Structural relationships in high-nuclearity heterobimetallic bismuth-oxo clusters

Article abstract of DOI:10.1002/ejic.200500636

The novel heterobimetallic sodium-bismuth-oxo clusters [Bi_2- Na₄O(OSiMe₃)₈] (1), [Bi₁₀Na ₅O₇(OH)₆(OSiMe₃)₁₅] ·1.5C₇H₈ (2·1.5C₇H₈), [Bi₁₅Na₃O₁₈(OSiMe₃) ₁₂]·C₇H₈ (3·C₇H ₈) and [Bi₁₄-Na₈O₁₈(OSiMe ₃)₁₄(THF)₄]·C₆H₆ (4·C₆H₆) were prepared starting from BiCl ₃ and NaOSiMe₃. Compound 1 crystallises in the trigonal space group R3c with the lattice constants a = 12.8844(3) A and c = 54.6565(3) A, compound 2·1.5C₇H₈ crystallises in the triclinic space group P1 with the lattice constants a = 15.0377(2) A, b = 16.0373(2) A, c = 27.8967(5) A, a = 87.1321(6)°, β = 86.6530(7)° and γ = 63.6617(6)°, compound 3·C ₇H₈ crystallises in the monoclinic space group C2/c with the lattice constants a = 54.311(11), b = 19.846(4), c = 22.885(5) A and β = 112.32(3)°, and compound 4·C₆H₆ crystallises in the trigonal space group R3 with the lattice constants a = 15.9786(4) A and c = 46.8329(17) A. The formation of M-O-M bonds results from both partial hydrolysis followed by condensation as well as from elimination of Me₃SiOSiMe₃ from M-OSiMe₃ groups. The hexanuclear metal-oxo silanolate 1 is more conveniently synthesised by the addition of NaOSiMe₃ to a toluene solution of in situ-prepared [Bi(OSiMe₃)₃]. The metal-oxo(hydroxo) silanolates differ significantly in composition, but show similar building units. Thermal decomposition of the metal-oxo silanolates in the solid state gave heterogeneous decomposition products containing bismuth silicates. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200500636

FULL PAPER
DOI: 10.1002/ejic.200500636
Structural Relationships in High-Nuclearity Heterobimetallic Bismuth-Oxo
Clusters
Michael Mehring,*[a] Sanna Paalasmaa,[a] and Markus Schürmann[a]
Keywords: Bismuth / Sodium / Silanolate / Metal-oxo cluster / Structure elucidation
The novel heterobimetallic sodium-bismuth-oxo clusters [Bi2-
Na4O(OSiMe3)8] (1), [Bi10Na5O7(OH)6(OSiMe3)15]·1.5C7H8
a = 15.9786(4) Å and c = 46.8329(17) Å. The formation of M–
O–M bonds results from both partial hydrolysis followed by
condensation as well as from elimination of Me3SiOSiMe3
from M–OSiMe3 groups. The hexanuclear metal-oxo silanol-
ate 1 is more conveniently synthesised by the addition of
NaOSiMe3 to a toluene solution of in situ-prepared [Bi-
(OSiMe3)3]. The metal-oxo(hydroxo) silanolates differ signifi-
cantly in composition, but show similar building units. Ther-
mal decomposition of the metal-oxo silanolates in the solid
state gave heterogeneous decomposition products containing
bismuth silicates.
(2·1.5C7H8), [Bi15Na3O18(OSiMe3)12]·C7H8 (3·C7H8) and [Bi14
-
Na8O18(OSiMe3)14(THF)4]·C6H6 (4·C6H6) were prepared
starting from BiCl3 and NaOSiMe3. Compound 1 crystallises
¯
in the trigonal space group R3c with the lattice constants a =
12.8844(3) Å and c = 54.6565(3) Å, compound 2·1.5C7H8 crys-
¯
tallises in the triclinic space group P1 with the lattice con-
stants a = 15.0377(2) Å, b = 16.0373(2) Å, c = 27.8967(5) Å, α
= 87.1321(6)°, β = 86.6530(7)° and γ = 63.6617(6)°, compound
3·C7H8 crystallises in the monoclinic space group C2/c with
the lattice constants a = 54.311(11), b = 19.846(4), c =
22.885(5) Å and β = 112.32(3)°, and compound 4·C6H6 crystal-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
¯
lises in the trigonal space group R3 with the lattice constants
materials[8,14] as well as for nanoparticles of zinc oxide[15]
and zinc silicate[16] was demonstrated.
Introduction
Bismuth alkoxides are valuable precursors for the synthe-
sis of bismuth oxide-based materials prepared via chemical
vapour deposition[1] or via the sol-gel process.[2,3] Their po-
tential application for the synthesis of materials such as
high-temperature superconductors or non-volatile random-
access memories has prompted several research groups to
investigate the reactivity and the structural chemistry of
homo- and heterometallic bismuth alkoxides in order to
control composition and morphology of the final material
on a molecular level.[3–6] Alternatively, bismuth silanolates
might serve as molecular precursors to bismuth-containing
materials. However, the chemistry of bismuth silanolates
was only scarcely explored so far.[7–11] In contrast to bis-
muth, metallasiloxanes of the heavier group 14 metals tin
and lead have received considerable interest.[7,8,12,13] It was
noticed that homoleptic heavy metal silanolates of the type
[M(OSiR3)2] (M = Sn, Pb) readily decompose at moderate
temperatures with elimination of R3SiOSiR3 to give the
parent metal oxide or metal-oxo clusters.[7,13] It is promising
to exploit this non-hydrolytic strategy for the synthesis of
tailor-made bismuth-oxo clusters and bismuth oxide-based
nanoparticles. Recently, the potential of metal silanolates
as molecular precursors for a variety of mixed metal oxide
Among the homoleptic bismuth silanolates the trimethyl-
silyl derivative [Bi(OSiMe3)3] is one of the most promising
candidates with respect to materials synthesis. The reaction
of BiCl3 with NaOSiMe3 was previously reported to give
[Bi(OSiMe3)3],[7] but the material obtained gave analytical
data which disagreed with the expected values. We have re-
visited this reaction and report here our findings including
the molecular structures of [Bi2Na4O(OSiMe3)8] (1),
[Bi10Na5O7(OH)6(OSiMe3)15]·1.5C7H8 (2·1.5C7H8), [Bi15-
Na3O18(OSiMe3)12]·C7H8 (3·C7H8), and [Bi14Na8O18-
(OSiMe3)14(THF)4]·C6H6 (4·C6H6).
