Tris(2-methyl-2-phenylpropyl)stannane derivatives, (Neo)3SnX, revisited. Comparison of crystal structures of (Neo)3SnX (X = Cl, Br, I, N3, NCS and OAc)

Article abstract of DOI:10.1016/S0277-5387(02)01030-6

The ¹H, ¹³C and ¹¹⁹Sn NMR and far-IR spectra of tris(neophyl)stannanes, (PhCMe₂CH₂)₃SnX, (Neo)₃SnX, [1: X = F, Cl, Br, 1, N₃, NCS, OSn(Neo)₃ and OAc], and the crystal structures of 1 (X = Br, I, N₃, NCS and OAc) are reported. The compounds 1 (X = Br, I, N₃ and NCS) and the previously reported 1 (X = Cl) all contain four-coordinate tin centers, with distorted tetrahedral geometries in the solid state. In contrast, 1 (X = OAc) is five-coordinate due to the acetate group acting as a chelating ligand. With the exception of 1 (X = Cl), all the compounds have entirely molecular structures with only van der Waals forces controlling the packing of the molecules. The molecules in 1 (X = Cl), with threefold axial symmetry, are packed head to tail in rows with weak C-H···Cl intermolecular contacts.

Full text of DOI:10.1016/S0277-5387(02)01030-6

Polyhedron 21 (2002) 1667ꢁ1676
/
www.elsevier.com/locate/poly
Tris(2-methyl-2-phenylpropyl)stannane derivatives, (Neo)3SnX,
revisited. Comparison of crystal structures of (Neo)3SnX
(Xꢀ
/
Cl, Br, I, N3, NCS and OAc)
Joao A.S. Bomfim a, Carlos A.L. Filgueiras a, R. Alan Howie b,*, John N. Low b,
˜
Janet M.S. Skakle b, James L. Wardell a, Solange M.S.V. Wardell c
a Departamento de Qu´ımica Inorgaˆnica, Instituto de Qu´ımica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil
b Department of Chemistry, University of Aberdeen, Old Aberdeen, AB24 3UE, Scotland, UK
c Departamento de Qu´ımica Orgaˆnica, Instituto de Qu´ımica, Universidade Federal Fluminense, 24020-150 Nitero´i, RJ, Brazil
Received 8 February 2002; accepted 26 April 2002
Abstract
The 1H, 13C and 119Sn NMR and far-IR spectra of tris(neophyl)stannanes, (PhCMe2CH2)3SnX, (Neo)3SnX, [1: Xꢀ
N3, NCS, OSn(Neo)3 and OAc], and the crystal structures of 1 (XꢀBr, I, N3, NCS and OAc) are reported. The compounds 1 (Xꢀ
Br, I, N3 and NCS) and the previously reported 1 (XꢀCl) all contain four-coordinate tin centers, with distorted tetrahedral
geometries in the solid state. In contrast, 1 (XꢀOAc) is five-coordinate due to the acetate group acting as a chelating ligand. With
the exception of 1 (XꢀCl), all the compounds have entirely molecular structures with only van der Waals forces controlling the
packing of the molecules. The molecules in 1 (XꢀCl), with threefold axial symmetry, are packed head to tail in rows with weak
CꢀHÁ Á ÁCl intermolecular contacts. # 2002 Elsevier Science Ltd. All rights reserved.
/F, Cl, Br, I,
/
/
/
/
/
/
/
Keywords: Organotin; Crystal structures; Halides; N-Thiocyanate; Azide; Acetate
1. Introduction
structures have been probed mainly by Mossbauer
¨
spectroscopy [4], and much less so by X-ray diffraction
Tris(neophyl)tin compounds, (PhCMe2CH2)3SnX, [1,
(Neo)3SnX] have attracted both industrial [1] and
[5ꢁ
various 1, including Xꢀ
tetraorganotin compound (1: Xꢀ
structures of 1 (XꢀCl [5,6], 1-triazolyl [5], OCO-
CH2OPh [7] and Neo [8,9]) have been reported. From
all these solid state studies, the compounds 1 are
indicated to be monomeric with four-coordinate tin
/
9]. Mossbauer spectral data have been provided for
¨
/
F, Cl, Br, I, N3 and OH and the
Neo), while X-ray
academic attention [2ꢁ
or so. A major interest has been their acaricidal
properties and uses, especially of 1 (XꢀOSn(Neo)3)
/
12] over the past four decades
/
/
/
[fenbutatin, Vendex† or Torque†] [1]. While the
agricultural use of fenbutatin, as with the general use
of all triorganotin compounds, is much curtailed cur-
rently, interest in such environmental effects as its
detection [13], and persistence [14], as well as the
developing resistance of targeted insects to the pesticide
[15], continue to be areas of much endeavor.
centers in all except 1 (XꢀOCOCH2OPh [7]), in which
/
the carboxylate group is weakly chelating, which leads
to five-coordinate tin centers. NMR spectral data in
solution for 1, mainly 1H NMR [2,3] but also 119Sn
NMR for 1 (Xꢀ
F [10] and Cl [10,12]) have been reported.
The crystal structures of 1 (XꢀBr, I, N3, NCS and
OAc) are reported here and are compared with those
previously reported for 1 (XꢀCl) [5,6] and 1 (Xꢀ
O2CCH2COPh) [7]. Attempts were also made to deter-
mine the crystal structures of 1 (XꢀF and OSn(Neo)3).
However, extreme disorder about the SnꢀF and Snꢀ
/
OH [10,12], OSn(Neo)3 [12], OAc [10],
Interest in 1 has also centered on the effects of the
bulky organic groups on the reactivities and especially
on the geometries at the tin centers [2,3]. Solid state
/
/
/
* Corresponding author. Tel.: ꢂ
272-921
E-mail address: r.a.howie@abdn.ac.uk (R. Alan Howie).
