Synthesis, characterisation and reaction chemistry of organotin-substituted bis(thiotetrazoles): Supramolecular metallotetrazole structures containing hard and soft donors

Article abstract of DOI:10.1039/a804928i

Four new organotin thiotetrazoles 1,4-(R₃SnSCN₄)₂C₆H₄ (R = Me, Et, Bu or Ph), along with their triphenyllead, diphenylthallium and phenylmercury analogues, have been synthesized. The supramolecular structure of 1,4-(Bu₃SnSCN₄)₂C₆H₄ has been found to consist of a 2-D sheet arrangement containing 32-membered (C₄NCSSnN₂CSSnN₃)₂ rings. In contrast, 1,4-(Me₃SnSCN₄)₂C₆H₄ crystallises as a bis(methanol) solvate in which 14-membered (SnSCN₂HO)₂ rings are linked through hydrogen bonds into a 1-D polymer.

Full text of DOI:10.1039/a804928i

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Synthesis, characterisation and reaction chemistry of organotin-
substituted bis(thiotetrazoles): supramolecular metallotetrazole
structures containing hard and soft donors
Sonali Bhandari, Mary F. Mahon, John G. McGinley, Kieran C. Molloy* and
Charlotte E. E. Roper
Department of Chemistry, University of Bath, Claverton Down, Bath, UK BA2 7AY.
E-mail: chskcm@bath.ac.uk
Received 29th June 1998, Accepted 24th July 1998
Four new organotin thiotetrazoles 1,4-(R3SnSCN4)2C6H4 (R = Me, Et, Bu or Ph), along with their triphenyllead,
diphenylthallium and phenylmercury analogues, have been synthesized. The supramolecular structure of
1,4-(Bu3SnSCN4)2C6H4 has been found to consist of a 2-D sheet arrangement containing 32-membered
(C4NCSSnN2CSSnN3)2 rings. In contrast, 1,4-(Me3SnSCN4)2C6H4 crystallises as a bis(methanol) solvate in
which 14-membered (SnSCN2HO)2 rings are linked through hydrogen bonds into a 1-D polymer.
potentially π-co-ordinated tetrazole in PbPh3SCN4Ph-1.10
Introduction
We now report our studies on the structural chemistry of
1,1Ј-p-phenylenebis[5(tributylstannylsulfanyl)tetrazole], 1,1Ј-
p-phenylenebis[5-(trimethylstannylsulfanyl)tetrazole] (solvated
with methanol) and related organometallic species, in which a
polyfunctional tetrazole-based ligand containing both hard (N)
and soft (S) donors is used as a component of supramolecular
assemblies.
We have been interested for some time in the supramolecular
architectures created by organotin derivatives of polyfunctional
tetrazoles.1–3 The latter combine with various R3Sn to yield
products containing, without exception, the trans-N2SnC3
moiety, the linear N–Sn–N component of which acts as a rigid
connector between azole units. The co-ordinatively versatile
heterocycle, with four available donors all of which can be util-
ised in bonding in varying combinations, acts as a fulcrum
about which lattice construction is orchestrated in two or more
dimensions. Organotin tetrazoles thus represent an uncommon
variant in supramolecular chemistry, where a combination of
rigid ligands linking metals of various co-ordination numbers
Results and discussion
Synthesis
The cycloaddition of a triorganotin azide with 1,4-bis(isothio-
cyanato)benzene leads to the formation of 1 and 2 in yields in
excess of 50% (Scheme 1). The course of the reactions was
monitored by the disappearance of ν(N3) and ν(NCS) in the IR
spectra at ca. 2076 and 2112 cmϪ1, respectively. Compound 1
was recrystallised from hot methanol but, surprisingly, 2 proved
insoluble in alcohols.
Compound 1 was converted into the metal-free tetrazole II
by refluxing with aqueous HCl, and the absence of an IR band
at ca. 2550 cmϪ1 corresponding to ν(SH) suggests II probably
4
and stereochemistries e.g. Cd(CN)2 is a more common
approach to lattice construction.
In our previous work we have been able to use organotin
tetrazoles to construct zigzag sheets [e.g. 1,2-(Et3SnN4C)2-
C6H4],1 planar sheets [e.g. 1,3,5-(Bu3SnN4C)3C6H3],3 bilayers
[e.g. 1,6-(Bu3SnN4C)2(CH2)6]2 and three-dimensional networks
[e.g. 1,2-(Bu3SnN4C)2C6H4].1 In addition to ligand design, our
experience suggests that the size of the hydrocarbon groups on
tin also plays a crucial role in the way the lattice is constructed,
by virtue of the fact that these groups need to be accom-
modated in any channels/cavities that are formed. The two
variants of 1,2-(R3SnN4C)2C6H4 cited above illustrate this
point. Similar comments can be made about derivatives of the
related ligand 1-phenyl-5-sulfanyl-1H-tetrazole (I), which we
demonstrated some time ago preferentially co-ordinates
through sulfur via its thiol (Ia), not thione (Ib), tautomer.5
exists in the thione form. Indeed, a band assignable to ν(C᎐S)
᎐
was observed at 1049 cmϪ1. The ammonium salt III was gener-
ated by bubbling ammonia through a solution of II for 30 min;
III then enabled the synthesis of both trimethyl- and triphenyl-
tin derivatives (3, 4) by a salt elimination process, the former
crystallising from methanol as a bis-solvate while the latter
was unsolvated. Reaction of 1 with 2 equivalents of PbPh3Cl
resulted in elimination of SnBu3Cl and formation of a bis-
(organolead) derivative 5. The bis(phenylmercury) analogue
6 was prepared similarly but proved difficult to characterise
structurally due to its insolubility. A condensation reaction
involving II and TlPh2(OH) led to the diorganothallium
analogue 7, which crystallised as a dihydrate.
