Synthesis and structural characterization of several tris(2-methyl-2-phenylpropyl)tin carboxylates containing germanium

Article abstract of DOI:10.1016/S0022-328X(00)00542-8

Thirteen tris(2-methyl-2-phenylpropyl)tin germylpropionates have been synthesized and their structures characterized by elemental analysis, IR, multinuclear NMR (¹H, ¹³C, ¹¹⁹Sn) and MS spectroscopies. The structure of (PhC(CH₃)₂CH₂)₃SnO ₂CCH₂CH(o-C₆H₄Cl)GePh₃ has been determined by X-ray diffraction study, which indicated that the tin in the compound possess a tetrahedral geometry. Bioassay results have shown that some of the compounds have good acaricidal activity.

Full text of DOI:10.1016/S0022-328X(00)00542-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 619 (2001) 43–48
Synthesis and structural characterization of several
tris(2-methyl-2-phenylpropyl)tin carboxylates containing
germanium
Xiaoniu Fang a, Xueqing Song b,*, Qinglan Xie b
a Department of Chemistry, Ji’an Teachers’ College, Ji’an, 343009, PR China
b Institute of Elemento-Organic Chemistry, Nankai Uni6ersity, Tianjin, 300071, PR China
Received 25 May 2000; received in revised form 24 July 2000
Abstract
Thirteen tris(2-methyl-2-phenylpropyl)tin germylpropionates have been synthesized and their structures characterized by
elemental analysis, IR, multinuclear NMR (1H, 13C, 119Sn) and MS spectroscopies. The structure of
(PhC(CH3)2CH2)3SnO2CCH2CH(o-C6H4Cl)GePh3 has been determined by X-ray diffraction study, which indicated that the tin in
the compound possess a tetrahedral geometry. Bioassay results have shown that some of the compounds have good acaricidal
activity. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Organotin; Organogermanium; Synthesis; IR; Multinuclear NMR; X-ray diffraction; Acaricial activity
possess significantly greater biocidal activity than the
compounds with the monomeric cis-C3SnO2 structural
type, i.e. compounds with chelating carboxylate ligand
spanning both equatorial and axial sites.
1. Introduction
Organotin compounds have been extensively studied
of their biological activity [1,2]. In general, the in vitro
fungicidal and antibacterial properties of organotins
have indicated that the order of activity is related to the
number of R groups attached to the tin atom. The
order of activity has been observed to be: RSnX3B
R2SnX2BR3SnX. The nature of the X group has rela-
tively little influence on the fungicidal activity of an
organotin compound [3]. However, studies have contin-
ued on the structures of various triorganotin com-
pounds, especially those containing X groups that
themselves have some biological activity [4–8]. In addi-
tion, these compounds show an interesting range of
structural variations leading to activity–structure rela-
tionships [9]. These latter studies have shown that tri-
organotin carboxylates that have either isolated
tetrahedral tin centers or trans R3SnO2 tin atom ge-
ometries (arising from bridging carboxylate ligands)
To link the biological active properties of organotin
and organogermanium compounds, we have previously
reported the biological activity of trialkyltin germylpro-
pionates [10] and the anticancer activity of dibutyl
digermylpropionates [11]. In the continuation of our
previous work [10,11], we now introduce a very bulky
R (2-methyl-2-phenylpropyl) group into the R3Sn moi-
ety, and have synthesized a series of triorganotin car-
boxylates containing the biologically active germyl
groups in the carboxylate ligands. The synthetic proce-
dures and their structural characterization using vari-
ous spectroscopic methods are reported herein.
2. Experimental
2.1. Materials
* Corresponding author. Current address: Department of Chem-
istry, The Catholic University of America, Washington, DC 20064,
USA. Fax: +1-202-2747466.
