Hypervalence at tin(IV) by transannular bonding of sulfur in an eight-membered ring: The case of dibenzostannocines [{S(C6H 4S)2}Sn]

Article abstract of DOI:10.1016/j.poly.2010.04.027

Treatment of Ph₂SnCl₂ with S(C₆H ₄SH)₂ in benzene leaded to the formation of [{S(C ₆H₄S)₂}SnPhCl] (1); the same reaction with 1,4-diazabicyclo-[2.2.2]-octane leaded [{S(C₆H₄S) ₂}SnPh₂] (4). The compounds [{S(C₆H ₄S)₂}SnPhHal] (Hal = Br, 2; I, 3) have been synthesized by halogen exchange from 1 and the corresponding potassium halide. The compound [{S(C₆H₄S)₂}SnCl₂] (5) was obtained from S(C₆H₄SH)₂ and SnCl₄. The reaction of 1 with NaS₂CNEt₂·3H₂O yielded [{S(C₆H₄S)₂}SnPh{S₂CNEt ₂}] (6). X-ray structure determinations of dibenzostannocines 1-6 revealed that the tin atom acts as an acceptor atom displaying an intramolecular transannular interaction with the sulfur (thioether-like) atom. The local geometry of the Sn atom in the compounds 1-5 is described as distorted trigonal bipyramidal with a TBP character spanning from 81% to 73%. In 6 the tin atom is six-coordinate with a distorted octahedral geometry.

Full text of DOI:10.1016/j.poly.2010.04.027

Polyhedron 29 (2010) 2283–2290
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Hypervalence at tin(IV) by transannular bonding of sulfur in an
eight-membered ring: The case of dibenzostannocines [{S(C6H4S)2}Sn]
a
a
José G. Alvarado-Rodríguez a, , Simplicio González-Montiel , Noemí Andrade-López ,
*
Juan Antonio Cogordan b, Laura L. Lima-Ortiz a
a Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, km. 4.5 Carretera Pachuca-Tulancingo, Col. Carboneras, Mineral de la Reforma,
Hidalgo, C.P. 42184, Mexico
b Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, D.F. México, C.P. 04510, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
Treatment of Ph2SnCl2 with S(C6H4SH)2 in benzene leaded to the formation of [{S(C6H4S)2}SnPhCl] (1);
the same reaction with 1,4-diazabicyclo-[2.2.2]-octane leaded [{S(C6H4S)2}SnPh2] (4). The compounds
[{S(C6H4S)2}SnPhHal] (Hal = Br, 2; I, 3) have been synthesized by halogen exchange from 1 and the cor-
responding potassium halide. The compound [{S(C6H4S)2}SnCl2] (5) was obtained from S(C6H4SH)2 and
SnCl4. The reaction of 1 with NaS2CNEt2Á3H2O yielded [{S(C6H4S)2}SnPh{S2CNEt2}] (6). X-ray structure
determinations of dibenzostannocines 1–6 revealed that the tin atom acts as an acceptor atom displaying
an intramolecular transannular interaction with the sulfur (thioether-like) atom. The local geometry of
the Sn atom in the compounds 1–5 is described as distorted trigonal bipyramidal with a TBP character
spanning from 81% to 73%. In 6 the tin atom is six-coordinate with a distorted octahedral geometry.
Ó 2010 Elsevier Ltd. All rights reserved.
Received 7 December 2009
Accepted 28 April 2010
Available online 12 May 2010
Keywords:
Tin
Hypervalent compounds
Structure elucidation
Dithioligands
1. Introduction
D
It is well known that heavier group 14 elements have the ability
to expand their coordination numbers above four, accommodating
formally more than eight electrons in their valence shell and to
form so-called hypervalent compounds [1–3]. To promote this
hypervalent bonding situation, some ligands capable of yielding
compounds containing five-membered chelate rings by means of
a DÁ Á ÁA donor–acceptor intramolecular bond have been used in or-
der to increase the coordination number of an acceptor atom A.
These compounds comprise the metallatranes [1] and metallo-
canes [4] which contain ethylene units quite flexible in the ring.
When these ethylene units are replaced by less flexible groups as
benzene rings, compounds of the type I containing p-block ele-
ments can be synthesized; they also display the same donor–
acceptor interaction (some examples are with D = S, SO2; E = O
and A = Si, P [5–8]; with D = S, Se; E = O and A = Ge [9–11]). We
have also studied these type of compounds with D = S, O; E = S
and A = Ge, [12,13] shown by X-ray diffraction and theoretical
methods the different degrees and nature of the DÁ Á ÁGe interaction,
observing the strongest interaction when the exocyclic ligands are
halides.
E
E
A
I
Herein, we report a structural study of organotin compounds with
tin(IV) as acceptor atom, an easy-to-follow nucleus by 119Sn NMR
spectroscopy, where the coordination number has been varied in
function of the nature of the different exocyclic ligands. After the
description of the synthesis of dibenzostannocines, Mass spectrom-
etry, NMR spectroscopy and X-ray crystallographic data are pre-
sented and discussed.
2. Experimental
2.1. Materials and methods
All manipulations were performed under a dry, oxygen-free
dinitrogen atmosphere using standard Schlenk techniques. Sol-
vents were dried by standard methods and distilled prior to use.
Melting points were determined on a Mel-Temp II instrument
and are uncorrected. Spectra were recorded with the following
instruments: Electron-impact mass spectra (EI-MS) were mea-
sured on either Finnigan MAT 8230 or Varian MAT CH5 instrument.
Elemental analyses were recorded on a Perkin–Elmer Series II
* Corresponding author. Tel.: +52 771 7172000.
E-mail address: jgar@uaeh.edu.mx (J.G. Alvarado-Rodríguez).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.04.027

2284
J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
CHNS/O Analyzer. IR spectra were recorded in the 4000–400 cmÀ1
range on a Perkin–Elmer System 2000 FT-IR spectrometer, as KBr
pellets. 1H, 13C{1H} and 119Sn{1H} NMR spectra were recorded on
a Jeol Eclipse 400 spectrometer operating at 399.78, 100.53, and
149.03 MHz, respectively; the spectra were acquired at room tem-
perature (25 °C) unless otherwise specified. The chemical shifts are
reported in ppm with respect to the references and stated relative
to external tetramethylsilane (TMS) for 1H and 13C NMR, and
Me4Sn for 119Sn NMR spectroscopy. S(C6H4SH)2 was synthesized
according to literature methods [14]. Ph2SnCl2, SnCl4, 1,4-diazabi-
cyclo-[2.2.2]-octane (DABCO), KBr, KI, NaS2CNEt2Á3H2O and HBr
were purchased from Aldrich and Fluka and used as supplied.
