Crystal structures of [Bu2Sn(O2PPh2) 2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O 2PPh2)OMe]2

Article abstract of DOI:10.1002/zaac.200600137

[(n-Bu)₂Sn(O₂PPh₂)₂] (1), and [Ph₂Sn(O₂PPh₂)₂] (2) have been synthesized by the reactions of R₂SnCl₂ (R=n-Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph ₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ (3) could be isolated. X-ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group P1, the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight-membered rings (SnOPO) ₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group P1 with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.

Full text of DOI:10.1002/zaac.200600137

DOI: 10.1002/zaac.200600137
Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and
[PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and
[PhClSn(O2PPh2)OMe]2
Abdel-Fattah Shihada*
Zarqa/Jordan, Department of Chemistry, Faculty of Science, Hashemite University
Frank Weller
Marburg, Fachbereich Chemie der Philipps Universität
Received May 9th, 2006.
Abstract. [(n-Bu)2Sn(O2PPh2)2] (1), and [Ph2Sn(O2PPh2)2] (2) have
been synthesized by the reactions of R2SnCl2 (Rϭn-Bu, Ph) with
HO2PPh2 in Methanol. From the reaction of Ph2SnCl2 with di-
phenylphosphinic acid a third product [PhClSn(O2PPh2)OMe]2 (3)
could be isolated. X-ray diffraction studies show 1 to crystallize
in the monoclinic space group P21/c with a ϭ 1303.7(1) pm, b ϭ
2286.9(2) pm, c ϭ 1063.1(1) pm, β ϭ 94.383(6)°, and Z ϭ 4. 2
pounds form arrays of eight-membered rings (SnOPO)2 linked at
the tin atoms to form chains of infinite length. The dimer 3 consists
of a like ring, in which the tin atoms are bridged by methoxo
¯
groups. It crystallizes triclinic in space group P1 with a ϭ
946.4(1) pm, b ϭ 963.7(1) pm, c ϭ 1174.2(1) pm, α ϭ 82.495(6)°,
β ϭ 66.451(6)°, γ ϭ 74.922(6)°, and Z ϭ 1 for the dimer. The
Raman spectra of 2 and 3 are given and discussed.
¯
crystallizes triclinic in the space group P1, the cell parameters being
a ϭ 1293.2(2) pm, b ϭ 1478.5(4) pm, c ϭ 1507.2(3) pm, α ϭ
98.86(3)°, β ϭ 109.63(2)°, γ ϭ 114.88(2)°, and Z ϭ 2. Both com-
Keywords: Tin; Crystal structure; Raman spectra; Diphenylphos-
phinates; Methoxo bridges
1 Introduction
In these polymeric compounds the diorganophosphinate
groups behave as bidentate bridges between the tin
atoms leading to (SnOPO)4 sixteen-membered rings for
[Et2Sn(O2PMe2)2] and to (SnOPO)2 eight-membered rings
for [R2Sn(O2PPh2)2] (R ϭ Me, Et) and [Ph2Sn(O2PMe2)2].
Similar polymeric structures with O2PR2 double bridges
and (PbOPO)2 eight-memebered rings were also found in
analogous organolead compounds [Ph2Pb(O2PMe2)2] and
[Ph2Pb(O2PPh2)2] [2]. By contrast, crystal structures of di-
methyltin bis(dialkyldithiophosphinates) [Me2Sn(S2PR2)2]
(R ϭ Me [5], Et [6]) show monomeric distorted octahedral
Organotin complexes with ligands derived from phos-
phorus-based acids have attracted considerable attention
due to their structural diversity as well as their possible
applications as catalysts and biocides [1].
Diorganotin bis(diorganophosphinates) [R2Sn(O2PRRЈ2)2]
(R,RЈϭ alkyl, aryl) have been synthesized by a variety of
methods including among others the treatment of R2SnCl2
with sodium or ammonium salts of the phosphinic acids
and condensation of R2SnO with HO2PR2 [1]. Diorganotin
bis(diorganophosphinates) obtained from such reactions
are usually high melting powders and insoluble in organic
solvents .
Ϫ
configuration with chealating anisobidentate S2PR2 li-
gands.
