Synthesis, spectroscopic properties and crystal structures of SnBr2 [S2CN(CH2CH2)2O]2, (4-F-C6H4CH2)2Sn(Cl)S2CN(CH2CH2)2O and (2-F-C6H4CH2)3SnS2CN (CH2CH2)2O

Article abstract of DOI:10.1016/j.jorganchem.2004.01.023

Three organotin(IV) complexes with dithiomorpholincarbamate ligand: SnBr₂[S₂CN(CH₂CH₂) ₂O]₂ (1), (4-F-C₆H₄ CH₂)₂Sn(Cl)S₂CN(CH_{2 2})₂O (2) and (2-F-C₆H₄ CH₂)₃SnS₂CN(CH₂ CH₂)₂O (3) have been synthesized and characterized by elemental analysis, IR, UV and NMR. Their crystal and molecular structures have been determined by X-ray single crystal diffraction. In the complex 1, the tin atom is rendered six-coordination in a distorted octahedron configuration. And in the complexes 2 and 3, the tin atoms are rendered five-coordination in a distorted trigonal bipyramidal structure.

Full text of DOI:10.1016/j.jorganchem.2004.01.023

Journal of Organometallic Chemistry 689 (2004) 1277–1283
www.elsevier.com/locate/jorganchem
Synthesis, spectroscopic properties and crystal structures of
SnBr2[S2CN(CH2CH2)2O]2, (4-F -C6H4CH2)2Sn(Cl)S2CN(CH2CH2)2O
and (2-F -C6H4CH2)3SnS2CN(CH2CH2)2O
*
Handong Yin , Chuanhua Wang, Mei Hong, Daqi Wang
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
Received 22 October 2003; accepted 23 January 2004
Abstract
Three organotin(IV) complexes with dithiomorpholincarbamate ligand: SnBr2[S2CN(CH2CH2)2O]2 (1), (4-F -C6H4CH2)2Sn(Cl)
S2CN(CH2CH2)2O (2) and (2-F -C6H4CH2)3SnS2CN(CH2CH2)2O (3) have been synthesized and characterized by elemental
analysis, IR, UV and NMR. Their crystal and molecular structures have been determined by X-ray single crystal diffraction. In the
complex 1, the tin atom is rendered six-coordination in a distorted octahedron configuration. And in the complexes 2 and 3, the tin
atoms are rendered five-coordination in a distorted trigonal bipyramidal structure.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Tin(IV) complex; Dithiomorpholincarbamate; Synthesis; Crystal structure
1. Introduction
2. Experimental
Metal N,N-dialkyldithiocarbamates have been syn-
thesized by the action of metal halides on sodium N,
N-dialkyldithiocarbamate in both aqueous and non-
aqueous solution [1–3]. More recently, pharmaceutical
properties of alkyltin(IV) complexes with dithiocarba-
mate ligands have been investigated for their antitumour
activity [4–9]. Crystallographic studies have revealed that
the coordination at the tin atom depends not only on the
factors such as R-radical stereochemistry, but also on
whether the 1,1-dithiolates behave as monodentate or
bidentate ligands and whether the complexes are mono-
meric or oligomeric. As an extension of our studies of
alkyltin(IV) complexes with dithiocarbamate ligands,
we have synthesized and structurally characterized
three novel organotin(IV) complexes with dithiomor-
pholincarbamate ligand: SnBr2[S2CN(CH2CH2)2O]2 (1),
(4-F -C6H4CH2)2Sn(Cl)S2CN(CH2CH2)2O (2) and (2-F -
C6H4CH2)3SnS2CN(CH2CH2)2O (3). And the results of
this study are reported herein.
