Syntheses and crystal structures of diorganotin derivatives of 2,5-dimercapto-1,3,4-thiadiazole

Article abstract of DOI:10.1002/ejic.200300860

Two novel trinuclear tin oxo clusters [(C₂S₃N ₂)R₆Sn₃O-(OH)Y]·L [R = CH₃, Y = OH, L = 1·5H₂O (1); R = PhCH₂, Y = OEt, L = 0 (2)], a pentanuclear tin macrocycle [(CH₃)₂Sn (C ₂N₂S₃)]₅·CH ₂Cl₂-3H₂O (3) and [(PhCH₂) ₄Cl₂Sn(C₂S₃N₂)] (4) have been synthesized by the reaction of 2,5-dimercapto-1,3,4-thiadiazole with dialkyltin dichloride in ethanol (95%) or dichloromethane. Complexes 1-4 have been characterized by elemental analysis and IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. The structures of 1-3 have been determined by X-ray crystallography. Complexes 1 and 2 display a unique tricyclic structure consisting of fused five-membered Sn₂ON ₂ and four-membered Sn₂O₂ rings that form a planar N₂Sn₃O₂ skeleton, with a distorted trigonal bipyramidal coordination at tin. Complex 3 is a pentanuclear 35-membered tin macrocycle containing the crown thioether-type ligand in which all five tin atoms bond to the sulfur and nitrogen atoms with distorted octahedral geometries. The structures of complexes 1 and 3 are stabilized by hydrogen bonds or intermolecular non-bonding S...S interactions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300860

FULL PAPER
Syntheses and Crystal Structures of Diorganotin Derivatives of
2,5-Dimercapto-1,3,4-thiadiazole
Chunlin Ma,*[a,b] Junhong Zhang,[a] Feng Li,[a] and Rufen Zhang[a]
Keywords: Macrocyclic ligands / N ligands / Oxo ligands / S ligands / Tin
Two novel trinuclear tin oxo clusters [(C2S3N2)R6Sn3O-
(OH)Y]·L [R = CH3, Y = OH, L = 1·5H2O (1); R = PhCH2, Y =
OEt, L = 0 (2)], a pentanuclear tin macrocycle [(CH3)2Sn
(C2N2S3)]5·CH2Cl2·3H2O (3) and [(PhCH2)4Cl2Sn(C2S3N2)]
(4) have been synthesized by the reaction of 2,5-dimercapto-
1,3,4-thiadiazole with dialkyltin dichloride in ethanol (95%)
or dichloromethane. Complexes 1−4 have been characterized
by elemental analysis and IR, 1H, 13C and 119Sn NMR spec-
troscopy. The structures of 1−3 have been determined by X-
ray crystallography. Complexes 1 and 2 display a unique
tricyclic structure consisting of fused five-membered Sn2ON2
and four-membered Sn2O2 rings that form a planar N2Sn3O2
skeleton, with a distorted trigonal bipyramidal coordination
at tin. Complex 3 is a pentanuclear 35-membered tin macro-
cycle containing the crown thioether-type ligand in which all
five tin atoms bond to the sulfur and nitrogen atoms with
distorted octahedral geometries. The structures of complexes
1 and 3 are stabilized by hydrogen bonds or intermolecular
non-bonding S···S interactions.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
of H2dmt, with four available donors all of which can be
utilized in bonding in varying combinations, as shown in
Scheme 1),[12] may act as a fulcrum about which lattice con-
struction is orchestrated in two or more dimensions.
Recent developments in coordination chemistry have pro-
duced numerous supermolecular and macrocyclic com-
plexes through the appropriate combination of organomet-
allic complexes and various organic ligands.[1Ϫ6] Organotin
macrocycles are attracting more and more attention for
their potential industrial applications and biological activi-
ties.[7,8] In these metallomacrocyclic systems, ligands with
multiply coordinating donor atoms and particular stereo-
chemistry may lead to different specific architectures. Het-
erocyclic thionate ligands,[5] which contain at least one de-
protonated heterocyclic thioamide group (NϪCϪS)Ϫ and
can act as monodentate, chelating or bridging ligands are
particularly important.[9] In our previous work, we studied
the ligand 2-mercaptonicotinic acid (Hmnc), which pos-
sesses one deprotonated heterocyclic thioamide group
(NϪCϪS)Ϫ, and found that the primary bond of the ligand
to the tin atoms occurs through sulfur rather than through
nitrogen. Moreover, different coordination patterns of the
ligand in the thiolic form have been found.[10,11]
Scheme 1. Tautomeric forms of H2dmt
In our previous work we reported a pentanuclear tin
macrocycle[13] in which the coordination of H2dmt is
through two sulfur atoms of the thiol (a) rather than the
thione (c) tautomer. While continuing our research on other
diorganotin complexes of H2dmt, we surprisingly obtained
four novel complexes [(C2S3N2)(CH3)6Sn3O(OH)2]·1.5H2O
(1), [(C2S3N2){(PhCH2)6Sn3O(OH)(OEt)}] (2) [(CH3)2Sn-
To continue our study in this field, we chose another li-
gand: 2,5-dimercapto-1,3,4-thiadiazole (H2dmt), which pos-
sesses a more complex deprotonated heterocyclic thioamide
group (SϪCϪNϪNϪCϪS)2Ϫ than Hmnc. The heterocycle
(C2N2S3)]5·CH2Cl2·3H2O
(3)
and
[(PhCH2)2ClSn-
(SϪC2SN2ϪS)SnCl(PhCH2)2] (4). It is worthwhile to note
that complexes 1 and 3 were obtained by the same reactants
in different solvents, and the complexes 2 and 4 were ob-
tained by the same reactants in different solvents, too, and
that H2dmt shows different coordination to the tin()
atom. All four complexes 1Ϫ4 were characterized by
[a]
Department of Chemistry, Liaocheng University,
Liaocheng 252059, P. R. China
Fax: ϩ86-538-671-5521
E-mail: macl@lctu.edu.cn
[b]
Department of Chemistry, Taishan University,
1
Taian 271021, P. R. China
elemental analysis and IR, H, 13C and 119Sn NMR spec-
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783
DOI: 10.1002/ejic.200300860
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2775

C. Ma, J. Zhang, F. Li, R. Zhang
FULL PAPER
troscopy and the structures of 1, 2 and 3 were determined of the R groups, the more difficult the substitution of the
by X-ray crystallography.
chlorine atoms.[16]
Description of the Structures
[(C2S3N2)(CH3)6Sn3O(OH)2]·1.5H2O (1) and
[(C2S3N2)(PhCH2)6Sn3O(OH)(OEt)] (2)
Results and Discussion
The molecular structures and unit cells of complexes 1
(Figure 1 and 2) and 2 (Figure 3 and 4) are shown below;
selected bond lengths and angles are collected in Table 1
and 2, respectively. Like other trinuclear organotin oxo clus-
ters,[17] complex 1 contains a tricyclic system formed by an
N2Sn2O ring and two Sn2O2 rings, in which the
N2Sn3O(OH)2 structural motif is almost planar with a
Complexes 1Ϫ4 were prepared by the reaction of dimeth-
yltin dichloride or dibenzyltin dichloride with 2,5-dimer-
capto-1,3,4-thiadiazole in either EtOH (95%) or CH2Cl2.
The reaction procedures are shown in Scheme 2.
˚
mean deviation of Ϯ0.0452 A. All three tin atoms show
severely distorted trigonal bipyramidal configurations.