Torque (tris(2-methyl-2-phenylpropyl)tin oxide) was
used as received since the melting point agreed with the
literature value [12]. Solvents were dried with Na metal
E-mail address: song@cua.edu (X. Song).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00542-8

44
X. Fang et al. / Journal of Organometallic Chemistry 619 (2001) 43–48
2.2. Synthesis of the products
All the compounds were synthesized using similar
procedures. The synthetic procedure is shown in
Scheme 1.
Typically, a mixture of Torque (1.0 mmol), substi-
tuted germylpropanoic acid (2.0 mmol) and toluene (50
ml) was refluxed for 6 h. The water liberated in the
reaction was removed azeotropically by a Dean–Stark
apparatus. Then the mixture was cooled down and the
toluene was removed using a rotary evaporator. The
sticky residue obtained was dried in vacuum to give a
white solid. Recrystallization of the white solid from a
mixture of chloroform and petroleum yielded fine crys-
tals. The analytical and physical data of the products
are given in Table 1.
Scheme 1. 1 (R3=Ph3, R1=H, R2=H), 2 (R3=Ph3, R1=CH3,
R2=H), 3 (R3=Ph3, R1=H, R2=CH3), 4 (R3=Ph3, R1=Ph,
R2=H), 5 (R3=Ph3, R1=p-C6H4OCH3, R2=H), 6 (R3=Ph3,
R1=o-C6H4OCH3, R2=H), 7 (R3=Ph3, R1=o-C6H4Cl, R2=H),
8
(R3=Ph3, R1=p-C6H4Cl, R2=H), (R3=Ph3, R1=2,4-
9
C6H3Cl2, R2=H), 10 (R3=Ph3, R1=p-C6H4CH3, R2=H), 11
(R3=(p-CH3C6H4)3, R1=H, R2=H), 12 (R3=(p-CH3C6H4)3,
R1=p-CH3C6H4, R2=H), 13 (R3=(p-CH3C6H4)3, R1=o-ClC6H4,
R2=H).
2.3. Crystallography
Intensity data for a colorless crystal 0.72×0.50×
0.26 mm were measured at r.t. on a Bruker SMART
1000 diffractometer fitted with graphite monochroma-
tized Mo–Ka radiation, u=0.71073, in the range of
2°BqB23° employing the ꢀ–2q scan techniques. The
data were corrected for Lorentz and polarization ef-
fects, and of 10032 unique data, 7970 satisfied the
I]2l (I) criterion of observability and were used in the
subsequent analysis.
before use. All the substituted germylpropanoic acids
were prepared according to known literature methods
[10,11].
The NMR data were recorded on a Bruker AC-P
200, using CDCl3 as the solvent, and the references
were TMS or Me4Sn (for 119Sn-NMR). The IR spectra
were recorded on a SHIMADZU IR-435 Spectrometer
using KBr disc. The elemental analyses were deter-
mined using a YANACO MT-3 analyzer. The MS data
were recorded on an HP-5988A mass spectrometer (EI
source at 200°C, 70 eV).
Crystals of compound 7 suitable for X-ray diffraction
experiments were obtained from solutions of chloro-
form–petroleum ether mixtures over a prolonged pe-
riod at room temperature (r.t.). The reflection data
were collected on a Brucker Smart 1000 diffractometer.
Crystal data for C57H61ClGeO2Sn: Mr=1004.5, tri-
(
clinic, space group P1 (no. 2), a=11.666(1), b=
,
15.354(1),
i=94.38(3)°, g=90.407(1)°, V=2540.4(3) A , Z=2,
calc=1.314 mg m−3, F(000)=1.36, v=1.175 mm−1
The structure was solved by direct methods, and
c=16.006(1)
A,
h=117.437(1)°,
3
,
D
.
refined by a full-matrix least-squares procedure based
on F. Nonhydrogen atoms were refined with an-
isotropic thermal parameters. The analysis of variance
Table 1
The analytical and physical data of tris(2-methyl-2phenylpropyl)tin germylpropionates
No.