2.2.3. Synthesis of [{S(C6H4S)2}SnPhI] (3)
Compound 1 (0.4 g, 0.83 mmol) and KI (0.7 g, 4.2 mmol) were
suspended in benzene (25 mL) and refluxed for 16 h. The yellow
suspension obtained was dried by means of a column filled with
Celite and anhydrous Na2SO4. After evaporation, the residue was
redissolved in chloroform (50 mL); the solution was slowly evapo-
rated with a dinitrogen gas flow to dryness, providing yellow-pale
crystals of 3, which were washed with hexanes (40 mL) and filtered
by suction. Yield: 380 mg (80%), m.p. 178 °C. Anal. Calc. for
[{S(C6H4S)2}SnPhI] (571.11): C, 37.85; H, 2.29. EI-MS: m/z
(%) = 444 (95) [M+ÀIÀ1], 368 (5) [S(C6H4S)2Sn], 216 (base peak)
[S(C6H4S)+]. Found: C, 38.15; H, 2.21. 1H NMR (CDCl3): d = 7.77
[m, 3J(1H–119Sn) = 93 Hz, 2H, H5], 7.68 (dd, 3JH 2 = 7.68 Hz, 4JH
1
1
–H
–
3 = 1.48 Hz, 2H, H1), 7.43 (dd, 3JH 3 = 7.68 Hz, 4JH 2 = 1.48 Hz,
4
4
H
–H
–H
2H, H4), 7.42 (m, 3H, H6 and H7), 7.28 (ddd, 3JH 1 = 3JH
2.2. Synthesis of the dibenzostannocine compounds
[{S(C6H4S)2}SnL1L2]
2
2
–H
–
3 = 7.68 Hz, 4JH 4 = 1.48 Hz, 2H, H2), 7.17 (ddd, 3JH 2 = 3JH
2
3
3
H
–H
–H
–
4 = 7.68 Hz, 4JH 1 = 1.48 Hz, 2H, H3) ppm. 13C{1H} NMR (CDCl3):
3
H
–H
d = 141.2 [3J(13C–119Sn) = 31 Hz, C4a], 140.9 [C5a], 134.2
[2J(13C–119Sn) = 65 Hz, C5], 133.8 [C4], 131.9 [2J(13C–119Sn) = 40 Hz,
C1], 131.2 [C7], 131.0 [C1a], 130.3 [C2], 129.4 [3J(13C–119Sn) =
92 Hz, C6], 127.1 [C3] ppm. 119Sn{1H} NMR (CDCl3):
2.2.1. Synthesis of [{S(C6H4S)2}SnPhCl] (1)
Ph2SnCl2 (1.38 g, 4.0 mmol) in benzene (25 mL) was added to a
solution of S(C6H4SH)2 (1.00 g, 4.0 mmol) in benzene (25 mL) at
5 °C. The yellow mixture was stirred and refluxed for 24 h. The
mixture was allowed to cool to room temperature. Colorless crys-
tals of 1 were obtained by slow evaporation. The crystals were sep-
arated by suction and washed with hexanes (40 mL). Yield: 1.75 g
(91%), m.p. 228 °C. Anal. Calc. for [{S(C6H4S)2}SnPhCl] (479.65): C,
45.07; H, 2.73. Found: C, 44.86; H, 2.81%. EI-MS: m/z (%) = 480
(10) [M+], 445 (10) [M+ÀCl], 367 (10) [S(C6H4S)2SnÀ1], 216 (base
peak) [S(C6H4S)+]. 1H NMR (CDCl3): d = 7.84 [m, 3J(1H–119Sn)
d = À180.8 ppm. IR (KBr):
t = 3043, 1570, 1443, 1430, 1251, 1105,
1037, 800, 752, 727, 687, 653 cmÀ1
.
2.2.4. Synthesis of [{S(C6H4S)2}SnPh2] (4)
A solution of S(C6H4SH)2 (0.5 g, 2.0 mmol) and DABCO (0.225 g,
2.0 mmol) in chloroform (25 mL) at 0 °C was stirred for 1 h; after-
ward a solution of Ph2SnCl2 (0.69 g, 2.0 mmol) in chloroform
(25 mL) was added. The mixture was refluxed for 24 h. Then, the
solution was dried by means of a column filled with Celite and
anhydrous Na2SO4. The solution was slowly evaporated with a
dinitrogen gas flow to dryness, providing colorless crystals of 4,
which were washed with hexanes (20 mL) and filtered by suction.
Yield: 0.93 g (90%), m.p. 132 °C. Anal. Calc. for [{S(C6H4S)2}SnPh2]
(521.30): C, 55.29; H, 3.48. Found: C, 55.99; H, 3.61%. EI-MS m/z
(%): 522 (10) [M+], 445 (85) [M+ÀPh], 368 (5) [S(C6H4S)2Sn], 216
= 94 Hz, 2H, H5], 7.69 (dd, 3JH 2 = 7.68 Hz, 4JH 3 = 1.44 Hz, 2H,
1
1
–H
–H
H1), 7.48 (dd, 3JH 3 = 7.68 Hz, 4JH 2 = 1.44 Hz, 2H, H4), 7.45 (m,
4
4
–H
–H
2
3H, H6 and H7), 7.29 (ddd, 3JH 1 = 3JH 3 = 7.68 Hz, 4JH
2
2
–H
3
–H
3
–
4 = 1.44 Hz, 2H, H2), 7.17 (ddd, 3JH 2 = 3JH 4 = 7.68 Hz, 4JH
3
H
–H
–H
–
1 = 1.44 Hz, 2H, H3) ppm. 13C{1H} NMR (CDCl3, 60 °C): d = 141.6
H
[3J(13C–119Sn) = 27 Hz, C1a], 141.2 [C5a], 134.6 [2J(13C–119Sn) =
64 Hz, C5], 133.6 [C4], 132.3 [3J(13C–119Sn) = 45 Hz, C1], 131.2
[C7], 130.7 [C1a], 130.4 [C2], 129.5 [3J(13C–119Sn) = 96 Hz, C6],
126.9 [C3] ppm. 119Sn{1H} NMR (CDCl3): d = À63.4 ppm. IR (KBr):
(base peak) [S(C6H4S)+]. 1H NMR (CDCl3): d = 7.71 (dd, 3JH
1
–
2 = 7.72 Hz, 4JH 3 = 1.48 Hz, 2H, H1), 7.65 (m, 2H, H5), 7.42 (dd,
1
H
–H
3JH 3 = 7.72 Hz, 4JH 2 = 1.48 Hz, 2H, H4), 7.37 (m, 3H, H6 and
4
4
= 3049, 1567, 1444, 1430, 1255, 1037, 752, 727, 688 cmÀ1
.
–H
–H
t
H7), 7.22 (ddd, 3JH 1 = 3JH 3 = 7.72 Hz, 4JH 4 = 1.48 Hz, 2H,
2
2
2
–H
–H
–H
H2), 7.11 (ddd, 3JH 2 = 3JH 4 = 7.72 Hz, 4JH 1 = 1.48 Hz, 2H,
3
3
3
–H
–H
–H
2.2.2. Synthesis of [{S(C6H4S)2}SnPhBr] (2)
H3) ppm. 13C{1H} NMR (CDCl3): d = 142.4 [C5a], 140.5
[3J(13C–119Sn) = 24 Hz, C4a], 135.5 [2J(13C–119Sn) = 50 Hz, C5],
134.8 [C1a], 133.8 [C4], 133.3 [3J(13C–119Sn) = 28 Hz, C1], 129.9
[4J(13C–119Sn) = 15 Hz, C7], 129.0 [C2], 128.9 [3J(13C–119Sn) =
65.4 Hz, C6], 126.6 [C6] ppm. 119Sn{1H} NMR (CDCl3):
Compound 1 (0.4 g, 0.83 mmol), KBr (0.5 g, 4.2 mmol), and HBr
48% (2 mL) were suspended in benzene (25 mL) and refluxed for
16 h. The water was removed by means of a Dean–Stark trap.
