Syntheses, characterization and crystal structure of diorganotin and triorganotin heterocyclicdicarboxylates with monomeric, 2D network and 3D framework structures

Article abstract of DOI:10.1016/j.ica.2006.12.012

A series of new diorganotin and triorganotin(IV) heterocyclicdicarboxylates [(ⁿBu₃Sn)₂(2,5-pdc)]_∞ (1), {[(2-FC₆H₄CH₂)₃Sn]₂(2,5-pdc)}_∞ (2), {[(2-ClC₆H₄CH₂)₃Sn]₂(2,5-pdc)}_∞ (3), {[(4-CNC₆H₄CH₂)₃Sn]₂(2,5-pdc)}_∞ (4), {[(4-ClC₆H₄CH₂)₃Sn]₂(2,5-pdc)}_∞ (5), [(Ph)₂Sn(2,6-pdc)(H₂O)]_∞ (6), {[ⁿBu₃Sn(2,6-pdc)SnⁿBu₃]₂(H₂O)₂} · C₂H₃N (7) and {[Ph₃Sn(2,3-pdz)SnPh₃]₂(H₂O)} (8) have been obtained by reactions of diorganotin(IV) and triorganotin (IV) oxide with 2,6 or 2,5-H₂pdc (pdc = pyridinedicarboxylate) or 2,3-H₂pdz (pdz = pyrazinedicarboxylate). Complexes 1-8 were characterized by elemental, IR and NMR spectra analyses. The crystal and molecular structures of compounds 1, 6, 7 and 8 have been determined by X-ray single crystal diffraction. Compound 1 has 2D network structures. Compound 6 has 1D polymeric chain and 3D framework supramolecular structures due to the coordinated water molecules. Compound 7 has a monomeric structure, but the supramolecular structures are network. Crown Copyright

Full text of DOI:10.1016/j.ica.2006.12.012

Inorganica Chimica Acta 360 (2007) 2797–2808
www.elsevier.com/locate/ica
Note
Syntheses, characterization and crystal structure of diorganotin and
triorganotin heterocyclicdicarboxylates with monomeric, 2D
network and 3D framework structures
*
Han Dong Yin , Fa Hui Li, Chuan Hua Wang
Department of Chemistry, Liaocheng University, Liaocheng 252059, China
Received 1 December 2006; accepted 6 December 2006
Available online 15 December 2006
Abstract
A series of new diorganotin and triorganotin(IV) heterocyclicdicarboxylates [(nBu3Sn)2(2,5-pdc)] (1), {[(2-FC6H4CH2)3Sn]2(2,5-
1
pdc)} (2), {[(2-ClC6H4CH2)3Sn]2(2,5-pdc)} (3), {[(4-CNC6H4CH2)3Sn]2(2,5-pdc)} (4), {[(4-ClC6H4CH2)3Sn]2(2,5-pdc)} (5),
1
1
1
1
[(Ph)2Sn(2,6-pdc)(H2O)] (6), {[nBu3Sn(2,6-pdc)SnnBu3]2(H2O)2} Æ C2H3N (7) and {[Ph3Sn(2,3-pdz)SnPh3]2(H2O)} (8) have been
1
obtained by reactions of diorganotin(IV) and triorganotin (IV) oxide with 2,6 or 2,5-H2pdc (pdc = pyridinedicarboxylate) or 2,3-
H2pdz (pdz = pyrazinedicarboxylate). Complexes 1–8 were characterized by elemental, IR and NMR spectra analyses. The crystal
and molecular structures of compounds 1, 6, 7 and 8 have been determined by X-ray single crystal diffraction. Compound 1 has 2D net-
work structures. Compound 6 has 1D polymeric chain and 3D framework supramolecular structures due to the coordinated water mol-
ecules. Compound 7 has a monomeric structure, but the supramolecular structures are network.
Crown Copyright ꢀ 2006 Published by Elsevier B.V. All rights reserved.
Keywords: Heterocyclicdicarboxylic acid; Diorganotin and triorganotin; Hydrogen bond; X-ray crystallography; Supramolecular structures
1. Introduction
zag chain [26] and cyclic structures [27]. Recently, our
interest has focused on triorganotin(IV) complexes con-
taining dicarboxylate ligands which have an additional het-
ero-donor atom (e.g., N, O) residing on the R group that is,
potentially pentadentate ligands, in order to examine what
effect the presence of the heteroatom has on the structure
adopted by these complexes [28]. As a part of our contin-
uing program in this area, we have synthesized and
structurally characterized diorganotin(IV) and triorgano-
tin(IV) pyridinedicarboxylates of 2,5 or 2,6-pyridinedicarb-
oxylic acid and 2,3-pyrazinedicarboxylic acid and the
results of this study are reported herein.
Organotin(IV) carboxylates have attracted much atten-
tion owing to their potential biocidal activities [1–4] and
cytotoxicities [5] as well as their industrial and agricultural
applications [6–11]. Among them, the study of the struc-
tural chemistry of triorganotin carboxylates has received
considerable attention owing to the various structural types
that may be adopted in the solid state [12–19]. Although a
large number of structural studies have been carried out on
the triorganotin esters of monofunctional carboxylic acids
[20], relatively little work has so far been undertaken on
the triorganotin esters of dicarboxylic acids [21–24]. The
organotin(IV) dicarboxylates have been studied in consid-
erable detail, and in general the reported organotin(IV)
dicarboxylates exist as dinuclear [25], one-dimensional zig-
2. Experimental
2.1. Materials and measurements
All the reactions were carried out under nitrogen atmo-
sphere. Ph2SnO, [(nBu)3Sn]2O, [Ph3Sn]2O, 2,5-pyridinedi-
carboxylic acid, 2,6-pyridinedicarboxylic acid and 2,3-
*
Tel./fax: +86 6358239121.
E-mail address: handongyin@sohu.com (H.D. Yin).
