Synthesis and spectral characterisation of organotin(IV) 1,3,5-triazine-2,4,6-trithiolato complexes, including the crystal structures of 1,3,5-(R3Sn)3C3N3S3 (R=Me, Ph)

Article abstract of DOI:10.1016/S0022-328X(00)00820-2

Novel organotin(IV) 1,3,5-triazine-2,4,6-trithiolato complexes: (R₃Sn)₃C₃N₃S₃, (R=Ph, Bz, Me, Bu) and (R₂Sn)₃(C₃N₃S₃) ₂, (R=Ph, Me) have been prepared and characterised by elemental analysis, FT-IR, M?ssbauer and multinuclear NMR spectroscopy. The crystal and molecular structures of 1,3,5-(R₃Sn)₃C₃N₃S₃ (R=Me, Ph) have been determined and contain tetrahedral organotin units in a 'manxane' arrangement about the central triazine. There are no close intermolecular interactions.

Full text of DOI:10.1016/S0022-328X(00)00820-2

Journal of Organometallic Chemistry 627 (2001) 6–12
www.elsevier.nl/locate/jorganchem
Synthesis and spectral characterisation of organotin(IV)
1,3,5-triazine-2,4,6-trithiolato complexes, including the crystal
structures of 1,3,5-(R3Sn)3C3N3S3 (R=Me, Ph)
Ionel Haiduc a, Mary F. Mahon b, Kieran C. Molloy b,*, Monica M. Venter a
a Department of Chemistry, Babes-Bolyai Uni6ersity, Cluj-Napoca RO-3400, Romania
b Department of Chemistry, Uni6ersity of Bath, Cla6erton Down, Bath BA2 7AY, UK
Received 11 July 2000; received in revised form 22 September 2000; accepted 22 September 2000
Abstract
Novel organotin(IV) 1,3,5-triazine-2,4,6-trithiolato complexes: (R3Sn)3C3N3S3, (R=Ph, Bz, Me, Bu) and (R2Sn)3(C3N3S3)2,
(R=Ph, Me) have been prepared and characterised by elemental analysis, FT-IR, Mo¨ssbauer and multinuclear NMR
spectroscopy. The crystal and molecular structures of 1,3,5-(R3Sn)3C3N3S3 (R=Me, Ph) have been determined and contain
tetrahedral organotin units in a ‘manxane’ arrangement about the central triazine. There are no close intermolecular interactions.
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Tin; 1,3,5-Triazine-2,4,6-trithiolato; Mo¨ssbauer; ‘Manxane’
1. Introduction
suggestive of the onset of p-bonding between the metal
and the 6e tetrazole ring [8].
While the co-ordination chemistry of heterocyclic
thiol/thione donors has, for many years, been of great
interest both from a biological and pharmaceutical
perspective [1], it is the supramolecular chemistry of
this class of compound which is currently exciting
interest [2]. The self-assembly of metal centers with
heterocyclic thiol/thione ligands containing different
binding sites results in the formation of novel
supramolecules which have intriguing novel structures
and/or magnetic properties. For example, organotin-
substituted tetrazole thiolates are known to adopt
monomer [3,4] trimer [5], polymer [6] and sheet [7]
structures all containing s-Sn–ligand bonds. In addi-
tion, one intriguing example of a lead compound,
Ph3PbSCN4Ph-1, has a polymeric arrangement similar
to that of Bz3SnSCN4Ph-1 [6] though the intermolecu-
lar interaction between lead and the tetrazole–thiol is
In this paper we wish to report of studies of organ-
otin derivatives of 1,3,5-triazine-2,4,6-trithiol (I) (also
referred to as 2,4,6-trimercaptotriazine or trithiocya-
nuric acid). Compound I, which can exist in either thiol
(1a) or thione (1b) forms, is an analytical reagent
currently used to remove heavy metals (Ag+, Hg2+
,
Cd2+, Pd2+, Cu2+) from waste waters [9]. Interest in
the coordination chemistry of the 1,3,5-triazine-2,4,6-
trithiolato anion [C3N3S33−] is more limited and is
mainly confined to derivatives of s- (Li+, Ca2+, Sr2+
,
Ba2+) [9,10] and d-block elements [11–17] where it can
behave as either a chelating [13] or bridging [15–17]
ligand. However, very few structural studies have been
reported, largely due to the lack of solubility of these
compounds [11,12]. Of the available structures, the
cobalt(III) complex [14] [{Co(en)2}2(m-C3N3S3)]-
[ClO4]3·2H2O incorporates only the bis-chelating co-or-
dination pattern (II) of C3N3S33− in the solid state,
while both bis- and tris-chelating (III) forms are present
in solution. No intermolecular interactions are men-
tioned for this complex.
