vacuum to form a white solid and recrys-
tallized from methanol to give colorless crystals. Yield: 81%
(104.8 mg). M.p. 151 °C. C46H42Cl4N6O8Sn2 (1186.0): calcd. C
46.54, H 3.54, N, 7.08; found C 46.66, H 3.51, N 7.05. 1H NMR
(CDCl3, 400 MHz): δ = 2.46 (s, 6 H, CH3), 3.19 (s, 8 H, ArCH2Sn),
7.05–7.54 (m, 16 H, Ar-H), 7.72 (d, J = 6.60 Hz, 4 H, 3,5-pyridine-
H), 8.70 (d, J = 4.80 Hz, 4 H, 2,6-pyridine-H) ppm. 119Sn NMR
(CDCl3): δ = –457.2 ppm.
ranuclear organotin complex, which exhibits a dimeric
structure containing a distannoxane unit with two types of
tin atoms that are seven- or four-coordinate.
Experimental Section
Diphenyltin oxide, di-n-octyltin oxide and bis(tri-n-butyltin) oxide
are commercially available, and were used without further purifica-
tion. The ligands, bis(triaryltin) oxide and triaryltin chloride were
prepared by the methods reported in the literature.[28–30] The melt-
ing points were obtained with a Kolfer micro melting point appara-
tus and are uncorrected. IR spectra were recorded with a Nicolet-
[(oFBz)2Sn{4-NC5H4CON2C(CH3)CO2}]2 (4): Complex 4 was pre-
pared in the same way as 3 by adding tri-o-fluorobenzyltin chloride
(2.0 mmol) to pyruvic acid isonicotinyl hydrazone (2.0 mmol). The
solid was then obtained from methanol. Yield: 80% (90.6 mg). M.p.
145 °C. C46H38F4N6O6Sn2 (1084.24): calcd. C 50.96, H 3.53, N
1
460 spectrophotometer, as KBr discs. H and 119Sn NMR spectra
were recorded with a Mercury Plus-400 NMR spectrometer in
CDCl3. The spectra were acquired at room temperature (298 K)
unless otherwise specified. The chemical shifts are reported in ppm
with respect to the references and are stated relative to external
tetramethylsilane (TMS) for 1H, and to neat tetramethyltin for
119Sn NMR spectroscopy. Elemental analyses were performed with
a PE-2400II elemental analyzer.
7.75; found C 50.84, H 3.48, N 7.88. IR (KBr): ν = 3007 cm–1 (m,
˜
Ar–H), 2937, 2738 (s, C–H), 1622 (s, C=N), 1608 (s, C=N–N=C),
1618, 1334 (s, CO2), 1229 (s, C–O), 694 (s, Sn–O), 480 (w, Sn–N).
1H NMR (CDCl3, 400 MHz): δ = 2.20 (s, 6 H, CH3), 3.15 (s, 8 H,
ArCH2Sn), 6.60–7.27 (m, 16 H, Ph-H), 7.78 (d, J = 5.60 Hz, 4 H,
3,5-pyridine-H), 8.74 (d, J = 5.80 Hz, 4 H, 2,6-pyridine-H) ppm.
119Sn NMR (CDCl3): δ = –456.3 ppm.
Pyruvic Acid Isonicotinyl Hydrazone: This Schiff base was prepared
from isonicotinic acid hydrazide and pyruvic acid in ethanol ac-
cording to the literature.[28] A white powder was obtained. Yield:
95% (864.2 mg). M.p. 222–223 °C. C9H9N3O3 (207.19): calcd. C
48.14, H 5.00, N 18.38; found C 48.00, H 4.89, N 18.67.
[(pFBz)2Sn{4-NC5H4CON2C(CH3)CO2}]2 (5): Complex 5 was pre-
pared in the same way as 3 by adding tri-p-fluorobenzyltin chloride
(2.0 mmol) to pyruvic acid isonicotinyl hydrazone (2.0 mmol). The
solid was then obtained from methanol. Yield: 86% (98.4 mg). M.p.
138 °C. C46H38F4N6O6Sn2 (1084.24): calcd. C 50.96, H 3.53, N
Pyruvic Acid Salicylhydrazone: This Schiff base was prepared from
salicylhydrazide and pyruvic acid in ethanol according to the litera-
ture.[29] White, needle-shaped crystals were obtained. Yield: 80%
(931.6 mg). M.p. 216 °C. C10H10N2O4 (222.19): calcd. C 54.92, H
4.54, N 12.61; found C 54.72, H 4.68, N 12.85.