We have found that crystals suitable for X-ray crystallo-
graphic studies can be isolated from the reactions of
R2SnCl2 with HO2PR2 in methanol at ambient
temperature. Accordingly, the crystal structures of
[Me2Sn(O2PPh2)2] [2], [Et2Sn(O2PPh2)2] [3], [Et2Sn-
(O2PMe2)2], and [Ph2Sn(O2PMe2)2] [4] have been deter-
mined.
X-ray diffraction studies of triorganotin diorganophos-
phinates show that [R3SnO2PR2] exhibit chain polymeric
structures for [Me3SnO2PMe2] [7] and [Bu3SnO2PPh2] [8]
and a tetrameric structure for [Me3SnO2PPh2] [9] and the
related lead complex [Me3PbO2PPh2] [10]. The R3M (M ϭ
Sn, Pb) groups are axially bridged by O-P-O linkages to
form trigonal bipyramids at the metal atoms. Moreover,
chain polymeric structures with OSPR2 bridges were also
reported for [Me3SnOSPMe2] [11] and [Ph3SnOSPPh2] [12].
The chalcogen atoms are in apical positions in the resulting
trigonal bipyramidal configuration.
* Prof. Dr. Abdel-Fattah Shihada
Department of Chemistry,
Faculty of Science, Hashemite University,
P.O.Box: 150459, Zarqa, 13115 Jordan.
Fax: 009625-3903349
Continuing our work on the preparation and structural
studies of organotin diorganophosphinates, we describe the
synthesis and crystal structures of[Bu2Sn(O2PPh2)2] (1),
E-Mail: ashihada@hu.edu.jo
2238
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Z. Anorg. Allg. Chem. 2006, 632, 2238Ϫ2243

[Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2
Table 1 Raman frequencies (1200Ϫ100 cmϪ1) of 2 and 3
[Ph2Sn(O2PPh2)2] (2), and [PhClSn(O2PPh2)OMe]2 (3). The
Raman spectra of 2 and 3 are given and discussed.
[Ph2Sn(O2PPh2)2] (2)
[PhClSn(O2PPh2)OMe]2 (3)
1195 vw
1180 vw
1155 vw
1139 s
δ(CH)-Ph in-plane
νas(PO2) in-phase
2 Results and Discussion
·
1161 w
1127 w
1076 w
Treatment of Bu2SnCl2 with HO2PPh2 in methanol at
ambient temperature gave [Bu2Sn(O2PPh2)2] (1) (eq.(1)) as
white needles. The reaction of Ph2SnCl2 with HO2PPh2
under similar conditions afforded needle-like crystals of
[Ph2Sn(O2PPh2)2] (2) (eq.(1)) along with [PhClSn(O2PPh2)-
OMe]2 (3) (eq.(2)) crystallizing as colorless blocks. Crystals
suitable for X-ray structure determination were isolated
from these reactions.
1134 w
1083 vw
1073 vw
1066 vw
δ(CH)-Ph in-plane
·
1026 s
1020 vw
1030 w
1021 vw
1004 w
998 vs
νs(PO2)
δ(CH)-Ph in-plane
ν(O-CH3)
1003 vs
997 s
843 vw
757 vw
Ph ring breathing
753 vw
736 vw
729 vw
730 vw
723 vw
700 m-s
697 m-s
668 vw
657 s
δ(CH)-Ph out-of-plane
R2SnCl2 ϩ 2 HO2PPh2 Ǟ [R2Sn(O2PPh2)2] ϩ
2 HCl (R ϭ n-Bu, Ph) (1)
·
704 w
696 w
662 s
δ(C-C) out-of-plane
(C-C-C) bend in-plane
2 Ph2SnCl2 ϩ 2 HO2PPh2 ϩ 2 HOMe Ǟ
617 m
618 w-m
616 w
555 vw
543 w
480 w
[PhClSn(O2PPh2)OMe]2 (3) ϩ 2 HPh ϩ 2 HCl (2)
δ(CH)-Ph out-of-plane
ν(Sn-O-Sn)
·
545 vw
[R2Sn(O2PPh2)2] (R ϭ Bu, Ph) can be synthesized by
treatment of R2SnCl2 with the sodium [13] or ammonium
[14] salts of diphenylphosphinic acid and by oxidation of
R2Sn(PPh3)2 with an ethanolic solution of H2O2 [15]. In
addition, 1 can also be prepared by the reaction of
Bu2Sn(OCOMe)2 with Ph2POCl in toluene [16] and by the
reaction ofBu2SnCl2with NMe4O2PPh2.H2O in ethanol
[17].