SH
S
Ph
Ph
N
N
N
NH
N
N
N
N
Ia
Ib
Spectroscopy
Since we published the structure of SnBu2(SCN4Ph)2, others
have shown the ligand can act in a chelating [e.g. SnPh3-
(SCN4Ph)]6 or bridging manner, the latter generating both
oligomers[e.g. (Me3SnSCN4Ph)3]7 andpolymers{e.g. [(PhCH2)3-
SnSCN4Ph]∞}.8 More recently, several neutral and anionic
transition metal derivatives have also been structurally charac-
terised9 and we have discovered the first example of a
Table 1 gives the Mössbauer and NMR data for the triorgano-
tin-substituted thiotetrazoles 1–4. The quadrupole splittings
(q.s.) for the three alkyltin species are in the range 3.32–3.39
mm sϪ1 which are consistent with a polymeric, five-co-ordinate
trans-XYSnC3 trigonal bipyramidal geometry in the solid
state.11 The arrangement (X = N, Y = S) has been confirmed in
J. Chem. Soc., Dalton Trans., 1998, 3425–3430
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Table 2 Selected metric data (bond lengths in Å, angles in Њ) for
compound 1*
N
N
N
N
N
N
N
N
Sn(1)–C(17)
Sn(1)–C(13)
Sn(1)–C(9)
Sn(1)–S(2)
Sn(1)–N(6Ј)
S(1)–C(1)
2.09(1)
2.10(1)
2.11(2)
2.574(2)
2.781(7)
1.716(9)
Sn(2)–C(29)
Sn(2)–C(21)
Sn(2)–C(25)
Sn(2)–S(1)
Sn(2)–N(2Љ)
S(2)–C(8)
2.11(1)
2.13(1)
2.13(1)
2.554(3)
2.810(7)
1.726(9)
S
S
PhnM
MPhn
5 M = Pb, n = 3
6 M = Hg, n = 1
2SnR3(N3) + SCN
NCS
2MPhnCl
–2SnBu3Cl
80–100 °C, 30 mins
C(17)–Sn(1)–C(13) 125.0(8)
C(29)–Sn(2)–C(21) 122.2(5)
C(29)–Sn(2)–C(25) 117.6(6)
C(21)–Sn(2)–C(25) 114.5(5)
C(17)–Sn(1)–C(9)
C(13)–Sn(1)–C(9)
C(17)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
C(9)–Sn(1)–S(2)
C(17)–Sn(1)–N(6Ј)
C(13)–Sn(1)–N(6Ј)
C(9)–Sn(1)–N(6Ј)
S(2)–Sn(1)–N(6Ј)
C(1)–S(1)–Sn(2)
110.8(8)
118.4(5)
92.9(4)
101.9(3)
98.8(4)
79.7(4)
82.6(4)
83.9(4)
172.6(2)
104.0(3)
N
N
R = Bu, Et
N
N
N
N
N
N
C(29)–Sn(2)–S(1)
C(21)–Sn(2)–S(1)
C(25)–Sn(2)–S(1)
C(29)–Sn(2)–N(2Љ)
C(21)–Sn(2)–N(2Љ)
C(25)–Sn(2)–N(2Љ)
S(1)–Sn(2)–N(2Љ)
C(8)–S(2)–Sn(1)
101.1(4)
89.5(3)
103.2(3)
82.0(4)
80.4(3)
84.0(4)
169.4(2)
101.8(3)
S
S
1 R = Bu
R3Sn
SnR3
2 R = Et
3 R = Me
4 R = Ph
HCl
–2SnBu3Cl
N
N
N
N
N
N
2R3SnCl
–2NH4Cl
HN
NH
R = Me, Ph
* Primed and double-primed atoms are related to their unprimed
counterparts by Ϫx ϩ 0.5, y ϩ 0.5, Ϫz and Ϫx ϩ 1.5, y ϩ 0.5, Ϫz ϩ 1,
respectively.
II
S
S
NH3
2–
N
N
N
N
N
N
N
N
2TIPh2(OH)
–2H2O
2[NH4]+
S
S
Table 3 Selected metric data (bond lengths in Å, angles in Њ) for
compound 3
III
N
N
N
N
N
N
N
N
Sn(1)–C(2)
Sn(1)–C(1)
Sn(1)–C(3)
2.132(7)
2.133(6)
2.141(7)
Sn(1)–O(1)
Sn(1)–S(1)
S(1)–C(4)
2.464(5)
2.607(2)
1.723(7)
S
S
Ph2TI
TIPh2
C(1)–Sn(1)–O(1)
C(3)–Sn(1)–O(1)
C(2)–Sn(1)–S(1)
C(1)–Sn(1)–S(1)
C(3)–Sn(1)–S(1)
O(1)–Sn(1)–S(1)
82.2(2)
85.0(2)
91.1(2)
99.3(2)
98.5(2)
174.7(1)
C(4)–S(1)–Sn(1)
C(2)–Sn(1)–C(1)
C(2)–Sn(1)–C(3)
C(1)–Sn(1)–C(3)
C(2)–Sn(1)–O(1)
101.1(2)
115.2(3)
120.9(3)
120.3(3)
83.7(2)
7
Scheme 1
Table 1 The NMRa and Mössbauer datab
Compound
δ(119Sn) 1J(Sn–13C)c
i.s.
q.s.
