Syntheses, characterization and crystal structures of di- and triorganotin (IV) derivatives with 6-amino-1,3,5-triazine-2,4-dithiol

Article abstract of DOI:10.1016/j.jorganchem.2005.11.018

A series of organotin (IV) complexes with 6-amino-1,3,5-triazine-2,4- dithiol of the type [(R_nSnCl_4-n)₂ (C ₃H₂N₄S₂)] (n = 3: R = Me 1, n-Bu 2, PhCH₂ 3, Ph 4; n = 2: R = Me 5, n-Bu 6, PhCH₂ 7, Ph 8) have been synthesized. All the complexes 1-8 have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectra. Among them complexes 1, 4, 5 and 8 have also been characterized by X-ray crystallography diffraction analyses, which revealed that the tin atoms of complexes 1, 4, 5 and 8 are all five-coordinated with distorted trigonal bipyramid geometries.

Full text of DOI:10.1016/j.jorganchem.2005.11.018

Journal of Organometallic Chemistry 691 (2006) 1606–1614
www.elsevier.com/locate/jorganchem
Syntheses, characterization and crystal structures of di- and
triorganotin (IV) derivatives with 6-amino-1,3,5-triazine-2,4-dithiol
a,b,
a
a
a
Chunlin Ma
*, Yongxin Li , Rufen Zhang , Daqi Wang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 6 November 2005; accepted 7 November 2005
Available online 19 December 2005
Abstract
A series of organotin (IV) complexes with 6-amino-1,3,5-triazine-2,4-dithiol of the type [(RnSnCl4ꢀn)2 (C3H2N4S2)] (n = 3: R = Me 1,
n-Bu 2, PhCH2 3, Ph 4; n = 2: R = Me 5, n-Bu 6, PhCH2 7, Ph 8) have been synthesized. All the complexes 1–8 have been characterized
1
by elemental analysis, IR, H and 13C NMR spectra. Among them complexes 1, 4, 5 and 8 have also been characterized by X-ray
crystallography diffraction analyses, which revealed that the tin atoms of complexes 1, 4, 5 and 8 are all five-coordinated with distorted
trigonal bipyramid geometries.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: 6-Amino-1,3,5-triazine-2,4-dithiol; Organotin (IV); Crystal structures
1. Introduction
there are several factors that can influence the topologies of
the organotin (IV) derivatives from heterocyclic thionates
such as the special geometries of ligand, the spatial resis-
tant from R, etc. To continue our studies in this field, we
choose another fascinating heterocyclic thionate: 6-
amino-1,3,5-triazine-2,4-dithiol, which possesses two –SH
groups, through which primary bonds to tin atoms are
likely formed. Moreover, the three potentially coordinating
nitrogen atoms of triazine make the ligand act as a fulcrum
about which lattice construction is orchestrated in one or
more dimensions.
Organotin (IV) complexes are attracting more and more
attention for their potential industrial applications and bio-
logical activities [1]. Recently, increasing investigation on
organotin (IV) complexes has been focused on acquiring
well-state structures to learn the nature of their versatile
bonding modes [2], especially those of some organotin
(IV) derivatives from heterocyclic thionates [3]. Heterocy-
clic thionates are ligands derived form heterocyclic thiones
that contain at least one deprotonated heterocyclic thioam-
ide group (N–C–S)ꢀ and can act as monodentate, chelating
and bridging ligands. In our previous work, we studied the
coordination chemistry of three ligands of such kind: 6-thi-
opurine, 1-(4-hydroxyphenyl)-1H-tetrazole-5-thiol and 2,5-
dimercapto-1,3,4-thiodiazole (bismuthiol-I), which pos-
sessed one or two deprotonated heterocyclic thioamide
group, respectively [4–6]. The X-ray analyses revealed that
In this paper, we report some details of the syntheses and
characterizations of a series of organotin (IV) complexes
with the ligand of the type [(RnSnCl4ꢀn)2 (C3H2N4S2)]
(n = 3: R = Me 1, n-Bu 2, PhCH2 3, Ph 4; n = 2: R = Me
5, n-Bu 6, PhCH2 7, Ph 8). The X-ray crystallography of
complexes 1, 4, 5 and 8 show that all the complexes contain
the thiolate form of the ligand, i.e. the ligand is linked to the
organometal moiety primarily through sulfur, resembling as
Hmnc and 1-phenyl-1H-tetrazole-5-thiol [3,7]. Interest-
ingly, the versatile hydrogen bonding, N–Hꢁ ꢁ ꢁX (X = N,
S, Cl) are found.
*
Corresponding author. Tel.: +86 635 8238121; fax: +86 538 6715521.
E-mail address: macl@lctu.edu.cn (C. Ma).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.11.018

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
1607
2. Experimental
NMR (CDCl3, ppm): d 178.8 (C–NH2), 197.7 (C–S),
197.7 (C–S), 17.4, 28.1, 26.6, 13.8 (n-Bu). IR (KBr,
cmꢀ1): m(C@N) 1632, m(Sn–C)as 528, m(Sn–C)s 502, m(Sn–
N) 567, m(Sn–S) 311.