0020-1693/$ - see front matter Crown Copyright ꢀ 2006 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.12.012

2798
H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
pyrazinedicarboxylic acid were used as received. The
[(2-FC6H4CH2)3Sn]2O, [(2-ClC6H4CH2)3Sn]2O, [(4-CNC6-
H4CH2)3Sn]2O, [(4-ClC6H4CH2)3Sn]2O and [(4-FC6-
H4CH2)3Sn]2O, were prepared by the reported method
[29]. The melting points were obtained with Kofler micro-
melting points apparatus and were uncorrected. Infrared
spectra were recorded on a Nicole-460 spectrophotometer
(1.007 g, 1.0 mmol) to 2,5-pyridinedicarboxylic acid
(0.167 g, 1.0 mmol). The solid was then recrystallized from
methanol and the colorless crystals were obtained. Yield:
69%. M.p. 211–213 ꢁC. Anal. Calc. for C49H39Cl6NO4Sn2:
C, 50.91; H, 3.40; N, 1.21. Found: C, 50.66; H, 3.46; N,
1.26%. IR (KBr, cmꢀ1): vas(COO), 1620; vs(COO), 1438;
v(Sn–C), 582, v(Sn–O), 467; 1H NMR (CDCl3, ppm):
3.01 (t, 6H, JSn–H = 61 Hz, –CH2–), 7.35–7.53 (m, 24H,
Ph–H), 7.63–7.86 (pyridine). 13C NMR (CDCl3, ppm): d
1
using KBr discs. H, 13C and 119Sn NMR spectra were
recorded on a Mercury Plus-400 NMR spectrometer.
Chemical shifts were given in ppm relative to Me4Si and
Me4Sn in CDCl3 solvent. Elemental analyses were per-
formed on PE-2400-II elemental analyzer.
1
31.3 (CH2Ar, J(119Sn–13C), 586 Hz), 173.8 (COO), 36.6
(CH2Ar), 127.0, 127.1, 129.2, 131.5, 132.7,137.1, 133.8,
137.6, 152.8 (Ar–C, pyridine). 119Sn NMR (CDCl3,
ppm): d ꢀ143.1.
2.2. Synthesis of the complexes
2.2.4. {[(4-CNC6H4CH2)3Sn]2(2,5-pdc)} (4)
1
2.2.1. [(nBu3Sn)2(2,5-pdc)] (1)
The compound 4 was prepared in the same way as that
of complex 1, by adding [(4-CNC6H4CH2)3Sn]2O (0.950 g,
1.0 mmol) to 2,5-pyridinedicarboxylic acid (0.167 g,
1.0 mmol). The solid was then recrystallized from methanol
and the colorless crystals were obtained. Yield: 59%. M.p.:
225–227 ꢁC. Anal. Calc. for C55H39N7O4Sn2: C, 60.09; H,
3.58; N, 8.92. Found: C, 60.32; H, 3.56; N, 8.99%. IR
(KBr, cmꢀ1): 2220 (s, C„N), vas(COO), 1636; vs(COO),
1458; v(Sn–C), 571, v(Sn–O), 478; 1H NMR (CDCl3,
ppm): 3.09 (t, 6H, JSn–H = 66 Hz, –CH2–), 7.27–7.48 (m,
24H, Ph–H), 7.58–7.75 (pyridine). 13C NMR (CDCl3,
ppm): d 32.1 (CH2Ar, 1J(119Sn–13C), 597 Hz), 172.6
(COO), 36.9 (CH2Ar), 115.2 (CN), 109.1, 125.1, 127.6
128.8, 130.6, 133.1, 138.5, 147.2, 150.2 (Ar–C, pyridine).
119Sn NMR (CDCl3, ppm): d ꢀ128.9.
1
The reaction was carried out under a nitrogen atmo-
sphere with use of a standard Schlenk technique. A mixture
of 2,5-pyridinedicarboxylic acid (0.167 g, 1.0 mmol) and
[nBu3Sn]2O (0.596 g, 1.0 mmol) in a 5:1 solvent mixture
of benzene and methanol (80 ml) was heated under reflux
for 8 h. After cooling down to room temperature, the solu-
tion was filtered. The solvent of the filtrate was gradually
removed by evaporation under vacuum until a solid prod-
uct was obtained. The solid was then recrystallized from
dichloromethane/methanol and colorless crystals were
formed. Yield: 72%. M.p.: 201–203 ꢁC. Anal. Calc. for
C31H57NO4Sn2: C, 49.96; H, 7.71; N, 1.88. Found: C,
49.61; H, 7.79; N, 1.93%. IR (KBr, cmꢀ1): vas(COO),
1622; vs(COO), 1445; v(Sn–C), 578, v(Sn–O), 486. 1H
NMR (CDCl3, ppm): 0.82 (t, 18H, CH3), 1.39–1.83 (m,
36H, CH2CH2CH2), 7.45–7.95 (pyridine). 13C NMR
2.2.5. {[(4-ClC6H4CH2)3Sn]2(2,5-pdc)} (5)
1
1
(CDCl3, ppm): 26.9 (aCH2, J(119Sn–13C), 682 Hz), 26.9
The compound 5 was prepared in the same way as that
of compound 1, by adding [(4-ClC6H4CH2)3Sn]2O (1.007 g,
1.0 mmol) to 2,5-pyridinedicarboxylic acid (0.167 g,
1.0 mmol). The solid was then recrystallized from methanol
and the colorless crystals were obtained. Yield: 66%. M.p.:
216–218 ꢁC. Anal. Calc. for C49H39Cl6NO4Sn2: C, 50.91;
H, 3.40; N, 1.21. Found: C, 50.66; H, 3.48; N, 1.25%. IR
(KBr, cmꢀ1): vas(COO), 1619; vs(COO), 1472; v(Sn–C),
(bCH2), 25.6 (cCH2), 13.6 (CH3), 172.6 (COO), 150.2,
151.6, 125.6, 131.8, 138.9 (Ar–C, pyridine). 119Sn NMR
(CDCl3, ppm): d ꢀ129.6.
2.2.2. {[(2-FC6H4CH2)3Sn]2(2,5-pdc)} (2)
1
The compound 2 was prepared in the same way as that
of compound 1, by adding [(2-FC6H4CH2)3Sn]2O (0.908 g,
1.0 mmol) to 2,5-pyridinedicarboxylic acid (0.167 g,
1.0 mmol). The solid was then recrystallized from methanol
and the colorless crystals were obtained. Yield: 62%. M.p.:
216–218 ꢁC. Anal. Calc. for C49H39F6NO4Sn2: C, 55.67; H,
3.72; N, 1.32. Found: C, 55.29; H, 3.78; N, 1.36%. IR (KBr,
cmꢀ1): vas(COO), 1634; vs(COO), 1466; v(Sn–C), 572, v(Sn–
1
568, v(Sn–O), 466; H NMR (CDCl3, ppm): 3.05 (t, 6H,
JSn–H = 58 Hz, –CH2–), 7.38–7.61 (m, 24H, Ph–H), 7.51–
7.72 (pyridine). 13C NMR (CDCl3, ppm): d 31.9 (CH2Ar,
1J(119Sn–13C), 578 Hz), 174.6(COO), 35.2 (CH2Ar), 151.2,
148.8, 135.4, 136.4, 127.6, 125.5, 111.4 (Ar–C, pyridine).
