Self-assembly syntheses and crystal structures of triorganotin(IV) pyridinecarboxylate: 1D polymers and a 42-membered macrocycle

Article abstract of DOI:10.1016/j.jorganchem.2009.09.001

A series of new triorganotin(IV) pyridinecarboxylates with 6-hydroxynicotinic acid (6-OH-3-nicH), 5-hydroxynicotinic acid (5-OH-3-nicH) and 2-hydroxyisonicotinic acid (2-OH-4-isonicH) of the types: [R₃Sn (6-OH-3-nic)·L]_n (I) (R = Ph,

Full text of DOI:10.1016/j.jorganchem.2009.09.001

Journal of Organometallic Chemistry 694 (2009) 4230–4240
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Self-assembly syntheses and crystal structures of triorganotin(IV)
pyridinecarboxylate: 1D polymers and a 42-membered macrocycle
a
a
a
Chunlin Ma a,b, , Qianli Li , Mengjie Guo , Rufen Zhang
*
a Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b Taishan University, Taian 271021, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 4 August 2009
Received in revised form 27 August 2009
Accepted 1 September 2009
Available online 4 September 2009
A series of new triorganotin(IV) pyridinecarboxylates with 6-hydroxynicotinic acid (6-OH-3-nicH), 5-
hydroxynicotinic acid (5-OH-3-nicH) and 2-hydroxyisonicotinic acid (2-OH-4-isonicH) of the types:
[R3Sn (6-OH-3-nic)ꢀL]n (I) (R = Ph, L = PhꢀEtOH, 1; R = Bn, L = H2OꢀEtOH, 2; R = Me, L = 0, 3; R = n-Bu,
L = 0, 4), [R3Sn (5-OH-3-nic)]n (II) (R = Ph, 5; R = Bn, 6; R = Me, 7; R = n-Bu, 8), [R3Sn (2-OH-4-isonicꢀL)]n
(III) (R = Bn, 9, L = MeOH; R = Me, L = 0, 10; R = Ph, 11, L = 0.5EtOH) have been synthesized. All the com-
plexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 119Sn) spectroscopy analyses.
Among them, except for complexes 5 and 6, all complexes were also characterized by X-ray crystallog-
raphy diffraction analysis. Crystal structures show that complexes 1–10 adopt 1D infinite chain struc-
tures which are generated by the bidentate O, O or N, O and the five-coordinated tin centers.
Significant O–Hꢀ ꢀ ꢀO, and N–Hꢀ ꢀ ꢀO intermolecular hydrogen bonds stabilize these structures. Complex
11 is a 42-membered macrocycle containing six tin atoms, and forms a 2D network by intermolecular
N–Hꢀ ꢀ ꢀO hydrogen.
Keywords:
Self-assembly
Triorganotin(IV)
Pyridinecarboxylate
Crystal structure
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
moiety; second, the spatial separation of the two groups attached
to the same pyridine ring should induce the formation either of a
Self-assembly of organotin (IV) pyridinecarboxylates are att-
racting more and more attention because the ligand with
multi-coordination may lead to different specific architectures
[1–9]. Recently, considerable advances have been made in this
area, mono-, dicarboxylic acids and substituted carboxylic acids
have been extensively investigated. Hopfl and co-workers have
carried out some very elegant work on such systems, having
reported a series of trinuclear macrocyclic organotin complexes
by the use of 2,5-pyridine dicarboxylic as ligands [1–3]. Amini
and co-workers have reported an interesting complex containing
two types of metals tin and sodium by the use of 2,6-pyridine
dicarboxylic as ligand [4]. In our previous work, we have also
synthesized a series of triorganotin pyridinedicarboxylates by
use of 2,6-,2,5- and 3,5-pyridinecarbozylate [10]. Specially, we
polymeric chain or of a cyclooligomeric ring structure. Herein,
we reported the syntheses and characterizations of 11 new organo-
tin polymers with the three acids.
2. Results and discussion
2.1. Syntheses
The syntheses procedures of complexes 1–11 are given in
Scheme 1.
2.2. IR spectra
reported
2-mercaptonicotinic acid [11].
a novel 18-tin-nuclear macrocyclic complex with
The stretching frequencies of interest are those associated
with the C(O)O, Sn–C and Sn–O groups. The strong absorption
appears at about 447–458 cmꢁ1 in the respective spectra of all
the complexes, which are absent in the free ligand, are assigned
to the Sn–O stretching modes of vibration. All these values are
consistent with those detected in a number of organotin(IV)-
To continue research in this area, we selected another three fas-
cinating ligands 6-hydroxynicotinic acid, 5-hydroxynicotinic acid,
2-hydroxyisonicotinic acid on the basis of the following consider-
ations: first, all of them have a carboxy group and a hydroxyl
group, so they should form strong covalent bonds with organotin
oxygen derivatives [12,13]. Besides, the value of
Dv [vas
(COO) ꢁ
v
s(COO)] for all the complexes located about 280 cmꢁ1
* Corresponding author. Address: Department of Chemistry, Liaocheng Univer-
sity, Liaocheng 252059, PR China. Tel.: +86 635 8230660; fax: +86 538 6715521.
E-mail address: macl@lcu.edu.cn (C. Ma).
revealing that the carboxylate ligand with monodentate modes
[14].
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.09.001

C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
4231
HOOC
O
EtONa
MeOH
R
R
R3SnCl
+
O
.
L
O
Sn
R
N
OH
HN
n
R=Ph, L=C6H6, EtOH, 1; R=Bn, L=EtOH, H2O 2; R=Me, L=0, 3; R=Bu, L=0, 4
OH
HOOC
OH
R
Sn
N
EtONa
MeOH
+
R3SnCl
O
N
R
R
n
O
5
6;
7
8
R=Ph, ; Bn, Me, ; Bu,
HN
O
.
