Studies of distannylated-1,2-dithiolato compounds: Synthesis of 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-thiones, (R3SnCH2)2(dmit), and 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-ones, (R

Article abstract of DOI:10.1016/j.jorganchem.2007.09.008

Title full: Studies of distannylated-1,2-dithiolato compounds: Synthesis of 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-thiones, (R₃SnCH₂)₂(dmit), and 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-o

Full text of DOI:10.1016/j.jorganchem.2007.09.008

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 692 (2007) 5583–5588
www.elsevier.com/locate/jorganchem
Studies of distannylated-1,2-dithiolato compounds: Synthesis of
4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-thiones,
(R3SnCH2)2(dmit), and 4,5-bis[(triorganostannylmethyl)thiolato]-
1,3-dithiole-2-ones, (R3SnCH2)2(dmio) – Crystal structures
of (Ph3SnCH2)2(dmit) and (Ph3SnCH2)2(dmio)
a
b
b
b
´
Thomas C. Baddeley , Jairo Bordinhao , Nadia M. Comerlato , Laila de Castro Cortas ,
˜
b
a
b,
*
Glaucio B. Ferreira , R. Alan Howie , James L. Wardell
a
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, Scotland, United Kingdom
ˆ
´
Departamento de Quı´mica Inorganica, Instituto de Quımica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil
b
Received 24 July 2007; received in revised form 5 September 2007; accepted 12 September 2007
Available online 20 September 2007
Abstract
The syntheses of 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-thione, (R3SnCH2)2(dmit) (5: R = Ph; 7: R3 = MePh2; 8:
R = Bu) and 4,5-bis[(triorganostannylmethyl)thiolato]-1,3-dithiole-2-one (6: Ph3SnCH2)2(dmio)], from the appropriate R3SnCH2I and
[NEt4]2[Zn(dmit)2] or [NEt4]2[Zn(dmio)2] are reported. Characterisation of 5–8 were generally achieved by NMR and IR spectra and
additionally for 5 and 6 by X-ray crystallography and mass spectrometry. Solution NMR data indicated four coordinate tin species,
while the single crystal structure determinations for 5 and 6 indicated distorted tetrahedral geometries around the tin atoms with only
very weak intermolecular interactions present, but none involve the tin atoms.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: 4,5-Dimercapto-1,3-dithiole-2-thione; 4,5-Dimercapto-1,3-dithiole-2-one; Organotin compounds; X-ray crystallography
1. Introduction
(dmio) (2: R = cyclohexyl or phenyl) [1] and the stannacy-
clic compounds, (6,6-diphenyl-6,7-dihydro-5H-1,3,4,
3
We have been investigating main group complexes of
the poly-sulfur containing 1,2-dithiolates, 4,5-dimercapto-
1,3-dithiole-2-thione, dmit, and 4,5-dimercapto-1,3-dithi-
ole-2-one, dmio, or as alternatively abbreviated, dmid,
for some time, see Fig. 1.
Tin dmit and dmio complexes have been of particular
interest [1–5]. Among the compounds obtained have been
the bis(triorganotin) species (Ph3Sn)2(dmit), 1 (R3Sn)2-
8-tetrathia-6-stannazulene-2-thione) and 4 (6,60-spirobi
[6,7-dihydro-5H-1,3,4,8-tetrathia-6-stannazulene]-2, 20-
dithione) [5]. The latter two compounds, as shown in
Scheme 1, were obtained from reactions of [NEt4]2[Zn-
(dmit)2] with Ph2Sn(CH2I)2 and Sn(CH2I)4, respectively.
We have continued this work with reactions of R3SnCH2I
with the dmit and dmio precursors, [NEt4]2[Zn(dmit)2] and
[NEt4]2[Zn(dmio)2], respectively, and have obtained the
bis(triorganostannylmethyl) derivatives, 5–8 and now we
wish to report our findings. Of particular interest were
the spatial arrangements of the two triorganostannyl moi-
eties in the solid state and any intramolecular interactions
involving the tin centres. Suitable crystals of 5 and 6 were
obtained, but not, unfortunately, of 7.