Scheme 2
When the reaction solvent is EtOH (95%), the complexes
1 and 2 were obtained. In view of the results of our present
studies[10,14] and those of earlier work,[15] the possible
mechanism of formation of complexes 1 and 2 is as follows.
Firstly, a hydrolysis reaction of R2SnCl2 occurs to form
R2(Cl)Sn(OH), which is then further hydrolyzed to produce
[R2(OH)SnY] (Y ϭ OH or OEt). Two R2(Cl)Sn(OH) mol-
ecules then condense to form [R2(Cl)Sn]2O, which then re-
acts with [R2(OH)SnY] to produce [R6Sn3O(Cl)2(OH)Y].[14]
Finally, the two chlorine atoms of [R6Sn3O(Cl)2(OH)Y] are
substituted by two nitrogen atoms of the sodium salt of
H2dmt [Na2(C2N2S3)] to produce the title complexes 1 and
2. As shown in Scheme 2, the H2dmt acts as tautomer c,
bonding to tin() through two nitrogen atoms in both com-
plexes 1 and 2.
Figure 1. Molecular structure of complex 1; ellipsoids at 30% prob-
ability
When the reaction solvent was replaced by CH2Cl2 we
obtained complexes 3 and 4. In this case the hydrolysis of
R2SnCl2 does not occur and the ligand coordinates to the
tin() center, through two sulfur atoms, as the thiol tau-
tomer (a).
Moreover, in complex 4, the spatial resistances of two
benzyl groups are strong enough to prevent another H2dmt
ligand chelating to the central tin atom, which is well con-
sistent with the sequence of steric constraints phenyl ഠ
benzyl Ͼ n-butyl Ͼ methyl: the larger the steric constraint Figure 2. Unit cell of complex 1
2776  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783

Diorganotin Derivatives of 2,5-Dimercapto-1,3,4-thiadiazole
FULL PAPER
Figure 3. Molecular structure of complex 2; ellipsoids at 30% probability
Sn(1) and Sn(3) have the same environment, where one µ3-
O atom and two C atoms of the methyl groups occupy the
equatorial positions [C(3), C(4) and O(2) for Sn(1); C(7),
C(8) and O(2) for Sn(3)], and the axial positions are occu-
pied by one N atom of the H2dmt and one O atom of the
hydroxyl group [N(1) and O(1) for Sn(1); N(2) and O(3) for
Sn(3)]. The geometry of Sn(2) is cis-R2SnO3, in which the
axial positions are occupied by the O(3) and O(1) atoms of
hydroxyl groups, and two C(5) and C(6) atoms of methyl
groups and one µ3-O(2) atom occupy the equatorial plane.
The distortion of the axial angles is very large at the three
tin atoms [O(1)ϪSn(1)ϪN(1) 150.4(2)°, O(3)ϪSn(3)ϪN(2)
150.0(2)° and O(3)ϪSn(2)ϪO(1) 144.1(2)° respectively]
compared to the ideal angle of 180°.
With regard to the hydrolysis, three [(CH3)2Sn] units are
bridged by one µ3-O atom and two O atoms of hydroxyl
groups, and thus form a trinuclear complex containing two
Sn2O2 rings. Three Sn atoms and three O atoms [Sn(1),
Sn(3), O(2), Sn(2), O(1), O(3)] comprise a fused ring system
and are nearly coplanar, with a mean deviation of Ϯ0.0326
˚
Figure 4. Unit cell of complex 2
A, which is similar to traditional hydrolytic products with a
ladder-type arrangement,[18] but different from the staircase
structure of [Me4Sn2(OSiMe3)2O]2.[19] The SnϪO distances
between µ3-O atom and the tin atoms are similar
˚
˚
[Sn(3)ϪO(2) 2.037(5) A, Sn(2)ϪO(2) 2.051(5) A and the two rings is 1.2°, which indicates that all the atoms of
˚
Sn(1)ϪO(2) 2.032 (5) A], but other SnϪO lengths between the two rings are almost planar. The SnϪN bond lengths
˚
˚
the O atoms of the hydroxyl and the tin atoms [Sn(1)ϪO(1) [Sn(1)ϪN(1) 2.274(6) A and Sn(3)ϪN(2) 2.246(7) A] are
˚
˚
˚
2.150(5) A, Sn(2)ϪO(1) 2.106(5) A, Sn(2)ϪO(3) 2.094(6) A, similar to the sum of the covalent radii of Sn and N (2.15
˚
˚
Sn(3)ϪO(3) 2.129(6) A] are slightly longer, and similar to A) and much shorter than the sum of the van der Waals
[21]
˚
the SnϪO bonds in the ladder structure [Me2Cl- radii of tin and nitrogen atoms (3.74 A),
which proves
[20]
˚
SnOSnMe2Cl]2 [2.115(9) A].
All of the above indicates that the nitrogen atoms coordinate to tin by strong chemical
that a strong oxo bridge exists in complex 1.
The two nitrogen atoms of the H2dmt ligand, which is a A, S(3)ϪC(2) 1.668(10) A] are similar to those in thiourea
five-membered ring, bond to tin atoms to form another (1.681 A),
bonds. Furthermore, the CϪS bonds [S(2)ϪC(1) 1.701(10)
˚
˚
[22]
˚
suggesting that they are CϭS double bonds
five-membered N2Sn2O ring. The dihedral angle between and therefore retain the thione form. All of above proves
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783