119Sn NMR (CDCl3, ppm): d ꢀ172.6.
O), 476. 1H NMR (CDCl3, ppm): 3.06 (t, 6H, JSn–H
68 Hz, –CH2–), 7.16–7.21 (m, 24H, Ph–H), 7.52–7.99 (pyr-
idine). 13C NMR (CDCl3, ppm):
32.3 (CH2Ar,
=
2.2.6. [Ph2Sn(2,6-pdc)(H2O)] (6)
1
d
The compound 6 was prepared in the same way as that
of compound 1, by adding Ph2SnO (0.289 g, 1.0 mmol) to
2,6-pyridinedicarboxylic acid (0.167 g, 1.0 mmol). The
solid was then recrystallized from methanol and the color-
less crystals were obtained. Yield: 82%. M.p.: 171–173 ꢁC.
Anal. Calc. for C38H30N2O10Sn2: C, 50.04; H, 3.32; N, 3.07.
Found: C, 50.39; H, 3.38; N, 3.12%. IR (KBr, cmꢀ1):
v(H–O–H), 3325; vas(COO), 1628, 1604; vs(COO), 1471,
1316; v(Sn–C), 569; v(Sn–N), 458; v(Sn–O), 485. 1H
1J(119Sn–13C), 562 Hz), 172.5 (COO), 35.8 (CH2Ar),
137.7, 136.4, 135.1, 131.5, 129.6, 125.0, 153.2, 126.8,
137.5 (Ar–C, pyridine). 119Sn NMR (CDCl3, ppm): d
ꢀ115.2.
2.2.3. {[(2-ClC6H4CH2)3Sn]2(2,5-pdc)} (3)
1
The compound 3 was prepared in the same way as that
of compound 1, by adding [(2-ClC6H4CH2)3Sn]2O

H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
2799
NMR (CDCl3, ppm): d 8.96 (s, H2O); 7.45–7.78 (m, 20H,
Ph–H); 7.62–8.22 (Ar–C, pyridine). 13C NMR (CDCl3,
ppm): d 127.2, 128.7, 130.6, 137.8, 139.8, 141.3, 146.9,
(Ar–C, pyridine), 173.6 (COO). 119Sn NMR (CDCl3,
ppm): d ꢀ341.5.
2.2.8. {[Ph3Sn(2,3-pdz)SnPh3]2(H2O)} (8)
The compound 7 was prepared in the same way as that
of compound 1, by adding [Ph3Sn]2O (0.716 g, 1.0 mmol)
to 2,3-pyrazinedicarboxylic acid (0.168 g, 1.0 mmol). The
solid was then recrystallized from methanol and the color-
less crystals were obtained. Yield: 52%. M.p.: 131–133 ꢁC.
Anal. Calc. for C84H66N4O9Sn4: C, 57.64; H, 3.80; N, 3.20.
Found: C, 57.36; H, 3.82; N, 3.30%. IR (KBr, cmꢀ1): v(H–
O–H), 3329, vas(COO), 1667, 1617; vs(COO), 1486, 1418;
2.2.7. {[nBu3Sn(2,6-pdc)SnnBu3]2(H2O)2} Æ CH3CN (7)
The compound 7 was prepared in the same way as that of
compound 1, by adding [(nBu)3Sn]2O (0.596 g, 1.0 mmol) to
2,6-pyridinedicarboxylic acid (0.167 g, 1.0 mmol). The solid
was then recrystallized from acetonitrile and the colorless
crystals were obtained. Yield: 62%. M.p. 128–130 ꢁC. Anal.
Calc. for C64H121N3O10Sn4: C, 49.04; H, 7.78; N, 2.68.
Found: C, 48.71; H, 7.86; N, 2.73%. IR (KBr, cmꢀ1):
v(H–O–H), 3327, vas(COO), 1645; vs(COO), 1336; v(Sn–
1
v(Sn–C), 576; v(Sn–O), 472; H NMR (CDCl3, ppm): d
8.97 (s, H2O); 7.28–7.71 (m, 70H, Ph–H), d 8.76 (s, 4H,
pdz-C–H). 13C NMR (CDCl3, ppm): d 123.6, 131.8,
138.6, 141.3, 144.5, 146.9, 149.4 (Ar–C, pyrazine),
171.1(COO). 119Sn NMR (CDCl3, ppm): d ꢀ129.1, 48.6.
1
C), 598, v(Sn–O), 467; H NMR (CDCl3, ppm): d 8.98 (s,
2.3. X-ray crystallographic studies
H2O); 7.56–8.07 (pyridine), 0.86 (t, 36H, CH3), 1.31–1.86
(m, 72 H, CH2CH2CH2), 1.96 (s, 3H, CH3CN). 13C NMR
X-ray crystallographic data for complexes 1, 6, 7 and 8
1
(CDCl3, ppm): d 27.7 (aCH2, J(119Sn–13C), 565 Hz), 27.3
were collected on a Bruker smart-1000 CCD diffractometer
1
(aCH2, J(119Sn–13C), 628 Hz), 27.1 (bCH2), 26.9 (bCH2),
using Mo Ka radiations (0.71073 A). The structures were
˚
26.6 (bCH2), 26.3 (cCH2), 25.9 (cCH2), 25.3 (cCH2), 13.6
(CH3), 13.8 (CH3), 172.6 (COO), 117.8 (CN), 146.7,
128.4, 138.8 (Ar–C, pyridine). 119Sn NMR (CDCl3, ppm):
d ꢀ116.8, 82.5.