/
44-1224-272-907; fax: ꢂ44-1224-
/
/
/
/O
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 0 3 0 - 6

1668
J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ1676
/
bonds prevented sensible conclusions being obtained, in
X bonds. In addition to the
2.1.4. 1 (Xꢀ
Solutions of 1 (XꢀBr) (0.60 mmol) in Et2O and NaF
(3.66 mmol) in water were mixed. A little decyltrimethy-
lammonium bromide was added and the mixture was
sonicated for 10 min. Sodium sulfate was added and the
organic phase collected. Slow evaporation of the organic
/
F)
particular regarding the Snꢀ
/
/
X-ray data, solution 1H, 13C and 119Sn NMR and far-IR
spectral data are presented.
2. Experimental
solution gave crystals of 1 (Xꢀ
[3] value 98ꢁ100 8C.
IR (CsI, cmꢃ1): n: 497(Snꢀ
/
F); m.p. 99ꢁ
/
100 8C; lit.
/
NMR spectra were run on Bruker 300 and Varian 400
MHz instruments, IR spectra on Nicolet Magna 760
FTIR and Nicolet Fourier-transform spectrometers.
Melting points were measured on a Melt-TempII
instrument and are uncorrected.
/
F), 444, 263, 178.
2.1.5. 1 (Xꢀ/N3)
To a solution of 1 (Xꢀ/Br) (0.25 mmol) in EtOH was
added a solution of NaN3 (2.5 mmol) in warm EtOH.
The reaction mixture was stirred at r.t. for 30 min,
filtered and the filtrate evaporated. The residue was
extracted with Et2O and the extracts gave colorless
2.1. Synthesis
Compound 1 (Xꢀ
published procedure and 1 (Xꢀ
from Dow Chemical Co.
Compound 1 (Xꢀ
Neo). IR (CsI, cmꢃ1): n: 462, 391,
259, 158. [1: Xꢀ
OSn(Neo)3]. IR (CsI, cmꢃ1): n: 454,
419, 396, 374, 256, 157.
/
Neo) [9] was obtained by a
crystals of 1 (Xꢀ
/
N3) on slow evaporation; m.p. 98ꢁ
/
/
OSn(Neo)3) was a gift
99.5 8C; lit. [3] value 96ꢁ96.5 8C.
/
IR (CsI, cmꢃ1): n: 2069 (N3), lit. [3] value 2072, 456,
386, 266, 153.
/
/
2.1.6. 1 (Xꢀ/NCS)
To a solution of 1 (Xꢀ/Br) (0.3 mmol) in Me2CO was
2.1.1. 1 (Xꢀ
To a solution of 1 (Xꢀ
Et2O was added aqueous HCl (2 ml of 1.0 M solution).
After sonification for 5 min, the organic phase was
/
Cl)
added a solution of KNCS (2.2 mmol) in warm acetone.
The reaction mixture was stirred at r.t. for 1 h, filtered
and the filtrate evaporated. The residue was extracted
with CH2Cl2 and the extracts gave colorless crystals of 1
/
OSn(Neo)3) (0.5 mmol) in
collected and evaporated. Crystals of 1 (Xꢀ
obtained by slow evaporation from an Et2O solution;
m.p. 117ꢁ119 8C; lit. [3] value 117.5ꢁ118.5 8C.
IR (CsI, cmꢃ1): n: 461, 394, 311(Snꢀ
Cl), 266, 160.
/
Cl) were
(Xꢀ
IR (CsI, cmꢃ1): n: 2021(NC), 459, 399, 303(Snꢀ
268, 167.
/
NCS) on slow evaporation; m.p. 98ꢁ
/
99.5 8C.
/
N),
/
/
/
2.1.7. 1 (Xꢀ
/
OAc)
2.1.2. 1 (Xꢀ
To a solution of 1 (Xꢀ
was added, dropwise with stirring, a solution of Br2 (2.0
ml) in CHCl3 at ꢃ10 8C. After addition was complete,
/
Br)
Compound 1 (XꢀOSn(Neo)3] (0.15 mmol) was
dissolved in acetic acid (3 ml, 5.2 mmol). The solution
was evaporated under vacuum and gently heated to
/
/
Neo) (2.0 mmol) in CHCl3
/
leave a residue of 1 (Xꢀ/OAc). This was recrystallized
the temperature was allowed to rise to ambient.
Complete reaction occurred after 2 h as shown by the
decoloration of the reaction mixture. The solvent was
removed under vacuum to leave a solid, which was
from acetic acid; m.p. 85ꢁ
/
88 8C; lit. [3] value 86.5ꢁ
/
87 8C.
IR (CsI, cmꢃ1): n: 1667 (CO) (lit. [3] value 1660), 456,
402, 292, 266, 160.
1
washed with cold MeOH. Crystals of 1 (Xꢀ
obtained by slow evaporation from an Et2O solution;
m.p. 112ꢁ113 8C; lit. [3] value 109.5ꢁ110 8C.
IR (CsI, cmꢃ1): n: 457, 398, 266, 212(Snꢀ
Br), 164.
/Br) were
Selected H, 13C and 119Sn NMR spectral data for 1
are displayed in Table 1.
2.2. Crystallography
2.2.1. Data collection
/
/
/
2.1.3. 1 (Xꢀ
/
I)
To a solution of 1 (Xꢀ/Br) (0.55 mmol) in Me2CO
Intensity data for 1 (XꢀBr, I, N3 and OAc) were
/
was added a solution of KI (1.75 mmol) in warm
Me2CO. The reaction mixture was stirred at room
temperature (r.t.) for 1 h, filtered and the filtrate
evaporated. The residue was extracted with CH2Cl2
and the extractions were partially evaporated. Colorless
obtained, at 150 K in all cases, by means of the Enraf
Nonius KappaCCD area detector diffractometer of the
EPSRC’s crystallography service at Southampton. The
entire process of data collection, cell refinement and
data reduction was accomplished by means of the
programs DENZO [16] and COLLECT [17]. Correction
for absorption by a semi-empirical method based upon
the variation in intensity of equivalent reflections was
achieved with the program SORTAV [18]. Data for 1
crystals of 1 (Xꢀ
evaporation; m.p. 117ꢁ
117.5 8C.