It is worth noting, that on the basis of Mössbauer and
vibrational spectra chain polymeric structures, with bridg-
ing O2PPh2 ligands and octahedral geometry around tin
have been suggested for 1 and 2 [14, 16Ϫ18].
The formation of [PhClSn(O2PPh2)OMe]2 (3) indicates
that Sn-Cl and Sn-C bonds of Ph2SnCl2 are cleaved. In our
previous studies on the reactions of HO2PMe2 with
Ph2SnCl2 [4] as well as HO2PPh2 with R2SnCl2 (R ϭ Me
[2], Et [3]), fission of only Sn-Cl bonds has been observed
leading to the corresponding diorganotin bis(diorgano-
phosphinates). Consequently, the Sn-Cl bonds are cleaved
favorably compared to the Sn-C bonds in such acidolysis re-
actions.
On the other hand, the reaction of Ph3PbCl with
HO2PMe2 and HO2PPh2 in methanol cause break of Pb-Cl
and Pb-C bonds to give [Ph2Pb(O2PMe2)2] and
[Ph2Pb(O2PPh2)2], respectively [2].
466 vw
458 vw
446 vw
434 vw
412 w
401 w
393 vw
366 vw
338 w
313 s
δ(PO2)
403 vw
395 vw
350 vw
δ(CPO)
ν(Sn-Cl)
291 vw
273 m
254 w
260 vw
244 vw
233 vw
221 w
229 vw
νs(SnPh2)
ν(SnPh) in-phase
215 w
196 w
191 w
183 m
173 s
208 w-m
δ(SnO2)
δ(SnPh)
δ(PPh)
157m
136 w
147 w
140 w
·
313 cmϪ1 in the Raman spectrum of 3 are ascribed to
ν(O-CH3), ν(Sn-O-Sn) and ν(Sn-Cl), respectively. The ab-
sence of these bands in the Raman spectrum of 2 supports
this assignment. The Raman spectrum of the dimeric
complex [Sn2Cl6(OH)2(H2O)2].4H2O shows ν(Sn-O-Sn) at
482 cmϪ1 [20]. The region of 480 to 530 cmϪ1 is given for
such ν(Sn-O-Sn) modes in the dimeric compounds contain-
ing bridging alkoxy groups [21].
Raman Spectra
The Raman spectra of 2 and 3 display the characteristic
very strong bands due to the phenyl ring breathing at 1003
and 998 cmϪ1, respectively. The bands at 617 cmϪ1 in the
Raman spectrum of 2 and at 618 cmϪ1 in the Raman spec-
trum of 3 are assigned to the phenyl (C-C-C) bending-in-
plane vibrations.
The IR and Raman spectra of [Bu2Sn(O2PPh2)2] (1) were
previously given and discussed [16]. The observed Raman
frequencies (1200-100 cmϪ1) of 2 and 3 (Table 1) are as-
signed by comparison with the Raman spectra of
[Ph3SnO2PPh2] [19], [Bu2Sn(O2PPh2)2] [16] and other re-
lated organotin complexes [3, 8].
The ν(PO2) frequencies are assigned in the region be-
tween 1200-1000 cmϪ1 which is consistent with bidentate
bridge O2PPh2 ligands. The bands at 1004, 480 and
Corresponding modes appear at 618-621 cmϪ1 in the
Raman spectra of [Ph3SnO2PRRЈ] (RRЈ ϭ Me2, MePh,
Ph2) [19], [Bu2Sn(O2PRRЈ)2] (RRЈ ϭ MePh, Ph2) [16],
[Et2Sn(O2PPh2)2] [3], and Bu3SnO2PPh2 [8].
Z. Anorg. Allg. Chem. 2006, 2238Ϫ2243
 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2239

A.-F. Shihada, F. Weller
atoms and the ring conformations. Compounds 1 and 2
represent two new types, one of them also containing chains
parallel to the c-axis (1), the other being distinguished by
chains along space diagonal [111] (2).
