Synthesis, characterization and crystal structures of (Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol and its o-tolylhalostannyl derivatives

Article abstract of DOI:10.1016/S0022-2860(03)00552-0

(Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol (1) was synthesized by the additive reaction of 1-Ethynylcyclohexanol with tri-o-tolyltin hydride. One or two of the o-tolyl groups of compound (1) was substituted by Cl, Br, I to yield derivatives of the type CH₂(CH₂) ₄CH(OH)CH=CHSn(o-tol)_3-nX_n [n = 1, X = Cl (2), Br (3), I (4); n = 2, X = Br (5)]. The compounds (1 - 5) were characterized by elemental analysis, ¹H NMR and FT-IR Spectroscopy. The crystal structures of (1) and (4) have been determined by single crystal X-ray diffraction analysis. The Sn atom in (1) exhibits tetrahedral geometry distorted towards trigonal bipyramid due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [2.764(5) ?], while the Sn atom in (4) adopts a trigonal bipyramidal geometry with a significant Sn(1) ← O interaction [2.571(4) ?].

Full text of DOI:10.1016/S0022-2860(03)00552-0

Journal of Molecular Structure 659 (2003) 89–95
www.elsevier.com/locate/molstruc
Synthesis, characterization and crystal structures
of (Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol
and its o-tolylhalostannyl derivatives
Dong-Sheng Zhua,b, Ze-Min Meia, Chun-Sheng Lu¨a, Yue-Tao Zhanga, Wei Gaoa,
a,
Ying Mu , Zong-Mu Wang
a
*
aSchool of Chemistry, Jilin University, Changchun 130023, People’s Republic of China
bSchool of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China
Received 22 May 2003; revised 31 July 2003; accepted 5 August 2003
Abstract
(Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol (1) was synthesized by the additive reaction of 1-Ethynylcyclohexanol
with tri-o-tolyltin hydride. One or two of the o-tolyl groups of compound (1) was substituted by Cl, Br, I to yield derivatives of
the type
½n ¼ 1; X ¼ Cl (2), Br (3), I (4); n ¼ 2; X ¼ Br (5)]. The compounds (1–5)
1
were characterized by elemental analysis, H NMR and FT-IR Spectroscopy. The crystal structures of (1) and (4) have been
determined by single crystal X-ray diffraction analysis. The Sn atom in (1) exhibits tetrahedral geometry distorted towards
˚
trigonal bipyramid due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [2.764(5) A], while the Sn
˚
atom in (4) adopts a trigonal bipyramidal geometry with a significant Sn(1) ˆ O interaction [2.571(4) A].
q 2003 Elsevier B.V. All rights reserved.
Keywords: Organotin compounds; Aryltin compounds; FT-IR spectroscopy; NMR spectroscopy; X-ray crystal structure
1. Introduction
[2–13]. The solid-state structures of (Z)–(Ar3Sn)–
CHyCH–C(OH)RR0 exhibit a weak intramolecular
HO ! Sn interaction. As a result, the Sn atom in these
compounds is located in a distorted tetrahedral
environment, while the Sn atom adopts a trigonal
bipyramidal geometry in the diarylhalostannyl and
aryldihalostannyl derivatives of the type (Z)–
ðAr32nXnSnÞ–CHyCH–C(OH)RR0 due to strong
HO ! Sn interaction. It has been reported that the
anti-tumor activity of these compounds is related to
the strength of the HO ! Sn interaction, which is
determined by the number and nature of the aryl
groups and the Lewis acidity of the central tin atom
Since Crowe et al. reported the anti-tumour activity
and hypotoxicity organotin compounds [1], great
attention has been paid to the synthesis, structure and
anti-tumor activity of such compounds. In particular,
compounds of the type (Z)–(Ar3Sn)–CHyCH–
C(OH)RR0 (Ar ¼ phenyl and p-tolyl) and their
arylhalostannyl derivatives have been actively studied
*
Corresponding author. Tel.: þ86-431-849-9136; fax: þ86-431-
894-9334.
E-mail address: ymu@mail.jlu.edu.cn (Y. Mu).