L
R=Me, L=0
R=Bn, L=MeOH
9
10
O
Me
O
Me
Sn
n
Me
Ph
O
Ph
COOH
HN
R=Ph
O
Sn
Ph
O
HN
L=0.5EtOH 11
O
O
EtONa
MeOH
Ph
O
+
R3SnCl
Ph Sn
O
Ph
N
OH
Ph
Sn
Ph
O
Ph
O
.
L
NH
.
HN
O
O
Ph
Ph Sn
Ph
O
Ph
Sn Ph
Ph
O
O
O
Ph
Sn
NH
O
O
NH
Ph Ph
O
Scheme 1.
2.3. NMR spectra
five-coordinate species [15], and this can be confirmed by the X-
ray crystal structures of the complexes.
The 1H NMR spectra show the expected integration and peak
multiplicities. In the spectra of the free ligands, the resonance ob-
served at about 10.8 ppm, which is absent in the spectra of all the
complexes, indicates the replacement of the carboxylic acid pro-
tons by organotin moiety on complex formation, while the reso-
nance for the N–H at about 11.5 ppm in complexes 1–4 and 9–11
suggests the interconvertions between the keto-form and the
enol-form on the ligand. For complexes 5–8, the resonance at
about 9.7 ppm ascribes to the hydroxy groups.
2.4. Description of crystal structures
2.4.1. Crystal structure of complex 1, 2, 3 and 4
The molecular structures and 1D infinite chain structures of
complexes 1–4 are illustrated in Figs. 1–4, and selected bond
lengths and angles are listed in Table 3, respectively. In the crys-
talline state, these complexes adopt an infinite 1D polymeric
chain structures with a five-coordinated tin center, which are
generated by the one carboxyl oxygen atom, one keto oxygen
atom and the Sn center. The central Sn atom exists in a trigonal
bipyramidal environment with two O atoms and three C atoms,
which exhibits a trans-R3SnO2 geometry. The axial position is
occupied by two oxygen atoms of the ligand, axial angles:
[O(1)–Sn(1)–O(3)#1 = 175.79(10)° (#1 x + 1/2, ꢁy + 3/2, z + 1/2)
for complex 1; O(1)–Sn(1)–O(3) = 168.3(15)° for complex 2;
The 13C NMR spectra of all complexes show a significant down-
field shift of all carbon resonance compared with the free ligands,
the shift is a consequence of an electron density transfer from the
ligand to the metal atoms. The single resonances at 164.26–168.36
are attributing to the COO groups in all the complexes.
The 119Sn NMR spectroscopic data of all the complexes show
only one resonance between ꢁ104.8 and ꢁ176.2 ppm, typical

4232
C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
Table 1
Crystal data and structure refinement parameters for complexes 1, 2, 3, 4 and 7.
Complex
1
2
3
4
7
Empirical formula
Formula weight
Wavelength (Å)
Crystal system
Space group
a (Å)
C32H31NO4Sn
612.27
0.71073
Monoclinic
P2(1)/n
8.9239(7)
18.146(2)
18.215(3)
90
C29H33NO5Sn
594.25
0.71073
Monoclinic
P2(1)
9.1760(12)
16.975(3)
9.9575(17)
90
C9H13NO3Sn
301.89
0.71073
Orthorhombic
Pna2(1)
14.149(2)
10.5466(14)
7.9595(10)
90
C18H31NO3Sn
428.13
C18H26N2O6Sn2
603.79
0.71073
Monoclinic
Cc
17.670(2)
8.9461(12)
14.2930(16)
90
0.71073
Orthorhombic
P2(1)2(1)2(1)
8.6910(16)
10.716(4)
22.502(5)
90
b (Å)
c (Å)
a
(°)
b (°)
91.729(2)
90
2948.3(6)
4
1.379
0.902
113.052(2)
90
1427.2(4)
2
1.383
0.931
90
90
1187.7(3)
4
1.688
90
90
2095.7(9)
4
1.357
90.898(2)
90
2259.2(5)
4
1.775
2.245
c
(°)
V (Å3)
Z
Dcalc (Mg/m3)
l
(mmꢁ1
)
2.135
1.232
F(0 0 0)
1248
608
592
880
1184
Crystal size (mm)
Reflections collected
Unique reflections (Rint
Data/restraints/
0.28 ꢂ 0.13 ꢂ 0.10
0.23 ꢂ 0.14 ꢂ 0.13
0.48 ꢂ 0.40 ꢂ 0.39
0.26 ꢂ 0.21 ꢂ 0.18
0.26 ꢂ 0.15 ꢂ 0.07
14 592
7226
4666
13 616
5548
)
5195 (Rint = 0.0395)
5195/0/364
4804 (Rint = 0.0432)
4804/1/346
1830 (Rint = 0.0260)
1830/1/125
5096 (Rint = 0.0329)
5096/0/210
2800 (Rint = 0.0252)
2800/2/361
parameters
Goodness-of-fit on F2
1.039
1.087
1.069
1.016
1.071
Final R indices [I > 2
R indices (all data)
r(I)]
R1 = 0.0376,
wR2 = 0.0750
R1 = 0.0643,
wR2 = 0.0872
R1 = 0.0877,
wR2 = 0.2354
R1 = 0.1159,
wR2 = 0.2580
R1 = 0.0379,
wR2 = 0.0958
R1 = 0.0451,
wR2 = 0.1029
R1 = 0.0376,
wR2 = 0.0831
R1 = 0.0673,
wR2 = 0.0943
R1 = 0.0241,
wR2 = 0.0465
R1 = 0.0288,
wR2 = 0.0490
Table 2
Crystal data and structure refinement parameters for complexes 8, 9, 10, and 11.