solved by direct method and difference Fourier map using
SHELXL-97 program, and refined by full-matrix least-
squares on F2. All non-hydrogen atoms were refined aniso-
tropically. Hydrogen atoms were located at calculated
Table 1
Crystal, data collection and structure refinement parameters for complexes 1, 6, 7 and 8
Compound
1
6
7
8
Empirical formula
Formula weight
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
C
745.16
0.71073
monoclinic
P21/c
31H57NO4Sn2
C38H30N2O10Sn2
912.02
0.71073
monoclinic
P21/c
C64H121N3O10Sn4
1567.40
0.71073
monoclinic
P21/n
C84H66N4O9Sn4
1750.17
0.71073
˚
triclinic
ꢀ
P1
˚
a (A)
8.974(2)
19.011(4)
22.223(5)
90
01.507(4)
90
9.779(2)
9.807(2)
19.334(4)
90
100.915(3)
90
15.783(12)
20.722(16)
25.033(19)
90
100.110(13)
90
9.634(12)
10.658(14)
19.61(2)
99.41(2)
91.16(2)
112.479(18)
1
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
Z
4
2
4
Absorption coefficient
1.374
1.432
1.272
1.413
(mmꢀ1
)
Crystal size (mm)
h Range for data collection 2.14–25.01
0.47 · 0.43 · 0.18
0.48 · 0.45 · 0.39
2.15–25.01
0.49 · 0.40 · 0.31
1.94–25.01
0.24 · 0.15 · 0.08
2.10–25.01
(ꢁ)
Index ranges
ꢀ10 6 h 6 10,
ꢀ11 6 h 6 11,
ꢀ11 6 k 6 11,
ꢀ12 6 l 6 22
9237
3206 (0.0307)
semi-empirical from
equivalents
ꢀ18 6 h 6 12,
ꢀ23 6 k 6 24,
ꢀ29 6 l 6 29
41864
14076 (0.1249)
semi-empirical from
equivalents
ꢀ11 6 h 6 11,
ꢀ12 6 k 6 12,
ꢀ23 6 l 6 20
9673
7780 (0.0430)
semi-empirical from
equivalents
ꢀ22 6 k 6 21,
ꢀ26 6 l 6 14
18962
Reflections collected
Unique reflections (Rint
Absorption correction
)
6530 (0.0907)
semi-empirical from
equivalents
Refinement method
full-matrix least-squares on
F2
full-matrix least-squares on
F2
full-matrix least-squares on
F2
full-matrix least-squares on
F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
[I > 2r(I)
R indices (all data)
6530/264/343
1.004
R1 = 0.0767,
xR2 = 0.1857
R1 = 0.1786,
xR2 = 0.2616
3206/0/235
1.001
R1 = 0.0238,
xR2 = 0.0569
R1 = 0.0337,
xR2 = 0.0628
14076/534/731
1.006
R1 = 0.0715,
xR2 = 0.1680
R1 = 0.2355
xR2 = 0.2308
7780/54/916
1.005
R1 = 0.0525,
xR2 = 0.0984
R1 = 0.0933,
xR2 = 0.1140

2800
H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
positions and refined isotropically. Further details are
given in Table 1.
complexes. The magnitude of (Dv = vas(COO) ꢀ vs(COO))
of about in the band of 147–182 cmꢀ1 for complexes 1–6
and 8 is comparable to those for the corresponding sodium
salts, which indicates the presence of bidentate carboxyl
groups [36]. Moreover, the magnitude of Dv also occurring
at about 249–312 cmꢀ1 for complexes 6 and 8 indicates that
the carboxylate ligands function as the type of monoden-
tate except bidentate, which was also confirmed by X-ray
structure analyses.
3. Results and discussion
3.1. Design of organotin (IV) complexes
Reactions of heterocyclicdicarboxylic acid with diorg-
anotin(IV) oxide or bis(triorganotin) oxide in 1:1 stoichi-
ometry in the 5:1 refluxing solvent mixture of benzene
and methanol, which afford air stable complexes. The syn-
thesis procedure of compound 1 is shown in Scheme 1.
Complexes 2–9 are similar to 1.
The 1H NMR spectra show the expected integration and
peak multiplicities. A single resonance of –OH in the spec-
tra of the free ligands is absent in the spectra of all the com-
plexes 1–8 indicating the replacement of the carboxylic acid
protons by a organotin moiety on complex formation. In
addition, the resonances appear at 8.96–8.98 ppm for 6–8
are attributed to the protons of coordinated water mole-
cules in the structures.
3.2. Spectroscopic studies
The infrared spectrum of the three free ligands show
v(C@O) of COOH at 1671, 1662 and 1681 cmꢀ1, respec-
tively, as a strong band, which indicate that there are inter-
molecular hydrogen bonds of the type C@O. . .HAO in the
uncoordinated 2,5-pyridinedicarboxylic acid, 2,6-pyridin-
edicarboxylic acid and 2,3-pyrazinedicarboxylic acid mole-
cules. This is commonly observed in the case of carboxylic
acids [30]. After deprotonation and coordinated to tin
atoms, these bands disappear and are replaced by strong
bands in the 1617–1604 and 1316–1486 cmꢀ1 regions,
which correspond to the asymmetric and symmetric vibra-
tions, respectively, of the COO moiety. Also strong absorp-
tion appear at 466–486 cmꢀ1 in the respective spectra of the
complexes 1–8, which is absent in the spectra of the free
ligands, and is assigned to the Sn–O stretching mode of
vibration. All these values are consistent with that detected
in a number of organotin(IV) derivatives [31–33]. The peak
at about 3325–3329 cmꢀ1 in the infrared spectrum indicates
the existence of the coordinated water molecules in com-
plexes 6–8. Besides, as reported in the literature [34,35],
the IR spectra can provide useful information concerning
the mode of coordination of the carboxylate in organotin
The 13C NMR spectra of all complexes show a signifi-
cant downfield shift of all carbon resonances compared
with the free ligands. The shift is a consequence of an elec-
tron density transfer from the ligand to the acceptor. The
single resonance at 171.1–174.6 is attributed to the COO
groups in complexes 1–8. These data are consistent with
the structures of 1–8.