* Corresponding author. Fax: +44-1225-826231.
E-mail address: chskcm@bath.ac.uk (K.C. Molloy).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00820-2

I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
7
More recently, the gold(I) complex [(Ph3P)Au]3-
[C3N3S3] has been prepared [16] and characterised struc-
turally [17] and shown to contain Au–S (rather than
Au–N) bonds in a C3h ‘manxane’ arrangement derived
from I. Gold complexes of this type decompose in
solution to yield [(AuC3N3S3)(AuL)2]2 (L=Me2PhP [16],
tBuNC [17]) which adopt two-dimensional supramolecu-
lar structures via intermolecular Au(I)···Au(I) interac-
tions and in which the C3N3S33− anions involve three
different binding modes (S-, N- and S,S-,). In contrast,
the copper(I) complex [(CuPPh3)3(C3N3S3)]2 provides
the single example of a hexadentate triazine-2,4,6-trithi-
olato ligand with all the available N, S binding sites
involved in co-ordination. The molecule shows a
self-assembled, dimeric, hexanuclear structure which
consists of two parallel triazine rings held in close prox-
Similarly, reaction of same sodium salt with diorgan-
otin(IV) dichlorides (2:3 ratio) in methanol yields the
diorganotin(IV) 1,3,5-triazine-2,4,6-trithiolato com-
plexes (R2Sn)3(C3N3S3)2, [R=Ph (5), Me (6)] as white
powder solids (Eq. (2)). The complexes 5 and 6 are air
stable and insoluble in common organic solvents, ren-
dering them difficult to purify.
(2)
Compounds 1–6 can also be prepared by reaction of
the corresponding organotin oxide and trithiocyanuric
acid; in a typical example, 4 was prepared in 62% from
(Bu3Sn)2O and C3N3S3H3. However, this offers little ad-
vantage over the methodology of Eqns 1, 2 as the free
acid needs to be purchased commercially at far greater
cost than its sodium salt, or prepared from the salt by
reaction with HCl.
(Me3SnS)3C3N3 (3) was heated over its melting point
(118°C) for 30 min after which time it recrystallised un-
changed as a colourless solid. Alternatively, 3 was
stirred in n-decane at ca. 140°C under N2 for 1 h and the
solvent was removed to low volume. In both cases the
product was isolated as a microcrystalline solid whose
IR data are consistent with unchanged starting material.
We have no evidence that these compounds dissociate
into R3SnSCN on heating.
,
imity (3.07 A) by six N–Cu–S bridges.
To our knowledge, no organometallic derivatives of I
have been studied. Organotin compounds suggested
themselves for investigation, both from their potential
for supramolecular assembly and as potential reagents
for the synthesis of other complexes of 1,3,5-triazine-
2,4,6-trithiol, particularly where non-aqueous chemistry
is required. The corresponding organotin derivatives of
cyanuric acid, (R3Sn)3C3N3O3 have, however, been
known since 1965. No structural studies have been
carried out on these species which have been assumed to
contain N-bonded tin [18].
2. Synthesis
3. Spectroscopy
Reaction of the tri-sodium salt of I (C3N3S3-
Na.39H2O) with triorganotin(IV) chlorides (1:3 ratio) in
ether or methanol yields the triorganotin(IV) 1,3,5-tria-
zine-2,4,6-trithiolato complexes (R3Sn)3C3N3S3 as crys-
talline solids [R=Ph (1), Bz (2), Me (3)] or oils [R=Bu
(4)] (Eq. (1)). All the complexes 1–4 are air stable in
their natural state and are soluble in most common or-
ganic solvents with the exception of 1 and 2 which are
insoluble in methanol and n-hexane.