Complex
8
9
10
11
Empirical formula
Formula weight
Wavelength (Å)
Crystal system
Space group
a (Å)
C18H31NO3Sn
428.13
0.71073
Monoclinic
P2(1)/n
10.2153(9)
14.450(2)
14.3812(19)
90
C145H117N6O18.5Sn6
2951.59
0.71073
C28H29NO4Sn
562.21
0.71073
Monoclinic
P2ð1Þ=n
10.4698(11)
16.1420(14)
16.1310(15)
90
C9H13NO3Sn
301.89
0.71073
Monoclinic
C2=c
24.540(2)
8.1950(8)
14.0910(17)
Hexagonal
ꢀ
R3
23.3453(19)
23.3453(19)
23.997(2)
90
b (Å)
c (Å)
a
(°)
90
b (°)
93.823(2)
90
2118.1(5)
4
1.343
1.219
90
120
11326.4(16)
3
1.036
0.931
105.5740(10)
90
2626.1(4)
4
1.422
1.005
124.077(2)
90
2347.2(4)
8
1.709
2.160
c
(°)
V (Å3)
Z
Dcalc (Mg/m3)
l
(mmꢁ1
)
F(0 0 0)
880
4431
1144
1184
Crystal size (mm)
Reflections collected
Unique reflections (Rint
0.48 ꢂ 0.40 ꢂ 0.32
0.40 ꢂ 0.28 ꢂ 0.13
0.22 ꢂ 0.20 ꢂ 0.08
0.28 ꢂ 0.25 ꢂ 0.20
10 207
7226
13 092
5732
)
3582 (Rint = 0.0781)
3582/10/319
1.035
4804 (Rint = 0.0432)
4804/1/346
1.087
4624 (Rint = 0.0500)
4624/0/309
1.097
2070 (Rint = 0.0187)
2070/0/127
1.123
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
r(I)]
R1 = 0.0961, wR2 = 0.2489
R1 = 0.1238, wR2 = 0.2893
R1 = 0.0394, wR2 = 0.0998
R1 = 0.0647, wR2 = 0.1124
R1 = 0.0385, wR2 = 0.0788
R1 = 0.0661, wR2 = 0.0887
R1 = 0.0215, wR2 = 0.0499
R1 = 0.0309, wR2 = 0.0579
O(1)–Sn(1)–O(3)#1 = 178.87(14)° (#1 x, y + 1, z) for complex 3,
O(1)–Sn(1)–O(3) = 178.2(2)° for complex 4.] are all slightly devi-
ated from the linear arrangement. Three alkyl groups defined
the equatorial plane and the sum of the angles subtended at
the central Sn atom are 358.8° for complex 1, 358.7° for complex
2, 358.7° for complex 3, 357.2° for complex 4, respectively. The
Sn–O bond lengths [Sn(1)–O(1) = 2.157(3) Å, Sn(1)–O(3)#1 =
2.358(3) Å for complex 1; Sn(1)–O(1) = 2.140(11) Å, Sn(1)–
O(3) = 2.346(11) Å for complex 2; Sn(1)–O(1) = 2.167(8) Å,
Sn(1)–O(3) = 2.367(6) Å for complex 3; Sn(1)–O(1) = 2.160(3) Å,
Sn(1)–O(3)#1 = 2.428(3) Å for complex 4] are little longer than
the sum of the covalent radii of Sn and O (2.13 Å), but much
shorter than the sum of the van der Waals radii of two atoms
(3.68 Å) [16]. The bond length of O(3)–C(6) 1.253(4) Å for 1,
O(3)–C(6)#1 1.265(16) Å for 2, O(3)–C(6)#1 1.263(10) Å for 3,
O(3)–C(3) 1.249(5) Å for 4, reveal that these bonds should be
keto C@O, just for this, intermolecular C@O ? Sn coordination in
complex leads to the forming of the infinite zigzag chain.
Besides, for complex 1 and 2, they crystallizes with two solvent
molecules of C6H6, EtOH and H2O, EtOH significant N–Hꢀ ꢀ ꢀO and
O–Hꢀ ꢀ ꢀO intermolecular hydrogen bonds were found. Just for that,
the supramolecular structure of a 2D network is formed. For com-
plex 3 and complex 4, a 3D framework and a dimer structure are
formed by N–Hꢀ ꢀ ꢀO intermolecular hydrogen bonds.

C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
4233
Fig. 1. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 1.
Fig. 2. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 2.

4234
C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
Table 3
plexes 7 and 8 are both infinite 1D polymeric chain structures,
the central tin atom in the two complexes is essentially five coor-
dinated, bound to three alkyl groups, one carboxylate oxygen atom,
and one nitrogen atom, so the geometry of the tin atom can be de-
scribed as a distorted trigonal bipyramidal geometry in which the
apical position is occupied by the oxygen atom and the nitrogen
atom. The axial angles [O(1)#1–Sn(1)–N(1) = 172.3(2)° for 7 and
O(1)–Sn(1)–N(1) = 175.4(3)° for 8] suggests that the structure are
near to normal trigonal bipyramid. The bond lengths of Sn(1)–
O(1)#1 = 2.196(5) for 7 and Sn(1)–O(1) = 2.183(8) for 8, are similar
to the complex 1–4. The Sn(1)–N(1) bond length 2.445(6) Å for 7
and 2.520(8) Å for 8 lies in the range recorded in the Cambridge
Crystallographic Database from 2.27 to 2.58 Å [17], slightly greater
than the sum of the covalent radii of tin and nitrogen atoms, but
much less than the sum of the van der Waals radii (3.74 Å) [18].
Besides, for complex 7 and 8, significant O–Hꢀ ꢀ ꢀO intermolecu-
lar hydrogen bonds are found, which link the complexes to 2D net-
work structures. The OꢀꢀꢀO, HꢀꢀꢀO distances and the O–Hꢀ ꢀ ꢀO angles
are 2.644 Å, 1.828 Å and 173.69° for 7 and 2.578 Å, 1.777 Å and
165.31° for 8, respectively.
Selected bond lengths (Å) and angles (°) for complex 1–4.