2.1. General procedure
Anhydrous sodium dithiomorpholincarbamate was
prepared according to the method described in the lit-
erature [10]. The solvent dichloromethane was dried
over phosphorus(V) oxide prior to use. Infrared spectra
were recorded on a Nicolet-460 spectrophotometer, us-
1
ing KBr as discs. H, 13C and 119Sn-NMR spectra were
obtained with Mercury Plus-400 NMR spectrometer
and the chemical shifts are given in ppm relative to
Me4Si, Me4Sn in CDCl3. Elemental analyses were per-
formed on PE-2400-II elemental analyzer. UV spectra
were obtained on a UV 210A spectrometer.
2.2. Synthesis of complexes 1, 2 and 3
2.2.1. Synthesis of complex 1
Anhydrous sodium dithiomorpholincarbamate (2.0
mmol) was added to 30 mL 95% ethanol solution of di(4-
fluorobenzyl)tin dibromide (1.0 mmol). Then the mixture
was heated under reflux for 6 h. The precipitated sodium
bromide was removed by filtration and the filtrate was
* Corresponding author. Tel.: +866358238121; fax: +866358238121.
E-mail address: handongyin@sohu.com (H. Yin).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.01.023

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H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
concentrated to about 5 mL under reduced pressure.
When hexane (5 mL) was added to this solution, imme-
diately, a precipitate was formed. The products were re-
crystallized from ethanol to give red crystals 0.39 g, yield
65%. M.p.: 143–145 °C. UV–Vis (CHCl3) kmax: 222, 265,
for C26H26F3NOS2Sn: C, 51.34; H, 4.31; N, 2.30;
S,10.54. Found: C, 51.07; H, 4.20; N, 2.19; S, 10.72%.
2.3. Crystallographic measurements
1
288 nm. H-NMR (CDCl3): d 4.10 (8H, t, J ¼ 7:8 Hz,
All X-ray crystallographic data were collected on a
Bruker smart-1000 CCD diffractometer with graphite
OCH2), 3.83 (8H, t, J ¼ 7:8 Hz, NCH2) ppm. 13C-NMR
(CDCl3): d 210.31(CS2), 68.32(CH2N), 56.29(CH2O)
ppm. 119Sn-NMR d )490.46 ppm. IR (KBr, cmꢀ1): 1463
(s, C–N), 1121, 995 (s, CS2), 457 (m, Sn–S). Anal. Calc.
for C10H16Br2N2O2S4Sn: C, 19.98; H, 2.75; N, 4.68; S,
21.20. Found: C, 19.92; H, 2.67; N, 4.65; S, 21.27%.
ꢀ
monochromated Mo Ka (0.71073 A) radiation. The
structures were solved by direct method and difference
Fourier map using SHELXL-97 program, and refined by
full-matrix least-squares on F 2. All non-hydrogen atoms
were refined anisotropically. Hydrogen atoms were lo-
cated at calculated positions and refined isotropically.
2.2.2. Synthesis of complex 2
Anhydrous sodium dithiomorpholincarbamate (1.0
mmol) were added to 30 mL dichloromethane solution
of di(4-fluorobenzyl)tin dichloride (1.0 mmol). The
mixture was stirred for 14 h at 30 °C. The precipitated
sodium chloride was removed by filtration and the fil-
trate was concentrated to about 5 mL under reduced
pressure. When hexane (5 mL) was added to this solu-
tion, immediately, a precipitate was formed. The prod-
ucts were recrystallized from dichloromethane-ethyl
ether to give colorless crystals 0.40 g, yield 75%. M.p.:
3. Results and discussion
3.1. The synthetic mechanism of complexes 1–3
Reaction of (4-F -C6H4CH2)2SnCl2 and (2-F –
C6H4CH2)3SnCl with sodium dithiomorpholincar-
bamate in 1:1 stoichiometry in dichloromethane gives
(4-F –C6H4CH2)2Sn(Cl)S2CN(CH2CH2)2O and (2-F –
C6H4CH2)3SnS2CN(CH2CH2)2O in 75% and 78% yield
after recrystallization:
1
133–134 °C. UV–Vis (CHCl3) kmax: 221, 257, 286. H-
NMR (CDCl3): d 6.80–7.05 (8H, m, ArH), 4.15 (4H, t,
J ¼ 10:8 Hz, OCH2), 3.85 (4H, t, J ¼ 10:5 Hz, NCH2),
2.84 (4H, t, JSnꢀH ¼ 70:7 Hz, ArCH2Sn) ppm.