2.1. Materials and measurements
Trimethyltin chloride, tri-n-butyltin chloride, triphenyl-
tin chloride, dimethyltin dichloride, di-n-butyltin dichlo-
ride, diphenyltin dichloride and 6-amino-1,3,5-triazine-2,
4-dithiol were commercially available, and they were used
without further purification unless otherwise noted. Trib-
enzyltin chloride and dibenzyltin dichloride were prepared
by a standard method reported in the literature [8]. The
melting points were obtained with Kofler micro-melting
point apparatus and were uncorrected. Infrared-spectra
were recorded on a Nicolet-460 spectrophotometer using
KBr discs and sodium chloride optics. 1H, 13C NMR spec-
tra were recorded on Varian Mercury Plus 400 spectrome-
ter operating at 400 and 100.6 MHz, respectively. The
spectra were acquired at room temperature (298 K) unless
otherwise specified; 13C spectra are broadband proton
decoupled. The chemical shifts were reported in ppm with
respect to the references and were stated relative to external
2.2.3. (PhCH2)3Sn(S–C3H2N4–S)Sn(PhCH2)3 (3)
Yield, 75%: m.p. 130–132 °C. Anal. Calc. for
C45H44N4S2Sn2: C, 57.35; H, 4.71; N, 5.95. Found: C,
57.39; H, 4.66; N, 5.99%. 1H NMR (CDCl3, ppm): d
7.45–7.78 (m, 30H, Sn–CH2C6H5), 2.82 (s, 12H,
CH2C6H5), 4.00 (s, 2H, C–NH2). 13C NMR (CDCl3,
ppm): d 178.8 (C–NH2), 197.7 (C–S), 197.7 (C–S), 15.9
(CH2–Ph), 142.8 (i-C), 129.1 (o-C), 128.7 (m-C), 125.8
(p-C). IR (KBr, cmꢀ1): m(C@N) 1631, m(Sn–C)as 460,
m(Sn–C)s 435, m(Sn–N) 564, m(Sn–S) 314.
2.2.4. Ph3Sn(S–C3H2N4–S)SnPh3 (4)
Yield, 74%: m.p. 177–179 °C. Anal. Calc. for
C39H32N4S2Sn2: C, 54.58; H, 3.76; N, 6.53. Found: C,
54.56; H, 3.71; N, 6.56%. 1H NMR (CDCl3, ppm): d
7.46–7.79 (m, 30H, Sn–C6H5), 4.00 (s, 2H, C–NH2). 13C
NMR (CDCl3, ppm): d 178.8 (C–NH2), 197.7 (C–S),
197.7 (C–S), 129 (i-C), 137.5 (o-C), 128.8 (m-C), 128.8
(p-C). IR (KBr, cmꢀ1): m(C@N) 1631, m(Sn–C)as 464,
m(Sn–C)s 429, m(Sn–N) 561, m(Sn–S) 312.
1
tetramethylsilane (TMS) for H and 13C NMR. Elemental
analyses (C, H, N) were performed with a PE-2400II
apparatus.
2.2. Syntheses of the complexes 1–8
2.2.5. [Me2SnCl(S–C3H2N4–S)SnClMe2] Æ
0.5C8H24Cl4O2Sn4 (5)
Complexes 1–8 were obtained following a procedure,
which is here reported for complex 1.
Yield, 74%: m.p. 118–120 °C. Anal. Calc. for
C36H80Cl12N16O2S8Sn12: C, 15.04; H, 2.80; N, 7.79. Found:
1
2.2.1. [Me3Sn(S–C3H2N4–S)SnMe3] Æ 0.5C2H5OH (1)
The reaction was carried out under dry nitrogen atmo-
sphere. The 6-amino-1,3,5-triazine-2,4-dithiol (0.160 g,
1 mmol) and sodium ethoxide (0.136 g, 2 mmol) was
added to benzene (20 ml) in a Schlenk flask, and the mix-
ture was stirred for 10 min, then add Me3SnCl (0.396 g,
2 mmol) to the mixture, the reaction mixture was stirred
for 12 h at 45 °C. After cooling down to the room temper-
ature, the solution was filtered. The solvent of the filtrate
was gradually removed by evaporation under vacuum
until solid product was obtained. The solid was then
recrystallized from ethanol. Yield, 72%: m.p. 102–
104 °C. Anal. Calc. for C20H46N8OS4Sn4: C, 23.60; H,
C, 15.01; H, 2.85; N, 7.84%. H NMR (CDCl3, ppm): d
2
0.95 (s, 6H, JSnH = 72 Hz), d 1.42 (s, 48H, Sn–CH3),
4.00 (s, 2H, C–NH2). 13C NMR (CDCl3, ppm): d 178.8
(C–NH2), 197.7 (C–S), 197.7 (C–S), 2.5 (Me). IR (KBr,
cmꢀ1): m(C@N) 1633, m(Sn–C)as 525, m(Sn–C)s 498, m(Sn–
N) 564, m(Sn–S) 311.
2.2.6. (n-Bu)2SnCl(S–C3H2N4–S)SnCl(n-Bu)2 (6)
Yield, 69%: m.p. 117–119 °C. Anal. Calc. for
C38H76Cl4N8S4Sn4: C, 32.84; H, 5.51; N, 8.06. Found: C,
32.80; H, 5.56; N, 8.13%. 1H NMR (CDCl3, ppm): d
0.86–1.75 (m, 72H, Sn–C4H9), 4.00 (s, 2H, C–NH2). 13C
NMR (CDCl3, ppm): d 178.8 (C–NH2), 197.7 (C–S),
197.7 (C–S), 13.7, 25.2, 25.8, 13.8 (n-Bu). IR (KBr,
cmꢀ1): m(C@N) 1632, m(Sn–C)as 530, m(Sn–C)s 504, m(Sn–
N) 558, m(Sn–S) 315.