The white suspension obtained was filtered and dried by means
of a column filled with Celite and anhydrous Na2SO4. After evapo-
ration, the residue was redissolved in chloroform (50 mL); the
solution was slowly evaporated with a dinitrogen gas flow to dry-
ness, providing colorless crystals of 2, which were washed with
hexanes (40 mL) and filtered by suction. Yield: 300 mg (68%),
m.p. 202 °C. Anal. Calc. for [{S(C6H4S)2}SnPhBr] (524.10): C,
41.25; H, 2.50. Found: C, 40.69; H, 2.41%. EI-MS: m/z (%) = 524
(13) [M+], 445 (50) [M+ÀBr], 367 (5) [S(C6H4S)2SnÀ1], 216 (base
peak) [S(C6H4S)+]. 1H NMR (CDCl3): d = 7.82 [m, 3J(1H–119Sn)
d = À18.4 ppm. IR (KBr):
t = 3060, 1569, 1441, 1427, 1245, 1101,
1066, 1039, 747, 724, 691 cmÀ1
.
2.2.5. Synthesis of [{S(C6H4S)2}SnCl2] (5)
To a solution of SnCl4 (0.52 g, 2.0 mmol) in benzene (25 mL) was
added S(C6H4SH)2 (0.5 g, 2.0 mmol) in benzene (25 mL) at 5 °C. The
mixture was stirred and refluxed for 6 h. The yellow solution was
dried by means of a column filled with Celite and anhydrous
Na2SO4. The solution was slowly evaporated with a dinitrogen
gas flow to dryness, providing crystals of 5, which were washed
with hexanes (40 mL) and filtered by suction. Yield: 0.34 g (43%),
m.p. 112 °C. Anal. Calc. for [{S(C6H4S)2}SnCl2] (438.00): C, 32.91;
H, 1.84. Found: C, 32.35; H, 1.90%. EI-MS: m/z (%) = 438 (5) [M+],
400 (8) [M+ÀCl], 368 (8) [S(C6H4S)2Sn], 216 (base peak)
= 96 Hz, 2H, H5], 7.68 (dd, 3JH 2 = 7.52 Hz, 4JH 3 = 1.44 Hz, 2H,
1
1
–H
–H
H1), 7.45 (dd, 3JH 3 = 7.52 Hz, 4JH 2 = 1.44 Hz, 2H, H4), 7.44 (m,
4
4
–H
–H
2
3H, H6 and H7), 7.28 (ddd, 3JH 1 = 3JH 3 = 7.52 Hz, 4JH
2
2
–H
3
–H
3
–
4 = 1.44 Hz, 2H, H2), 7.17 (ddd, 3JH 2 = 3JH 4 = 7.52 Hz, 4JH
3
H
–H
–H
–
1 = 1.44 Hz, 2H, H3) ppm. 13C{1H} NMR (CDCl3): d 141.3 [C5a],
H
141.1 [3J(13C–119Sn) = 27 Hz, C4a], 134.6 [2J(13C–119Sn) = 65 Hz,
C5], 133.7 [C4], 132.2 [3J(13C–119Sn) = 40 Hz, C1], 131.3 [C7],
130.6 [C1a], 130.4 [C2], 129.5 [3J(13C–119Sn) = 90 Hz, C6], 127.0
[C3] ppm. 119Sn{1H} NMR (CDCl3): d = À95.1 ppm. IR (KBr):
[S(C6H4S)+]. 1H NMR (CDCl3): d = 7.71 (dd, 3JH 2 = 7.72 Hz, 4JH
1
1
–H
–
3 = 1.48 Hz, 2H, H1), 7.54 (dd, 3JH 3 = 7.72 Hz, 4JH 2 = 1.48 Hz,
4
4
H
–H
–H
2H, H4), 7.34 (ddd, 3JH 1 = 3JH 3 = 7.72 Hz, 4JH 4 = 1.48 Hz,
2
2
2
–H
3
–H
–H
2H, H2), 7.27 (ddd, 3JH 2 = 3JH 4 = 7.72 Hz, 4JH 1 = 1.48 Hz,
3
3
–H
–H
–H
t
= 3050, 1568, 1445, 1442, 1249, 1081, 1039, 862, 735, 730, 710,
2H, H3) ppm. 13C{1H} NMR (CDCl3): d = 139.1 [3J(13C–119Sn) =
35 Hz, C4a], 133.6 [C4], 131.8 [3J(13C–119Sn) = 69 Hz, C1], 131.1
692 cmÀ1
.

J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
2285
[C2], 130.0 [2J(119Sn–13C) = 40 Hz, C1a], 127.8 [C3] ppm. 119Sn{1H}
NMR (CDCl3): d = À142.8 ppm. IR (KBr): = 3047, 1569, 1441,
1245, 1101, 1039, 747 cmÀ1
[15]. An empirical absorption correction based on the multiple
measurement of equivalent reflections was applied by using the
program SADABS [16]. The displacement parameters of non-hydro-
gen atoms were refined anisotropically. The positions of the hydro-
gen atoms were kept fixed with a common isotropic displacement
parameter. Selected crystallographic data are given in Table 1.
t
.
2.2.6. Synthesis of [{S(C6H4S)2}SnPh{S2CNEt2}] (6)
Compound 1 (0.1 g, 0.20 mmol) and NaS2CNEt2Á3H2O (0.125 g,
0.60 mmol) were suspended in benzene (25 mL) and refluxed for
16 h. The yellow suspension obtained was dried by means of a col-
umn filled with Celite and anhydrous Na2SO4. After evaporation,
the residue was redissolved in chloroform (40 mL); the solution
was slowly evaporated with a dinitrogen gas flow to provide yel-
low crystals of 6, which were washed with hexanes (40 mL) and fil-
tered by suction. Yield: 90 mg (80%), m.p. 140 °C. Anal. Calc. for
[{S(C6H4S)2}SnPh{S2CNEt2}] (592.47): C, 46.63; H, 3.91. Found: C,
46.78; H, 3.94%. 1H NMR (CDCl3): d = 7.89 [m, 3J(1H–119Sn) = 94 Hz,
3. Results and discussion
3.1. Synthesis
Treatment of Ph2SnCl2 in benzene at reflux with the ligand
S(C6H4SH)2 yielded the corresponding organotin compound
[{S(C6H4S)2}SnPhCl] (1) (see Scheme 1); the Sn–Ph cleavage reac-
tion was favored by the HCl formed in the reaction. The same reac-
tion in chloroform in presence of the base 1,4-diazabicyclo-[2.2.2]-
octane (DABCO) yielded the corresponding diphenylated com-
pound [{S(C6H4S)2}SnPh2] (4). The addition of the base DABCO
avoided the Sn–C cleavage reaction by trapping the HCl formed.