7.75; found C 50.91, H 3.61, N 7.61. IR (KBr): ν = 3021 cm–1 (s,
˜
Ar–H), 2944 (s, C–H), 1620 (s, C=N), 1605 (m, C=N–N=C), 1617,
1341 (s, CO2), 1233 (s, C–O), 688 (m, Sn–O), 491 (w, Sn–N). 1H
NMR (CDCl3, 400 MHz): δ = 2.25 (s, 6 H, CH3), 3.23 (s, 8 H,
[Ph2Sn{4-NC5H4CON2C(CH3)CO2}(H2O)]2 (1): Pyruvic acid ison-
icotinyl hydrazone (2.0 mmol) was added to a benzene/ethanol (3:1,
Eur. J. Inorg. Chem. 2005, 4572–4581
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4579

H.-D. Yin, M. Hong, H.-L. Xu, Z.-J. Gao, G. Li, D.-Q. Wang
FULL PAPER
ArCH2Sn), 6.63–7.39 (m, 16 H, Ph-H), 7.78 (d, J = 4.80 Hz, 4 H,
3,5-pyridine-H), 8.89 (d, J = 6.40 Hz, 4 H, 2,6-pyridine-H) ppm.
119Sn NMR (CDCl3): δ = –449.8 ppm.
was evaporated under vacuum to form a white solid and recrys-
tallized from methanol to give colorless crystals. Yield: 85%
(111.8 mg). M.p. 131 °C. C50H48Cl4N4O10Sn2 (1244.1): calcd. C
48.27, H 3.89, N, 4.49; found C 48.36, H 3.71, N 4.55. IR (KBr):
[(pCNBz)2Sn{4-NC5H4CON2C(CH3)CO2}]2 (6): Complex 6 was
prepared in the same way as 3 by adding tri-p-cyanobenzyltin chlo-
ride (2.0 mmol) to pyruvic acid isonicotinyl hydrazone (2.0 mmol).
The solid was then obtained from methanol. Yield: 91%
(115.8 mg). M.p. 210 °C. C50H38N10O6Sn2 (1112.3): calcd. C 53.98,
ν = 3417 cm–1 (m, OH), 3021 (m, Ar–H), 2916 (m, C–H), 1618 (m,
˜
C=N), 1603 (s, C=N–N=C), 1586, 1321 (s, CO2), 1209 (m, C–O),
1
677 (m, Sn–O), 525 (w, Sn–C), 465 (w, Sn–N). H NMR (CDCl3,
400 MHz): δ = 1.66 (s, 12 H, CH3), 3.39 (s, 8 H, ArCH2Sn), 6.84–
7.59 (m, 24 H, Ar-H and Ph-H), 8.09 (s, 2 H, R-OH), 11.16 (s, 2
H, Ar-OH) ppm. 119Sn NMR (CDCl3): δ = –445.8 ppm.
H 3.42, N 12.60; found C 53.62, H 3.41, N 12.77. IR (KBr): ν =
˜
3007 cm–1 (m, Ar–H), 2922, 2852 (s, C–H), 1630 (m, C=N), 1619,
1385 (m, CO2), 1602 (m, C=N–N=C), 1200 (m, C–O), 692 (m, Sn–
[(pClBz)2Sn{2-HOC6H4CON2C(CH3)CO2}]2 (11): Complex 11 was
prepared in the same way as 10 by adding tri-p-chlorobenzyltin
chloride (2.0 mmol) to pyruvic acid salicylhydrazone (2.0 mmol).
The solid was then obtained from methanol. Yield: 87%
(115.3 mg). M.p. 144 °C. C48H40Cl4N4O8Sn2 (1179.6): calcd. C
1
O), 540 (w, Sn–C), 478 (w, Sn–N). H NMR (CDCl3, 400 MHz): δ
= 2.42 (s, 6 H, CH3), 3.08 (s, ArCH2Sn), 7.21–7.35 (m, 16 H, Ph-
H), 7.22 (d, J = 8.00 Hz, 4 H, 3,5-pyridine-H), 7.57 (d, J = 8.40 Hz,
4 H, 2,6-pyridine-H) ppm. 119Sn NMR (CDCl3): δ = –453.9 ppm.
48.84, H 3.39, N 4.75; found C 48.91, H 3.47, N 4.62. IR (KBr): ν
˜
[(nBu)2Sn{2-HOC6H4CON2C(CH3)CO2}{(nBu)3SnOH}]2 (7): Py-
ruvic acid salicylhydrazone (1.0 mmol) was added to a benzene sus-
pension (30 mL) of bis(tri-n-butyltin) oxide (1.0 mmol), then the
mixture was stirred and heated at reflux for 6 h. The clear solution
obtained after fliteration was evaporated in vacuo to give a solid,
which was then recrystallized from dichloromethane/hexane to give
colorless crystals. Yield: 83% (71.5 mg). M.p. 101 °C.