Ref.
intermolecular interactions in solid 1 are lost and that tin has a
tetrahedral environment in solution. Similarly, a co-ordination
number (c.n.) of 4 is maintained by compound 4 in solution.
Both δ(119Sn) and 1,2J data are consistent with c.n. = 5 for both 2
and 3 in solution, but in both cases it is likely that this is
achieved by dmso co-ordination to tin. Similarly, δ(207Pb) for
5 (Ϫ235.5) is also indicative of a co-ordination number of 5 at
the metal, and is comparable with data for other triphenyllead
tetrazoles in dmso (Ϫ251 to Ϫ360),14 where once again dmso, as
solvent, is probably involved in complexation.
SnBu3SCN4Ph
SnPh3SCN4Ph
1
2
3ؒ2MeOH
4
5
112.5
Ϫ69.4
122.8
Ϫ10.3
Ϫ23.7
Ϫ65.0
Ϫ235.5e
328
1.48 3.32
1.33 2.38
1.50 3.32 This work
1.52 3.39 This work
1.38 3.35 This work
1.22 2.29 This work
This work
5
6
327
474
491, 515d
—
a For (CD3)2SO solutions at 25 ЊC except for compound 4 which was
heated to 100 ЊC; δ in ppm relative to SnMe4, J in Hz. b Recorded at 78
K and data given as mm sϪ1 c For unresolved 117,119Sn couplings.
.
d 2J(117,119Sn–1H) (unresolved): 68.5 Hz. e δ(207Pb).
1
The H and 13C NMR data are unremarkable, save for the
occurrence of the quaternary ring carbon at ca. δ 160 in the 13
spectra which confirms the presence of the tetrazole ring.
C
(Me3SnSCN4Ph)3 (q.s. 3.15 mm sϪ1
)
while SnBu3(SCN4Ph),
7
which has not been crystallographically characterised, has a q.s.
of 3.32 mm sϪ1.5 In 3, which crystallises with two molecules of
MeOH, both trans-NSSnC3 and trans-OSSnC3 arrangements
are possible. A Me(H)O→Sn co-ordination has been observed
previously in 1,3-(Bu3SnN4C)2C6H4ؒ2MeOH,1 but literature
precedent for a trans-SOSnC3 tin environment, as well as
related Mössbauer data, is scarce. The compound SnMe3-
[O(S)P(OMe)2] has a q.s. of 3.89 mm sϪ1 12 and presumably
adopts the same trans-OSSnC3 structure as SnMe3[O(S)PMe2]13
but there is no direct analogy for 3 where a co-ordinated sol-
vent is incorporated, which, by its nature, is likely to be more
weakly bound to tin and hence exhibit a lower q.s. Mössbauer
spectroscopy is therefore not sufficient to distinguish
unambiguously between the two possibilities but crystal-
lography has confirmed a trans-SOSnC3 centre (see below). The
q.s. for 4 is 2.29 mm sϪ1 and is comparable with the value 2.38
mm sϪ1 for SnPh3(SCN4Ph) which is essentially tetrahedral at
tin with only a very weak chelating interaction with a ring
nitrogen [3.275(3) Å].6
Crystallography
Selected metric data for compounds 1 and 3 are given in Tables
2 and 3, respectively. For purposes of comparison, the Sn–S,
Sn–N, C–S bond lengths and the C–Sn–C bond angle of
previously known organotin-substituted thiotetrazoles are
summarised in Table 4. For descriptive purposes, we number
the tetrazole ring nitrogens as 1–4 for comparing the co-
ordination mode of the tetrazole, while with respect to tin we
group the nitrogens into either N1 (i.e. N1 or N4) or N2 (i.e. N2
or N3) categories, these representing the two differing degrees
of hindrance for metal binding. The system can equally well be
applied to the thiotetrazoles, though here N1 is arylated and
cannot co-ordinate further to a metal.
R
S
4N
N1
4 N
3 N N 2
N1
R
3 N N 2
The NMR data (Table 1), recorded in dmso, indicate that any
tetrazole
thiotetrazole
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Table 4 Comparative geometric data for compounds 1 and 3 and related compounds
Compound
Sn–S/Å
Sn–N/Å
C–S/Å
C–Sn–C/Њ
Ref.