IR (CsI, cmꢃ1): n: 454, 396, 268, 172(Snꢀ
/
I) were obtained by further slow
/
118 8C; lit. [3] value 116.5ꢁ
/
/
I).

J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ
/1676
1669
Table 1
Selected NMR spectral data for 1 in CDCl3
X
F
d
119Sn
d1H(CH2)
d1H(Me)
d
13C(CH2)
H)] [J(119,117Snꢁ13
d
13C(Me)
[J(119,117Snꢁ13
d
13C(CMe2)
[J(119,117Snꢁ13
C)]
d(others)
[J(119,117Snꢁ
/H)]
[J(119,1117Snꢁ
/
/
C)]
/
C)]
/
138.8
[146]
1.01
[48.9]
1.18
[ca. 5]
39.8
[350]
38.6
[20.5]
33.8
[44.1]
1J(SnꢀF)ꢀ2301
3J(FꢀCH2)ꢀ3.1
2J(FꢀCH2)ꢀ7.6
a
c
0.95
1.22
c
[52.4]
1.11
[ꢁ]
/
Cl
118.4
[118]
1.18
[5.8]
40.4
[334,319]
38.9
[21.3]
33.9
[46.4]
[47.2]
a
b
c
c
c
[117.7]
1.05
[47.8]
1.19
[5.8]
1.19
[5.8]
1.20
[5.9]
1.19
[6.2]
1.19
[6.2]
1.22
[6.2]
1.19
[6.2]
1.12
[5.1]
c
Br
I
92.3
1.23
[46.5]
39.1
[323,309]
38.1
[22.0]
32.9
[46.4]
c
c
c
1.07
[48.4]
c
14.7
1.38
[45.1]
39.3
[309,295]
39.6
[22.0]
34.0
[46.3]
c
c
c
1.34
[44.5]
c
NCS 47.9
N3
1.05
[49.0]
1.03
[48]
37.5
[354,339]
37.5
37.6
[22.8]
37.6
32.8
[46.0]
32.8
1J(SnꢀN)ꢀ125
[ꢁ
37.3
[356]
/]
[ꢁ]
37.8
/
[ꢁ]
32.87
[44.1]
/
OAc 83.4
[79]
1.07
[50.6]
d
d
13C(CO)ꢀ176.2
13C(CH3)ꢀ22.6
[20.1]
a
d1H(CH2)ꢀ1.89
c
c
c
c
1.04
[51.7]
0.99
1.25
[5.2]
1.20
[4.6]
1.16
d1H(CH2)ꢀ1.82
c
OH 77.1
37.8
37.3
33.1
b
[75.9]
Neo ꢃ52.5
[50.4]
0.80
[47.9]
[ꢁ
31.2
[ꢁ
/]
[ꢁ]
38.5
/
[41.9]
33.6
[34.5]
[ꢁ/]
/]
[18.6]
a
[10].
[12].
b
c
[3].
(Xꢀ
/
NCS) were obtained at 297 K with a Bruker
3. Results and discussion
SMART 1000 CCD area detector diffractometer.
SMART software [19] was used for data collection and
the program SAINT [19] for cell refinement and data
reduction. A semi-empirical correction for absorption
similar to that noted above was applied by means of the
program SADABS [19].
3.1. General
The syntheses of the various compounds 1 were
achieved by bromo-dealkylation of 1 (XꢀNeo) or by
anion exchange using as reagents either 1 (XꢀBr), with
Yꢃ (Yꢀ
F, I, NCS or N3), or 1 (XꢀOSn(Neo)3), with
/
/
/
/
2.2.2. Structure solution and refinement
HCl or HOAc. Complete anion exchanges were indi-
cated from the physical properties, including NMR and
far IR spectra.
The same procedure was used for all 1. Structure
solutions providing positions for the majority of the
non-H atoms were obtained by application of the direct
methods procedure of SHELXS-97 [20]. Thereafter dif-
ference map calculations to find any missing non-H
atoms and completion of the refinement process were
carried out with SHELXL-97 [21]. In the final stages of
refinement H atoms were placed in calculated positions
and refined with a riding model. Further details of the
processes of data collection and structure refinement are
available in Table 2. The program, ORTEP-3 [22], was
used to obtain the Figures.
3.2. Crystallography
The solid state structures were not merely studied to
determine the coordination at tin, but to investigate the
conformations and molecular arrangements in 1, com-
pounds in which there are three relative bulky hydro-
phobic groups (the neophyl ligands) and a relatively
small polar region (the Snꢀ
/
X fragment).

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J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ1676
/
Table 2
a
Crystal data and structure refinement for (1: XꢀBr, I, N3, NCS and OAc)
X
Br
I
N3
NCS
OAc
Empirical formula
M
C
30.25H39.25BrCl0.75Sn C30.25H39.25Cl0.75ISn
C30H39N3Sn
560.33
150(2)
C31H39NSSn
576.38
297(2)
C32H42O2Sn
577.35
150(2)
628.05
150(2)
0.71073
P21
675.04
150(2)
0.71073
P21
T (K)
Wavelength (A)
˚
0.71073
P21/n
0.71073
P21/c
0.71073
P1
Space group
Cell dimension
˚
a (A)
17.9633(4)
17.9225(4)
18.3954(6)
90
18.0069(3)
17.9500(3)
18.4313(4)
90
18.7224(2)
17.2884(2)
19.4326(4)
90
17.7105(7)
18.7575(8)
18.3223(8)
90
12.2476(2)
15.3004(2)
16.9444(2)
104.3450(8)
103.4030(7)
100.7490(6)
2890.50(7)
4
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
103.9165(9)
90
103.4000(7)
90
117.2747(5)
90
100.7760(10)
90
3
˚
V (A )
Z
Calculated density
(Mg mꢃ3
Absorption coefficient
5748.5(3)
8
1.451
5795.25(19)
8
1.547
5590.63(14)
8
1.331
5979.4(4)
8
1.281
1.327
)
2.365
2.032
0.936
0.942
0.909
(mmꢃ1
F(000)
Crystal color
)
2548
colorless
2692
colorless
2320
colorless
2384
colorless
1200
colorless
Crystal size (mm)
uRange for data
collection (8)
0.10ꢄ0.10ꢄ0.10
0.35ꢄ0.10ꢄ0.04
0.20ꢄ0.20ꢄ0.10
0.30ꢄ0.20ꢄ0.20
0.20ꢄ0.20ꢄ0.12
2.91ꢁ
/
27.44
3.00ꢁ
/
30.83
3.13ꢁ
/
27.51
2.08ꢁ
/
32.51
2.94ꢁ30.77
/
Index range
ꢃ235h 522,
ꢃ195k 521,
ꢃ195l 523
36 214/22 983
ꢃ245h 524,
ꢃ225k 522,
ꢃ215l 526
45 544/26 606
ꢃ245h 521,
ꢃ205k 521,
ꢃ255l 525
42 274/12 668
ꢃ265h 517,
ꢃ285k 525,
ꢃ255l 527
61 105/21 502
ꢃ165h 517,
ꢃ195k 521,
ꢃ235l 520
30 901/22 786
Reflections collected/
unique
[Rint
]
0.0754
27.44, 95.6%
0.0451
30.83, 82.1%
0.0523
27.51, 98.4%
0.0533
32.51, 99.2%
0.0341
30.77, 74.4%
Completeness to 2u
limit (%)
Max. and min.