1
4.56; N, 11.01. Found: C, 23.68; H, 4.53; N, 11.09%. H
2
NMR (CDCl3–D2O, ppm): d 0.73 (s, 9H, JSnH = 58 Hz),
d 0.76 (s, 36H, Sn–CH3), 3.74 (m, 1H, CH3CH2OH), 1.25
(t, 3H, CH3CH2OH), 2.00 (t, 1H, CH3CH2OH), 4.00 (s,
2H, C–NH2). 13C NMR (CDCl3): d 178.8 (C–NH2),
197.7 (C–S), 197.7 (C–S), 1.9 (Sn–Me). IR (KBr, cmꢀ1):
m(C@N) 1630, m(Sn–C)as 532, m(Sn–C)s 503, m(Sn–N)
561, m(Sn–S) 312.
2.2.7. (PhCH2)2SnCl(S–C3H2N4–S)SnCl(PhCH2)2 (7)
Yield, 76%: m.p. 108–110 °C. Anal. Calc. for
C31H30Cl2N4S2Sn2: C, 46.61; H, 4.49; N, 6.39. Found: C,
46.67; H, 4.53; N, 16.37%. 1H NMR (CDCl3, ppm): d
6.80–7.05 (m, 20H, Sn–CH2C6H5), 3.52 (s, 8H, CH2C6H5),
4.00 (s, 2H, C–NH2). 13C NMR (CDCl3, ppm): d 178.8 (C–
NH2), 197.7 (C–S), 197.7 (C–S), 19.1 (CH2–Ph), 142.8
(i-C), 129.1 (o-C), 128.7 (m-C), 125.8 (p-C). IR (KBr,
cmꢀ1): m(C@N) 1634, m(Sn–C)as 465, m(Sn–C)s 434, m(Sn–N)
561, m(Sn–S) 315.
2.2.2. (n-Bu)3Sn(S–C3H2N4–S)Sn(n-Bu)3 (2)
Yield, 68%: m.p. 70–72 °C. Anal. Calc. for
C27H56N4S2Sn2: C, 43.92; H, 7.65; N, 7.59. Found: C,
43.85; H, 7.66; N, 7.55%. 1H NMR (CDCl3, ppm): d
0.84–1.71 (m, 54H, Sn–C4H9), 4.00 (s, 2H, C–NH2). 13C

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
Table 1
Table 2
Crystal data and structure refinement parameters for complexes 1 and 4
Crystal data and structure refinement parameters for complexes 5 and 8
Complex
1
4
Complex
5
8
Empirical formula
Formula weight
Wavelength (A)
C20H46N8OS4Sn4
1017.65
0.71073
C39H32N4S2Sn2
858.19
0.71073
Empirical formula
Formula weight
Wavelength (A)
C36H80Cl12N16O2S8Sn12
2875.32
0.71073
C27H22Cl2N4S2Sn2
774.89
0.71073
˚
˚
Crystal system
Space group
Triclinic
Monoclinic
P2(1)/n
Crystal system
Space group
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
Unit cell dimensions
a (A)
Unit cell dimensions
a (A)
˚
˚
11.689(2)
13.436(3)
13.932(3)
70.346(3)
85.406(3)
86.479(3)
2052.6(7)
2
9.632(3)
57.269(18)
14.093(4)
90
96.758(6)
90
7720(4)
8
1.433
3408
11.308(2)
15.540(3)
17.815(3)
108.664(2)
92.226(2)
108.424(3)
2779.9(9)
1
9.266(2)
11.129(4)
16.863(4)
99.015(2)
103.315(2)
98.996(2)
1637.4(8)
2
˚
˚
b (A)
b (A)
˚
˚
c (A)
c (A)
a (°)
b (°)
c (°)
a (°)
b (°)
c (°)
3
˚
3
˚
V (A )
V (A )
Z
Z
l (mmꢀ1
F(000)
)
2.632
988
l (mmꢀ1
F(000)
)
3.114
1.837
1356
756
Reflections collected
10728
40439
Reflections collected
Independent
14234
9474 [0.0194]
7536
5289 [0.0426]
Independent reflections [Rint
Data/restraints/parameters
Final R indices [I > 2r(I)]
]
7133 [0.0179]
7133/4/337
R1 = 0.0331
wR2 = 0.0888
R1 = 0.0506
wR2 = 0.0992
0.998
13498 [0.1095]
13498/0/847
R1 = 0.0761
wR2 = 0.1701
R1 = 0.1730
wR2 = 0.2220
1.026
reflections [Rint
Data/restraints/
parameters
]
9474/0/388
5289/0/334
R indices (all data)
Final R indices
[I > 2r(I)]
R indices (all data)
R1 = 0.0359
wR2 = 0.0850
R1 = 0.0591
wR2 = 0.1002
1.000
R1 = 0.0582
wR2 = 0.1385
R1 = 0.0797
wR2 = 0.1561
0.992
Goodness-of-fit
H Range for data collection (°)
1.83–25.03
2.03–25.03
Goodness-of-fit
H Range for
2.91–25.03
2.05–25.03
data collection (°)
2.2.8. Ph2SnCl(S–C3H2N4–S)SnClPh2 (8)
Yield, 71%: m.p. 159–161 °C. Anal. Calc. for
C27H22Cl2N4S2Sn2: C, 41.85; H, 2.86; N, 7.23. Found: C,
41.88; H, 2.83; N, 7.29%. 1H NMR (CDCl3, ppm): d
7.46–7.79 (m, 20H, Sn–C6H5), 4.00 (s, 2H, C–NH2). 13C
NMR (CDCl3, ppm): d 178.8 (C–NH2), 197.7 (C–S),
197.7 (C–S), 129 (i-C), 137.5 (o-C), 128.8 (m-C), 128.8
(p-C). IR (KBr, cmꢀ1): m(C@N) 1635, m(Sn–C)as 460,
m(Sn–C)s 425, m(Sn–N) 561, m(Sn–S) 317.
