-
Indian Journal of Chemistry Vol. 42A . January 2003, pp.
48-52
One-dimensional infinite chain organotin complexes: Synthesis
and structural characterization of triphenyltin(IV)
thiophen-2-carboxylate and triphenyltin(IV)
4-pyridinylcarboxylate
Handong Yin*, Chuanhua Wang, Yong Wang & Chunlin Ma
Department of Chemistry, Liaocheng Teachers University,
Liaocheng 252059, P R China
Received J 3 OClober 200 I ; revised 3 Seplelllber 2002
Triphenyltin(lV) thiophen-2-carboxylate (1) and triphenyltin(lV)
4-pyridinylcarboxylate (2) have been synthesized by the react ion
of sodium 2-thiophenylcarboxylate and sodium 4-pyrid
inylcarboxylate with the triphenyltin(l V) chloride and
characterized by lR, 'H NMR. MS and sing le crystal X-ray
diffraction. In the crystals of 1, the tin atoms are rendered
four-coordinated in a di storted tetrahedral structure. Due to the
presence of a close intermolec ular Sn "'S interact ion of 3.339 A.
the structure can be described as a weak ly-bridged one-d
imensional chain polymer. In the crystal s of 2, the tin atom is fi
ve-coordinated with bridging pyridine N atom and resulting struct
ure is one-dimensiona l chain polymer.
Organotin(lV) carboxylates are widely used as biocides,
fungicide and in industry as homogeneous catalysts '-) . In order
to study the relationship between biological activity and
structure, a number of investi gations of such molecules have been
reported in recent years. Studies on organotin complexes having
carboxylate ligands with additional donor atoms, such as a
nitrogen, available for coordination to tin atom, has revealed new
structural types which may lead to complexes with di fferent
activity. For example, dimethyltin 2-pyridinylcarboxylate4 has
seven-coordinated tin atom, owing to the multi dentate nature of
the bridging 2-pyridinylcarboxylate ligand which utilizes both the
carboxylate 0 and the pyridine N atoms in coord ination to Sn. In
contrast, dimethyl 2-furanylcarboxylate and diethyl
2-thiophenyl-carboxylate have six-coordinated tin centers5. As an
extension of our studies of organotin carboxylate with additional
donor atoms residing on the carboxylate ligand, we now report the
synthesis and st ructure of triphenyltin(lV) thiophen-2-carboxylate
(1) and tri pheny Itin(l V) 4-pyridiny Icarboxylate (2) .
Materials and Methods Al l reactions were carried out under
nitrogen
atmosphere using standard Schlenk technique. Benzene was
distilled under nitrogen in the presence of sodium and benzopenone
before use. IR spectra were recorded with a Nicolet-460
spectrophotometer, as KBr discs. I H NMR spectra were recorded on
Jeol-FX-90Q NMR spectrometer, chemical shifts are given
in ppm relative to Me4Si in CDCl" solvent. Elemental analyses
were performed in a Carlo-Erba 1106 elemental analyzer, Tin was
estimated as Sn02. The mass spectra were recorded on a HP-5988A
spectrometer operati ng at 70 e V.
Synthesis of(1) and (2) Anhydrous sod ium
2-thiophenylcarboxylate or
sodium 4-pyridinecarboxylate (1.2 mmol) was added to a benzene (
10 mL) solution of Ph ,SnCI ( 1.0 mmol ) and stirred for 15 h at
40°C. The precipitaled salts were removed by fi ltration . The
solvent was removed gradually by evaporation under vacuum until
solid products were obtained. The products were recrystallized from
CH2CI2-C6H 14 to give a colorless crystals.
Triphenyltin(lV) thiophen-2-carboxylate (1): Yield 0.429 g
(90%), m.p. 88-90°C Anal. Found: C, 57.68; H, 3.72; S, 6.84 Sn,
24.59. Calc. For C2j HIS0 2SSn: C, 57.90; H, 3.80; S, 6.72; Sn,
24.88. TR(KBr) : u(Ar-H ) 3064, 3043, uas(COO) 1623 , us(COO) 1326,
u(Sn-C) 547, u (Sn-O)443 cm-I. IH NMR (CHCI» : 7.36-7 .79 (l8H, m,
Ph-H, thiophene-H). mlz: 405 (M+ -C6H6-H. 11.5%), 351 (Ph)Sn+,
100%), 27 3 [(C6H4h Sn+H, 9.8%], 127 (C4H3SC02+, 5.4%), 120 (Sn+,
45.4 %).
