Organotin(IV) complexes of 4,6-dimethylpyrimidine-2-thione, Me2PymtH. Preparation, characterization and crystal structure determination of cis-[Ph2Sn(Me2Pymt)2] and [Ph3Sn(Me2Pymt)]

Article abstract of DOI:10.1016/S0277-5387(02)00996-8

The coordination mode of the ambidentate ligand 4,6-dimethylpyrimidine-2-thione (Me₂PymtH) was investigated with respect to the organotin(IV) compounds, namely Me₂SnCl₂, n-Bu₂SnCl₂, Ph₂SnCl₂ and Ph₃SnCl. An X-ray crystal structure determination carried out on cis-[Ph₂Sn(Me₂Pymt)] (3) and [Ph₃Sn(Me₂Pymt)] (4) revealed that the Me₂Pymt^- ligand is N,S-coordinated in both complexes. The Sn(IV) atom is six-coordinated in 3 and five-coordinated in 4. The similarities observed in the IR, NMR (¹H, ¹³C) and mass spectroscopy are indicative of a similar behavior of the ligand in all the complexes, thus suggesting a six-coordination in the dimethyltin (1) derivative and five-coordination in the dibutyltin (2) one. The complexes were characterized by means of elemental analysis, IR, NMR (¹H, ¹³C) and mass spectroscopic methods.

Full text of DOI:10.1016/S0277-5387(02)00996-8

Polyhedron 21 (2002) 1149Á1153
/
www.elsevier.com/locate/poly
Organotin(IV) complexes of 4,6-dimethylpyrimidine-2-thione,
Me2PymtH. Preparation, characterization and crystal structure
determination of cis-[Ph2Sn(Me2Pymt)2] and [Ph3Sn(Me2Pymt)]
Ramao M. Fernandes a, Ernesto S. Lang a, Ezequiel M.V. Lo´pez b,
˜
Gerima´rio F. de Sousa c,*
a Departamento de Qu´ımica Inorgaˆnica, Universidade Federal de Santa Maria, 97119-900 Santa Maria, RS, Brazil
b Departamento de Qu´ımica Inorga´nica, Facultade de Ciencias-Qu´ımicas, E-36200 Vigo, Galicia, Spain
c Instituto de Qu´ımica, Universidade de Bras´ılia, 70919-970 Bras´ılia, DF, Brazil
Received 7 September 2001; accepted 19 March 2002
Abstract
The coordination mode of the ambidentate ligand 4,6-dimethylpyrimidine-2-thione (Me2PymtH) was investigated with respect to
the organotin(IV) compounds, namely Me2SnCl2, n-Bu2SnCl2, Ph2SnCl2 and Ph3SnCl. An X-ray crystal structure determination
carried out on cis-[Ph2Sn(Me2Pymt)] (3) and [Ph3Sn(Me2Pymt)] (4) revealed that the Me2Pymtꢀ ligand is N,S-coordinated in both
complexes. The Sn(IV) atom is six-coordinated in 3 and five-coordinated in 4. The similarities observed in the IR, NMR (1H, 13C)
and mass spectroscopy are indicative of a similar behavior of the ligand in all the complexes, thus suggesting a six-coordination in
the dimethyltin (1) derivative and five-coordination in the dibutyltin (2) one. The complexes were characterized by means of
elemental analysis, IR, NMR (1H, 13C) and mass spectroscopic methods. # 2002 Published by Elsevier Science Ltd.