Results and Discussion
Reaction of NaOSiMe3 with BiCl3 in a 3:1 stoichiometry
using THF as solvent gave a solid material the EDX analy-
sis of which accounted for the presence of both bismuth
and sodium. Crystallisation from hot toluene gave single
crystals of the heterometallic bismuth-oxo silanolate [Bi2-
Na4O(OSiMe3)8] (1). The low yield was only slightly im-
proved to approximately 10% when the reaction was carried
out in toluene and the stoichiometry was modified to a bis-
muth-to-sodium ratio of 1:5 (Scheme 1).
[a] Universität Dortmund, Anorganische Chemie II,
44221 Dortmund, Germany
Oxygen incorporation into compound 1 does not result
from hydrolysis, but from the reaction of M–OSiMe3
groups to give Me3SiOSiMe3 and the corresponding metal-
Fax: +49-231-755-5048
E-mail: michael.mehring@uni-dortmund.de
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Scheme 1.
oxo fragment. The 29Si NMR spectrum of a crude reaction process involving the trimethylsilanolate groups. Further
mixture according to Scheme 1 (x = 5) showed a signal at δ NMR studies in solution, such as variable temperature
= 7.2 ppm assigned to Me3SiOSiMe3 and a broad signal at NMR, were hampered by the low solubility of compound
δ = –2.9 ppm assigned to unreacted NaOSiMe3. Due to its 1.
poor solubility, no 29Si NMR signal was observed for [Bi2-
Na4O(OSiMe3)8] (1). Compound 1 was obtained with a sig-
nificantly higher yield when in situ-prepared [Bi(OSiMe3)3]
(29Si NMR δ = 10.9 ppm) and NaOSiMe3 were used as
starting materials [Equation (1)]. The synthesis and molecu-
lar structure of [Bi(OSiMe3)3] was reported recently.[11b]
(1)
The molecular structure of compound 1 is best described
to be composed of an octahedron with two bismuth atoms
and four sodium atoms occupying the corners and a µ6-
oxygen atom being enclosed within the octahedron (Fig-
Figure 1. ORTEP diagram of [Bi2Na4O(OSiMe3)8] (1) showing
ure 1). Eight silanolate groups cap the trigonal faces. The
30% displacement ellipsoids and the atom numbering scheme. Hy-
¯
compound crystallises in the space group R3c and only one
drogen atoms are omitted. The positions of the metal atoms are
occupied by both sodium and bismuth atoms with occupancies of
2/3 and 1/3, respectively. Selected bond lengths [Å] and bond angles
[°] (M = Na, Bi): M(1)–O(3) 2.289(1), M(1)–O(2) 2.361(2), M(1)–
O(2B) 2.422(2), M(1)–O(2C) 2.405(2), M(1)–O(1) 2.361(2); M(1)–
O(3)–M(1E) 180.00(1), M(1)–O(3)–M(1B) 89.55(1), M(1)–O(3)–
M(1C) 90.45(1), M(1)–O(2)–M(1A) 84.88(5), M(1)–O(2B)–M(1D)
84.61(5), M(1)–O(1)–M(1C) 86.11(8), O(1)–M(1)–O(2) 86.39(4),
O(1)–M(1)–O(3) 73.56(5), O(2)–M(1)–O(3) 74.51(4), O(2)–M(1)–
O(2B) 86.09(4), O(2)–M(1)–O(2C) 147.06(7). Symmetry operations
used to generate equivalent atoms: A = –y, x – y, z; B = y, –x +
y, –z; C = –x + y, –x, z; D = x – y, x, –z; E = –x, –y, –z.
crystallographic independent position for the metal atoms
is found. Each position is occupied by both sodium and
bismuth atoms with occupancies of 2/3 and 1/3, respectively.
The analogous problem of disorder was reported for the
closely related molecular structures of [Sb2Na4O-
(OSiMe3)8],[17] [Bi2Na4O(OtBu)8],[18] [Sb2M4O(OtBu)8-
(thf)n] (M = Na, n = 0; M = K, n = 0, 4),[18] and
[Bi2Na4O(OC6F5)8(thf)4].[19] For these compounds it was
shown by means of solid state NMR, variable-temperature
NMR in solution and crystallography that both in the solid
state and in solution the group 15 atoms are located in cis-
The reaction of BiCl3 with NaOSiMe3 in 1:3 stoichiome-
position of the octahedron. We have carried out a theoreti- try according to Scheme 1 gave a solid material containing
cal study of cis- and trans-[Bi2Na4O(OSiMe3)8] (1) at the sodium, bismuth and silicon as was shown by EDX analy-
RHF/LANL2DZ level of theory which confirms that a cis- sis. The 29Si NMR spectrum of the supernatant solution
arrangement is favoured (∆Ecis/trans = 3.92 kcalmol–1). At showed only one signal assigned to Me3SiOSiMe3. Crystal-
room temperature only one 1H NMR signal is observed for lisation from toluene gave a crop of single crystals of the
the methyl protons, which is indicative of a fast exchange novel heterobimetallic compound of the formula [Bi10-
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Figure 2. Molecular structure of [Bi10Na5O7(OH)6(OSiMe3)15] (2); hydrogen atoms are omitted; typical bond lengths [Å] and bond angles
[°] are found in the ranges: Bi–O 2.056(4)–2.728(5), Na–O 2.369(4)–2.710(5); O–Bi–O 64.5(2)–98.8(2) and 128.0(2)–166.5(2), O–Na–O
62.0(2)–99.2(2) and 122.1(2)–156.7(2), O–Na(2)–O 65.4(2)–106.3(2) and 112.6(2)–175.9(2), Bi–O–Bi 84.9(2)–137.1(2), Bi–O–Na 79.4(2)–
158.7(2), Na–O–Na 79.9(2)–168.3(2). Additionally, weak secondary bonds between bismuth and oxygen with distances of 3.0 Å are
observed for Bi(7) and Bi(9).
