Synthesis and characterization of di-/triorgano stannates bearing tin-sulfonate bonds

Article abstract of DOI:10.1016/j.ica.2012.02.040

The synthesis of new stannates, [Et₃NMe]₂[R ₂Sn(OSO₂Me)₄] [R = Me (1), Et (2), Ph (3)] and [Et₃NMe][Ph₃Sn(OSO₂Me)₂] (4) has been achieved from a one pot reaction between R₂SnO (R = Me, Et, Ph) or (Ph₃Sn)₂O and dimethylsulfite [(MeO)₂S = O] in the presence of triethylamine. An important step in this synthetic protocol involves a sulfur-centered Arbuzov-type rearrangement in dimethylsulfite and in situ formation of the methanesulfonate moiety. On the contrary, direct reaction of diphenyl/triphenyltin oxide and dimethylsulfite proceeds without such rearrangement and affords [Ph₂Sn(OMe)OS(O)OMe]_n (5) and (Ph₃SnO)₂SO (6), respectively. Structural aspects of 1-4 have been elucidated by X-ray crystallography.

Full text of DOI:10.1016/j.ica.2012.02.040

Inorganica Chimica Acta 387 (2012) 420–425
Contents lists available at SciVerse ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis and characterization of di-/triorgano stannates bearing
tin-sulfonate bonds
a
a
b
b
Ravi Shankar a, , Atul Pratap Singh , Archana Jain , Gabriele Kociok-Köhn , Kieran C. Molloy
⇑
a Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India
b Department of Chemistry, University of Bath, Bath BA2 7AY, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis of new stannates, [Et3NMe]2[R2Sn(OSO2Me)4] [R = Me (1), Et (2), Ph (3)] and [Et3NMe][Ph3S-
n(OSO2Me)2] (4) has been achieved from a one pot reaction between R2SnO (R = Me, Et, Ph) or (Ph3Sn)2O
and dimethylsulfite [(MeO)2S = O] in the presence of triethylamine. An important step in this synthetic
protocol involves a sulfur-centered Arbuzov-type rearrangement in dimethylsulfite and in situ formation
of the methanesulfonate moiety. On the contrary, direct reaction of diphenyl/triphenyltin oxide and dim-
ethylsulfite proceeds without such rearrangement and affords [Ph2Sn(OMe)OS(O)OMe]n (5) and
(Ph3SnO)2SO (6), respectively. Structural aspects of 1–4 have been elucidated by X-ray crystallography.
Ó 2012 Elsevier B.V. All rights reserved.
Received 30 August 2011
Received in revised form 7 January 2012
Accepted 22 February 2012
Available online 3 March 2012
Keywords:
Dimethylsulfite
Rearrangement
Stannates
Methanesulfonate
1. Introduction
di-n-butyltin oxide with dimethyl sulfite in the presence of trieth-
ylamine or tetraethyl ammonium iodide. The approach has also
The coordination chemistry of organotin compounds derived
from trifluoromethanesulfonic and arenesulfonic acids has been
extensively studied in the past with emphasis on delineating the
fundamental issues related to the bonding behavior of these ambid-
entate ligands towards Lewis acidic tin centers [1–4]. X-ray crystal-
lographic studies of several tin complexes from among this family
have revealed that the ligand character is either ionic or weakly
coordinating in nature and contributes to the primary and/or sec-
ondary coordination spheres of the tin centers. For example,
proved to be convenient to generate the alkanesulfonate moieties
from higher dialkyl sulfites. A mechanistic rationale for the forma-
tion of such anionic tin-sulfonates has been elucidated [12]. In the
present work, the validity of this synthetic protocol has been fur-
ther substantiated by the isolation of new tetra(methanesulfona-
to)diorganostannates, [Et3NMe]2[R2Sn(OSO2Me)4] [R = Me (1), Et
(2), Ph (3)] along with the first example of a penta-coordinate stan-
nate, [Et3NMe][Ph3Sn(OSO2Me)2] (4) among this family.
organotin cations such as [Bu2Sn(H2O)4]2+, [Bu2Sn(OH)(H2O)]2
2+
2. Results and discussion
and [t-Bu2Sn(O2PPh2)]22+ are known to exist as ion pairs with sulfo-
nate anions [5–7] and show high catalytic activity in various organ-
ic transformations [8–10]. These organotin esters are generally
prepared by azeotropic dehydration reaction between a di-/triorga-
notin oxide and a sulfonic acid, or treatment of an organotin halide
with a silver salt of the sulfonic acid. Nevertheless, synthesis and
structural aspects of anionic organotin complexes bearing direct
tin-sulfonate bonds have not received adequate attention so far.