The IR spectra of C3N3S3Na3·9H2O and the corre-
sponding organotin(IV) complexes (1–6) were recorded
in the 4500–500 cm−1 spectral range. The assignments
of w(N2CS) and l(C3N3) (out of plane ring bending by
‘sextants’) modes in the spectrum of C3N3S3Na3·9H2O
at 1216 and 850 cm−1 respectively, are in good agree-
ment with the corresponding vibrational data published
for the neutral ligand [11]. In comparison with the data
(1)

8
I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
1
for C3N3S3Na3·9H2O, the IR spectra of 1–6 reveal a
significant shift of w(N2CS) from 1216 cm−1 to higher
frequencies (1234–1242 cm−1), which we ascribe to the
co-ordination of sulphur to the metal centre.
data is maintained in solution. The J(SnC) couplings
observed in the 13C-NMR spectra of 3, 4 (329–376 Hz)
are also indicative of a tetrahedral geometry at tin
[19,21].
The quadrupole splittings (q.s.) for 1–3 are in the
range 1.84–2.21 mm s−1 which is consistent with a
tetrahedral geometry about tin [7,19]. The q.s. of 6
(2.96 mm s−1) is comparable with the value 2.98 mm
s−1 for Me2Sn(S2CNMe2)Cl which is essentially cis-
trigonal bipyramidal at tin [19] and it is in good agree-
ment with the q.s. calculated for diorganotin(IV)
complexes exhibiting cis-R2SnX3 coordination environ-
ment based upon a point charge model (ca. 3.07 mm
4. The structures of (Ph3SnS)3C3N3 (1) and
(Me3SnS)3C3N3 (3)
The asymmetric unit of 1 is shown in Fig. 1. As
implied by the collective spectroscopic data tin is
bonded to the thiocyanuric acid via sulphur (i.e. the
thiol form of the ligand) and the geometry about tin is
tetrahedral. The structure is similar to that of
(Ph3PAu)3C3N3S3 [17] which has been described as
s
−1) [20]. In the case of 5 the q.s. (2.68 mm s−1) is
intermediate between those corresponding to tetrahe-
dral and trigonal bipyramidal geometries, thus suggest-
ing a weak contribution by the ring nitrogen to the
metal coordination. Considering the low solubility of 5,
6 it would appear that this latter interaction is inter-
molecular in nature and that the two species are poly-
meric materials.
incorporating
a
‘manxane’
core,
and
[Os3H(CO)10]3C3N3S3 [13]. The Sn–S bonds are similar,
,
though Sn(1)–S(1) [2.435(3) A] is marginally shorter
than distances involving the other two metal centres
,
[2.457(3), 2.453(3) A] and are short with respect to
Sn–S bonds in a range of organotin tetrazole-thioates
1
The H- and 13C-NMR data show no unusual fea-
[2.477(4)–2.607(2) A]. The Sn–S bond in Ph3SnSPh
,
,
tures, suggesting in all cases the equivalence of the
R3Sn groups as well as the ring carbon atoms. The
resonance at ca. l 180 ppm due to C–S in the 13C
spectra confirms the presence of the triazine ring. The
119Sn-NMR data of 1, 3, and 4 indicate that the co-or-
dination number of four suggested by the Mo¨ssbauer
[2.421(1) A] [22] is, however, directly comparable. There
is no discrimination in the lengths of the C–S bonds
,
[1.726(9)–1.744(8) A], while the C–N bonds are consis-
,
tent with a delocalised system [1.325(11)–1.352(11) A].
The bond angles at each tin show a consistent trend
and in each case a wide range of angles is observed
Fig. 1. The asymmetric unit of 1 showing the labelling scheme used in the text and tables. Thermal ellipsoids are at the 30% probability level.

I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
9
Fig. 2. The asymmetric unit of 3 showing the labelling scheme used in the text and tables. Thermal ellipsoids are at the 30% probability level.