Na5O7(OH)6(OSiMe3)15]·1.5C7H8 (2·1.5C7H8) (Figure 2). scribed to be composed of the different subunits A, AЈ and
Apparently, partial hydrolysis of initially formed com- B, which are connected via Na(2) placed in the centre of
pounds took place as a result of contact with air moisture. the metal-oxo core (Figure 3). At the periphery of the mole-
Noteworthy, formation of single crystals of the metal oxo cule a total of fifteen µ2- and µ3-silanolate groups is found.
cluster 2 were also observed when a C6D6 solution of “[Bi-
(OSiMe3)3]”, prepared from NaOSiMe3 and BiCl3, was
kept for approximately two weeks under atmospheric condi-
tions. We recently noticed, that reaction of BiCl3 with NaO-
SiMe3 (ratio 1:3) at room temperature under rigorous ex-
clusion of air moisture again produced compound 1 as
major product, but additionally single crystals of the bis-
muth-oxo silanolates [Bi18Na4O20(OSiMe3)18] and [Bi33-
NaO38(OSiMe3)24] were obtained from toluene/benzene. A
detailed comparison of the molecular structures of these
bismuth-rich compounds with polynuclear homometallic
bismuth-oxo silanolates is reported elsewhere.[11c] In conclu-
sion, [Bi2Na4O(OSiMe3)8] (1) is always obtained as the
major product by the metathesis route and subtle changes
regarding temperature, moisture and choice of the solvent
lead to various heterobimetallic oxo(hydroxy)silanolates as
byproducts.
Figure 3. View of the [Bi10Na5O28] core structure of compound 2
(Me3Si groups and H atoms are omitted; six oxygen atoms are cov-
ered by polyhedra). The sodium atom Na(2) connects the frag-
ments A, AЈ and B.
The molecular structure of [Bi10Na5O7(OH)6(OSiMe3)15]
(2) is shown in Figure 2 and selected bond lengths and bond
Both pentanuclear fragments A and AЈ are composed of
angles are given in the Figure caption. Compound 2 is com- three bismuth atoms, two sodium atoms and thirteen oxy-
posed of a metal-oxo core comprising 15 metal atoms and gen atoms. The five metal atoms occupy the corners of a
15 trimethylsilyl groups. The metal-oxo core is best de- square pyramid with four µ3-silanolate groups capping each
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trigonal face (Figure 4). A µ5-oxygen atom occupies ap- ported recently, in which an asymmetric structure with an
proximately the centre of the basal plane. In addition, four µ4-oxo ligand in the centre of an octahedron is favoured
oxygen atoms are coordinated terminal to the metal atoms over the more symmetric structure which requires an ideal
of the basal plane of A and four oxo ligands are bidentate µ6-oxo ligand.[24]
bridging. The subunits A and AЈ are not related by sym-
The structural fragment B consists of four bismuth atoms
metry, but show similar bond lengths and bond angles. The and fifteen oxygen atoms (Figure 4). The [Bi4O15] fragment
basic structural motif of the [Bi3Na2O13] fragment A is resembles the Bi4O6-ladder-type arrangement (C) which
closely related to the metal-oxo core of [Bi2Na4O- was described as a central structural motif in other bis-
(OSiMe3)8] (1) as is shown in Figure 4. Other examples with muth-oxo compounds.[6,25] However, in contrast to the lad-
related molecular structures were reported among pentanu- der-type arrangement C fragment B is strongly distorted
clear metal µ5-oxo alkoxides,[20,21] several hexanuclear com- and an additional µ2-oxo ligand connects the two central
pounds with µ6-oxo ligands[17–19,21,22] and hexanuclear bis- bismuth atoms to give an structural arrangement, which is
muth-oxo-hydroxo cations with a [Bi6O8] fragment (Fig- better assigned to type CЈ. Molecular structures based on
ure 4).[23]
this motif have been reported for the bismuth-oxo alkoxides
[Bi6O3(OR)12] (R = C6F5,[6] 2,6-C6H3Cl2[26]). Both struc-
tural arrangements C and CЈ can formally be reduced to
the trinuclear fragment D, which might be expected to be
the most stable building unit of bismuth-oxo clusters. How-
ever, so far discrete trinuclear units similar to type D were
solely observed for hydrolysis products of bismuth trifluo-
roacetate, such as [Bi3(OH)(OOCCF3)8].[23k,27]
The more symmetric ladder-type arrangement C is ob-
served for the central metal-oxo core composed of Bi(7)–
Bi(9) and Na(2) (Figure 5). Each bismuth atom belongs to
a different subunit [Bi(7) in A, Bi(9) in AЈ and Bi(8) in B;
see Figure 3 and Figure 4] which are connected by Na(2).
Figure 4. View of the structural fragments, which constitute the
metal-oxo clusters 1, 2 (A and B) and the [Bi6O8] fragment of pre-
viously described hexanuclear bismuth-oxo-hydroxo cations.[23]
In compound 1 the oxygen atom is located in the centre
of the cluster and thus all M–O (M = Na, Bi) bond lengths
equally amount to 2.289(1) Å. This is a result of the disor-
der model suggested for the symmetric cluster 1. In con-
trast, fragment A shows two short Bi–µ5-O distances [Bi(4)–
O(32) 2.192(4) Å, Bi(6)–O(32) 2.086(4) Å], a longer Bi–µ5-
O bond length [Bi(7)–O(32) 2.425(4) Å] and two similar
Na–µ5-O distances [Na(1)–O(32) 2.559(5) Å, Na(4)–O(32)
2.588(5) Å]. However, the average M–µ5-O distance in A
(av. M–O 2.365 Å) is close to the M–O distance in com-
pound 1. Comparison of the metal-oxo core structure of 1
with that of A sheds some light on the disorder problem
reported above for compound 1. The higher oxophilicity of
Figure 5. View of the central metal-oxo core of compound 2, which
connects the three subunits A, AЈ and C.