13C-NMR (CDCl3): d 168.45, 148.82, 129.81, 121.32,
29.72 (4-F-C6H4CH2), 201.48(CS2), 67.62(CH2N),
54.85(CH2O) ppm. 119Sn-NMR d )315.82 ppm. IR
(KBr, cmꢀ1): 1478 (s, C–N), 1131, 998 (s, CS2), 554 (m,
Sn–C), 455 (m, Sn–S). Anal. Calc. for C19H20Cl
F2NOS2Sn: C, 42.69; H, 3.77; N, 2.62; S,11.99. Found:
C, 42.49; H, 3.58; N, 2.74; S, 12.17%.
ð4-F -C6H4CH2Þ SnCl2 þ NaS2CNðCH2CH2Þ O
2
2
! ð4-F -C6H4CH2Þ SnðClÞS2CNðCH2CH2Þ O ð2Þ
2
2
ð2-F -C6H4CH2Þ SnCl þ NaS2CNðCH2CH2Þ O
3
2
! ð2-F -C6H4CH2Þ SnS2CNðCH2CH2Þ O ð3Þ
3
2
As we know, a few papers about the synthesis and
structural study of SnX2(S2CNR2)2 have been reported
[10,11]. However, the study on this type compound
which was synthesized by the reaction of dialkyltin
dihalide with N,N-dialkyldithiocarbamate has not been
seen in previous literatures. When the reaction of (4-F -
C6H4CH2)2SnBr2 with NaS2CN(CH2CH2)2O in 1:2
molar ratio occured, an unexpected complex
Br2Sn[S2CN(CH2CH2)2O]2 (1) was obtained instead of
the expected (4-F -C6H4CH2)2Sn[S2CN(CH2CH2)2O]2.
A possible mechanism is given in Scheme 1. During the
reaction, the little H2O in solvent may be major factor
which results in dealkyltion. The synthetic mechanism of
this complex is similar to those of drum organooxotin
cluster [12–14]. Moreover, under anhydrous conditions,
using dichloromethane or anhydrous ethanol as solvent,
we have synthesized the complex (4-F -C6H4CH2)2Sn
[S2CN(CH2CH2)2O]2 at room temperature. The results
also make sure of our conclusion for the synthetic
mechanism of the complex 1.
2.2.3. Synthesis of complex 3
Anhydrous sodium dithiomorpholincarbamate (1.0
mmol) was added to 30 mL dichloromethane solution of
tri(2-fluorobenzyl)tin chloride (1.0 mmol). The mixture
was stirred for 18 h at 30 °C. The precipitated sodium
chloride was removed by filtration and the filtrate was
concentrated to about 5 mL under reduced pressure.
When hexane (5 mL) was added to this solution, im-
mediately, a precipitate was formed. The products were
recrystallized from dichloromethane-hexane to give
colorless crystals 0.47 g, yield 78%. M.p.: 121–122 °C.
UV–Vis (CHCl3) kmax
:
223, 262, 280. 1H-NMR
(CDCl3): d 6.92–7.02 (8H, m, ArH), 4.04 (4H, t, J ¼
11:2 Hz, OCH2), 3.77 (4H, t, J ¼ 11:2 Hz, NCH2), 2.62
(4H, t, JSnꢀH ¼ 75:3 Hz, ArCH2Sn) ppm. 13C-NMR
(CDCl3): d 160.15, 130.25, 126.82, 125.32, 123.69,
117.53,
28.98
(2-F-C6H4CH2),
189.23
(CS2),
d
3.2. Spectroscopic properties
68.76(CH2N), 59.60(CH2O) ppm. 119Sn-NMR
)211.35 ppm. IR (KBr, cmꢀ1): 1490 (s, C–N), 1142,
1003 (s, CS2), 545 (m, Sn–C), 462 (m, Sn–S). Anal. Calc.