3.2. IR spectroscopic studies of the complexes 1–8
The explicit feature in the IR spectra of the eight com-
plexes 1–8 is the absence of the band in the region 2550–
2430 cmꢀ1, which appears in the free ligand as the m(S–H)
vibration, thus indicating metal–ligand bond formation
through this site. While in the far-IR spectra, a strong
absorption appears in the range 285–344 cmꢀ1 in the spec-
tra of complexes 1–8, which is absent in the spectrum of the
ligand, is assigned to the Sn–S stretching mode of the
vibration and all the values are consistent with that
detected in a number of organotin (IV)–sulfur derivatives
[10].
Furthermore, in organotin complexes, the IR spectra
can provide useful information concerning the geometry
of the SnCn moiety [11]. In the case of our complexes,
two bands were assigned to SnC2 asymmetric (460–
530 cmꢀ1) and symmetric (425–504 cmꢀ1) vibrations of
diorganotin (IV) derivatives and to SnC3 asymmetric
(460–532 cmꢀ1) and symmetric (429–503 cmꢀ1) vibrations
of triorganotin (IV) derivatives. Thus, suggesting nonlinear
SnC2 units for diorganotins and non-planar SnC3 frag-
ments for triorganotins, respectively. The middle intensity
bands observed at about 1600 cmꢀ1 in the spectra of all
complexes have been assignable to m(C@N) according to
the literatures [12,13], which suggested the coordinates of
free ligand to these complexes is through sulfur atoms via
thiolate form.
2.3. X-ray crystallographic studies of complexes 1, 4, 5 and 8
Crystals were mounted in Lindemann capillaries under
nitrogen. All X-ray crystallographic data were collected
on a Bruker SMART CCD 1000 diffractometer with
graphite monochromated Mo Ka radiation (k =
˚
0.71073 A) at 298(2) K. Correction for semi-empirical from
equivalents was applied. And the structure was solved by
direct methods and refined by a full-matrix least-squares
procedure based on F2 using the SHELXL-97 program system
[9]. The positions of hydrogen atoms were calculated, and
their contributions were included in structural factor calcu-
lations. Crystal data and experimental details of the struc-
ture determinations are listed in Tables 1 and 2.
3. Results and discussion
3.1. Syntheses of the complexes 1–8
The synthesis procedure is given in Scheme 1.

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
1609
NH2
NH2
R
EtONa
.
N
N
N
N
L
R
R
Sn
R
2R3SnCl
+
N
S
N
S
SH
HS
Sn
R
(L=0.5C2H5OH, R=Me1; L=0, R=Bu 2; PhCH2 3; R=Ph 4)
R
NH2
N
NH2
R
EtONa
N
.
N
N
Cl Sn
R
L
R
2R2SnCl2
+
N
S
N
S
SH
HS
(L=0.25 C8H24Cl4O2Sn4, R=Me 5; L=0, R=Bu 6; PhCH2 7; R=Ph 8)
Sn
Cl
R
Scheme 1.
1
3.3. H and 13CNMR data of the complexes 1–8
NMR spectra show that the chemical shifts of the phenyl
group (Sn–C6H5) in complexes 4 and 8, 7.46–7.79 ppm,
and those of methylene connected directly with tin in com-
plexes 1, 2, 3, 5, 6 and 7, 1.71–3.52 ppm, upfield shift as
compared with those of their corresponding precursors.
1H NMR data showed that the signal of the –SH proton
in the spectrum of the ligand is absent in all of the com-
plexes 1–8, indicating the removal of the –SH proton and
the formation of Sn–S bonds. The formation accords well
1
with what the IR data have revealed. Moreover, the H
Fig. 1. Crystal structure of the complex 1.
Fig. 2. Perspective view showing the 1D polymer of complex 1.
Fig. 3. Crystal structure of the complex 4.

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
The structural changes occurring in ligand upon depro-
in these complexes act as thiolate form. All of the above
analyses are confirmed by X-ray diffraction.
tonation and coordination to the Sn atom should be
reflected by the changes in the 13C NMR spectra of our
complexes. If the ligand chelate tin through thiolate form,
C–S should be further low frequency in the spectra of all
complexes compared with those in free ligands. As shown
above, the chemical shifts of C–S in complexes 1–8 are
shifted by 8 ppm to low frequency compared with the free
ligand (d 176.2 ppm), indicating that the ligands involved
3.4. Crystal structures of complexes 1, 4, 5 and 8
The crystal structures or perspective view of complexes
1, 4, 5 and 8 are shown in Figs. 1–8. All H atoms have been
omitted for the purpose of clarity. Tables 1 and 2 list the
crystal data and structure refinement parameters for com-
Fig. 4. The dimer of the complex 4.
Fig. 6. Perspective view showing the 2D network of the complex 5.
Fig. 5. Molecular structure of the complex 5.

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
1611
Fig. 7. Crystal structure of complex 8.