In 1, which more resembles the species already known,
the tin atoms lie on general positions close to the c glide
plane, so the eight-membered rings are generated by glide
reflection of the asymmetric unit [R2Sn(O2PR2)2], leading
to a distorted boat conformation with the SnO4 best planes
tilted against each other by an angle of about 47.3 degrees
(see Fig 1). Somewhat unexpectedly the best planes of the
n-butyl groups do not meet at a right angle like the phenyl
substituents in some cases [2, 4] nor are parallel like ethyl
and phenyl groups in other examples [2, 3], but are set at
an angle of about 55.8°.
A somewhat remarkable arrangement of the chains is
found in 2. There are two different tin atom sites one of
which (Sn(1)) lies on the origin of the triclinic cell, the other
1 1 1
(Sn(2)) taking a general position close to , , . As a result
3 3 3
two kinds of rings with principally different, but similar
chair-like conformation occur: ring 1 (see Fig. 2) connecting
tin atoms Sn(1) and Sn(2), not subject to any nontrivial
symmetry, and ring 2, centrosymmetric, connecting Sn(2)
with its inverse equivalent. So the succession of rings in the
chain along the the space diagonal of the unit cell is (ring
1, ring 2, ring1Ј etc). Compared with the dibutyl tin com-
pound ring bending is much weaker Ϫ the largest distance
of a ring atom from the best planes is 35 pm, and the SnO4
Ϫ planes of Sn(1) and Sn(2) just intersect with an angle of
about 15.5°. Phenyl group order around the tin atoms is
parallel at centrosymmetric Sn(1) and roughly rectangular
(79,2°) at Sn(2).
Figure 1 Perspective view [27] of a section of a chain in 1. Atom-
numbering is given for the asymmetric unit excepting phenyl groups
The band at 221 cmϪ1 in the Raman spectrum of 2 is
attributed to νs(SnPh2) and the band at 215 cmϪ1 in the
Raman spectrum of 3 is assigned to ν(SnPh) in-phase. The
νas(SnPh2) of the trans SnPh2 group in 2 and the ν(SnPh)
out-of-phase in the centrosymmetric dimer 3 are Raman in-
active.
Structural results
In spite of strongly differing ring conformations most
bond lengths in 1 and 2 are restricted to narrow ranges
(tables 2 and 3). P-O distances range from 149.9 to
151.2 pm, Sn-C distances are between 212.3 pm (aliphatic)
In the diorgano tin phosphinates with eight-membered ring
chain structures reported in the past [2Ϫ4] three structural
types occur with the chains running along or parallel to cell
edges, principally differing in the positions of the heavy
Figure 2 Succession of rings in the unit cell of 2 [27], a straight line Sn(1)-Sn(1)Ј denoting space diagonal [111]. Atom numbering is given
for an asymmetric unit and for some transformed atoms. For clarity phenyl substituents are drawn as simple hexagons.
2240
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 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 2238Ϫ2243

[Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2
Table 2 Selected bond lengths/pm and angles/° for Bu2Sn-
(O2PPh2)2 (1).
Table 4 Selected bond lengths/pm and angles/° for [PhClSn-
(O2PPh2)(OMe)]2 (3).