www.eurjic.org  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2777

C. Ma, J. Zhang, F. Li, R. Zhang
FULL PAPER
[a]
˚
˚
Table 1. Selected bond lengths (A) and angles (°) for 1
Table 2. Selected bond lengths (A) and angles (°) for 2
Sn(1)ϪO(2)[a]
Sn(1)ϪC(4)
Sn(1)ϪC(3)
Sn(1)ϪO(1)
Sn(1)ϪN(1)
Sn(2)ϪO(2)
Sn(2)ϪC(6)
Sn(2)ϪO(3)
Sn(2)ϪO(1)
Sn(2)ϪC(5)
N(1)ϪC(1)
N(1)ϪN(2)
N(2)ϪC(2)
2.032(5)
2.079(8)
2.096(9)
2.150(5)
2.274(6)
2.051(5)
2.075(10)
2.094(6)
2.106(5)
2.121(10)
1.325(9)
1.388(8)
1.330(9)
Sn(3)ϪO(2)
Sn(3)ϪC(8)
Sn(3)ϪC(7)
Sn(3)ϪO(3)
Sn(3)ϪN(2)
S(1)ϪC(1)
S(1)ϪC(2)
S(2)ϪC(1)
S(3)ϪC(2)
O(1)···S(2)i
O(3)···S(3)ii
O(4)···O(5)iii
S(3)···S(3)
2.037(5)
Sn(1)ϪO(1)
Sn(1)ϪO(2)
Sn(1)ϪC(10)
Sn(1)ϪC(3)
Sn(1)ϪN(1)
Sn(3)ϪO(1)
Sn(3)ϪO(3)
Sn(3)ϪO(2)
Sn(3)ϪC(38)
Sn(3)ϪC(31)
N(1)ϪC(1)
2.047(5)
2.186(6)
2.170(8)
2.136(9)
2.224(7)
2.053(5)
2.137(6)
2.139(6)
Sn(2)ϪO(1)
Sn(2)ϪO(3)
Sn(2)ϪC(24)
Sn(2)ϪC(17)
Sn(2)ϪN(2)
S(1)ϪC(2)
2.054(5)
2.223(6)
2.143(9)
2.134(9)
2.230(7)
1.747(10)
1.755(9)
1.672(10)
1.687(9)
1.317(10)
1.389(9)
2.104(10)
2.107(10)
2.129(6)
2.246(7)
1.714(9)
1.743(10)
1.701(10)
1.668(10)
3.178
S(1)ϪC(1)
S(2)ϪC(1)
2.163(12) S(3)ϪC(2)
2.127(11) N(2)ϪC(2)
1.333(11) N(1)ϪN(2)
3.206
2.085
3.274
C(3)ϪSn(1)ϪC(10)
O(1)ϪSn(1)ϪC(3)
O(1)ϪSn(1)ϪC(10)
O(2)ϪSn(1)ϪC(3)
O(2)ϪSn(1)ϪC(10)
O(1)ϪSn(1)ϪO(2)
O(1)ϪSn(1)ϪN(1)
O(2)ϪSn(1)ϪN(1)
C(3)ϪSn(1)ϪN(1)
C(10)ϪSn(1)ϪN(1)
134.8(4)
112.8(3)
112.2(3)
96.7(3)
93.5(3)
71.7(2)
79.4(2)
151.1(2)
94.1(3)
97.7(3)
C(17)ϪSn(2)ϪC(24) 130.6(4)
O(1)ϪSn(2)ϪC(17)
O(1)ϪSn(2)ϪC(24)
O(3)ϪSn(2)ϪC(17)
O(3)ϪSn(2)ϪC(24)
O(1)ϪSn(2)ϪO(3)
O(1)ϪSn(2)ϪN(2)
O(3)ϪSn(2)ϪN(2)
C(17)ϪSn(2)ϪN(2)
C(24)ϪSn(2)ϪN(2)
Sn(2)ϪO(1)ϪSn(3)
Sn(2)ϪO(3)ϪSn(3)
Sn(1)ϪO(1)ϪSn(2)
Sn(1)ϪN(1)ϪN(2)
Sn(2)ϪN(2)ϪN(1)
N(2)ϪN(1)ϪC(1)
N(1)ϪN(2)ϪC(2)
N(1)ϪC(1)ϪS(2)
N(2)ϪC(2)ϪS(3)
C(1)ϪS(1)ϪC(2)
114.1(3)
115.0(3)
94.2(3)
96.0(3)
71.3(2)
79.5(2)
150.9(2)
98.7(3)
O(2)ϪSn(1)ϪC(4) 113.8(3)
O(2)ϪSn(1)ϪC(3) 111.0(3)
C(4)ϪSn(1)ϪC(3) 135.2(4)
O(2)ϪSn(1)ϪO(1)
C(4)ϪSn(1)ϪO(1)
C(3)ϪSn(1)ϪO(1)
O(2)ϪSn(1)ϪN(1)
C(4)ϪSn(1)ϪN(1)
C(3)ϪSn(1)ϪN(1)
O(1)ϪSn(1)ϪN(1) 150.4(2)
O(2)ϪSn(2)ϪC(6) 116.6(4)
O(2)ϪSn(2)ϪO(3)
C(6)ϪSn(2)ϪO(3)
O(2)ϪSn(2)ϪO(1)
C(6)ϪSn(2)ϪO(1)
O(3)ϪSn(2)ϪO(1) 144.1(2)
O(2)ϪSn(2)ϪC(5) 117.4(3)
C(6)ϪSn(2)ϪC(5) 126.0(5)
O(3)ϪSn(2)ϪC(5)
O(1)ϪSn(2)ϪC(5)
C(1)ϪN(1)ϪN(2)
O(1)ϪH(1)···S(2)i
O(2)ϪSn(3)ϪC(8)
O(2)ϪSn(3)ϪC(7)
C(8)ϪSn(3)ϪC(7)
112.7(3)
112.8(3)
134.3(4)
71.3(2)
96.5(4)
93.7(4)
78.8(2)
97.3(4)
95.5(4)
150.0(2)
125.5(6)
71.77(18) O(2)ϪSn(3)ϪO(3)
94.0(3)
97.6(3)
78.8(2)
95.2(3)
95.6(3)
C(8)ϪSn(3)ϪO(3)
C(7)ϪSn(3)ϪO(3)
O(2)ϪSn(3)ϪN(2)
C(8)ϪSn(3)ϪN(2)
C(7)ϪSn(3)ϪN(2)
O(3)ϪSn(3)ϪN(2)
C(1)ϪN(1)ϪSn(1)
95.3(3)
C(38)ϪSn(3)ϪC(31) 125.0(5)
112.4(2)
103.0(3)
135.6(3)
123.3(5)
122.2(5)
114.8(7)
114.3(7)
124.6(7)
124.8(7)
90.6(4)
O(1)ϪSn(3)ϪO(2)
O(1)ϪSn(3)ϪO(3)
O(2)ϪSn(3)ϪO(3)
C(38)ϪSn(3)ϪO(2)
C(38)ϪSn(3)ϪO(1)
C(38)ϪSn(3)ϪO(3)
C(31)ϪSn(3)ϪO(1)
C(31)ϪSn(3)ϪO(3)
C(31)ϪSn(3)ϪO(2)
72.7(2)
73.2(2)
145.9(2)
100.0(3)
119.8(4)
97.5(3)
115.2(4)
97.4(4)
96.3(4)
71.8(2)
99.1(4)
N(2)ϪN(1)ϪSn(1) 121.4(5)
C(2)ϪN(2)ϪN(1)
115.1(7)
121.8(6)
72.32(18) C(2)ϪN(2)ϪSn(3)
98.6(3)
N(1)ϪN(2)ϪSn(3) 123.1(5)
Sn(2)ϪO(1)ϪSn(1) 104.64(19)
Sn(1)ϪO(2)ϪSn(3) 138.0(3)
Sn(1)ϪO(2)ϪSn(2) 111.2(2)
Sn(3)ϪO(2)ϪSn(2) 110.9(2)
Sn(2)ϪO(3)ϪSn(3) 105.7(2)
O(4)ϪH(3)···O(5)iii 124.44
97.0(4)
97.5(3)
113.1(7)
174.32
O(3)ϪH(2)···S(3)ii
158.81
˚
˚
[from 2.047 A to 2.224(6) A] are all similar to those found
in complex 1, which indicates that the (PhCH2)2SnCl2 was
also hydrolyzed and the ligand coordinates to tin()
through two nitrogen atoms as the tautomer c. The differ-
ence between complexes 1 and 2 lies in the co-ligands
formed during the hydrolysis reaction. As shown in Fig-
ure 1 and 3 the products of the hydrolysis reaction are
[a]
Symmetry transformations used to generate equivalent atoms:
(i) x, Ϫy, z ϩ 1/2; (ii) Ϫx ϩ 1/2, y, z ϩ 1/2; (iii) Ϫx ϩ 1, y, Ϫz ϩ
3/2.
indirectly that H2dmt bonds to tin as the nitrogen tautomer
c and not the sulfur tautomer.
As can be seen in Figure 2, molecules of 1 are joined
into a network of 2D dimers in a head-to-tail fashion by
intermolecular hydrogen bonds. Each monomeric unit
forms two weak hydrogen bonds between the O atom of the
hydroxyl and the uncoordinated S atom of a neighboring
[(CH3)2Sn(OH)2] for complex
1 and [(PhCH2)2Sn(O-
H)(OEt)] for complex 2, respectively. Such a difference may
be due to the larger steric constraints of PhCH2 groups
than CH3.