Formula
State
M.p. (°C)
Yield (%)
Elemental analysis (%)
C
H
1
2
3
4
5
6
7
8
9
10
11
12
13
C
51H58GeO2Sn
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
White crystal
90–93
104–105
83–85
91
86
87
85
83
75
87
94
79
83
86
98
60
68.40(68.50)
68.85(68.76)
68.79(68.76)
70.60(70.55)
69.97(69.63)
70.00(69.63)
68.21(68.13)
68.35(68.13)
65.75(65.87)
70.52(70.77)
69.60(69.27)
71.30(71.38)
69.06(68.84)
6.70(6.54)
6.61(6.66)
6.88(6.66)
6.64(6.44)
6.72(6.45)
6.52(6.45)
6.41(6.12)
6.30(612)
5.74(5.82)
6.74(6.66)
7.07(6.89)
7.02(6.87)
6.64(6.45)
C52H60GeO2Sn
C52H60GeO2Sn
C57H62GeO2Sn
C58H64GeO3Sn
C58H64GeO3Sn
C57H61ClGeO2Sn
C57H61ClGeO2Sn
C57H60Cl2GeO2Sn
C58H64GeO2Sn
C55H66GeO2Sn
C62H73GeO2Sn
C61H69ClGeO2Sn
102–104
116–118
112–124
134–136
117–119
102–104
110–112
137–139
100–102
134–136

X. Fang et al. / Journal of Organometallic Chemistry 619 (2001) 43–48
45
(w(COO)as) and symmetric (w(COO)s) absorption fre-
quencies is below 200 cm−1 for the five-coordinated
structure of triorganotin carboxylates, but greater than
200 cm−1 for the four-coordinated one. As shown in
Table 2, all the values of Dw are between 252 and 282
cm−1, and strongly indicate that all the title com-
pounds are four-coordinated. The preference to form-
ing a five-coordinated structure is probably due to the
steric effect of the 2-methyl-2-phenylpropyl group.
Scheme 2.
showed no special feature and the maximum residual in
the final difference map was 0.52 e A
1
The H-, 13C- and 119Sn-NMR data of the title com-
−3
,
.
1
pounds are given in Table 3. All the H-NMR data are
in good agreement with the expected structures.
To confirm the structure of the title compounds, 13C-
and 119Sn-NMR data were also recorded for four of
these compounds. These parameters are very useful for
the determination of the coordination number of tin, its
molecular geometry and stereochemistry. It is reported
[16] that in the alkyltin carboxylates, four-coordinate
tin has l (119Sn) values range from about +200 to
−60 ppm, five-coordinate tin from −90 to −190
ppm, and six-coordinate tin from −200 to −400 ppm.
A single resonance in the range of 83ꢀ89 ppm, com-
patible with the tetrahedral geometry proposed for the
solution structure, is observed for the selected four
compounds. Substitution of a chloride for a carboxy-
late induces only slight upfield shift of the 119Sn reso-
nance, which is unlikely to arise from a significant
additional coordination by the oxygen atom of the
carbonyl group (the l value of a tetra-coordinated tin
compound R3SnCl is 118.5 ppm).
3. Results and discussion
3.1. Spectroscopy
It is well established that triorganotin carboxylates
adopt three structural types in the solid state [13] as
shown in Scheme 2.
The monomeric structure (A) is four-coordinated,
whereas the polymeric structure (C) generally contains
five-coordinate tin atoms. A second five-coordinate
structure can exist as structural type (B). This inevitably
occurs when the carboxylates group acts as a chelating
ligand. The different structures can be inferred by the
analysis of the IR, NMR and MS data of the
compounds.
The main IR spectral data are listed in Table 2. The
assignments of was(Sn–C) and was(Sn–O) are consistent
with the values reported in the literature [14]. The
bonding of the carboxylate groups can be deduced by
IR spectroscopy.
