Chem. Commun., 2001, 23542355 M.mehring [631871]

Communication
www.rsc.org/chemcommCHEMCOMM
The first bismuth phosphonate cluster. X-Ray single crystal structure
of [(ButPO 3)10(ButPO 3H)2Bi14O10·3C 6H6·4H 2O]†
Michael Mehring* and Markus Schürmann
Universität Dortmund, Lehrstuhl für Anorganische Chemie II D-44221. Dortmund, Germany.
E-mail: [anonimizat]
Received (in Cambridge, UK) 9th August 2001, Accepted 8th October 2001
First published as an Advance Article on the web 26th October 2001
The reaction of triphenylbismuth and tert-butylphosphonic
acid gives the bismuth phosphonate phase (ButPO 3H)3Bi
and the first bismuth phosphonate cluster [(ButPO 3)10(But-
PO 3H)2Bi14O10·3C 6H6·4H 2O].
In the past three decades phosphate and phosphonate ligands
have been widely used to prepare polynuclear oxo anions suchas vanadates and molybdates.
1A fascinating example of this
class of compounds is the cluster [V 18O25(H2O)2(Ph-
PO3)20Cl4]42.2In addition to the soluble metallaoxo anions,
poorly soluble oxo–vanadium phosphonates such as [VO(Ph-PO
3)·H2O]nhave also been reported.3The latter phosphonate
forms a layered structure with well-defined internal void spacesand coordination sites which are accessible for organicmolecules such as alcohols. Similarly, zirconium phosphatesand phosphonates are composed of two-dimensional layeredstructures and show properties which make them useful as ionexchangers, sorbents, sensors, proton conductors, non-linearoptical materials, photochemically active materials, catalysts,and hosts for the intercalation of a broad spectrum of guests.
4
Several other metal phosphonates which exhibit two- and three-dimensional structures in the solid state have been reported,including recent examples of Al, Zn, Cu, and Ga, amongothers.
4,5The only bismuth phosphonate characterised by a
single crystal X-ray structure analysis is Bi(O 3PC2H4CO 2)·H2O
which has a two-dimensional layered structure.6The chemistry
of uncharged organophosphonate clusters which are soluble incommon organic solvents and serve as molecular models forphosphate and phosphonate based materials is more recent.
7,8
Herein we report our results on the reaction of BiPh 3with
ButPO3H2which was undertaken initially in order to obtain
soluble organobismuth phosphonate compounds viathe elim-
ination of benzene. A 1 +1 mixture of BiPh 3and ButPO3H2was
heated at 50 °C for three days in THF to give a suspension. Thesolid material was filtered off and the solvent removed in vacuo .
The residue was dissolved in CHCl
3/benzene and by slow
evaporation of the solvent colourless single crystals of [(ButP-
O3)10(ButPO3H)2Bi14O10·3C 6H6·4H 2O]‡ ( 1) were obtained in
low yield. The major product was identified as (ButPO3H)3Bi
(2) which can be prepared almost quantitatively by choosing the
appropriate stoichiometry. EDX analysis of analytically pure 2
shows a phosphorus-to-bismuth ratio of approximately 3 +1 and
in the 31P MAS NMR only one signal at d36.0 is observed. The
IR spectrum of 2shows a broad absorption (3100 cm21) in the
n(P–OH) region. In the PO 3vibration domain three strong
absorption bands at 1066, 1017 and 934 cm21are observed. The
absorption band at 1192 cm21is indicative for a P NO group.
The TGA shows a weight loss of 4.7% in the temperature range230–320 °C as a result of a condensation reaction of theBu
tPO3H moieties (weight loss calc. for 1.5 H 2O 4.6%). In the
range 400–470 °C cleavage of the C–P bonds occurs (weightloss 27.9%; calc. for three Bu
tgroups 27.6%). Additional
weight loss in the temperature range 320–400 °C (1.8%) and480–550 °C (2.7%) was observed giving a ceramic yield at 550°C of 62.9% which is lower than the calculated ceramic yield for
Bi(PO
3)3of 71.9%. The X-ray powder diffraction data show
broad diffraction peaks which are indicative for the bismuthphosphonate phase 2to be amorphous.
The single crystal X-ray structure analysis of 1§ revealed the
formation of a bismuth phosphonate oxo cluster containing 14bismuth atoms and 12 tert-butylphosphonate groups (Fig. 1). In
the crystal structure of 1(space group Immm with Z= 2) the
cluster, the water and the benzene molecules show mmm
symmetry.