The heavy metal bismuth in [Bi10Na5O7(OH)6-
the bismuth atom compared with the sodium atom should (OSiMe3)15]·1.5C7H8 (2·1.5C7H8) does not unambiguously
favour the formation of short Bi–O distances to give a cis- allow the location of OH hydrogen atoms. However, dif-
arrangement in compound 1 as it was observed for subunit ferent O···O distances make an assignment of hydroxy
A. This result is in agreement with our theoretical model. groups possible. Thus, O(35) [O(35)···O(1) 2.618(7) Å],
A cis-arrangement gives a structure of lower symmetry. O(37) [O(37)···O(13) 2.680(7) Å], O(23) [O(23)···O(26)
Thus, we suggest the disorder observed in compound 1 to 2.564(6) Å], O(22) [O(22)···O(2) 2.766(7) Å], and O(24)
be a result of disordered molecules in the crystal lattice [O(24)···O(4) 2.783(7) Å] are assigned to hydroxo ligands.
rather than disordered metal atoms. Noteworthy, another In addition, we suggest O(36), which is located at the pe-
example, namely [(Cp*Zr)6(µ4-O)(µ2-O)4(µ2-OH)8], was re- riphery of the metal-oxo silanolate, to be a hydroxo ligand.
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Figure 6. Molecular structure of [Bi15Na3O18(OSiMe3)12] (3); hydrogen atoms are omitted; typical bond lengths [Å] and bond angles [°]
are found in the following ranges: Bi–O 2.033(9)–2.737(9), Na–O 2.264(10)–2.606(12); O–Bi–O 64.9(3)–160.1(3), O–Na–O 70.1(3)–
165.1(4), Bi–O–Bi 93.9(3)–134.3(4), Bi–O–Na 84.6(3)–138.0(4). Additionally, weak secondary bonds between bismuth and oxygen with
distances in the range of 3.2–3.5 Å are observed for Bi(2), Bi(5), Bi(9) and Bi(11)–Bi(13).
After the batch of single crystals of 2·1.5C7H8 had been
separated by filtration, a second crystal fraction, hereafter
referred to as 3·C7H8 (Figure 6), was obtained. The molecu-
lar structure of [Bi15Na3O18(OSiMe3)12]·C7H8 (3·C7H8) is
closely related to that of compound 2 although both com-
pounds differ significantly in composition. The metal-oxo
core of compound 3 is best described to be composed of
three [Bi5O12] subunits of type E, which are connected via
three sodium atoms (Figure 7). Each subunit E, EЈ and EЈЈ
shares four oxygen atoms with a neighbouring subunit. The
[Bi5O12] subunits E, EЈ and EЈЈ show similar structural pa-
rameters and thus only E is discussed in more detail (Fig-
ure 8).
Figure 7. View of the [Bi15Na3O30] core structure of 3 (Me3Si
The [Bi5O12] subunit E is composed of five bismuth
atoms, which occupy the corners of a square pyramid (Fig-
ure 8). Two µ3-silanolate groups and two µ3-oxygen atoms
groups are omitted). Three sodium atoms connect the subunits E,
EЈ and EЈЈ.
cap the trigonal faces. Each bismuth atom of the basal
plane is connected to two bismuth atoms of the same plane
by two oxo ligands. These oxo ligands further link each sub- the molecular structures of the recently reported nonanu-
unit to another subunit and/or a sodium atom to give six clear bismuth-oxo cations [Bi9(µ3-O)8(µ3-OR)6]5+ (R = H,
µ3- and six µ4-oxo ligands. In addition, six silanolate groups Et)[25d] show a remarkable structural relationship with com-
bridge adjacent corners of two subunits. Four of these li- pound 3. The cations might be described to be composed
gands additionally coordinate to a sodium atom, which re- of a [Bi5O6(OR)6] subunit of type E and two edge-sharing
sults in four µ3- and two µ2-OSiMe3 ligands. Noteworthy, trigonal [Bi3(µ3-O)] subunits.
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2.084(10)–2.378(9) Å, a significantly longer Bi–O bond
length of 2.737(9) Å and O–Bi(6)–O angles in the range
65.7(3)–158.4(4)° (Figure 8). The coordination geometry in
the first-coordination shell might be described as distorted
pseudo-trigonal bipyramid (BiO4X) built from O(5), O(17),
O(24), O(27) and a stereochemically active lone pair. An
additional secondary Bi–O bond to O(2) completes the co-
ordination sphere to give a [4+1] coordination. Similarly, all
bismuth atoms in compound 3 show irregular coordination
geometries which are best described as 4-, [4+1] and [4+2]
coordination, respectively.
The metal-oxo silanolate [Bi2Na4O(OSiMe3)8] (1) can be
recrystallised from benzene or toluene, but attempts to
recrystallise it from THF failed. Instead, the novel heterobi-
metallic compound [Bi14Na8O18(OSiMe3)14(thf)4]·C6H6
(4·C6H6) was obtained. Its molecular structure is shown in
Figure 9.
Figure 8. View of the [Bi5O12] subunit E including Me3Si groups.
Two additional Bi–O bonds of Bi(2) and Bi(3) to O(29) and O(15),
which are part of EЈ and EЈЈ, are omitted. Selected bond lengths
[Å] and angles [°]: Bi(3)–O(1) 2.532(11), Bi(3)–O(2) 3.196(11),
Bi(3)–O(16) 2.310(9), Bi(3)–O(20) 2.066(9), Bi(3)–O(27) 2.254(10),
Bi(4)–O(2) 2.260(9), Bi(4)–O(7) 2.243(9), Bi(4)–O(16) 2.033(9),
Bi(4)–O(24) 2.079(9), Bi(6)–O(2) 2.737(9), Bi(6)–O(5) 2.378(9),
Bi(6)–O(17) 2.084(10), Bi(6)–O(24) 2.214(9), Bi(6)–O(27) 2.115(8);
Bi(4)–O(2)–Bi(3) 89.7(3), Bi(4)–O(2)–Bi(6) 96.0(3), Bi(3)–O(2)–
Bi(6) 83.7(3), Bi(3)–O(16)–Bi(4) 127.8(4), Bi(3)–O(27)–Bi(6)
130.6(4), Bi(4)–O(24)–Bi(6) 120.5(4), O(2)–Bi(6)–O(5) 128.8(3),
O(2)–Bi(6)–O(17) 135.6(3), O(2)–Bi(6)–O(24) 65.7(3), O(2)–Bi(6)–
O(27) 76.7(3), O(5)–Bi(6)–O(17) 87.3(3), O(5)–Bi(6)–O(24)
158.4(4), O(5)–Bi(6)–O(27) 74.6(3), O(17)–Bi(6)–O(24) 73.2(4),
O(17)–Bi(6)–O(27) 93.0(4), O(24)–Bi(6)–O(27) 96.8(4).