Keywords: Organotin(IV) complexes; Dimethylpyrimidinethione; Crystal structures
1. Introduction
The variety of coordination modes of 4,6-dimethyl-
pyrimidine-2-thione (Me2PymtH) has been demon-
strated in a number of complexes [1] and their
This ligand was chosen since it has the potential to
form four-, five-or hexacoordinate metal complexes
which the polyhedral of these compounds assuming
biological applications have been of considerable inter-
est for years [2]. Insofar as many organotin(IV) com-
plexes are also noteworthy for the same reason [3], a
structures that are considerably distorted from ideal
combination of the two chemistry is an interesting topic
configuration. These distorted structures in many orga-
to pursue.
notin(IV) complexes are thought to be due to a number
The present work deals with the preparation and
of factors, such as steric requirements, electronic effects
arising from different electronegativities of the ligands,
intermolecular interactions and crystal packing require-
characterization of four new organotin(IV) complexes
with the Me2PymtH ligand, whose structure is shown
below.
ments [4]. Pyridines and pyrimidines substituted with an
SH or an OH group at the two or four positions are
fundamentally tautomeric heterocyclic system and many
experimental studies have been reported [5,6]. The
complexes were studied by microanalyses, IR, NMR
(1H, 13C), mass spectroscopy and crystal X-ray diffrac-
tion.
* Corresponding author. Tel.: ꢁ
4149.
E-mail address: gfreitas@unb.br (G.F. de Sousa).
/
55-61-307-2165; fax: ꢁ55-61-273-
/
0277-5387/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 0 9 9 6 - 8

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R.M. Fernandes et al. / Polyhedron 21 (2002) 1149Á1153
/
2. Experimental
CCD for 3 and an EnrafÁNonius MACH3 for 4. The
/
data were corrected for absorption effects by an
empirical correction (SADABS 7b) (3) or using c-scans
7a (4).
Solvents were purified and dried according to stan-
dard procedures. Thiourea, pentane-2,4-dione and or-
ganotin(IV) chlorides were obtained from Aldrich and
used without further purification. IR spectra were
recorded on a Bruker IFS-28 spectrophotometer in the
Structural solutions were determined by direct meth-
ods [8]. Least-squares full-matrix refinement on F2 was
performed using the program SHELXL-97 [8]. All non-H
atoms were refined anisotropically. H atoms were
calculated and refined as ridding atoms (HFIX [8]).
Atomic scattering factors and anomalous dispersion
corrections for all atoms were taken from International
Tables for Crystallography [9]. Graphics were obtained
with ZORTEP [10].
4000Á
400 cmꢀ1 range using KBr pellets. NMR (1H,
/
13C) spectra were obtained from a Bruker DPX-200
spectrometer using CDCl3 as the solvent with chemical
shifts in parts per million downfield from Me4Si. The
mass spectra were recorded on a Micromass 7070-F
instrument, using FABꢁXe at 8 eV and alcohol 3-
/
nitrobenzilic as matrix. Microanalyses were performed
in a VARIO EL (Elementar Analysensysteme GmbH)
instrument.
3. Results and discussion
2.1. Synthesis
3.1. Infrared spectroscopy
The ligand was prepared according to the literature [2]
and the complexes by the following procedure: 0.28 g (2
mmol) of Me2PymtH was dissolved in 30 ml of THF
(freshly distilled) in a Schlenk tube kept under N2
atmosphere. To the solution, 0.84 ml (6 mmol) of
triethylamine (Et3N) was added via a syringe and the
resulting solution was stirred for 30 min. To this
solution was added, during 10 min, 1 mmol of the
appropriate organotin(IV) species dissolved in 3 ml of
THF, and the mixture was refluxed for about 4 h. A
white flocculent precipitate identified as triethylamine
chloride (Et3NHCl) was produced and filtered. Slowly
evaporation of the solvent led to the appearance of
white amorphous crystalline solids with yields of the
order 70%. Well formed crystals suitable for X-ray
studies were only obtained for complexes 3 and 4 by
Table 1 shows the assignment of the main IR
absorptions of the ligand and its complexes. The
Me2PymtH ligand shows a rather complicated spectrum
in the 3100Á
/
2600 cmꢀ1 range where CÃ
/
H and NÃ
/
H
stretching absorptions occur. Thus, the spectra of
complexes retain those absorptions found in free ligand.
The ring stretching vibrations, n(CÄ
shifted to lower frequencies, together with the shift in
opposite direction of the ligand band at 1235 cmꢀ1
assigned to mixed n(CÃS)ꢁn(CÃN) absorption bands.