Two of the phosphonate groups are not fully deprotonated
and give two Bu
tPO3H units which form strong hydrogen bonds
to adjacent ButPO3groups with O(2’)–O(2’E) and O(2’A)–
O(2’D) distances of 2.327 Å. The molecular formulation[(Bu
tPO3)10(ButPO3H)2Bi14O10·3C 6H6·4H 2O] ( 1) was con-
firmed by elemental analysis. The 10 m3-oxygen atoms are most
likely the result of partial hydrolysis of BiPh 3caused by residual
water present in ButPO3H2. The difficulty to obtain water-free
ButPO3H2was previously noticed in context with the synthesis
of tert-butylphosphonate clusters of titanium.8,9Cluster 1shows
D2hsymmetry which results in the observation of only two
crystallographically independent phosphonate groups, fourindependent bismuth atoms, Bi(1)–Bi(4), and three independentm
3-oxygen atoms, O(3)–O(5). The m3-oxygens O(3)–O(5) are
incorporated inside the cluster and show Bi–O distances in therange 2.093(16)–2.237(9) Å. The oxygen O(3) is trigonal planarcoordinated which is indicated by the sum of the O–Bi–O anglesS360.0°, whereas the m
3-oxygens O(4) and O(5) show sums of
the O–Bi–O angles of S342.7 and 339.2°, respectively. The
coordination geometry both at Bi(2) and Bi(4) is best describedas a square pyramid with four phosphorus-bonded oxygen
† Electronic supplementary information (ESI) available: Fig. S1: XRD
pattern for 2. See http://www.rsc.org/suppdata/cc/b1/b107220j/ Fig. 1 General view of 1showing the molecular structure and the atom
numbering scheme (symmetry transformations used to generate equivalent
atoms: a = x, y, 2z+ 1; b = 2x, y, 2z+ 1; c = x, 2y, z; d = x, 2y, 2z
+ 1; e = 2x, 2y, z; f = 2x, y, z; g = 1 2x, 2y, z).
This journal is © The Royal Society of Chemistry 20012354 Chem. Commun. , 2001, 2354–2355 DOI: 10.1039/b107220j
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atoms occupying the corners of the base. The corresponding
bond distances Bi(2) –O(P) and Bi(4) –O(P) are in the range
2.212(11) –2.439(11) Å. The apex of each of the pyramids is
occupied by an oxygen atom with Bi(2) –O(3) and Bi(4) –O(5)
bond distances of 2.093(16) and 2.119(12) Å, respectively. In
addition, both Bi(2) and Bi(4) are each coordinated to a benzenemolecule with Bi –C distances in the range 3.428 –3.459 and
3.376 –3.564 Å, respectively, which is comparable with the
bismuth –benzene coordination in BiCl
3·C6H6with Bi –C dis-
tances in the range 3.219 –3.621 Å.10The benzene molecules
coordinated to Bi(2) link adjacent clusters to give a linearpolymeric arrangement with a Bi –benzene
centroid distance of
3.194 Å. A similar polymeric structure with collinear bismuth
atoms and arene centers was recently reported for [Bi 2(O2-
CCF 3)4](C 6Me 6).11The benzene molecules coordinated to
Bi(4), Bi(4A), Bi(4B) and Bi(4C) and having an occupancy of0.5 occupy a void built up by four chains of the bismuth clusters.The coordination geometry at Bi(1) is best described as that ofa strongly distorted square pyramid with four phosphorus-bonded oxygen atoms occupying the corners of the base (Bi –
O(P) 2.237(9) –2.577(10) Å). The O(1) –Bi(1) –O(1A) angle of
147.8(5) ° deviates strongly from the ideal value of 90 °
indicating a stereochemically active lone pair. The apex of thepyramid is occupied by a m
3-oxygen with a Bi(1) –O(3) distance
of 2.228(6) Å. In addition, a water molecule is weakly
coordinated to Bi(1) with a Bi(1) –O(31) distance of 3.066 Å.