In addition, the metal-oxo core of the [Bi5O12] subunit E
shows some structural relationship to the [Bi3Na2O13] sub-
unit A (Figure 4). The basic structural motif of both A and
E is a square pyramid with the metal atoms occupying the
corners (Figure 8). An additional oxygen atom in A occu-
pies a position within the oxo cage. However, both subunits
E and A can be deduced from the metal-oxo core of bis-
muth-oxo-hydroxo complexes[23] of the type [Bi6O4+x
-
[6–x]+
(OH)4–x
]
by removal of one bismuth atom (Figure 4).
It might be assumed that only in octahedral structures of
the type [BixNayOz] (x + y = 6) and [BixNayᮀOz] (x + y =
5, ᮀ = metal vacancy) with at least two sodium atoms the
octahedral void might be occupied by an oxygen atom.
Noteworthy, the additional oxygen atom in A results in a
smaller instead of the expected larger volume of subunit A
Figure 9. Molecular structure of [Bi14Na8O18(OSiMe3)14(thf)4] (4);
hydrogen atoms are omitted.
The molecular structure of compound 4 is best described
compared with that of E. This is best demonstrated by the to be composed of a symmetric [(BiO2)6]6– unit [Bi(2), O(3)
metal–metal distances along the edges of the pyramid. In and O(5)] which is sandwiched between two [Bi4Na4O3(OSi-
structure fragment A these distances are in the range Me3)7(thf)2]3+ subunits (Figure 10). The [(BiO2)6]6– unit
3.290(2)–3.460(2) Å whereas those in fragment E are in the resembles a small cylinder which is closed from both sides
range 3.430(1)–3.958(1) Å. In subunit E the Bi–O distances by Na(2) and Na(2D), respectively [Na(2)–Na(2D)
are in a large range between 2.033(9) Å and 3.196(12) Å, 3.515(5) Å,
Bi(2)–Bi(2A)
5.965(1) Å,
Bi(2)–Bi(2D)
which is attributed to the combination of strong primary 6.888(1) Å]. The bismuth atoms within the [(BiO2)6]6– ring
bonds and weak secondary interactions. As a result large show a pseudo-trigonal bipyramidal coordination geometry
distortions of the coordination polyhedra are observed. For with Bi(2)–O distances of 2.103(3) Å and 2.268(3) Å. The
example, Bi(6) shows four Bi–O bond lengths in the range cis-O–Bi–O angles amount to 74.70(9)° and 97.13(5)°, and
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Heterobimetallic Bismuth-Oxo Clusters
FULL PAPER
the trans-O–Bi–O angle is 156.39(12)°. A similar cyclic
structural arrangement of eight such [BiO2] moieties was
recently reported for the ethanol solvate of [Bi(OEt)3]8.[28]
The subunit [Bi4Na4O3(OSiMe3)7(thf)2]3+ is composed of a
symmetric layer, which consists of three bismuth and three
sodium atoms [Bi(1) and Na(1)], three µ5-oxygen atoms
[O(4)] and six µ2-OSiMe3 ligands [O(1) and O(2)]. The so-
dium atom Na(2) is placed above the layer and the bismuth
atom Bi(3), two thf ligands as well as a silanolate ligand are
placed below the layer. Within the layer the bond lengths
between the metal atoms and the oxygen atoms of the silan-
olate ligands are found to be similar for sodium and bis-
muth with values in the range 2.270(3)–2.319(3) Å. In con-
trast Bi(1)–O(4) amounts to 2.057(3) Å and Na(1)–O(4) to
2.583(3) Å. The µ5-oxygen atom O(4) is further coordinated
to Na(1A), Na(2) [Na(2)–O(4) 2.540(3) Å] and Bi(3) [Bi(3)–
O(4) 2.138(3) Å]. The coordination geometry of Bi(3) is
best described as trigonal pyramidal [O(4)–Bi(3)–O(4A)
83.69(5)°]. Additionally, secondary bonds of Bi(3) to the
three oxygen-donor ligands thf and OSiMe3 are observed
[Bi(3)–O(6) 2.776(5) Å]. A similar coordination of the bis-
muth atom was reported for [Bi(OSiPh3)3(thf)3],[9] but in
contrast to the terminal coordination of the thf ligands in
the bismuth triphenylsilanolate those in compound 4 are
bridging between Bi(3) and Na(1) [Na(1)–O(6) 2.513(4) Å].
The two subunits [(BiO2)6]6– and [Bi4Na4O3(OSiMe3)7-
(thf)2]3+ are linked via O(3), O(5) and their symmetry re-
lated counterparts. Thus, µ4-O(5) is connected to Na(1A),
Na(2), Bi(2) and Bi(2B), and µ3-O(3) to Bi(1), Bi(2) and
Bi(2C) [O(5)–Na(1A)/Na(2)/Bi(2)/Bi(2B) 2.388(5)/2.446(3)/
Figure 10. View of the metal-oxo core structure of 4 (Me3Si groups,
C and H atoms are omitted) showing the atom numbering scheme.