119Sn NMR chemical shift values may be used to give
tentative indications of the environment around each tin
atom. Seven-coordinate Sn has d(119Sn) values ranging
from about ꢀ525 to ꢀ786 ppm, six-coordination Sn from
ꢀ333 to ꢀ395 ppm [37,38], five-coordination Sn from
ꢀ90 to ꢀ190 and four-coordination Sn from +200 to
ꢀ60 in solution [39]. The 119Sn NMR spectra of complexes
1–5 exhibit signals between ꢀ115.2 and ꢀ172.6 ppm., sug-
gesting there is five-coordination in the distannoxane. The
value of ꢀ341.5 of compound 6 indicates six-coordination
other than seven-coordination. The deviation may be
because the intermolecular Sn–N or Sn–O interaction
probably does not survive in solution. Therefore it can rea-
sonably be assumed that the structure in solution of com-
Scheme 1.

H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
2801
pound 6 is different from that observed in the solid state.
Complexes 7–8 (d =ꢀ116.8–129.1 ppm) and (d = 48.6 and
82.5 ppm, respectively) lie between four- and five-coordina-
tion. This is confirmed by the X-ray crystal structures of
complexes 1, 6, 7 and 8.
in Table 2. The tributyltin groups are linked by a carboxyl-
ate of each pdc ligand in 1, in turn, employs its two biden-
tate carboxylic groups to coordinate to two metal centers.
Thus, two ligands are linked by two metal centers into a
18-membered macrocycle, which is further linked to four
nearest-neighbor tin centers by four 18-membered macro-
cycle to give rise to a 34-membered macrocycle. The lattice
2D network with two types of cavity can be evaluated by
the Sn. . .Sn and transannular O. . .O distances, which are
3.3. X-ray crystal structures
3.3.1. Structure of [(nBu3Sn)2(2,5-pdc)]n (1)
˚
The molecular structure and cyclic unit are illustrated in
Figs. 1 and 2, respectively. It consists of infinite 2D net-
work extending through the cell in the bc plane, as indi-
cated in Fig. 2. Bond lengths and bond angles are given
6.722–18.436 and 9.289–15.861 A, respectively. Similar
cavities have been found within the polymeric crystal struc-
tures of microporous metal-organic frameworks formed
between 2,5-pyridinedicarboxylic acid and Sn centers [40].
Fig. 1. Molecular structure of compound 1.
Fig. 2. Packing of the molecules in a unit cell of compound 1.

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H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
Table 2
˚
Selected bond distances (A) and angles (ꢁ) for complexes 1, 6, 7 and 8
Complex 1
Sn(1)–C(8)
Sn(1)–C(16)
Sn(1)–C(12)
Sn(1)–O(1)
Sn(1)–N(1)
2.091(17)
2.137(14)
2.140(16)
2.164(9)
Sn(2)–C(24)
Sn(2)–C(28)
Sn(2)–C(20)
Sn(2)–O(3)
2.10(2)
2.120(16)
2.132(15)
2.182(8)
2.405(9)
2.889(10)
Sn(2)–O(2)#1
C(8)–Sn(1)–C(16)
C(16)–Sn(1)–C(12)
C(16)–Sn(1)–O(1)
C(8)–Sn(1)–N(1)
C(12)–Sn(1)–N(1)
C(24)–Sn(2)–C(28)
C(28)–Sn(2)–C(20)
C(28)–Sn(2)–O(3)
C(24)–Sn(2)–O(2)#1
C(20)–Sn(2)–O(2)#1
C(6)–O(2)–Sn(2)#2
Symmetry code:
110.1(7)
113.3(6)
87.9(5)
78.2(5)
75.2(5)
115.3(8)
114.2(7)
93.5(5)
84.3(6)
83.9(6)
C(8)–Sn(1)–C(12)
C(8)–Sn(1)–O(1)
C(12)–Sn(1)–O(1)
C(16)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
C(24)–Sn(2)–C(20)
C(24)–Sn(2)–O(3)
C(20)–Sn(2)–O(3)
C(28)–Sn(2)–O(2)#1
O(3)–Sn(2)–O(2)#1
131.0(7)
101.9(5)
101.5(6)
150.8(5)
62.9(3)
129.3(8)
94.6(6)
92.9(6)
91.5(6)
174.9(3)
142.9(9)
#1 x, ꢀy + 1/2, z ꢀ 1/2
#2 x, ꢀy + 1/2, z + 1/2
Complex 6
Sn(1)–C(8)
Sn(1)–C(14)
Sn(1)–O(1)
Sn(1)–O(5)
2.112(3)
2.125(3)
2.223(2)
2.267(2)
Sn(1)–O(3)
Sn(1)–N(1)
O(4)–Sn(1)#2
Sn(1)–O(4)#1
2.449(2)
2.342(2)
2.383(2)
2.383(2)
C(8)–Sn(1)–C(14)
C(8)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
C(8)–Sn(1)–O(5)
C(14)–Sn(1)–O(5)
O(1)–Sn(1)–O(5)
C(8)–Sn(1)–N(1)
C(14)–Sn(1)–N(1)
C(14)–Sn(1)–O(3)
O(5)–Sn(1)–O(3)
O(4)#1–Sn(1)–O(3)
Symmetry code:
172.56(13)
95.54(12)
91.44(10)
87.04(10)
92.50(10)
73.53(7)
90.44(10)
94.39(10)
88.92(10)
O(1)–Sn(1)–N(1)
O(5)–Sn(1)–N(1)
C(8)–Sn(1)–O(4)#1
C(14)–Sn(1)–O(4)#1
O(1)–Sn(1)–O(4)#1