Triphenyltin(lV) 4-pyridinylcarboxy late (2): Yield 0.453 g
(85%), m.p. 205-206°C. Anal. Found: C 57.30, H 3.85, N 2.8 1, Sn
23.33 . Calc. for C24.5 H2oCIN02Sn C 57.19, H 3.92, N 2.72, Sn
23.07. IR(KBr): u(Ar-H) 3065, 3040, uas(COO) 1646, us(COO) 1329,
u(Sn-C)544, u(Sn-N)498, u(Sn-O)4SS
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YIN et al.: ONE-DIMENSIONAL INFINITE CHAIN ORGANOTIN COMPLEXES
49
cm· l . IH NMR (CHCI): 8.80 (2H, d, 2, 6-pyridine-H), 7.80 (2H,
d, 3, 5-pyridine-H), 7.36-7.72 (15H, m, ph-H) . m/z:400 (M+-C6H6-H,
8.5 %), 351 (Ph)Sn+, 100%), 273 [(C6H4hSn+H, 6.4 %], 122
(C5H4NC02+, 3.2%), 120 (Sn+, 45.4%).
Crystal structure The X-ray diffraction experiments for
triphenyltin(lV) thiophen-2-carboxylate (1) and triphenyltin(lV)
4-pyridinylcarboxylate (2) were made on a Bruker Smart 1000 CCD
diffractometer with graphite monochromated MoKa (A,=O.71 073 A)
radiation . The structure was solved by direct method and expanded
method using Fourier techniques with Shelxl-97 program. The
non-hydrogen atoms were refined an isotropically by full-matrix
least-squares calculations. Crystallographic data for 1 and 2 are
li sted in Table I.
Results and Discussion The crystal structure and stereogram of
the
complexes 1 and 2 packing in a crystal unit cell are shown in
(I) and (II) respectively. Selected bond distances and angles are
listed in Tables 2 and 3.
The basic structure of the complex 1, resu lts from a distortion
from tetrahedral geometry induced by the approach of an oxygen
atom, 0(2), of the carboxylate group at a tetrahedral face opposite
one of the tin phenyl groups. The distortion is toward a trigonal
bipyramid that contains 0(2) and the latter phenyl group at axial
sites [Structure (I)]. The axial
(I)
Table I-Crystallographic data for triphenyltin(IV )
thiophen-2-carboxylate (1) and triphenyltin(lV)
4-pyridinylcarboxylate
(2)
Crystal data 1 2
Molecu lar formul a C23HIs0 2SSn C2oH2oCIN02Sn Formul ar weight
477. 12 514.55 Crystal system Monoclinic Monoc linic Space group P2
1/n P2 1 Unit cell dimensions a(A) 13.429(7) 12.269(3) b(A)
11.1773(6) 14.987(4) c(A) 14.241(8) 24.3 18(7) j3( ) 11 6.5 19(6)
90.040(5) V(A3) 2014.6(18) 4471 (2) Z 4 8 Dc, I(Mg/m
3) 1.573 1.529
J1 (mm· l ) 1.386 1.282 F (000) 952 2056 Crystal size (mm)
0.50xO.40xO.20 0.40xO.30xO.20 Theta range/o 2.36::::11::::25 .03
1.60::::11::::25.03 Observed/cut-off 3544/20(1) 14 770120( I) Rint
0.0548 0.0404 R/wR2 0.039110.0943 0.0543/0.1086 Largest difference
0.402/-0.517 0.927/-0.679 Peak and hole (e·k3)
Sn(l ) ·0(2) (2 .774 A) length is considerably longer than the
equatorial Sn(l )-0(1) (2.081 A) bond length. On the basis of such
interaction, the O( I )-Sn( I )-C(6) (94.32°) angle significantly
deviates from the ideal tetrahedral angle. However, other angles
around the central Sn atom are comparable to tetrahedral angle. Due
to the presence of a close intermolecular SnS interaction of 3.339
A, the structure can be described as a weakly-bridged
one-dimensional chain polymer.