C30H54N2O5Sn2 (759.12): calcd. C 47.40, H 7.16, N 3.68; found C
= 3379 cm–1 (s, OH), 3023 (m, Ar–H), 2916 (m, C–H), 1633 (m,
C=N), 1602 (s, C=N–N=C), 1594, 1367 (s, CO2), 1202 (m, C–O),
1
685 (m, Sn–O), 525 (w, Sn–C), 474 (w, Sn–N). H NMR (CDCl3,
400 MHz): δ = 1.66 (s, 6 H, CH3), 3.26 (s, 8 H, ArCH2Sn), 6.26–
7.63 (m, 24 H, Ar-H and Ph-H), 11.18 (s, 2 H, Ar-OH) ppm. 119Sn
NMR (CDCl3): δ = –443.5 ppm.
[(pCNBz)2Sn{2-HOC6H4CON2C(CH3)CO2}]2 (12): Complex 12
was prepared in the same way as 10 by adding tri-p-cyanobenzyltin
chloride (2.0 mmol) to pyruvic acid salicylhydrazone (2.0 mmol).
The solid was then obtained from methanol. Yield: 72% (92.1 mg).
M.p. 215 °C. C52H40N8O8Sn2 (1142.3): calcd. C 54.67, H 3.53, N
47.32, H 7.15, N 3.77. IR (KBr): ν = 3423 cm–1 (m, OH), 2955 (s,
˜
Ar–H), 2922, 2853 (s, C–H), 1627 (m, C=N), 1608, 1334 (s, CO2),
1583 (m, C=N–N=C), 1205 (s, C–O), 672 (m, Sn–O), 560 (w, Sn–
1
C), 502 (w, Sn–N). H NMR (CDCl3, 400 MHz): δ = 0.83 (t, J =
9.81; found C 54.81, H 3.44, N 9.72. IR (KBr): ν = 3411 cm–1 (m,
6.40 Hz, 15 H, CH3), 1.19–1.61 (m, 30 H, SnCH2CH2CH2), 2.38
(s, 3 H, CH3), 6.88–7.35 (m, 4 H, Ph-H), 11.22 (s, 1 H, Ar-OH)
ppm. 119Sn NMR (CDCl3): δ = 102.3, –453.9 ppm.
˜
OH), 3102 (m, Ar–H), 2922 (m, C–H), 1612 (m, C=N), 1600 (m,
C=N–N=C), 1588, 1352 (s, CO2), 1206 (m, C–O), 677 (w, Sn–O),
1
523 (m, Sn–C), 459 (w, Sn–N). H NMR (CDCl3, 400 MHz): δ =
[Bz2Sn{2-HOC6H4CON2C(CH3)CO2}{Bz3SnOH}]2 (8): Complex 8
was prepared in the same way as 7 by adding bis(tribenzyltin) oxide
(1.0 mmol) to pyruvic acid salicylhydrazone (1.0 mmol). The solid
was then obtained from dichloromethane/hexane. Yield: 91%
(82.2 mg). M.p. 215 °C. C45H43N2O5Sn2 (929.25): calcd. C 58.10,
1.52 (s, 6 H, CH3), 3.35 (s, 8 H, ArCH2Sn), 6.35–7.61 (m, 24 H,
Ar-H and Ph-H), 10.87 (s, 2 H, Ar-OH) ppm. 119Sn NMR (CDCl3):
δ = –452.8 ppm.
X-ray Crystallographic Study: All measurements were made on a
Bruker Smart 1000 CCD diffractometer at 298(2) K with graphite-
monochromated Mo-Kα (λ = 0.71073 Å). Semi-empirical absorp-
tion corrections were applied using the SADABS program. The
structures were solved by direct methods and difference Fourier
maps using SHELXL-97,[31] and refined by full-matrix least-
squares on F2. All non-hydrogen atoms were included in the model
at their calculated positions.