/
C)ꢁ
/
n(CÄ/N), are
,
/
/
/
1
These results suggest, in accordance with H NMR, an
N,S-chelation of the aromatic Me2Pymtꢀ anion around
the Sn(IV) ion. Similar results have been reported for
tiolate complexes of 2-PySH (2-mercaptopyridine) and
2-PymSH (2-mercaptopyrimidine) and different metal
ions such as Ni(II) [11] and Pt(II) [12], as well as with
Re(V) complex of Me2PymtH [13].
recrystallization from
dichloromethaneÁn-hexane. The microanalyses were
performed in a PerkinÁElmer 2400C analyzer, giving
for C, H and N the following results: [Me2Sn(Me2-
Pymt)2] (1): (m.p. 197Á199 8C). Anal. Found: C, 40.66;
a
1:1 (v/v) mixture of
/
In the IR spectrum of [Me2Sn(Me2Pymt)2] the asym-
/
metric SnÃ
/
C stretching band at 551 cmꢀ1 indicates that
this complex has the trans arrangement of the methyl
groups [14].
/
H, 4.78; N, 13.55. Calc. for (C14H20N4S2Sn): C, 39.37;
H, 4.72; N, 13.12%. [Bu2SnCl(Me2Pymt)] (2): (m.p.
212Á
Calc. for (C14H25ClN2SSn): C, 41.26; H, 6.18; N, 6.87%.
cis-[Ph2Sn(Me2Pymt)2] (3): (m.p. 202Á204 8C). Anal.
Found: C, 52.17; H, 4.58; N, 10.62. Calc. for
(C24H24N4S2Sn): C, 52.29; H, 4.39; N, 10.16%.
/
211 8C). Anal. Found: C, 43.32; H, 6.46; N, 6.72.
3.2. NMR spectroscopy
1
Table 2 lists H chemical shifts for the free ligand
/
Me2PymtH and its complexes. The 13C NMR spectrum
to complex 1 showed a J(119SnÃ
/
CH3) coupling con-
stant of 600 Hz and the 1H NMR spectrum showed one
doublet and a singlet in the methyl region occurring at
1
[Ph3Sn(Me2Pymt)] (4): (m.p. 206Á
/
208 8C). Anal.
Found: C, 58.67; H, 4.57; N, 5.84. Calc. for
(C24H22N4S2Sn): C, 58.92; H, 4.53; N, 5.73%.
2.37 and 1.03 [2J(119SnÃ
magnetically non-equivalent methyl groups bonded in
/
CH3) 83 Hz] due to two
1
2.2. X-ray studies
NÄ
2J coupling constants data can be used to estimate the
CH3 angle in complex 1, and according to the
/
CHÃ
/
CH3 and SnÃ
/
CH3, respectively. These J and
Colourless single crystals of compounds 3 and 4
which were suitable for X-ray diffractometric studies
were selected and data collected on a Bruker Smart
CH3Ã
/
SnÃ
/
literature [15,16], two empirical equations can be set up
for this estimate:

R.M. Fernandes et al. / Polyhedron 21 (2002) 1149Á
/1153
1151
Table 1
Main IR absorptions (cmꢀ1) for Me2PymtH and its Sn(IV) complexes
a
Compound
C.N.
n(NÃH)ꢁn(CÃH)
n(CÄC)ꢁn(CÄN)
n(CÃS)ꢁn(CÃN)
Me2PymtH
2911
2916
2921
3038
3038
1625, 1569, 1432
1578, 1543, 1435
1578, 1539, 1437
1579, 1525, 1430
1584, 1524, 1427
1235
1257
1257
1255
1255
[Me2Sn(Me2Pymt)2] (1)
[Bu2SnCl(Me2Pymt)] (2)
cis-[Ph2Sn(Me2Pymt)2] (3)
[Ph3Sn(Me2Pymt)] (4)
6
5
6
5
a
C.N.ꢂcoordination number.