The coordination number of tin affects the absorp-
tion vibration frequency of carbonyl group. The Dw
(Dw=w(COO)as−w(COO)s) value, which is useful in
drawing structural influences in the case of metal car-
boxylate, is used to determine the nature of bonding of
carboxylate to tin(IV) [15] compounds. It is generally
believed that the difference in Dw between asymmetric
Holecek et al. [17–20] reported that the 1J (13C,
119Sn) coupling constant can be a function of the coor-
dination number of triorganotin compounds, ranging
between 327 and 387 Hz for tetra-coordinated com-
pounds, and between 442 and 509 Hz for penta-coordi-
nated ones. The triorganotin germylpropionates exhibit
1J coupling constants ranging from 349.6 to 353.9 Hz
indicating tetra-coordination in chloroform solution, in
agreement with our IR spectroscopic study and the
119Sn-NMR data.
Table 2
The IR data of the title compounds (cm−1
)
Compound
w(COO)as
w(COO)s
Dw
was(Sn–O)
was(Sn–C)
1
2
3
4
5
6
7
8
9
10
11
12
13
1649
1650
1650
1653
1647
1652
1665
1658
1649
1659
1652
1658
1652
1356
1361
1359
1360
1358
1358
1359
1358
1377
1361
1380
1376
1388
293
289
291
293
289
294
306
300
272
298
272
282
272
457
465
468
462
465
460
467
461
461
465
463
462
464
555
557
556
555
554
553
552
552
567
556
563
556
558

46
X. Fang et al. / Journal of Organometallic Chemistry 619 (2001) 43–48
Table 3
The NMR data of the title compounds
No. 1H-NMR (ppm)
119Sn-NMR
(ppm)
1J (Hz)
13C–119Sn)
(
1
2
3
4
5
1.13, 6H[s, 3×CH2]; 1.17, 18H[s, 3×C(CH3)2]; 1.80, 2H[t, GeCH2]; 2.20–2.25, 2H[t, CH2CO2]; 83.2
7.00–7.60, 30H[m, 6×C6H5]
349.6
1.13, 6H[s, 3×CH2]; 1.17, 18H[s, 3×C(CH3)2]; 1.25, 3H[dd, GeCH(CH3)]; 2.20–2.25, 2H[t,
CH2CO2]; 2.25–2.65, 1H[dd, J=12, CHCO2]; 7.00–7.60, 30H[m, 6×C6H5]
1.09, 6H[s, 3×CH2]; 1.17, 18H[s, 3×C(CH3)2]; 1.50–1.70, 1H[dd, GeCH]; 2.00–2.20, 1H[d,
J=12, GeCH]; 2.45–2.70, 1H[t, CHCO2]; 7.00–7.60, 30H[m, 6×C6H5]
0.91, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.70–2.95, 2H[m, CH2CO2]; 3.50–3.70, 1H[q,
GeCH]; 6.80–7.60, 35H[m, 7×C6H5]
83.4
86.1
353.9
352.8
0.92, 6H[s, 3×CH2]; 1.05, 18H[s, 3×C(CH3)2]; 2.87, 2H[d, J=8, CH2CO2]; 3.60, 1H[t,
GeCH]; 3.72, 3H[s, OCH3]; 6.55–6.73, 2H[d, J=8, 1/2C6H4OCH3]; 6.75–6.88, 2H[d, J=8,