*
´
Corresponding author. Present address: Departamento de Quımica,
Instituto de Cieˆncias Exatas, Universidade Federal de Minas Gerais,
Avenida Antoˆnio Carlos 6627, Pampulha 31270-901, Belo Horizonte,
MG, Brazil. Fax: +55 21 2552 0435.
E-mail address: j.wardell@abdn.ac.uk (J.L. Wardell).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.09.008

5584
T.C. Baddeley et al. / Journal of Organometallic Chemistry 692 (2007) 5583–5588
S
R3SnS
R3SnS
R3SnCH2S
S
S
S
S
S
S
X
X
X
R3SnCH2S
S
X = S: dmit2-
X =O: dmio2-
5; R = Ph; X = S
1: R = Ph; X = S
2: R = Ph or cyclohexyl;
X = O
6: R = Ph; X = O
7: R3 = Ph2Me; X = S
8: R = Bu; X = S.
Fig. 1. Formation of compounds 3 and 4.
Ph
S
S
S
S
Sn
S
Ph2Sn(CH2I)2
Ph
3
S
S
S
S
S
S
S
S
NEt4
S
Zn
S
2
Sn(CH2I)4
S
S
S
S
S
S
S
S
S
Sn
S
4
Scheme 1.
2. Experimental
for 2 h, concentrated under vacuo and filtered. The crude
solid product was recrystallized from chloroform/metha-
nol. The red-brown crystals were found to be suitable for
X-ray crystallography. Yield 54.5%, m.p. 127–128 ꢁC.
Anal. Calc. for C41H34S5Sn2: C, 53.21; H, 3.81. Found:
C, 52.99; H, 3.73%.
2.1. General
All the synthetic procedures were carried out under
argon atmospheres using standard Schlenck techniques
with solvents dried prior to use. Compounds [NEt4]2[Zn(d-
mit)2] [6], [NEt4]2[Zn(dmio)2] [7], Ph3SnCH2I, MePh2CH2I
and Bu3SnCH2I [8] were obtained by published procedures.
Infrared spectra were obtained in CsI pellets on a Nicolet
1H NMR (300 MHz, CDCl3); d: 2.85 (s, 4H,
J
119,117Sn–1H = 45.1, 43.4 Hz), 7.45–7.52 (m, 18H,
p- + m-Ph), 7.65–7.70 (m, 12H, o-Ph).
13C (75 MHz, CDCl3); d: 15.2 (CH2, J119,117Sn–13C =
282, 270 Hz), 128.8 (119,117Sn–13C = 52 Hz, m-Ph), 129.5
Magna 760 FT-IR instrument. H, 13C and 119Sn NMR
1
spectra were run on Variant 300 MHz or Bruker
400 MHz Instruments. Melting points were measured on
a Melt-TempII. Elemental analyses were obtained using a
Perkin–Elmer 2400 apparatus. MS data were obtained on
a Waters Quattro Premier Triple quadruple instrument
was used, in ES+ and ESꢀ modes, for the MS data on
MeOH solutions, with source T = 100 ꢁC and desolvation
T = 150 ꢁC: mass of tin containing peaks are based on
Sn = 120. Daughter peaks were obtained with a collision
voltage of 15 V.
(
119,117Sn–13C = 12 Hz, p-Ph), 136.4 (J119,117Sn–13C
= 542, 519 Hz, i-Ph), 136.9 (119,117Sn–13C = 39 Hz, o-Ph),
138.3 (C@C), 211.0 (C@S).
119Sn (113 MHz, CDCl3); d: ꢀ119.9.