Sn-O(1)
Sn-O(2)
Sn-O(3)Ј
Sn-O(4)Ј
Sn-C(11)
Sn-C(21)
P(1)-O(1)
P(1)-O(3)
P(2)-O(2)
P(2)-O(4)
P(1)-C(111)
P(1)-C(121)
P(2)-C(211)
P(2)-C(221)
220.4(3)
222.1(3)
219.3(3)
222.3(3)
212.3(4)
212.6(4)
151.1(3)
150.9(3)
150.1(3)
150.3(3)
182.0(2)
180.7(2)
181.3(2)
181.3(3)
O(1)-Sn-O(2)
92.59(11)
85.81(11)
176.00(11)
178.12(12)
90.85(11)
90.72(11)
91.47(14)
88.18(13)
92.83(14)
90.68(14)
90.49(15)
83.88(14)
95.16(14)
87.84(15)
171.9(2)
150.2(2)
149.9(2)
148.4(2)
148.8(2)
117.6(3)
114.7(3)
116.4(2)
117.8(2)
105.7(14)
105.3(2)
Sn-O(1)
Sn-O(2)
Sn-O(3)
Sn-O(3)Ј
Sn-Cl
Sn-C(11)
P-O(1)Ј
P-O(2)
211.71(12)
213.69(12)
207.97(12)
216.13(13)
239.30(5)
213.15(14)
153.15(13)
153.21(14)
180.8(2)
O(3)-Sn-O(2)
O(1)-Sn-O(3)Ј
O(2)-Sn-O(3)Ј
O(3)-Sn-O(1)
O(1)-Sn-O(2)
O(3)-Sn-O(3)Ј
O(1)-Sn-Cl
O(2)-Sn-Cl
O(3)-Sn-Cl
O(3)Ј-Sn-Cl
C(11) -Sn- O(1)
C(11)-Sn-O(2)
C(11)-Sn-O(3)Ј
C(11)-Sn-O(3)
C(11)-Sn-Cl
PЈ-O(1)-Sn
81.64(5)
82.97(5)
83.51(5)
80.02(5)
159.40(5)
75.74(5)
94.00(4)
95.89(4)
91.87(4)
167.56(3)
98.27(5)
97.92(5)
93.17(5)
168.89(5)
99.21(4)
130.53(8)
126.63(7)
123.96(11)
120.77(11)
104.26(5)
116.76(7)
109.89(7)
106.50(6)
108.15(7)
107.88(6)
107.26(6)
O(1)-Sn-O(3)Ј
O(1)-Sn-O(4)Ј
O(2)-Sn-O(3)Ј
O(2)-Sn-O(4)Ј
O(3)Ј-Sn-O(4)Ј
C(11)-Sn-O(1)
C(11)-Sn-O(2)
C(11)-Sn-O(3)Ј
C(11)-Sn-O(4)Ј
C(21)-Sn-O(1)
C(21)-Sn-O(2)
C(21)-Sn-O(3)Ј
C(21)-Sn-O(4)Ј
C(11)-Sn-C(21)
P(1)-O(1)-Sn
P-C(21)
P-C(31)
O(3)-C(4)
179.9(2)
144.5(2)
P(1)-O(3)-SnЉ
P(2)-O(2)-Sn
P-O(2)-Sn
C(4)-O(3)-Sn
C(4)-O(3)-SnЈ
Sn-O(3)-SnЈ
O(1)Ј-P-O(2)
O(1)Ј-P-C(21)
O(1)Ј-P-C(31)
O(2)-P-C(21)
O(2)-P-C(31)
C(31)-P-C(21)
P(2)-O(4)-SnЉ
C(12)-C(11)-Sn
C(22)-C(21)-Sn
O(1)-P(1)-O(3)
O(2)-P(2)-O(4)
C(111)-P(1)-C(121)
C(211)-P(2)-C(221)
Symmetry transformations used to generate equivalent atoms:
ElЈ : x,Ϫyϩ1/2,zϩ1/2 ElЉ : x,Ϫyϩ1/2,zϪ1/2
Symmetry transformations used to generate equivalent atoms:
ElЈ : Ϫx,Ϫy,Ϫz
and 213.1 to 215.5 pm (aromatic), and P-C bonds have
lengths from 179.9 to 182.0 pm, which are values in good
accordance with the known species of [R2Sn(O2PR2Ј)2]n.
An obvious exception is found for the Sn-O bonds which
are significantly shorter in the phenyl compound 2 (214.2
to 218.9 pm) than in 1 (219.3 to 222.3 pm) which may be
due to the electron-withdrawing power of the phenyl
groups.
As shown by reaction schemes (1) and (2) Ph2SnCl2 re-
acts with HO2PPh2 not only to form [Ph2Sn(O2PPh2)2], but
also undergoes a second reaction from which the dimeric
[PhClSn(O2PPh2)OMe]2 (3) results. Similar clusters have
been prepared from n-BuSn(OH)2Cl and (t-Bu)2P(O)OH
along with higher aggregated species [22] and from
n-BuSn(O)OH and (c-Hex)2PO2H as a mixture with other
oligomers [23].