Complex 1
Sn(1)–C(7)
Sn(1)–C(19)
Sn(1)–C(13)
C(7)–Sn(1)–C(19)
C(7)–Sn(1)–C(13)
C(19)–Sn(1)–C(13)
C(7)–Sn(1)–O(1)
C(19)–Sn(1)–O(1)
2.123(4)
2.130(4)
2.144(4)
127.16(16)
118.58(15)
112.97(16)
92.65(13)
98.34(13)
Sn(1)–O(1)
Sn(1)–O(3)#1
2.157(3)
2.358(3)
C(13)–Sn(1)–O(1)
C(7)–Sn(1)–O(3)#1
C(19)–Sn(1)–O(3)#1
C(13)–Sn(1)–O(3)#1
O(1)–Sn(1)–O(3)#1
89.94(13)
85.96(13)
85.65(13)
87.24(12)
175.79(10)
Complex 2
Sn(1)–C(14)
Sn(1)–C(7)
Sn(1)–O(1)
C(14)–Sn(1)–C(7)
C(14)–Sn(1)–O(1)
C(7)–Sn(1)–O(1)
C(14)–Sn(1)–C(21)
C(7)–Sn(1)–C(21)
2.13(4)
Sn(1)–C(21)
Sn(1)–O(3)
2.16(4)
2.346(11)
2.136(12)
2.140(11)
114.8(17)
86.7(13)
93.1(5)
O(1)–Sn(1)–C(21)
C(14)–Sn(1)–O(3)
C(7)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
C(21)–Sn(1)–O(3)
101.6(14)
86.8(12)
80.8(5)
168.3(15)
90.1(13)
128.8(7)
115.1(19)
Complex 3
Sn(1)–C(8)
Sn(1)–C(7)
Sn(1)–C(9)
C(8)–Sn(1)–C(7)
C(8)–Sn(1)–C(9)
C(7)–Sn(1)–C(9)
C(8)–Sn(1)–O(1)
C(7)–Sn(1)–O(1)
2.119(9)
2.118(8)
2.135(13)
115.0(5)
124.5(4)
118.2(4)
97.8(4)
Sn(1)–O(1)
Sn(1)–O(3)
2.167(8)
2.367(6)
C(9)–Sn(1)–O(1)
C(8)–Sn(1)–O(3)
C(7)–Sn(1)–O(3)
C(9)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
95.8(4)
83.7(3)
87.5(3)
84.0(5)
178.2(2)
2.4.3. Crystal structure of complex 9 and 10
The molecular structures and 1D infinite chain structures of
complexes 9 and 10 are illustrated in Figs. 7 and 8, and selected
bond lengths and angles are listed in Table 5, respectively. As com-
plexes 1–4, the central Sn atoms for complexes 7 and 8 are also
five-coordinate with trigonal bipyramidal geometry, bound to
three alkyl groups, one carboxylate oxygen atom, one keto oxygen
atom. Intermolecular C@O ? Sn coordination in complex leads to
the forming of the infinite zigzag chain. The Sn–O bond lengths
[Sn(1)–O(1) = 2.154(3) Å, Sn(1)–O(3) = 2.407(3) Å for 1; Sn(1)–
O(1) = 2.182(2) Å, Sn(1)–O(3) = 2.334(3) Å for 2] and axial angles
[O(1)–Sn(1)–O(3) = 174.30(10)° for complex 1; O(1)–Sn(1)–
O(3) = 168.38(9)° for complex 2] are similar to the complexes 1–4.
Besides, it should be noted, complex 9 crystallizes with one sol-
vent molecule of H2O, just for that, significant O–Hꢀ ꢀ ꢀO and N–
Hꢀ ꢀ ꢀO intermolecular hydrogen bonds are found, which link the
complex into a 2D network structure. For complex 10, the supra-
molecular structure of a 2D network is also formed by intermolec-
ular N–Hꢀ ꢀ ꢀO hydrogen bond.
90.9(3)
Complex 4
Sn(1)–C(8)
Sn(1)–C(16)
Sn(1)–C(12)
C(8)–Sn(1)–C(16)
C(8)–Sn(1)–C(12)
C(16)–Sn(1)–C(12)
C(8)–Sn(1)–O(1)
C(16)–Sn(1)–O(1)
2.127(5)
2.130(5)
2.142(5)
127.2(2)
114.8(2)
115.2(2)
95.98(14)
96.67(17)
Sn(1)–O(1)
Sn(1)–O(3)#1
2.160(3)
2.428(3)
C(12)–Sn(1)–O(1)
C(8)–Sn(1)–O(3)#1
C(16)–Sn(1)–O(3)#1
C(12)–Sn(1)–O(3)#1
O(1)–Sn(1)–O(3)#1
93.50(16)
83.08(15)
83.44(18)
87.46(17)
178.87(14)
Symmetry code for complex 1: #1 x + 1/2, ꢁy + 3/2, z + 1/2.
Symmetry code for complex 4: #1 x, y + 1, z.
2.4.2. Crystal structure of complex 7 and 8
The molecular structures and 1D infinite chain structures of
complexes 7 and 8 are illustrated in Figs. 5 and 6, and selected
bond lengths and angles are listed in Table 4, respectively. Com-
Fig. 3. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 3.

C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
4235
Fig. 4. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 4.
Fig. 5. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 7.

4236
C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
Fig. 6. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 8.
Table 4
EtOH, but the obvious interactions between the 11 moiety and
the solvent molecule are not found. The macrocyclic [Ph3Sn(o-
OC5H4NCO2)]6 component consists of six Ph3Sn fragments linked
together through six bridging [o-OC5H4NCO2] ligands to afford a
hexanuclear Sn6O12 macrocycle, which can be described as a car-
bon-studded molecular b angle [4]. As can be seen from Fig. 9, com-
plex 11 is a 42-membered macrocycle, each of the tin atom is
essentially penta-coordinated, bounded to three phenyl groups,
one carboxyl oxygen atom and one keto oxygen, so the geometry
of the tin atom can be described as a distorted trigonal bipyramid.