[Sn(1): 95.8(2)–123.4(3); Sn(2): 97.3(3)–117.4(4); Sn(3):
96.6(3)–117.6(3)°]. In Ph3SnSPh the bond angles at tin
are more regular [106.4(1)–112.1(1)°] [22] suggesting
that asymmetry in the angles about tin in 1 is largely a
result of crowding of three bulky Ph3Sn groups around
the periphery of the heterocycle.
For all compounds, infrared spectra were recorded as
nujol mulls on KBr plates and all NMR data were
recorded on saturated solutions in CDCl3 at room
temperature (r.t.); chemical shifts are in ppm relative to
either Me4Si (1H, 13C) or Me4Sn (119Sn), coupling con-
stants are in Hz.
The structure of 3 (Fig. 2) is very similar to that of 1.
The three Sn–S bonds are marginally longer [2.4611(9),
Tribenzyltin chloride was prepared by a literature
method [24]. Other organotin reagents and trithiocya-
nuric acid trisodium salt were purchased from Aldrich
and used without further purification.
,
2.4708(8), 2.4735(9)A] while the angles about each tin
are somewhat less distorted [Sn(1): 97.7(1)–114.7(2);
Sn(2): 96.9(1)–115.4(2); Sn(3): 98.02–115.9(2)°], pre-
sumably due to decreased steric congestion.
5.1. Synthesis of 1,3,5-(Ph3Sn)3C3N3S3 (1)
In both structures, however, the three tins lie essen-
tially in the plane of the C3N3 ring and the BC–S–Sn
is reduced to ca. 96–99°. This has the effect of bringing
each tin into the proximity of a ring nitrogen (ca.
A mixture of excess C3N3S3Na3.9H2O (0.20 g, 0.5
mmol) and Ph3SnCl (0.46 g, 1.2 mmol) in methanol (40
ml) was stirred under N2 at r.t. for 2 h. The resultant
white precipitate was washed with methanol and the
product was extracted with ether and recrystallised
from ether/hexane to yield 1 as a white microcrystalline
solid (0.28 g. 58%). m.p. 177°C. Analysis: Found (Calc.
for C57H45N3S3Sn3): C 55.7(55.9), H 3.71(3.71), N
3.41(3.43)%. IR (cm−1): 2924 vs, 2725 w, 1460 vs, 1377
vs, 1234 s,1156 w, 1073 w, 1020 w, 996 w, 847 m, 788
w, 724 vs, 694 s. Mo¨ssbauer (mm s−1): i.s. 1.30, q.s.
,
2.9–3.1 A), which can be considered as reflecting the
onset of very weak chelation. It should be noted,
however, that the approach of nitrogen is only loosely
trans to a Sn–C bond (BN–Sn–C: ca. 155°) and in
more strongly chelating analogues the angle at sulphur
is reduced to ca. 78° [14].
1
5. Experimental
2.21. H-NMR: 7.37 m (27H, m- and p-C6H5), 7.67 dd
3
4
3
(18H, o-C6H5); J=6.5, J=3.0; J(SnH)=55.9 (unre-
solved). 13C-NMR: 128.7 (Cp), 129.6 (Cm), 136.8 (Co),
138.8 (Ci), 179.7 (C–S); 2J(SnC)=45.1 (unresolved).
119Sn-NMR: −100.5.
Spectra were recorded on the following instruments:
JEOL GX270 (1H-, 13C-NMR), GX400 (119Sn-NMR),
Perkin–Elmer 599B (IR). Details of our Mo¨ssbauer
spectrometer and related procedures are given else-
where [23]. Isomer shift data are relative to CaSnO3.
Also prepared by the same method were the
following.

10
I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
5.2. 1,3,5-(Bz3Sn)3C3N3S3 (2)
(nujol, cm−1): 1576 m, 1537 s, 1258 m, 1125 s, 848 w,
785 w, 741 m.
Ether as solvent, reaction time 4 h. Yield 57%, m.p.