Treatment of S(C6H4SH)2 with SnCl4 in hot benzene yielded
[{S(C6H4S)2}SnCl2] (5). [{S(C6H4S)2}SnPhBr] (2) was synthesized
from 1 by treatment with an excess of KBr in a refluxing HBr/ben-
zene mixture, giving 2 as colorless crystals. The compounds
[{S(C6H4S)2}SnPhI] (3) and [{S(C6H4S)2}SnPh{S2CNEt2}] (6) were
obtained by the reaction of 1 with an excess of KI and NaS2C-
NEt2Á3H2O, respectively (see Section 2 for details).
2H, H5], 7.62 (dd, 3JH 2 = 7.72 Hz, 4JH 3 = 1.48 Hz, 2H, H1), 7.48
1
1
–H
–H
(dd, 3JH 3 = 7.72 Hz, 4JH 2 = 1.48 Hz, 2H, H4), 7.35 (m, 3H, H6
4
4
–H
–H
and H7), 7.21 (ddd, 3JH 1 = 3JH 3 = 7.72 Hz, 4JH 4 = 1.48 Hz,
2
2
2
–H
–H
–H
2H, H2), 7.07 (ddd, 3JH 2 = 3JH 4 = 7.72 Hz, 4JH 1 = 1.48 Hz,
3
3
3
–H
–H
–H
3
3
2H, H3), 3.65 (c, JH–H = 7.14 Hz, 4H, CH2), 1.24 (t, JH–H = 7.14 Hz,
6H, CH3) ppm. 13C{1H} NMR (CDCl3, 60 °C): d = 197.7 [C@N],
150.2 [C5a], 145.2 [3J(113C–119Sn) = 20 Hz, C4a], 135.0 [C1a],
133.8
[2J(13C–119Sn) = 30 Hz,
C5],
133.3
[C4],
132.9
[3J(13C–119Sn) = 40 Hz, C1], 129.3 [C7], 128.5 [3J(13C–119Sn) =
40.0 Hz, C6], 125.4 [C3], 51.3 [CH2], 12.0 [CH3] ppm. 119Sn{1H}
NMR (CDCl3): d = À322.6 ppm. IR (KBr):
t = 3043, 2929, 2869,
1570, 1443, 1430, 1251, 1105, 1037, 800, 752, 727, 687, 653 cmÀ1
.
All compounds are air-stable, soluble in benzene, toluene,
dichloromethane and chloroform, and insoluble in pentane, hexane
and isopropanol.
2.3. X-ray crystallography
Suitable single crystals of compounds 1, 2, 3 and 5 were grown
by slow evaporation from a benzene solution. Compounds 4 and 6
were grown by slow evaporation from a chloroform solution. X-ray
diffraction data on 1–6 were collected at room temperature on a
3.2. Mass spectra
Electron-impact mass spectra for 1–5 were obtained at 70 eV.
Spectra for 1, 2, 4 and 5 exhibit a low intensity ion with the appro-
priate isotopic ratio representing the molecular ion (M+). In the
compounds 1–4 was observed a peak at 445 m/z corresponding
to the fragment M–L [L = Cl (1), Br (2), I (3), Ph (4)] and assigned
in all cases to the [{S(C6H4S)2}SnPh]+ fragment, confirming the
binding of tin to the sulfur atoms. In 5 was observed a low intensity
CCD SMART 6000 diffractometer through the use of Mo Ka radia-
tion (k = 0.71073 Å, graphite monochromator). Data were inte-
grated, scaled, sorted and averaged using the SMART software
package. The structures were solved by direct methods, using SHEL-
XTL NT Version 5.1 and refined by full-matrix least squares against F2
Table 1
Selected crystallographic data for dibenzostannocines 1–6.
1
2
3
4
5
6
Empirical formula
Molecular weight (g/mol)
Crystal size (mm)
Crystal system
C
18H13ClS3Sn
C18H13BrS3Sn
524.06
0.5 Â 0.30 Â 0.12
monoclinic
P21/c
C18H13IS3Sn
571.05
0.25 Â 0.17 Â 0.07
monoclinic
P21/c
C24H18S3Sn
521.25
C12H8Cl2S3Sn
437.95
C23H23NS5Sn
592.41
479.60
0.45 Â 0.30 Â 0.15
monoclinic
P21/c
0.60 Â 0.30 Â 0.14
0.56 Â 0.30 Â 0.09
0.50 Â 0.40 Â 0.35
triclinic
triclinic
triclinic
ꢀ
ꢀ
ꢀ
Space group
P1
P1
P1
qcalc (mg mÀ3
)
1.714
1.833
1.936
1.588
1.881
1.549
Z
4
4
4
2
4
4
a (Å)
b (Å)
c (Å)
9.9842(7)
10.3455(7)
18.2982(12)
90
100.469(2)
90
9.9795(9)
10.5556(8)
18.3338(16)
90
100.496(2)
90
10.0005(5)
10.8314(5)
18.3957(9)
90
100.4690(10)
90
9.9619(8)
10.3246(9)
11.2615(10)
73.151(2)
79.617(2)
88.713(2)
1089.85(16)
1.467
10.7133(13)
12.1698(15)
12.2679(15)
88.048(3)
89.735(3)
75.314(3)
1546.3(3)
2.381
10.2910(5)
15.7117(8)
17.1812(9)
70.9350(10)
76.2620(10)
80.6230(10)
2539.5(2)
1.428
a
(°)
b (°)
(°)
V (Å3)
c
1858.6(2)
1.851
1899.0(3)
3.775
1959.44(16)
3.195
l
(mmÀ1
)
F(0 0 0)
GOF
944
0.919
1016
0.864
1088
1.021
520
0.997
848
0.993
1192
1.107
Absorption correction
Reflections collected
Unique reflections
Rint
SADABS
SADABS
SADABS
SADABS
SADABS
SADABS
12,114
3666
0.0683
12,275
3711
0.0606
12,772
3849
0.0356
7279
4256
0.0200
9943
6119
0.0479
18,784
9943
0.0273
R1, wR2 [I > 2
r
(I)]
0.0357, 0.0735
0.0561, 0.0793
0.0383, 0.0776
0.0784, 0.1089
0.0328, 0.0849
0.0463, 0.0911
0.0294, 0.0695
0.0388, 0.0726
0.0591, 0.1631
0.0989, 0.1843
0.0405, 0.1269
0.0539, 0.1645
R1, wR2 (all data)
Large residuals (e ÅÀ3
)
0.828/À0.606
0.655/À0.777
0.414/À1.204
0.320/À0.463
1.225/À0.874
0.673/À1.072

2286
J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
S
S
S
Ph2SnCl2/DABCO
CHCl3
SnCl4
C6H6
S
S
S
S
Sn
Sn
SH HS
Ph
Ph
Cl
Cl
4
5
Ph2SnCl2
C6H6
S
S
S
KI
C6H6
KBr/HBr
C6H6
S
S
S
I
S
S
S
Sn
Sn
Sn
Ph
Ph
Cl
Br
Ph
1
3
2
C6H6
NaS2CNEt2 .3 H2O
S
S
S
Sn
Ph
S2CNEt2
6
Scheme 1. Synthesis of compounds [{S(C6H4S)2}SnL1L2].
peak at 403 m/z assignable to the loss of a chloro ligand. In all com-
pounds was observed a peak at 368 m/z corresponding to the tricy-
clic moiety {S(C6H4S)2}Sn. For 1, 2, 4 and 5 was observed a base
peak at 216 m/z assigned to the thianthrenic fragment S(C6H4)2S;
in 3 the base peak was assigned to the loss of the iodo ligand. In
all compounds a peak was also observed at 184 m/z attributable
to the dibenzothiophene fragment. No more peaks could be
assigned.