Selected bond lengths [Å] and angles [°]: Bi(1)–O(1) 2.319(3), Bi(1)–
O(2) 2.295(3), Bi(1)–O(3) 2.045(3), Bi(1)–O(4) 2.057(3), Bi(2)–O(3)
2.268(3), Bi(2)–O(3B) 2.263(3), Bi(2)–O(5) 2.103(2), Bi(2)–O(5C)
2.097(3), Bi(3)–O(4) 2.138(3), Bi(3)–O(6) 2.776(5), Na(1)–O(2)
2.270(3), Na(1)–O(1E) 2.277(3), Na(1)–O(5E) 2.388(3), Na(1)–O(6)
2.513(4), Na(1)–O(4) 2.583(3), Na(1)–O(4E) 2.535(3), Na(2)–O(5)
2.446(3), Na(2)–O(4) 2.540(3); O(1)–Bi(1)–O(2) 161.7(1), O(1)–
Bi(1)–O(3) 81.0(1), O(1)–Bi(1)–O(4) 91.7(1), O(2)–Bi(1)–O(3)
80.9(1), O(2)–Bi(1)–O(4) 91.6(1), O(3)–Bi(1)–O(4) 90.6(1), O(5C)–
Bi(2)–O(5) 94.3(1), O(5C)–Bi(2)–O(3B) 89.5(1), O(5)–Bi(2)–O(3B)
74.7(1), O(5C)–Bi(2)–O(3) 74.7(1), O(3)–Bi(2)–O(5) 88.9(1), O(3)–
Bi(2)–O(3B) 156.4(1), O–Na(1)–O 67.6(1)–160.1(1), O–Na(2)–O
68.2(1)–148.2(1), Bi(1)–O(3)–Bi(2) 129.1(1), Bi(2)–O(5)–Bi(2B)
110.2(1), Bi(2)–O(3)–Bi(2C) 99.0(1). Symmetry operations used to
generate equivalent atoms: A = –x + y + 1, –x, z; B = y + 2/3, –x
+ y + 1/3, –z + 1/3; C = x – y – 1/3, x – 2/3; –z + 1/3; D = – x +
2/3; –y – 2/3; –z + 1/3; E = x – y – 1; x – 1, –z.
2.103(2)/2.103(2) Å;
O(3)–Bi(1)/Bi(2)/Bi(2C)
2.045(3)/
2.268(3)/2.268(3) Å]. The coordination geometry of Bi(1) is
best described as pseudo-trigonal bipyramidal assigned to
BiO4X (X = lone pair). The cis-O–Bi–O angles are in the
range 80.91(11)–91.66(10)° and the trans-O–Bi–O angle
amounts to 161.65(11)°. Two short bonds between the bis-
muth atom and the cis-positioned oxygen atoms O(3) and
O(4) [Bi(1)–O(3) 2.045(3) Å, Bi(1)–O(4) 2.057(3) Å] as well
as two elongated bonds to the trans-located oxygen atoms
O(1) and O(2) [Bi(1)–O(1) 2.319(3) Å, Bi(1)–O(2)
2.295(3) Å] are observed. Noteworthy, the sodium-rich bis-
muth-oxo cluster 4 is neither composed of the above-men-
tioned [M5O12] subunits nor of ladder type arrangements
of type C. The structural relationship is restricted to the
formation of trinuclear [Bi3O] subunits, planar four-mem-
bered [Bi2O2] and [NaBiO2] rings and strongly distorted bis-
muth-oxygen polyhedra.
Studies on the thermal behaviour of compounds 1–3
were carried out. The thermal stability of the clusters 2 and Si2.5O10 (calcd. 26.6%, 2b) and Bi15Na4Si3O30 (calcd.
3 is rather low as was shown by DTA-TG measurements. 19.0%, 3b). It should be noted that the sillenite-type bis-
The onset of decomposition starts below 120 °C and is at- muth silicate Bi12SiO20 was observed upon thermal decom-
tributed to the loss of solvate molecules. The major weight position of [Bi22O16(OSiMe2tBu)22].[10] Similarly, the pow-
loss for compounds 1–3 is observed between 150 °C and der X-ray data of the decomposition products 2b and 3b
250 °C. The observed weight loss (1 39.8%; 2 27.6%; 3 were also indicative of Bi12SiO20 (JCPDS No. 76–726) as
18.8%) is lower than calculated for the formation of pure major crystalline material. In case of compound 2 Na2SiO3
Na/Bi/O phases and indicates formation of silicates. The (JCPDS No. 82–0604) was observed as an additional minor
observed values correspond to mixtures with general for- product. The latter was the only crystalline material in the
mulas such as Bi2Na4Si2.5O10 (calcd. 40.3%, 1b), Bi10Na5- mainly amorphous decomposition product 1b.
Eur. J. Inorg. Chem. 2005, 4891–4901
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4897

M. Mehring, S. Paalasmaa, M. Schürmann
FULL PAPER
against Me4Si. The IR spectra were run as Nujol mulls and absorp-
tion bands assigned to the compounds in the range 400–1400 cm–1
are listed. Celite® (FLUKA) and sodium silanolate (Aldrich) were
dried in vacuo at 120 °C prior to use. Bismuth trichloride (Lancas-
ter) was heated at reflux in thionyl chloride, washed with pentane
and dried in vacuo. [Bi(OtBu)3][5] and Me3SiOH[30] were prepared
according to literature procedures.
Conclusions
Both partial hydrolysis and elimination of Me3SiOSiMe3
from [Bi(OSiMe3)3] contribute to the formation of heterobi-
metallic bismuth-oxo silanolates. We assume that [Bi-
(OSiMe3)3] is formed in situ by reaction of BiCl3 with NaO-
SiMe3, but the reaction of the bismuth silanolate with ad-
ditional NaOSiMe3 to give Me3SiOSiMe3 is faster than the
metathesis reaction. The favoured product is [Bi2Na4O(OSi-
Me3)8] (1). Several different heterobimetallic byproducts are
observed, the amounts of which depend on subtle changes
in the reaction conditions. The use of THF as solvent fav-
ours the elimination of Me3SiOSiMe3, but its formation is
also observed in non-polar solvents. It is noteworthy that
in contrast to [Bi(OSiMe3)3], the corresponding alkoxide
[Bi(OtBu)3] is accessible via salt elimination. Despite of the
ready M–O–M bond formation by elimination of Me3SiOS-
iMe3, thermolysis of heterometallic bismuth-oxo silanolates
in the solid state results in silicate materials instead of het-
erobimetallic oxides. The Bi–OSiMe3 moiety is very sensi-
tive towards hydrolysis, and trace amounts of water induce
hydrolysis/condensation processes to take place until the re-
activity of the metal-oxo silanolate is significantly reduced.
The resulting heterobimetallic compounds are covered by
Me3SiO ligands which are still moisture-sensitive but pre-
vent further aggregation.