96°C. Analysis: Found (Calc. for C66H63N3S3Sn3): C
58.7(58.7), H 4.70(4.77), N 3.24(3.11)%. IR (cm−1): 2928
vs, 1596 ms, 1490 vs, 1456 vs, 1377 vs, 1237 vs, 1206 s,
1180 w, 1094 w, 1048 w, 1028 w, 902 w, 847 s, 797 w,
788 w, 755 vs, 723 s, 696 vs. Mo¨ssbauer (mm s−1): i.s.
A mixture of excess C3N3S3H3 (0.40 g, 2.3 mmol) and
(Bu3Sn)2O (1.80 g, 3 mmol) in benzene (50 ml) was
refluxed for 2 h and the water was removed azeotropi-
cally using a Dean and Stark apparatus. The solvent was
removed in vacuo to yield the product as colourless oil
(1.30 g, 62%). The product was identified as 4 by spectral
comparison.
1
1.45, q.s. 1.86. H-NMR: 2.59 s (18H, SnCH2), 6.77 d
3
3
(18H, o-C6H5; J=7.3); 6.97 t (9H, p-C6H5; J=7.3);
3
2
7.10 dd (18H, m-C6H5; J=7.3, 7.3), J(SnH)=65.6
5.6. Synthesis of 1,3,5-(Ph2Sn)3(C3N3S3)2 (5)
(unresolved). 13C-NMR: 24.2 (SnCH2), 124.3 (Cp), 127.9
2
(Cm), 128.6 (Co), 139.9 (Ci), 180.1 (C–S); J(SnC)=
A mixture of C3N3S3Na3·9H2O (0.30 g, 0.74 mmol,
20% excess) and Ph2SnCl2 (0.31 g, 0.9 mmol) in methanol
(30 ml) was stirred under N2 at r.t. for 2 h. After removing
the solvent, the resultant white precipitate was washed
with methanol and water. Yield 0.16 g, 70%. 5 is insoluble
in common organic solvents. Analysis: Found (Calc. for
280.9 (unresolved). 119Sn-NMR: −7.7.
5.3. 1,3,5-(Me3Sn)3C3N3S3 (3)
Reaction time 24 h, crude product washed with water
before recrystallisation from methanol to give the
product as colourless crystalline solid. Yield 53%, m.p.
118°C. Analysis: Found (Calc. for C12H27N3S3Sn3): C
21.7(21.7), H 4.08(4.09), N 6.26(6.31). IR (cm−1): 2928
vs, 1460 vs, 1377 vs, 1242 vs, 1188 w, 972 w, 892 w, 849
s, 771 s, 722 s. Mo¨ssbauer (mm s−1): i.s. 1.28, q.s. 1.84.
C42H30N6S6Sn3):
C
40.7(43.2),
H
2.65(2.59),
N
5.93(7.20). IR (cm−1): 2922 vs, 2725 w, 1577 w, 1456 vs,
1377 vs, 1303 w, 1237 vs (w N2CS), 1157 w, 1073 w, 1022
w, 996 w, 966 w, 856 s, 783 w, 722 s, 690 ms. Mo¨ssbauer
(mm s−1): i.s. 1.27, q.s. 2.68.
Also prepared by the same method was the following.
2
1H-NMR: 0.57 s (27 H, SnCH3); J(SnH)=57.3 (unre-
5.7. 1,3,5-(Me2Sn)3(C3N3S3)2 (6)
solved). 13C-NMR: −3.13 (SnCH3), 180.0 (C–S);
1J(SnC)=359, 377. 119Sn-NMR: 74.4.
Reaction time 2 h, yield 62%. 6 is insoluble in common
organic solvents. Analysis: Found (Calc. for
5.4. 1,3,5-(Bu3Sn)3C3N3S3 (4)
C12H18N6S6Sn3):
C
17.6(18.1),
H
2.28(2.28),
N
9.88(10.57)%. IR (cm−1): 2924 vs, 2725 w, 1460 vs, 1377
vs, 1307 w, 1275 w, 1240 vs, 1192 w, 972 w, 861 s, 783
s, 722 s. Mo¨ssbauer (mm s−1): i.s. 1.38, q.s. 2.96.