1
2.574(2), 2.554(3)
2.607(2)
2.477(4)
2.781(7),a 2.810(7)a
2.464(5)b
1.716(9), 1.726(9)
1.723(7)
1.76(2)
110.8(8)–125.0(8)
115.2(3)–120.9(3)
130.7(4)
This work
This work
5
8
3
SnBu2(SCN4Ph)2
[(PhCH2)3SnSCN4Ph]∞
2.99c
2.565(4), 2.614(5)
2.68(1),a 2.56(1)a
3.16,c 3.20c
1.72(1)
111.4(4)–126.1(5)
SnPh3(SCN4Ph)
(Me3SnSCN4Ph)3
2.482(1)
2.565(4)
3.275(3)c
1.728(4)
1.73(2)
113.6(1)–122.7(1)
115.8(8)–120(1)
6
7
2.75(1),a 3.29(1)c
a Intermolecular. b Sn–O. c Intramolecular.
Fig. 1 The asymmetric unit of compound 1 showing the labelling scheme used in the text and tables. Thermal ellipsoids are at the 30% level.
Compound 1. The asymmetric unit of compound 1 contains
two trigonal bipyramidal trans-NSSnC3 centres (Fig. 1) consist-
ent with the Mössbauer q.s. data (see above). Each tin is directly
bonded to the sulfur of the attached ligand and is further co-
ordinated intermolecularly by a nitrogen [either N(2Ј) or N(6Ј)]
from the tetrazole of a neighbouring molecule. Both nitrogen
and sulfur attached to a given tin form part of the same ligand
group, i.e. the structure can be viewed as parallel chains, one
based on Sn(1) and the ligand containing S(2), N(6) the other
based on Sn(2), S(1), N(2) groupings. The arrangement can be
seen as identical to that of Sn(CH2Ph)3(SCN4Ph)8 but with the
phenyl group attached to the tetrazole common to a pair of
parallel strands (Fig. 2). The two Sn–S distances [Sn(1)–S(2)
2.574(2); Sn(2)–S(1) 2.554(3) Å] are comparable with the Sn–S
bond lengths of previously known organotin thiotetrazoles
(Table 4) although they are at the longer end of the range. The
intermolecular Sn–N bonds [Sn(1)–N(6Ј) 2.781(7); Sn(2)–N(2Љ)
2.810(7) Å] are similar to the intermolecular Sn–N bond
Fig. 2 The sheet structure of compound 1 viewed along the Ϫ1, 0, 1
direction.
lengths of [(PhCH2)3SnSCN4Ph]∞ and (Me3SnSCN4Ph)3 (Table
4) but longer than the intermolecular Sn–N bond length of
hydrated 2,2Ј-p-phenylenebis(tributylstannyltetrazole) [Sn(1)–
N(6Ј) 2.573(6) Å],14 presumably as a result of the lower Lewis
acidity of tin arising from S, rather than N, primary bonding.
Metal–ligand bonding thus takes place primarily through the
sulfur exocyclic to the tetrazole rather than the nitrogen. The
N–Sn–S bond angles approach 180Њ [N(6Ј)–Sn(1)–S(2)
172.6(2); S(1)–Sn(2)–N(2Љ) 169.4(2)Њ].
comparison with known organotin tetrazoles, each tetrazole
can be described as bidentate and exhibiting N1 ϩ N3 co-
ordination, the N1 site in the thiotetrazoles being occupied by
the phenyl ring. The N1 ϩ N3 mode of co-ordination is the
most common for organotin tetrazole and organtin thio-
tetrazoles.15
The supramolecular structure of compound 1 is dominated
by two-dimensional sheets as shown in Fig. 2. Atoms Sn(1) and
Sn(2) in the asymmetric unit interact with N(6) and N(2) of
The N3 co-ordination of the tetrazole with respect to the
tin is that of lowest steric hindrance and is the mode adopted
8
in both [(PhCH2)3SnSCN4Ph]∞ and (Me3SnSCN4Ph)3.7 For
J. Chem. Soc., Dalton Trans., 1998, 3425–3430
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the lattice neighbours generated via the symmetry operators
0.5 Ϫ x, 0.5 ϩ y, Ϫz and 1.5 Ϫ x, 0.5 ϩ y, 1 Ϫ z, respectively.
The axial nitrogens co-ordinated to the tin lie in the plane of the
polymer sheets. These sheets are dominated by 32-membered
rings containing four tins, four sulfurs, twelve tetrazole nitro-
gens, four tetrazole carbons and eight phenyl carbons. The
interlayer region is filled by the equatorial n-butyl groups as
shown Fig. 3. The supramolecular arrays of other organotin
tetrazoles also include planar and puckered two-dimensional
arrays. The closest analogies for 1 can be drawn with nitro-
tris[2-(2-tributylstannyltetrazol-5-yl)ethyl]methane and 1,3,5-
tris(tributylstannyltetrazol-5-yl)benzene which are also two-
dimensional sheet structures,3 though these are built to include
only 24-atom (Sn6N18) rings. Indeed, the size of the rings in 1,
enlarged as they are by the phenylene groups inherent in the
ligand, is surprisingly large for accommodating only four of the
butyl groups of the associated tin atoms. In contrast, both
planar tris-substituted tetrazoles pack ten butyl groups from
six tins into the cavity of the 24-atom ring. This suggests that
with suitable ligand design far more porous structures than
previously identified are achievable.