Table 2
1H NMR data in CDCl3 solutiona
Me2PymtH
6.49 (s, 1H, CÃH); 2.39 (t, 6H, CÃCH3)
[Me2Sn(Me2Pymt)2] (1) 6.69 (s, 2H, CÃH); 2.37 (d, 12H, CÃCH3);
1.03 (s, 6H, SnÃCH3) 2J(119SnÃCH3)ꢂ
83/75
[Bu2SnCl(Me2Pymt)]
(s, 2H, CÃH); 2.37 (d, 6H, CÃCH3);
1.64-1.55 (m, 4H, SnÃCH2ÃC); 1.42Á
(m, 4H, CÃCH2ÃC); 0.79 (t, 6H, BuÃCH3)
cis-[Ph2Sn(Me2Pymt)2] 7.88Á7.26 (m, 10H, SnÃC6H5);
6.52 (s, 2H, CÃH); 2.18 (s, 6H, CÃCH3)
7.80Á7.23 (m, 10H, SnÃC6H5);
6.55 (s, 2H, CÃH); 2.13 (s, 6H, CÃCH3)
(2)
/1.26
/
(3)
[Ph3Sn(Me2Pymt)] (4)
/
a
sꢂSinglet, dꢂdoublet, mꢂmultiplet, d in ppm, J in Hz.
119
13
1J( Snà CH3)ꢂ11:4uꢀ875
(1)
(2)
2
2
2
uꢂ0:0161f J(119SnÃCH3)g ꢀ1:32f J(119SnÃCH3)g
Fig. 1. Fragmentation scheme proposed for complexes 1Á3.
/
ꢁ133:4
3.3. Mass spectroscopy
1
2
Using J into Eq. (1) and J into Eq. (2), one finds
values of u of 1358 and 1298, respectively. These angles
values might suggests that in solution the dimethyltin
derivative is a distorted trans octahedral complex and
the basic structural features of the solid-state phase
remain in CDCl3 solution. For dibutyl derivative,
similar structural considerations in solution might hold.
Similar results were reported for octahedral com-
plexes with analogous trans arrangement, namely
Table 3 shows the FAB mass spectra of compounds
1Á4 and Fig. 1 presents a fragmentation scheme
proposed for complexes 1Á3 compatible with literature
/
/
data [4,19]. The molecular ion for complexes 1, 3 and 4
were detectable at m/z 429, 553 and 489, respectively.
The spectra of complexes 1 and 3 showed that the
base peaks are the ions R2Sn(Me2Pymt)ꢁ (Rꢂ
Me, Ph),
/
in agreement with reported works [4,19]. This contrasts
with the spectra of compounds 2 and 4, in which the
base peaks appeared at m/z 882 (not attributed) and m/
z 291 (probably due to the ion Ph2Sn(H2O)ꢁ), respec-
tively.
[Me2Sn(dtc)2] [17] [2J(119SnÃ
1J(119SnÃ13CH3) 670 Hz], [Me2SnCl2×
[2J(119SnÃ
CH3) 86 Hz] and [Me2Sn(CH3COO)2] [18]
[2J(119SnÃ
CH3) 82 Hz], where Hdtcꢂditiocabamic acid
and DMSOꢂdimethylsulfoxide.
/
CH3) 84 Hz and
(DMSO)2] [15]
/
/
/
/
/
/
Table 3
Fragment-ions observed in the FAB mass spectra of compounds 1Á
/4
a
Me2Sn (1) m/z (abundance) Bu2Sn (2) m/z (abundance) Ph2Sn (3) m/z (abundance) Ph3Sn (4) m/z (abundance)
a
a
a
Fragment-ion
R3Sn(Me2Pymt)ꢁ
489(8)
ꢁ
R2Sn(Me2Pymt)2
R2Sn(Me2Pymt)ꢁ 289(100)
429(33)
553(15)
413(100)
258(9)
373(64)
ꢁ
RSn(Me2Pymt)2
Sn(Me2Pymt)ꢁ
413(16)
259(18)
279(9)
259(22)
279(16)
259(24)
279(48)
259(25)
ꢁ
(Me2Pymt)2
a
Nominal values calculated using the most abundant isotope 120Sn.