The coordination environment of Bi(3) consists of fourphosphonate-oxygens and three m
3-oxygens. The Bi –O(P)
distances are in the range 2.555(10) –2.664(10) Å and the Bi –O
distances amount to 2.208(13) –2.231(7) Å. In the crystal lattice
huge voids extend along the a-axis at (0,0,0) and (0,1/2,1/2)
which are partially filled with water molecules (Fig. 2). The IR
spectrum of 1shows a broad absorption band in the region
3000 –3500 cm21which is indicative for OH vibrations in
agreement with the single crystal X-ray structure analysis. Onlytwo strong and relatively broad absorption bands are observedat 1059 and 970 cm
21, which are assigned with caution to n(P–
O–Bi) vibrations. A n(PNO) absorption band is observed at
1190 cm21.
In conclusion, the single crystal X-ray structure analysis of
the first bismuth phosphonate cluster 1is reported which, to the
best of our knowledge, is the largest bismuth containing clusterreported so far and a rare example of a linear p-coordination
copolymer of a main group metal cluster and an arene molecule.We have shown that novel hybrid organic –inorganic bismuth
compounds are easily accessible under mild reaction conditionsstarting from a commercially available organobismuth com-pound and phosphonic acids.We are grateful to Professor Dr K. Jurkschat (Universit ät
Dortmund, Lehrstuhl f ür Anorganische Chemie II) for his
generous support.
Notes and references
‡Synthesis of [(ButPO) 3)10(ButPO3H)2Bi14O10·3C6H6·4H2O (1) and (But-
PO3H)3Bi (2): to a solution of BiPh 3(900 mg, 2.04 mmol) in 20 mL of THF
was added ButPO3H2(282 mg, 2.04 mmol). The reaction mixture was
stirred at 50 °C for three days to give a cloudy solution. The precipitate was
isolated by filtration and dried in vacuo to give 280 mg (66%) of 2as a
colourless solid. The solvent was removed to give a slightly yellow oil
which was dissolved in a CHCl 3/benzene mixture. Slow evaporation of the
solvent afforded colourless crystals of analytically pure 1(20 mg). A second
crop of crystals (25 mg) contained small amounts of the starting material
BiPh 3as impurity. 1: Decomp. > 200 °C. IR (KBr) n/cm21: 3400br,
2950m, 2903w, 2867w, 1643w, 1479m, 1403w, 1362w, 1190m, 1059s,
970s, 831w, 656m, 498s, 331w. Anal. Found: C, 15.9; H, 2.7. Calc. C, 15.8;
H, 2.7%. 2: Decomp. > 150 °C. IR (KBr) n/cm21: 3100br, 2970m, 2906w,
2870w, 1479m, 1395w, 1365w, 1192m, 1066s, 1017s, 934s, 830w, 729w,
694w, 657m, 507m, 331w. 31P MAS NMR (161.98 MHz): d36.0. Anal.
Found: C, 23.3; H, 4.7. Calc. C, 23.2; H, 4.9%.
§Crystal data for 1: C66H136Bi14O50P12, M= 5027.11, crystal size 0.05 3
0.03 30.03 mm3, orthorhombic, space group Immm , Z= 2, a= 15.628(1),
b= 17.977(2), c= 30.189(3), V= 8481.4(13) Å3, Dc= 1.968 g cm23,
F(000) = 4548, m(Mo-K a) = 0.7107 mm21, T= 171(1) K, 3.31 @2q@
25.35, Completeness to 2 q: 99.2%, max./min. residual electron density:
1.516/21.244 e Å23. Data were collected on a Nonius Kappa CCD
diffractometer. Of a total of 18370 reflections collected, 4236 reflections
were independent ( Rint= 0.098). The structure was solved by direct
methods (SHELXS97)12and successive difference Fourier syntheses.
Refinement applied full-matrix least-squares methods SHELX97.13Final
R1 = 0.054 (for 4236 reflections I> 2s(I)) and wR2 = 0.130 (all data).
The H atoms were placed in geometrically calculated positions using a
riding model with Uisoconstrained at 1.2 for non-methyl groups and 1.5 for
methyl groups times Ueqof the carrier C atom. Disordered solvent
molecules of benzene and water were found with occupancies of 0.25
(O(21)) and of 0.5 (C(41), C(42), C(43)), whereas all solvent molecules,except O(31), were refined isotropically. CCDC 162527. See http:/
/www.rsc.org/suppdata/cc/b1/b107220j/ for crystallographic data in CIF or
other electronic format.
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Chem. Commun. , 2001, 2354 –2355 2355
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