In a preliminary communication, we have demonstrated the
scope of dialkyl sulfites, (R1O)2S = O for the synthesis of neutral
[11] as well as anionic organotin derivatives [12] bearing
alkanesulfonate ligands. For, example, formation of the dianion
[Bu2Sn(OSO2Me)4]2ꢀ as its tetraalkylammonium salt, [R3R1N]+
(R = R1 = Et; R = Et, R1 = Me) has been accomplished by reacting
2.1. Synthesis
The synthesis of di-/triorganostannates, 1–4 has been achieved
by reacting an appropriate organotin oxide with excess dimethyl
sulfite at 110–120 °C in the presence of triethylamine (Scheme 1).
The role of triethylamine in the isomerization of dimethyl sulfite
into methanesulfonate groups and formation of the stannates 1–4
has been validated by studying a direct reaction between Ph2SnO
or (Ph3Sn)2O and dimethyl sulfite under identical conditions. This
has led to the isolation of organotin sulfites, [Ph2Sn(OMe)OS(O)O-
Me]n (5) and (Ph3SnO)2SO (6) respectively, the former being consid-
ered as the outcome of C–O bond cleavage in dimethyl sulfite while
the later as a simple insertion of SO2 into the Sn–O bond in bis(tri-
phenyltin)oxide [13,14]. The verstality of dimethyl sulfite as alkyl-
ating, alkoxylating and acetylzing agent as well as source of SO2 in
the presence of nucleophiles has been reported earlier [15,16].
⇑
Corresponding author. Tel.: +91 011 2659 1513 (O), +91 011 2659 6454 (Lab).
E-mail address: shankar@chemistry.iitd.ac.in (R. Shankar).
0020-1693/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2012.02.040

R. Shankar et al. / Inorganica Chimica Acta 387 (2012) 420–425
421
Scheme 1. Synthesis of compounds, 1–4.
2.2. X-ray crystal structures
The stannates, 1–4 have been structurally characterized by sin-
gle crystal X-ray diffraction. The molecular structures of 1–3 are
shown in Figs. 1–3 while the crystal data and selected bond lengths
and angles are given in Tables 1 and 2, respectively. The dianion in
each molecule is isostructural and is comprised of four uniquely
disposed monodentate methanesulfonate groups on the tin center
forming the equatorial SnO4 plane (RO–Sn–O: =360°). The hydro-
carbon groups adopt a trans disposition with C–Sn–C angles in 2
[174.59(6)°] being marginally narrower than those observed in
the dimethyl- and diphenylstannate analogs, 1 and 3 (180.0°). As
a result, each stannate molecule adopts a distorted trans-C2SnO4
octahedral geometry around the tin atom. The observed Sn–O
(methanesulfonate) bond lengths lie in the range of 2.2–2.3 Å
and suggest a predominant covalent character, irrespective of the
nature of alkyl/aryl substituents on the tin atom. The metrical
parameters associated with N-methyltriethylammonium cation in
all the compounds corroborate well with those reported earlier
[17,18].
The crystal data of 4 is summarizedin Table 1 whileselected bond
lengths and angles are shown in Table 3. The molecular structure
(Fig. 4a) is composed of discrete [Ph3Sn(OSO2Me)2]ꢀ anion, featuring
a trigonal bipyramidal geometry around the tin atom. The phenyl
groups occupy the equatorial position to form SnC3 basal plane
Fig. 2. Molecular structure of 2. Thermal ellipsoids are drawn at 30% probability
level, and the hydrogen atoms are omitted for clarity.
(RC–Sn–C: 359 0.01°) while the monodentate methanesulfonate
(vide supra). The phenyl groups in the molecule exhibit a propeller
shape conformation as evident from an examination of the dihedral
angles Cipso–Sn–C0ipso–C0ortho subtended between the phenyl rings
(Table 3). The mean value of these dihedral angles (39.3°) finds a
close analogy with a few reported examples of pentacoordinated
triphenylantimony(V) and bismuth(V) complexes derived from car-
boxylate and benzenesulfonate ligands [19,20]. This arrangement
arises in order to minimize ring-ring and ring-ligand interactions.