In complexes 1, 2 and 3, as can be shown from UV
spectra, the band 1 at kmax 222, 221 and 223 nm which

H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
1279
Scheme 1.
belongs to strong absorption, is a K band due to p–pꢁ
transition of dithiomorpholincarbamate NCS. The band
2 at kmax 265, 257 and 262 nm which belongs to medium
absorption due to p–pꢁ transition of SCS moiety reveals
a hypsochromic shift 18–26 nm in comparison with that
of the appropriate sodium salt of dithiomorpholincar-
bamate acid [10]. The band 3 at kmax 288, 286 and 280
nm which belongs to a weak absorption is attributed to
electron-transfer transition n ꢀ pꢁ in CS2 group, exhib-
iting a hypsochromic shift by 15–23 nm when compared
with the corresponding band of salts of dithiomor-
pholincarbamate acid [10]. This suggests that sulphur
atoms of dithiomorpholincarbamate groups coordinate
to tin atom.
downfield shift in the position of CCꢀN and CCꢀO signals
and an upfield shift in the position of CCSS signal. These
shifts indicate the bidentate behaviour of the dithio-
morpholincarbamate moieties in the complexes.
The 119Sn chemical shift values in three complexes are
found to be in the range of )211.35 to 490.46 ppm. The
appearance of chemical shift values in this region indi-
cates five- and six-coordination environment [19] around
the central tin atoms in these complexes.
3.3. Molecular structures of complexes 1–3
Crystallographic data, together with refinement de-
tails of complexes 1, 2 and 3 are given in Table 1.
The selected bond distances and angles are given in
Tables 2–4, their molecular structures were illustrated in
Figs. 1–3.
In IR spectra of complexes 1–3, a new absorption
band appears at 455–462 cmꢀ1 which is the characteristic
vibrations of Sn–S bond [7–9]. One obvious feature of the
IR spectra is the similarity of the stretching bands arising
from the dithiocarbamate ligands. The relatively high
value (1463–1490 cmꢀ1) for m(C–N) is similar to that re-
ported for analogous tin complexes [7–9]. This suggests
that the dithiomorpholincarbamate ligand of three
complexes are linked to Sn atom in a bidentate fashion
[7–9]. In IR spectra the important bands arising from
m(CS2)asym and m(CS2)sym appear at 1121–1142 cmꢀ1 and
3.3.1. Complex 1
As was showed in Fig. 1, the coordination at the tin
atom is octahedral geometry, surrounded by four sul-
phur atoms and two bromine atoms. So the tin atom is
rendered six-coordinate for complex SnBr2[S2CN
(CH2CH2)2O]2 (1). Thus, the structure is similar to those
of the complexes: SnCl2[S2CN(C2H5)2]2 [7] and SnBr2
(S2COC2H5)2 [11].
995–1003 cmꢀ1, respectively. The Dm values [m(CS2)asym
–
m(CS2)sym] (126–139 cmꢀ1) is much smaller than the Dmꢁ
of the R2NCS2R0 [10], but it is larger than the Dm0 of the
corresponding sodium dithiomorpholincarbamate [10].
This information shows the dithiomorpholincarbamate
group in three complexes coordinates to tin in an aniso-
bidentate fashion [4–6], and the analysis is consistent with
X-ray single crystal diffraction results.
The 1H-NMR spectra of complexes 2 and 3 show that
the chemical shifts of the protons on the benzyl group
exhibit two signals about 6.80–7.05 ppm as multiplet
and 2.84, 2.62 ppm as a triplet which is caused by the tin
The tin atom has a highly distorted octahedral con-
figuration. The distortion is reflected in the cis angles
which vary from 70.57(4)° to 103.14(4)°, the range of
trans angles is from 156.76(7)° to 163.62(3)°. These trans
angles result from the necessity for the two bidentate
dithiomorpholincarbamate ligands to have a smaller bite
than usual (i. e. in the order of 63–71°) [15–17]. The
binding of the dithiomorpholincarbamate group is found
to be in an anisobidentate fashion in many structures.