1/2C6H4OCH3]; 6.90–7.60, 30H[m, 6×C6H5]
6
7
0.90, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.70–2.95, 2H[m, CH2CO2]; 3.17, 3H[s, OCH3];
4.06–4.25, 1H[m, GeCH]; 6.40–7.60, 34H[m, 6×C6H5+C6H4]
0.96, 6H[s, 3×CH2]; 1.03, 18H[s, 3×C(CH3)2]; 2.70–2.95, 2H[m, CH2CO2]; 4.20–4.45, 1H[m,
GeCH]; 6.80–7.60, 34H[m, 6×C6H5+C6H4]
89.0
352.0
8
0.91, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.70–2.95, 2H[d, J=8, CH2CO2]; 3.40–3.80,
1H[t, J=8, GeCH]; 6.80–7.60, 34H[m, 6×C6H5+C6H4]
9
0.92, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.70–2.95, 2H[d, J=8, CH2CO2]; 4.10–4.35,
1H[t, J=8, GeCH]; 6.80–7.60, 33H[m, 6×C6H5+C6H3]
10
11
12
13
0.91, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.25, 3H[s, C6H4CH3]; 2.70–2.95, 2H[m,
CH2CO2]; 3.50–3.80, 1H[m, GeCH]; 6.60–7.60, 33H[m,6×C6H5+C6H4]
0.92, 6H[s, 3×CH2]; 1.03, 18H[s, 3×C(CH3)2]; 2.34, 9H[s, 3×C6H4CH3]; 2.75–2.92, 2H[m,
CH2CO2]; 4.25–4.35, 1H[m, GeCH]; 6.90–7.25, 31H[m, 3×C6H5+4×C6H4]
1.04–1040, 26H[m, CH2CO2+3×SnCH2C(CH3)2]; 2.29–2.45, 11H[m, 3×C6H4CH3+GeCH2];
7.00–7.30, 27H[m, 3×(C6H5+C6H4)]
0.90, 6H[s, 3×CH2]; 1.04, 18H[s, 3×C(CH3)2]; 2.25, 3H[s, C6H4CH3]; 2.34, 9H[s,
3×C6H4CH3]; 2.75–2.85, 2H[m, CH2CO2]; 3.65–3.75, 1H[m, GeCH]; 6.80–7.25, 31H[m,
3×C6H5+4×C6H4]
The main mass spectra data of the title compounds
peak. A possible fragmentation pattern for Ph3GeCH2-
CH2CO2Sn(CH2CMe2C6H5)3 is given in Scheme 3.
In conclusion, all the spectral data for the com-
pounds support a tetrahedral geometry for the tin
atoms. Thus, the structure of the compounds contains a
four-coordinated tin as depicted in structure A.
are in good agreement with the expected structure, and
generally they have almost the same fragmentation
pattern with either Ph3Ge+ or PhCH2+ as the basic
3.2. Crystal structure of compound 7
In order to confirm the structure of these com-
pounds, the solid structure of 7 was determined by
Scheme 3.
Fig. 1. X-ray molecular structure of compound 7.

X. Fang et al. / Journal of Organometallic Chemistry 619 (2001) 43–48
47
Table 4
Table 5
,
Selected bond lengths(A) and bond angles(°) for the compound 7
Some comparable structural parameters of R3SnO2CCR%
, ,
Sn–O(1) (A) Sn–O(2) (A) Ref.