CCDC-250084 (1), -255498 (2), -255497 (3), -269987 (7), and
-269988 (10) 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.
H 4.77, N 3.01; found C 58.25, H 4.53, N 3.11. IR (KBr): ν =
˜
3411 cm–1 (m, OH), 3035 (s, Ph–H), 2952, 2859 (s, C–H), 1630 (s,
C=N), 1596, 1347 (s, CO2), 1579 (m, C=N–N=C), 1202 (s, C–O),
1
679 (m, Sn–O), 555 (m, Sn–C), 477 (w, Sn–N). H NMR (CDCl3,
400 MHz): δ = 2.65 (d, J = 5.60 Hz, 3 H, CH3), 2.81 (t, JSn,H
=
68.88 Hz, 6 H, ArCH2Sn), 3.16 (s, 4 H, ArCH2Sn), 6.93–7.28 (m,
29 H, Ar-H and Ph-H), 11.43 (s, 1 H, Ar-OH) ppm. 119Sn NMR
(CDCl3): δ = 111.7, –449.5 ppm.
[(pCNBz)2Sn{2-HOC6H4CON2C(CH3)CO2}{(pCNBz)3SnOH}]2
(9): Complex 9 was prepared in the same way as 7 by adding bis(tri-
p-cyanobenzyltin) oxide (1.0 mmol) to pyruvic acid salicylhydra-
zone (1.0 mmol). The solid was then obtained from dichlorometh-
ane/hexane. Yield: 93% (99.7 mg). M.p. 218 °C. C50H38N7O5Sn2
(1054.30): calcd. C 56.91, H 3.72, N 9.29; found C 57.15, H 3.55,
Supporting Information (see footnote on the first page of this arti-
cle): Figures S1, S2, S3, and S4 show the unit cell of complexes 2,
3, 7, and 10, respectively Crystal data and details of the structure
determinations are listed in Tables S1 and S2.
N 9.21. IR (KBr): ν = 3423 cm–1 (s, OH), 3017 (s, Ph–H), 2988,
˜
2889 (m, C–H), 1621 (m, C=N), 1606, 1367 (s, CO2), 1542 (s, C=N–
N=C), 1211 (s, C–O), 674 (m, Sn–O), 547 (w, Sn–C), 485 (w, Sn–
1
N). H NMR (CDCl3, 400 MHz): δ = 2.44 (d, J = 5.40 Hz, 3 H,
CH3), 2.79 (t, JSn,H = 65.48 Hz, 6 H, ArCH2Sn), 3.22 (s, 4 H, Acknowledgments
ArCH2Sn), 6.81–7.42 (m, 24 H, Ar-H and Ph-H), 10.91 (s, 1 H,
Ar-OH) ppm. 119Sn NMR (CDCl3): δ = 109.5, –452.3 ppm.
We acknowledge the financial support of the Natural Science
Foundation of China (no. 20271025), the Shandong Province Sci-
ence Foundation (no. L2003B01), and the State Key Laboratory of
Crystal Materials, Shandong University, P. R. China.
[(oClBz)2Sn{2-HOC6H4CON2C(CH3)CO2}(CH3OH)]2 (10): Pyru-
vic acid salicylhydrazone (2.0 mmol) and tri-o-chlorobenzyltin
chloride (2.0 mmol) were added to a solution of absolute toluene
(30 mL) and heated under reflux, with stirring, for 1 h. After the
addition of triethylamine (2.0 mmol) to the reactor, the reaction
mixture was refluxed for 1 h more. The clear solution thus obtained
[1] L. Sacconi, Coord. Chem. Rev. 1966, 1, 126–142.
[2] S. Yamada, Coord. Chem. Rev. 1966, 1, 415–441.
4580
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 4572–4581

Self-Assembly of Organotin() Moieties with Schiff-Base Ligands
FULL PAPER
[3]
[19] F. Q. Liu, J. T. Wang, R. J. Wang, H. G. Wang, X. K. Yao, J.
Organomet. Chem. 1989, 371, 35–41.
C. Mehrotra, G. Srivastava, B. S. Saraswat, Rev. Silicon, Ger-
manium, Tin Lead Compd. 1982, 6, 171–194.
[20] M. Gielen, H. Dalil, L. Ghys, B. Boduszek, E. R. T. Tiekink,
J. C. Martins, M. Biesemans, R. Willem, Organometallics 1998,
17, 4259–4263.