0022-2860/$ - see front matter q 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-2860(03)00552-0

90
D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
[5,11,12]. Effects of the phenyl and p-tolyl groups on
both the structure and the anti-tumor activity of this
type of compounds have been well studied in previous
work. However, no o-tolyl substituted organotin
compound of this type has been described. In this
paper, the synthesis and structure of (Z)-1-[2-(tri-o-
tolylstannyl)vinyl]-1-cyclohexanol (1) and it’s o-
tolyhalostannyl derivatives were reported. Their
structural features, particularly the HO ! Sn coordi-
nation interaction are discussed. These compounds
are likely to serve as new models for further
investigation on the structure-anti-tumor activity
relationship.
1H NMR (CDCl3): d 1.21 (s, 1H, OH); 2.28 (s, 9H,
Ph–CH3); 6.22 (d, JHH ¼ 12.6 Hz, 1H, Sn–CH); 6.81
(d, JHH ¼ 12.6 Hz, 1H, yCH); 7.11–7.32 (m, 9H, m,
p-H of Ph); 7.54 (d, JHH ¼ 7.5 Hz, 3H, o-H of Ph).
2.3. Syntheses of (Z)-1-[2-(chlorodi-o-
tolylstannyl)vinyl]-1-cyclohexanol (2)
A solution of ICl (0.81 g, 5.0 mmol) in 20 ml of
CCl4 was added dropwise with stirring to a solution of
(1) (2.58 g, 5.0 mmol) in 30 ml of CCl4 at 0 8C. The
color of ICl disappeared immediately. The mixture
was stirred for 1 h, then was allowed to warm to room
temperature and stirred for further 1 h. The solvent
was evaporated off and the residue was recrystallized
two times from CHCl3/cyclohexane (1:5 by volume)
to yield 1.86 g (80.6%) of compound (2) as white
needles. m.p. 131.8–132.9 8C. Anal. Calcd for C22-
H27ClOSn: C, 57.24; H, 5.90; Sn, 25.71. Found: C,
2. Experimental
2.1. General procedures
Cyclohexanone, tri-o-tolyltin chloride, LiAlH4,
iodonium chlorine, bromine and iodine were obtained
from commercial sources and used without further
purification. 1-Ethynylcyclohexanol was prepared by
a modified literature method [14]. Tri-o-tolyltin
hydride was obtained from reaction of tri-o-tolyltin
chloride with LiAlH4 in dried diethyl ether [15,16].
Diethyl ether was dried and distilled from Na–K alloy
under nitrogen. Other solvents were used without
purification.
57.29; H, 5.85; Sn, 25.68. IR (KBr pellets): nCO
1
:
1042 cm21, nOH : 3350 cm21. H NMR (CDCl3): d
2.53 (s, 1H, OH); 2.58 (s, 6H, Ph–CH3); 6.60 (d,
JHH ¼ 10.8 Hz,
1H,
Sn–CH);
6.75
(d,
JHH ¼ 10.8 Hz, ¼ CH); 7.23–7.40 (m, 6H, m, p-H
of Ph); 7.56 (d, JHH ¼ 6.8 Hz, 2H, o-H of Ph).
2.4. Syntheses of (Z)-1-[2-(bromodi-o-
tolylstannyl)vinyl]-1-cyclohexanol (3)
2.2. Syntheses of (Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-
cyclohexanol (1)
Bromine (0.48 g, 3.0 mmol) in 15 ml of CCl4 was
added slowly with stirring to a solution of (1) (1.55 g,
3.0 mmol) in 20 ml of CCl4 at 25 8C. The color of
bromine disappeared immediately. The mixture was
allowed to warm to room temperature and stirred for
1 h. The solvent was evaporated off and the residue
was recrystallized from cyclohexane to give 1.25 g
(82.34%) of compound (3) as white crystals. m.p.
137.8–138.6 8C. Anal. Calcd for C22H27BrOSn: C,
52.22; H, 5.38; Sn, 23.45. Found: C, 52.31; H, 5.35;
1-Ethynylcyclohexanol (12.42 g, 100 mmol) and
dibenzoyl peroxide (200 mg) were added to a solution
of tri-o-tolyltin hydride in diethyl ether prepared from
the reaction of tri-o-tolyltin chloride (53.44 g,
125 mmol) with LiAlH4 (4.74 g, 125 mmol). The
mixture was stirred for 35 h at room temperature
under nitrogen and the solvent was evaporated off.