[(CH3)2Sn(C2N2S3)]5·CH2Cl2·3H2O (3)
˚
˚
molecule of H2dmt [O(1)ϪH(1) 0.897 A, H···S(2) 2.302 A,
O(1)···S(2) 3.178, O(1)ϪH(1)···S(2) 174.32°; O(3)ϪH(2)
The molecular structure and unit cell of complex 3 are
˚
˚
˚
0.886 A, H···S(3) 2.364 A, O(3)···S(3) 3.206 A, shown in Figure 5 and 6, respectively; Figure 7 shows the
O(3)ϪH(2)···S(3) 158.81°]. Moreover, S···S weak intermo- crystal structure of the same component with all co-crys-
lecular non-bonding interactions also help to stabilize the tallized solvent molecules omitted. Selected bond lengths
˚
structure. The S(3)···S(3) distance of 3.274 A is significantly and angles are listed in Table 3.
shorter than the sum of the van der Waals radii of two
As shown in Figure 5, the coordination of H2dmt in com-
sulfur atoms (3.7 A).[23] Therefore in these two cases hydro- plex 3 is different from that in complex 1, but is similar
gen bonds and intermolecular non-bonding interactions to our previously reported complex (Bu2SnC2N2S3)5;[13] the
lead to aggregation and formation of a supramolecular as- ligand is found as the thiol tautomer a when bonded to
˚
sembly.[24]
tin. The pentanuclear tin complex is characterized by a 35-
The tin environment in complex 2 is the same as that of membered C10S10N10Sn5 macrocycle ring system with all
˚
complex 1. The SnϪN distance [Sn(1)ϪN(1) 2.224(7) A, ten sulfur atoms pointing to the exterior of the cavity,
Sn(2)ϪN(2) 2.230(7) A], the CϪS bonds [S(2)ϪC(1) thereby acting as a crown thioether.[25] All five tin atoms
˚
˚
˚
1.673(9) A, S(3)ϪC(2) 1.688(9) A] and the SnϪO distance have the same arrangement — they are hexacoordinate with
2778
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org Eur. J. Inorg. Chem. 2004, 2775Ϫ2783

Diorganotin Derivatives of 2,5-Dimercapto-1,3,4-thiadiazole
FULL PAPER
Figure 5. Molecular structure of complex 3; ellipsoids at 30% prob-
ability
Figure 7. Molecular structure of complex 3 (all solvent molecules
omitted)
˚
chemical bonds. The average SnϪN bond length (2.778 A)
is much longer than that in complex 1, but is similar to the
˚
SnǟN (2.787 A) intermolecular bond found in the trimeric
[Me3SnSCN4Ph]3 unit.[29] All the SnϪN distances are mid-
way between the covalent radii and the sums of the van der
[21]
˚
Waals of Sn and N (2.15 and 3.74 A)
and can be re-
garded as weak coordination bonds. Thus the coordination
number of the tin atom is increased to six through SnǟN
intermolecular bonds. All above information suggests that
the primary bonds of the H2dmt ligand to tin atoms are
through sulfur atoms with the ligand appearing as the thiol
tautomer a. This situation is similar to that in the reported
complex (Bu2SnC2N2S3)5.[13]
Figure 6. Unit cell of complex 3
The CϪS bond lengths are in the range from 1.695 to
˚
˚
1.750 A with an average value of 1.723 A for the chelating
˚
distorted octahedral geometries. Two sulfur atoms and two ligands, similar to the CϪS single bond (1.724 A) in tri-
carbon atoms occupy the equatorial positions and the axial phenyltin benzoxazole-2-thiolate,[30] thereby confirming the
positions are occupied by two azole-N atoms. The deviation above proposal.
from an ideal octahedron is manifested by the bond angles
It is worthwhile to note that the critical cross-ring in-
˚
N(1)ϪSn(1)ϪN(10)
[149.5(2)°],
N(2)ϪSn(2)ϪN(3) teratomic distances of the cavity are 10.904 A [N(1)···Sn(4)]
˚
[148.7(2)°], N(4)ϪSn(3)ϪN(5) [150.3(2)°], N(6)ϪSn(4)Ϫ and 10.897 A [N(4)···Sn(5)], which are larger than those
N(7) [147.0(3)°] and N(8)ϪSn(5)ϪN(9) [149.0(2)°], all of found in dimethyl- and di-n-butyltin() complexes with
which deviate from the ideal value of 180°.
phthalic and isophthalic acid.[8] Furthermore, as shown in
˚
˚
The Sn···S (from 2.483 A to 2.502 A) and Sn···N dis- Figure 5, there are weak intermolecular non-bonding S···S
˚
˚
tances (from 2.701 A to 2.890 A) are similar to those in the interactions between the coordinated S atom and the unco-
˚
reported complex (Bu2SnC2N2S3)5 (average value: 2.494 A ordinated S atom of the neighboring ligand. The S···S dis-
[13]
˚
and 2.762 A, respectively). The longest SnϪS distance is tances [S(1)···S(8) 3.489 and S(9)···S(15) 3.449] are all
slightly longer than the sum of the covalent radii of Sn and shorter than the sum of the Van der Waals radii of two
[26]
[23]
˚
˚
S
(2.44 A),
but consistent with SnϪS in sulfur atoms (3.7 A),
which indicate that these intermo-
[27]
˚
tBu2Sn(S2CNEt2)2 (2.554 A),
and is much shorter than lecular non-bonding interactions lend the crystal stability
[28]
˚
the sum of the van der waals radii of 4.0 A. This proves and compactness and result in a one-dimensional supra-
that the sulfur atoms coordinate to the tin atoms by strong molecular polymers arrangement.[5]
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2779

C. Ma, J. Zhang, F. Li, R. Zhang
FULL PAPER
˚
Spectroscopic Data
Table 3. Selected bond lengths (A) and angles (°) for 3
Sn(1)ϪC(11)
Sn(1)ϪC(12)
Sn(1)ϪS(15)
Sn(1)ϪS(2)
Sn(1)ϪN(10)
Sn(1)ϪN(1)
Sn(2)ϪC(13)
Sn(2)ϪC(14)
Sn(2)ϪS(3)
Sn(2)ϪS(5)
Sn(2)ϪN(3)
Sn(2)ϪN(2)
Sn(3)ϪC(15)
Sn(3)ϪC(16)
Sn(3)ϪS(8)
Sn(3)ϪS(6)
Sn(3)ϪN(4)
Sn(3)ϪN(5)
N(1)ϪC(1)
N(1)ϪN(2)
N(2)ϪC(2)
N(3)ϪC(3)
N(3)ϪN(4)
N(4)ϪC(4)
N(5)ϪC(5)
N(5)ϪN(6)
N(6)ϪC(6)
N(7)ϪC(7)
N(7)ϪN(8)
N(8)ϪC(8)
N(9)ϪC(9)
N(9)ϪN(10)
N(10)ϪC(10)
S(1)···S(8)
2.086(11)
2.090(10)
2.484(3)
2.487(3)
2.722(8)
2.890(8)
2.092(9)
2.124(9)
2.483(3)
2.495(3)
2.777(8)
2.781(8)
2.088(9)
2.140(9)
2.492(3)
2.502(3)
2.701(8)
2.835(8)
1.293(10)
1.373(9)
1.280(10)
1.297(10)
1.330(9)
1.310(10)
1.319(10)
1.371(9)
1.327(10)
1.332(10)
1.377(9)
1.303(10)
1.290(10)
1.357(9)
1.283(10)
3.489
Sn(4)ϪC(18)
Sn(4)ϪC(17)
Sn(4)ϪS(11)
Sn(4)ϪS(9)
Sn(4)ϪN(7)
Sn(4)ϪN(6)
Sn(5)ϪC(19)
Sn(5)ϪC(20)
Sn(5)ϪS(14)
Sn(5)ϪS(12)
Sn(5)ϪN(9)
Sn(5)ϪN(8)
S(1)ϪC(2)
S(1)ϪC(1)
S(2)ϪC(1)
S(3)ϪC(2)
S(4)ϪC(3)
S(4)ϪC(4)
S(5)ϪC(3)
S(6)ϪC(4)
S(7)ϪC(6)
2.116(9)
2.117(9)
2.492(3)
2.500(3)
2.727(8)
2.770(8)
2.098(9)
2.109(9)
2.489(3)
2.495(3)
2.780(8)
2.797(8)
1.735(9)
1.743(9)
1.742(9)
1.733(9)
1.695(10)
1.719(10)
1.745(10)
1.729(11)
1.707(10)
1.727(10)
1.730(10)
1.715(10)
1.724(9)
1.726(9)
1.715(9)
1.747(9)
1.723(10)
1.727(9)
1.728(10)
1.750(10)
2.361
IR Spectra
The strong broad bands in the IR spectra of complexes
1Ϫ3 in the region 3440Ϫ3000 can be attributed to the OϪH
stretching vibration.