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50 INDIAN J CHEM, SEC A, JANUARY 2003
Table 2-Selected bond distances (A) and angles n for complex 1
Sn( I )-O( I ) 2.08 1 (3) Sn(l) 0(2) 2.774 Sn( I )-C( 18) 2. 120(4)
Sn(I)-C(12) 2.124(4) Sn( I )-C(6) 2.126(4) Sn( I )S (1)# 3.339 S( I
)-C(5) 1.671 (6) S(I )-C(2) 1.699( 4) O( I )-C( I) 1.309(5)
O(2)-C(l ) 1.223(5) C(I )-C(2) 1.466(6) C(2)-C(3) 1.07(6)
O( I )-Sn( I )-C( 18) I 08.35( I ) O( I )-Sn( I )-C( 12) 109.25(
14) O( I )-Sn( I )-C(6) 94.32( 13) C( 18)-Sn( I )-C( 12) 117.86(1 )
C( 18)-Sn( I )-C(6) 113.52( 16) C( 12)-Sn( I )-C(6) 110.87( 15)
C(5)-S( I )-C(2) 92.5(3) C( I )-O( I )-Sn( I ) 108.4(3) C( II
)-C(6)-Sn(l ) 120.8(3) C(7)-C(6)-Sn( I ) 121.9(3) C( 17)-C( 12)-Sn(
I ) 121.5(4) 0 (2)-C( I )-O( I) 121.9(4) 0(2)-C( I )-C(2) 123.0(4)
O( I )-C( I )-C(2) 11 5. 1(4) C(3)-C(2)-S( I ) 111 .7(3) C( I
)-C(2)-S( I ) 11 9.0(3) C(4)-C(5)-S( I ) 112.4(4) C( 13)-C( 12)-Sn(
I) 120.3(3) C(23 )-C( 18)-Sn( I ) 12 1.5(3) C( 19)-C( 18)-Sn( I )
119.5(3) C( 17)-C( 12 )-C( 13) 11 8.2(4) O( I )-Sn( I )0(2) 5
1.8(2) 0(2)' Sn( I )-C( 18) 85.2( I ) 0(2)Sn( I )-C( 12) 8 1.2(6)
0(2)Sn( I )-C(6) 145.9(2) 0(1 )-Sn(l ) · S ( 1)# 167.0( 1) C(1)-Sn(
I ) 'S ( 1)# 72.6(8) C( 12)-Sn( I )S( 1)# 76.4(8) C( 18)-Sn(l ) S (
1)# 77.7( 1) 0(2)Sn( I )S( 1)# 141.0(2)
Table 3--Selected bond distances (A) and angles (0) for complex
2
BOlld dis/{/Ilces
A B A B
Sn( I )-C(25) 2. 123( 11 ) 2. 11 6(1 1 ) Sn(2)-N( I ) 2.557(9)
2.553(9) Sn( I )-C( 19) 2. 130(11 ) 2. 117( 13) N(I)-C(4) 1.291(
13) 1.313( 13) Sn( I )-C( 13) 2. 132(12) 2. 145( 12) N( I )-C(5)
1.36 1 ( 14) 1.380( 15) Sn(I)-O( I ) 2. 170(7) 2. 173(7) N(2)-C( II
) 1.336( 13) 1.322( 13 Sn(I) .. . O(2) 3.082 3.054 N(2)-C(10)
1.371(13) 1.339( 14) Sn(2)-C(3 1) 2. 120( 13) 2. 126( 12) 0 (1 )-C(
I ) 1.252( 13) 1.273( 13) Sn(2)-C(43) 2. 161(12) 2. 140( 14) O( I
)-C(2) 1.1 96( I I ) 1.1 83( II ) Sn(2)-C(37) 2. 177( 11 ) 2.151 (
12) O(3)-C(7) 1.278( 13) 1.285( 14) Sn(2)-0(3) 2. 148(7) 2.159(7)
0(4)-C(7) 1.236( 12) 1.222( 13) Sn(2) ... 0(4) 3. 106 3. 110 C( I
)-C(2) 1.562( i 3) 1.507( 13) Sn( I )-N(2)# 2.60 1( 12) 2.584(9)
C(2)-C(6) 1.400( 14) 1.408( 13)
BOlld allgles
C( 13)-Sn( I )-O( I ) 89 .1 (3) 88.4(3) C( 44 )-C( 43 )-Sn(2) 11
6.5(9) 118.3( 11 ) C(25)-Sn( 1 )-C( 19) 126.5(5) 126.7(5) C(4)-N( I
)-C(5) 11 7.9(10) 116.4( 10) C(25)-Sn( 1 )-C( 13) 11 8.3(5) 11
8.7(5) C(4)-N( I )-Sn(2) 125.2(8) 125 .8(8) C( 19)-Sn( I )-C( 13)
11 3.2(5) 11 2.6(5) C(4)-N( I )-Sn(2) 11 6.7(8) 117.3(8) C(2S)-Sn(
I )-O( I ) 96. 1 (3) 96.5(3) C( 11 )-N(2)-C( 10) 11 8.7(9) 120.9( I
0) C( 19)-Sn( I )-O( I ) 98. 1(3) 98.2(3) C( 13)-Sn( I )-N(2)#
84.6(9) 84.4(3) C(31 )-Sn(2)-0(3) 93. 1(4) 98.2(3) C(25)-Sn( I