The peculiarity of sodium and bismuth to assemble into
diverse heterobimetallic complexes is explained by their
similar ionic radii, and their rich and variable coordination
chemistry. As a consequence, heterobimetallic metal-oxo
subunits such as the ladder-type [Bi3–xNaxOy] and square
pyramidal [Bi5–xNaxOy] fragments constitute basic building
blocks. Thermolysis of bismuth-oxo silanolates gives com-
pounds of the Sillenite-type family, which are extensively
studied because of their interesting optical properties such
as photorefractivity and photoconductivity.[29] It might be
anticipated that novel heterometallic bismuth compounds
are accessible starting from heterobimetallic bismuth-oxo
silanolate derivatives. Such bismuth-rich metal-oxo silanol-
ates might serve as molecular precursors for doped materi-
als of the Sillenite-type family.
Synthesis of [Bi2Na4O(OSiMe3)8] (1) (Method a): To a solution of
NaOSiMe3 (12.70 g, 113.2 mmol) in toluene (100 mL) was added
anhydrous BiCl3 (7.00 g, 22.2 mmol) in small portions at room tem-
perature. The beige suspension was stirred at room temperature for
one hour and heated at reflux for two hours. The solid material
was filtered off through Celite® and the clear solution was concen-
trated to approximately 50 mL. Crystallisation at 4 °C gave colour-
less crystals of compound 1. The first crop of crystals isolated was
not analytically pure and an EDX analysis revealed the presence
of chloride in addition to bismuth, sodium and silicon. The second
crop of crystals (1.20 g, 9%) was analytically pure 1, which decom-
poses upon heating above 150 °C. A small quantity of compound
1 was suspended in THF/benzene and after stirring overnight a
clear yellow solution was obtained. From this solution moisture-
sensitive single crystals of [Bi14Na8O18(OSiMe3)14(thf)4]·C6H6
(4·C6H6) were obtained and dried in vacuo.
Synthesis of 1 (Method b): A solution of Me3SiOH (1.64 g,
18.2 mmol) in toluene (10 mL) was added dropwise to a solution
of [Bi(OtBu)3] (2.61 g, 6.1 mmol) in toluene. All volatile compo-
nents were removed in vacuo and the residue was dissolved in tolu-
ene. To this solution NaOSiMe3 (1.36 g, 12.1 mmol) was added
portionwise and the resulting suspension was heated at reflux for
1.5 h. The solid material was isolated by filtration and dried in
vacuo to give compound 1 (2.86 g, 76%).
1: C24H72Bi2Na4O9Si8 (1239.4): C 23.3, H 5.9; found C 24.0, H 6.4.
IR (Nujol) ν = 1298 w, 1258 m, 1246 m, 1021 m, 996 w, 980 w,
˜
967 w, 925 m, 894 s, 829 s, 742 m, 724 sh, 675 w, 660 w, 620 vw,
584 w, 537 w, 462 w, 414 cm–1 w.
4: C42H126Bi14Na8O32Si14 (4646.3): C 10.9, H 2.7; found C 11.4, H
2.9. IR (Nujol) ν = 1257 m, 1241 m, 1051 w, 941 m, 910 m, 826 m,
˜
740 m, 725 m, 668 w, 593 cm–1 m.
Synthesis of [Bi10Na5O7(OH)6(OSiMe3)15] (2) and [Bi15-
Na3O18(OSiMe3)12] (3): To a solution of BiCl3 (11.88 g, 37.4 mmol)
in THF (180 mL) was added NaOSiMe3 (12.70 g, 113.2 mmol) in
small portions at room temperature to give a beige suspension. The
solvent was evaporated, the residue extracted with hot toluene
(150 mL) and the solid material filtered through Celite®. Evapora-
tion of the solvent gave a solid containing Na, Bi and Si according
to an EDX analysis. The residue was dissolved in toluene and the
solution stored at 4 °C for several weeks. Single crystals of 2 were
isolated by filtration and dried in vacuo to give 410 mg 2. The
filtrate was collected, the amount of the solvent was reduced to
approximately 20 mL, and the solution was kept at 4 °C for several
months to give single crystals of 3. The colourless crystals were
isolated by filtration and the solvent was removed from the crystals
in vacuo to give 550 mg of 3. Both compounds show a poor solubil-
ity, are moisture sensitive and decompose upon heating above
120 °C.
Experimental Section
General Remarks: All manipulations were performed with ex-
clusion of oxygen and moisture by using Schlenk-type techniques
and argon atmosphere. Solvents were distilled from appropriate
drying agents prior to use. Elemental analyses were performed on
a LECO-CHNS-932 analyser. No satisfactory elemental analyses
were obtained for compound 1 which is assigned to partial substi-
tution of OSiMe3 by OtBu – isostructural [Bi2Na4O(OtBu)8] was
reported previously[18] – and for compound 2 which is assigned
to its high moisture sensitivity. The DTA-TG measurements were
performed at a heating rate of 6 °C min–1 to a maximum tempera-
ture of 700 °C in an atmosphere of flowing argon using Al2O3 as
reference material. The residues were examined by powder X-ray
2: C45H141Bi10Na5O28Si15 (3756.6): C 14.4, H 3.8; found: C 13.4,
H 3.0. IR (Nujol) ν = 3450 br, 1257 m, 1244 m, 1021 w, 925 s, 830 s,
˜
741 m, 669 w, 632 w, 584 w, 536 w, 501 w, 410 cm–1 br.
diffraction using a Phillips PW1050/25 diffractometer. H and 29Si
3: C43H116Bi15Na3O30Si12 (4654.1): C 11.1, H 2.5; found: C 10.9,
1
NMR spectra were recorded at 400.13 MHz and 59.6 MHz, respec-
tively. Chemical shifts (δ values given in ppm) were referenced
H 2.5. IR (Nujol) ν = 1258 m, 1244 m, 934 s, 921 s, 907 s, 828 s,
˜
742 m, 674 w, 652 w, 632 m, 600 s, 543 w, 496 m, 442 w, 414 cm–1 w.
4898
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Eur. J. Inorg. Chem. 2005, 4891–4901

Heterobimetallic Bismuth-Oxo Clusters
FULL PAPER
Table 1. Crystallographic data for [Bi2Na4(O)(OSiMe3)8] (1), [Bi10Na5O7(OH)6(OSiMe3)15]·1.5C7H8 (2·1.5C7H8), [Bi15Na3O18(OSiMe3)12]·
C7H8 (3·C7H8) and [Bi14Na8O18(OSiMe3)14(thf)4] (4·C6H6).