The structure of 4 also reveals significant intramolecular CHꢁ ꢁ ꢁO
hydrogen bonding involving phenyl groups and oxygen atoms of
the methanesulfonate ligands [C(7)–H(7) = 0.950(2), O(5)ꢁ ꢁ ꢁH(7) =
2.396(2), C(7)ꢁ ꢁ ꢁO(5) = 3.272(3) Å, C(7)–H(7)–O(5) = 153.16(13)°;
C(14)–H(14) = 0.949(2), O(2)ꢁ ꢁ ꢁH(14) = 2.482(1), O(2)ꢁ ꢁ ꢁC(14) =
3.315(3) Å, O(2)–H(14)–C(14) = 146.52(13)°; C(6)–H(6) = 0.950(2),
O(1)ꢁ ꢁ ꢁH(6) = 2.481(1), O(1)ꢁ ꢁ ꢁC(6) = 3.059(2) Å, O(1)–H(6)–C(6) =
119.19(12)°)]. These molecules are held together by additional
intermolecular CHꢁ ꢁ ꢁO hydrogen bonds involving H(20B) and O(3)
atoms of methanesulfonate groups. The metrical parameters associ-
ated with these bonds are as follows: [C(20)–H(20B) = 0.980(2),
groups adopt a trans-disposition [O(1)–Sn–O(4) = 179.93(6)°]. The
Sn–O bond lengths [Sn–O(1) = 2.2173(13), Sn–O(4) = 2.2468(13) Å]
compare well with those observed for the dianionic stannates 1–3
O(3)ꢁ ꢁ ꢁH(20B) = 2.487(2),
O(3)ꢁ ꢁ ꢁC(20) = 3.221(3) Å,
C(20)–
H(20B)–O(3) = 131.51(13)°]. As a result, the structure extends into
one-dimensional polymeric assembly along the b-axis (Fig. 4b).
2.3. Structural studies of 1–4 in solution
The identity of 1–4 in solution has been examined by multinu-
Fig. 1. Molecular structure of 1. Thermal ellipsoids are drawn at 30% probability
level, and the hydrogen atoms are omitted for clarity.
clear (1H, 13C and 119Sn) NMR and mass spectral studies. The 1H

422
R. Shankar et al. / Inorganica Chimica Acta 387 (2012) 420–425
Table 2
Selected bond lengths (Å) and bond angles (°) for 1–3.
For 1
Sn–C(3)
2.0951(12)
2.2427(9)
2.2494(9)
180.0
92.48(4)
87.52(4)
Sn–C(3)i
2.0951(12)
2.2427(9)
2.2494(9)
87.52(4)
Sn–O(4)
Sn–O(4)i
Sn–O(1)i
Sn–O(1)
C(3)–Sn–C(3)i
O(4)i–Sn–O(1)i
O(4)i–Sn–O(1)
O(4)–Sn–O(1)i
O(4)–Sn–O(1)
92.48(4)
For 2
Sn–C(7)
Sn–O(4)
Sn–O(7)
C(7)–Sn–C(5)
O(4)–Sn–O(7)
O(7)–Sn–O(10)
2.1209(16)
2.2148(11)
2.2531(11)
174.59(6)
88.09(4)
Sn–C(5)
Sn–O(1)
Sn–O(10)
O(4)–Sn–O(1)
O(1)–Sn–O(10)
2.1213(15)
2.2312(11)
2.3070(12)
86.88(4)
98.14(4)
86.89(4)
For 3
Sn–C(1)
Sn–O(4)
Sn–O(1)
2.1184(16)
2.1970(11)
2.2044(12)
180.00(9)
92.42(4)
Sn–C(1)i
2.1184(16)
2.1970(11)
2.2044(12)
87.58(4)
Sn–O(4)i
Sn–O(1)i
C(1)–Sn–C(1)i
O(4)–Sn–O(1)i
O(4)i–Sn–O(1)
O(4)i–Sn–O(1)i
O(4)–Sn–O(1)
87.58(4)
92.42(5
i
Symmetry transformations used to generate equivalent atoms: for 1: ꢀx + 1,
i
ꢀy + 1, ꢀz + 1; for 3: 2 ꢀ x, ꢀy, ꢀz.
