A Tetrameric Neodymium Silanolate: [Nd(OSiMe3)3]4

The title compound [Nd(OSiMe₃)₃]₄ ( 1 ) was prepared by reaction of [Nd{N(SiMe₃)₂}₃] with Me₃SiOH in toluene at room temperature. Compound 1 crystallized from a concentrated toluene solution in the monoclinic space group P2₁/n with the lattice constants a = 15.144(1) Å, b = 25.142(1) Å, c = 20.391(1) Å and β = 103.755(2)°. In the solid state a tetramer is observed which shows Nd‐O bond distances in the range 2.129(2)‐2.675(2) Å.     

[Bi(OSitBuPh2)3]: A Metal Silanolate with a Weak Bismuth ‐ π Arene Interaction

The title compound [Bi(OSitBuPh₂)₃] ( 1 ) was prepared by the reaction of [Bi(OtBu)₃] with tBuPh₂SiOH in toluene at room temperature. The compound crystallizes in the monoclinic space group P2₁/n with the lattice constants a = 17.610(1), b = 20.153(1), c = 26.655(1) Å and β = 105.503(3)°. In the solid state a dimer is observed as a result of weak bismuth π‐arene interactions. The bismuth arene centroid distance amounts to 3.340(7) Å. Thermolysis of compound 1 performed under argon gave a heterogeneous product. The powder X‐ray diffraction analysis of the latter shows elementary bismuth as the only crystalline phase.     

Direct Synthesis of a Dimeric Mixed-Anions Bismuth(III) Complex: Synthesis and Structural Characterization of [Bi2(Phen)4(No3)4.4I0.6]I3 (A New Dimeric Compound)

A direct synthetic method of mixing Bi(NO₃)₃ and NaI with 1,10-phenanthroline yielded red crystals of [Bi₂(phen)₄(NO₃)_4.4I_0.6]I₃. In this complex the cationic part is in fact binuclear and contains two [Bi(phen)(NO₃)_1.7I_0.3] groups linked via a bridging NO^? ₃ anion. The I^? ₃ anion was not coordinated to bismuth(III) and the lone pair of valence electrons of the bismuth(III) ions appears to be stereochemically inactive. There are two independent NO^? ₃ anions, one coordinated to bismuth but another shares a position with I^? anion. The final results of crystallography show that 40% of these positions are occupied by NO^? ₃ anions and 60% by I^? anions that are coordinated to bismuth atom in bidentate fashion (NO^? ₃) and in unidentate fashion (I^?). An interesting point is that the I^? ₃ anion was produced by direct synthetic method (Branched tube method). There is a π-π stacking interaction between the parallel aromatic rings around the Bi(III) ion.     

Coordination of Bimuth(III) to Cucurbit[8]uril. Preparation and X‐ray Structure of [{Bi(NO3)(H2O)5}2(Q8)][Bi(NO3)3(H2O)4]2[Bi(NO3)5]2·Q8·19H2O

Bi(NO₃)₃ reacts with cucurbit[8]uril, (Q8), in 3M HNO₃ to give the title complex whose structure includes three discrete Bi complexes: [{Bi(NO₃)(H₂O)₅}₂(Q8)]⁴⁺ (CN of Bi = 9, both NO₃^— and cucurbit[8]uril are bidentate), [Bi(NO₃)₅]^2— (CN of Bi = 10, all NO₃^— are bidentate), and [Bi(NO₃)₃(H₂O)₄] (CN of Bi = 10, all NO₃^— are bidentate).     