The axial position is occupied by O(1) and O(3), which forms an an-
gle of 175.75(12)° for Sn(1), the basal plane is defined by C(7),
C(13) and C(19) and the sum of the angles subtended at the tin
atom is 359.2°, so that the atoms Sn(1), C(7), C(13) and C(19) are
almost in the same plane. The bond lengths of Sn(1)–O(1), Sn(1)–
O(3) are 2.156(3) Å and 2.303(3) Å, respectively. The size of cavity
in this macrocycle can be evaluated from the SnꢀꢀꢀSn and transan-
nular OꢀꢀꢀO distances, which are 14.207 Å and 13.976 Å, respec-
tively, larger than our previous reported on [(Ph3Sn)6(O3POPh)3]2
[19]. Worth mentioning here is that although the dimensions of
the cavity in this complex are ostensibly large enough to capture
guest molecules, they are almost completely occupied by the phe-
nyl groups on tin atoms. Besides, may be related to steric effects
and to the different sorts of coordinated atoms, the macrocycle is
twisted, in fact, Sn1, Sn1A and Sn1B occupy a plane 4.977 Å distant
from the plane which the rest three tin atoms defined by.
Selected bond lengths (Å) and angles (°) for complex 7–8.
Complex 7
Sn(1)–C(7)
Sn(1)–C(9)
Sn(1)–C(8)
Sn(1)–O(1)#1
Sn(1)–N(1)
Sn(2)–C(16)
Sn(2)–C(170)
C(7)–Sn(1)–C(9)
C(7)–Sn(1)–C(8)
C(9)–Sn(1)–C(8)
C(7)–Sn(1)–O(1)#1
C(9)–Sn(1)–O(1)#1
2.114(7)
2.117(7)
2.118(7)
2.118(7)
2.445(6)
2.009(13)
2.028(14)
116.8(3)
119.6(3)
123.6(3)
95.9(2)
Sn(2)–C(18)
2.111(8)
2.131(10)
2.155(10)
2.198(14)
2.213(14)
2.512(11)
2.532(12)
91.2(2)
91.6(2)
89.7(3)
86.8(2)
172.3(2)
Sn(2)–O(50)#2
Sn(2)–O(5)#2
Sn(2)–C(17)
Sn(2)–C(160)
Sn(2)–N(2)
Sn(2)–N(20)
C(8)–Sn(1)–O(1)#1
C(7)–Sn(1)–N(1)
C(9)–Sn(1)–N(1)
C(8)–Sn(1)–N(1)
O(1)#1–Sn(1)–N(1)
85.1(3)
Complex 8
Sn(1)–C(7)
1.89(9)
2.07(5)
2.11(10)
2.1(3)
133(5)
122(3)
104(5)
94(2)
Sn(1)–C(11)
Sn(1)–O(1)
Sn(1)–C(70)
2.13(19)
2.183(8)
2.22(7)
2.520(8)
83(3)
85(2)
89(2)
93(3)
175.4(3)
Sn(1)–C(15)
Sn(1)–C(150)
Sn(1)–C(110)
Sn(1)–N(1)
C(15)–Sn(1)–C(11)
C(7)–Sn(1)–C(15)
C(7)–Sn(1)–C(11)
C(7)–Sn(1)–O(1)
C(15)–Sn(1)–O(1)
C(11)–Sn(1)–O(1)
C(7)–Sn(1)–N(1)
C(15)–Sn(1)–N(1)
C(11)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
95(2)
Symmetry code for complex 7: #1 x, ꢁy + 1, z ꢁ ½ and #2 x, y ꢁ 1, z.
2.4.4. Crystal structure of complex 11
A perspective view of the molecular structure is shown in Fig. 9,
and selected bond lengths and angles are listed in Table 5, respec-
tively. It should be noted that the macrocyclic component,
[Ph3Sn(o-OC5H4NCO2)]6, crystallizes with solvent molecule of
Furthermore, significant N–Hꢀ ꢀ ꢀO intermolecular hydrogen
bond stabilize these structure, the HꢀꢀꢀO, NꢀꢀꢀO distance and the
N–HꢀꢀꢀO angle are 1.874 Å, 2.732 Å and 174.85°, respectively. Just

C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
4237
Fig. 7. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 9.
Fig. 8. Perspective views of a–b are showing the molecular structure and the 1D chain structure of complex 10.

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C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
Table 5
3. Experimental details
Selected bond lengths (Å) and angles (°) for complex 9–11.
Complex 9
Sn(1)–C(7)
Sn(1)–C(9)
Sn(1)–C(8)
C(7)–Sn(1)–C(9)
C(7)–Sn(1)–C(8)
C(9)–Sn(1)–C(8)
C(7)–Sn(1)–O(1)
C(9)–Sn(1)–O(1)
3.1. Materials and measurements
2.113(4)
2.114(4)
2.125(4)
123.00(18)
118.86(18)
117.97(18)
86.29(13)
92.35(14)
Sn(1)–O(1)
Sn(1)–O(3)
O(3)–C(2)#1
C(8)–Sn(1)–O(1)
C(7)–Sn(1)–O(3)
C(9)–Sn(1)–O(3)
C(8)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
2.182(2)
2.334(3)
1.268(4)
95.56(13)
84.28(13)
87.13(14)
94.93(13)
168.38(9)
Trimethyltin chloride, triphenyltin chloride, tri-n-butyltin chlo-
ride, 6-hydroxynicotinic acid, 5-hydroxynicotinic acid and 2-
hydroxyisonicotinic acid were commercially available, and they
were used without purification. Tribenzyltin(IV) chloride was pre-
pared by a standard method reported in the literature [20], The
melting points were obtained with an X-4 digital micro melting-
point apparatus and were uncorrected. Infrared-spectra were re-
corded on a Nicolet-5700 spectrophotometer using KBr discs and
sodium chloride optics. 1H, 13C and 119Sn NMR spectra were re-
corded on Varian mercury Plus 400 spectrometer operating 400,
100.6 and 149.2 MHz, respectively. The spectra were acquired at
room temperature (298 K) unless otherwise specified; 13C spectra
are broadband proton decoupled. The chemical shifts are reported
in ppm with respect to the references and are stated relative to
external tetramethylsilane (TMS) for 1H and 13C NMR and Me4Sn
for 119Sn NMR. Elemental analyses (C, H and N) were performed
with a PE-2400II apparatus.