Section 3). The 119Sn NMR spectra of 1 and 2 in CDCl3 solution reveal
a single resonance at d ꢀ335 and ꢀ356 respectively and theobserved
chemical shift values are significantly downfield in comparison to
the solid state NMR (CPMAS) data (d ꢀ413) of an analogous six-coor-
dinated di-n-butylstannate, [Bu2Sn(OSO2Me)4]2ꢀ reported earlier
[12]. The results suggest that these stannates do not retain their
structural identity in solution. This preposition is further supported
by the identical 119Sn NMR chemical shift (d ꢀ257) of di-/triphenyl
stannates 3 and 4 which are comprised of C2SnO4 and C3SnO2
framework structures respectively in the solid state. This accidental
chemical shift degeneracy finds a close analogy with related penta-
coordinated stannates, [Ph2SnCl3]ꢀ (d ꢀ250) and [Ph3SnCl2]ꢀ (d
ꢀ251) as reported by Dakternieks et al. [21,22] and provide a basis
to conclude the existence of anionic pentacoordinate stannate,
Fig. 3. Molecular structure of 3. Thermal ellipsoids are drawn at 30% probability
level, and the hydrogen atoms are omitted for clarity.
and 13C NMR spectra distinctly reveal the presence of methanesulfo-
nate groups (d 2.62–2.87/38.95–39.20) and accord the composition
of each compound. The mass spectra of an acetonitrile solution of
1–3 reveal isotopic cluster patterns at m/z 435, 462 and 558 respec-
tively corresponding to anionic pentacoordinated organotin species,
[R2Sn(OSO2Me)3]ꢀ. In addition, the spectrum of 1 also exhibits ions
with higher m/z values at 891 and 987 which are ascribed to ditin
species comprising of monoanionic and/or dianionic stannate (see
Table 1
Summary of crystallographic data for 1–4.
1
2
3
4
Empirical formula
Mr
T (K)
Crystal system
Space group
a (Å)
C
20H54N2O12S4Sn
C22H58N2O12S4Sn
789.63
150(2)
C30H58N2O12S4Sn
885.71
150(2)
C27H39NO6S2Sn
656.4
150(2)
monoclinic
P121/n1
10.0659(1)
16.1424(1)
18.2049(2)
761.58
150(2)
triclinic
triclinic
triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
8.3516(1)
10.1434(1)
10.7919(1)
104.661(1)
97.713(1)
107.302(1)
822.428(15)
1
11.1015(2)
11.5543(2)
15.0755(2)
107.417(1)
103.038(1)
92.897(1)
1782.95(5)
2
9.5999(1)
10.1404(1)
11.4500(2)
80.792(1)
79.567(1)
64.146(1)
982.33(2)
1
b (Å)
c (Å)
a
(°)
b (°)
96.639(1)
c
(°)
V (Å3)
2938.24(5)
4
1.484
Z
qcalcd (g cmꢀ3
F(000)
)
1.538
398
1.471
828
1.497
462
1352
Crystal size (mm)
h range for data collection (°)
Reflections collected
Independent reflections
Rint value
0.50 ꢂ 0.30 ꢂ 0.20
3.38 to 37.90
29456
8821
0.0434
0.50 ꢂ 0.50 ꢂ 0.50
3.54 to 30.07
42354
10386
0.0336
0.25 ꢂ 0.25 ꢂ 0.23
3.37 to 30.08
24092
5748
0.0346
0.30 ꢂ 0.30 ꢂ 0.05
3.38 to 30.06
68052
8589
0.0559
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
R1, wR2
[I > 2s (I)]
R1, wR2 (all data)
8821/0/182
1.049
R1 = 0.0307
wR2 = 0.0737
R1 = 0.0359
wR2 = 0.0763
10386/0/449
1.058
R1 = 0.0260,
wR2 = 0.0617
R1 = 0.0323,
wR2 = 0.0651
5748/86/291
1.038
R1 = 0.0276
wR2 = 0.0618
R1=0.0323
wR2 = 0.0644
8589/0/340
1.056
R1 = 0.0323
wR = 0.0728
R1=0.0483
wR = 0.0793

R. Shankar et al. / Inorganica Chimica Acta 387 (2012) 420–425
423
Table 3
3. Experimental
Selected bond lengths (Å) and bond angles (°) for 4.