Reaction time 24 h. After filtration and solvent evap-
oration the product was obtained as an analytically pure
oil in quantitative yield. Analysis: Found (Calc. for
C39H81N3S3Sn3):
C
45.0(44.9),
H
7.83(7.82),
N
4.04(4.02)%. IR (cm−1): 2923 vs, 2729 w, 1492 m, 1456
vs, 1377 s, 1340 w, 1319 w, 1292 w, 1238 vs (w N2CS),
1181 w, 1152 w, 1074 mw,1045 w, 1022 w, 961 w, 876
m, 846 vs, 790 mw, 770 w, 674 w. Mo¨ssbauer (mm s−1):
i.s. 1.37, q.s. 2.27. 1H-NMR: 0.90 t [27 H, Sn(CH2)3CH3],
1.29 m [18 H, SnCH2CH2CH2CH3], 1.35 m [18 H,
6. Crystallography
Suitable crystals of 1 and 3 for X-ray diffraction
analysis were each obtained from ether/hexane by solvent
diffusion over a period of one week. Crystal and exper-
imental details are given in Table 1. Software used:
SHELX86 [25], SHELX97 [26], ORTEX [27]. The asymmetric
units of 1 and 3 are shown in Figs. 1 and 2, respectively;
significant metrical data are given in Tables 2 and 3.
SnCH2CH2CH2CH3],
1.60
m
[18
H,
SnCH2CH2CH2CH3]. 13C-NMR: 13.6 [Sn(CH2)3CH3],
15.8 [SnCH2(CH2)2CH3], 27.1 [Sn(CH2)2CH2CH3], 28.8
1
[SnCH2CH2CH2CH3], 180.4 [C–S]; J(SnC)=329, 345;
3J(SnC)=64 (unresolved). 119Sn-NMR: 68.3.
7. Supplementary material
5.5. 1,3,5-(Bu3Sn)3C3N3S3 (4): alternati6e strategy
Crystallographic data for the structure analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 146550 and 146551 for com-
pounds 1 and 3, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax:
+44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
Thiocyanuric acid (C3N3S3H3) was prepared by the
reaction of C3N3S3Na3.9H2O (8.10 g, 20 mmol) in
aqueous solution with the stoichiometric amount of a
concentrated HCl (5.02 ml, 1.18 g cm−3). The resultant
yellow precipitate was washed with water and dried at
room temperature (3.10 g, 88%). Analysis: Found (Calc.
for C3N3S3H3): C 20.3(20.3), H 1.7(1.7), N 23.3(23.7). IR

I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
11
Table 1
Table 3
,
Crystal and experimental data
Selected bond lengths (A) and bond angles (°) for 3
1
3
Bond lengths
Sn(1)–C(5)
Sn(1)–C(4)
Sn(1)–C(6)
Sn(1)–S(1)
Sn(2)–C(9)
Sn(2)–C(7)
Sn(2)–C(8)
Sn(2)–S(2)
2.128(3)
2.131(4)
2.135(3)
2.4708(8)
2.122(3)
2.129(3)
2.143(3)
2.4611(9)
Sn(3)–C(10)
Sn(3)–C(11)
Sn(3)–C(12)
Sn(3)–S(3)
S(1)–C(1)
2.124(3)
2.134(4)
2.140(5)
2.4735(9)
1.742(3)
1.743(3)
1.743(3)
Empirical formula
Crystal size
C
57H45N3S3Sn3 C12H27N3S3Sn3
0.2×0.25×0.28 0.25×0.17
×0.05
S(2)–C(2)
S(3)–C(3)
Temperature (K)
Diffractometer a
293(2)
170(2)
Kappa CCD
0.71070