O(5)–Sn(1)–O(4)#1
N(1)–Sn(1)–O(4)#1
C(8)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
N(1)–Sn(1)–O(3)
69.72(7)
142.73(7)
86.57(12)
86.06(10)
151.67(7)
78.39(7)
138.59(7)
87.89(11)
135.56(7)
65.95(7)
150.86(7)
72.67(7)
#1 ꢀx + 1, y ꢀ 1/2, ꢀz + 1/2
#2 ꢀx + 1, y + 1/2, ꢀz + 1/2
Complex 7
Sn(1)–C(8)
Sn(1)–O(1)
Sn(1)–O(5)
Sn(2)–O(3)
Sn(2)–C(28)
Sn(3)–C(43)
Sn(3)–O(6)
Sn(4)–C(59)
Sn(4)–O(8)
2.041(16)
2.160(9)
2.661(9)
2.125(9)
2.26(2)
2.060(16)
2.203(9)
1.77(3)
Sn(1)–C(12)
Sn(1)–C(16)
Sn(2)–C(24)
Sn(2)–C(20)
Sn(3)–C(39)
Sn(3)–C(47)
Sn(3)–O(10)
Sn(4)–C(55)
Sn(4)–C(51)
2.122(17)
2.169(16)
2.117(17)
2.18(2)
2.06(2)
2.066(16)
2.412(8)
2.10(2)
2.117(11)
2.14(3)
C(8)–Sn(1)–C(12)
C(12)–Sn(1)–O(1)
C(12)–Sn(1)–C(16)
C(8)–Sn(1)–O(5)
O(1)–Sn(1)–O(5)
C(24)–Sn(2)–O(3)
O(3)–Sn(2)–C(20)
O(3)–Sn(2)–C(28)
C(39)–Sn(3)–C(43)
C(43)–Sn(3)–C(47)
C(43)–Sn(3)–O(6)
C(39)–Sn(3)–O(10)
C(47)–Sn(3)–O(10)
C(59)–Sn(4)–C(55)
C(55)–Sn(4)–O(8)
C(55)–Sn(4)–C(51)
120.7(7)
100.1(5)
121.9(7)
86.2(5)
172.9(3)
92.8(5)
103.8(6)
100.5(7)
108.9(8)
120.9(7)
89.3(6)
87.0(6)
84.8(5)
119.6(12)
94.2(8)
110.9(11)
C(8)–Sn(1)–O(1)
C(8)–Sn(1)–C(16)
O(1)–Sn(1)–C(16)
C(12)–Sn(1)–O(5)
C(16)–Sn(1)–O(5)
C(24)–Sn(2)–C(20)
C(24)–Sn(2)–C(28)
C(20)–Sn(2)–C(28)
C(39)–Sn(3)–C(47)
C(39)–Sn(3)–O(6)
C(47)–Sn(3)–O(6)
C(43)–Sn(3)–O(10)
O(6)–Sn(3)–O(10)
C(59)–Sn(4)–O(8)
C(59)–Sn(4)–C(51)
O(8)–Sn(4)–C(51)
96.9(6)
113.8(7)
91.9(5)
83.7(4)
81.0(5)
117.7(8)
123.1(9)
112.2(9)
128.8(8)
97.9(6)
94.1(5)
86.6(6)
174.5(3)
99.1(9)
120.0(11)
107.6(8)

H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
2803
Table 2 (continued)
Complex 8
Sn(1)–C(19)
Sn(1)–C(13)
Sn(1)–O(5)
Sn(2)–C(37)
Sn(2)–C(25)
Sn(3)–O(6)
Sn(3)–C(49)
Sn(3)–O(7)
Sn(4)–C(67)
Sn(4)–C(79)
2.043(17)
2.107(15)
2.518(10)
2.065(18)
2.128(17)
2.042(10)
2.108(14)
2.835(11)
2.082(18)
2.137(16)
Sn(1)–O(1)
Sn(1)–C(7)
Sn(2)–O(3)
Sn(2)–C(31)
Sn(2)–O(4)
Sn(3)–C(61)
Sn(3)–C(55)
Sn(4)–O(8)
Sn(4)–C(73)
Sn(4)–O(9)
2.100(10)
2.148(15)
2.025(11)
2.117(17)
2.876(11)
2.043(17)
2.116(16)
2.076(11)
2.094(16)
2.661(10)
C(19)–Sn(1)–O(1)
O(1)–Sn(1)–C(13)
O(1)–Sn(1)–C(7)
C(19)–Sn(1)–O(5)
C(13)–Sn(1)–O(5)
O(3)–Sn(2)–C(37)
C(37)–Sn(2)–C(31)
C(37)–Sn(2)–C(25)
O(3)–Sn(2)–O(4)
C(31)–Sn(2)–O(4)
O(6)–Sn(3)–C(61)
C(61)–Sn(3)–C(49)
C(61)–Sn(3)–C(55)
O(6)–Sn(3)–O(7)
C(49)–Sn(3)–O(7)
O(8)–Sn(4)–C(67)
C(67)–Sn(4)–C(73)
C(67)–Sn(4)–C(79)
O(8)–Sn(4)–O(9)
C(73)–Sn(4)–O(9)
100.2(5)
C(19)–Sn(1)–C(13)
C(19)–Sn(1)–C(7)
C(13)–Sn(1)–C(7)
O(1)–Sn(1)–O(5)
C(7)–Sn(1)–O(5)
O(3)–Sn(2)–C(31)
O(3)–Sn(2)–C(25)
C(31)–Sn(2)–C(25)
C(37)–Sn(2)–O(4)
C(25)–Sn(2)–O(4)
O(6)–Sn(3)–C(49)
O(6)–Sn(3)–C(55)
C(49)–Sn(3)–C(55)
C(61)–Sn(3)–O(7)
C(55)–Sn(3)–O(7)
O(8)–Sn(4)–C(73)
O(8)–Sn(4)–C(79)
C(73)–Sn(4)–C(79)
C(67)–Sn(4)–O(9)
C(79)–Sn(4)–O(9)
116.9(6)
102.4(5)
90.5(5)
80.7(5)
79.9(5)
94.5(5)
112.3(7)
108.2(7)
49.6(4)
79.6(6)
116.4(5)
111.1(6)
110.8(7)
49.7(4)
143.1(4)
104.0(6)
111.3(7)
125.2(7)
52.5(4)
147.2(5)
117.2(5)
120.5(6)
176.6(4)
86.2(5)
108.3(6)
105.5(6)
123.8(6)
143.6(5)
90.0(6)
94.3(5)
106.7(5)
116.8(6)
84.0(4)
85.9(5)
94.7(5)
107.8(5)
109.2(6)
80.2(5)
85.2(5)
In other related polymeric systems so far only dimeric [41],
hexameric [42], and chainlike [43] motifs have been
reported. All the tin atoms in 1 possess a same coordina-
tion environment. The coordination about the tin atoms
are both distorted from regular trigonal bipyramidal geom-
etry. Associated with the Sn(1)–O(4#) (symmetry code:
3.3.2. The structure of [Ph2Sn(2,6-pdc)(H2O)]n (6)
The Ph2Sn(2,6-pdc) units are connected in polymeric
structures as shown in Figs. 3–5, selected bond lengths
˚
(A) and angles (ꢁ) are listed in Table 2. Intermolecular
Sn(1)–O(4)#1 (symmetry code: ꢀx + 1, y ꢀ 1/2, ꢀz + 1/
˚
2) bond [2.383(2) A] is comparable to the intramolecular
˚
˚
ꢀx + 1, ꢀy + 1, ꢀz + 1) distance [2.701(2) A] is a little
tin–oxygen bonds [Sn(1)–O(1), 2.223(2) A and Sn(1)–
˚
longer than reported in [Me2Sn(pca)Cl]3 (2.527 A) [44].