Bond lengths
Cl–C(72)
R
R%
1.742(4)
2.056(2)
2.143(4)
2.150(3)
2.155(3)
1.953(4)
1.954(4)
1.955(3)
1.990(3)
1.287(4)
1.195(4)
1.516(4)
1.528(5)
1.491(5)
1.534(5)
1.511(6)
1.523(6)
1.554(6)
1.377(6)
1.398(7)
1.367(9)
1.383(6)
1.355(9)
1.358(8)
1.544(5)
1.527(5)
1.528(5)
1.526(5)
1.379(5)
1.396(5)
C(26)–C(25)
C(26)–C(27)
C(28)–C(27)
C(28)–C(29)
C(30)–C(31)
C(32)–C(31)
C(34)–C(31)
C(33)–C(31)
C(37)–C(38)
C(37)–C(36)
C(34)–C(35)
C(34)–C(39)
C(36)–C(35)
C(38)–C(39)
C(51)–C(52)
C(51)–C(56)
C(53)–C(52)
C(53)–C(54)
C(55)–C(54)
C(55)–C(56)
C(61)–C(66)
C(61)–C(62)
C(63)–C(62)
C(63)–C(64)
C(65)–C(64)
C(65)–C(66)
C(71)–C(72)
C(71)–C(76)
C(73)–C(72)
C(73)–C(74)
1.374(6)
1.354(7)
1.374(7)
1.387(6)
1.545(5)
1.527(5)
1.528(5)
1.545(5)
1.356(9)
1.384(9)
1.376(6)
1.396(6)
1.391(7)
1.374(8)
1.381(5)
1.390(5)
1.380(6)
1.358(7)
1.364(7)
1.375(6)
1.387(5)
1.393(5)
1.382(5)
1.363(7)
1.369(7)
1.398(6)
1.388(5)
1.388(6)
1.390(6)
1.350(7)
Sn(1)–O(1)
Sn(1)–C(10)
Sn(1)–C(20)
Sn(1)–C(30)
Ge(1)–C(51)
Ge(1)–C(81)
Ge(1)–C(61)
Ge(1)–C(3)
O(1)–C(1)
c-Hexyl CF3
Ph
2.08(4)
2.083(2)
2.12(3)
2.086(3)
2.048(4)
2.043(3)
2.060(2)
2.054(3)
3.11(4)
3.071(2)
2.95(4)
2.929(4)
2.861(4)
2.823(3)
2.783(3)
2.781(3)
2.78(1)
[21]
[22]
[23]
[6]
[24]
[25]
[22]
[22]
[26]
This
C6H4OH-o
c-Hexyl CH3
c-Hexyl CH2(C8H5N) a
Ph
Ph
Ph
Ph
C6H4Cl-p
C6H4NH2-o
C6H4SCH3-p
C6H4OCH3-o
c-Hexyl CH2(C8H6NCH3) b 2.05(1)
C(1)–O(2)
C(1)–C(2)
C(2)–C(3)
Neophyl Germyl
2.056(2)
3.269(3)
carboxylate c
paper
C(3)–C(71)
C(10)–C(11)
C(11)–C(14)
C(11)–C(13)
C(11)–C(12)
C(19)–C(14)
C(19)–C(18)
C(18)–C(17)
C(14)–C(15)
C(17)–C(16)
C(15)–C(16)
C(20)–C(21)
C(24)–C(21)
C(23)–C(21)
C(22)–C(21)
C(24)–C(29)
C(24)–C(25)
a Indole-3-acetic acid.
b N-methylindole-3-acetic acid.
c See Scheme 1.
Table 6
The insecticidal and acaricidal activity of some compounds
Compound Average percentage inhibition after 24 h (%)
Tetraanychus Urticae koch (200 Culicidae (10
ppm)
ppm)
1
2
3
4
7
93.7
17.7
15.1
93.4
11.8
11.3
8.3
100
0
0
100
0
0
8
9
Bond angles
0
O(1)–Sn(1)–C(10)
O(1)–Sn(1)–C(20)
C(10)–Sn(1)–C(20)
O(1)–Sn(1)–C(30)
C(10)–Sn(1)–C(30)
C(30)–Sn(1)–C(20)
C(51)–Ge(1)–C(81)
C(51)–Ge(1)–C(61)
C(81)–Ge(1)–C(61)
C(81)–Ge(1)–C(3)
C(61)–Ge(1)–C(3)
C(51)–Ge(1)–C(3)
C(1)–O(1)–Sn(1)
O(2)–C(1)–O(1)
93.22(13) C(24)–C(21)–C(22)
98.57(14) C(24)–C(21)–C(20)
118.22(14) C(22)–C(21)–C(20)
111.24(12) C(24)–C(21)–C(23)
113.90(14) C(22)–C(21)–C(23)
117.15(13) C(20)–C(21)–C(23)
110.65(15) C(29)–C(24)–C(21)
110.13(14) C(25)–C(24)–C(21)
109.71(15) C(31)–C(30)–Sn(1)
110.34(14) C(32)–C(31)–C(34)
105.94(14) C(32)–C(31)–C(33)
109.99(13) C(34)–C(31)–C(33)
111.8(3)
112.1(3)
108.3(3)
107.6(3)
109.3(3)
107.5(3)
123.7(3)
120.2(3)
117.2(2)
112.7(3)
108.2(3)
108.6(3)
107.1(3)
111.7(3)
108.4(3)
120.2(4)
121.7(4)
120.4(5)
121.3(3)
121.2(3)
120.4(3)
121.5(3)
123.4(3)
121.4(3)
119.8(3)
117.0(3)
117.8(4)
120.4(3)
121.8(3)
10
96.3
100
X-ray structure determination. The crystal structure
with numbering scheme is shown in Fig. 1. Selected
bond lengths and bond angles were listed in Table 4.