Sn–C(1)
Sn–C(13)
Sn–O(4)
C(1)–Sn–C(12)
C(1)–Sn–C(13)
2.1284(18)
1.1305(18)
2.2468(13)
122.50(7)
125.86(7)
Sn–C(12)
Sn–O(1)
2.136(2)
2.2173(13)
3.1. Material and methods
All operations were carried out using standard Schlenk line
techniques under dry nitrogen atmosphere. Diethyl ether was
freshly distilled over sodium benzophenone before use. Glassware
was dried in an oven at 110–120 °C and further flame dried under
vacuum prior to use. 1H and 13C{1H} NMR spectra were recorded in
CDCl3 solution on BRUKER DPX-300 spectrometer at 300 and
75.47 MHz while 119Sn{1H} NMR spectra were taken on BRUKER
AVANCE II 400 spectrometer at 149.19 MHz. 1H and 13C{1H} chem-
ical shifts are quoted with respect to the residual protons of the
while 119Sn NMR data are given using tetramethyltin as external
standard. The electrospray mass spectra were recorded on a
MICROMASS QUATTRO II triple quadruple mass spectrometer.
The samples dissolved in acetonitrile were introduced into the
C13–Sn–C12
O(1)–Sn–O(4)
111.63(7)
179.93(6)
Dihedral angles
C(1)–Sn–C12–C11
C(12)–Sn–C(1)–C(6)
C(13)–Sn–C(12)–C(11)
129.72
ꢀ60.37
ꢀ49.34
C(1)–Sn–C(13)–C(14)
C(12)–Sn–C(13)–C(14)
C(13)–Sn–C(1)–C(6)
ꢀ41.12
137.90
118.56
[Ph2Sn(OSO2Me)3]ꢀ via dissociation of 3 in solution. The observed
119/117Sn satellites in the 13C{1H} NMR spectra allow a measure of
the 1J(119Sn–13C) coupling values which are also found to be quite
similar for 3 (831 Hz) and 4 (830 Hz) and are in accord with those re-
ported earlier for anionic pentacoordinated di-/triphenyltin com-
plexes [23]. The 1J(119Sn–13C) coupling values for 1 and 2 (963 and
830 Hz) compares well with those reported earlier for neutral di-
methyl/diethyl tin-methanesulfonates [24]. The IR and multinuclear
(1H, 13C and 119Sn) NMR spectral data of 5 and 6 are summarized in
the experimental section. Particularly noteworthy is the closely
placed 1H and 13C NMR signals at d 3.40/3.58 and 53.0/51.8 associ-
ated with methoxy and methylsulfite moieties in 5.
In conclusion, the reaction of dimethyl/diethyl/diphenyl/tri-
phenyltin oxide, dimethyl sulfite and triethyl amine proceeds via
sulfur-centered Arbuzov-type rearrangement and affords the
formation of di-/triorganostannates 1–4. These studies validate
the generality of dimethylsulfite as the reagent in the synthetic
domain of anionic organotin-sulfonate derivatives as well as
closely related organotin sulfites.
ESI source through a syringe pump at the rate of 5 lL per min.
The ESI capillary was set at 3.5 kV and the cone voltage was
40 V. The spectra were collected in 6 s scans and the print outs
are averaged spectra of 6–8 scans. IR spectra were recorded on
Nicolet protege 460 E.S.P. spectrophotometer using KBr pallet.
Elemental analysis (C, H and N) was performed on a Perkin–Elmer
model 2400 CHN elemental analyzer.
3.2. Synthesis of dimethyl/diethyl/diphenyl/triphenylstannate, 1–4
Dimethyl/diethyl/diphenyltin oxide (0.45/0.53/0.79 g, 2.73
mmol), dimethyl sulfite (3.0 g, 27.3 mmol) and triethylamine
(0.55 g, 5.46 mmol) were heated at 100–110 °C on an oil bath. A clear
Fig. 4. (a) Molecular structure of 4. Thermal ellipsoids are drawn at 30% probability level, and the hydrogen atoms are omitted for clarity. (b) 1D structure of 4 (along b-axis)
showing C–Hꢁ ꢁ ꢁO contacts, and the hydrogen atoms (except H6, H7, H14 and H20B) are omitted for clarity.

424
R. Shankar et al. / Inorganica Chimica Acta 387 (2012) 420–425
solution was obtained within one hour. The reaction mixture in each
case was heated for 20 h to ensure completion of reaction. To the
resulting clear solution, diethyl ether (50–60 mL) was added with
stirring. The white solid obtained in each case was filtered, washed
with the solvent and dried under vacuum. The compounds thus iso-
lated were identified as 1–3, respectively. Following the similar pro-
cedure, the reaction between bis(triphenyltin) oxide (1.95 g,
2.72 mmol), dimethyl sulfite (3.0 g, 27.2 mmol) and triethylamine
(0.55 g, 5.46 mmol) afforded 4 as a white solid.
resultant colorless solution was cooled and n-hexane was added
into it to precipitate as white solid. Following similar
conditions, the reaction between bis(triphenyltin)oxide (1.95 g,
2.72 mmol) and dimethyl sulfite (3.0 g, 27.2 mmol) yields a viscous
oil which was fractionally distilled under vacuum (125–127 °C) to
obtain 6 in analytically pure form.