Compound 3ؒ2MeOH. X-Ray quality crystals of compound 3
were obtained by slow evaporation of a methanolic solution at
room temperature; data were collected at low temperature as
the crystals desolvated at ambient temperatures in the absence
of mother-liquor. The asymmetric unit (Fig. 4) was found to
consist of one half of the molecule, the remainder being gener-
ated by an inversion centre at the midpoint of the C6 ring. Each
tin is trigonal bipyramidal trans-SOSnC3 with the axial posi-
tions occupied by O(1) of the co-ordinated methanol molecule
and S(1) of the thiotetrazole. The O–Sn–S bond angle is close
to 180Њ [O(1)–Sn(1)–S(1) 174.7(1)Њ]. The Sn(1)–S(1) bond
length [2.607(2) Å] is the longest such distance observed when
compared with those of 1 and with other known organotin-
substituted thiotetrazoles (Table 4). No other data for solvated
organotin thiotetrazoles exist for comparison of the Sn(1)–O(1)
bond length [2.464(5) Å], although it is longer than the analo-
gous bond in related 1,3-(Bu3SnN4C)2C6H4ؒ2MeOH [2.398(9)
Å].1 In addition, comparison can be made with data for
(Me3SnOSPMe2)∞ which also has a trans-SOSnC3 centre where
the Sn–O bond is, as expected, stronger [2.267(6) Å].13 The
tetrazole adopts the common N1 ϩ N3 co-ordination mode
(N1 bonded to the phenyl ring) seen in 1.
The salient feature of the supramolecular structure of com-
pound 3 is that of a one-dimensional hydrogen-bonded poly-
mer, as shown in Fig. 5, in which the co-ordinated methanol
hydrogen bonds to N(2) of a neighbouring tetrazole [O(1) ؒ ؒ ؒ
N(2) 2.801(8); H(1) ؒ ؒ ؒ N(2) 1.84(3) Å; O(1)–H(1)–N(2)
173(5)Њ]. The polymers are, in effect, fourteen-membered
(SnSCN2HO)2 rings linked by phenylene bridges. We have
observed similar twelve-membered rings in the structure of
1-phenyl 5-diphenylthallium tetrazole which simply lacks the
sulfurs of the thiotetrazole in 3.14
Conclusion
Four organotin thiotetrazoles 1,4-(R3SnSCN4)2C6H4 (R = Me,
Et, Bu or Ph) along with the triphenyllead, diphenylthallium
and phenylmercury analogues have been synthesized. The
Fig. 3 The sheet structure of compound 1 viewed along b to illustrate
the filling of the interlayer region by the butyl groups on tin.
Fig. 4 The symmetric unit of compound 3 showing the labelling scheme used in the text and tables. Thermal ellipsoids are at the 30% level.
Fig. 5 The polymeric structure of compound 3 showing the intermolecular hydrogen bonds.
3428
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supramolecular structure of 1,4-(Bu3SnSCN4)2C6H4 has been
found to consist of a 2-D sheet arrangement containing 32-
membered (C4NCSSnN2CSSnN3)2 rings. In contrast, 1,4-(Me3-
SnSCN4)2C6H4 crystallises as a bis(methanol) solvate in which
14-membered (SnSCN2HO)2 rings are linked through hydrogen
bonds into a 1-D polymer.
(decomp.) [Found (Calc. for C8H6N8S2ؒCH3OH): C, 34.9 (34.7);
H, 2.05 (2.74); N, 38.5 (38.1)%]. 1H NMR: δ 8.17 (s, 4 H, C6H4)
and 3.18 (s, 3 H, CH3OH). 13C NMR: δ 162.5 (CN4), 134.5 (C1,4
of C6H4) and 125.4 (C2,3,5,6 of C6H4). IR (cmϪ1, KBr disc): 3553,
3414, 3069, 2937, 2750, 1637, 1616, 1522, 1477, 1385, 1350,
1296, 1275, 1217, 1049, 989, 851, 767, 657 and 590.
Diammonium 1,1Ј-p-phenylenebis(tetrazole-5-thiolate) III.
Ammonia gas was bubbled through a solution of compound II
in methanol (350 mL) for 30 min. The methanol was removed in
vacuo to yield III in quantitative yield, mp 190 ЊC (decomp.)
[Found (Calc. for C4H6N5S): C, 31.4 (30.8); H, 3.90 (3.85); N,
44.2 (44.9)%]. 1H NMR: δ 8.16 (s, 4 H, C6H4) and 7.30 (s, 8 H,
NH4ϩ). 13C NMR: δ 167.5 (CN4), 135.5 (C1,4 of C6H4) and 123.5
(C2,3,5,6 of C6H4). IR (cmϪ1, Nujol): 3443, 2955, 2924, 2855,
2363, 2342, 1734, 1653, 1559, 1516, 1458, 1420, 1375, 1358,
1292, 1283, 1219, 1089, 1040 and 1013.
Experimental
Spectra were recorded on the following instruments: JEOL
GX270 (1H, 13C NMR), GX400 (119Sn NMR), Perkin-Elmer
599B (IR). Details of our Mössbauer spectrometer and related
procedures are given elsewhere.16 Isomer shift data are relative
to CaSnO3. For all compounds, infrared spectra were recorded
as Nujol mulls on KBr plates and all NMR data on saturated
solutions in (CD3)2SO unless indicated otherwise.
Organotin azides SnR3(N3) (R = Bu17 or Et1) and TlPh2-
(OH)18 were prepared by literature methods. Other reagents
were obtained commercially and used without further purifi-
cation.