Table 2
1H NMR chemical shifts (d values, ppm) for dibenzostannocines 1–6.
L1
H-1
H-2
H-3
H-4
H-5
H-6
H-7
1
2
3
4
5
6
Cl
Br
I
Ph
7.69
7.68
7.68
7.71
7.71
7.62
7.29
7.28
7.28
7.22
7.34
7.21
7.17
7.17
7.17
7.11
7.27
7.07
7.48
7.48
7.43
7.42
7.54
7.48
7.84
7.82
7.77
7.65
–
7.45
7.44
7.42
7.37
–
7.45
7.44
7.42
7.37
–
Cl
S2CNEt2
7.89
7.35
7.35
3.3. NMR spectra
3.3.2. 13C{1H} NMR spectra
NMR spectra of compounds 1–6 were recorded in the non-coor-
dinating solvent CDCl3, at room temperature unless otherwise
specified. The assignments of these compounds were performed
by 1D (1H, 13C and 119Sn) and 2D 1H–1H COSY, 1H–13C HETCOR
and COLOC as well as 1H–119Sn HETCOR spectroscopy. The num-
bering scheme for the assignment of the 1H and 13C{1H} NMR sig-
nals are shown in Scheme 2, and the 1H, 13C{1H} and 119Sn{1H}
NMR chemical shifts are shown in Tables 2–4, respectively.
Proton decoupled 13C spectra of compounds 2, 3 and 4 display
the expected ten signals in the aromatic region while 1 and 6 just
display nine signals at room temperature; the missing signals
could be observed at higher temperatures. The spectrum of com-
pound 5 displays the expected six signals. The ethyl groups of
the dithiocarbamate moiety in 6 are equivalents; the methyl group
is observed at 12.0 ppm and the methylene at 51.3 ppm, whereas
the C@N group is observed at 197.1 ppm. A noteworthy observa-
tion is that the magnitude of the 3J(13C–119Sn) coupling constant
involving the ortho-carbon C-1 in the dibenzostannocine moiety
is dependent of the nature of the exocyclic ligands binded to the
tin atom; the highest value is observed in 5 (69 Hz, two chloro li-
gands), whereas the lowest value is observed in 4 (28 Hz, two phe-
nyl groups).
3.3.1. 1H NMR spectra
The 1H NMR spectra of 1–6 show four signals in an ABCD pat-
tern, typical of ortho-substituted benzenic rings. In solution, the
two S(C6H4S)Sn halves are equivalent. The protons H-5 in 1, 2, 3
and 6 show coupling with the 119Sn isotope [3J(1H–119Sn) ranging
from 93 to 96 Hz]; in 4 the coupling constant was not observed.
For 6 the ethyl groups displayed only two signals at 1.24 (CH3)
and 3.65 (CH2) ppm.
3.3.3. 119Sn{1H} NMR spectroscopy
The 119Sn NMR spectra were obtained in the non-coordinating
solvent CDCl3. 119Sn spectra of the compounds 1–6 showed a sharp
signal indicating the existence of a single tin compound (see Table
4). In seminal papers, has been noted that the 119Sn chemical shifts,
4
4
3
3
S
S
2
2
d
119Sn), move to lower frequencies as the coordination number in-
1
1
creases, although the d119Sn) ranges are somewhat dependent on
the nature of the substituents [17,18]. In this work, all tin com-
pounds contain the potentially tridentate {S(C6H4S)2}2À moiety,
so they can be compared when the pendant exocyclic ligands L1
and L2 are changed. For example, 4 has two phenyl groups attached
to the tin atom; it is well known that organic fragments usually
diminishes the acceptor abilities of a central atom. Hence, is plau-
S
L1
S
S
S
Sn
Sn
Cl
Cl
5
7
6
L1 = Cl(1), Br(2), I(3), Ph(4), S2CNEt2(6)
5
Scheme 2. Labeling of compounds [{S(C6H4S)2}SnL1L2].

J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
2287
Table 3
13C{1H} NMR chemical shifts (d values, ppm) and coupling constants [nJ(13C–119Sn), nJ in Hz] for dibenzostannocines 1–6.
L1
Cl
C-1
C-2
C-3
127
C-4
C-1a
C-4a
C-5
C-5a
C-6
C-7
a
1
132.4
3J = 45
132.3
3J = 45
132.2
3J = 40
131.9
3J = 40
133.3
3J = 28
131.8
3J = 69
133.9
3J = 40
132.9
3J = 40
130.4
133.6
140.9
3J = 27
141.6
3J = 27
141.1
3J = 27
141.2
3J = 31
140.5
3J = 24
139.1
3J = 35
145
134.7
2J = 64
134.6
2J = 64
134.6
2J = 65
134.2
2J = 65
135.5
2J = 50
–
141.2
129.6
3J = 96
129.5
3J = 96
129.5
3J = 90
129.3
3J = 92
128.9
3J = 65
–
131.3
131.2
131.3
131.2
1b
2
Cl
130.3
130.4
130.3
129
126.9
127
133.6
133.7
133.8
133.8
133.6
132.9
133.3
130.7
130.6
131
141.2
141.3
140.9
142.4
Br
3
I
127.1
126.6
127.8
125.5
125.4
4
Ph
134.8
130
129.9
4J = 15
–
5
Cl
131.1
129.2
129
–
a
6
S2CNEt2
S2CNEt2
134.9
135
133.8
2J = 30
133.8
2J = 30
128.6
3J = 40
128.5
3J = 40
129.4
129.3
3J = 20
145.2
3J = 20
6b
150.2
a
Not observed at room temperature.
At 60 °C.
b
Table 4
119Sn{1H} NMR data (ppm) for 1–6 compounds in chloroform solution (25 °C) and
and 2.69 Å in SnI4) [32]. The Sn–Cl distance in 1 is shorter than the
reported for the analog stannocane [2.453(1) Å in
coordination number assigned in solution (CN).
S(CH2CH2S)2SnPhCl] [25]. There are two different Sn–Cl distances
in 5 and are similar to those found for S(CH2CH2S)2SnCl2 [2.392(3)
and 2.348(3) Å], a compound where has been described a trigonal
bipyramidal (TBP) local geometry for the tin atom; where the lon-
gest distance corresponds to the chloro ligand in an axial position
[21]. The Sn–Br distance in 2 is similar to other one observed for
stannocanes with bromo ligands in axial position [24]. The Sn–I in
3 is shorter than the observed for stannocanes with tin bonded to
an iodo ligand in axial position [2.804(2) Å S(CH2CH2S)2SnI2] [24].
