catena-poly[[triphenyltin(IV)]-μ-hydroxo-κ2O:O] at 120 K

Article abstract of DOI:10.1107/S0108270102001798

The structure of the title compound, [Sn(C₆H₅)₃(OH)]_n, has been re-investigated at 120 (2) K. The hydroxyl H atom was readily located and the threefold coordination about the O atom is planar. There are no hydro

Full text of DOI:10.1107/S0108270102001798

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
axis in P2 2 2 , show there is no change of phase between 293
1
1 1
and 120 K.
In the original structure analysis, the overall precision was
Ê
Ê
ISSN 0108-2701
rather modest [ꢀ(SnÐO) 0.005 A, ꢀ(SnÐC) 0.008 A and
Ê
(CÐC) 0.01±0.02 A]. The present re®nement has reduced
these ꢀ values to 0.0017, 0.003 and 0.004±0.005 A, respectively.
Although the bond angles in the SnC O core unit indicate
almost ideal trigonal±bipyramidal geometry, with axial O and
equatorial C atoms, as expected, the two independent SnÐO
ꢀ
Ê
catena-Poly[[triphenyltin(IV)]-l-
hydroxo-j O:O] at 120 K
3
2
2
Ê
distances nonetheless differ by ca 0.07 A (Table 1). Similarly,
a
b
Christopher Glidewell, * John N. Low, ² Jo Äa o A. S.
although the three independent SnÐC distances are almost
identical, the conformation of the Ph Sn fragment is very far
c
c
c
Bomfim, Carlos A. L. Filgueiras and James L. Wardell
3
from the idealized C local symmetry, as demonstrated by the
3
a
School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST,
b
OÐSnÐCÐC torsion angles. The unique SnÐOÐSn angle is
very large, and the hydroxyl H atom is located very close to
Scotland, Department of Chemistry, University of Aberdeen, Meston Walk, Old
c
Aberdeen AB24 3UE, Scotland, and Instituto de Qu Âõ mica, Departamento de
i
the plane de®ned by the SnÐOÐSn fragment [symmetry
Qu Âõ mica Inorg aÁ nica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de
Janeiro, RJ, Brazil
1
1
code: (i) x � , � y, � z], with the sum of the bond angles at O
2
2
Correspondence e-mail: cg@st-andrews.ac.uk
ꢀ
being almost 360 .
It is striking that the hydroxyl group in (I) does not parti-
cipate in any hydrogen bonds, either with the O atom as
hydrogen-bond donor to another O atom or to an aryl group,
or with the O atom as acceptor from either O or C atoms. The
disposition of the zigzag chains is, in fact, such that the only C
Received 24 January 2002
Accepted 28 January 2002
Online 12 March 2002
The structure of the title compound, [Sn(C H ) (OH)] , has
6
5 3
n
been re-investigated at 120 (2) K. The hydroxyl H atom was
readily located and the threefold coordination about the O
atom is planar. There are no hydrogen bonds involving the
hydroxyl group, either as donor or as acceptor.
Ê
or O atoms within 3.50 A of O1 at (x, y, z) are those within the
same chain, and all are ipso- or ortho-C atoms in the two
Ph Sn units bonded to O1. Table 2 lists the shortest intra-chain
3
non-bonding contacts involving the O atom as a potential
hydrogen-bond donor and as an acceptor, and the contacts
with both the shortest HÁ Á ÁO and the shortest CÁ Á ÁO distances
are shown. These data, particularly the DÐHÁ Á ÁA angles,
demonstrate that, even within a given chain, the hydroxyl
group acts neither as a donor nor as an acceptor of hydrogen
bonds.
Comment
The structure of the title compound, (I), was reported many
years ago (Glidewell & Liles, 1978), but the data set employed
(
293 K, 1767 re¯ections uncorrected for absorption) did not
permit either the anisotropic re®nement of the C atoms or the
location of the H atoms, although H atoms bonded to C atoms
were included in the ®nal re®nement in calculated positions.
Crucially, however, it was not possible at the time to identify
the H atom of the hydroxyl group, and hence it was not
possible either to assess whether the coordination about the O
atom was planar or pyramidal, or to analyse whether there are
signi®cant hydrogen bonds within the structure.
By use of a larger low-temperature data set collected using
a CCD diffractometer (120 K, 3376 re¯ections corrected for
absorption, of which 3120 are labelled observed), it has been
possible not only to re®ne all non-H atoms anisotropically, but
to locate all of the H atoms from difference maps, including
that bonded to the O atom. The cell dimensions and space
group, and the general structural features, with planar Ph Sn
3
Figure 1
groups and OH units alternating in chains generated by a 21
Aview of the molecular structure of (I), showing the coordination around
Sn and the atom-labelling scheme. Displacement ellipsoids are drawn at
the 30% probability level and H atoms are shown as small spheres of
² Postal address: School of Engineering, University of Dundee, Dundee
DD1 4HN, Scotland.
1
1
arbitrary radii [symmetry code: (i) + x, � y, � z].
2
2
Acta Cryst. (2002). C58, m199±m201
DOI: 10.1107/S0108270102001798
# 2002 International Union of Crystallography m199