Compound
1
2·1.5C7H8
3·C7H8
4·C6H6
Empirical formula
Formula weight
Crystal system
C24H72Bi2Na4O9Si8 C45H141Bi10Na5O28Si15·1.5C7H8 C36H108Bi15Na3O30Si12·C7H8 C42H126Bi14Na8O32Si14·4thf·C6H6
1239.46
trigonal
3894.88
triclinic
¯
4654.11
monoclinic
C2/c
5012.85
trigonal
¯
¯
Space group
R3c
P1
R3
Cell constants [Å, °]
a = 12.8844(3)
a = 15.0377(2)
b = 16.0373(2)
c = 27.8967(5)
α = 87.1321(6)
β = 86.6530(7)
γ = 63.6617(6)
6016.8(2)
a = 54.311(11)
b = 19.846(4)
c = 22.885(5)
a = 15.9786(4)
c = 54.6565(3)
c = 46.8329(17)
β = 112.32(3)
Volume [Å3]
7857.8(3)
6
1.572
6.961
22819(8)
8
2.709
10355.2(5)
3
2.412
Z
2
dcalcd. [g·cm–3
]
2.150
14.788
Absorption coefficient [mm–1
Crystal size [mm]
]
23.230
17.976
0.23×0.15×0.10
0.15×0.15×0.05
2.93 to 27.52
70719
27464 [Rint = 0.059]
0.0371
0.15×0.08×0.03
2.94 to 25.41
174201
20955 [Rint = 0.133]
0.0445
0.20×0.18×0.05
2.98 to 27.49
62724
5276 [Rint = 0.073]
0.0217
θ range for data collection [°] 3.16 to 27.46
No. of reflections collected
No. of unique reflections
R [I Ͼ 2σ(I)]
16688
2006 [Rint = 0.039]
0.0285
wR2 (all data)
Largest diff. peak/hole [e·Å–3
0.0381
0.318/–0.479
0.0627
1.559/–1.526
0.0809
3.240/–1.579
0.0386
1.832/–1.956
]
Structure Determination: See Table 1. Intensity data for the colour-
less crystals were collected on a Nonius KappaCCD diffractometer
with graphite-monochromated Mo-Kα radiation at 173 K. The
data collection covered almost the whole sphere of reciprocal space
occupancies of 0.33 and the C atoms of the solvent molecule THF
(C7–C10) were refined with occupancies of 0.66. Si3, C7–C10 were
refined anisotropically and C11–C13 were refined isotropically. The
figures were created by SHELXTL[34] and DIAMOND (release
with two (1), four (2·1.5C7H8) and seven sets (3·C7H8, 4·C6H6) at 2.1e, 2001).
different κ-angles and 202 (1), 510 (2·1.5C7H8), 652 (3·C7H8) and
CCDC-276495 (for 1), -276497 (for 2·1.5C7H8), -276496 (for
592 (4·C6H6) frames via ω-rotation (∆/ω = 1°) at two times 30 s
(1), 60 s (2·1.5C7H8), 157 s (3·C7H8) and 60 s (4·C6H6) per frame.
The crystal–detector distance was 3.4 cm (1, 4·C6H6), 4.4 cm (2)
and 3.8 cm (3·C7H8). Crystal decay was monitored by repeating the
initial frames at the end of data collection. Analysing the duplicate
reflections there was no indication for any decay. The structures
were solved by direct methods SHELXS97[31] and successive differ-
ence Fourier syntheses. Refinement applied full-matrix least-
squares methods SHELXL97.[32] The H atoms were placed in geo-
metrically calculated positions using a riding model with Uiso con-
strained at 1.2 times Ueq of the carrier C atom for non-methyl and
1.5 times Ueq of the carrier C atom for methyl groups. Atomic
scattering factors for neutral atoms and real and imaginary disper-
sion terms were taken from the International Tables for X-ray Crys-
tallography. Absorption correction was carried out with multi-scan
3·C7H8) and -276498 (for 4·C6H6) contain the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
We acknowledge the Deutsche Forschungsgemeinschaft, the Fonds
der Chemischen Industrie, the Fachbereich Chemie of Dortmund
University (support of young scientists) and Professor Dr. K. Jurk-
schat for support of this work. S. P. is grateful to the department
of chemistry at the University of Joensuu (Finland) and the foun-
dation of Heikki and Hilma Honkanen for financial support as
well as for receipt of an ERASMUS grant.
using SCALEPACK[33] [Tmin = 0.310, Tmax = 0.543 (1); Tmin
=
0.245, Tmax = 0.525 (2·1.5C7H8); Tmin = 0.085, Tmax = 0.543
(3·C7H8); Tmin = 0.119, Tmax = 0.467 (4·C6H6)]. In 1 disorder of
the metal atoms was found. Bi1 and Na1 were refined with equal
position and occupancies of 0.33 and 0.66, respectively. In
2·1.5C7H8 disorder over two positions was found for C6C, C6CЈ,
C8A, C8AЈ, C8B, C8BЈ with occupancies of 0.5. All solvent mole-
cules toluene (C51–C57, C61–C67) and disordered atoms were re-
fined isotropically. One solvent molecule toluene (C61–C67) was
refined with occupancies of 0.5. In 3·C7H8 disorder over two posi-
tions was found for C5A–C5Ј, C6A–C6Ј, C8A, C8Ј, C8B, C8ЈЈ,
C9A–C9Ј, C10A–C10Ј, C11A–C11Ј with occupancies of 0.5, for
C12A, C12B with occupancies of 0.7 and for C12Ј, C12ЈЈ with oc-
cupancies of 0.3. All solvent molecules toluene (C21–C27, C31–
C37) and disordered atoms were refined isotropically. The solvent
molecules toluene were refined with occupancies of 0.5. In 4·C6H6
a trimethylsilanolate ligand and a solvent molecule THF share the
oxygen atom O6. The SiMe3 group (Si3, C11–C13) was refined with
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4899

M. Mehring, S. Paalasmaa, M. Schürmann
FULL PAPER
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