The Sn–C distances are in good agreement with other organotin
compounds [23,24,33–35]. In particular the compounds 4 and 5
display two different tin-exocyclic ligand bond lengths, indicating
the different environment of these ligands (vide infra).
1
2
3
4
5
6
d(119Sn)
da
CN
À63.4
45.0
4
À95.1
76.7
5
À180.8
162.4
5
À18.4
À142.8
124.4
5
À322.6
304.2
6
D
–
4
a
D
d: chemical shift variation.
sible to propose that 4 might show the lowest coordination num-
ber in the series (CN = 4). Respect to the d(119Sn) of the monohalo-
genate tin compounds 1, 2 and 3, they were observed at low
frequencies according to the electronegativity of the halogen sub-
stituents; by quoting the Otera’s ranges [17], only 2 and 3 would
display a coordination number of 5. On the other hand, the
d(119Sn) of the compounds 4, 1 and 5 were observed at lower fre-
quencies as the number of the chloro ligands increases, respec-
tively. Moreover, in 5 the presence of two chloro ligands should
increase the Lewis acidity on the tin atom, enhancing the increase
of the coordination number [19].
In addition to the expected covalent bonding of the two sulfur
atoms (thiolate-like) and the two exocyclic L1 and L2 ligands to
tin, a relatively transannular short distance involving the sulfur do-
nor (thioether-like) and tin atoms is observed in all compounds
(see Table 5). The SÁ Á ÁSn distances are 12–30% longer than the
When the monodentate chloro ligand in 1 is replaced by a
covalent radii sum of Sn and S [
nificantly shorter than the van der Waals radii sum [
R
rcov(Sn, S) = 2.43 Å] [36] but sig-
rvdW(Sn,
dithiocarbamate bidentate ligand, the d(119Sn) experiences a low-
R
frequency shift, with a variation of the chemical shift (
Dd) of 6
S) = 3.96 Å] [37]. The magnitude of these distances is consistent
with the existence of a secondary bonding [38]. These SÁ Á ÁSn dis-
tances in 1 and 5 are similar to those observed in the correspond-
ing stannocanes and similar compounds containing tin–chloro
exocyclic bonds [2.866(2) Å in S(CH2CH2S)2SnPhCl, 2.760(3) Å in
S(CH2CH2S)2SnCl2, 2.863(1) Å in S(CH2CH2S)2SnMeCl and
2.785(1) Å in S(CH2CH2S)2Sn(n Bu)Cl] [21,23,25,29]. As has been
mentioned for 5, there are two different Sn–Cl bond distances,
being the trans distance to the interaction the longest. For 2 the
SÁ Á ÁSn distance is similar to that observed in S(CH2CH2S)2SnMeBr
[2.835(2) Å] [23] but longer than that found in S(CH2CH2S)2SnBr2
[2.767(2) Å] [24]. For 3 the distance SÁ Á ÁSn is longer than the found
in S(CH2CH2S)2SnI2 [2.779(2) Å] [24], whereas in 4 the distance
SÁ Á ÁSn is shorter than the observed in the stannocanes
S(CH2CH2S)2SnPh2 and S(CH2CH2S)2SnMe2 [3.246(1) and
3.514(1) Å, respectively] [23,26]. Furthermore, in 4 the longer
Sn–Ph bond distance is observed for the phenyl group trans to
the interaction, as observed for the compound 5. If the four cova-
lent bonds and the transannular interaction SÁ Á ÁSn observed in
compounds 1–5 are taken into account, the tin atom has expanded
its coordination number from four to five, and the local coordina-
tion geometry is in the pathway from tetrahedral to trigonal bipy-
ramidal. In order to evaluate the geometry displacement at the tin
compared with 4 of 304.2 ppm; the d values obtained in a same
fashion suggest higher coordination numbers than four in solution
for the compounds 2, 3, 5 and 6.
D
3.4. X-ray structures of compounds 1–6
The solid-state structures of 1–6 were determined by single-
crystal X-ray diffraction analyses. The structures are depicted in
Fig. 1. Selected bond lengths, angles and torsion angles are given
in Table 5. The unit cells of the compounds 5 and 6 have two crys-
tallographically independent molecules (5a, 5b and 6a, 6b,
respectively).
The analog organotin compounds [{S(C6H4S)2}SnPhHal]
(Hal = Cl, 1; Br, 2; I, 3) are isomorphic and isostructural with very
small differences in the lattice constants; the smallest volume is
observed in the chloro organotin compound 10 and goes up as
the halogen size increases.
In all compounds, the Sn–S(thiolate-like) distances are in good
agreement with those reported for eight-membered heterocycles
and several other compounds with tin–sulfur bonds [20–31].
The Sn–Hal distances in 1, 2, 3 and 5 are only 0.5–4.0% longer
than the accepted Sn–Hal bond length (2.33 in SnCl4, 2.46 in SnBr4

2288
J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
Fig. 1. ORTEP diagrams of [{S(C6H4S)2}SnPhCl] (1), [{S(C6H4S)2}SnPhBr] (2), [{S(C6H4S)2}SnPhI] (3), [{S(C6H4S)2}SnPh2] (4), [{S(C6H4S)2}SnCl2] (5) and
[{S(C6H4S)2}SnPh{S2CNEt2}] (6) (50% probability ellipsoids).
atom and the magnitude of the interaction, we have used the
Holmes approach [39–41] and the Pauling type Bond Order based
on interatomic distances [42,23], respectively. These results are
presented in Table 6. As in the lighter dibenzogermocines [12],
the TBP% and the BO in the 1–5 tin compounds are strongly depen-
dent of the number and nature of the electronegative ligands at-
tached to the tin acceptor atom.
In the dibenzostannocines 1–5, the local geometry at the tin
atom is best described as trigonal bipyramidal, where the halogen
(for 1, 2, 3 and 5) or carbon (for 4) and the sulfur (thioether-like)
atoms are in the axial positions, meanwhile the two thiolate-like
sulfur and carbon for 1, 2, 3 and 4 or chloro for 5 atoms are occu-
pying equatorial positions.
From the TBP% character and BO calculated data, can be ob-
served that the interaction between the sulfur (thioether-like)
atom and the tin atom decreases in the order of the trans substit-
uents Cl > Br > I > Ph, with the shortest SÁ Á ÁSn distance of
2.735(2) Å in the case of the dichlorocompound 5. The longest dis-
tance of 3.1615(9) Å in the case of the diphenylated compound 4 is
consistent with the 119Sn NMR data, where a coordination number
of four in solution was proposed. In addition, the tin atom displays
a more pronounced Lewis acidity that the germanium atom when
are compared dibenzostannocines respect to dibenzogermocines
[12] [{S(C6H4S)2}A] (A = Sn, Ge), with higher TBP% and BO values.