Fig. 8. Perspective view showing the 1D polymer of complex 8.
plexes 1, 4, 5 and 8 and their selected bond lengths and
angles are shown in Tables 3–6, respectively.
As exhibited, the compounds are formed by discrete
molecules in which the tin atoms are indeed bound to the
sulfur atoms of the triazine, which together with the methyl
(or phenyl) groups defines a distorted tetrahedron around
the tin atoms.
3.4.1. [(Me3Sn)2(C3H2N4S2)] Æ 0.5C2H5OH (1) and
[(Ph3Sn)2(C3H2N4S2)] (4)
Selected bond lengths and bond angles for complexes
1 and 4 are given in Tables 3 and 4 and their molecular
structures are shown in Figs. 1–4, respectively. For com-
plex 1 and 4, the asymmetric units both contain two
monomers A and B, which are different from a crystallo-
graphically point of view. The conformations of the two
independent molecules A and B are almost the same,
with only small differences in bond lengths and bond
angles.
For complex 1, the four Sn–S bond lengths lie toward
the middle of the range reported for trialkyltin heteroaren-
˚
ethiolates (2.405–2.481 A) and approach the sum of the
˚
covalent radii of tin and sulfur (2.42 A) [5,14,15]. Besides,
there exist intramolecular Sn–N interactions, common
observed in trialkyltin heteroarenethiolates [16]. The dis-
tance of four Sn–N bonds are midway between the sums
of the van der Walls radii and covalent radii of tin and
˚
nitrogen (2.15–3.74 A) [17] and can be regarded as weak

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
Table 3
Table 4
Selected bond lengths (A) and bond angles (°) for complex 4
˚
˚
Selected bond lengths (A) and bond angles (°) for complex 1
Molecule A
Molecule B
Molecule A
Molecule B
˚
˚
Bond lengths (A)
Sn(1)–C(6)
Sn(1)–C(5)
Sn(1)–C(4)
Sn(1)–S(1)
Sn(1)ꢁ ꢁ ꢁN(1)
Sn(2)–C(7)
Sn(2)–C(8)
Sn(2)–C(9)
Sn(2)–S(2)
Bond lengths (A)
Sn(1)–C(10)
Sn(1)–C(16)
Sn(1)–C(4)
Sn(1)–S(1)
2.129(7)
2.132(6)
2.144(7)
2.4462(16)
2.950(4)
2.117(6)
2.117(7)
2.137(7)
2.4632(15)
2.929(4)
Sn(3)–C(14)
Sn(3)–C(13)
Sn(3)–C(15)
Sn(3)–S(3)
Sn(3)ꢁ ꢁ ꢁN(7)
Sn(4)–C(16)
Sn(4)–C(17)
Sn(4)–C(18)
Sn(4)–S(2)
2.109(7)
2.112(7)
2.123(6)
2.4501(16)
2.953(4)
2.114(8)
2.123(8)
2.162(7)
2.4727(15)
2.853(4)
2.108(14)
2.120(14)
2.153(13)
2.453(4)
Sn(3)–C(49)
Sn(3)–C(55)
Sn(3)–C(43)
Sn(3)–S(3)
2.091(12)
2.118(13)
2.164(112)
2.452(3)
Sn(1)ꢁ ꢁ ꢁN(1)
2.850(10)
1.324(14)
1.789(13)
2.109(13)
2.116(14)
2.120(14)
2.433(3)
2.915(10)
1.339(13)
1.754(12)
Sn(3)ꢁ ꢁ ꢁN(5)
N(5)–C(40)
S(3)–C(40)
Sn(4)–C(73)
Sn(4)–C(67)
Sn(4)–C(61)
Sn(4)–S(2)
Sn(4)ꢁ ꢁ ꢁN(2)
N(6)–C(41)
S(4)–C(41)
2.943(10)
1.321(13)
1.770(12)
2.103(14)
2.103(14)
2.124(13)
2.442(3)
2.898(9)
1.356(13)
1.715(12)
N(1)–C(1)
S(1)–C(1)
Sn(2)–C(34)
Sn(2)–C(28)
Sn(2)–C(22)
Sn(2)–S(2)
Sn(2)ꢁ ꢁ ꢁN(2)
Sn(4)ꢁ ꢁ ꢁN(2)
Bond angles (°)
C(6)–Sn(1)–C(5)
C(6)–Sn(1)–C(4)
C(5)–Sn(1)–C(4)
C(6)–Sn(1)–S(1)
C(5)–Sn(1)–S(1)
C(4)–Sn(1)–S(1)
C(6)–Sn(1)–N(1)
C(5)–Sn(1)–N(1)
C(4)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
C(7)–Sn(2)–C(8)
C(7)–Sn(2)–C(9)
C(8)–Sn(2)–C(9)
C(7)–Sn(2)–S(2)
C(8)–Sn(2)–S(2)
C(9)–Sn(2)–S(2)
C(7)–Sn(2)–N(2)
C(8)–Sn(2)–N(2)
C(9)–Sn(2)–N(2)
S(2)–Sn(2)–N(2)
Sn(2)ꢁ ꢁ ꢁN(2)
116.2(3)
C(14)–Sn(3)–C(13)
C(14)–Sn(3)–C(15)
C(13)–Sn(3)–C(15)
C(14)–Sn(3)–S(3)
C(13)–Sn(3)–S(3)
C(15)–Sn(3)–S(3)
C(14)–Sn(3)–N(7)
C(13)–Sn(3)–N(7)
C(15)–Sn(3)–N(7)
S(3)–Sn(3)–N(7)
C(16)–Sn(4)–C(17)
C(16)–Sn(4)–C(18)
C(17)–Sn(4)–C(18)
C(16)–Sn(4)–S(4)
C(17)–Sn(4)–S(4)
C(18)–Sn(4)–S(4)