transmission
0.838 and 0.733
22 983/1/1213
0.995 and 0.908
26 606/1/1213
0.904 and 0.828
12 668/0/625
0.912 and 0.808
21 502/0/625
0.910 and 0.846
22 786/3/1261
Data/restraints/
parameters
Goodness-of-fit on F2
Final R indices
[I ꢀ2s(I)]
1.002
1.010
1.030
0.807
1.103
R1ꢀ0.0604,
wR2ꢀ0.1275
R1ꢀ0.1199,
wR2ꢀ0.1687
0.001(11)
R1ꢀ0.0470,
wR2ꢀ0.0947
R1ꢀ0.0763,
wR2ꢀ0.1081
ꢃ0.042(15)
R1ꢀ0.0410,
wR2ꢀ0.0915
R1ꢀ0.0678,
wR2ꢀ0.1022
R1ꢀ0.0356,
wR2ꢀ0.0633
R1ꢀ0.1258,
wR2ꢀ0.0816
R1ꢀ0.0374,
wR2ꢀ0.1049
R1ꢀ0.0450,
wR2ꢀ0.1209
ꢃ0.047(14)
R indices (all data)
Absolute structure
parameter
Largest diff. peak and
0.862 and ꢃ1.050
0.967 and ꢃ1.593
0.904 and ꢃ1.074
0.623 and ꢃ0.369
0.877 and ꢃ1.362
ꢃ3
˚
hole (e A
)
a
In all cases, absorption correction was semi-empirical from equivalents and refinement by full-matrix least-squares on F2.
The crystals used in the crystallography were grown
by evaporation of CHCl3 solutions. Unsolvated com-
complicated by the fact that the asymmetric unit of 1
(XꢀN3) and 1 (XꢀNCS) contains two complete
molecules and that of 1 (XꢀBr), 1 (XꢀI) and 1
(XꢀOAc) no less than four. This has prompted the
following labeling convention. The atoms of every
neophyl group have been labeled numerically in the
same manner (Fig. 1), e.g. in every case C1 is bonded to
Sn1 and the methyl and phenyl groups are C3 and C4
and C5 to C10, respectively. There is not, however,
complete consistency in the numbering of the atoms of
the methyl and phenyl groups in relation to their
orientation with respect to the molecule as a whole.
/
/
pounds were obtained for 1 (Xꢀ
while solvates, [1×1/4CHCl3] were isolated for 1 (Xꢀ
and I).
As well as the structures of 1 (Xꢀ
OAc), the structure of the previously reported com-
pound 1 (XꢀCl) [6] at 150 K is also discussed here. All
/N3, NCS and OAc),
/
/
/
/Br
/
/Br, I, N3, NCS and
/
these molecules are themselves not inconsiderable in size
requiring the placement, in the absence of coincident
crystallographic and molecular symmetry, of at least 32
non-H atoms per molecule. The situation is further

J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ
/1676
1671
are influenced by both the size of the ligand X and the
X bond lengths,
length of the Snꢀ
/
X bond. The Snꢀ
/
averages for all but 1 (Xꢀ
/
Cl), are 2.382(3), 2.545(2),
˚
2.714(8) A for Xꢀ
/Cl, Br and I, respectively, and are
close to the appropriate sums of the covalent radii of
˚
2.39, 2.54 and 2.73 A [23].
The average SnꢀN bond lengths in 1 (Xꢀ
1 (XꢀN3) are 2.119(2) and 2.247(12) A, respectively,
/
/NCS) and
˚
/
compared with the sum of the covalent radii for Sn and
˚
N of 2.15 A [24]. There are no intermolecular SnÁ Á ÁN
contacts in 1 (Xꢀ
/
N3) or SnÁ Á ÁS contacts in 1 (Xꢀ
/
˚
NCS) less than 4.0 A. The closest intermolecular
contacts in a particular molecule of 1 (Xꢀ
/
NCS) are
that is close to the sum of the
˚
SÁ Á ÁS at 3.6429(16) A*
/
Fig. 1. The general atom numbering scheme used for the carbon atoms
of the neophyl groups in 1, see text. The example shown is the
van der Waals radii. Smaller triorganotin N-thiocya-
nates, such as Me3SnNCS {SnꢀN and SnꢀSꢀ2.15(6)
and 3.13(2) A} [24], Ph3SnNCS {SnꢀN and SnꢀSꢀ
2.199(11)ꢁ2.248(10), and 2.897(4)ꢁ2.952(4) A} [25,26]
N and SnꢀSꢀ2.195(5)
asymmetric unit of 1 (Xꢀ
/
Cl) omitting the Cl atom. Non-H atoms are
/
/
/
shown as 30% ellipsoids and H atoms as small circles.