˚
The Sn(1)–O(1) distance [2.164(9) A] is close to the distance
between coordinated O atom and central tin atom in other
organotin complexes [45], but much shorter than the sum
˚
of the van der Waals radii of Sn and O (3.68 A). The angle
O(1)–Sn(1)–O(4#) 172.09(6)ꢁ is close to a linear arrange-
ment. The sum of the angles subtended at the tin atom in
the equatorial plane is 354.3ꢁ for Sn(1), so that the atoms
Sn(1), C(8), C(12) and C(16) are almost in the same plane.
˚
The Sn–C distances [2.091(17)–2.140(16) A] are equal
within experimental error and close to the single-bond
value for trigonal bipyramidal tin [46]. It is noteworthy that
short contact is recognized between Sn. . .N (Sn(1)–N(1)
˚
2.889(10) A) and this distance is significantly less than the
˚
sum of the van der Waal’s radii for Sn and N of 3.74 A
[47]. If the short contact of tin–nitrogen is considered, the
geometry of the Sn(1) is best described as distorted octahe-
dron and the coordinate ligands are quinquidentate. These
Sn. . .N bonds not only contribute to the crystal stability
and compactness but also partial result in a macrocycle
arrangement (Figs. 1 and 2).
Fig. 3. Molecular structure of compound 6.

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H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
Fig. 4. 1D zigzag structure of compound 6.
Fig. 5. Perspective view showing the 3D framework of compound 6.
˚
O(3), 2.449(2) A] and close the sum of the covalent radii of
and angles (ꢁ) are listed in Table 2. For compound 7, the
asymmetric unit contains two monomers A and B
(Fig. 7), which are crystallographically nonequivalent.
The conformations of the two independent molecules A
and B are almost same, with only small differences in bond
lengths and bond angles. As can be seen from Fig. 6, com-
pound 7 is a tributyltin ester of 2,6-pyridinedicarboxylic
acid. The two monomers structure with four tributyltin
centers. Take A for example, each 2,6-pyridinedicarboxylic
acid dianion bridges two tin centers via only one O atom
derived from the monodentate carboxylate moiety. Obvi-
ously, one tin center [Sn(2)] is four-coordination and the
other [Sn(1)] is five-coordination due to the coordinated
water molecule. The four-coordination central tin atom
forms four primary bonds: three to the n-butyl groups
and one to the oxygen atom derived of the monodentate
carboxyl group. Thus, the geometry of the tin center dis-
plays a distorted tetrahedral coordinated sphere with six
angles ranging from 92.8(5)ꢁ to 123.1(9)ꢁ. The Sn–C bond
˚
tin and oxygen, 2.13 A, creating a continuous zigzag poly-
meric chain (Fig. 4). For compound 6, one ligand is chelate
to one tin, bonding through the nitrogen atom and two
oxygen atoms from different carboxyl groups. Therefore,
the coordinate ligands in this compound is quadridentate.
Due to the coordinated water molecule, the overall config-
uration at tin is best described as pentagonal bipyramidal:
tin, the bonded oxygen and nitrogen atoms are nearly
coplanar and deviate only slightly from regular pentagonal
geometry, mean deviation from plane is 0.0522 A. The aryl
groups occupy the apical position, the axial–Sn–axial,
C(8)–Sn(1)–C(14) is 172.56(13)ꢁ. The Sn(1)–N(1) distance
2.342(2) A is in keeping with those reported in Sn–N com-
˚
˚
plexes Me2SnCl(2-Pic) [48], Me2Sn(2-Pic)2 [49] and
{[nBu2Sn(2-Pic)]2O}2 [50]. Through the coordinated water
molecules to the tin atoms, the chain structures are associ-
ated with each other via hydrogen bonds, so that a 3D
framework is formed (Fig. 5). The distances of hydrogen-
bonding, O(5)–H. . .O(2#) (symmetry code: ꢀx + 1,
ꢀy + 1, ꢀz) and O(5)–H. . .O(3#) (symmetry code:
˚
lengths [2.117(17)–2.26(2) A] are consistent with those
reported in other triorganotin carboxylates [38]. The
˚
˚
ꢀx + 1, y ꢀ 1/2, ꢀz + 1/2) are 2.669 and 2.676 A, respec-
Sn(2)–O(3) distance [2.125(9) A] is a little longer than
˚
tively, and the O(5)–H. . .O(2#) and O(5)–H. . .O(3#)
angles are 166.68ꢁ and 165.73ꢁ, respectively. This confirms
that the water molecules play an important role in the sta-
bilization of the polymer.
reported in [Ph3Sn(O2CC6H5)] (2.073 A) [46] and
approaches the sum of the covalent radii of Sn and O
˚
(2.13 A). The Sn(1) atom is rendered five-coordination by
coordinating with the water molecule. It is rendered a dis-
torted trigonal bipyramidal type, surrounded axially by
two oxygen atoms and equatorially by three carbon atoms
of the n-butyl groups. The O atoms occupy the axial sites
3.3.3. Structure of {[nBu3Sn(2,6-
pdc)SnnBu3]2(H2O)2} Æ CH3CN (7)
The crystal and the polymeric structures are illustrated
in Figs. 6 and 7, respectively, selected bond lengths (A)
˚
[Sn(1)–O(1) 2.160(9), Sn(1)–O(5) 2.661(9) A and O(1)–
˚
Sn(1)–O(5) 172.9(3)ꢁ]. Despite rather high estimated stan-

H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
2805
Fig. 6. Molecular structure of compound 7. (For clarity, only the first carbon atoms of the n-butyl chain linked to Sn are shown.)