5
a
3.3.1. Ph2Sn(OMe)OS(O)OMe (5)
Yield: 61%. 1H NMR: d 7.60, 7.30 (ring protons), 3.5 (br, OCH3+O-
S(O)OMe). 13C{1H} NMR: d 137.2 (C-1), 136.6 (C-2/6), 129.1 (C-4),
128.6 (C-3/5) (SnC6H5, 1J(Sn–C) = 656/683, 2J(Sn–C) = 45, 3J(Sn–
C) = 80, 4J(Sn–C) = 21 Hz), 53.0 (OCH3). 119Sn NMR: d ꢀ130. IR
3.2.1. [Et3NMe]2[Me2Sn(OSO2Me)4] (1)
Yield: 76%. 1H NMR: d 3.45 (q, 3J(H–H) = 7.2 Hz, 12H, NCH2), 3.10
(s, 6H, NCH3), 2.87 (s, 12H, SCH3), 1.38 (t, 3J(H-H) = 7.2 Hz, 18H,
NCH2CH3), 1.31 (s, 6H, SnCH3). 13C{1H} NMR: d 55.02 (NCH2), 46.05
(NCH3), 39.07 (SCH3), 14.70 (SnCH3, 1J(Sn–C) = 963/916 Hz), 7.12
(Nujol, cmꢀ1): 1000, 940 (
mSO3).
3.3.2. (Ph3SnO)2SO (6)
(NCH2CH3). 119Sn NMR: d ꢀ335. IR (Nujol, cmꢀ1
) mSO3 1201, 1048.
Yield: 66%. 1H NMR: d 7.60, 7.35 (ring protons), 3.5 (br,
OCH3 + OS(O)OMe). 13C{1H} NMR: d 139.3 (C-1), 136.7 (C-2/6),
129.5 (C-4), 128.5 (C-3/5) (SnC6H5, 1J(Sn–C) = 689/658 Hz), 53.0
(OCH3). 119Sn NMR: d ꢀ98.6. IR (Nujol, cmꢀ1): 1000, 970, 946,
ESI(negative-ion):
m/z
306
[(Et3NMe)(OSO2Me)2]ꢀ,
435
[Me2Sn(OSO2Me)3]ꢀ, 891 {2[Me2Sn(OSO2Me)3] + Na}ꢀ, 987
{[Me2Sn(OSO2Me)3 + [Me2Sn(OSO2Me)4] + Na+H}ꢀ. Anal. Calc. for
C20H54N2O12S4Sn: C, 31.54; H, 7.15; N, 3.68. Found: C, 31.53; H,
858 (mSO3).
7.21; N, 3.64%.
3.4. X-ray crystallography
3.2.2. [Et3NMe]2[Et2Sn(OSO2Me)4] (2)
Yield: 75%. 1H NMR: d 3.46 (q, 3J(H–H) = 7.2 Hz, 12H, NCH2),
3.11 (s, 6H, NCH3), 2.85 (s, 12H, SCH3), 1.96 (q, 3J(H–H) = 7.8 Hz,
4H, SnCH2CH3), 1.45 (t, 3J(H–H) = 7.8 Hz, 6H, SnCH2CH3), 1.38 (t,
3J(H–H) = 7.2 Hz, 18H, NCH2CH3). 13C{1H} NMR: d 55.31 (NCH2),
46.33 (NCH3), 39.20 (SCH3), 27.07 (SnCH2 1J(Sn–C) = 830/793 Hz),
9.27 (SnCH2CH3, 2J(Sn–C) = 49 Hz), 7.39 (NCH2CH3). 119Sn NMR: d
All crystals suitable for X-ray diffraction studies were mounted
on glass fibers and were used for data collection at 150(2) K. The
intensity data were collected on Nonius Kappa CCD diffractometer
equipped with molybdenum sealed tube (Mo
Ka radiation,
k = 0.71073 Å) and graphite monochromator at T = 150(2) K. Cell
parameters, data reduction and absorption corrections were per-
formedwith Nonius software (DENZO and SCALEPACK) [25]. The structure
were solved by direct methods using SIR97 [26] and refined by full
matrix least-squares method on F2 using SHELXL-97 [27]. All calcula-
tions were performed using WINGX [28]. In compound 2, one of the
cations shows disorder for N1 and C21–C26 atoms in two locations
in 50:50 ratio, while in 3, cations are present in severely disordered
state. All atoms of the cations, N1 and C9–C15 show disorder in two
locations in 87:13 ratios. The C–N and C–C distances in these disor-
dered fragments were restrained to idealized values in the final
least-squares cycles. All the non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in geometrically
calculated positions using a riding model.