CAUTION: Owing to their potentially explosive nature, all
preparations and subsequent reactions with organotin azides
were conducted under an inert atmosphere behind a rigid safety
screen.
1,1Ј-p-Phenylenebis[(5-trimethylstannylsulfanyl)tetrazole]–
methanol (1/2) 3. A solution of trimethyltin chloride (0.62 g,
3.12 mmol) in methanol (100 mL) was added dropwise to a
well stirred solution of compound III (0.50 g, 1.56 mmol) in
methanol (200 mL) and the reaction mixture refluxed for 3 h.
Subsequently, the methanol was removed in vacuo and the white
solid refluxed in acetone (300 mL) for 30 min. Hot filtration
resulted in a yellow solution. The acetone was removed in vacuo
and the resulting yellow-white solid recrystallised from
methanol to yield 3 as a yellow crystalline product (0.73 g,
77%), mp 175 ЊC (decomp.) [Found (Calc. for C7H11N4-
SSnؒCH3OH): C, 28.5 (28.7); H, 4.32 (4.49); N, 17.0 (16.8)%].
1H NMR: δ 8.06 (s, 4 H, C6H4), 3.16 (s, 6 H, CH3OH), 0.64 (s,
12 H, SnCH3); 2J[1H–117,119Sn] 68.5 Hz (unresolved). 13C NMR:
δ 164.7 (CN4), 135.1 (C1,4 of C6H4), 124.5 (C2,3,5,6 of C6H4), 48.7
Syntheses
1,1Ј-p-Phenylenebis[(5-tributylstannylsulfanyl)tetrazole] 1. A
mixture of tributyltin azide (6.96 g, 21.0 mmol) and 1,4-
diisothiocyanatobenzene (2.04 g, 10.6 mmol) were heated while
stirring under N2 at 100 ЊC for half an hour. The resultant
yellow-white solid was recrystallised from hexanes yielding
compound 1 as a white microcrystalline solid (5.02 g, 55%),
m.p. 122 ЊC [Found (Calc. for C16H29N4SSn): C, 44.6 (44.9); H,
1
(CH3OH) and 0.9 (CH3); J[13C–117,119 Sn] 491, 515 Hz. 119Sn
NMR: δ Ϫ23.7. IR (cmϪ1, KBr disc): 3245, 2924, 2855, 2363,
2342, 1520, 1512, 1464, 1368, 1352, 1298, 1277, 1219, 1117,
1098, 1082, 1020, 1010, 837 and 789. 119mSn Mössbauer (mm
1
6.81 (6.83); N, 13.0 (13.1)%]. H NMR: δ 8.01 (s, 4 H, C6H4),
1.62 [m, 12 H, SnCH2CH2CH2CH3]; 1.54 (m, 12 H, SnCH2-
CH2CH2CH3), 1.48 (m, 12 H, SnCH2CH2CH2CH3) and 0.91
[t, 18 H, (CH2)3CH3]. 13C NMR: δ 155.7 (CN4), 135.1 (C1,4
of C6H4), 124.6 (C2,3,5,6 of C6H4), 28.5 (SnCH2CH2CH2CH3),
27.0 [Sn(CH2)2CH2CH3], 16.6 [SnCH2(CH2)2CH3] and 13.6
[(CH2)3CH3]; 1J[13C–117,119Sn] 327 (unresolved), 3J[13C–117,119Sn]
66 Hz (unresolved). 119Sn NMR: δ 122.8. IR (cmϪ1, Nujol):
3457, 2924, 2855, 2363, 2340, 2168, 1653, 1601, 1509, 1464,
1418, 1375, 1300, 1277, 1219, 1080, 1039, 1011 and 837. 119mSn
Mössbauer (mm sϪ1): i.s. = 1.50; q.s. = 3.32.
s
Ϫ1): i.s. = 1.38; q.s. = 3.35.
1,1Ј-p-Phenylenebis[(5-triphenylstannylsulfanyl)tetrazole] 4.
A solution of triphenyltin chloride (0.76 g, 1.97 mmol) in
methanol (10 mL) was added dropwise to a well stirred solution
of compound III (0.31 g, 0.99 mmol) in methanol (250 mL) and
the reaction refluxed for 3 h. The reaction was worked up in the
same way as for 3 to yield 4 as a white powder (0.42 g, 40%), mp
160–162 ЊC [Found (Calc. for C22H17N4SSn): C, 53.2 (54.1); H,
3.46 (3.48); N, 11.5 (11.5)%]. 1H NMR (100 ЊC): δ 7.89–7.42 (m,
34 H, phenyl). 13C NMR (100 ЊC): δ 141.7, 135.7, 134.9, 129.0,
128.3, 125.2, 124.0 and 118.0 (phenyl). 119Sn NMR (100 ЊC):
δ Ϫ65.0. IR (cmϪ1, KBr disc): 3414, 3067, 1637, 1618, 1522,
1479, 1429, 1379, 1238, 1226, 1091, 1074, 1016, 997, 837, 731,
696, 619, 574 and 453. 119mSn Mössbauer (mm sϪ1): i.s. = 1.22;
q.s. = 2.29.