A
medium-strength band of
δ(HϪOϪH) is also present at about 1650 cmϪ1 in com-
plexes 1 and 3; the strong absorption at 1286 cmϪ1 in com-
plex 2 is attributed to the CϪO vibration of the EtO group.
The main feature in the infrared spectra of complexes 1Ϫ4
is the absence of a band in the region 2550Ϫ2430 cmϪ1
,
which appear in the free ligand as the ν(SϪH) vibration. In
complexes 1 and 2, the absorption at 1210 cmϪ1 is assigned
to the CϭS vibration[31] and the new medium-strength
band at 445 cmϪ1 for 1 and 480 cmϪ1 for 2 is assigned
to the SnϪN stretching,[32] both of which indicate that the
(dmt)2Ϫ coordinates to tin through its nitrogen atoms as
tautomer c. The strong absorptions at 597 cmϪ1 for 1 and
627 cmϪ1 for 2 are assigned to SnϪOϪSn stretching. In the
far-infrared spectra a strong absorption at 317 cmϪ1 for 3
and 321 cmϪ1 for 4, which are absent in the spectrum of
the ligand, are assigned to the SnϪS stretching vibration.
These values are consistent with those reported for a num-
ber of organotin() sulfur derivatives.[16,33] The ν(SnϪCl)
absorption at 277 cmϪ1 in complex 4 is close to that found
in trichloromethylbis(imidazole)tin·H2O (275 cmϪ1).[34] The
middle-intensity bands observed at 1635 cmϪ1 in complexes
3 and 4 are assignable to ν(CϭN) according to the litera-
ture,[35] which suggests that the coordination of dmt to tin
is through the sulfur atoms of the thiol tautomer a, as re-
ported previously.[36]
S(7)ϪC(5)
S(8)ϪC(5)
S(9)ϪC(6)
S(10)ϪC(7)
S(10)ϪC(8)
S(11)ϪC(7)
S(12)ϪC(8)
S(13)ϪC(9)
S(13)ϪC(10)
S(14)ϪC(9)
S(15)ϪC(10)
O(2)···O(3)
S(9)···S(15)
3.449
C(11)ϪSn(1)ϪC(12)
C(11)ϪSn(1)ϪS(15)
C(12)ϪSn(1)ϪS(15)
C(11)ϪSn(1)ϪS(2)
C(12)ϪSn(1)ϪS(2)
S(15)ϪSn(1)ϪS(2)
C(11)ϪSn(1)ϪN(10)
C(12)ϪSn(1)ϪN(10)
S(15)ϪSn(1)ϪN(10)
S(2)ϪSn(1)ϪN(10)
C(11)ϪSn(1)ϪN(1)
C(12)ϪSn(1)ϪN(1)
S(15)ϪSn(1)ϪN(1)
S(2)ϪSn(1)ϪN(1)
N(10)ϪSn(1)ϪN(1)
C(13)ϪSn(2)ϪC(14)
C(13)ϪSn(2)ϪS(3)
C(13)ϪSn(2)ϪS(5)
C(14)ϪSn(2)ϪS(5)
S(3)ϪSn(2)ϪS(5)
C(13)ϪSn(2)ϪN(3)
C(14)ϪSn(2)ϪN(3)
S(3)ϪSn(2)ϪN(3)
S(5)ϪSn(2)ϪN(3)
C(13)ϪSn(2)ϪN(2)
C(14)ϪSn(2)ϪN(2)
S(3)ϪSn(2)ϪN(2)
S(3)ϪSn(2)ϪN(2)
S(5)ϪSn(2)ϪN(2)
N(3)ϪSn(2)ϪN(2)
C(15)ϪSn(3)ϪC(16)
C(15)ϪSn(3)ϪS(8)
C(16)ϪSn(3)ϪS(8)
C(15)ϪSn(3)ϪS(6)
C(16)ϪSn(3)ϪS(6)
S(8)ϪSn(3)ϪS(6)
128.8(5)
107.3(3)
110.3(3)
105.7(3)
108.2(3)
89.37(10)
85.9(4)
N(4)ϪSn(3)ϪN(5)
S(6)ϪSn(3)ϪN(5)
S(8)ϪSn(3)ϪN(5)
C(16)ϪSn(3)ϪN(5)
C(15)ϪSn(3)ϪN(5)
S(6)ϪSn(3)ϪN(4)
S(8)ϪSn(3)ϪN(4)
C(18)ϪSn(4)ϪC(17)
C(18)ϪSn(4)ϪS(11)
C(17)ϪSn(4)ϪS(11)
C(18)ϪSn(4)ϪS(9)
C(17)ϪSn(4)ϪS(9)
S(11)ϪSn(4)ϪS(9)
C(18)ϪSn(4)ϪN(7)
C(17)ϪSn(4)ϪN(7)
S(11)ϪSn(4)ϪN(7)
S(9)ϪSn(4)ϪN(7)
C(18)ϪSn(4)ϪN(6)
C(17)ϪSn(4)ϪN(6)
S(11)ϪSn(4)ϪN(6)
S(9)ϪSn(4)ϪN(6)
N(7)ϪSn(4)ϪN(6)
C(19)ϪSn(5)ϪC(20)
C(19)ϪSn(5)ϪS(14)
C(20)ϪSn(5)ϪS(14)
C(19)ϪSn(5)ϪS(12)
C(20)ϪSn(5)ϪS(12)
S(14)ϪSn(5)ϪS(12)
C(19)ϪSn(5)ϪN(9)
C(20)ϪSn(5)ϪN(9)
S(12)ϪSn(5)ϪN(9)
S(14)ϪSn(5)ϪN(9)
C(19)ϪSn(5)ϪN(8)
C(20)ϪSn(5)ϪN(8)
S(12)ϪSn(5)ϪN(8)
S(14)ϪSn(5)ϪN(8)
N(9)ϪSn(5)ϪN(8)
150.3(2)
148.06(18)
59.96(18)
81.7(3)
85.1(3)
61.57(18)
149.64(18)
130.0(4)
105.8(3)
109.2(3)
107.8(3)
105.5(3)
91.99(9)
83.8(3)
NMR Spectra
82.8(3)
1
In the H NMR spectra of complexes 1Ϫ4 the signal at
61.37(19)
150.70(19)
88.3(3)
δ ϭ 1.6 ppm for the -SH protons of the ligand are absent,
thus demonstrating that the ligand is deprotonated.