In order to expand the coordination number of the tin atom in
the dibenzostannocines, we synthesized the compound 6 contain-
ing a dithiocarbamate ligand with a high bidentate character. In
solution, the 119Sn NMR signal is observed at low frequencies indi-
cating the expansion of the tin coordination number from four to
six (Table 4). This chemical shift in solution can be explained by
means of the presence of a transannular interaction SÁ Á ÁSn and a
bidentate coordination mode of the dithiocarbamate ligand, beside
to the four expected covalent bonds. This was confirmed in the so-
lid state. The compound 6 displays in the unit cell two crystallo-
graphically independent molecules that are practically
superimposable. In fact a computer fitting of molecules 6a and
6b shows as the only difference between the conformers the orien-
tation of the phenyl group. The SÁ Á ÁSn distance observed in com-

J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
2289
Table 5
Selected bond lengths (Å), angles, and torsion angles (°) for dibenzostannocines [{S(C6H4S)2}SnL1L2].
1
2
3
4
5a
5b
6a
6b
L1
Cl1
C13
S3
Br1
C13
S3
I1
C13
S3
C19
C13
S3
Cl1
Cl2
S3
Cl3
Cl4
S6
C13
S4, S5
S3
C36
S9, S10
S8
L2
Sa
SÁ Á ÁSn
2.827(1)
2.407(1)
2.404(1)
2.397(1)
2.118(4)
112.75(4)
166.93(4)
91.6(1)
98.48(4)
91.52(4)
101.0(1)
–
101.9(2)
98.4(1)
À31.8(2)
130.1(3)
À73.6(4)
2.834(2)
2.416(2)
2.409(2)
2.5475(8)
2.121(7)
112.25(7)
167.92(5)
90.7(2)
98.81(5)
91.87(5)
100.9(2)
–
102.0(3)
98.3(2)
À33.3(3)
128.9(6)
À74.8(6)
2.840(1)
2.415(1)
2.405(1)
2.7417(5)
2.130(5)
111.55(5)
168.98(3)
89.7(1)
99.35(3)
92.57(3)
100.9(1)
–
102.7(2)
98.9(2)
À34.2(2)
127.5(4)
À75.5(4)
3.1615(9)
2.4373(9)
2.4254(9)
2.151(3)
2.138(3)
111.00(3)
164.65(8)
83.96(8)
104.3(1)
99.08(9)
111.3(1)
–
102.8(1)
92.6(1)
À9.9(1)
132.0(2)
À65.2(3)
2.735(2)
2.394(2)
2.399(3)
2.361(3)
2.341(3)
122.4(1)
176.3(1)
86.0(1)
97.4(1)
97.8(1)
97.4(1)
–
106.2(5)
À96.4(3)
36.4(5)
À135.4(8)
81.3(9)
2.725(2)
2.398(3)
2.396(2)
2.359(3)
2.348(3)
127.5(1)
175.3(1)
88.1(1)
98.4(1)
95.0(1)
96.6(1)
–
103.8(4)
85.4(3)
À37.4(4)
136.4(7)
À87.3(8)
2.824(1)
2.500(1)
2.496(1)
2.152(5)
2.592(1), 2.559(1)
102.66(5)
171.0(1)
89.11(4), 84.93(4)
101.5(1)
97.1(1)
101.1(1), 99.3(1)
69.80(4)
101.2(2)
108.3(2)
À31.4(2)
132.8(4)
À69.8(4)
2.872(1)
2.4750(16)
2.5021(14)
2.163(5)
2.611(2), 2.558(1)
102.58(6)
172.5(2)
92.04(5), 83.75(5)
101.9(2)
99.8(1)
Sn–S(L)b
Sn–S(L)b
Sn–L1
Sn–L2
S(L)–Sn–S(L)b
SÁ Á ÁSn–L1
SÁ Á ÁSn–L2
L1–Sn–S(L)b
L1–Sn–S(L)b
L1–Sn–L2
S(dtc)–Sn–S(dtc)c
C–S–C
94.5(2), 102.0(2)
69.60(5)
101.7(3)
S(L)–Sn–S(L)–Cd
S(L)–Sn–S(L)–Cd
C–C–S–Ce
C–C–S–Ce
106.6(2)
À28.6(2)
131.8(4)
À65.0(5)
a
b
c
S = sulfur thioether-like donor atom.
S(L) = each sulfur thiolate-like atoms in the S(C6H4S)2 moiety.
S(dtc) = each sulfur of the dithiocarbamate ligand.
Each torsion angle in the central eight-membered ring containing both sulfur thiolate-like, tin and one benzenic carbon atoms.
Each torsion angle in the central eight-membered ring containing the sulfur thioether-like donor atom and three benzenic carbon atoms.
2À
d
e
[{S(C6H4S)2}SnL1L2] by using the {S(C6H4S)2}2À potentially triden-
tate ligand. In this study, the nature of the substituents L1 (Cl, Br,
I and Ph) and L2 (Cl and Ph) is a determinant factor in the enhanc-
ing of the intramolecular interaction between the sulfur and the tin
atoms; the SÁ Á ÁSn distance is shorter when the substituents are
highly electronegative atoms such as the halogen ligands and is
longer when the substituents are less electronegative such as the
phenyl group. In the solid state, the dibenzostannocines with two
chloro ligands display the highest TBP% character and BO while
the lowest values are observed in the dibenzostannocines with
two phenyl ligands. Lastly, the insertion of the dithiocarbamate li-
gand prompts the increase of the coordination number of the tin
atom, remaining the interaction SÁ Á ÁSn.
Table 6
Comparison of SÁ Á ÁSn–L1 geometrical bond parameters in dibenzostannocines
[{S(C6H4S)2}SnL1L2] 1–5; bond lengths (Å), bond angles (°), TBP% and Bond Order.
L1
L2
SÁ Á ÁSn
SÁ Á ÁSn–L1
TBP%
D
da
BObSÁ Á ÁSn
1
2
3
4
5a
5b
Cl
Br
I
Ph
Cl
Cl
Ph
Ph
Ph
Ph
Cl
2.827(1)
2.834(2)
2.840(1)
3.162(9)
2.725(2)
2.735(2)
166.9(4)
167.9(5)
169.0(3)
164.6(8)
176.3(1)
175.3(1)
74.1
73.6
73.2
52.2
80.7
80.1
0.397
0.404
0.410
0.732
0.295
0.305
0.275
0.269
0.264
0.093
0.384
0.372
Cl
a
Bond widening,
S) 2.43 Å.
D
d = (dexp
À
R
rcov), according to standard bond distances d(Sn,
d).
b
Mode of calculation BO = 10 À (1.41
D
pound 6 is shorter than the observed in stannocanes containing an
hexacoordinate tin atom [3.074(3) and 3.241(3) Å in
{S(CH2CH2S)2}Sn] [28]. In both conformers the diethyldithiocarba-
mate ligand is symmetrically coordinated to the tin atom; the Sn–
S(dtc) distances are slightly different, see Table 5, with bite angles
of 69.80(4)° and 69.60(5)°. Hence, the geometry of the coordina-
tion sphere of the tin atom can be described as distorted octahe-
5. Supplementary data
CCDC 756927, 756928, 756929, 756930, 756931, and 756932
contains the supplementary crystallographic data for 1, 2, 3, 4, 5
and 6. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
dral. The tridentate ligand {S(C6H4S)2}2À is occupying
a fac
position into the octahedron. It is interesting to note the geometri-
cal change in the position of the phenyl group; in the parent com-
pound 1 as well as in the other halocompounds 2 and 3, the phenyl
group is in a cis position respect to the transannular interaction
SÁ Á ÁSn whereas in the dithiocarbamate compound 6 is in a trans po-
sition, showing the higher electronic requirements of the Ph group
as compared with the dithiocarbamate ligand when they are coor-
dinated to the tin included in the dibenzostannocine moiety.