metal-organic compounds
It is interesting to note that, in all compounds of type
Ph MOH, for M = C, Si, Ge, Sn or Pb, the location of the
Crystal data
3
[Sn(C H ) (OH)]
6
5 3
Mo Kꢁ radiation
Cell parameters from 3376
re¯ections
r
M = 367.00
Orthorhombic, P2 2 2
1
a = 8.2573 (2) A
b = 10.2229 (2) AÊ
c = 17.6996 (5) A
Ê
V = 1494.09 (6) A
hydroxyl H atom has hitherto proved troublesome. When M =
C, the molecules form tetrahedral tetramers, but the hydroxyl
H atoms could not be located from ambient-temperature
X-ray data (Ferguson, Gallagher, Glidewell et al., 1992). These
H atoms are, in fact, mobile over a number of sites at ambient
temperature (Aliev et al., 1998), and neutron diffraction at
1
1
Ê
ꢀ
ꢂ = 3.0±27.5
�
1
ꢃ = 1.70 mm
T = 120 (2) K
Block, colourless
Ê
3
Z = 4
D = 1.632 Mg m
0.40 Â 0.22 Â 0.20 mm
�
3
x
1
00 K was required to locate these H-atom sites unambigu-
ously (Serrano-Gonz a lez et al., 1999). The compounds
Ph SiOH (Puff et al., 1991) and Ph GeOH (Ferguson, Galla-
gher, Murphy et al., 1992) are isostructural, both forming cyclic
Data collection
3
3
Nonius KappaCCD area-detector
diffractometer
1968 independent re¯ections (plus
1408 Friedel-related re¯ections)
3120 re¯ections with I > 2ꢀ(I)
'
scans, and ! scans with ꢄ offsets
tetramers with S (4) symmetry. In neither structure was the
4
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski &
Minor, 1997)
Rint = 0.062
ꢀ
site of the hydroxyl H atom identi®ed. Ph PbOH is isostruc-
3
ꢂmax = 27.5
h = � 9 ! 10
k = � 13 ! 11
l = � 18 ! 22
tural with Ph SnOH (Glidewell & Liles, 1978) and, again, the
3
Tmin = 0.554, Tmax = 0.712
0 366 measured re¯ections
hydroxyl H atom could not be located. The structure analyses
for M = Si, Ge and Pb were all based on ambient-temperature
data. The success of the present analysis for M = Sn indicates
1
Re®nement
that re-investigation of the analogous Ph MOH structures
3
2
2
2
2
Re®nement on F
2
o
w = 1/[ꢀ (F ) + (0.0221P)
using low-temperature CCD data should readily reveal the
hydroxyl H atom when M = Si or Ge, although when M = Pb
this task may be more taxing.
2
R[F > 2ꢀ(F )] = 0.025
wR(F ) = 0.060
S = 1.00
+ 1.0158P]
where P = (F
(Á/ꢀ)max = 0.001
2
2
2
c
o
+ 2F
)/3
Ê
� 3
3
1
376 re¯ections
81 parameters
Áꢅmax = 0.68 e A
Ê
� 3
Áꢅmin = � 1.06 e A
H-atom parameters constrained
Absolute structure: Flack (1983)
Flack parameter = � 0.01 (3)
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
Sn1ÐC11
Sn1ÐC21
Sn1ÐC31
2.133 (3)
2.125 (3)
2.126 (3)
Sn1ÐO1
Sn1ÐO1
2.1797 (17)
2.2500 (17)
i
i
O1ÐSn1ÐO1
Sn1ÐO1ÐSn1
Sn1ÐO1ÐH1
176.842 (12)
137.66 (10)
106
C11ÐSn1ÐO1
C21ÐSn1ÐO1
C31ÐSn1ÐO1
C11ÐSn1ÐO1
C21ÐSn1ÐO1
C31ÐSn1ÐO1
92.79 (10)
93.29 (9)
90.36 (8)