Synthesis,Crystal Structure,Vibrational Spectra,and Thermal Behaviour of [Ph4P]2[Bi2(μ‐Br)2Br6 (CH3COCH3)2]

[Ph₄P]₂[Bi₂Br₈(CH₃COCH₃)₂] ( 1 ) was obtained by the reaction of [Ph₄P]Br and BiBr₃ in acetone. Single crystals were grown by allowing a layer of n‐hexane to diffuse into the acetonic solution of 1 . The crystal structure was determined by means of X‐ray diffraction. 1 crystallises with monoclinic symmetry in the space group P2₁/n, No. 14 with the lattice parameters: a = 13.358(2), b = 12.637(2), c = 18.565(3) Å, β = 102.62(1)°, V = 3058.1(8) ų and Z = 4. The structure is characterised by the anion [Bi₂Br₈(CH₃COCH₃)₂]^2– which is embedded in a matrix of [Ph₄P]⁺ cations. The anion can be described as two edge‐sharing square pyramids with the apical bromide ions in anti‐position. Acetone co‐ordinates the bismuth atoms via oxygen atoms and increases the co‐ordination number of central bismuth atoms to six which results in the formation of a distorted bi‐octahedron. The distortion is due to the difference in terminal and bridging Bi–Br bond lengths. FT‐IR and Raman spectroscopic data are presented. In addition, the thermal behaviour of the compound was studied with the aid of TG/DSC coupled with MS revealing that acetone leaves the crystal in two steps. The compound melts at 203 °C and transforms into a glass on cooling.     

Synthesis and Structures of Homoleptic Methyl‐ and Phenylthiomethylaluminium Complexes [Al(CH2SR)3](R = Me,Ph)

Sulfur‐substituted methylmercury compounds [Hg(CH₂SR)₂]( 1a, R = Me; 1b, R = Ph ) react with aluminium amalgam in refluxing toluene with transmetallation to give homoleptic tris(thiomethyl)aluminium complexes [Al(CH₂SR)₃]( 2a, R = Me; 2b, R = Ph ) (degree of conversion: >80%, isolated yields: 2a 63%, 2b 41%). Their identities were confirmed by NMR spectros‐copy (¹H, ¹³C) and X‐ray crystal structure analyses. In crystals of compound 2a the aluminium atoms possess a trigonal‐bipyramidal arrangement with the coordination polyhedron defined by three carbon and two sulfur atoms. Two of the three CH₂SMe ligands are bridging ligands (μ‐η²; 1kC:2kS), the third one is terminal bound (η¹; kC). The structure is polymeric. Crystals are threaded by helical chains built up of six‐membered Al₂C₂S₂ rings. Crystals of 2b are built up of centrosymmetrical dimers with six‐membered Al₂C₂S₂ rings having bridging CH₂SPh ligands (μ‐η²; 1kC:2kS). On each Al atom two terminal (η¹; kC)CH₂SPh ligands are bound. They exhibit quite different Al‐C‐S angles (116.7(4) and 106.5(3)?). Similar values (114.32115.7? and 109.52109.9?) were found in ab initio calculations of model compounds [{Al(CH₂SR)₃}₂]( 3a, R=H; 3b, R=Me; 3c, R=CH=CH₂ ). A conformational energy diagram for rotation of one of the terminal CH₂SH ligand in the parent compound 3a around the Al‐C bond is discussed in terms of repulsive interactions of lone electron pairs of sulfur atoms.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.     

Bismuth Polyanions in Solution: Synthesis and Structural Characterization of (2, 2, 2‐crypt‐A)2Bi4 (A = K,Rb) and the Formation of the Laves Phases ABi2 (A = K,Rb, Cs) from Solution

The possibility to synthesize and isolate different types of bismuth polyanions by dissolving various intermetallic precursors (binary samples from A‐Bi or ternary samples from A‐A'‐Bi systems, A and A' = K, Rb, Cs) in ethylenediamine or dimethylform amide in the presence of sequestering agents (2, 2, 2‐crypt or 18‐crown‐6) was investigated. The crystals of (2, 2, 2‐crypt‐K)₂Bi₄ ( 1 ) and (2, 2, 2‐crypt‐Rb)₂Bi₄ ( 2 ) compound were obtained from such solutions, the latter for the first time, and their structures were determined. The two compounds are isostructural (P1, Z=1, a = 11.052(2) Å, b = 11.370(2) Å, c = 11.698(2) Å, α = 61.85(3) °, β = 82.58(3) °, γ = 81.87(3) °, R₁ = 0.058, wR² = 0.149 for 1 and a = 11.181(2) Å, b = 11.603(2) Å, c = 11.740(2) Å, α = 61.96(3) °, β = 81.45(3) °, γ = 82.26(3) °, R₁ = 0.041, wR² = 0.109) and contain Bi₄^2— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi₂ (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi₂ is proposed.     

Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

Synthese und Kristallstrukturen von heteronuklearen AgI/FeII‐Koordinationspolymeren: (Me3PhN)2[Ag2Fe(SCN)6], (Me3PhN)6[Ag6Fe3(ECN)18] (E = S,Se) und (Me3PhN)4[Ag2Fe(SCN)8]

The reaction of AgSCN with (Me₃PhN)₃[Fe(NCS)₆] in DMF yields two‐dimensional polymeric, heteronuclear complexes (Me₃PhN)₂[Ag₂Fe(SCN)₆] ( 1 ) and (Me₃PhN)₆[Ag₆Fe₃(SCN)₁₈] · CH₂Cl₂·DMF ( 2a ) with bridging SCN^? ligands, whereas additional (Me₃PhN)(SCN) leads to (Me₃PhN)₄[Ag₂Fe(SCN)₈] ( 3 ) with a one‐dimensional structure. The selenocyanato complex 2b , homologous to 2a , could also be prepared. Single crystal X‐ray structure determinations show, that the Ag⁺ ions in 1 and 2a are coordinated tetrahedrally by four S atoms, in 3 by one N and three S atoms of the bridging SCN^? ligands; six N atoms of the SCN^? or SeCN^? ligands bind to Fe²⁺ in an octahedral arrangement.     

Bi37InBr48: Eine polares Subhalogenid mit Bi95+‐Polykationen,komplexen Bromobismutat(III)‐Anionen [Bi3Br13]4— und [Bi7Br30]9— sowie Pentabromoindat(III)‐Anionen [InBr5]2—

Bi₃₇InBr₄₈: a Polar Subhalide with Bi₉⁵⁺ Polycations, Complex Bromobismuthate(III) Anions [Bi₃Br₁₃]^4— and [Bi₇Br₃₀]^9—, and Pentabromoindate(III) Anions [InBr₅]^2— Black crystals of Bi₃₇InBr₄₈ were synthesized from bismuth, indium and BiBr₃ by cooling stoichiometric melts from 570 K to 470 K. X‐ray diffraction on powders and single‐crystals revealed that the compound crystallizes with space group P 6₃ (a = 2262.6(4); c = 1305.6(2) pm). The Bi₉⁵⁺ polycations in the polar crystal structure have the shape of heavily distorted tri‐capped trigonal prisms with approximate C_s symmetry. The high complexity of the structure results from three coexisting types of anionic groups: Three edge‐sharing [BiBr₆] octahedra constitute the trigonal bromobismuthate(III) anion [Bi₃Br₁₃]^4—. Four [BiBr₆] and three [BiBr₅] polyhedra share common vertices to form the [Bi₇Br₃₀]^9— hemi‐sphere, in which the trigonal bipyramid of the pentabromoindat(III) ion [InBr₅]^2— is embedded.     

The Stereochemical Activity of the Lone Pair in [Bi(NO3)3{(iPrO)2(O)PCH2P(O)(OiPr)2}2] — Comparison of Bismuth,Lanthanum and Praseodymium Nitrate Complexes