The residue was recrystallized from ethanol to yield
33.53 g (64.8%) of (1) as white crystalline solid.
Single crystals suitable for X-ray analysis were
obtained by slow evaporation of ethanol solution at
room temperature over one week. m.p. 122.0–
122.9 8C. Anal. Calcd for C29H34OSn: C, 67.34; H,
6.63; Sn, 22.95. Found: C, 67.22; H, 6.61; Sn, 23.10.
Sn, 23.48. IR (KBr pellets): nCO : 1056 cm21, nOH
:
1
3400 cm21. H NMR (CDCl3): d 2.31 (s, 1H, OH);
2.55 (s, 6H, Ph–CH3); 6.58 (d, JHH ¼ 11.1 Hz, 1H,
Sn–CH); 6.69 (d, JHH ¼ 11.1 Hz, 1H, yCH); 7.16–
7.32 (m, 6H, m, p-H of Ph); 7.55 (d, JHH ¼ 6.9 Hz,
2H, o-H of Ph).
IR (KBr pellets): nCO : 1053 cm21, nOH : 3586 cm21
.

D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
91
2.5. Syntheses of (Z)-1-[2-(iododi-o-
tolylstannyl)vinyl]-1-cyclohexanol (4)
were applied in case. The structures were solved by
the heavy-atom method (SHELXTL-97 [17]) and
refined by full-matrix least-squares on F2 (SHELXTL-
97 [18]). All non-hydrogen atoms were refined
anisotrpically, and the positions of hydrogen atoms
on carbon atoms were calculated theoretically.
Iodine (0.76 g, 3.0 mmol) dissolved in 60 ml
of CCl4 was added dropwise with stirring to a solution
of (1) (1.55 g, 3.0 mmol) in 20 ml of CCl4 at room
temperature. The color of iodine disappeared immedi-
ately. The mixture was stirred for 1.5 h and the solvent
was then evaporated off. The residue was recrystal-
lized from cyclohexane to yield 1.26 g (75.94%) of
compound (4) as white crystals which are suitable
for X-ray analysis. m.p. 138.7–139.8 8C. Anal.
Calcd for C22H27IOSn: C, 47.78; H, 4.92; Sn, 21.46.
Found: C, 47.82; H, 4.89; Sn, 21.53. IR (KBr pellets):
Elemental analyses were carried out on a Perkin–
1
Elmer PE 2400 CHN instrument. H NMR spectra
were recorded in CDCl3 on a Varian Mercury
300 MHz spectrometer. Infrared spectra (KBr pellets)
were recorded on an Alpha Centauri FI/IR spec-
trometer (400–4000 cm21 range).
nCO : 1044 cm21, nOH : 3540 cm21
.
1H NMR
3. Results and discussion
(CDCl3): d 2.13 (s, 1H, OH); 2.60 (s, 6H, Ph–CH3);
6.58 (d, JHH ¼ 11.4 Hz, 1H, Sn–CH); 6.70 (d,
JHH ¼ 11.4 Hz, 1H, yCH); 7.16–7.29 (m, 6H, m,
p-H of Ph); 7.51 (d, JHH ¼ 7.2 Hz, 2H, o-H of Ph).
3.1. Synthesis
Compounds (1–5) were synthesized according to
Scheme 1. (Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclo-
hexanol (1) was synthesized by addition of the
corresponding tri-o-tolyltin hydride to the triple
bond of 1-ethynylcyclohexanol. Reactions of com-
pound (1) with halogens in a 1:1 molar ratio yield the
corresponding monohalides (2–4), respectively.
2.6. Syntheses of (Z)-1-[2-(dibromo-o-
tolylstannyl)vinyl]-1-cyclohexanol (5)
Bromine (0.16 g, 1.0 mmol) dissolved in 15 ml of
CCl4 was added slowly with stirring to a solution of
(3) (0.51 g, 1.0 mmol) in 20 ml of CCl4 at 25 8C. The
color of bromine disappeared immediately.