IR: (CsI): 3064, 3045, 3017, 2989, 2951, 2901, 1481,
1458, 1429, 1458, 1059, 728, 697, 516, 465, 446, 265, 243,
238 cmꢀ1
.
MS (ES+): 949 [(M + Na)+ < 1%], 926 [M+, 0.2%], 383
[Ph3SnS+, <1%], 351 [Ph3Sn+, 12%], 197 [PhSn+, 4%],
130 [100%].
MS (ESꢀ): 970, 958, 820, 561.
2.2. Preparation of (Ph3SnCH2)2dmit (5)
2.3. Preparation of (Ph3SnCH2)2dmio (6)
(Iodomethyl)triphenylstannane (1.96 g, 4.0 mmol) was
added to
a
solution of [NEt4]2[Zn(dmit)2] (0.73 g,
This was prepared analogously to 5 from Ph3SnCH2I
1.0 mmol) in acetone. The reaction mixture was refluxed
(1.96 g, 4.0 mmol) and [NEt4]2[Zn(dmio)2] (0.68 g

T.C. Baddeley et al. / Journal of Organometallic Chemistry 692 (2007) 5583–5588
5585
1.0 mmol). The crude product was recrystallized from chlo-
2.4. Preparation of (MePh2SnCH2)2dmit (7)
roform/methanol on cooling to give orange crystals. Yield
55%, m.p. 115–116 ꢁC.
This was prepared analogously to 5 from MePh2SnCH2I
(1.72 g, 4.0 mmol) and [NEt4]2[Zn(dmit)2] (0.73 g 1.0
mmol). The crude product was recrystallized from chloro-
form/methanol on cooling to give orange crystals. Yield
62%.
Anal. Calc. for C41H34S4OSn2: C, 54.15; H, 3.88.
Found: C, 53.80; H, 3.80%.
1H NMR (400 MHz, CDCl3); d: 2.84 (s, 4H,
J
119,117Sn–1H = 45.7, 44.8 Hz), 7.32–7.41 (m, 18H,
p- + m-Ph), 7.55–7.60(m, 12H, o-Ph).
1H NMR (400 MHz, CDCl3); d: 0.67 (s, 6H, J119,117
-
13C (100 MHz, CDCl3); d: 15.1 (CH2, J119,117Sn–13C =
286, 273 Hz), 128.7 (J119,117Sn–13C = 53.3 Hz, C-m),
129.0 (C@C), 129.8 (J119,117Sn–13C = 12 Hz C-p), 136.4
(J119,117Sn–13C = 541, 517 Hz, C-i), 136.8 (J119,117Sn–13C
= 38.6 Hz, C-o), 190.0 (C@O).
Sn–1H = 56 Hz, Me), 2.66 (s, 4H, J119,117Sn–1H = 43.0 Hz,
CH2), 7.22–7.37 (m, 12H, p- + m-Ph), 7.43–7.55 (m, 8H,
o-Ph).
13C (100 MHz, CDCl3); d: ꢀ9.1 (Me, J119,117Sn–13C =
375, 356 Hz), 13.3 (CH2, J119, 117Sn–13C = 258, 247 Hz),
128.4 (119,117Sn–13C = 50 Hz, m-Ph), 128.91 (119,117Sn–
13C = 11 Hz, p-Ph), 135.9 (119,117Sn–13C = 37 Hz, o-Ph),
138.3 (C@C), 140.3 (i-Ph), 210.9 (C@S).
119Sn (113 MHz, CDCl3); d: ꢀ119.8.
IR (CsI): 3063, 3048, 3011, 2987, 2948, 1664, 1610, 1480,
1430, 1074, 998, 730, 698, 455, 444, 378, 268, 229 cmꢀ1
.
MS (ES+, 60 eV): 409 [(Ph3SnC2H2S)+, 12%], 351
(Ph3Sn+, 100%), 197 (PhSn+, 22%), 130 (20%).
119Sn (113 MHz, CDCl3); d: ꢀ74.1.