In the 13C NMR spectra of complexes 1Ϫ4 the chemical
shifts of the signals are quite similar to those of the parent
ligand. Only a shift in the positions of two carbon atoms in
the deprotonated group (SϪCϪNϪNϪCϪS)2Ϫ of H2dmt
are seen; these data reflect the differences between the thiol-
C and thione-C atoms. The thiol-to-thione evolution is re-
sponsible for the marked deshielding of thione-C,[37] which
further proves that the coordination between complexes 1,
2 and 3, 4.
77.7(3)
148.08(17)
59.24(16)
149.5(2)
127.0(4)
108.2(3)
107.0(3)
108.9(3)
91.18(9)
86.6(3)
83.1(3)
61.01(19)
152.89(19)
81.6(3)
83.9(3)
151.85(19)
60.10(19)
147.0(3)
129.1(4)
109.8(3)
106.0(3)
105.1(3)
109.4(3)
90.75(9)
83.0(3)
79.2(3)
150.79(17)
60.01(17)
81.2(3)
For the methyl derivatives 1 and 3, substitution of the
2J
(83.2 and 78.1 Hz, respectively) and J119
val-
1
13
119Sn,1
Sn,
C
85.4(3)
60.27(17)
60.27(17)
151.25(18)
148.7(2)
133.5(4)
104.5(3)
106.7(3)
108.8(3)
105.7(3)
88.39(10)
82.9(3)
ues (618.4 and 595.0 Hz, respectively) into the correspond-
ing LockhartϪManders equations[38] (empirical relation-
ship between the coupling constants and the CϪSnϪC an-
gle) gives CϪSnϪC angles of 135.0° and 131.5° for complex
1 and 128.5° and 129.0° for complex 3. These values indi-
cate that the data are reliable.
84.9(3)
150.45(18)
60.03(18)
80.6(3)
85.3(3)
The 119Sn chemical shifts of tin complexes appear to de-
pend not only on coordination number, but also on the type
of donor atoms bonded to the metal ion.[39] As reported in
the literature,[40] chemical shifts in the range δ ϭ Ϫ210 to
60.11(18)
150.85(18)
149.0(2)
C(15)ϪSn(3)ϪN(4)
C(16)ϪSn(3)ϪN(4)
87.1(3)
2780
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783

Diorganotin Derivatives of 2,5-Dimercapto-1,3,4-thiadiazole
FULL PAPER
(CDCl3): δ ϭ Ϫ179.6 ppm. C46H48N2O3S3Sn3 (1129.1): calcd. C
48.93, H 4.29, N 2.48; found C 48.82, H 4.28, N 2.50.
Ϫ400 ppm, Ϫ90 to Ϫ190 ppm and 200 to Ϫ60 ppm have
been associated with six-, five- and four-coordinate tin cen-
ters, respectively. The value of δ ϭ Ϫ121.2 ppm for complex
1, δ ϭ Ϫ179.6 ppm for 2 and δ ϭ Ϫ187.8 ppm for 4 are
within the range expected for five-coordinate complexes.
The chemical shift for complex 3 in CDCl3 indicates a
change to a lower coordination than in the solid state, as
the value of δ ϭ Ϫ83.6 ppm seems to indicate tetracoordi-
nation (Me2S2)[41] instead of hexacoordination. This change
could be explained by the rupture of the weak SnϪN bonds
in solution, these bonds being longer than those in other
previously published complexes with S,N ligands.[42]
[(CH3)2Sn(C2N2S3)]5·CH2Cl2·3H2O (3): The reaction was carried
out under nitrogen atmosphere with use of standard Schlenk tech-
niques. H2dmt (0.30 g, 2 mmol) was added to a solution of di-
chloromethane (40 mL) and sodium ethoxide (0.272 g, 4 mmol),
and the mixture was stirred for 30 minutes. (CH3)2SnCl2 (0.439 g,
2 mmol) was then added to the mixture, continuing the reaction for
16 h at 30 °C. After cooling to room temperature the mixture was
filtered. The solvent of the filtrate was gradually removed by evap-
oration under vacuum until a solid product was obtained. The solid
was then recrystallized from dichloromethane/ethanol (95%) to give
colorless crystals of 3. Yield, 72%. m.p. Ͼ 240 °C (dec.). IR (KBr):
ν˜ ϭ 3430 (s, OϪH), 2923 (m, CϪH), 1635 (m, CϭN), 701 (s, CϪS),
563 (m, SnϪC), 317 (m, SnϪS) cmϪ1. 1H NMR (CDCl3/D2O): δ ϭ
Experimental Section
2
0.95 [t, 30 H, CH3, J
ϭ 78.1 Hz] ppm. 13C NMR (CDCl3):
119Sn,1
δ ϭ 168.0 (C-1), 168.0 (C-1Ј), 5.8 [CH3, 1J119
ϭ 595.0 Hz].
13
Sn,
C
Materials and Methods: Dimethyltin dichloride (Aldrich) and 2,5-
dimercapto-1,3,4-thiadiazole (H2dmt) were used as received. Di-
benzyltin dichloride was prepared by a standard method reported
in the literature.[43] The melting points were obtained with a Kofler
micro melting point apparatus and are uncorrected. IR spectra
were recorded on a Nicolet-460 spectrophotometer using KBr discs
and sodium chloride optics. 1H, 13C and 119Sn spectra were re-
corded on a Bruker AMX-300 spectrometer operating at 300, 75.3
and 111.9 MHz, respectively. The spectra were acquired at room
temperature (298 K) unless otherwise specified; 13C spectra are
broadband proton decoupled. The chemical shifts are reported in
ppm with respect to the references (external tetramethylsilane
(TMS) for 1H and 13C NMR and neat tetramethyltin for 119Sn).
Elemental analyses were performed with a PE-2400II apparatus.
119Sn (CDCl3): δ ϭ Ϫ83.6 ppm. C26H38Cl2N10O3S15Sn5 (1683.9):
calcd. C 18.55, H 2.27, N 8.32; found C 18.52, H 2.25, N 8.31.
[(PhCH2)2SnCl(S-C2SN2-S)SnCl(PhCH2)2] (4): The synthesis pro-
cedure was the same as that of complex 3. H2dmt (0.30 g, 2 mmol)
was added to a solution of dichloromethane (40 mL) and sodium
ethoxide (0.272 g, 4 mmol), and the mixture was stirred for 30 mi-
nutes. (PhCH2)2SnCl2 (0.744 g, 2 mmol) was then added; reaction
time 16 h; temperature 30 °C. Recrystallized from ether/dichloro-
methane. M.p. 196Ϫ198 °C. Yield, 72%. IR (KBr): ν˜ ϭ 1635 (Cϭ
N), 701 (s, C-S), 561 (m, SnϪC), 321 (m, SnϪS), 277 (m, SnϪCl)
1
cmϪ1. H NMR (CDCl3): δ ϭ 7.32Ϫ7.86 (m, 20 H, aromatic-H),
3.26 [s, 8 H, CH2ϪPh, 2J
1 ϭ 79.0 Hz] ppm. 13C NMR (CDCl3):
119Sn,
δ ϭ 168.5 (C-1), 168.5 (C-1Ј), 38.5 (CH2ϪPh, 1J119
C ϭ 546 Hz),
ϭ 26 Hz, p-C),
؍ 36 Hz, i-C)
C
13
Sn,
13
13
125.4 (4J119
ϭ 30 Hz, m-C), 127.0 (5J119
[{C2S3N2(CH3)2Sn}2O(CH3)2Sn(OH)2]·1.5H2O (1): Sodium ethox-
ide (0.136 g, 2 mmol) was added to a solution of 2,5-dimercapto-
1,3,4-thiadiazole (0.150 g, 1 mmol) in 95% ethanol (25 mL) and the
mixture was stirred for 30 min. (CH3)2SnCl2 (0.659 g, 3 mmol) was
then added to the mixture, continuing the reaction for 10 h at 40
°C. After cooling to room temperature, the mixture was filtered and
the solvent was gradually removed by evaporation under vacuum to
give the solid product. The solid was then recrystallized from etha-
nol to give colorless crystals of 1. Yield, 80%. m.p. Ͼ 220 °C (dec.).