C(16)–Sn(4)–N(5)
C(17)–Sn(4)–N(5)
C(18)–Sn(4)–N(5)
S(2)–Sn(2)–N(2)
117.7(3)
N(2)–C(2)
111.2(3)
110.5(3)
112.7(2)
104.81(15)
98.0(2)
110.6(3)
109.3(3)
109.6(2)
109.6(2)
98.3(2)
S(2)–C(2)
Bond angles (°)
C(10)–Sn(1)–C(16)
C(10)–Sn(1)–C(4)
C(16)–Sn(1)–C(4)
C(10)–Sn(1)–S(1)
C(16)–Sn(1)–S(1)
C(4)–Sn(1)–S(1)
C(10)–Sn(1)–N(1)
C(16)–Sn(1)–N(1)
C(4)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
C(34)–Sn(2)–C(28)
C(34)–Sn(2)–C(22)
C(28)–Sn(2)–C(22)
C(34)–Sn(2)–S(2)
C(28)–Sn(2)–S(2)
C(22)–Sn(2)–S(2)
C(34)–Sn(2)–N(2)
C(28)–Sn(2)–N(2)
C(22)–Sn(2)–N(2)
S(2)–Sn(2)–N(2)
106.2(5)
C(49)–Sn(3)–C(55)
C(49)–Sn(3)–C(43)
C(55)–Sn(3)–C(43)
C(49)–Sn(3)–S(3)
C(55)–Sn(3)–S(3)
C(43)–Sn(3)–S(3)
C(49)–Sn(3)–N(5)
C(55)–Sn(3)–N(5)
C(43)–Sn(3)–N(5)
S(3)–Sn(3)–N(5)
C(73)–Sn(4)–C67)
C(73)–Sn(4)–C(61)
C(67)–Sn(4)–C(61)
C(73)–Sn(4)–S(4)
C(67)–Sn(4)–S(4)
C(61)–Sn(4)–S(4)
C(34)–Sn(4)–N(6)
C(28)–Sn(4)–N(6)
C(22)–Sn(4)–N(6)
S(4)–Sn(4)–N(6)
112.4(5)
108.4(5)
113.6(5)
115.1(4)
96.2(4)
116.7(4)
84.6(4)
154.1(4)
83.9(4)
58.1(2)
112.8(5)
108.4(5)
107.2(6)
113.9(3)
116.7(4)
96.0(4)
86.0(4)
85.6(5)
154.0(4)
58.0(2)
112.9(4)
108.4(5)
110.6(3)
116.2(4)
95.2(3)
84.7(3)
76.9(2)
79.7(2)
82.6(2)
154.8(2)
57.74(9)
114.5(3)
111.5(3)
111.3(3)
108.3(2)
110.3(2)
100.0(2)
78.3(2)
156.0(2)
57.74(8)
114.6(3)
111.4(4)
111.4(4)
114.0(2)
107.8(2)
96.2(2)
79.9(2)
82.1(2)
154.3(2)
58.32(9)
85.8(4)
81.0(4)
152.0(4)
57.76(19)
120.2(5)
107.2(5)
109.4(5)
109.8(4)
111.2(3)
96.3(3)
82.8(4)
83.7(4)
154.5(4)
58.3(2)
80.2(2)
157.8(2)
57.82(8)
coordination bonds. All above information suggests that
the primary bonds of the 6-amino-1,3,5-triazine-2,4-dithiol
to tin atoms are through sulfur atoms via its thiolate form.
The same coordination mode occurs in complex 4.
ognized, which associates the discrete molecule into a
dimer. Those hydrogen bonds play an important role in
the stabilization of the polymers.
Besides, for complex 1, the co-crystallized solvent etha-
nol molecule is found with the molar ratio of [(Me3Sn)2
(C3H2N4S2)]:EtOH is 2:1.
The C–S bond distances of complexes 1 and 4 (1.745(5)
˚
˚
and 1.757(12) A) are close to C–S single bond (1.730 A) in
triphenyltin derivatives with thiolate ligands [16], Which
indicates C–S existing as single bond and further proves
indirectly the 6-amino-1,3,5-triazine-2,4-dithiol bonding
to tin atoms via thiolate form, which keeps accordance
with the result from the IR spectral data.
Including the tin–nitrogen interactions, the geometry at
tin atoms in both complexes 1 and 4 become distorted cis-
trigonal bipyramid with the axial-tin-axial angles N(1)–
Sn(1)–C(4) of 154.8(2)° for complex 1 and N(1)–Sn(1)–
C(16) of 154.1(4)° for complex 4.
3.4.2. [(Me2SnCl)2(C3H2N4S2)] Æ 0.5C8H24Cl4O2Sn4 (5)
and [Ph2SnCl]2(C3H2N4S2)] (8)
Selected bond lengths and bond angles for complex 5
and 8 is given in Tables 5 and 6 and their molecular struc-
tures are shown in Figs. 5–8.
In contrast with the triorganotin derivatives mentioned
above, diorganotin dichlorides have two chlorine atoms
that can be substituted. Together with the particular stereo-
chemistry of the 6-amino-1,3,5-triazine-2,4-dithiol, their
reaction may form special cyclic or polymeric complexes
such as reported in our previous work [18]. However, when
large stereo-constraint functions, the situation may change
and this is the case of complexes 5 and 8, which are dinu-
clear complexes as shown in Figs. 5–8.