1,1Ј-p-Phenylenebis[(5-triethylstannylsulfanyl)tetrazole] 2. A
mixture of triethyltin azide (2.91 g, 11.73 mmol) and 1,4-
diisothiocyanatobenene (1.13 g, 5.87 mmol) was heated while
stirring under N2 at 88 ЊC for half an hour. The resultant
yellow-white solid was washed with hexanes leaving the product
as an analytically pure white powder (2.12 g, 53%); mp 184 ЊC
(decomp.) [Found (Calc. for C10H17N4SSn): C, 34.9 (34.9); H,
1
4.80 (4.94); N, 16.7 (16.3)%]. H NMR: δ 8.06 (s, 4 H, C6H4)
and 1.20–1.30 (m, 30 H, CH2CH3); 2J[1H–117,119Sn] 90 Hz
(unresolved). 13C NMR: δ 163.0 (CN4), 135.1 (C1,4 of C6H4),
124.7 (C2,3,5,6 of C6H4), 11.5 (CH2CH3) and 10.5 (CH2CH3);
1J[13C–117,119Sn] 237 Hz (unresolved). 119Sn NMR: δ Ϫ10.3.
IR (cmϪ1, KBr): 2947, 1606, 1518, 1446, 1371, 1300, 1277,
1218, 1120, 1082, 1039, 1010, 952, 839, 715 and 677. 119mSn
Mössbauer (mm sϪ1): i.s. = 1.52; q.s. = 3.39.
1,1Ј-p-Phenylenebis[(5-triphenylplumbylsulfanyl)tetrazole]-
toluene (2/1) 5. A solution of triphenyllead chloride (0.56 g,
1.18 mmol) in methanol (200 mL) was added dropwise to a well
stirred solution of compound 1 (0.50 g, 0.58 mmol) also in hot
methanol (150 mL). The resultant clear solution was refluxed
for 10 h. Subsequently, methanol was removed in vacuo and the
resulting white product washed with hexanes and recrystallised
from toluene to give 5 as a white crystalline product (0.22 g,
33%), mp 218–220 ЊC (decomp.) [Found (Calc. for C44H34N8-
Pb2S2ؒ0.5CH3C6H5): C, 47.7 (47.5); H, 3.32 (3.17); N, 9.48
(9.35)%]. 1H NMR: δ 7.84, 7.74, 7.60–7.32 (phenyl) and 3.07 (s,
CH3C6H5). 13C NMR: δ 160.0 (CN4), 135.8, 134.5, 129.4, 128.7
1,1Ј-p-Phenylenebis(5-thioxotetrazole)–methanol (1/1) II.
Concentrated hydrochloric acid (1.50 mL, 18 mmol) was added
dropwise to a well stirred solution of compound 1 (3.0 g, 3.5
mmol) in hot methanol (300 mL). The resultant colourless solu-
tion was refluxed for an hour. After cooling, methanol was
removed in vacuo and the remaining white solid washed with
hexanes to remove SnBu3Cl and recrystallised from methanol
to give the product as a white solid (0.96 g, 99%); mp 200 ЊC
and 124.3 (phenyl). 207Pb NMR: δ Ϫ235.5 (100 ЊC). IR (cmϪ1
,
Nujol): 2926, 2855, 1933, 1836, 1715, 1633, 1603, 1568, 1435,
1377, 1335, 1298, 1233, 1098, 1026, 1011, 997, 857, 760, 741 and
696.
J. Chem. Soc., Dalton Trans., 1998, 3425–3430
3429

View Article Online
Table 5 Crystallographic data for compounds 1 and 3*
Compound 1. A crystal of approximate dimensions 0.4 ×
0.4 × 0.4 mm was used for data collection. In the final least
squares cycles all atoms were allowed to vibrate anisotropically.
Hydrogen atoms were included at calculated positions where
relevant. The C–C bond lengths in the butyl group containing
carbons C(17)–C(20) were constrained to an ideal distance of
1.54 Å, as early refinement cycles indicated some instability in
this region of the electron density map. This action was
reflected in an improvement of residuals. The asymmetric unit
is shown in Fig. 1.
1
3
Empirical formula
M
Crystal system
Space group
T/K
a/Å
b/Å
c/Å
C32H58N8S2Sn2
856.36
Monoclinic
P21/a
C8H15N4OSSn
333.99
Triclinic
P1
170(2)
6.755(2)
10.253(4)
10.452(4)
70.44(4)
83.67(4)
70.84(3)
644.3(4)
2
¯
293(2)
17.602(2)
12.639(2)
18.733(6)
—
93.79(1)
—
4158(2)
4
1.332
α/Њ
β/Њ
Compound 3. A crystal of approximate dimensions 0.5 ×
0.4 × 0.25 mm was used for data collection. In the final least
squares cycles all atoms were allowed to vibrate anisotropically.
Hydrogen atoms were included at calculated positions where
relevant, except for the methanolic proton [H(1)] which was
located and refined at a distance of 0.98 Å from O(1). The
asymmetric unit is shown in Fig. 4 (unprimed labels).
CCDC reference number 186/1107.