ꢀ356. IR (Nujol, cmꢀ1
) mSO3 1194, 1056. ESI(negative-ion): m/z
463 [Et2Sn(OSO2Me)3]ꢀ, 306 [(Et3NMe)(OSO2Me)2]ꢀ. Anal. Calc.
for C22H58N2O12S4Sn: C, 33.46; H, 7.40, N, 3.55. Found: C, 33.43;
H, 7.47; N, 3.53%.
3.2.3. [Et3NMe]2[Ph2Sn(OSO2Me)4] (3)
Yield: 80%. 1H NMR: d 8.14 (d, 3J(H–H) = 6.6 Hz, 4H, o-hydrogen of
phenyl groups), 7.44–7.38 (m, 6H, m- and p-hydrogen of phenyl
groups), 3.27 (q, 3J(H–H) = 6.6 Hz, 12H, NCH2), 2.89 (s, 6H, NCH3),
2.62 (s, 12H, SCH3), 1.25 (t, 3J(H–H) = 6.6 Hz, 18H, NCH2CH3).
13C{1H} NMR: d 141.85 (ipso, 1J(Sn–C) = 831/794 Hz), 136.13 (ortho,
2J(Sn–C) = 48 Hz), 128.69 (para), 127.70 (meta, 3J(Sn–C) = 72.45 Hz),
54.96 (NCH2), 45.85 (NCH3), 38.95 (SCH3), 7.09 (NCH2CH3). 119Sn
NMR: d ꢀ257. IR (Nujol, cmꢀ1
) mSO3 1054, 1231. ESI(negative-ion):
Acknowledgements
m/z 559 [Ph2Sn(OSO2Me)3]ꢀ, 306 [(Et3NMe)(OSO2Me)2]ꢀ. Anal. Calc.
for C30H58N2O12S4Sn: C, 40.68; H, 6.60, N, 3.16. Found: C, 40.61; H,
6.71; N, 3.12%.
This research was supported by Grants from CSIR and DST (In-
dia). We thank UGC for providing Senior Research Fellowship to A.J.
3.2.4. [Et3NMe][Ph3Sn(OSO2Me)2] (4)
2Yield: 78%. 1H NMR: d 8.06 (d, 3J(H–H) = 7.5 Hz, 6H, o-hydrogen
of phenyl groups), 7.46–7.35 (m, 9H, m and p-hydrogen of phenyl
groups), 3.15 (q, 3J(H–H) = 7.2 Hz, 6H, NCH2), 2.76 (s, 3H, NCH3),
2.45 (s, 6H, SCH3), 1.15 (t, 3J(H–H) = 7.2 Hz, 9H, NCH2CH3). 13C{1H}
NMR: d 141.76 (ipso, 1J(Sn–C) = 830/794 Hz), 136.05 (ortho, 2J(Sn–
C) = 48 Hz), 128.62 (para), 127.63 (meta, 3J(Sn–C) = 72.46 Hz),
54.90 (NCH2), 45.82 (NCH3), 38.88 (SCH3), 7.04 (NCH2CH3). 119Sn
Appendix A. Supplementary material
CCDC 737005, 737006, 737007 and 737008 contain the supple-
mentary crystallographic data for compounds 1, 2, 3 and 4, respec-
tively. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/
j.ica.2012.02.040.
NMR: d ꢀ258. IR (Nujol, cmꢀ1
) mSO3 1053, 1196. ESI(negative-ion):
m/z 541 [Ph3Sn(OSO2Me)2]ꢀ, 306 [(Et3NMe)(OSO2Me)2]ꢀ. Anal. Calc.
for C27H39NO6S2Sn: C, 49.40; H, 5.99, N, 2.13. Found: C, 49.34; H,
6.41; N, 2.10%.
References
[1] V. Chandrasekhar, S. Nagendran, B. Basker, Coord. Chem. Rev. 235 (2002) 1.
[2] J. Beckmann, D. Dakternieks, A. Duthie, F.S. Kuan, E.R.T. Tiekink,
Organometallics 22 (2003) 4399.