MS (ESꢀ, 60 eV): 439 (Ph3SnC2H2S2þ, 78%), 407,
(Ph3SnC2S+, 8%), 383 (Ph3SnS+, 100%), 351 (Ph3Sn+, 42%).
MS (ESꢀ, 40 ev): 806 [(M-104)+, 5%], 545
2.5. Preparation of (Bu3SnCH2)2dmit (8)
This was prepared analogously to 5 from Bu3SnCH2I
(1.71 g, 4.0 mmol) and [NEt4]2[Zn(dmit)2] (0.68 g 1.0
mmol). A high boiling oil was obtained after work-up
and was purified by column chromatography on silica gel
using CHCl3/hexane as eluent. Yield 47%.
[Ph3SnCH2(dmio)+, 12%], 439 (Ph3SnC2H2Sþ, 100%), 383
2
(Ph3SnS+, 46%), 351 (Ph3Sn+, 20%).
MS (ESꢀ, 30 eV): 625 (75%), 545 [Ph3SnCH2(dmio)+,
48%], 439 (Ph3SnC2S2H2+, 59%), 383 (Ph3SnS+, 65%),
381 (100%).
Table 1
Crystal data and structure refinement for 5 and 6 at 120 K
5
6
Empirical formula
Formula weight
Temperature (K)
C41H34S5Sn2
924.36
120(2)
C41H34OS4Sn2
908.30
120(2)
˚
Wavelength (A)
0.71073
0.71073
Crystal system, space group
Unit cell dimensions
Monoclinic, P21/n
Monoclinic, P21/c
˚
a (A)
19.3725(4)
9.4163(2)
13.2254(2)
30.8810(7)
˚
b (A)
˚
c (A)
21.3612 (4)
9.70930(10)
b (ꢁ)
93.3864(8)
3889.85(14)
4, 1.578
1.581
105.5886(7)
3819.55(11)
4, 1.580
1.558
3
˚
Volume (A )
Z, calculated density (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
1840
1808
Crystal size (mm)
Theta range for data collection (ꢁ)
Index ranges
0.36 · 0.26 · 0.13
2.99–27.51
0.40 · 0.20 · 0.20
3.29–27.49
ꢀ24 6 h 6 25,
ꢀ12 6 k 6 11,
ꢀ27 6 l 6 27
43354/8902 [0.0430]
0.996
ꢀ17 6 h 6 17,
ꢀ40 6 k 6 40,
ꢀ12 6 l 6 12
52822/8774 [0.0385]
0.995
Reflections collected/unique [R(int)]
Completeness to hmax
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Semi-empirical from equivalents
1.0000 and 0.7859
Full-matrix least-squares on F2
8902/0/433
Semi-empirical from equivalents
1.0000 and 0.8078
Full-matrix least-squares on F2
8774/0/433
1.033
1.036
Final R indices [I > 2r(I)]
R1 = 0.0277,
wR2 = 0.0554
R1 = 0.0433,
wR2 = 0.0600
0.446 and ꢀ0.584
R1 = 0.0241,
wR2 = 0.0526
R1 = 0.0326,
wR2 = 0.0557
0.457 and ꢀ0.673
R indices (all data)
3
˚
Largest difference peak and hole (e/A )

5586
T.C. Baddeley et al. / Journal of Organometallic Chemistry 692 (2007) 5583–5588
1H NMR (400 MHz, CDCl3); d: 0.72–1.02 (m), 1.22–
The d119Sn NMR values for 5 and 6 in CDCl3 solution
are essentially the same, ꢀ119.9 and ꢀ119.8 ppm, and are
in the range, ꢀ118 to ꢀ121 ppm, reported for Ph3Sn-
CH2SC6H4X-p compounds in the same solvent [16]. Thus
the different electronic effects of the mercaptide groups in
these sulfidomethylstannanes are insulated from the tin
centre by the intervening methylene group. The d119Sn
NMR values for 5 and 6 and those for 7 (ꢀ74.1 ppm) and
8 (ꢀ7.9 ppm) are all close to the values for the correspond-
1.38 (m), 1.40–1.57 (m), 2.29 (s, 4H, J119,117Sn–1H = 37 Hz,
CH2S).