In the dimer 3 (Fig.3) two tin atoms related by an inver-
sion centre are connected in bidentate fashion by two di-
methyl phosphinate bridges and two methoxy groups, thus
achieving a distorted octahedral coordination with axial
angles of 159.5° (O(1)-Sn-O(2)), 168.9° (C11-Sn-O(3)), and
167.6° (Cl-Sn-O(3)Ј) (table 2). The phosphinates bridge al-
most symmetrically, whereas the Sn-O distances of the me-
thoxo oxygen atoms differ significantly depending on the
ligand in trans-position (208 and 216 pm (trans to the
chloro ligand), respectively). As the corresponding bond
lengths in related compounds with OH linked tin atoms [22,
23] are shorter and lie within a narrow range, this must
be attributed to the trans effect of the chloro ligand. The
centrosymmetric ring Sn2O2 is planar with pyramidal con-
figuration at the oxygen atoms (sum of bond angles at oxy-
Table 3 Selected bond lengths/pm and angles/° for (Ph2Sn)3-
(O2PPh2)6 (2).
Sn(1)-O(1)
Sn(1)-O(6)
Sn(2)-O(2)
Sn(2)-O(3)Ј
Sn(2)-O(4)
214.2(3)
217.4(3)
217.8(3)
218.0(3)
218.9(3)
215.4(3)
215.5(2)
215.0(2)
213.1(2)
151.2(3)
150.4(3)
150.4(3)
149.9(3)
150.8(3)
150.6(3)
180.5(2)
180.0(2)
180.0(2)
180.9(2)
181.0(2)
180.8(2)
178.42(10)
154.9(2)
154.7(2)
158.3(2)
163.9(2)
151.8(2)
157.5(2)
117.4(2)
116.3(2)
116.8(2)
106.49(13)
109.14(11)
103.98(11)
O(1)-Sn(1)-O(6)Љ
O(1)-Sn(1)-O(6)
O(1)-Sn(1)-C(11)
O(1)-Sn(1)-C(11)Љ
O(6)-Sn(1)-C(11)
O(6)Љ-Sn(1)-C(11)
O(5)-Sn(2)-O(2)
O(5)-Sn(2)-O(3)Ј
O(3)Ј-Sn(2)-O(4)
O(2)-Sn(2)-O(3)Ј
O(5)-Sn(2)-O(4)
O(2)-Sn(2)-O(4)
C(21)-Sn(2)-O(5)
C(21)-Sn(2)-O(4)
C(21)-Sn(2)-O(2)
C(21)-Sn(2)-O(3)Ј
C(31)-Sn(2)-O(2)
C(31)-Sn(2)-O(3)Ј
C(31)-Sn(2)-O(5)
C(31)-Sn(2)-O(4)
91.78(11)
88.22(11)
87.88(10)
92.12(10)
87.70(9)
92.30(9)
92.46(11)
87.28(12)
93.63(11)
176.51(9)
178.83(10)
86.58(11)
88.45(9)
92.21(9)
89.66(9)
93.81(9)
91.06(9)
85.48(9)
92.93(9)
86.42(9)
Sn(2)-O(5)
Sn(1)-C(11)
Sn(2)-C(21)
Sn(2)-C(31)
P(1)-O(2)
P(1)-O(6)
P(2)-O(5)
P(2)-O(1)
P(3)-O(3)
P(3)-O(4)
P(1)-C(41)
P(1)-C(51)
P(2)-C(61)
P(2)-C(71)
P(3)-C(81)
P(3)-C(91)
C(31)-Sn(2)-C(21)
P(1)-O(6)-Sn(1)
P(1)-O(2)-Sn(2)
P(2)-O(5)-Sn(2)
P(2)-O(1)-Sn(1)
P(3)-O(4)-Sn(2)
P(3)-O(3)-Sn(2)Ј
O(6)-P(1)-O(2)
O(1)-P(2)-O(5)
O(4)-P(3)-O(3)
C(51)-P(1)-C(41)
C(61)-P(2)-C(71)
C(91)-P(3)-C(81)
Symmetry transformations used to generate equivalent atoms:
ElЈ : 1Ϫx, 1Ϫy, 1Ϫz
ElЉ : Ϫx, Ϫy, Ϫz
Z. Anorg. Allg. Chem. 2006, 2238Ϫ2243
 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2241

A.-F. Shihada, F. Weller
3 Experimental
The chemical reagents employed were obtained from commercial
sources and were used without further purification. The Raman
spectra were recorded using a Jobin Yvon Labram HR 800 instru-
ment with 632.8 nm helium neon laser excitation.