With respect to the eight-membered ring conformation in the
dibenzostannocines 1–6 it can be described as twist-boat (C1 sym-
metry), description based on the non equivalence of the torsion an-
gles, see Table 5.
Acknowledgment
The financial support of the CONACYT (Project 83157) is grate-
fully acknowledged.
References
[1] Y.I. Baukov, S.N. Tandura, Hypervalent compounds of organic germanium, tin
and lead derivatives, in: Zvi Rappoport (Ed.), The Chemistry of Organic
Germanium Tin and Lead Compounds, vol 2, John Wiley and Sons, England,
2002.
[2] T. Munguia, M. López Cardoso, F. Cervantes Lee, K.H. Panell, Inorg. Chem. 46
(2007) 1305.
[3] K. Tani, S. Kato, T. Kanda, S. Inagaki, Org. Lett. 3 (2001) 655.
[4] R. Cea Olivares, V. García Montalvo, M.M. Moya Cabrera, Coord. Chem. Rev. 249
(2005) 859 (and references therein cited).
4. Conclusion
[5] N.V. Timosheva, T.K. Prakasha, A. Chandrasekaran, R.O. Day, R.R. Holmes, Inorg.
Chem. 35 (1996) 3614.
[6] T.K. Prakasha, S. Srinivasan, A. Chandrasekaran, R.O. Day, R.R. Holmes, J. Am.
Chem. Soc. 117 (1995) 10003.
In order to study the phenomena of hypervalence in eight-
membered ring compounds we have synthesized and structurally
characterized six new dibenzostannocines of the type

2290
J.G. Alvarado-Rodríguez et al. / Polyhedron 29 (2010) 2283–2290
[7] A. Chandrasekaran, R.O. Day, R.R. Holmes, Inorg. Chem. 36 (1997) 2578.
[8] A. Chandrasekaran, P. Sood, R.O. Day, R.R. Holmes, Inorg. Chem. 38 (1999)
3952.
[9] S.D. Pastor, V. Huang, D. NabiRahni, Inorg. Chem. 36 (1997) 5966.
[10] T. Thompson, S.D. Pastor, G. Rihs, Inorg. Chem. 38 (1999) 4163.
[11] M.Y. Chiang, J.W. Lin, W.F. Zeng, Acta Crystallogr., Sect. C 61 (2005) m84.
[12] S. González-Montiel, N. Andrade-López, V. García-Montalvo, J.A. Cogordan, J.G.
Alvarado-Rodríguez, Eur. J. Inorg. Chem. (2006) 4752.
[13] B. Flores Chávez, J.G. Alvarado-Rodríguez, N. Andrade-López, V. García-
Montalvo, E. Aquino-Torres, Polyhedron 28 (2009) 782.
[14] D. Sellmann, D. Haussinger, Eur. J. Inorg. Chem. (1999) 1715.
[15] G.M. Sheldrick, SHELXTL 5.10, Bruker AXS, Inc., Madison, WI, USA, 1998.
[16] G.M. Sheldrick, SADABS Area-Detector Absorption Correction, Siemens Industrial
Automation, Inc., Madison, WI, 1996.
[28] R. Cea-Olivares, V. Lomeli, S. Hernández-Ortega, S.I. Haiduc, Polyhedron 14
(1995) 747.
[29] P.G. García, R. Cruz-Almanza, R.A. Toscano, R. Cea-Olivares, J. Organomet.
Chem. 598 (2000) 160.
[30] A.L. Beauchamp, S. Latour, M.J. Olivier, J.D. Wuest, J. Am. Chem. Soc. 105 (1983)
7778.
[31] P. García y García, A.M. Cotero-Villegas, M. López-Cardoso, V. García-Montalvo,
R.A. Toscano, A. Gómez-Ortíz, R. Ferrari Zijlstra, R. Cea-Olivares, J. Organomet.
Chem. 587 (1999) 214.
[32] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry: Principles of Structure
and Reactivity, fourth ed., Harper Collins College Publishers, USA, 1993. p. A30.
[33] P.T. Greene, R.F. Bryan, J. Chem. Soc. A (1971) 2549.
[34] J.S. Tse, F.L. Lee, E.J. Gabe, Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 42
(1986) 1876.
[17] J. Otera, J. Organomet. Chem. 221 (1981) 57.
[35] M. Charisse, B. Mathiasch, M. Draeger, U. Russo, Polyhedron 14 (1995) 2429.
[18] J. Holecek, M. Nadvornik, K. Handlir, J. Organomet. Chem. 241 (1983) 177.
[19] B. Wrackmeyer, Modern Magnetic Resonance, Part 1, in: A. Graham Webb
(Ed.), Springer, Netherlands, 2008, p. 461.
[36] W.W. Porterfield, Inorganic Chemistry:
Academic Press, Inc., USA, 1993. p. 214.
[37] A. Bondi, J. Phys. Chem. 68 (1964) 441.
A Unified Approach, second ed.,
[20] M. Draeger, J. Organomet. Chem. 251 (1983) 209.
[38] N.W. Alcock, Adv. Inorg. Chem. Radiochem. 15 (1972) 1.
[21] M. Draeger, R. Engler, Chem. Ber. 108 (1975) 17.
[39] A. Chandrasekaran, P. Sood, R.O. Day, R.R. Holmes, Inorg. Chem. 38 (1999)
[22] M. Draeger, Chem. Ber. 114 (1981) 2051.
3369.
[23] U. Kolb, M. Beuter, M. Gerner, M. Draeger, Organometallics 13 (1994) 4413.
[24] U. Kolb, M. Beuter, M. Draeger, Inorg. Chem. 33 (1994) 4522.
[25] M. Draeger, Z. Anorg. Allg. Chem. 527 (1985) 169.
[40] N.V. Timosheva, A. Chandrasekaran, R.O. Day, R.R. Holmes, Inorg. Chem. 37
(1998) 3862.
[41] D.J. Sherlock, A. Chandrasekaran, R.O. Day, R.R. Holmes, Inorg. Chem. 36 (1997)
[26] M. Draeger, H.J. Guttmann, J. Organomet. Chem. 212 (1981) 171.
[27] J.J. Zhang, W.X. Du, S.M. Hu, S.Q. Xia, L.S. Wang, X.T. Wu, Inorg. Chem.
Commun. 6 (2003) 387.
5082.
[42] L. Pauling, The Nature of the Chemical Bond, third ed., Cornell University Press,
Ithaca, NY, 1960. p. 239.