13C (100 MHz, CDCl3); d: 9.9, 13.7, 27.3, 28.9 (all Bu),
13.1 (CH2), 138.7 (C@C), 211.6 (C@S).
119Sn (113 MHz, CDCl3); d: ꢀ7.9.
IR (CsI): 1460, 1074, 1057, cmꢀ1
.
2.6. X-ray crystallography
ing
(iodomethyl)triorganostannanes
[
119Sn = ꢀ120.0,
Intensity data were obtained at 120(2) K with Mo Ka
radiation by means of the Enraf-Nonius Kappa CCD area
detector diffractometer of the EPSRC National crystallo-
graphic service at the University of Southampton, UK.
Data collection were carried out under the control of the
program COLLECT [9] and data reduction and unit cell
refinement was achieved with the COLLECT and DENZO [10]
software combination. Correction for absorption, by com-
parison of the intensities of equivalent reflections, was
applied by means of the program SADABS [11]. The program
ORTEP-3 for Windows [12] has been used in the preparation
of the figures and SHELXL-97 [13] and PLATON [14] in the cal-
culation of molecular geometry.
ꢀ70.1 and ꢀ2.9 for Ph3SnCH2I, MePh2SnCH2I and
Bu3SnCH2I, respectively]. Unambiguous proof of the for-
1
mation of 5–8 came however from H, 13C NMR and IR
spectra. Significant IR frequencies observed for 5 are 1458
(mC@C) and 1059 cmꢀ1(mC@S), and for 6 at 1480 (mC@C)
and 1664 cmꢀ1(mC@O), close to values found for other
tin-dmit and tin-dmio compounds [1–5].
Ready fragmentations of 5 and 6 were observed in the
mass spectral experiments. For compound 5, at a cone volt-
age of 60 EV and in the ES+ mode, a very low intensity m/e
cluster, [M+Na], <1%, was observed, along with cluster of
ions, Ph3Sn (12%) and PhSn [5%]. At the reduced cone volt-
age of 30ev and in the ESꢀ mode, higher value m/e peaks,
based on Sn = 120, were observed at 972 [M+2Na] (5%),
822 [Mꢀ104] (16%), 561 [Ph3SnCH2(dmit)] (100%).
Both structures were solved by direct methods using
SHELXS-97 [15] and in each case the initial solution was
expanded and fully refined by means of the program
SHELXL-97 [13]. In the final stages of the refinements hydro-
gen atoms, as appropriate, were introduced in calculated
Table 2
˚
Selected geometric parameters (A, ꢁ), for 5 and 6
˚
positions with C–H = 0.95, and 0.99 A for aryl and meth-
5
6
ylene, respectively, and refined with a riding model with
isotropic displacement parameters set to 1.2 times the
equivalent isotropic displacement parameter of the carbon
atom to which they are attached. Crystal data and struc-
ture refinement details are in Table 1.