Monoclinic
P21/a
CAD-4
0.71069
Monoclinic
Cc
,
Wavelength (A)
Crystal system
Space group
Bond angles
C(5)–Sn(1)–C(4) 114.7(2)
C(5)–Sn(1)–C(6) 113.1(1)
C(4)–Sn(1)–C(6) 112.9(2)
C(5)–Sn(1)–S(1) 105.5(1)
C(4)–Sn(1)–S(1) 111.5(1)
C(7)–Sn(2)–S(2)
C(8)–Sn(2)–S(2)
C(10)–Sn(3)–C(11)
C(10)–Sn(3)–C(12)
C(11)–Sn(3)–C(12)
C(10)–Sn(3)–S(3)
C(12)ꢀSn(3)ꢀS(3)
C(11)–Sn(3)–S(3)
C(1)–S(1)–Sn(1)
C(2)–S(2)–Sn(2)
C(3)–S(3)–Sn(3)
107.8(1)
96.9(1)
115.9(2)
107.7(2)
113.6(2)
115.0(1)
98.0(2)
105.3(1)
99.3(1)
97.7(1)
96.2(1)
Unit cell dimensions
,
a (A)
19.019(2)
28.301(3)
10.553(2)
108.62(1)
4
12.742(1)
9.971(1)
18.617(1)
96.70(1)
4
,
b (A)
,
c (A)
i (°)
C(6)–Sn(1)–S(1)
97.7(1)
Z
Absorption coefficient (mm−1
)
1.536
3.429
C(9)–Sn(2)–C(7) 115.4(2)
C(9)–Sn(2)–C(8) 112.2(2)
C(7)–Sn(2)–C(8) 112.7(2)
C(9)–Sn(2)–S(2) 110.1(1)
Crystal size (mm)
0.2×0.25×0.28 0.25×0.17
×0.05
3.52–30.08
32566
Theta range (°)
Reflections collected
Independent reflections
2.11–25.02
4889
4889
6862
Acknowledgements
(Rint=0.0000) (Rint=0.0568)
Absorption correction
None
Multiscan
Max./min. transmission
Data/restraints/parameters
Final R indices [I\2|(I)]
1.118 and 0.869
6862/0/200
R1=0.0299,
wR2=0.0737
R1=0.0443,
wR2=0.0823
0.678 and
We wish to thank NATO for financial support in the
form of a collaborative research grant (no. 970107) to
K.C.M. and I.H.
4889/2/595
R1=0.0371,
wR2=0.0883
R1=0.0506,
wR2=0.0932
0.667 and
R indices (all data)
Largest difference peak and
References
−3
,
hole (e A
)
−0.764
−1.082
[1] E.S. Rasper, Coord. Chem. Rev. 61 (1985) 115.
[2] C.J. Jones, Chem. Soc. Rev. 27 (1998) 289.
a Enraf–Nonius.
[3] R.J. Deeth, K.C. Molloy, M.F. Mahon, S. Whitaker, J.
Organomet. Chem. 430 (1992) 25.
[4] J. Bravo, M.B. Cordero, J.S. Casas, A. Sanchez, J. Sordo, E.E.
Castellano, J. Zukerman-Schpector, J. Organomet. Chem. 482
(1994) 147.
Table 2
,
Selected bond lengths (A) and bond angles (°) for 1
[5] R. Cea-Olivares, O. Jimenez-Sandoval, G. Espinosa-Perez, C.
Silvestru, J. Organomet. Chem. 484 (1994) 33.
[6] R. Cea-Olivares, O. Jiminez-Sandoval, G. Espinosa-Perez, C.
Silvestru, Polyhedron 13 (1994) 2809.
[7] S. Bhandari, M.F. Mahon, J.G. McGinley, K.C. Molloy, C.E.
Roper, J. Chem. Soc. Dalton Transactions (1998) 3425.
[8] M. Barret, S. Bhandari, M.F. Mahon, K.C. Molloy, J.
Organomet. Chem. 587 (1999) 101.
[9] K. Henke, D.A. Atwood, Inorg. Chem. 37 (1998) 224.
[10] W. Clegg, J.E. Davies, M.R.J. Elsegood, E. Lamb, J.J. Lon-
gridge, J.M. Rawson, R. Snaith, A.E.H. Wheatley, Inorg. Chem.
Commun. 1 (1998) 58.