γ/Њ
U/Å3
Z
µ(Mo-Kα)/mmϪ1
Reflections collected
Goodness of fit on F2
R1, wR2
2.128
2790
1.165
0.0347, 0.0978
6015
1.003
0.0496, 0.1059
[I > 2σ(I)]
(all data)
0.1341, 0.1524
0.0512, 0.1051
* Details in common; λ(Mo-Kα) 0.70930 Å; full-matrix least-squares
refinement on F2.
References
1 M. Hill, M. F. Mahon, J. G. McGinley and K. C. Molloy, J. Chem.
Soc., Dalton Trans., 1996, 835.
2 A. Goodger, M. Hill, M. F. Mahon, J. G. McGinley and
K. C. Molloy, J. Chem. Soc., Dalton Trans., 1996, 847.
3 M. Hill, M. F. Mahon and K. C. Molloy, J. Chem. Soc., Dalton
Trans., 1996, 1857.
4 J. Kim, D. Whang, Y.-S. Koh and K. Kim, J. Chem. Soc., Chem.
Commun., 1994, 637.
5 R. J. Deeth, K. C. Molloy, M. F. Mahon and S. Whitaker,
J. Organomet. Chem., 1992, 430, 25.
6 J. Bravo, M. B. Cordero, J. S. Casas, A. Sanchez, J. Sordo, E. E.
Castellano and J. Zukerman-Schpector, J. Organomet. Chem., 1994,
482, 147.
1,1Ј-p-Phenylenebis[(5-phenylmercuriosulfanyl)tetrazole] 6.
This was prepared in a similar manner to compound 5 from a
methanolic solution (100 mL) of 1 (0.53 g, 0.61 mmol) and a
solution of phenylmercury() chloride (0.38 g, 1.27 mmol) in
methanol (130 mL). A white precipitate formed instant-
aneously, which was collected by washing with hexanes and
filtering. The product was found to be insoluble in most
commonly available solvents (0.40 g, 80%), mp 190–192 ЊC
(decomp.) [Found (Calc. for C10H7HgN4S): C, 28.2 (28.9); H,
1.74 (1.68); N, 13.0 (13.5)%], IR (cmϪ1, Nujol): 3441, 2955,
2924, 2855, 1624, 1524, 1464, 1431, 1372, 1294, 1271, 1235,
1094, 1041, 1020, 997, 982, 843, 723 and 629.
7 R. Cea-Olivares, O. Jimenez-Sandoval, G. Espinosa-Perez and
C. Silvestru, J. Organomet. Chem., 1994, 484, 33.
8 R. Cea-Olivares, O. Jiminez-Sandoval, G. Espinosa-Perez and
C. Silvestru, Polyhedron, 1994, 13, 2809.
9 H. Nöth, W. Beck and K. Burger, Eur. J. Chem., 1998, 93.
10 M. Barret, S. Bhandari, M. F. Mahon and K. C. Molloy, un-
published work.
11 A. G. Davies and P. J. Smith, in Comprehensive Organometallic
Chemistry, eds. G. Wilkinson, F. G. A. Stone and E. W. Abel,
Pergamon, Oxford, 1982, p. 529.
12 F. A. K. Nasser and J. J. Zuckerman, J. Organomet. Chem., 1983,
244, 17.
13 A.-F. Shihada, I. A.-A. Jassim and F. Weller, J. Organomet. Chem.,
1984, 268, 125.
1,1Ј-p-Phenylenebis[(5-diphenylthalliosulfanyl)tetrazole]
dihydrate 7. A solution of diphenylthallium hydroxide (0.100 g,
0.267 mmol) in methanol (200 mL) was added dropwise to a
well stirred solution of compound II (0.04 g, 0.134 mmol) in
hot methanol (60 mL). After refluxing for 3 h the cloudy solu-
tion was cooled to room temperature and the volume of solvent
decreased under reduced pressure, resulting in the precipitation
of a white solid which was collected by filtration and dried in
vacuo (0.06 g, 43%), mp 202 ЊC (decomp.) [Found (Calc. for
C11H12N4STlؒH2O): C, 38.7 (37.3); H, 2.42 (2.72); N, 11.3
14 S. Bhandari, Ph.D. Thesis, University of Bath, 1998.
15 D. S. Moore and S. D. Robinson, Adv. Inorg. Chem., 1988, 32, 171.
16 K. C. Molloy, T. G. Purcell, K. Quill and I. Nowell, J. Organomet.
Chem., 1984, 267, 237.
1
(10.9%)]. H NMR δ 8.28–7.29 (m, 24 H, phenyl). 13C NMR
δ 164.0 (CN4), 137.3, 136.9, 135.6, 130.9, 128.8, 126.5 and 123.9
(phenyl). IR (cmϪ1, KBr): 3414, 3044, 2924, 1616, 1510, 1475,
1431, 1363, 1340, 1296, 1280, 1215, 1093, 1078, 1006, 997, 841,
723, 688 and 451.
17 W. T. Reichle, Inorg. Chem., 1964, 3, 237.
18 J. S. Casas, E. E. Castellano, A. Castineiras, A. Sanchez, J. Sordo,
E. M. Vazquez-Lopez and J. Zuckerman-Schpector, J. Chem. Soc.,
Dalton Trans., 1995, 1403.
X-Ray crystallography
Crystal data are summarised in Table 5.
Paper 8/04928I
3430
J. Chem. Soc., Dalton Trans., 1998, 3425–3430