˚
/
/
/
˚
/
/
For 1 (Xꢀ
/
N3) and 1 (XꢀNCS), the two independent
/
and (p-MeC6H4)3SnNCS {Snꢀ
/
/
/
molecules are termed I and II: in molecule I, the tin
atom is Sn1a, the three neophyl ligands/their constituent
atoms are identified by the suffices A/a, B/b and C/c,
while in molecule II, the tin atom is Sn1b and the
suffixes used for the three neophyl groups/atoms are D/
˚
and 3.0255(2) A} [26], exist in the solid state as zig-zag
polymers due to NCS bridging with five-coordinate tin
atoms. The more hindered compounds, Me2[(PhMe2-
˚
Si)3C]SnNCS {Snꢀ
/
Nꢀ2.12(3) A} [27] and (o-
/
˚
MeC6H4)3SnNCS {Snꢀ
/
Nꢀ2.067(6) and 2.066(6) A}
/
d, E/e and F/f. In each of 1 (Xꢀ
/
Br), 1 (XꢀI) and 1
/
[26], on the other hand, are monomeric in the solid state
with four-coordinate tin centers. Compound (o-
(XꢀOAc), which have four independent molecules in
/
the asymmetric unit, a similar system is utilized. The
four independent molecules are termed I, II, III and IV,
having tin atoms Sn1a, Sn1b, Sn1c and Sn1d, respec-
tively. The neophyl group suffices are here A, B and C
(in molecule I), D, E and F (in molecule II), G, H and I
(in molecule III) and J, K and L (in molecule IV): the
atoms within each neophyl ligand take the appropriate
lower case suffix. A similar strategy as used for Sn has
been applied to the labeling of the halide, X, in
˚
2.090(5) A} [26], is also
molecular, but here there is a suggestion of a weak
MeOC6H4)3SnNCS {Snꢀ
/
Nꢀ
/
˚
intramolecular Snꢀ
NꢀSnꢀOꢀ152.19(17)8] and hence an increase in the
coordination number at Sn to 5, but this clearly has little
effect on the SnꢀN bond length.
The SnꢀN bond length in monomeric t-Bu3SnN3 [28]
is a little shorter, at 2.101(4) A, than those found in 1
(XꢀN3). Smaller triorganotin azides, e.g. Me3SnN3
[29], are N-bridged in the solid state. The SnꢀN bond
lengths in [(1: Xꢀtriazole)×0.5H2O] [5] are 2.123(6) and
/
O interaction [Snꢀ
/
O 2.961(4) A, Ú
/
/
/
/
/
/
˚
/
molecules of 1 (Xꢀ
numbering of the other X group atoms are (Sn1)ꢀ
N2ꢀN3 in 1 (XꢀN3), and (Sn1)ꢀN1ꢀC11ꢀS1 in 1
(XꢀNCS) and (Sn1)ꢀO1ꢀC11(O2)ꢀC12 in 1 (Xꢀ
OAc).
/
Br) and 1 (Xꢀ/I). The general
/
/
N1ꢀ
/
/
/
/
/
/
/
/
˚
2.105(7) A.
/
/
/
/
/
Compound 1 (Xꢀ/OAc) was the only trineophyltin
compound studied here that was other than four-
coordinate, as a result of the acetate group tending to
be a bidentate chelating ligand and the tin centers
becoming five-coordinate (Fig. 2). As shown by the
3.2.1. Geometry at tin
Selected bond lengths and angles for 1 (Xꢀ
N3 and NCS) are listed in Tables 3 and 4, while selected
geometric data for 1 (XꢀOAc) are provided in Table 5.
Molecules of 1 (XꢀCl, Br, I, N3 and NCS) clearly
/Cl, Br, I,
Snꢀ
acetate chelate bonding, with one strong and one weak
bond: the primary SnꢀO1 bond lengths fall in the range
O2 separations be-
/
O distances, there is a strong asymmetry in the
/
/
/
˚
contain four-coordinate tin centers, with distorted
tetrahedral geometries. Each independent molecule of
2.070(5)ꢁ
/
2.117(4) A with the Snꢀ
/
˚
tween 2.963 and 3.069 A. These values can be compared
each compound 1 (Xꢀ
very similar geometry, with relatively small differences
in the CꢀSnꢀX and CꢀSnꢀC bond angles for each X. In
each molecule, the three smallest angles subtended at tin
are the CꢀSnꢀX angles. The bulk of the neophyl groups
results in the opening up of the CꢀSnꢀC angles. The
average CꢀSnꢀX angles are 99.678, 101.68, 102.58,
100.68 and 99.78 in 1 (XꢀCl, Br, I, N3 and NCS) and
/
Cl, Br, I, N3 and NCS) has a
with sums of covalent radii and van der Waals radii of
˚
2.15 and 3.70 A [23]. Noticeably too, the primary Cꢀ
/
/
/
/
/
Snꢀ
ranges of 93.8489
0.558, see Table 5. The Cꢀ
also show a slightly greater variation than those in 1
(XꢀCl, Br, I, N3 and NCS). The geometry at tin is best
described as being on the pathway from tetrahedral to
/
O1 angles fall into three distinct groupings, with
0.828, 103.13891.338 and 107.7589
SnꢀC angles in 1 (XꢀOAc)
/
/
/
/
/
/
/
/
/
/
/
/
/
/

1672
J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ1676
/
Table 3
a
˚
Selected bond lengths (A) for 1 (XꢀCl, Br, I, N3 and NCS)
X
Mol
Sn1ꢀX1
Sn1ꢀC1(n)
[n]
[n]
[n]
Cl
Br
2.382(3)
2.149(5)
2.149(5)
2.149(5)
I
2.5473(14)
2.5427(13)
2.5440(15)
2.5438(14)
2.7496(6)
2.7333(6)
2.7441(6)
2.7424(6)
2.259(5)
2.150(12) [a]
2.147(12) [e]
2.151(11) [g]
2.170(10) [j]
2.154(6) [b]
2.159(6) [f]
2.143(7) [g]
2.161(6) [l]
2.147(3) [b]
2.143(3) [e]
2.138(3) [b]
2.141(2) [e]
2.157(10) [c]
2.147(10) [f]
2.170(11) [h]
2.173(10) [l]
2.162(7) [a]
2.160(7) [d]
2.156(7) [h]
2.166(6) [j]
2.150(3) [a]
2.150(3) [f]
2.142(2) [a]
2.141(2) [f]
2.172(9) [b]
2.171(9) [d]
2.172(10) [i]
2.184(11) [k]
2.164(6) [c]
2.163(7) [e]
2.163(6) [i]
2.166(6) [k]
2.156(3) [c]
2.150(3) [d]
2.147(2) [c]
2.149(2) [d]
II
III
IV
I
I
II
III
IV
I
N3
II
I
2.235(3)
2.117(3)
2.121(3)
NCS
II
a
The three Sn*C1(n) bond lengths in each molecule have been placed in order of increasing bond length. The particular C1(n) atom involved in
/
each bond has been indicated by the lower case letter, a, b, c etc., which, as indicated in the text, are associated with neophyl ligands, A, B, C etc.