However, the Sn–S distances [0.25184(17), 0.25636(17)
nm] in this structure show much smaller anisobonding.
Though this can be attributed to the presence of non-
bulky bromine groups in the coordination sphere, the
observation that in the structure of dibenzyltin bis(dith-
iotetrahydropyrrolocarbamate) [18], the reported Sn–S
bond distances [0.25209(12) and 0.29083(13) nm] show
both the packing forces and coordination geometry most
probably play a vital role in the very near isobonding
(
119Sn) hydrogen coupling. And the spin-spin coupling
1
constant JSnꢀH is equal 70.7 and 75.3 Hz. In the H-
NMR spectra of complexes 1–3, the NCH2 and OCH2
protons give rise to triplet signals at 3.83, 4.10; 3.85, 4.15
and 3.77, 4.04 ppm, as expected.
A comparison of the 13C-NMR spectra of the ligand.
With the corresponding organotin complexes shows a

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H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
Table 1
Crystallographic data of complexes 1, 2 and 3
1
2
3
Molecular formula
Formula weight
Crystal system
Space group
Unit cell dimensions
a (nm)
b (nm)
c (nm)
a (°)
b (°)
C10H16Br2N2O2S4Sn
605.01
C19H20ClF2NOS2Sn
534.62
C26H26F3NOS2Sn
608.29
Triclinic
Tetragonal
I4ð1Þ=a
Orthorhombic
Pbca
ꢁ
P1
1.7567(8)
1.7567(8)
1.3637(17)
1.1710(15)
1.0745(16)
1.383(2)
1.952(3)
1.7596(11)
90
2.768(3)
90
99.62(2)
103.83(2)
90
90
90
90
c (°)
104.13(2)
2.651(7)
V (nm3)
5.430(5)
4.421(10)
Z
8
1.480
2336
8
1.606
2128
4
1.524
1224
Dcal (kg/cm3)
F (0 0 0)
Crystal size (mm)
Scan range h (°)
Index ranges
0.50 ꢂ 0.30 ꢂ 0.20
2.84 6 h 6 26.37
ꢀ21 6 h 6 21, ꢀ21 6 k 6 6,
ꢀ21 6 l 6 21
13895/2618/0.0369
4.194
0.27 ꢂ 0.23 ꢂ 0.15
1.47 6 h 6 25.03
ꢀ8 6 h 6 16, I ꢀ 13 6 k 6 13,
ꢀ31 6 l 6 32
21875/3902/0.0525
1.491
0.50 ꢂ 0.40 ꢂ 0.15
2.39 6 h 6 25.03
ꢀ9 6 h 6 12, ꢀ16 6 k 6 14,
ꢀ23 6 l 6 23
8717/7177/0.0243
1.161
Total/unique/Rint
l (mmꢀ1
R1=wR2
)
0.0398/0.0884
1.033
0.663/–392
0.0362/0.0848
0.957
0.0464/0.1161
0.954
Goodness-of-fit on F 2
q
max=qmin (e nmꢀ3
)
0.509/)493
0.828/)838
Table 2
Selected bond distances (nm) and angles (°) of complex 1
Table 3
Selected bond distances (nm) and angles (°) of complex 2
Sn(1)–Br(1)
Sn(1)–S(1)
0.27107(12) S(1)–C(1)
0.25184(17) S(2)–C(1)
0.25636(17) N(1)–C(1)