Five coordination compounds of bismuth, lanthanum and praseodymium nitrate with the oxygen‐coordinating chelate ligand (ⁱPrO)₂(O)PCH₂P(O)(OⁱPr)₂ (L) are reported: [Bi(NO₃)₃(L)₂] ( 1 ), [La(NO₃)₃(L)₂] ( 2 ), [Pr(NO₃)₃(L)₂] ( 3 ), [La(NO₃)₃(L)(H₂O)] ( 4 ) and [Pr(NO₃)₃(L)(H₂O)] ( 5 ). The compounds were characterized by means of single crystal X‐ray crystallography, ¹H and ³¹P NMR spectroscopy in solution, solid‐state ³¹P NMR spectroscopy, IR spectroscopy, DTA‐TG measurements ( 1 , 2 and 4 ), conductometry and electrospray ionization mass spectrometry (ESI‐MS). In addition, DFT calculations for model compounds of 1 and 2 support our experimental work. In the solid state mononuclear coordination compounds were observed for 1 — 3 , whereas compounds 4 and 5 gave one‐dimensional hydrogen‐bonded polymers via water‐nitrate coordination. Despite of the similar ionic radii of bismuth(III), lanthanum(III) and praseodymium(III) for a given coordination number the bismuth and lanthanide compounds 1 — 3 are not isostructural. The bismuth compound 1 shows a 9‐coordinate bismuth atom whereas lanthanum(III) and praseodymium(III) atoms are 10‐coordinate in the lanthanide complexes 2 — 5 . The general LnO₁₀ coordination motif in compounds 2 — 5 is best described as a distorted bi‐capped square antiprism. The BiO₉ polyhedron might be deduced from the LnO₁₀ polyhedron by replacing one oxygen ligand with a stereochemically active lone pair. The one‐to‐one complexes 4 and 5 dissociate in solution to give the corresponding one‐to‐two complexes 2 and 3 , respectively, and solvated Ln(NO₃)₃. In contrast to the lanthanides, the one‐to‐two bismuth complex 1 is less stable in CH₃CN solution and partially dissociates to give solvated Bi(NO₃)₃ and (ⁱPrO)₂(O)PCH₂P(O)(OⁱPr)₂.     

[Me3SnVO3] und [(Me2Sn)4V2O9], zwei Organozinnvanadate mit neuen 3D‐Netzwerkstrukturen

[Me₃SnVO₃] and [(Me₂Sn)₄V₂O₉], two Organotin Vanadates with Novel 3D Network Structures Two new organotin vanadates [Me₃SnVO₃] ( 1 ) and [(Me₂Sn)₄V₂O₉] ( 2 ) have been prepared by the reaction of NH₄VO₃ with Me₃SnBr and Me₂SnBr₂ resp. in agar gel. The structures of 1 and 2 have been determined by x‐ray crystallography at 220 K. 1 crystallizes monoclinic in the space group P2₁/c with a = 1335.6(2), b = 1144.4(2), c = 1118.8(2) pm, β = 113.54(2)°. 2 crystallizes orthorhombic in the space group Pnnm with a = 1257.6(2), b = 1345.4(2), c = 1323.1(1) pm. 1 consists of infinite metavanadate chains which are linked by Me₃Sn⁺ cations. 2 exhibits a complex 3D‐ network structure with VO₄ tetrahedra, Me₂SnO₃ trigonal bipyramides and Me₂SnO₄ octahedra linked by common oxygen atoms.     

Synthesis and crystal structure of two new Bi(III) complexes {(Me2NCS2)3Bi}2 and {[(CH2)5NCS2]2BiI}2

Six bismuth(III) complexes containing dithio-ligands formulated as (R₂NCS₂)₃Bi [R₂NCS₂M?=?Me₂NCS₂Na, C₄H₈NCS₂Na, Bz₂NCS₂Na] and [(R₂NCS₂)₂BiI]₂ [R₂NCS₂M?= C₅H₁₀NCS₂Na, ⁿ Bu₂NCS₂Na, OC₄H₈NCS₂Na] have been obtained by reactions of bismuth(III) halides with dithiocarbamate ligands in 1?:?2 or 1?:?3 stoichiometry. All compounds were characterized by elemental and IR analyses. The crystal structures of complexes 1 and 4 have been determined by X-ray single crystal diffraction. The structure analyses reveal that Bi^III in complex 1 adopts a distorted pentagonal–pyramidal coordination, due to its stereochemically active lone pair of electrons. A long Bi?·?S contact of 3.218 (3)?Å leads to dimeric associations of molecules in the crystal structure. The structure of complex 4 is six-coordination with a distorted octahedral configuration. Intramolecular S?·?S weak interactions contribute to the stability and lead to a one-dimensional chain structure.     