Sn1–C11
Sn1–C21
Sn1–C31
Sn1–C4
S1–C1
S1–C4
S2–C2
S2–C5
S3–C3
2.132(2)
2.132(2)
2.136(2)
2.151(2)
1.755(2)
1.805(3)
1.750(2)
1.799(2)
1.729(2)
2.139(2)
2.133(2)
2.141(2)
2.164(2)
1.757(2)
1.799(2)
1.755(2)
1.799(2)
1.773(2)
3. Results and discussion
C1–S1–C4
C2–S2–C5
C3–S3–C1
C3–S4–C2
C2–C1–S3
C2–C1–S1
X5–C3–S4a
Sn2–C51
Sn2–C61
Sn2–C41
Sn2–C5
S3–C1
101.06(11)
102.03(11)
97.93(12)
98.07(12)
115.92(19)
124.82(19)
122.16(15)
2.126(2)
2.133(2)
2.141(2)
2.170(2)
1.749(3)
103.81(10)
103.27(10)
97.15(10)
97.04(10)
116.95(15)
123.87(16)
124.36(17)
2.137(2)
2.133(2)
2.131(2)
2.174(2)
1.753(2)
3.1. Synthesis and spectra
Compounds 5–8 were synthesized from reactions of
R3SnCH2I with either [NEt4]2[Zn(dmit)2] or NEt4]2[Zn(d-
mio)2], Eq. (1). Alkylation of the dmit and dmio moieties
proceeded readily with all the (iodomethyl)triorganostann-
anes used. The targeted products were purified by recrystal-
lisation of the reaction products, if solid, from chloroform/
methanol mixtures or in the case of 8, by chromatography.
S4–C3
1.738(3)
1.775(2)
S4–C2
1.742(2)
1.647(3)
1.357(3)
1.754(2)
1.213(2)
1.345(3)
X5–C3a
C1–C2
S3–C1–S1
C1–C2–S4
C1–C2–S2
S4–C2–S2
S3–C3–S4
X5–C3–S3a
a
119.25(14)
115.79(19)
123.78(19)
120.43(14)
112.29(14)
125.54(15)
118.76(11)
117.03(15)
125.86(16)
117.09(11)
111.76(12)
123.88(17)
ð1Þ
X for 5 = S; X for 6 is O.

T.C. Baddeley et al. / Journal of Organometallic Chemistry 692 (2007) 5583–5588
5587
ideal tetrahedral angle of 109.5ꢁ, being between 107.80(9)
and 115.07(10) in 5, and 105.55(8) and 115.69(8)ꢁ in 6.
Selected bond lengths and angles are shown in Table 2.
The atom arrangements and numbering systems are shown
in Fig. 2. The Sn–C bond lengths and the geometric param-
eters of the dmit and dmio moieties are in the ranges found
for other tin derivatives of these dithiolato ligands [1–5].
The dmit and dmio rings are essentially planar.
There are neither intramolecular Sn–Sn nor Sn–S inter-
actions in either 5 or 6. The compounds are essentially
molecular with only weak intermolecular interactions pres-
ent, none of which involve the tin centres, for example in 5,
there are a number of C–H–p contacts and a C–H–Sthione
hydrogen-bond. Each triphenylstannyl moiety in 5 and 6
has a propeller arrangement and the orientations of the
phenyl groups in neither compound allow for any intramo-
lecular p–p contacts.
Acknowledgements
We are grateful to Dr. E. Miguez and Prof. M.I.B. Tav-
´
ares (Instituto de Macromoleculas, UFRJ, Brazil) for
NMR spectra. We acknowledge the use of the Chemical
Data base Service at Daresbury and the X-ray crystallo-
graphic service at the University of Southampton, both
provided by the EPSRC, UK. J.L.W. thanks CNPq and
FAPEMIG, Brazil for financial support.
Fig. 2. (a) Atom arrangements and numbering scheme for 5. (b) Atom
arrangements and numbering scheme for 6. Hydrogen atoms have been
omitted for clarity and displacement ellipsoids are drawn at the 50%
probability level in both cases.
Appendix A. Supplementary material
The largest m/e values observed in the ES+/MS for 6 at
60 eV were for clusters of ions [Ph3SnC2H2S], [Ph3Sn] and
[PhSn]. At 60 eV in the ESꢀ/MS the largest m/e values were
for clusters of ions, [Ph3SnC2S2], [Ph3SnS] and [Ph3Sn]. The
use of reduced cone voltages results in the detection of
higher m/e fragments, thus at 40 eV clusters of ions, con-
taining two tin atoms, around 806 [Mꢀ106], are seen.