0.1731(5)
0.1711(5)
0.1300(6)
0.1463(7)
90.96(6)
Sn(1)–C(6)
Sn(1)–C(13)
Sn(1)–Cl(1)
Sn(1)–S(1)
Sn(1)–S(2)
F(1)–C(10)
F(2)–C(17)
0.2141(6)
0.2157(6)
0.2491(3)
0.2466(2)
0.2684(2)
0.1359(8)
0.1368(8)
S(1)–C(1)
S(2)–C(1)
0.1743(5)
0.1694(6)
0.1324(7)
0.1475(7)
0.1468(7)
0.1566(9)
0.1561(9)
69.54(10)
157.29(6)
117.8(3)
123.4(4)
118.8(4)
88.8(2)
Sn(1)–S(2)
N(1)–C(5)
N(1)–C(1)
N(1)–C(2)
0.1477(8)
156.76(7)
70.57(4)
93.04(4)
N(1)–C(2)
S(2)–Sn(1)–Br(1A)
S(1)–Sn(1)–S(1A)
S(1)–Sn(1)–S(2)
S(1A)–Sn(1)–S(2)
N(1)–C(5)
O(1)–C(3)
O(1)–C(4)
S(2A)–Sn(1)–Br(1A) 163.62(3)
S(1)–Sn(1)–Br(1)
S(1A)–Sn(1)–Br(1)
S(2)–Sn(1)–Br(1)
C(1)–S(1)–Sn(1)
C(1)–S(2)–Sn(1)
C(1)–N(1)–C(2)
C(1)–N(1)–C(5)
C(2)–N(1)–C(5)
93.20(4)
103.14(4)
163.62(3)
86.70(17)
85.66(18)
123.7(5)
121.4(4)
114.4(5)
S(1A)–Sn(1)–S(2A) 70.57(4)
S(2)–Sn(1)–S(2A) 92.09(8)
Br(1A)–Sn(1)–Br(1) 90.64(6)
C(6)–Sn(1)–C(13) 129.5(3)
S(1)–Sn(1)–S(2)
Cl(1)–Sn(1)–S(2)
S(2)–C(1)–S(1)
N(1)–C(1)–S(2)
N(1)–C(1)–S(1)
C(1)–S(1)–Sn(1)
C(1)–S(2)–Sn(1)
C(7)–C(6)–Sn(1)
C(6)–Sn(1)–S(1)
C(13)–Sn(1)–S(1)
C(6)–Sn(1)–Cl(1)
111.34(19)
117.63(19)
94.3(2)
N(1)–C(1)–S(2)
N(1)–C(1)–S(1)
S(2)–C(1)–S(1)
C(3)–O(1)–C(4)
121.9(4)
121.1(4)
117.0(3)
108.4(6)
C(13)–Sn(1)–Cl(1) 98.83(18)
S(1)–Sn(1)–Cl(1)
C(6)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
C(9)–C(10)–F(1)
87.75(10)
94.3(2)
82.8(2)
113.7(4)
91.75(18)
118.7(7)
C(14)–C(13)–Sn(1) 117.1(4)
N(1)–C(2)–C(3)
C(5)–C(4)–O(1)
C(11)–C(10)–F(1) 118.5(7)
C(2)–C(3)–O(1)
110.2(6)
110.8(7)
nature of the dithiomorpholincarbamate group. The
bond distance, Sn–Br [0.27107(12) nm] is much larger
than that found in Br2Sn(S2COC2H5)2 [11] [0.2537(2)
nm], which suggests that the halogides are weakly coor-
dinated in this complex. We believe that the weak coor-
dination of the halogide should be the result of packing
forces and the presence of bulky hydrophobic groups.
The N(1)–C(1) distance of 0.1300(6) nm is similar to
those reported for other dialkyldithocarbamate moieties
[7–9]. This distance suggest that the C(sp2)–N(sp2) bond
has a high double bond character, an observation con-
sistent with the IR data. The N(1)–C(2) and N(1)–C(5)
bond distance are 0.1463(7) and 0.1477(8) nm, respec-
tively and approximate from the N–C single bond dis-
tance (0.148 nm).