)-N(2)# 84.8(7) 84.8(4) C(3 1 )-Sn(2)-C( 43) 124.9(5) 123.8(5) C(
19)-Sn( I )-N(2)# 86.4(9) 87. 1(3) 0(3 )-Sn(2 )-C( 43) 96.5(3)
96.5(3) O( I )-Sn( I )-N(2)# 173.3(3) 172.6(3) C(31 )-Sn(2)-C(37)
122.9(5) 124.6(6) C( I 0)-N(2)-Sn( 1)# 11 6.8(5) 117.2(7)
0(3)-Sn(2)-C(37) 90.4(4) 89.6(4) C(lI)-N(2)-Sn( I )# 120.7(8) 12
1.9(8) C(43)-Sn(2)-C(37) 111.1 (5) 110.6(5) C( I )-O( I )-Sn( I )
11 5.3(7) 116.0(7) C(31 )-Sn(2)-N( I ) 83.8(4) 83.8(4)
C(7)-0(3)-Sn(2) 117.8(7) 116.0(7) 0(3)-Sn(2)-N( I ) 175.8(3) 176.
1(3) 0(2 )-C( I )-O( I ) 127 .3( 10) 124.2( 10) C(43)-Sn(2)-N( I )
87.6(4) 87.4(4) O(2)-C(I )-C(2) 11 8. / ( II ) 120.3( I 0)
C(37)-Sn(2)-N( I ) 88.9(4) 89.0(4) O( I )-C( I )-C(2) 114.5( II )
11 5.5( 10) C( II )-N(2)-C( I 0) 11 8.7(9) 120.9(10) C(3)-C(2)-C(6)
119.9( 10) 117.2(9) C(3)-C(2)-C( I ) 122.0(10) 12 1.9(9) 0(4
)-C(7)-0(3) 124.4( I 0) 126.6( II ) N( I )-C(4)-C(3) 123.3( 11)
124. / ( 11 ) 0(4)-C(7)-C(8) 11 9.6( II ) 120.0( 12) N( I
)-C(5)-C(6) 124.3( 12) 122.7( 11 ) 0(3)-C(7)-C(8) 11 5.9( 11 ) 11
3.4( II ) N(2)-C( 10)-C(9) 11 9.5(9, 11 9.9( 10) C( 14)-C( 13)-Sn(
l ) 120.5(8) 120.2(9) N(2)-C( II )-C( 12) 123.2(1 1) 12 1.0( 11 )
C( 18)-C( 13)-Sn( I ) 11 9.3(9) 120.2( I 0)
C(20)-C( 19)-Sn( I ) 11 6. / ( 10) 117.7(8) C(30)-C(25)-Sn( I )
12/.8(8) 11 7.2( 10)
C(24 )-C( 19)-Sn( I ) 11 9.3(9) 12 1.4(9) C(26)-C(25)-Sn( 1) 11
8.0(9) 11 8.6(8) C(32)-C(3 1 )-Sn(2) 12 1.4( 10) 124. 1( 12) C(
42)-C(37)-Sn(2) 11 6.2(9) 11 5.2( 11 ) C(36)-C(3 1 )-Sn(2) 117. / (
II ) 11 8.5( I I) C(48)-C( 43)-Sn(2) 11 8.6( 10) 120.6( 11 )
C(38)-C(37)-Sn(2) 122. /(11 ) 121.3( I I)
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YIN el al.: ONE-DIMENSIONAL INFINITE CHAIN ORGANOTIN COMPLEXES
51
From unit cell, it is found that complex 2 contains two
independent molecules. A computer fitting of molecules A and B
shows a very marginal difference in the orientation of molecular
chains and relevant bond lengths and angles, and two kinds of tin
atoms with different chemical environment can be found in the
molecule A or B. The molecule A or molecule B of crystal 2 unit
cell possesses an unequivocal polymeric structure, but this
structure differs from the tributyltin
2-(5-tert-butyl)furanylcarboxylate6 and tri benzy I ti n 2-(5-tert
-buty I )furany Icarbox y late6. Each tin atom is rendered
five-coordinated in a trigonal bipyramidal structure by
coordination of the nitrogen atom of 4-pyridinylcarboxylate group
from an adj acent molecule. The central tin atoms are surrounded
axially by one oxygen, one nitrogen atoms and equatorially by the
three carbon atoms of the phenyl groups. The intramolecular Sn( I
)-0(1), Sn(2)-0(3), Sn(3)-0(5) and Sn(4)-0(7) bond distances are 2.