Synthesis of [Bu2Sn(O2PPh2)2] (1)
A solution of 0.42 g (1.9 mmol) HO2PPh2 in 30 mL methanol was
added to 0.60 g (2.0 mmol) Bu2SnCl2 in 10 mL methanol. Directly
after the addition a small quantity of precipitate was formed, which
was filtered off and the mother liquor was set aside at ambient
temperature in a closed flask. After 14 d needle-like crystals (30 mg)
of Bu2Sn(O2PPh2)2 (1) were formed and filtered off. Another por-
tion of the white needles (135 mg) of 1 which separated from the
mother liquor after partial evaporation of methanol at room tem-
perature were filtered off, washed with methanol and dried.
Figure 3 ORTEP perspective view [28] of a dimer of 3 at a 50 %
probability level. Atoms of the asymmetric unit are numbered
along with adjacent equivalent atoms.
Synthesis of [Ph2Sn(O2PPh2)2] (2) and
[PhClSn(O2PPh2)OMe]2 (3)
A solution of 0.43 g (2.0 mmol) HO2PPh2 in 50 mL methanol was
added to a solution of 0.70 g (2.0 mmol) Ph2SnCl2 in 20 mL meth-
anol. After few seconds a white precipitate was formed which was
filtered off and the mother liquor was set aside at ambient tempera-
gen is 349°), whilst in the eight-membered ring the maximal
deviation of a ring atom from the best plane is 16 pm.
Table 5 Crystal data, measurement and structure refinement details for 1, 2, and 3
1
2
3
Formula
Bu2Sn(O2PPh2)2
667.25
monoclinic
P21/c
1303.7(1)
2286.9(2)
1063.1(1)
(Ph2Sn)1.5 (O2PPh2)3
1060.85
PhClSn(O2PPh2)(OMe)
479.45
Formula weight
Crystal system
Space group
a / pm
b / pm
c / pm
triclinic
triclinic
¯
¯
P1
P1
1293.2(2)
1478.5(4)
1507.2(3)
946.4(1)
963.7(1)
1174.2(1)
α / deg
β / deg
96.86(3)
109.63(2)
82.495(6)
66.451(6)
94.383(6)
γ / deg
114.88(2)
74.922(6)
V / pm3 x 10Ϫ4
Cell determination
ρcalc / g x cmϪ3
Z
3.1603(4) x 105
12107 refl. θ ϭ 1.8 to 27.1°
1.402
4
2.3447(9) x 105
0.9474(1) x 105
8000 refl. θ ϭ 8.95 to 26.85°
1.503
2
6913 refl. θ ϭ 1.8 to 29.5°
1.681
2
F(000)
1368
9.43
1074
9.59
476
15.89
µ (MoKα) / cmϪ1
Diffractometer type
Wavelength / pm
T / K
IPDS II (Stoe)
71.073
192(2)
omega
IPDS I (Stoe)
71.073
192(2)
phi
IPDS II (Stoe)
71.073
192(2)
omega
Scan mode
hkl range
Ϫ16ՅhՅ13;Ϫ29ՅkՅ28;Ϫ13ՅlՅ13
1.78 to 26.84
17600
6694 [R(int)ϭ0.0844)
6694
4688 [I>2sigma(I)]
based on equivalent reflections
Ϫ17ՅhՅ17;Ϫ20ՅkՅ20;Ϫ20ՅlՅ20
2.55 to 29.22°
Ϫ12ՅhՅ12;Ϫ12ՅkՅ13;Ϫ16ՅlՅ16
1.89 to 29.15°
Theta range for data coll.