The mixture was allowed to warm to room tempera-
ture and stirred for 1 h. The solvent was evaporated
off and the residue was recrystallized from cyclohex-
ane to give 0.41 g (82.86%) of compound (5) as
white crystals. m.p. 144.0–145.1 8C. Anal. Calcd for
C15H20Br2OSn: C, 36.41; H, 4.07; Sn, 23.99.
Found: C, 36.36; H, 4.15; Sn, 24.05. IR (KBr pellets):
nCO : 1054 cm21, nOH : 3327 cm21
.
1H NMR
(CDCl3): d 2.54 (s, 3H, Ph–CH3); 2.86 (s, 1H, OH);
6.48 (d, JHH ¼ 10.2 Hz, 1H, Sn–CH); 6.80 (d,
JHH ¼ 10.5 Hz, 1H, yCH); 7.22–7.36 (m, 3H, m,
p-H of Ph); 7.70 (d, JHH ¼ 6.6 Hz, 1H, o-H of Ph).
2.7. Crystal structure determination and physical
measurements
Diffraction data of compound (1) and (4) were
collected on a Rigaku RAXIS-RAPID diffractometer
at room temperature with graphite monochromatized
˚
Mo Ka radiation ðl ¼ 0.71073 A) by the v scan
Scheme 1.
mode. Empirical absorption corrections (multi-scan)

92
D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
Reaction of monobromide (3) with bromine in a 1:1
molar ratio produces the corresponding dibromide (5).
time and (1) was produced in better yield. In
addition, hexa-o-tolylditin was observed as an
insoluble by-product in these reactions.
1
Compounds (1–5) were all characterized by IR, H
NMR and elemental analysis.
Compound (1) reacts with ICl, Br2 or I2 in
carbon tetrachloride or chloroform to produce
monohalides (2–4), but the yields of (2–4)
produced in chloroform are lower. It was found
that the reactivity of halogens is in the order
ICl . Br2 . I2. The fact that (2–4) were obtained
in high yields indicates that the addition reaction
of the CyC double bond of the vinyl group in (1)
with halogen is less reactive than the substitution
reaction of the o-tolyl group by halogen atom. Pure
(2–4) were obtained by recrystallization from
cyclohexane. In order to isolate the product in
During the synthesis of compound (1), a small
amount of dibenzoyl peroxide was added to the
reaction mixture as evocating agent and the reaction
was carried out under nitrogen. The reaction has
been tried in different solvents such as THF,
benzene and toluene, and it was found that (1)
could be obtained in higher yield from the reaction
carried out in diethyl ether. When pure tri-o-tolyltin
hydride was used instead of the one formed in situ
by the reaction of tri-o-tolyltin chloride with
LiAlH4, the reaction went to completion in less
Fig. 1. The vinyl and o-tolyl regions of 1H NMR spectra of (1) and (5). a: (Z)-1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol (1), b: (Z)-1-[2-
(dibromo-o-tolylstannyl)vinyl]-1-cyclohexanol (5).

D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
93
high yield, o-toluene halide formed in the reaction
as a by-product should be removed together with the
reaction solvent before recrystallization. Compound
(5) was synthesized in two ways. One is from the
reaction of (1) with bromine in 1:2 molar ratio. The
other way is from the reaction of (3) with bromine
in 1:1 molar ratio. Higher yield was obtained from
the latter reaction. Attempts to make tribromide
derivative by substituting all of the three o-tolyl
groups in (1) with bromine atoms were not
successful. When the reaction of (1) with bromine
was carried out in 1:3 molar ratio, the color of
bromine did not disappear after the reaction mixture
was stirred for 5 h and the dibromide derivative (5)
was obtained as major product. Pure (5) was
isolated by recrystallization from mixed solvent of
CHCl3/cyclohexane (1:4 by volume).