110.7(7)
3.3.2. Complex 2
The tin atom is five-coordinated [Sn(1)–S(1)
0.2466(2), Sn(1)–S(2) 0.2684(2), Sn(1)–Cl(1) 0.2491(3),
Sn(1)–C(6) 0.2141(6), Sn(1)–C(13) 0.2157(6) nm], with a
distorted trigonal bipyramid. The structure differs from
those of the complexes (PhCH2)2SnCl(S2CNC5H10) [19],
(PhCH2)2SnCl(S2CNMe2) [20] and (PhCH2)2SnCl
(S2CNC4H8O) [21], But it is similar to that of the
complex Ph2SnCl(S2CN(C2H5)2 [22].
The geometry is approximately based on a trigonal
bipyramid, with atom C(6), S(1) and C(13) occupying
equatorial positions. As an indication the sum of the

H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
1281
Table 4
Selected bond distances (nm) and angles (°) of complex 3
equatorial angles (358.47°) at the tin atom by the two
coordinated carbon atoms and one sulfur atom [C(13)–
Sn(1)–S(1) 117.63(19)°, C(6)–Sn(1)–S(1) 111.34(19)°,
C(6)–Sn(1)–C(13) 129.5(3)°] deviates at most by 1.53°
from the 360°, so the atoms C(6), S(1), C(13) and Sn(1)
are almost in a same plane. The Cl atom occupies ap-
proximately one apical position of the trigonal bipyra-
mid. Conversely, due to the constraint of the chelate [the
angle [S(1)–Sn(1)–S(2)] is not 90° but only 69.54(10)°],
the S(2) atom cannot exactly occupy the corresponding
trans axial position of the trigonal bipyramid, the angle
Cl(1)–Sn(1)–S(2) being 157.29(6)°.
Sn(1)–C(6)
Sn(1)–C(13)
Sn(1)–C(20)
Sn(1)–S(1)
Sn(1)–S(2)
S(1)–C(1)
0.2146(7)
0.2163(6)
0.2187(8)
0.2464(4)
0.3122(5)
0.1745(8)
0.1697(7)
Sn(2)–C(39)
Sn(2)–C(32)
Sn(2)–C(46)
Sn(2)–S(3)
Sn(2)–S(4)
S(3)–C(27)
S(4)–C(27)
0.2144(8)
0.2161(7)
0.2185(8)
0.2463(4)
0.3054(4)
0.1766(7)
0.1673(7)
S(2)–C(1)
C(6)–Sn(1)–C(13) 113.3(3)
C(6)–Sn(1)–C(20) 108.6(3)
C(13)–Sn(1)–C(20) 109.5(3)
C(39)–Sn(2)–C(32) 115.6(3)
C(39)–Sn(2)–C(46) 108.2(3)
C(32)–Sn(2)–C(46) 108.1(3)
C(6)–Sn(1)–S(1)
C(13)–Sn(1)–S(1)
C(20)–Sn(1)–S(1)
C(6)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
C(20)–Sn(1)–S(2)
S(1)–Sn(1)–S(2)
114.2(2)
114.3(2)
95.4(2)
82.1(2)
81.5(2)
158.6(2)
63.23(6)
C(39)–Sn(2)–S(3)
C(32)–Sn(2)–S(3)
C(46)–Sn(2)–S(3)
C(39)–Sn(2)–S(4)
C(32)–Sn(2)–S(4)
C(46)–Sn(2)–S(4)
S(3)–Sn(2)–S(4)
113.3(2)
113.9(2)
95.6(2)
The N(1)–C(1) distance of 0.1324(7) nm is similar to
those of complexes (PhCH2)2SnCl(S2CNMe2) [20] and
(PhCH2)2SnCl(S2CNC5H10) [19], but longer than that
of complex 1. The S(1)–C(1) [0.1743(5) nm] and S(2)–
C(1) [0.1694(6) nm] bond lengths appear to be charac-
82.1(2)
81.36(19)
159.9(2)
64.29(8)
Fig. 1. The molecular structure of complex 1.
Fig. 2. The molecular structure of complex 2.