Reflections collected
Independent reflections
Refl. used for refinement
Observed reflections
Absorption correction
31427
16777
11598 [R(int)ϭ0.074]
11598
7342 [I>2sigma(I)]
numerical
5064 (R(int)ϭ0.0244)
5064
4399 [I>2sigma(I)]
based on equivalent reflections
Programs used
Solution direct/ difmap
Refinement
SHELXS-97[25], SHELXL-97[25], PLATON-89[26], SCHAKAL-97[27], SHELXTL[28]
Direct Methods, difmap
Patterson Methods
Direct Methods, difmap
Full-matrix least-squares on F2
refined parameters
wR2 [all reflections]
R1[I>2sigma(I)]
(shift/error)max
314
0.0952
0.0440
Ϫ0.002
0.849 / Ϫ2.142
484
0.0782
0.0383
Ϫ0.001
0.993 / Ϫ0.683
195
0.0471
0.0209
0.001
Ϫ1
˚
ρfin (max/min) / eA
0.528 / Ϫ0.471
2242
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 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 2238Ϫ2243

[Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2
ture in a closed flask. After one month the white crystalline mixture
(40 mg) of [Ph2Sn(O2PPh2)2] (2) and [PhClSn(O2PPh2)OMe]2 (3)
was filtered off, washed with methanol and dried.
[7] F. Weller, A.-F. Shihada, J. Organomet. Chem. 1987, 322, 185.
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Soc., Chem. Commun. 1993, 1229.
[10] R. A. Varga, J. E. Drake, C. Silvestru, J. Organomet. Chem.
2003, 675, 48.
X-ray structural investigations
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[12] A. Silvestru, J. E. Drake, J. Yang, Polyhedron 1997, 16, 4113.
[13] S. K. Pandit, C. Copinathan, Indian J. Chem. 1977, 15A, 463.
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[15] H. Schumann, H. Köpf, M. Schmidt, J. Organomet. Chem.
1964, 2, 159.
[16] A.-F. Shihada, Z. Naturforsch. 1995, 50b, 745.
Single crystals of 1, 2, and 3 were taken from the filtrate of the
reaction mixture after due time (see experimental section). All of
them, the needles of 1 and 2 and the blocks of 3 were handled in
oil, mounted on glass threads, and measured at Ϫ80 °C on Stoe
Diffractometers IPDS I (2) and IPDS II (1 and 3) (see table 5 for
crystal and experimental details and for structure solution and re-
finement). After data reduction [24] the data were corrected for
absorption basing on equivalent reflections (1 and 3) and numeri-
cally (2). The structures were solved by direct methods (1 and 3)
and by interpretation of Patterson maps (2) Ϫ refinement of the
models was done by successive refinement cycles and difference
Fourier syntheses [25]. For the input of hydrogen atoms at methyl,
butyl and phenyl substituents a rigid group model with “riding” H
atoms was applied. Geometrical calculations were carried out with
PLATON [26].
´
[17] M. Sidibe, M. Lahlou, L. Diop, B. Mahieu, Main Group Met.
Chem. 1998, 21, 605.
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Met. Chem. 1991, 14, 257.
[19] A.-F. Shihada, Z. Naturforsch. 1994, 49b, 1319.
[20] A.-F. Shihada, A. S. Abushamleh, F. Weller, Z. Anorg. Allg.
Chem. 2004, 630, 841.
Crystallographic data (excluding structure factors) have been
deposited with the Cambridge Crystallographic Data Centre as
supplementary publications nrs. CCDC-608554 (1), CCDC-608555
(2), and CCDC-608553 (3). Details are available, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: (ϩ44) 1223/336033; e-mail: deposit@ccdc.cam.ac.uk).
[21] R. C. Paul, V. Nagpal, S. L. Chadha, Inorg. Chim. Acta 1972,
6, 335.
[22] K. C. Kumara Swamy, R. O. Day, R. R. Holmes, Inorg. Chem.
1992, 31, 4184.
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Day, J. Am. Chem. Soc. 1988, 110, 7060.
[24] K. Harms, XCAD4 Program for Data Reduction, Marburg,
1993.
[25] G. M. Sheldrick, SHELXS-97, SHELXL-97 Programs for the
Solution and Refinement of Crystal Structures, Göttingen,
1997.
[26] A. L. Spek, PLATON-89, University of Utrecht, 1989.
[27] E. Keller, SCHAKAL 97, A Computer Program for the
Graphical Representation of Molecular and Crystallographic
Models, Freiburg, 1997.
References
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Z. Anorg. Allg. Chem. 2006, 2238Ϫ2243
 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2243