In the structure, the two atoms Sn and Ge are both
occupying essentially tetrahedral geometries, the aver-
age bond angles around each metal being 110.2° and
101.0°, respectively. The bond length of Sn–O(1) is
126.4(2)
124.6(3)
122.7(3)
112.6(3)
113.2(3)
114.8(3)
110.7(2)
110.8(2)
119.9(3)
112.9(4)
111.0(3)
109.2(3)
108.2(3)
108.6(4)
106.7(4)
120.4(4)
122.8(4)
117.9(2)
C(32)–C(31)–C(30)
C(34)–C(31)–C(30)
C(33)–C(31)–C(30)
C(35)–C(34)–C(31)
C(39)–C(34)–C(31)
C(38)–C(39)–C(34)
C(52)–C(51)–Ge(1)
C(56)–C(51)–Ge(1)
C(66)–C(61)–Ge(1)
C(62)–C(61)–Ge(1)
C(72)–C(71)–C(3)
C(76)–C(71)–C(3)
C(71)–C(72)–Cl
O(2)–C(1)–C(2)
O(1)–C(1)–C(2)
C(1)–C(2)–C(3)
,
2.056(2) A, and for Sn–O(2) the bond length is 3.269(3)
,
A, which is far from the sum of their Van der Waal’s
C(71)–C(3)–C(2)
C(71)–C(3)–Ge(1)
C(2)–C(3)–Ge(1)
C(11)–C(10)–Sn(1)
C(14)–C(11)–C(13)
C(14)–C(11)–C(10)
C(13)–C(11)–C(10)
C(14)–C(11)–C(12)
C(13)–C(11)–C(12)
C(10)–C(11)–C(12)
C(19)–C(14)–C(11)
C(11)–C(14)–C(15)
C(21)–C(20)–Sn(1)
radii, and suggests that there is no interaction between
the carbonyl group and the Sn(1) atom. The carbonyl
group, C(1)–O(2), is sterically encumbered by the three
neophyl groups attached to the tin atom, as well as by
the germyl substitution on the carboxylate group, all of
which act as a barrier preventing the carbonyl oxygen
from approaching to the tin in the neighbouring
molecule, to form associated polymeric structure. The
bond lengths of the two C–O bonds in the COO
C(73)–C(72)–Cl
C(82)–C(81)–C(86)
C(82)–C(81)–Ge(1)
C(86)–C(81)–Ge(1)
,
fragment are 1.20 and 1.29 A, which are consistent with
the general single and the double bond lengths, respec-
tively. Some important comparable structural parame-
.

48
X. Fang et al. / Journal of Organometallic Chemistry 619 (2001) 43–48
[7] S. Chandra, B.D. James, R.J. Magee, W.C. Patalinghug, B.W.
Skeleton, A.H. White, J. Organomet. Chem. 346 (1988) 7.
[8] B.D. James, S. Giosks, S. Chandra, R.J. Magee, J. Dcashion, J.