[21] F. Kayser, M. Biesemans, M. Boualam, E. R. T. Tiekink, A.
El Khloufi, J. Meunier-Piret, A. Bouhdid, K. Jurkschat, M. Gi-
elen, R. Willem, Organometallics 1994, 13, 1098–1104.
[22] J. Holecek, M. Nadvornik, K. Handlir, A. Lycka, J. Or-
ganomet. Chem. 1986, 315, 299–305.
[23] D. Dakternieks, A. Duthie, D. R. Smyth, C. P. D. Stapleton,
E. R. T. Tiekink, Organometallics 2003, 22, 4599–4603.
[24] F. P. Pruchnik, M. Banbula, Z. Ciunik, M. Latocha, B. Skop,
T. Wilczok, Inorg. Chim. Acta 2003, 356, 62–68.
[25] A. Bondi, J. Phys. Chem. 1964, 68, 441–445.
[26] a) C. S. Parulekar, V. K. Jain, T. K. Das, A. R. Gupta, B. F.
Hoskins, E. R. T. Tiekink, J. Organomet. Chem. 1989, 372,
193–199; b) T. P. Lockhart, F. Davidson, Organometallics 1987,
6. 2471–2477.
[4]
[5]
M. Nath, S. Goyal, Main Group Met. Chem. 1996, 19, 75–89.
R. S. Collinson, D. E. Ferton, Coord. Chem. Rev. 1996, 148,
19–40.
P. Yang, M. Guo, Coord. Chem. Rev. 1999, 185, 189–211.
M. Gielen, Metal-Based Drugs 1994, 1, 213–220.
M. Nath, S. Pokharia, R. Yadav, Coord. Chem. Rev. 2001, 215,
99–149.
A. J. Crowe, P. J. Smith, C. J. Cardin, H. E. Parge, F. E. Smith,
Cancer Lett. 1984, 24, 45–48.
V. I. Bregadze, S. A. Glazun, P. V. Petrovakii, Z. A. Starikova,
V. Y. Rochev, H. Dalil, M. Biesemans, R. Willem, M. Gielen,
D. D. Vos, Appl. Organomet. Chem. 2003, 17, 453–459.
[6]
[7]
[8]
[9]
[10]
[11] K. C. Joshi, V. N. Pathak, P. Panwar, Agric. Biol. Chem. 1977,
41, 543–548.
[12] A. Saxena, J. P. Tandon, A. J. Crowe, Polyhedron 1985, 4, 1085–
1089.
[13] G. Y. Yeap, H. K. Fun, S. B. Teo, S. G. Teoh, Acta Crystallogr.,
Sect. C 1992, 48, 1109–1110.
[27] H. D. Yin, C. H. Wang, Y. Wang, C. L. Ma, J. X. Shao, Chem.
J. Chin. Univ. 2003, 24, 68–72.
[28] Z. Y. Yang, L. F. Wang, J. G. Wu, X. Y. Li, Chin. J. Appl.
Chem. 1992, 9, 31–36.
[14] H. D. Yin, Q. B. Wang, S. C. Xue, J. Organomet. Chem. 2004,
689, 2480–2485.
[15] H. D. Yin, M. Hong, Q. B. Wang, Indian J. Chem. 2004, 43A, [29] S. Y. He, W. K. Cao, J. L. Chen, J. S. Zhao, Q. Z. Shi, R. X.
2301–2306.
Wang, J. Sun, Chem. J. Chin. Univ. 2002, 23, 991–995.
[30] Q. L. Xie, X. H. Xu, D. K. Zhang, Acta Chim. Sin. (Chin. Ed.)
1992, 50, 508–514.
[16] M. Hong, H. D. Yin, D. Q. Wang, Acta Crystallogr., Sect. E
2005, 61, 801–803.
[17] D. K. Rastogi, S. K. Dua, V. B. Rana, S. K. Shni, J. India
Chem. Soc. 1978, 1323–1331.
[18] J. T. Wang, F. Q. Liu, Y. W. Zhang, R. J. Wang, H. G. Wang,
X. K. Yao, J. Organomet. Chem. 1989, 375, 173–181.
[31] G. M. Sheldrick, SHELXL-97 and SHELXS-97, University of
Göttingen, Germany, 1997.
Received: May 8, 2005
Published Online: October 13, 2005
Eur. J. Inorg. Chem. 2005, 4572–4581
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4581