Bond lengths
Sn(1)–C(10)
Sn(1)–C(4)
Sn(1)–C(16)
Sn(1)–S(1)
Sn(2)–C(28)
Sn(2)–C(34)
Sn(2)–C(22)
Sn(2)–S(3)
2.136(10)
2.137(10)
2.152(8)
2.435(3)
2.127(10)
2.139(9)
2.140(9)
2.457(3)
Sn(3)–C(52)
Sn(3)–C(46)
Sn(3)–C(40)
Sn(3)–S(2)
S(1)–C(1)
2.108(12)
2.114(10)
2.142(9)
2.453(3)
1.730(9)
1.726(9)
1.744(8)
S(2)–C(2)
S(3)–C(3)
Bond angles
C(10)–Sn(1)–C(16) 107.7(3)
C(22)–Sn(2)–S(3)
115.6(2)
[11] J.C. Chudy, A.W. Dalziel, J. Inorg. Nucl. Chem. 37 (1975) 2459.
[12] D.R. Cobin, L.C. Francesconi, D.N. Hendrickson, G.D. Stucky,
Inorg. Chem. 18 (1979) 3069.
[13] E.W. Ainscough, A.M. Brodie, R.K. Coll, A.J.A. Mair, J.M.
Waters, Inorg. Chim. Acta 214 (1993) 21.
[14] K. Yamanari, Y. Kushi, M. Yamamoto, A. Fuyuhiro, S.
Kaizaki, T. Kawamoto, Y. Kushi, J. Chem. Soc. Dalton Trans.
(1993) 3715.
[15] C.-K. Chan, K.-K. Cheung, C.-M. Che, J. Chem. Soc. Chem.
Commun. (1996) 227.
C(4)–Sn(1)–C(16)
C(10)–Sn(1)–S(1)
C(4)–Sn(1)–S(1)
C(16)–Sn(1)–S(1)
C(28)–Sn(2)–C(34) 111.4(4)
C(28)–Sn(2)–C(22) 117.4(4)
C(34)–Sn(2)–C(22) 105.8(4)
107.7(4)
110.3(3)
123.4(3)
95.8(2)
C(52)–Sn(3)–C(46) 112.6(4)
C(52)–Sn(3)–C(40) 108.8(4)
C(46)–Sn(3)–C(40) 108.5(4)
C(52)–Sn(3)–S(2)
C(46)–Sn(3)–S(2)
C(40)–Sn(3)–S(2)
C(1)–S(1)–Sn(1)
C(2)–S(2)–Sn(3)
C(3)–S(3)–Sn(2)
117.6(3)
111.2(3)
96.6(3)
98.6(3)
95.5(3)
96.6(3)
C(28)–Sn(2)–S(3)
C(34)–Sn(2)–S(3)
107.5(3)
97.3(3)

12
I. Haiduc et al. / Journal of Organometallic Chemistry 627 (2001) 6–12
[16] B.-C. Tzeng, C.-M. Che, S.-M. Peng, J. Chem. Soc. Chem.
Commun. (1997) 1771.
[17] W.J. Hunks, M.C. Jennings, R.J. Puddephatt, Inorg. Chem. 38
(1999) 5930.
[18] W. Stamm, J. Org. Chem. 30 (1965) 693.
[19] A.G. Davies, P.J. Smith, in: G. Wilkinson, F.G.A. Stone, E.W.
Abel (Eds.), Comprehensive Organometallic Chemistry, vol. 2,
Pergamon Press, Oxford, 1982, p. 519.
[20] G.M. Bancroft, V.G.K. Das, T.K. Sham, M.G. Clark, J. Chem.
Soc. Dalton Trans. (1976) 643.
[21] J. Holecek, A. Lycka, Inorg. Chim. Acta 118 (1986) L15.
[22] N.L. Speziali, B.G. Guimaraes, R.M. Silva, P.H. Duarte, S.R.
Aguiar, Acta Crystallogr. Sect. C50 (1994) 1059.
[23] K.C. Molloy, T.G. Purcell, K. Quill, I. Nowell, J. Organomet.
Chem. 267 (1984) 237.
[24] K. Sisido, Y. Takeda, Z. Kinugawa, J. Am. Chem. Soc. 83
(1961) 538.
[25] G.M. Sheldrick, University of Go¨ttingen, Go¨ttingen, 1986.
[26] G.M. Sheldrick, University of Go¨ttingen, Go¨ttingen, 1997.
[27] P. McArdle, J. Appl. Crystallogr. 28 (1995) 65.
.