Complex 10
Sn(1)–C(7)
Sn(1)–C(14)
Sn(1)–C(21)
C(7)–Sn(1)–C(14)
C(7)–Sn(1)–C(21)
C(14)–Sn(1)–C(21)
C(7)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
2.139(4)
2.145(4)
2.150(5)
116.48(17)
128.05(18)
113.47(19)
95.33(14)
93.13(13)
Sn(1)–O(1)
Sn(1)–O(3)
2.154(3)
2.407(3)
C(21)–Sn(1)–O(1)
C(7)–Sn(1)–O(3)
C(14)–Sn(1)–O(3)
C(21)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
95.33(16)
89.30(15)
81.80(13)
84.37(17)
174.30(10)
Complex 11
Sn(1)–C(13)
Sn(1)–C(19)
Sn(1)–C(7)
C(13)–Sn(1)–C(19)
C(13)–Sn(1)–C(7)
C(19)–Sn(1)–C(7)
C(13)–Sn(1)–O(1)
C(19)–Sn(1)–O(1)
2.119(5)
2.122(5)
2.133(5)
120.9(2)
119.8(2)
118.59(19)
95.97(16)
95.00(16)
Sn(1)–O(1)
Sn(1)–O(3)
O(3)–C(2)
C(7)–Sn(1)–O(1)
C(13)–Sn(1)–O(3)
C(19)–Sn(1)–O(3)
C(7)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
2.156(3)
2.303(3)
1.260(5)
87.55(15)
84.21(15)
88.53(16)
88.68(16)
175.75(12)
3.2. Syntheses of the complex 1–11
3.2.1. Synthesis of complex 1
The 6-hydroxynicotinic acid (0.139 g, 1 mmol) and the sodium
ethoxide (0.068 g, 1 mmol) were added to the solution of methanol
(30 ml) in a Schlenk flask and stirred for 30 min. Then the triphen-
yltin chloride (0.385 g, 1 mmol) was added to the reactor, the reac-
tion mixture was stirred for 12 h at 40 °C. Then filtrated, the solvent
of the filtrate was gradually removed by evaporation under vacuum
until solid product was obtained. The solid was recrystallized from
benzene and a transparent colorless crystal was formed. Yield: 77%.
m.p. > 250 °C. Anal. Calc. for C32H31NO4Sn: C, 62.77; H, 5.10; N, 2.29.
Found: C, 62.93; H, 5.38; N, 2.01%. IR (KBr, cmꢁ1):
s(COO), 1370; (Sn–C), 558;
(Sn–O), 447. 1H NMR [(CD3)2SO,
mas(COO), 1653;
m
m
m
ppm]: d = 7.28–7.49 (m, 21H, –Ph), 7.75–8.37 [m, 3H, pyridine
(@CH)], 11.55 (s, 1H, N–H). 13C NMR [(CD3)2SO, ppm]: d 164.26
(COO); 112.15, 118.57, 138.71, 140.45, 162.31 [pyridine (@C)],
130.41–137.48 (Ar–C). 119Sn NMR [(CD3)2SO, ppm]: ꢁ124.8.
3.2.2. Synthesis of complex 2
The procedure is similar to that of complex 1, 6-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
and tribenzyltin chloride (0.427 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from ether, a transparent colorless crystal
was formed. Yield: 73%. m.p. > 250°C. Anal. Calc. for C29H33NO5Sn:
C, 58.61; H, 5.60; N, 2.36. Found: C, 58.33; H, 5.92; N, 2.07%. IR
Fig. 9. The molecular structure of 11.
for that, the supramolecular structure of a 2D network is formed
(Fig. 10).
(KBr, cmꢁ1):
mas(COO), 1655; ms(COO), 1371; m(Sn–C), 571; m(Sn–
O), 453. 1H NMR [(CD3)2SO, ppm]: d = 11.72 (s, 1H, N–H), 8.19 (s,
2H, H–O–H), 7.62–8.09 [m, 3H, pyridine (@CH)], 7.00–7.34 (m,
15H, –Ph), 4.87 (1H, EtO–H), 3.33 (–CH2), 2.54 (6H, Ph–CH2), 1.25
2.5. TGA studies
(–CH3). 13C NMR [(CD3)2SO, ppm]:
d 165.56 (COO); 112.84,
118.03, 127.92, 140.52, 163.09 [pyridine (@C)]; 128.52–137.65
(Ar–C); 58.31 (–OCH2); 27.23 (Ph–CH2); 17.9 (–CH3). 119Sn NMR
[(CD3)2SO, ppm]: ꢁ138.4.
To study the stability of complexes 1–11, thermogravimetric
analysis (TGA) was performed in the temperature range of 50–
600 °C under N2 atmosphere. The TGA curves of these complexes
exhibit one primary continuous weight loss stages in the range of
50–600 °C. In general, all these complexes exhibit good thermal
stability. Specially, we analyze the TGA curve of complex 11 in
detail. The TGA of 11 (Fig. 11) show a continuous loss (found:
5.222%) from 134.72 °C to 207.73 °C, which is attributed to the
loss of the 0.5CH3OH and C6H4NO3 (calc: 5.341%). Then the host
framework begins to decompose from 207.73 °C to 490.82 °C
(found: 33.10%), corresponding to 2Ph3Sn and 2C6H4NO3 (calc:
33.07%).
3.2.3. Synthesis of complex 3
The procedure is similar to that of complex 1, 6-hydroxynicotinic
acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and tri-
methyltin chloride (0.199 g, 1 mmol) were reacted for 12 h at 40 °C.
Recrystallized from ether, a transparent colorless crystal was formed.