Selen‐Polykationen stabilisiert durch polymere Chlorobismutat‐Anionen: Synthesen und Kristallstrukturen von Se4[Bi4Cl14] und Se10[Bi5Cl17]

Selenium Polycations Stabilized by Polymeric Chlorobismuthate Anions: Syntheses and Crystal Structures of Se₄[Bi₄Cl₁₄] and Se₁₀[Bi₅Cl₁₇] Reactions of selenium with selenium(IV) chloride and bismuth(III) chloride in sealed evacuated glass ampoules at temperatures between 110 and 155 °C yield a series of compounds which are composed of discrete selenium polycations and polymeric chlorobismutate anions. Besides the already known Se₈[Bi₄Cl₁₄] two new compounds have been identified by crystal structure analyses as Se₄[Bi₄Cl₁₄] (tetragonal, P4/n, a = 1089.1(2) pm, c = 993.7(2) pm, Z = 2) and Se₁₀[Bi₅Cl₁₇] (monoclinic, P2₁/c, a = 1079.24(8) pm, b = 2062.9(2) pm, c = 1676.1(2) pm, β = 90.87(1)°, Z = 4). Se₄[Bi₄Cl₁₄] was obtained as red transparent platelike crystals and is the first example of a compound with (chalcogen₄)²⁺ ions of exact square‐planar symmetry and molecular point group D_4h in the solid state. The cations are surrounded by layers of two‐dimensional polymeric anions [Bi₄Cl₁₄]^2–. Se₁₀[Bi₅Cl₁₇] forms dark grey crystals with a reddish luster. The structure contains the known bicyclic polycation Se₁₀²⁺ which is disordered over two positions and the first three‐dimensional polymeric chlorobismutate anion [Bi₅Cl₁₇]^2–. The different BiCl_x polyhedra are linked by sharing common vertices, edges, and faces.     

Polymorphism in Bi2(SO4)3

A new polymorph of Bi₂(SO₄)₃ was prepared by reaction of LiBiO₂ with H₂SO₄ and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi₂(SO₄)₃ presents a layered structure made of SO₄ sulfate groups and signs of stereochemically active Bi³⁺ lone pairs. The new Bi₂(SO₄)₃ absorbs water to form Bi₂(H₂O)₂(SO₄)₂(OH)₂ through an intermediate Bi₂O(OH)₂SO₄ phase, and the transition is reversible when heated under vacuum.     

Synthesis,Structure and Thermal Decomposition of the Bismuth Silyltellurolate Bi(TeSitBu2Ph)3

The compound Bi(TeSitBu₂Ph)₃ ( 1 ) was obtained from the reaction of BiCl₃ with tBu₂PhSiTeSiMe₃ in diethyl ether. The single crystal structure analysis revealed a trigonal pyramidal structure of the BiTe₃ core and weak Bi···C_(arene) contacts. Compound 1 was characterized by multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis. Thermogravimetric experiments show that compound 1 decomposes with formation of Bi₂Te₃ or a mixture of elemental bismuth and Bi₄Te₃, depending on the pressure conditions.     

Synthesis and crystal structure of a mixed-ligand bismuth(III) complex, [Bi2(phen)2Br5(NO3)] n (phen = 1,10-phenanthroline)

Complex [Bi₂(phen)₂Br₅(NO₃)] _n has been synthesized by reaction of Bi(NO₃)₃ with potassium bromide and 1,10-phenanthroline. The complex has been isolated and characterized by IR-, ¹H NMR-, ¹³C NMR spectrum and elemental analysis. The structure of the [Bi₂(phen)₂Br₅(NO₃)] _n was confirmed by X-ray crystallography which shows the complex to be a one-dimensional polymer as a result of bridging bromides. The two Bi atoms have different environments, six and seven coordinate.