IR (KBr): ν˜ ϭ 3410 (s, OϪH), 2923 (m, CϪH), 1210 (w, CϭS),
Sn,
C
Sn,
C
13
13
130.5 (3J119
ϭ 44 Hz, o-C), 139.0 (2J119
Sn,
C
Sn,
ppm. 119Sn NMR (CDCl3): δ ϭ ؊187.8 ppm. C30H28Cl2N2S3Sn2
(821): calcd. C 43.89, H 3.43, N 3.07; found C 43.86, H 3.40, N
3.05.
Crystal Structures of Complexes 1, 2 and 3: All X-ray crystallo-
graphic data were collected on a Bruker SMART-1000-CCD dif-
fractometer. A criterion of observability was used for the solution
and refinement. The structure was solved by direct methods and
refined by a full-matrix least-squares procedure based on F2 using
the SHELXL-97 program. All data were collected at 298(2) K using
561 (m, SnϪC), 597 (s, SnϪOϪSn), 445 (m, SnϪN) cmϪ1 1H
.
NMR (CDCl3/D2O, 300 MHz): δ ϭ 5.15 (s, 2 H, OϪH), 0.96 (s,
18 H, CH3, 2J
1 ϭ 83.2 Hz) ppm. 13C NMR (CDCl3, 300 MHz):
˚
119Sn,
graphite-monochromated Mo-Kα radiation (λ ϭ 0.71073 A) and
δ ϭ 173.2 (C-1), 173.2 (C-1Ј), 6.3 [CH3, 1J119
ϭ 618.4 Hz]
13
corrected for Lorentz and polarization effects but not for absorp-
tion. All non-H atoms were included in the model at their calcu-
lated positions. The positions of the hydrogen atoms were calcu-
lated, and their contributions in structural factor calculations were
included. Table 4 lists the crystal data and structure refinement par-
ameters.
CCDC-215777 (for 1), -183604 (for 2) and -215778 (for 3) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of the charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Center, 12 Union Road, Cambridge, CB2 1EZ, UK; Fax: ϩ44-
1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
Sn,
C
ppm. 119Sn NMR (CDCl3): δ ϭ Ϫ121.2 ppm. C8H23N2O4.5S3Sn3
(671.53): calcd. C 14.31, H 3.45, N 4.20; found C 14.34, H 3.42,
N 4.17.
[{C2S3N2(PhCH2)2Sn}2O(PhCH2)2Sn(OH)(OEt)] (2): The syn-
thesis procedure was the same as complex 1. H2dmt (0.150 g,
1 mmol), sodium ethoxide (0.272 g, 4 mmol), and (PhCH2)2SnCl2
(1.116 g, 3 mmol) in 95% ethanol (30 mL); reaction time 10 h; tem-
perature 40 °C. Recrystallized from ethanol as colorless crystals.
Yield, 89%. m.p. Ͼ200 °C(dec.). IR (KBr): ν˜ ϭ 3420 (OϪH), 3021
(w, PhϪH), 2923 (m, CϪH), 1631, 1597, 1491, 1451 (m, Ph), 1286
(s, CϪO), 561 (m, SnϪC), 627 (s, SnϪOϪSn), 513 (s, SnϪOR),
1
480 (m, SnϪN). H NMR (CDCl3): δ ϭ 7.l5Ϫ7.56 (m, 30 H, Ph),
5.15 (s, 1 H, OϪH), 3.75 [q, 3J(119SnϪ1H) ϭ 5.8 Hz, 2 H, OϪCH2],
Acknowledgments
2.28 (m, 12 H, CH2ϪPh, 2J
1 ϭ 86 Hz,), 1.25 [t, 4J(119SnϪ1H) ϭ
119Sn,
1.2 Hz, 3 H, CH3] ppm. 13C NMR (CDCl3, 300 MHz): δ ϭ 173.4 We thank the National Natural Science Foundation of China
1
13
(C-1), 173.4 (C-1Ј), 37.5 [CH2ϪPh, J119
ϭ 624.1 Hz], 127.4 (20271025) and the Natural Science Foundation of Shandong Prov-
Sn,
C
(m-C), 128.2 (p-C), 129.3 (o-C), 135.2 (i-C) ppm. 119Sn NMR ince for financial support.
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2781

C. Ma, J. Zhang, F. Li, R. Zhang
C26H38Cl2N10O3S15Sn5
FULL PAPER
Table 4. Crystal data and structure refinement parameters for 1, 2 and 3
Empirical formula
C8H23N2O4.5S3Sn3
C46H48N2O3S3Sn3
Formula mass
671.53
298(2)
0.71073
1129.11
293(2)
0.71073
1683.91
298(2)
0.71073
Temperature (K)
˚
Wavelength (A)
Crystal system
Space group
orthorhombic
Pcca
27.831(15)
11.259(6)
14.492(8)
90
monoclinic
P21/c
20.036(3)
23.284(3)
22.212(3)
114.523(2)
9427(2)
monoclinic
P21/n
15.856(5)
15.207(5)
25.173(8)
103.611(5)
5899(3)
˚
a (A)
˚
b (A)
˚
c (A)
β (°)
3
˚
V (A )
4541(4)
Z
8
8
4
Dc (Mg·mϪ3
)
1.964
3.562
2552
1.591
1.750
4480
1.896
2.746
3248
µ (mmϪ1
F(000)
)
Crystal size (mm)
θ limits (°)
0.29 ϫ 0.20 ϫ 0.13
2.72Ϫ25.03
Ϫ30 Յ h Յ 33
Ϫ13 Յ k Յ 13
Ϫ17 Յ l Յ 16
0.6546,0.4248
0.40 ϫ 0.30 ϫ 0.20
1.33Ϫ24.83
Ϫ23 Յ h Յ 23
Ϫ18 Յ k Յ 27
Ϫ26 Յ l Յ 24
0.7210,0.5412
0.32 ϫ 0.18 ϫ 0.12
2.68Ϫ25.03
Ϫ11 Յ h Յ 18
Ϫ18 Յ k Յ 18
Ϫ29 Յ l Յ 27
0.7340,0.4736
Index ranges
Max., min. transmission
Refinement method
Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Reflections collected
Unique reflections
Data, restraints, parameters
Goodness of fit on F2
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
22346
3989 (Rint ϭ 0.0686)
3989, 6, 194
48195
16226 (Rint ϭ 0.0546)
16226, 0, 1031
30356
10294 (Rint ϭ 0.0675)
10294, 9, 522
0.914
1.000
0.824
R1 ϭ 0.0420, wR20.0914
R1 ϭ 0.0913, wR2 ϭ 0.1094
) 0.616, Ϫ0.483
R1 ϭ 0.0500, wR2 ϭ 0.1195
R1 ϭ 0.1204, wR2 ϭ 0.1537
0.875, Ϫ0.696
R1 ϭ 0.0472, wR2 ϭ 0.0920
R1 ϭ 0.1334, wR2 ϭ 0.1139
0.960, Ϫ0.867
Ϫ3
˚
Largest peak, hole difference (e·A
[20]
[1]
P. G. Harrison, M. J. Begley, K. C. Molloy, J. Organomet.
Chem. 1980, 186, 213Ϫ236.