90.36 (9)
85.43 (9)
87.81 (8)
ii
ii
i
i
i
Sn1 ÐO1ÐH1
C11ÐSn1ÐC21
C21ÐSn1ÐC31
C31ÐSn1ÐC11
115
116.84 (11)
120.24 (11)
122.51 (11)
i
O1 ÐSn1ÐC11ÐC12
O1ÐSn1ÐC11ÐC12
O1ÐSn1ÐC21ÐC22
O1ÐSn1ÐC31ÐC32
147.0 (2)
78.8 (2)
45.2 (2)
� 33.1 (2)
� 98.3 (2)
i
O1 ÐSn1ÐC21ÐC22
i
O1 ÐSn1ÐC31ÐC32 � 137.3 (2)
1
2
1
2
1 1
Symmetry codes: (i) ‡ x; � y; � z; (ii) x �
;
2 2
� y; � z.
Table 2
Short intra-chain non-bonded contacts (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH1Á Á ÁC32
C12ÐH12Á Á ÁO1
C36ÐH36Á Á ÁO1
Symmetry code: (i) ‡ x; � y; � z.
0.90
0.95
0.95
2.75
2.69
2.71
3.289 (4)
3.178 (4)
3.134 (4)
120
113
108
Figure 2
Part of the crystal structure of (I), showing the formation of a zigzag chain
i
i
1
generated by the 2
or hash (#) are at the symmetry positions ( + x, � y, � z) and (x � , � y,
1
axis along (x, , 0). Atoms marked with an asterisk (*)
1
4
1
1
1
1
2
1
2
2
2
2
2
�
z), respectively.
Compound (I) crystallized in the orthorhombic system; space
group P2 was uniquely assigned from the systematic absences.
All H atoms were located from difference maps. H atoms bonded to
Experimental
1 1 1
2 2
A sample of compound (I) was prepared by hydrolysis of tri-
phenyltin(IV) azide in an ethanol±water mixture (97:3 v/v). Crystals
of (I) suitable for single-crystal X-ray diffraction were grown by slow
evaporation of a solution in ethanol.
Ê
C atoms were treated as riding, with CÐH = 0.95 A. The H atom
attached to the hydroxyl O atom was allowed to ride at the position
found in the difference map.
ꢁ
m200 Christopher Glidewell et al.
6 5
[Sn(C H )
3
(OH)]
Acta Cryst. (2002). C58, m199±m201

metal-organic compounds
Data collection: KappaCCD Server Software (Nonius, 1997); cell
re®nement: DENZO±SMN (Otwinowski & Minor, 1997); data
reduction: DENZO±SMN; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
References
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(1998). J. Phys. Chem. B, 102, 2165±2175.
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(
1992). Acta Cryst. C48, 1272±1275.
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Holden, H. D. (1992). Acta Cryst. C48, 1228±1231.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
The X-ray data were collected at the EPSRC X-ray Crys-
tallographic Service, University of Southampton, England.
The authors thank the staff for all their help and advice. JNL
thanks NCR Self-Service, Dundee, for grants which have
provided computing facilities for this work. JASB, CALF and
JLW thank CNPq, FUBJ and FAPERJ for ®nancial support.
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The Netherlands.
ꢁ
Acta Cryst. (2002). C58, m199±m201
Christopher Glidewell et al.
6 5
[Sn(C H )
3
(OH)] m201