trigonal bipyramidal, with the carbonyl oxygens, O2, in
quasi axial positions and O1 in the quasi equatorial
sites. A similar situation of a cis-R3SnO2 arrangement
the phenyl groups of the neophyl substituents are
displaced in a clockwise direction. In the other (type
L) the displacement is anticlockwise. In 1 (XꢀCl), the
/
pertains in 1 (XꢀO2CCH2OPh) [7] and in other
/
example shown in Fig. 3, both forms are present due to
the operation of the crystallographic bar4 (fourfold
rotary inversion axis) and equivalently the d-glide of the
cubic space group I-43d and the structure is racemic. It
is, however, polar because the space group lacks a center
of symmetry and the bar4 creates a molecular arrange-
ment with the overall symmetry of a regular tetrahedron
whose orientation relative to the unitcell edges can differ
hindered triorganotin carboxylates [30]. The most fre-
quently found structural type, however, for unhindered
triorganotin carboxylates is a carboxylate bridged poly-
meric chain with trans-R3SnO2 cores [31], for example,
as found in Me3SnOAc [32].
3.2.2. The existence of rotamers
from one crystal to another. The structures of 1 (Xꢀ
/
In all of the structures discussed here the molecules
are propeller shaped (Fig. 3) and as a consequence can,
and do, exist in two rotameric forms. In one form (type
N3) and 1 (XꢀNCS), being centrosymmetric, are of
/
course racemic and non-polar. By accident of choice in
both cases both molecules of the bimolecular asym-
R), when viewed along the Snꢀ
/
X bond from X to Sn,
Table 4
Selected bond angles (8) in 1 (XꢀCl, Br, I, N3 and NCS)
a
X
Mol C1(n)ꢀSn1ꢀX1
C1(n)ꢀSn1ꢀC1(n?)
[n]
[n]
[n]
[n,n?]
[n,n?]
[n,n?]
Cl
Br
99.67(15)
99.6(3) [c]
99.67(15)
102.2(4) [a]
101.4(3) [f]
99.67(15)
117.24(8)
117.24(8)
117.24(8)
I
103.2(3) [b]
102.5(3) [d]
102.9(3) [i]
115.0(4) [c,b]
115.3(4) [e,f]
114.7(4) [g,h]
115.4(4) [j,l]
115.7(4) [a,c]
116.2(4) [e,d]
116.5(4) [g,i]
115.5(4) [l,k]
115.3(2) [b,c]
115.7(2) [f,e]
114.9(3) [h,i]
115.9(2) [j,k]
115.92(11) [b,a]
117.10(12) [e,f]
116.56(10) [a,c]
117.48(10) [e,f]
B117.3(4) [a,b]
116.7(4) [f,d]
116.9(4) [h,i]
117.4(4) [j,k]
116.0(2) [b,a]
116.0(2) [d,e]
115.0(3) [g,i]
116.0(2) [l,k]
117.50(12) [a,c]
117.18(12) [f,d]
118.05(10) [b,c]
118.09(10) [e,d]
II
III
IV
I
100.9(3) [e]
100.2(4) [h]
100.3(4) [l]
101.8(3) [g]
101.4(3) [j]
102.8(3) [k]
104.41(18) [b]
103.13(18) [d]
I04.2(2) [i]
I
100.7(2) [c]
101.14(19) [e]
102.24(17) [g]
100.8(2) [l]
102.8(2) [a]
101.90(19) [f]
C103.2(2) [h]
102.71(18) [j]
102.18(15) [a]
100.58(12) [d]
99.92(11) [c]
99.28(11) [d]
114.8(3) [a,c]
115.6(3) [f,d]
114.9(3) [g,h]
115.3(2) [l,j]
II
III
IV
I
102.78(19) [k]
102.49(16) [b]
101.04(12) [e]
100.72(12) [a]
100.70(12) [f]
N3
98.72(15) [c]
100.39(12) [f]
99.65(11) [b]
98.09(12) [e]
115.69(12) [b,c]
115.68(12) [e,d]
116.38(10) [b,a]
116.67(10) [f,d]
II
I
NCS
II
a
The three C1(n)*
/
Sn1*
/
X1, and three C1(n)*
/
Sn*C1(n?) bond angles in each molecule have been placed in order of increasing size. The
/
particular C1(n) and C1(n?) atoms involved have been indicated by the lower case letter, a, b, c etc., which, as indicated in the text, are associated with
neophyl ligands, A, B, C etc.