Fig. 2. The molecular structure and crystallographic numbering
scheme for compound (1).
procedure information corresponding to data collec-
tion and structure refinement are given in Table 1. The
selected distances and bond angles are listed in
Table 2. The central tin atom in (1) exhibits a four-
coordination environment with three o-tolyl groups
and the C(1) atom of the vinyl residue, leading to a
distorted tetrahedral geometry. The Sn–C distances
1
3.2. H NMR and IR spectra
The solution 1H NMR spectra of compounds (1–5)
are consistent with their structures. All spectra show
characteristic ethylenic proton signals of doublet of
3
doublets with J(HCyCH) ¼ 10.2–12.6 Hz in the
˚
are in the range from 2.097(4) to 2.152(3) A and the
regions of 6.26–6.58 and 6.69–6.81 ppm. As
1
example, the vinyl and o-tolyl regions of H NMR
C–Sn–C bond angles are in the range from
104.63(12) to 115.21(12)8, The Sn(1)–C(21) bond
˚
distance of 2.152(3) A is longer than the Sn(1)–C(11)
and Sn(1)–C(31) bond distances of 2.113(3) and
spectra of (1) and (5) are shown in Fig. 1. The
3J(HCyCH) coupling constant of 12.6 Hz observed for
(1) is quite large since cis coupling constant in similar
compounds with a five-membered ring substituent
usually amounts to 8 Hz or even less [19]. In regard to
˚
2.141(3) A. In addition, C(11)–Sn(1)–C(31) bond
3
the stannyl group, the J(HCyCH) coupling constant
decreases in the order Sn(o-tolyl)3 . Sn(o-tolyl)2I .
Sn(o-tolyl)2Br . Sn(o-tolyl)2Cl . Sn(o-tolyl)Br2.
The chemical shift of OH shifts to high field in the
same order, which indicates that the strength of the
HO ! Sn interaction increases with the decrease in
the steric hindrance of the stannyl group.
The infra-red spectra of all compounds (1–5) show
the presence of strong absorptions in the regions of
1032–1054 and 3327–3586 cm21, which can be
assigned to n(CO) and n(OH) stretching vibrations,
respectively.
3.3. Crystal structures
The molecular structures of compound (1) and (4)
are given in Figs. 2 and 3. The crystal parameters and
Fig. 3. The molecular structure and crystallographic numbering
scheme for compound (4).

94
D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
Table 1
Table 2
Selected bond distance (A) and angles (8) in (1) and (4)
˚
Crystal data and details of structure refinement parameters for
compounds (1) and (4)
(1)
(4)
(1)
(4)
Sn(1)–C(1)
Sn(1)–C(11)
Sn(1)–C(31)
Sn(1)–C(21)
Sn(1)–O(1)
O(1)–C(41)
C(1)–C(2)
2.097(4)
2.113(3)
2.141(3)
2.152(3)
2.764(5)
1.396(4)
1.315(6)
1.484(6)
Sn(1)–C(1)
Sn(1)–C(11)
Sn(1)–C(21)
Sn(1)–I(1)
Sn(1)–O(1)
O(1)–C(3)
C(1)–C(2)
C(2)–C(3)
2.113(7)
2.142(6)
2.154(6)
2.7817(8)
2.571(4)
1.423(10)
1.390(12)
1.431(13)
Empirical formula
Formula weight
Temperature (K)
C29H34OSn
517.25
C22H27IOSn
553.03
293(2)
293(2)
˚
Wavelength (A)
0.71073
Triclinic
ꢀ
P1
0.71073
Monoclinic
P21=c
Crystal system
Space group
C(2)–C(41)
Unit cell dimensions