Yield: 73%. m.p. > 250°C. Anal. Calc. for C9H13NO3Sn: C, 35.80; H, 4.34;
N, 4.64. Found: C, 35.53; H, 4.59; N, 4.35%. IR (KBr, cmꢁ1):
1656; ms(COO), 1373; m(Sn–C), 571; m
m
as(COO),
(Sn–O), 449. 1H NMR [(CD3)2SO,

C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
4239
Fig. 10. The 2D network structure of complex 11 connected by intermolecular N–HꢀꢀꢀO hydrogen bond (the
a- carbon of phenyl ring is reserved, and the other carbons are
omitted for clarity).
and triphenyltin chloride (0.325 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from ether, a transparent colorless crystal
was formed. Yield: 85%. m.p. > 250 °C. Anal. Calc. for C32H31NO3Sn:
C, 59.05; H, 3.92; N, 2.87. Found: C, 58.71; H, 4.17; N, 2.61%. IR
(KBr, cmꢁ1):
mas(COO), 1647; ms(COO), 1363; m(Sn–C), 554; m(Sn–
O), 457. 1H NMR [(CD3)2SO, ppm]: d = 9.76 (s, 1H, –OH); 8.01–
8.54 [m, 3H, pyridine (@CH)]; 7.48–7.80 (m, 15H, Ph). 13C NMR
[(CD3)2SO, ppm]: 168.32 (COO); 122.74, 125.57, 138.71, 140.44,
159.31 [pyridine (@C)]; 132.41–138.36 (Ar–C). 119Sn NMR
[(CD3)2SO, ppm]: ꢁ104.8.
3.2.6. Synthesis of complex 6
The procedure is similar to that of complex 1, 5-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
and tribenzyltin chloride (0.427 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from ether, a transparent colorless crystal
was formed. Yield: 73%. m.p. > 250 °C. Anal. Calc. for C27H25NO3Sn:
C, 61.16; H, 4.75; N, 2.64. Found: C, 60.88; H, 4.97; N, 2.47%. IR
Fig. 11. TGA curve of complex 11.
(KBr, cmꢁ1):
mas(COO), 1645; ms(COO), 1375; m(Sn–C), 528; m(Sn–
O), 475. 1H NMR [(CD3)2SO, ppm]: d = 9.80 (s, 1H, –OH), 7.79–
8.38 [m, 3H, pyridine (@CH)], 7.28–7.49 (m, 15H, Ph), 2.69 (s, 6H,
Ph–CH2). 13C NMR [(CD3)2SO, ppm]: d 167.36 (COO); 118.84,
124.23, 138.67, 140.75, 153.09 [pyridine (@C)]; 131.16–137.31
(Ar–C), 27.11 (Ph–CH2). 119Sn NMR [(CD3)2SO, ppm]: ꢁ126.7.
ppm]: d = 11.71 (s, 1H, N–H), 7.78–8.11 (m, 3H, pyridine), 0.88 (t, 9H,
CH3, JSn–H = 67.6 Hz). 13C NMR [(CD3)2SO, ppm]: d 166.34 (COO);
2
113.04, 118.13, 138.51, 140.66, 162.67 [pyridine (@C)]; 14.2 (–CH3,
1JSn–C = 652 Hz). 119Sn NMR [(CD3)2SO, ppm]: ꢁ159.3.
3.2.4. Synthesis of complex 4
3.2.7. Synthesis of complex 7
The procedure is similar to that of complex 1, 6-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
and tri-n-butyltin chloride (0.325 g, 1 mmol) were reacted for
12 h at 40 °C. Recrystallized from ether, a transparent colorless
crystal was formed. Yield: 77%. m.p. 176–178 °C. Anal. Calc. for
C18H31NO3Sn: C, 50.49; H, 7.30; N, 3.27. Found: C, 50.18; H, 7.59;
The procedure is similar to that of complex 1, 5-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
and trimethyltin chloride (0.199 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from ether, a transparent colorless crystal
was formed. Yield: 83%. m.p. > 250 °C. Anal. Calc. for C9H13NO3Sn:
C, 35.80; H, 4.34; N, 4.64. Found: C, 35.56; H, 4.63; N, 4.38%. IR
N, 3.01%. IR (KBr, cmꢁ1):
574;
(Sn–O), 458. 1H NMR [(CD3)2SO, ppm]: d = 11.67 (s, 1H, N–
mas(COO), 1653; ms(COO), 1370; m(Sn–C),
(KBr, cmꢁ1):
mas(COO), 1649; ms(COO), 1371; m(Sn–C), 550; m(Sn–
m
O), 446. 1H NMR [(CD3)2SO, ppm]: d = 9.66 (s, 1H, O–H), 7.99–
H), 7.79–8.05 [m, 3H, pyridine (@CH)], 1.30–1.41 (m, 18H,
CH2CH2CH2), 0.95 (t, 9H, CH3). 13C NMR [(CD3)2SO, ppm]: d
168.07 (COO); 113.04, 118.13, 138.51, 140.77, 162.67 [pyridine
(@C)]; 13.74, 18.74 (1JSn–C = 452 Hz), 26.54, 27.69 (n-Bu). 119Sn
NMR [(CD3)2SO, ppm]: ꢁ141.9.
2
8.46 [m, 3H, pyridine (@CH)], 0.91 (t, 9H, CH3, JSn–H = 67.6 Hz).
13C NMR [(CD3)2SO, ppm]:
d 168.16 (COO); 119.04, 122.13,
138.51, 140.66, 152.67 [pyridine (@C)]; 13.3 (–CH3,
1JSn–C = 439 Hz). 119Sn NMR [(CD3)2SO, ppm]: ꢁ119.3.
3.2.8. Synthesis of complex 8
3.2.5. Synthesis of complex 5
The procedure is similar to that of complex 1, 5-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
The procedure is similar to that of complex 1, 5-hydroxynico-
tinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol)
and tri-n-butyltin chloride (0.325 g, 1 mmol) were reacted for

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C. Ma et al. / Journal of Organometallic Chemistry 694 (2009) 4230–4240
12 h at 40 °C. Recrystallized from ether, a transparent colorless
crystal was formed. Yield: 77%. m.p. 155–157 °C. Anal. Calc. for
C18H31NO3Sn: C, 50.49; H, 7.30; N, 3.27. Found: C, 50.18; H, 7.61;
atoms were placed in calculated positions. Crystal data and exper-
imental details of the structure determinations are listed in Tables 1
and 2.