J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ
/1676
1673
Table 5
Selected geometric parameters for 1 (XꢀOAc)
a
Molecule
C1
C2
I
II
III
IV
C1c
C2b
C3a
C1d
C2f
C3e
C1I
C2h
C3g
C1l
C2j
C3k
C3
Bond lengths
Sn1ꢀO1
Sn1ꢀO2
Sn1ꢀC1
Sn1ꢀC2
Sn1ꢀC3
C11ꢀO1
C11ꢀO2
C11ꢀC12
2.070(5)
3.069(7)
2.137(6)
2.143(6)
2.163(5)
1.266(8)
2.117(4)
3.052(5)
2.142(6)
2.145(5)
2.155(5)
1.266(8)
2.086(4)
3.004(5)
2.151(5)
2.152(5)
2.170(5)
1.279(8)
1.214(9)
1.5222(9)
2.074(4)
2.963(4)
2.147(5)
2.150(5)
2.164(5)
1.295(7)
1.221(7)
1.489(8)
1.221(10) 1.202(8)
1.498(10) 1.489(10)
Bond angles
Equatorial/equatorial
O1ꢀSn1ꢀC1
O1ꢀSn1ꢀC2
C1ꢀSn1ꢀC2
108.3(2)
102.6(2)
115.0(2)
107.2(2)
102.0(2)
118.7(2)
107.79(19)
101.8(2)
118.5(2)
104.46(18)
107.68(17)
119.63(19)
Axial/equatorial (C3)
C3ꢀSn1ꢀO1
C3ꢀSn1ꢀC1
C3ꢀSn1ꢀC2
93.3(2)
116.3(2)
117.2(2)
93.11(19)
115.1(2)
115.7(2)
94.65(19)
114.2(2)
115.6(2)
93.02(19)
114.1(2)
113.6(2)
Axial/equatorial (O2)
O2ꢀSn1ꢀO1
O2ꢀSn1ꢀC1
O2ꢀSn1ꢀC2
45.2(2)
77.2(3)
87.4(2)
45.45(15)
79.10(19)
85.4(2)
47.30(16)
78.08(18)
84.9(2)
47.94(13)
84.36(16)
81.26(16)
Trans axial
O2ꢀSn1ꢀC3
137.1(2)
137.93(19)
141.11(19)
140.78(17)
a
Distance and angle table for bidentate acetate anion comprising
carboxyl O1, O2 and C11 and methyl group C12 which creates a
trigonal bipyramidal coordination around Sn1 with equatorial O1, C1
and C2 (Sn1*
/
C1<Sn1*C2) and axial O2 and C3.
/
Fig. 3. Two molecules of 1 (Xꢀ/Cl) displaying (a) the ‘clockwise’ type
R rotamer and (b) the ‘anticlockwise’ type L rotamer. Non-H are
shown as 30% ellipsoids and H have been omitted for clarity. Selected
atoms are labeled with symmetry codes for (a) 1: z, x, y; 2: y, z, x and
(b) 3: 1/4ꢂ
/
x, 1/4ꢂ
/
z, 1/4ꢂ
/
y; 4: 1/4ꢂ
/
y, 1/4ꢂ
/
x, 1/4ꢂ
/
z and 5: 1/4ꢂz,
/
1/4ꢂy, 1/4ꢂ
/
/
x.
Fig. 2. Trineophyltin carboxylates (1: XꢀOAc or O2CCH2COPh).
/
Fig. 4. A portion of a linear chain of head to tail molecules, as indicated by PLATON [39] of 1 (Xꢀ
cubic unitcell [111]. Non-H are shown as 30% ellipsoids and H7, involved in C*
HÁ Á ÁCl intermolecular contacts (dashed lines), is the only H shown.
The molecules in the portion of the chain shown alternate in terms of rotameric type as R at the extremes and L in the center. The parameters
/Cl) propagated in the direction of a diagonal of the
/
˚
associated with the C7*
/
H7Á Á ÁCl contacts are C*
/
H, HÁ Á ÁCl and CÁ Á ÁCl 0.95, 2.79 and 3.622(8) A, respectively, and C*HÁ Á ÁCl 146.478.
/

1674
J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ1676
/
metric unit are of the same hand but of type L for 1
(XꢀN3) and type R for 1 (XꢀNCS). In each of 1 (Xꢀ
Br), 1 (XꢀI) and 1 (XꢀOAc) all of the molecules in
the asymmetric unit are of the same hand, type R for 1
(XꢀBr) and isostructural 1 (XꢀI) and type L for 1
(XꢀOAc). Since all of these last three structures lack a
center of symmetry or any other form of crystallo-
graphic symmetry element to bring about inversion of
molecular symmetry, all of the molecules in a particular
crystal must then be of the same hand. However, since
there is no element of handedness in the synthesis of the
compounds, and no evidence of disorder, a bulk sample
of any one of them must contain crystals of one hand in
admixture with crystals of the other in equal parts by
volume which allows for variation in crystal size.
3.3. Spectroscopy
/
/
/
NMR spectral data obtained for 1 in this study were
in agreement with those reported in the literature. In the
/
/
/
/
humid atmosphere of Rio de Janeiro, 1 [Xꢀ
/
OSn(Neo)3]
OH), as
/
in solution was rapidly hydrolyzed to 1 (Xꢀ
/
shown by the d119Sn value 77.1 ppm, obtained after
several minutes in solution. Lockhart [12] reported
values of 54.8 and 75.9 ppm for 1 (Xꢀ
/
OSn(Neo)3)
and 1 (XꢀOH), respectively, in CDCl3 solution. The
/
3.2.3. Molecular packing
With one slight exception, all of the compounds have
entirely molecular structures with only van der Waals
forces controlling the packing of the molecules and three
situations arise. The first is the exception namely 1 (Xꢀ
/
Cl). Here the molecules, with crystallographic threefold
axial symmetry, are packed head to tail in rigorously
linear rows (Fig. 4). This arrangement permits weak H-
bond like intermolecular contacts of the form C7ꢀ
H7Á Á ÁCl? with, for the 150 K structure [6] (CSD ref.
code FOZRER) [33], symmetry code 5/4ꢃy, 3/4ꢃx, zꢃ
1/4 and CꢀH, HÁ Á ÁCl and CÁ Á ÁCl 0.95, 2.79 and 3.622(8)
A, respectively, and CꢀHÁ Á ÁCl 146.478. The second case
is that of 1 (XꢀOAc) in which the molecules can be
/
/
/
/
/
˚
/
/
perceived as forming layers parallel to (001) with
molecules II and III forming one layer centered
approximately on zꢀ/0.15 and molecules I and IV
forming the other centered on zꢀ/0.65 (Fig. 5). The
third and last case applies to all of the other structures.