˚
a (A)
˚
b (A)
C(1)–Sn(1)–C(11)
C(1)–Sn(1)–C(31)
110.88(15) C(1)–Sn(1)–C(11)
112.41(15) C(1)–Sn(1)–C(21)
125.8(3)
112.7(3)
8.5592(17)
9.3016(19)
16.368(3)
83.76(3)
10.505(2)
10.076(2)
20.869(4)
90.00
C(11)–Sn(1)–C(31) 115.21(12) C(11)–Sn(1)–C(21) 110.1(2)
˚
c (A)
C(1)–Sn(1)–C(21)
106.71(15) C(1)–Sn(1)–I(1)
95.9(2)
a (8)
b (8)
g (8)
C(11)–Sn(1)–C(21) 104.63(12) C(11)–Sn(1)–I(1)
C(31)–Sn(1)–C(21) 106.20(12) C(21)–Sn(1)–I(1)
103.97(15)
104.79(16)
68.8(6)
82.69(3)
99.36(3)
90.00
78.05(3)
C(1)–Sn(1)–O(1)
C(11)–Sn(1)–O(1)
C(21)–Sn(1)–O(1)
C(31)–Sn(1)–O(1)
Sn(1)–O(1)–C(41)
Sn(1)–C(1)–C(2)
C(1)–C(2)–C(41)
C(2)–C(41)–O(1)
66.4(4)
79.9(3)
172.9(4)
76.3(4)
111.8
C(1)–Sn(1)–O(1)
C(11)–Sn(1)–O(1)
C(21)–Sn(1)–O(1)
I(1)–Sn(1)–O(1)
Sn(1)–O(1)–C(3)
Sn(1)–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–O(1)
3
˚
Volume (A )
1260.0(4)
2
2179.7(8)
4
88.4(5)
Z
88.8(6)
Dcalc (g cm23
)
1.363
1.031
1.685
2.595
162.9(6)
113.5(6)
120.9(6)
126.8(7)
105.1(6)
Absorption coefficient
(mm21
126.7(3)
127.8(4)
107.2(3)
)
Fð000Þ
532.0
1080
Crystal size (mm)
u Range for data
collection (8)
0.44 £ 0.43 £ 0.29 0.58 £ 0.32 £ 0.21
1.26–27.32
5579
1.96–27.43
Reflections collected
4925
a trigonal bipyramid with the trigonal plane defined
by C(1), C(11) and C(21) atoms and the I(1) and
O(1) atoms in the axial positions. The distances from
Sn to the vinyl group and the o-tolyl groups are
slightly longer than the ones in (1), with Sn(1)–C(1),
Sn(1)–C(11) and Sn(1)–C(21) bond distances of
Independent reflections 4852
3510
½Rint ¼ 0:0000ꢀ
98.4
½Rint ¼ 0:0000ꢀ
99.1
Completeness to
u ¼ 27:328 (%)
Refinement method
Full-matrix least-
squares on F2
Full-matrix least-
squares on F2
˚
2.113(7), 2.142(6) and 2.154(6) A, respectively. The
˚
Sn(1)–O(1) bond distance of 2.571(4) A in (4) is
remarkably shorter than the corresponding one in (1).
Goodness-of-fit on F2
Final R indices
1.089
0.994
R1 ¼ 0:0377;
wR2 ¼ 0:1030
R1 ¼ 0:0466;
wR2 ¼ 0:1142
R1 ¼ 0:0476;
wR2 ¼ 0:1424
R1¼0:0683;
wR2 ¼ 0:1561
½I . 2sðIÞꢀ
R-indices (all data)
˚
The Sn(1)–I(1) distance is 2.7817(8) A and the I(1)–
Sn(1)–O(1) bond angle is 162.9(6)8. The mean
deviation of the O(1) atom from the five-membered
˚
ring is 0.38(1) A, and the five-membered chelating
angle of 115.21(12)8 is rather larger than C(11)–
Sn(1)–C(21) and C(31)–Sn(1)–C(21) bond angles of
104.63(12) and 106.20(12)8, respectively. It is
obvious that there is a weak interaction between Sn
and O atoms, with the Sn(1)–O(1) distance of
ring is almost coplanar. The difference in structures
of (1) and (4) indicates that the steric and electronic
effects of the substituents at Sn atom on the
properties of the stannyl group and the whole
compound are significant.
˚
2.764(5) A. The presence of O(1) atom influences
the Sn–C bond distances and the C–Sn–C bond
angles, which results in the distortion of the
tetrahedral geometry towards trigonal bipyramid.