1152
R.M. Fernandes et al. / Polyhedron 21 (2002) 1149Á1153
/
Table 4
Crystallographic data for the X-ray diffraction studies for 3 and 4
3
4
Formula
C
551.28
24H24N4S2Sn
C24H22N2SSn
498.19
Formula weight
Crystal system
Space group
Z
monoclinic
P21/c
orthorhombic
Pbca
4
8
˚
A (A)
9.6990(3)
17.0580(5)
15.9182(4)
106.0652(8)
2528.14(13)
1.448
8.7994(14)
17.513(3)
28.826(5)
90
˚
B (A)
˚
C (A)
Fig. 2. Perspective view of cis-[Ph2Sn(Me2Pymt)2] (3) showing the
atom numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level.
b (8)
3
V (A )
˚
4442.2(13)
1.463
Dcalc (g cmꢀ3
)
Crystal size (mm)
Index ranges
0.45ꢃ0.30ꢃ0.20
ꢀ125h 512
ꢀ185k 522
ꢀ215l 521
1.194
0.48ꢃ0.16ꢃ0.08
05h 510
05k 521
05l 535
1.255
m (mmꢀ1
T (K)
F(000)
)
293(2)
1112
293(2)
1968
Reflections collected
Independent reflections
Reflections observed
R [I ꢀ2s(I)]
16755
6151
4477
4477
4230
0.0397
1507
0.0525
Rw
0.0852
1.016
0.0881
0.894
Goodness-of-fit
conclusions are drawn with caution, it would appear
N bond distances
in 3 versus [Ph2Sn(2-SPy)2] and [Me2Sn(2-SPy)2] [21] is
most reasonable that the disparate SnÃ
/
Fig. 3. Perspective view of [Ph3Sn(Me2Pymt)] (4) showing the atom
numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level.
probably due to the electronic effects caused by un-
complexed N(12) and N(22) atoms in complex 3. The
˚
C bond distances (mean value of 2.12 A) is typical,
SnÃ
/
3.4. X-ray structures of cis-[Ph2Sn(Me2Pymt)2] (3)
and [Ph3Sn(Me2Pymt)] (4)
and compares favorably with the analogous bond in
related compounds, in particular [Ph2Sn(2-SPy)2] [20]
˚
˚
(2.13 A) and [Me2Sn(2-SPy)2] [21] (2.13 A), with which it
shows striking structural similarities.
The molecular structures of 3 and 4 are given in Figs.
2 and 3, respectively. Tables 4 and 5 summarize the
crystal data and selected bond lengths and bond angles
for the two compounds, respectively.
The geometry about Sn(IV) in 3 is best described as a
distorted octahedral with the two Me2Pymtꢀ anions
The geometry about Sn(IV) in 4 is best described as a
strongly distorted trigonal bipyramid (TBP) configura-
tion where two phenyl groups and a S atom are at the
equatorial plane while N(16) atom and other phenyl
group occupy the axial position.
˚
S bond distance [2.433(2) A] found in 4 is
acting as bidentate ligands with cis PhÃ
[117.42(13)8] and cis SÃSnÃS [84.50(3)8] arrangements.
The bond distances [2.4476(10); 2.4515(10) A] in the
/
SnÃ
/
Ph
The SnÃ
/
/
/
˚
˚
within the range (2.405Á2.481 A) [22,23] recently
/
reported for triphenyltin(IV) thiolates compounds
SnÃ
/
S bond lengths found in 3 are shorter than the SnÃ
/
S
˚
bond distances [2.476(2); 2.485(1) A], [2.477(3) A] and
˚
R3SnL, containing potentially bidentate ligand. Simi-
˚
C distances [mean 2.14 A] agree well with
˚
[2.487(2) A] found in [Ph2Sn(2-SPy)2] [20], [n-Bu2Sn(2-
larly, the SnÃ
/
those previously reported [22,23].