Organomet. Chem. 436 (1992) 155.
ters for this type of structure reported in the literature
were listed in Table 5, the structure of the title com-
pound is mostly like that of (cyclo-C6H11)3SnO2CCF3.
[9] S.J. Blunden, P.J. Smith, B. Sugavanaman, Pest. Sci. 15 (1984)
253.
[10] Q.L. Xie, L.J. Sun, H. Liu, Appl. Organomet. Chem. 8 (1994)
57.
3.3. Biological test
The preliminary insecticidal and acaricidal activities
of compounds 1–10 are given in Table 6. The biologi-
cal tests showed that the compounds 1, 4 and 10 have
good acaricidal activity against Tetraanychus Urticae
koch (200 ppm) and Culicidae (10 ppm), and the results
of bioassay have shown that all these compounds have
poor fungicidal activity on the Aphis cracci6ora (not
listed).
[11] X.Q. Song, Z.Q. Yang, Q.L. Xie, J. Organomet. Chem. 566
(1998) 103.
[12] C.A. Horne, Ger. Offen. 2, 115 (1971) 666.
[13] E.R.T. Tiekink, Appl. Organomet. Chem. 5 (1991) 1.
[14] Q.L. Xie, Z.Q. Yang, Z.X. Zhang, Appl. Organomet. Chem. 6
(1992) 193.
[15] B.Y.K. Ho, J.J. Zuckerman, Inorg. Chem. 12 (1973) 1552.
[16] D. Chaitali, B. Basudeb, Indian J. Chem. 35B (1996) 196.
[17] J. Holecek, M. Nadvornik, K. Handlir, J. Organomet. Chem.
241 (1983) 177.
[18] R. William, A. Bouhdid, B. Mahieu, J. Organomet. Chem. 531
(1997) 151.
[19] E.R.T. Tiekink, M. Gielen, A. Bouhdid, J. Organomet. Chem.
494 (1995) 280.
References
[1] I. Omae, Organotin Chemistry, J. Organomet. Chem. Library,
Elsevier, Amsterdam, 1989, p. 21.
[20] R. William, A. Bouhdid, M. Biesemans, J. Organomet. Chem.
514 (1996) 203.
[2] A.G. Davies, P.J. Smith, in: G. Wilkinson (Ed.), Comprehensive
Organometallic Chemistry, vol. 2, Pergamon Press, Oxford,
1982, p. 519.
[3] G.J.M. Van der Kerk, J.G. Aluijten, J. Appl. Chem. 4 (1954)
314.
[21] S. Calogero, P. Ganis, V. Peruzzo, G. Tagliavini, J. Organomet.
Chem. 191 (1980) 381.
[22] J.F. Vollano, R.O. Day, D.N. Rau, V. Chandrasekhar, R.R.
Holmes, Inorg. Chem. 23 (1984) 3153.
[23] N.W. Alock, R.E. Timms, J. Chem. Soc.(A) (1968) 1876.
[24] R.R. Holmes, R.O. Day, V. Chandrasekhar, J.F. Vollano, J.M.
Holmes, Inorg. Chem. 25 (1986) 2490.
[4] E.M. Holt, F.A.K. Nasser, A. Wilson, J.J. Zukerman,
Organometallics 4 (1985) 2073.
[5] K.C. Molloy, M.B. Hossain, D. Van der Helm, J.J. Zuckerman,
I. Haiduc, Inorg. Chem. 18 (1979) 3507.
[25] R.G. Swisher, J.F. Vollano, V. Chandrasekhar, R.O. Day, R.R.
Holmes, Inorg. Chem. 23 (1984) 3174.
[6] K.C. Molloy, T.G. Purcell, E. Hahn, H. Schumann, J.J. Zucker-
man, Organometallics 5 (1986) 85.
[26] K.C. Molloy, T.G. Purcell, M.F. Mahon, E. Minshall, Appl.
Organomet. Chem. 1 (1987) 507.