There exist two kinds of hydrogen bonds in the crystal
of complex 1. One strong H-bond is N–Hꢁ ꢁ ꢁN, N(4)–
˚
˚
Hꢁ ꢁ ꢁN(3A) 2.984 A and N(8A)–Hꢁ ꢁ ꢁN(4) 3.245 A. And
the other weak H-bond is N–Hꢁ ꢁ ꢁS, N(4)–Hꢁ ꢁ ꢁS(4A)
˚
3.573 A. Those two kinds of hydrogen bonds help the con-
struction of 1D polymer for complex 1. For complex 4 only
strong intermolecular hydrogen bonding N(4A)–
Hꢁ ꢁ ꢁN(7A) 2.964 A and N(3A)–Hꢁ ꢁ ꢁN(8A) 3.088 A is rec-
˚
˚

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
1613
˚
Table 5
Selected bond lengths (A) and bond angles (°) for complex 5
and Sn(2)–S(2) 2.453(2) A) for complex 8 approach the
˚
˚
covalent radii of Sn and S (2.42 A) [19]. Concerning the
Molecule A
Molecule B
Sn–N bonds lengths, though there are small differences
between them, they are both midway between the sums
of the covalent radii and van der Waals radii of tin and
˚
Bond lengths (A)
Sn(1)–C(4)
Sn(1)–C(5)
Sn(1)–Cl(1)
Sn(1)–S(1)
Sn(1)–N(1)
Sn(2)–C(7)
Sn(2)–C(6)
Sn(2)–Cl(2)
Sn(2)–S(2)
2.103(7)
2.112(6)
2.4375(18)
2.4695(18)
2.555(5)
2.100(7)
2.111(8)
2.4472(19)
2.4942(18)
2.418(4)
Sn(3)–C(11)
Sn(3)–C(12)
Sn(3)–Cl(3)
Sn(3)–S(3)
Sn(3)–N(5)
Sn(4)–C(14)
Sn(4)–C(13)
Sn(4)–Cl(4)
Sn(4)–S(4)
Sn(4)–N(6)
2.103(7)
2.111(7)
2.4267(18)
2.4739(17)
2.588(5)
2.091(7)
2.097(7)
2.4417(19)
2.4836(19)
2.428(4)
˚
nitrogen (2.15–3.74 A) [19]. As the case for complexes 1
and 4, the primary bonds of the 6-amino-1,3,5-triazine-
2,4-dithiol to the tin atoms in complexes 5 and 8 are
through sulfur atoms and the 6-amino-1,3,5-triazine-2,4-
dithiol appears mainly as thiolate form when reacting with
dialkyltin dichloride. There also two Sn–Cl bonds (Sn(1)–
˚
˚
Cl(1) 2.4375(18) A and Sn(1)–Cl(1) 2.4472(19) A) in com-
Sn(2)–N(2)
˚
plex 5 and two (Sn(1)–Cl(1) 2.410(2) A and Sn(1)–Cl(1)
2.4065(19) A) in complex 8, which are typical Sn–Cl bond
lengths (2.32–2.58 A) found in chloroorganotin (IV) com-
Bond angles (°)
C(4)–Sn(1)–C(5)
C(4)–Sn(1)–Cl(1)
C(5)–Sn(1)–Cl(1)
C(4)–Sn(1)–S(1)
C(5)–Sn(1)–S(1)
Cl(1)–Sn(1)–S(1)
C(4)–Sn(1)–N(1)
C(5)–Sn(1)–N(1)
Cl(1)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
C(7)–Sn(2)–C(6)
C(7)–Sn(2)–Cl(2)
C(6)–Sn(2)–Cl(2)
C(7)–Sn(2)–S(2)
C(6)–Sn(2)–S(2)
Cl(2)–Sn(2)–S(2)
C(7)–Sn(2)–N(2)
C(6)–Sn(2)–N(2)
Cl(3)–Sn(2)–N(2)
S(2)–Sn(2)–N(2)
˚
131.7(3)
C(11)–Sn(3)–C(12)
C(11)–Sn(3)–Cl(3)
C(12)–Sn(3)–Cl(3)
C(11)–Sn(3)–S(3)
C(12)–Sn(3)–S(3)
Cl(3)–Sn(3)–S(3)
C(11)–Sn(3)–N(5)
C(12)–Sn(3)–N(5)
Cl(3)–Sn(3)–N(5)
S(3)–Sn(3)–N(5)
C(14)–Sn(4)–C(13)
C(14)–Sn(4)–Cl(4)
C(13)–Sn(4)–Cl(4)
C(14)–Sn(4)–S(4)
C(13)–Sn(4)–S(4)
Cl(2)–Sn(2)–S(2)
C(14)–Sn(4)–N(6)
C(13)–Sn(4)–N(6)
Cl(4)–Sn(4)–N(6)
S(4)–Sn(4)–N(6)
131.9(3)
˚
102.6(2)
101.4(2)
110.3(2)
111.0(2)
89.96(6)
88.9(3)
102.2(2)
101.8(2)
109.1(2)
111.7(2)
90.66(6)
88.7(2)
plexes in general [20]. Thus, the geometry at tin atoms of
complex 5 and 8 become distorted trigonal bipyramidals
with C(4)–C(5)–S(1) and C(4), C(10), S(1) atoms occupying
the equatorial planes and the axial angles, Cl(1)–Sn(1)–
N(1) is 152.42(11)° and Cl(1)–Sn(1)–N(1) is 153.08(12)°,
respectively.