Fig. 7. Perspective view showing the 2D network of compound 7. (For clarity, only the first carbon atoms of the n-butyl chain linked to Sn are shown.)
dard deviations in the C–O bond distances, a clear trend in
these parameters may be discerned. As expected, the C–O
are associated with each other via hydrogen bonds, which
A 2D network is formed (Figs. 6 and 7). The distances of
hydrogen-bondings, O(5)–H. . .O(9#) (symmetry code:
x ꢀ 1/2, ꢀy + 3/2, z + 1/2), O(5)–H. . .O(7#) (symmetry
code: x ꢀ 1/2, ꢀy + 3/2, z + 1/2), O(5)–H. . .N(2#)
(symmetry code: x ꢀ 1/2, ꢀy + 3/2, z + 1/2), O(10)–
H. . .O(4#) (symmetry code: ꢀx + 1, ꢀy + 1, ꢀz + 1) and
O(10)–H. . .O(2#) (symmetry code: ꢀx + 1, ꢀy + 1,
˚
bond distances [C(1)–O(2) 1.208(15) A, C(7)–O(4)
˚
1.223(14) A] associated with the non-coordinating O atoms
are shorter than the coordinating C–O bond distances
˚
˚
[C(1)–O(1) 1.248(14) A, C(7)–O(3) 1.295(14) A]. Although
not involved in coordination to tin, the O(2), O(4) [for A]
and O(7), O(9) [for B] atoms form significant intermolecu-
lar contacts in the crystal lattice. Through the coordinated
water molecules and N atoms, the monomeric structures
˚
ꢀz + 1) are 2.867, 2.738, 2.936, 2.843 and 2.832 A, respec-
tively. Also, for compound 7, cocrystallization is found in

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H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
the crystals and the co-crystallized solvent is acetonitrile
with the molar ratio of {[nBu3Sn(2,6-pdc)SnnBu3]2(H2O)2}:
C2H3N is 1:1.
bonds: three to the phenyl groups and one to the oxygen
atom derived from the monodentate carboxyl group. Thus,
the geometry of the tin center also displays a distorted tet-
rahedral. The other tin atom is rendered a distorted trigonal
bipyramidal type, surrounded axially by two oxygen atoms
and equatorially by three carbon atoms of the n-butyl
groups. Furthermore, it is noteworthy that a weak intramo-
lecular Sn. . .O interaction is recognized between the Sn(2)
and O(4), O(4) derived from the monodentate carboxyl
3.3.4. Structure of {[Ph3Sn(2,3-pdz)SnPh3]2(H2O)} (8)
The crystal and the polymeric structures are illustrated in
˚
Figs. 8 and 9, respectively, selected bond lengths (A) and
angles (ꢁ) are listed in Table 2. For compound 8, the asym-
metric unit also contains two crystallographically non-
equivalent monomers A and B (Fig. 8). In the case of A,
the structure is similar to that in compound 7. One tin cen-
ter [Sn(2)] is four-coordination and the other [Sn(1)] is five-
coordination due to the coordinated water molecule. For
the four-coordination central tin atom forms four primary
˚
group. The Sn(2). . .O(4) distance [2.876(11) A] is consider-
˚
ably less than the sum of the van der Waals radii (3.68 A)
(Fig. 8). The B structure is similar to the A but have no
water molecular coordinate to tin atom. Interestingly, the
two tin atoms in B possess different coordination environ-
Fig. 8. Molecular structure of complex 8.
Fig. 9. The polymeric chain in the lattice.

H.D. Yin et al. / Inorganica Chimica Acta 360 (2007) 2797–2808
2807
[10] I.W. Nowell, J.S. Brooks, G. Beech, R. Hill, J. Organomet. Chem.
244 (1983) 119.
ment. There are two distinct coordinate carboxyl groups,
one is monodentate and the other is didentate, which make
the overall configurations at tin are distorted tetrahedral
and distorted trigonal bipyramidal, respectively.
The salient feature of the supramolecular of compound
is that of an 1D chain polymer (Fig. 9) arising from A, in
which the chain structure molecules are connected through
intermolecular weak interacrions of the N atoms and the
water oxygen atoms from adjacent sides.
[11] C.S. Parulekar, V.K. Jain, T.K. Das, A.R. Gupta, B.F. Hoskins,
E.R.T. Tiekink, J. Organomet. Chem. 372 (1989) 193.
[12] M.M. Amini, S.W. Ng, K.A. Fidelis, M.J. Heeg, C.R. Muchmore,
D. van der Helm, J.J. Zuckerman, J. Organomet. Chem. 365 (1989)
103.
[13] S.W. Ng, C. Wei, V.G. Kumar Das, J. Organomet. Chem. 345 (1988)
59.
[14] K.C. Molloy, S.J. Blunden, R. Hill, J. Chem. Soc., Dalton Trans.
(1988) 1259.
[15] G.K. Sandhu, S.P. Verma, E.R.T. Tiekink, J. Organomet. Chem. 393
(1990) 195.
4. Conclusions
[16] S.W. Ng, J.M. Hook, Main Group Metal Chem. 22 (1999) 163.
[17] P.G. Harrison, K. Lambert, T.J. King, B. Majee, J. Chem. Soc.,
Dalton Trans. (1983) 363.
[18] J. Holecek, A. Lycka, D. Micak, L. Nagy, G. Vanko, J. Brus, S.S.S.
Raj, H.K. Fun, S.W. Ng, Collect. Czech. Chem. Commun. 64 (1999)
1028.
[19] S.W. Ng, J.M. Hook, Acta Crystallogr., Sect. C 55 (1999) 310.
[20] V. Chandrasekhar, S. Nagendran, V. Baskar, Coord. Chem. Rev. 235
(2002) 1.
[21] R. Willem, I. Verbruggen, M. Gielen, M. Biesemans, B.
Mahieu, T.S. Basu Baul, E.E.T. Tiekink, Organometallics 17
(1998) 5758.
From the crystal structures mentioned above, we can
conclude that it is crucial to form bridging O–Sn–O or
O–Sn–N linkages for the formation of multiform cyclooli-
gomeric and polymeric chain structure. Meanwhile, these
ligands with multi-coordination may lead to different archi-
tectures and those dicarboxylate ligands with additional
donor atoms among most common ligands are very useful
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Acknowledgements
We acknowledged the National Natural Foundation PR
China (20543004) and the Shandong Province Science
Foundation (2005ZX09).
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Appendix A. Supplementary material
CCDC 291170, 291173, 610972 and 291172 contain the
supplementary crystallographic data for 1, 6, 7 and 8.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk. Supplementary data asso-
ciated with this article can be found, in the online version,
at doi:10.1016/j.ica.2006.12.012.
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