The central Sn atom in (4) is coordinated by
five groups and the geometry about the Sn atom is
4. Conclusions
We have synthesized and characterized (Z)-
1-[2-(tri-o-tolylstannyl)vinyl]-1-cyclohexanol and

D.-S. Zhu et al. / Journal of Molecular Structure 659 (2003) 89–95
95
[3] F. Kayser, M. Biesemans, H. Pan, M. Gielen, R. Willem,
Magn. Reson. Chem. 30 (1992) 877.
several mono- and dihalide derivatives. (Z)-1-[2-(tri-
o-tolylstannyl)vinyl]-1-cyclohexanol adopts a dis-
torted tetrahedral geometry, while the Sn atom in
the mono- and dihalide derivatives is located inside a
trigonal bipyramid geometry.
[4] M. Gielen, H. Pan, R. Willem, D. De Vos, Pharmachemie
B.V., Eur. Pat. 90202936.2-, 06/11/90, Antitumor compo-
sitions and compounds, Chem. Abstr. 116 (1992) 235873q.
[5] M. Gielen, P. Lelieveld, D. De Vos, H. Pan, R. Willem,
M. Biesemans, H.H. Fiebig, Inorg. Chim. Acta 196 (1992)
115.
[6] F.F. Xin, S.X. Lin, F.Y. Jie, H. Pan, B. Mahieu, M. Gielen, F.
Kayser, R. Willem, Z. Anorg. Allg. Chem. 620 (1994) 1006.
[7] F. Kayser, M. Biesemans, H. Pan, M. Gielen, R. Willem,
J. Chem. Soc., Perkin Trans. 11 (1994) 297.
5. Supplementary data
Crystallographic data for the structural analysis
have been deposited with the Cambridge Crystal-
lographic Data Center, CCDC 216137 for compound
C29H34OSn (1) and CCDC 216138 for compound
C22H27IOSn (4). Copies of this information may be
obtained free of charge from The Director, CCDC 12
Union Road, Cambridge CB2 1EZ, UK (Fax: þ44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
[8] F. Kayser, M. Biesemans, A. Delmotte, I. Verbruggen, I. De
Borger, M. Gielen, R. Willem, Organometallics 13 (1994)
4026.
[9] R. Willem, A. Delmotte, I. De Borger, M. Biesemans, M.
Gielen, F. Kayser, J. Organomet. Chem. 480 (1994) 255.
[10] F. Kayser, M. Biesemans, F. Fu, H. Pan, M. Gielen, R. Willem,
J. Organomet. Chem. 486 (1994) 263.
[11] F. Fu, H. Li, D. Zhu, Q. Fang, H. Pan, E.R.T. Tiekink, F.
Kayser, M. Biesemans, I. Verbruggen, R. Willem, M. Gielen,
J. Organomet. Chem. 490 (1995) 163.
[12] H.C. Dai, Q.H. Ying, X.H. Wang, S.M. Yue, H.D. Pan, X.
Chen, Polyhedron 17 (1998) 2503.
[13] D.C. Deka, M. Helliwell, E.J. Thmas, Tetrahedron 57 (2001)
10017.
Acknowledgements
[14] H.D. Vercruijsse, W. De Graaf, L. Brandsma, Synthetic
Comm. 18 (1988) 131.
This work was supported by the National Natural
Science Foundation of China (No. 29734143 and No.
29672013).
[15] H.D. kuivila, O.F. Beumel Jr., J. Am. Chem. Soc. 83 (1961)
1246.
[16] D.H. Lorenz, P. Shapiro, A. Stern, E.I. Becker, J. Org. Chem.
28 (1964) 2335.
[17] G.M. Sheldrick, Program for Crystal Structure Solution,
´ ´
University of Gottingen, Gottingen, 1997.
References
[18] G.M. Sheldrick, Program for Crystal Structure Refinement,
´
´
[1] A.J. Crowe, P.J. Smith, G. Atassi, Chem. Biol. Interact. 32
(1980) 171.
University of Gottingen, Gottingen, 1997.
[19] R.M. Silverstein, C.G. Bassler, T.C. Morrill, Spectrometric
Identification of Organic Compounds, fourth ed., Wiley, New
York, 1981, pp. 235.
[2] H. Pan, R. Willem, J. Meunier-Piret, M. Gielen, Organome-
tallics 9 (1990) 2199.