The SnÃN bond length [2.835(7) A] is equal to the
length of SnÃ
SPy-5-NO2)2] [4] and [Me2Sn(2-SPy)2] [21], respectively,
where 2-SPyH is 2-pyridinethione and 2-SPyH-5-NO2 is
˚
/
˚
N bond [2.836(3) A] found in [Ph3Sn(o-
/
5-nitropyridinethione.
˚
N bond distances [2.754(3) and 3.083(3) A]
quinolinylthiolate)] [22], in which sulfur and nitrogen
The SnÃ
/
atoms are bonded to the Sn(IV) atom forming five-
found in complex 3 are shorter than the sun of the van
˚
membered chelate ring. On the other hand, the SnÃ
/
N
der Waals radii (3.75 A) [20] indicating the bidentate
nature of the Me2Pymtꢀ ligand. However, these dis-
length in 4 is smaller than that of the SnÃN bond
/
˚
tances are longer than the SnÃ
/
N distances [2.636(4);
[2.88(5) A] found in [Ph3Sn(2-Pymt)] [24], where 2-
PymtH is 2-pyrimidinethione, suggesting that the methyl
group, C(151), does not cause steric effect. In contrast,
˚
2.698(3) A] and [2.702(5) A] found in [Ph2Sn(2-SPy)2]
˚
[20] and [Me2Sn(2-SPy)2] [21], respectively. Although

R.M. Fernandes et al. / Polyhedron 21 (2002) 1149Á
/1153
1153
Table 5
CCDC, 12 Union road, Cambridge CB2 1EZ, UK (fax:
44-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
˚
Selected bond distances (A) and angles (8) for 3 and 4
ꢁ
/
3
4
Bond distances
SnÃS(1)
SnÃS(2)
SnÃC(31)
SnÃC(41)
SnÃN(16)
SnÃN(26)
C(11)ÃN(12)
C(11)ÃN(16)
C(21)ÃN(22)
C(21)ÃN(26)
S(1)ÃC(11)
S(2)ÃC(21)
2.4515(10) SnÃS
2.4476(10) SnÃN(16)
2.433(2)
2.835(7)
2.159(8)
2.117(8)
2.134(9)
1.752(9)
1.334(10)
1.320(10)
1.326(11)
1.344(11)
1.359(13)
1.371(11)
Acknowledgements
2.124(3)
2.116(3)
3.083(3)
2.754(3)
1.327(5)
1.334(4)
1.341(5)
1.331(5)
1.755(4)
1.740(4)
SnÃC(21)
SnÃC(31)
SnÃC(41)
SÃC(11)
C(11)ÃN(12)
C(11)ÃN(16)
C(13)ÃN(12)
C(15)ÃN(16)
C(13)ÃC(14)
C(14)ÃC(15)
The authors are grateful for financial support from
CNPq in Brazil.
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N(26)ÃSnÃS(1)
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85.23(11) C(21)ÃSnÃN(16)
85.04(12) C(31)ÃSnÃS
116.8(3)
106.9(3)
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83.3(3)
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115.2(3)
100.7(2)
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111.93(9)
113.03(10) C(21)ÃSnÃS
84.50(3)
SÃSnÃN(16)
160.02(10) C(11)ÃSÃSn
C(41)ÃSnÃS
(b) G.M. Sheldrick, SADABS, University of Gottingen, Germany,
¨
55.75(6)
N(12)ÃC(11)ÃN(16)
127.7(9)
116.3(7)
115.9(8)
1996.
[8] G.M. Sheldrick, SHELX-97, Program for the Solution and
Refinement of Crystal Structures, University of Gottingen,
¨
59.71(8)
140.25(6)
144.21(8)
N(16)ÃC(11)ÃS
N(12)ÃC(11)ÃS
N(12)ÃC(13)ÃC(131) 117.9(11)
N(16)ÃC(15)ÃC(151) 115.5(9)
C(13)ÃC(14)ÃC(15)
Germany, 1997.