1282
H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
Fig. 3. The molecular structure of complex 3.
teristic of the dithiocarbamate group that these two
distances are both intermediate between the values ex-
pected ‘‘single’’ and ‘‘double’’ bond [23].
trigonal bipyramidal symmetry are reflected in the in-
teratomic angles. The sum of equatorial angles C(6)–
Sn(1)–S(1) (114.2(2)°), C(13)–Sn(1)–C(20) (109.5(3)°)
and C(13)–Sn(1)–S(1) (114.3(2)°) is equal to 338°, which
shows that these atoms are not co-planar. The angles
C(6)–Sn(1)–S(2) 82.1(2)°, C(13)–Sn(1)–S(2) 81.5(2)° and
S(1)–Sn(1)–S(2) 63.23(6)° are all less than 90°. In con-
trast, the angles C(6)–Sn(1)–C(20) 108.6(3)°, C(13)–
Sn(1)–C(20) 109.5(3)° and C(20)–Sn(1)–S(1) 95.4(2)° are
greater than 90°, because the 2-fluorobenzyl group is on
the side of the plane having more sterical hindrance
than the S(2) atom on the other side. The C(20) atom
occupies approximately one apical position of the tri-
gonal bipyramid. Conversely, due to the constraint of
the chelate [the angle [S(1)–Sn(1)–S(2)] is not 90° but
only 62.7(5)°], the S(2) atom cannot exactly occupy the
corresponding trans axial position of the trigonal
bipyramid, and the angle C(18)–Sn(1)–S(2) only is
158.6(2)° deviating from linear angle 180°. From this,
the tin atom of this complex is distorted trigonal
bipyramid configuration.
3.3.3. Complex 3
In crystal of complex 3, the unit cell contains two
independent molecules that are practically superimpos-
able. In fact a computer fitting of molecules A and B
shows only a very marginal difference in the bond
lengths and angles. One of the two molecules is repre-
sented in Fig. 3 with its numbering scheme. The mole-
cule A is discussed in this paper. In complex 3, the
coordination at the tin atom is trigonal bipyramid,
surrounded axially by two sulphur atoms and three
carbon atoms. Thus, the structure is similar to those of
the complexes (PhCH2)3S2CNC4H8O [24] and
(PhCH2)3S2CNC5H10 [25].
The Sn(1)–S(1) bond length is 0.2464(4) nm, it is
almost equal to the bond distance of complexes
Me3SnS2CNMe2 (0.246 nm) [23] and (PhCH2)3-
SnS2CNC5H10 (0.2481 nm) [22] but shorter than that of
tBu2Sn(S2CNEt2)2 (0.255 nm) [22]. The Sn(1)–S(2) dis-
tance is 0.3122(5) nm, which is well within the sum of the
van der Waals radii of 4.00 nm for Sn and S atoms. It is
almost equal to the bond distance of complex
Me3SnS2CNMe2 (0.316 nm) [23] but slightly longer than
that of complex (PhCH2)3S2CNC5H10 (0.3027 nm) [25].
The information showed the two S atoms coordinate to
Sn atom. So the tin atom could be considered five coor-
dinate within a trigonal bipyramidal environment.
The geometry of complex 3 is loosely based on a
trigonal bipyramid, with atom C(6), S(1) and C(20)
occupying equatorial positions. Distortions from true
4. Supplementary material
Crystallographic data for the structural analysis
have been deposited with the Cambridge Crystallo-
graphic Data Center, CCDC No. 221746 for complex
1, CCDC No. 221748 for complex 2 and CCDC
No.221747 for compound 3. Copies of this information
may be obtained from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: +44-1233-336-
033; E-mail: deposit@ccdc.cam.ac.uk).

H. Yin et al. / Journal of Organometallic Chemistry 689 (2004) 1277–1283
1283
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Acknowledgements
We acknowledge the financial support of the Shan-
dong Province Science Foundation, and the State Key
Laboratory of Crystal Materials, Shandong University,
PR China.
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