The molecules are now found in columns in which all of
the molecules are the same (all molecule I or all molecule
II etc. but never mixed) and all of the same rotameric
type (R or L, see above) because each molecule is related
to the next by the operation of a crystallographic
twofold screw axis propagating the columns in the
direction of b (Fig. 6).
In all of 1 (Xꢀ
columns pass through the unit cell and in 1 (Xꢀ
1 (XꢀI) all of the molecules in all of the columns are of
the same type and, as it happens, of type R. In
centrosymmetric and therefore racemic 1 (XꢀN3) and
1 (XꢀNCS), however, it is the all-molecule I or all-
/Br, I, N3 and NCS), four such
/Br) and
/
/
/
molecule II columns which are related in pairs by the
crystallographic centers of symmetry and hence there is
still no mixture of R and L type molecules within a
single column. The chloroform solvate molecules of 1
Fig. 5. Molecules of 1 (Xꢀ
(a) molecules I and IV in a layer centered on zꢀ
II and III in a layer centered on zꢀ0.15. Non-H are shown as 50%
ellipsoids and H have been omitted for clarity. Labels on selected Sn
and O and group suffices (see text) identify the molecules and neophyl
groups.
/
OAc) in layers parallel to (001) comprising
/
0.65 and (b) molecules
/
(Xꢀ
/
Br) and 1 (XꢀI), simply occupy cavities between
/
the columns.

J.A.S. Bomfim et al. / Polyhedron 21 (2002) 1667ꢁ
/1676
1675
Fig. 6. A portion of a chain of molecules I in 1 (Xꢀ
omitted for clarity. In addition to labeled Sn and Br atoms, neophyl groups are identified by group suffices, A, B and C. Symmetry codes for primed
atoms: ꢃx, yꢂ1/2, 1ꢃz (left) and ꢃx, yꢃ1/2, 1ꢃz (right).
/Br) propagated in the direction of b. Non-H atoms are shown as 50% ellipsoids and H have been
/
/
/
/
/
/
product isolated from solutions, however, was always 1
[XꢀOSn(Neo)3]. Lockhart also indicated similar effects
[12].
Triorganotin chlorides, bromides and iodides, R3SnX
(Rꢀunfunctionalised organyl group; XꢀCl, Br or I),
are generally monomeric four-coordinate species in non-
coordinating solvents and in the solid state [34]. Hence
there are much data available on spectral parameters for
such species in solution. On the other hand, R3SnF,
except the most hindered compounds, such as (2.4,6-
Me3C6H2)3SnF [35], Ph2[(Me3Si)3C]SnF [36], Me2[(Ph-
species as solids are quoted as 340ꢁ
n(SnꢀX) values for 1 (XꢀCl, Br or I) in CsI, viz. 311,
212 and 172 cmꢃ1 respectively, fall in the expected
regions. The n(Snꢀ
F) value [497 cmꢃ1] in molecular 1
(XꢀF) can be compared with the values, 535 and 537
/
380 cmꢃ1 [37]. The
/
/
/
/
/
/
/
cmꢃ1, found in (2.4,6-Me3C6H2)3SnF [35] and (o-
MeOC6H4)3SnF [38], respectively, both shown by X-
ray crystallography to be monomeric. The latter com-
pound, just like (o-MeOC6H4)3SnNCS [26], has indica-
tions of Sꢀ
/
O intramolecular interaction and hence a
higher coordination.
Me2Si)3C]SnF [36] and 1 (XꢀF), are aggregated species
/
in the solid state and are poorly soluble in organic
solvents. Reported NMR data for triorganotin fluorides
4. Supplementary material
in solution are thus limited. The 1J(119Snꢀ
/
19F) value for
1 (Xꢀ
/
F) ꢀ2301 ppm in CDCl3 solution is similar to
/
Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic
Data Center, CCDC numbers 178628ꢁ
the reported values for other monomeric R3SnF com-
pounds, Ph2[(Me3Si)3C]SnF, Me2[(PhMe2Si)3C]SnF and
/178632 for
Me2[(Me3Si)3C]SnF [24] [1J(119Snꢀ
/
19F)ꢀ
2376, 2374
/
compounds (1: XꢀBr, I, N3, NCS and OAc), respec-
/
and 2463 ppm, respectively]. The d119Sn values for the
tively. Copies of this information may be obtained free
of charge from the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: ꢂ44-1223-336033; e-
monomeric trialkyltin fluorides are also similar: d119Sn
values for
Me2[(Me3Si)3C]SnF are 138.8, 124.5 and 146.9 ppm,
1
(XꢀF), Me2[(PhMe2Si)3C]SnF and
/
/
mail: deposit@ccdc.cam.ac.uk).
1
respectively. The J(119Snꢀ
and Me2[(PhMe2Si)3C]SnNCS [27] are very close, 125
/
14N) values in 1 (Xꢀ
NCS)
/
and 123 Hz, respectively, and are appreciably greater
Acknowledgements
than those [909
and (o-MeOC6H4)3SnNCS [26]. The n(NC)ꢀ
cmꢃ1 value in 1 (Xꢀ
NCS) is lower than quoted values
/
4 Hz] quoted for (o-MeC6H4)3SnNCS
/2021
The authors thank the ESPSRC X-ray service at the
University of Southampton for data collection, and
CPNq and FAPERJ, Brazil for financial support. We
acknowledge the use of the Chemical Database of
EPSRC at Daresbury.
/
for four-coordinate triorganotin N-thiocyanates, e.g.
Me2[(PhMe2Si)3C]SnNCS {2066 cmꢃ1} [27] and (o-
MeC6H4)3SnNCS {2045 cmꢃ1} [26].
Values of n(Snꢀ
Bu, Ph) are generally in the regions: 170ꢁ
220ꢁ265 (XꢀBr), and 325ꢁ
385 cmꢃ1 (Xꢀ
/
X) in simple R3SnX (e.g. Rꢀ
210 (Xꢀ
Cl), irre-
/
Me, Et,
/
/I),
/
/
/
/
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