N, 2.99%. IR (KBr, cmꢁ1):
536;
m
as(COO), 1651;
ms(COO), 1372; m(Sn–C),
m
(Sn–O), 471. 1H NMR [(CD3)2SO, ppm]: d = 9.71 (s, 1H,
4. Conclusions
–OH), 8.00–8.54 [m, 3H, pyridine (@CH)], 1.26–1.39 (m, 18H,
CH2CH2CH2); 0.91 (t, 9H, CH3). 13C NMR [(CD3)2SO, ppm]: d
166.02 (COO); 118.14, 122.37, 139.75, 141.31, 152.95 [pyridine
(@C)]; 14.02, 18.21 (1JSn–C = 377 Hz), 27.51, 29.38 (n-Bu). 119Sn
NMR [(CD3)2SO, ppm]: ꢁ129.6.
In summary, a series new triorganotin(IV) pyridinecarboxylates
have been synthesized and characterized. Detailed studies on the
structures of these complexes indicate that the complexes based
on 6-hydroxynicotinic acid and 2-hydroxyisonicotinic acid, the
carboxylate oxygen atoms and the keto oxygen atoms coordinate
to Sn centers forming a chain/cycle. However, in the complexes
based on 5-hydroxynicotinic acid, instead of the keto oxygen
atoms, the N atoms and carboxylate oxygen atoms coordinate to
Sn centers.
3.2.9. Synthesis of complex 9
The procedure is similar to that of complex 1, 2-hydroxyisonicot-
inic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol), and
trimethyltin chloride (0.199 g, 1 mmol) were reacted for 12 h at
40 °C. Recrystallized from methanol and a transparent colorless crys-
tal was formed. Yield: 81%. m.p. 188–190 °C. Anal. Calc. for
C9H13NO3Sn: C, 35.80; H, 4.34; N, 4.64. Found: C, 35.54; H, 4.61; N,
Acknowledgment
4.36%. IR (KBr, cmꢁ1):
mas(COO), 1655; ms(COO), 1372; m(Sn–C), 568;
We thank the National Natural Science Foundation of China
(20741008) for financial support.
m
(Sn–O), 457. 1H NMR [(CD3)2SO, ppm]: d = 0.64 (s, 9H, Sn–CH3,
2JSn–H = 72.2 Hz), 7.77–8.12 [m, 3H, pyridine (@CH)], 11.75 (s, 1H,
N–H). 13C NMR [(CD3)2SO, ppm]: d 167.34 (COO); 113.04, 122.10,
1
Appendix A. Supplementary material
138.51, 140.66, 162.67 [pyridine (@C)], 11.13 (CH3, JSn–C = 640 Hz).
119Sn NMR [(CD3)2SO, ppm]: ꢁ151.2.
CCDC 681949, 681953, 681951, 740924, 740928, 740927,
707748, 742093, and 707749 contains the supplementary crystal-
lographic data for complexes 1, 2, 3, 4, 7, 8, 9, 10, and 11. These
data can be obtained free of charge via http://www.ccdc.cam.a-
c.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.
3.2.10. Synthesis of complex 10
The procedure is similar to that of complex 1, 2-hydroxyisoni-
cotinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol),
and tribenzyltin chloride (0.427 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from methanol and a transparent colorless
crystal was formed. Yield: 81%. m.p. 97–99 °C. Anal. Calc. for
C28H29NO4Sn: C, 59.81; H, 5.20; N, 2.49. Found: C, 60.18; H, 4.97;
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2009.09.001.
N, 2.27%. IR (KBr, cmꢁ1):
571;
(Sn–O), 453. 1H NMR [(CD3)2SO, ppm]: d = 11.49 (s, 1H, N–
mas(COO), 1654; ms(COO), 1372; m(Sn–C),
m
References
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4.83 (–OH), 3.61 (–OCH3), 2.75 (s, 6H, Ph–CH2). 13C NMR [(CD3)2SO,
ppm]: d 170.75 (COO); 112.84, 118.63, 138.67, 140.75, 158.09 [pyr-
idine (@C)]; 131.07–138.51 (Ar–C), 58.31 (–OCH3), 28.13 (Ph–CH2),
17.9 (–CH3). 119Sn NMR [(CD3)2SO, ppm]: ꢁ136.8.
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3.2.11. Synthesis of complex 11
The procedure is similar to that of complex 1, 2-hydroxyisoni-
cotinic acid (0.139 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol),
and triphenyltin chloride (0.385 g, 1 mmol) were reacted for 12 h
at 40 °C. Recrystallized from methanol and a transparent colorless
crystal was formed. Yield: 78%. m.p. 188–190 °C. Anal. Calc. for
C145H117N6O18.5Sn6: C, 59.00; H, 4.00; N, 2.85. Found: C, 58.69; H,
4.21; N, 2.58%. IR (KBr, cmꢁ1):
mas(COO), 1659; ms(COO), 1372;
m(Sn–C), 572;
m
(Sn–O), 446. 1H NMR [(CD3)2SO, ppm]: d = 7.26–
7.51 (s, 90H, Sn–Ph), 7.74–8.13 [m, 3H, pyridine (@CH)], 11.67 (s,
6H, N–H). 13C NMR [(CD3)2SO, ppm]: d 168.15 (COO); 113.58,
122.37, 135.99, 141.31, 159.61 [pyridine (@C)], 129.33–138.68
(Ar–C). 119Sn NMR [(CD3)2SO, ppm]: ꢁ176.2.
3.3. X-ray crystallographic studies
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Diffraction data were collected on a Smart CCD area-detector
with graphite monochromated Mo Ka radiation (k = 0.71073 Å). A
semiempirical absorption correction was applied to the data. The
structure was solved by direct methods using SHELXS-97 and refined
against F2 by full-matrix least squares using SHELXL-97. Hydrogen
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