88.6(2)
88.3(2)
152.42(11)
62.47(11)
132.0(4)
99.7(2)
100.5(2)
108.0(2)
114.3(2)
91.95(7)
89.6(2)
152.90(11)
62.27(10)
131.7(3)
99.8(2)
100.1(2)
111.0(2)
111.5(2)
91.95(7)
89.6(2)
The X-ray diffraction investigation of complex 8 has
shown that the asymmetric unit also contains two mono-
mers A and B as complexes 1 and 4, which are different
from a crystallographic point of view, and the molecules
A and B of complex 8 are associate in polymeric chains
through intermolecular, dative N ! Sn bonds. In addition,
there exist intramolecular Sn–N interactions. The distance
of two Sn–N bonds are midway between the sums of the
van der Waals radii and covalent radii of tin and nitrogen
89.8(2)
124.37(12)
63.32(12)
89.7(2)
155.83(12)
63.69(11)
˚
(2.15–3.74 A) [18] and can be regarded as weak coordina-
tion bonds.
Two kinds of hydrogen bonds are recognized in complex
5. One strong H-bond is N–Hꢁ ꢁ ꢁN, N(7B)–Hꢁ ꢁ ꢁN(4C)
Table 6
˚
Selected bond lengths (A) and bond angles (°) for complex 8
˚
Bond lengths (A)
˚
˚
3.012 A and N(8B)–Hꢁ ꢁ ꢁN(3C) 3.007 A. And the other
˚
weak H-bond is N–Hꢁ ꢁ ꢁCl, N(4)–Hꢁ ꢁ ꢁCl(2A) 3.381 A.
Sn(1)–C(4)
Sn(1)–C(10)
Sn(1)–Cl(1)
Sn(1)–S(1)
Sn(1)–N(1)
S(1)–C(1)
2.112(7)
2.125(8)
2.410(2)
2.470(2)
2.544(5)
1.745(7)
1.359(8)
Sn(2)–C(22)
Sn(2)–C(16)
Sn(2)–Cl(2)
Sn(2)–S(2)
Sn(2)–N(2)
S(2)–C(2)
2.135(7)
2.157(8)
2.4065(19)
2.453(2)
2.641(5)
1.739(7)
1.340(9)
Besides, there exist Snꢁ ꢁ ꢁCl weak interactions,
˚
Sn(4)ꢁ ꢁ ꢁCl(1) 3.637 (2) A. Those interactions help the con-
struction of a 2D network for complex 5. For complex 8,
there exist intermolecular hydrogen bonding and Sꢁ ꢁ ꢁCl
non-bonded weak interactions [12]. The former is N(4A)–
N(1)–C(1)
N(1)–C(1)
˚
Hꢁ ꢁ ꢁN(3) 3.090 A and N(4)–Hꢁ ꢁ ꢁN(3A) 3.090, the later is
Bond angles (°)
C(4)–Sn(1)–C(10)
C(4)–Sn(1)–Cl(1)
C(10)–Sn(1)–Cl(1)
C(4)–Sn(1)–S(1)
C(10)–Sn(1)–S(1)
Cl(1)–Sn(1)–S(1)
C(4)–Sn(1)–N(1)
C(10)–Sn(1)–N(1)
Cl(1)–Sn(1)–N(1)
S(1)–Sn(1)–N(1)
˚
Sꢁ ꢁ ꢁCl 3.545 A. As far as bond lengths, bond angles, inter-
121.6(3)
102.4(2)
99.1(2)
117.7(2)
115.5(2)
90.94(8)
93.5(2)
90.6(2)
153.08(12)
62.31(11)
C(22)–Sn(2)–C(16)
C(22)–Sn(2)–Cl(2)
C(16)–Sn(2)–Cl(2)
C(22)–Sn(2)–S(2)
C(16)–Sn(2)–S(2)
Cl(2)–Sn(2)–S(2)
C(22)–Sn(2)–N(2)
C(16)–Sn(2)–N(2)
Cl(2)–Sn(2)–N(2)
S(2)–Sn(2)–N(2)
129.0(3)
99.9(2)
97.8(2)
113.4(2)
113.8(2)
90.98(7)
93.9(3)
91.3(2)
153.02(13)
62.19(13)
molecular hydrogen bonding and Clꢁ ꢁ ꢁS non-bonded inter-
action are concerned, the supramolecular structure of
complex 8 is constructed as a 1D polymer.
4. Supplementary material
Crystallographic data (excluding structure factors) for
the structure analysis of complexes 1, 4, 5 and 8 have been
deposited with the Cambridge Crystallographic Data Cen-
ter, CCDC Nos. 262019, 262018, 262017 and 262020. Cop-
ies of these information can be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44 1223 336033; e-mail: depos-
it@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
For complexes 5 and 8, two Sn–S and Sn–N bonds are
basically identical, respectively. Both of the Sn–S bond
˚
and Sn(2)–S(2)
lengths (Sn(1)–S(1) 2.4695(18)
A
˚
˚
2.4942(18) A) for complex 5 and (Sn(1)–S(1) 2.470(2) A

1614
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 1606–1614
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Acknowledgements
We thank the National Natural Science Foundation of
China (20271025) and the Natural Science Foundation of
Shandong Province for financial support.
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