The ion with m/e of 625 in the ESꢀ/MS of 6 at 30 eV
remains unidentified. The envelope pattern of the ion
clearly indicates the presence of only a single tin atom.
The m/e value corresponds to Mꢀ285. Daughter ions
derived from this ion (using cone and collision voltages
of 30 and 15 eV) had m/e values of 545 [Ph3SnCH2(dmio)],
485 [Ph3SnC3H2S3] (weak) and 439 [Ph3SnC2S2], i.e.,
continuing fragmentation of the original dmio moiety is
occurring.
CCDC 654235 and 654236 contain the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2007.09.008.
References
[1] J. Bordinhao, N.M. Comerlato, G.B. Ferreira, R.A. Howie, C.X.A.
˜
da Silva, J.L. Wardell, J. Organomet. Chem. 691 (2006) 1598, and
references therein.
[2] G.B. Ferreira, E. Hollauer, N.M. Comerlato, J.L. Wardell, Spectro-
chim. Acta, Part A 62 (2005) 681.
[3] N.M. Comerlato, G.B. Ferreira, W.T.A. Harrison, R.A. Howie, J.L.
Wardell, Acta Crystallogr., Sect. C 61 (2005) m139.
[4] G.M. Allan, R.A. Howie, J.M.S. Skakle, J.L. Wardell, S.M.S.V.
Wardell, J. Organomet. Chem. 62 (2001) 189.
[5] W.T.A. Harrison, R.A. Howie, J.M.S. Skakle, J.L. Wardell, Acta
Crystallogr., Sect. C 58 (2002) m-351.
[6] L. Valade, J.P. Legros, M. Bousseau, P. Cassoux, J. Chem. Soc.,
Dalton Trans. (1985) 783.
[7] J.L. Wardell, Z.H. Chohan, R.A. Howie, R. Wilkens, S.M.S.V.
Doidge-Harrison, Polyhedron 16 (1995) 2689.
[8] L.A. Burnett, S.J. Garden, R.A. Howie, H. Rufino, J.L. Wardell, J.
Chem. Res. S (1998) 418.
The electronic effects on tin on changing the (CH2)2dmit
moieties for phenyltin groups are clearly seen in the d119Sn
values for 3 {Sn[(CH2)2dmit]2}, 4, {Ph2Sn[‘(CH2)2dmit]},
and 5 {(Ph3Sn)2[(CH2)2dmit]} of ꢀ30.0, ꢀ94.8 and
ꢀ119.9 ppm, respectively [5].
3.2. Solid state structures of 5 and 6
Both compounds, 5 and 6, contain 4-coordinate tin-cen-
tres, with the C–Sn–C bond angles ranging around the
[9] R.W.W. Hooft, COLLECT, Nonius BV, Delft, The Netherlands,
1998.

5588
T.C. Baddeley et al. / Journal of Organometallic Chemistry 692 (2007) 5583–5588
[10] Z. Otwinowski, W. Minor, Methods in enzymology, in: C.W.
CarterJr., R.M. Sweet (Eds.), Macromolecular Crystallography, Part
A, vol. 276, Academic Press, New York, 1997, p. 307.
[11] G.M. Sheldrick, SADABS Version 2.10, Bruker AXS Inc., Madison,
WI, USA, 1997.
[14] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
[15] G.M. Sheldrick, SHELXS-97, University of Go¨ttingen, Germany,
1997.
[16] J.M.S. Skakle, J.L. Wardell, S.M.S.V. Wardell, Acta Crystallogr.,
Sect. C 58 (2002) m-413;
[12] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
[13] G.M. Sheldrick, SHELXL-97, University of Go¨ttingen, Germany, 1997.
J.D. Kennedy, W. McFarlane, H.S. Pyne, P.L. Clarke, J.L. Wardell,
J. Chem. Soc., Perkin Trans II (1975) 1234.