J. E. Hubeey, E. A. Keiter, R. L. Keiter, Principles and Appli-
cations of Inorganic Chemistry, 4th ed., Harper Collins, New
York, 1993, pp 121Ϫ124.
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G.
Orpen, R. J. Taylor, J. Chem. Soc., Perkin Trans. 2 1987, S1.
G. Barone, T. G. Hibbert, M. F. Mabon, K. C. Molloy, I. P.
Parkin, L. S. Price, I. Silaghi-Dumitrescu, J. Chem. Soc., Dalton
Trans. 2001, 3435Ϫ3445.
A. Galani, M. A. Demertzis, M. Kubicki, D. Kovala-Demertzi,
Eur. J. Inorg. Chem. 2003, 1761Ϫ1767.
G. J. Grant, S. S. Shoup, C. L. Baucom, W. N. Setzer, Inorg.
Chim. Acta 2001, 317, 91Ϫ102.
L. Pauling, The Nature of the Chemical Bond, 3rd edn., Cornell
University Press, Ithaca, 1960, 64.
S. Z. Hu, D. S. Shi, T. S. Huang, J. Z. Wan, Z. X. Huang, J.
L. Yang, C. H. Xu, Inorg. Chim. Acta 1990, 173, 1Ϫ4.
A. Bondi, J. Phys. Chem. 1964, 68, 441Ϫ451.
C. O. Raymando, J. S. Omar, E. P. Georgina, S. Cristiam, J.
Organomet. Chem. 1994, 484, 33Ϫ36.
N. G. Fumanova, Yu. T. Strchkov, E. M. Rokhlina, D. N.
Kravtsov, J. Struct. Chem. 1980, 21, 766Ϫ772.
H. Hadjiliadis, T. Theophanides, Can. J. Spectrosc. 1977, 22,
51Ϫ57.
M. Eshel, A. Bino, Inorg. Chim. Acta 2001, 320, 127Ϫ132.
O. I. Shchegolikhina, V. A. Igonin, Yu. A. Molodtsova, Yu. A.
Pozdniakova, A. A. Zhdanov, T. V. Strelkova, S. V. Lindeman,
J. Organomet. Chem. 1998, 562, 141Ϫ151.
E. Kiss, K. Petrohan, D. Sanna, E. Garribba, G. Micera, T.
Kiss, Polyhedron 2000, 19, 55Ϫ61.
D. Dakternieks, A. Duthie, B. Zobel, K. Jurkschat, M.
Schürmann, E. R. T. Tiekink, Organometallics 2002, 21,
647Ϫ652.
[2]
[21]
[3]
[4]
[22]
[23]
[5]
[6]
S. Bhandari, M. F. Mahon, J. G. McGinley, K. C. Molloy, C.
E. E. Roper, J. Chem. Soc., Dalton Trans. 1998, 3425Ϫ3430.
M. Verdenelli, S. Parola, L. G. Hubert-Pfalzgraf, S. Lecocq,
Polyhedron 2000, 19, 2069Ϫ2075.
[24]
[25]
[26]
[27]
[7]
[8]
S. K. Duboy, U. Roy, Appl. Organomet. Chem. 2003, 17, 3Ϫ8.
´
R. Garcıa-Zarracino, J. Ramos-Quin˜ones, H. Höpfl, Inorg.
Chem. 2003, 42, 3835Ϫ3845.
[9]
E. S. Raper, Coord. Chem. Rev. 1996, 153, 199Ϫ255.
C. L. Ma, Q. Jiang, R. F. Zhang, D. Q. Wang, J. Chem. Soc.,
Dalton Trans. 2003, 2975Ϫ2978.
[10]
[28]
[29]
[11]
[12]
C. L. Ma, Q. Jiang, R. F. Zhang, J. Organomet. Chem. 2003,
678, 148Ϫ155.
[30]
[31]
[32]
[33]
[34]
[35]
[36]
ˇ
M. V. Castano, M. M. Plasencia, A. Macias, J. S. Casas, J.
Sordo, E. E. Castellano, J. Chem. Soc., Dalton Trans. 1989,
1409Ϫ1411.
C. L. Ma, F. Li, D. Q. Wang, H. D. Yin, J. Organomet. Chem.
2003, 667, 5Ϫ7.
[13]
J. R. Durig, R. Layton, D. W. Sink, B. R. Mitchell, Spectro-
chim. Acta 1965, 21, 1367Ϫ1378.
R. Schmiedgen, F. Huber, H. Preut, G. Ruisi, R. Barbieri, Appl.
Organomet. Chem. 1994, 8, 397Ϫ401.
R. Visalakshi, V. K. Jain, S. K. Kulshreshtha, G. S. Rao, Indian
J. Chem. 1989, 28A, 51Ϫ57.
B. S. Sarawat, G. Srivastava, R. C. Mehrotra, J. Organoment.
Chem. 1979, 164, 153Ϫ158.
N. Kottmair, W. Beck, Inorg. Chim. Acta 1979, 34, 137Ϫ144.
[14]
[15]
[16]
C. L. Ma, F. Li, Chin. J. Chem. 2003, 21, 146Ϫ152.
Y. M Chow, Inorg. Chem. 1971, 10, 673Ϫ677.
A. P. G. de Sousa, R. M. Silva, A. Cesar, J. L. Wardell, J. C.
Huffman, A. Abras, J. Organomet. Chem. 2000, 605, 82Ϫ88.
H. Reuter, PhD thesis, University of Bonn, Germany, 1986.
H. Puff, I. Bung, E. Friedrichs, A. Jansen, J. Organomet. Chem.
1983, 254, 23Ϫ32.
[17]
[18]
[19]
R. Okawara, Proc. Chem. Soc. London 1961, 383Ϫ385.
2782
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783

Diorganotin Derivatives of 2,5-Dimercapto-1,3,4-thiadiazole
FULL PAPER
[37]
[41]
[42]
A. Tarassoli, A. Asadi, P. B. Hitchcock, J. Organomet. Chem.
A. Tarassoli, T. Sedaghat, B. Neumüller, M. Ghassemzadeh,
Inorg. Chim. Acta 2001, 318, 15Ϫ22.
2002, 645, 105Ϫ111.
[38]
´ ´
J. S. Casas, A. Castin˜eiras, M. C. Rodrıguez-Argüelles, A. San-
T. P. Lockhart, W. F. Manders, Inorg. Chem. 1986, 25,
´
´
´
´
892Ϫ895.
chez, J. Sordo, A. Vazquez-Lopez, E. M. Vazquez-Lopez, J.
Chem. Soc., Dalton Trans. 2000, 2267Ϫ2272.
K. Sisido, J. Am. Chem. Soc. 1961, 83, 538Ϫ541.
Received November 22, 2003
[39]
C. H. Yoder, L. A. Margolis, J. M. Horne, J. Organomet. Chem.
[43]
2001, 633, 33Ϫ38.
J. Holecek, M. Nadvornık, K. Handlzr, A. Lycka, J. Or-
ganomet. Chem. 1986, 315, 299Ϫ308.
[40]
ˇ
´
´
ˇ
ˇ
Early View Article
Published Online April 26, 2004
Eur. J. Inorg. Chem. 2004, 2775Ϫ2783
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2783