[9] International Tables for Crystallography, vol. C, Kluwer Aca-
demic, Dordrecht, The Netherlands, 1992.
N(16)ÃC(11)ÃS(1) 117.3(3)
N(26)ÃC(21)ÃS(2) 117.6(4)
118.3(11)
[10] L. Zsolnai, G. Huttner, ZORTEP, A Program for the Representa-
tion of Crystal Structures, University of Heidelberg, 1994.
[11] G.F. de Sousa, C.A.L. Filgueiras, Transition Met. Chem. 15
(1990) 286.
˚
the Snꢀ ꢀ ꢀN interaction [2.920(3) A], found in
[Ph3Sn(mimt)] [22], where mimtH is 1-methyl-2(3H)-
imidazolinethione, slightly distorts the Sn(IV) coordina-
tion geometry from that a perfect tetrahedron.
[12] G.F. de Sousa, C.A.L. Filgueiras, Transition Met. Chem. 15
(1990) 290.
Around the Sn(IV) atom, the SÃ
SnÃC(41) and C(41)ÃSnà equatorial angles of
110.0(2)8, 116.8(3)8, 115.2(3)8 and the NÃSnÃC(21)
/
SnÃ
/
C(31), C(31)Ã
/
[13] G. Battistuzzi, A.B. Corradi, D. Dallari, M. Saladini, R.
Battistuzzi, Polyhedron 18 (1998) 57.
/
/
/S
[14] M. McGrady, R.S. Tobias, J. Am. Chem. Soc. 87 (1965) 1909.
[15] T.P. Lockhart, W.F. Manders, J. Am. Chem. Soc. 107 (1985)
4546.
/
/
axial angle of 159.7(3)8, are smaller than the ideal
trigonal bipyramid angles.
[16] T.P. Lockhart, W.F. Manders, J. Organomet. Chem. 25 (1986)
892.
The bite angle of the chelating ligand is similar for
both complexes and quite acute, 59.71(8)8 for 3 and
59.03(17)8 for 4. In both cases, the phenyl groups (C31
[17] M. Honda, M. Komura, Y. Kawasaki, T. Tanaka, R. Okawara, J.
Inorg. Nucl. Chem. 30 (1968) 3231.
[18] Y. Maeda, C.R. Dillard, R. Okawara, Inorg. Nucl. Chem. Lett. 2
(1966) 197.
[19] W.O. George, Spectroscopic Methods in Organometallic Chem-
and C41) bend away the coordinate SnÃ
/
S bonds,
generating an PhÃ
/
SnÃ
/
Ph angle of 117.42(13)8 in the
case 3 and 116.8(3)8 in 4.
istry, Butterworths, London, 1970, pp. 95Á131.
/
[20] R. Schmiedgen, F. Huber, H. Preut, Acta Crystallogr., Sect. C 49
(1993) 1735.
[21] M.V. Castano, A. Mac´ıas, A. Castineiras, A.S. Gonza´lez, E.G.
˜
˜
4. Supplementary data
Mart´ınez, J.S. Casas, J. Sordo, W. Hiller, E.E. Castellano, J.
Chem. Soc., Dalton Trans. (1990) 1001.
[22] J.S. Casas, A. Castin˜eiras, E.G. Mart´ınez, A.S. Gonza´lez, A.
Sa´nchez, J. Sordo, Polyhedron 16 (1997) 795.
Crystallographic data (excluding structure factors) for
the structures have been deposited with the Cambridge
Crystallographic Data Center as supplementary pub-
lication nos. 167994 (3) and 167995 (4). Copies of the
data can be obtained, free of change, on application to
[23] B.D. James, R.J. Magee, W.C. Patalinghug, B.W. Skelton, A.H.
White, J. Organomet. Chem. 467 (1994) 51.
[24] L. Petrilli, F. Caruso, E. Rivarola, Main Group Met. Chem. 17
(1994) 439.