3.3. Synthesis of diphenyltin(methoxy)methylsulfite (5) and
bis(triphenyltin)sulfite (6)
[3] A. Orita, J. Xiang, K. Sakamoto, J. Otera, J. Organomet. Chem. 624 (2001) 287.
[4] R. Kapoor, A. Gupta, P. Venugopalan, A.P.S. Pannu, M.S. Hundal, P. Kapoor, J.
Organomet. Chem. 694 (2009) 623.
[5] V. Chandrasekhar, R. Boomishankar, A. Steiner, J.F. Bickely, Organometallics 22
(2003) 3342.
The reaction between diphenyltin oxide (0.79 g, 2.73 mmol)
and dimethyl sulfite (3.0 g, 27.3 mmol) was performed under
reflux (127 °C) for 20–25 h under dry nitrogen atmosphere. The

R. Shankar et al. / Inorganica Chimica Acta 387 (2012) 420–425
425
[6] K. Sakamoto, H. Ikeda, H. Akashi, T. Fakuyama, A. Orita, J. Otera, Organometallics
19 (2000) 3242.
[19] H. Barucki, S.J. Coles, J.F. Costello, T. Gelbrich, M.B. Hursthous, Dalton Trans.
(2000) 2319.
[7] J. Beckmann, D. Dakternieks, A. Duthie, C. Mitchell, Organometallics 22 (2003)
2161.
[8] A. Orita, J. Otera, in: H. Yamamoto, K. Oshima (Eds.), Main Group Metals in
Organic Synthesis, vol. 2, Wiley-VCH, 2004, p. 705.
[9] D.L. An, Z. Peng, A. Orita, A. Kurita, S. Man-e, K. Ohkubo, X. Li, S. Fukuzumi, J.
Otera, Chem. Eur. J. 12 (2006) 1642.
[10] X. Li, A. Kurita, S. Man-e, A. Orita, J. Otera, Organometallics 24 (2005) 2567.
[11] R. Shankar, A.P. Singh, S. Upreti, Inorg. Chem. 45 (2006) 9166.
[12] R. Shankar, A.P. Singh, M.F. Mahon, K.C. Molloy, G. Hundal, M. Biesemans, R.
Willem, Inorg. Chem. 47 (2008) 790.
[13] A.J. Bloodworth, A.G. Davies, S.C. Vassishta, J. Chem. Soc. C (1967) 1309.
[14] A.G. Davies, P.G. Harrison, J. Chem. Soc. C (1967) 1313.
[15] H.F. Van Woerden, Chem. Rev. 63 (1963) 557.
[16] J.J. Grabowski, R.C. Lum, J. Am. Chem. Soc. 112 (1990) 607.
[17] E.G. Martinez, A.S. Gonzalez, A. Castineiras, J.S. Casas, J. Sordo, J. Organomet.
Chem. 469 (1994) 41.
[20] R. Ruther, F. Huber, H. Preut, Z. Anorg. Allg. Chem. 539 (1986) 110.
[21] R. Colton, D. Dakternieks, Inorg. Chim. Acta 148 (1988) 31.
[22] D. Dakternieks, H. Zhu, Organometallics 11 (1992) 3820.
[23] J. Holecek, M. Nadvornik, K. Handlir, A. Lycka, J. Organomet. Chem. 241 (1983)
177.
[24] R. Shankar, A. Jain, A.P. Singh, G. Kociok-Köhn, K.C. Molloy, Inorg. Chem. 48
(2009) 3608.
[25] HKL DENZO and SCALEPACK vl.96: Z. Otwinowski, W. Minor, Processing of X-ray
diffraction data collected in oscillation mode, in: C.W. Carter Jr., R.M. Sweet
(Eds.), Meth. Enzymol.: Macromol. Crystallogr., Part A, vol. 276, Academic
Press, San Diego, CA, 1997; p. 307.
[26] A. Altomare, M.C. Burla, M. Carnalli, G. Cascarano, C. Giacovazzo, A. Guagliardi,
A.G.G. Moliterni, G. Polidori, R. Spagan, J. Appl. Crystallogr. 32 (1999) 115.
[27] G. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement; Institüt für
Anorganische Chemie der Unversität, Tammanstrasse 4, D-3400 Göttingen,
Germany.
[18] T.P. Lockhart, J.C. Calabrese, F. Davidson, Organometallics 6 (1987) 2479.
[28] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.