170(7) A, 2.173(7) A, 2.148(7) A and 2.159(7) A which are longer
than that in {["Bu2Sn(2-pic)hO} / (2.0544 A and 2.1 IO A), but
shorter than that in
o 0 8 Me)Sn02CCsH4N' H20 (2. 18 A and 2.21 A). The Sn( I )-0(2)
, Sn(2)-0(4), Sn(3)-0(6) and Sn(4)-0(8) di stances are 3.082 A,
3.054 A, 3.106 A and
(II)
3.110 A, respectively and are larger than the sum of the
covalent radii for Sn and 0 of 2.07 A. It is shown that the 0(2),
0(4), 0(6) and 0(8) atoms do not make any significant contact with
the Sn atom. The Sn( 1)-N(2)#, Sn(2)-N(1), Sn(3)-N(4)# and
Sn(4)-N(3) bond distances are 2.601(12) A, 2.557(9) A 2.584(9) A
and 2.553(9) A, respectively which are larger than the sum of the
covalent radii of Sn and N(2 . 15 A) , but considerably less than
the sum of the Van der Waals radii (3.75 A) and should be
considered as a bonding interaction.
In complex 2 the distortions from true tri gonal bipyramidal
symmetry are reflected in the interatomic angles. For instance,
around the Sn(2) atom o f molecule A the angles of
0(3)-Sn(2)-C(3I)l93.1 (4 t ] and 0(3)-Sn(2)-C(43)[96.5(3n are
greater than 90°, and only 0(3)-Sn(2)-C(37) [90.4(4n approximates
to 90°. In contrast, the angles C(31 )-Sn(2)-N(1 )[83.8(4 )0], C(
43)-Sn(2)-N(1 )[87 .6( 4 )0] and C(37)-Sn(2)-N(l)[88.9(4)0] are all
less than 90°. The angle 0(3)-Sn(2)-N(1) [175.8(3n shows that the
atoms 0(3), Sn(2) and N( I) are nearly linear. Other tin atoms are
similar to Sn(2) atom. All are disto rted trigonal bipyramidal
structure.
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52 TNDIAN J CHEM, SEC A, JANUARY 2003
The assignment of IR bands of triphenyltin(lV)
thiophen-2-carboxylate (1) and triphenyltin(lV)
4-pyridinylcarboxylate (2) have been made by comparison with the IR
spectra of the related sodium 2-thiophenylcarboxylate, sodium
4-pyridinyl-carboxylate and Ph3SnCI. The difference flv of
U,.,(coo) and u£coo) is important since these frequencies can be
used for determining the type of bonding between metal and
carboxyI3,9, The flv [uas(coo)-us(coo)] values of 297 cm- I and 317
cm- I for complexes 1 and 2 respectively strongly indicate the
unibidentate chelating of the carboxylate groupIO,II,
The bands in the region 443 and 455 cm- I are assigned to
v(Sn-O), The IR spectra of complex 2 at 498cm- 1 exhibit U Sn.N
confirming that the N hetero atom in the pyridine group coordinates
to tin atom 12,
In mass spectra, the molecular ions were not detected for
complexes 1 and 2, M+-C6H6-H and C6H4h Sn+H were the main
tin-containing fragment. The most abundant ions were Ph3Sn + (mJz =
351). Ions of mass higher than parent species were not detected nor
were there fragments containing more than one tin atom. This
indicates that inter-molecular Sn ' S or Snf-N bond has been broken
up, and the complexes take only monomeric structure in gaseous
state.
Acknowledgement We acknowledge the Financial support of the
Shandong Province Science Foundation , and the State Key
Laboratory of Crystal Materials, Shandong University, P R
China,
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