Bi Cl Research Articles

Bis(dihydrogen norfloxacinium) tri-μ2-chlorido-bis[trichloridobismuthate(III)] chloride dihydrate

The title compound, {systematic name: (3-carb­oxy-1-ethyl-6-fluoro-7-piperazin-4-ium-1-yl-1H-quinolin-4-yl­idene)oxonium tri-μ2-chlorido-bis­[trichloridobismuthate(III)] chloride dihydrate], (C16H20FN3O3)2[Bi2Cl9]Cl·2H2O, is composed of [Bi2Cl9]3− anions lying on crystallographic twofold rotation axes, Cl− anions also on twofold axes, C16H20FN3O3 2+ cations, and water mol­ecules. The BiIII coordination polyhedron is a distorted octa­hedron and two such octa­hedra share a triangular face to form the complex anion. There are three short terminal Bi—Cl bonds [2.5471 (6)–2.5781(5 Å] and three longer bridging bonds [2.8599 (5)–2.9984 (6) Å] in each octa­hedron. Anions, cations and water mol­ecules are linked by hydrogen bonds to form a three-dimensional network. There are also π–π stacking inter­actions between quinoline ring systems, with an inter­planar distance of 3.27 (1) Å.

Molecular to ionic transition of BiCl 3 in LiCl–KCl eutectic melt

The local structures of molten BiCl 3 and its mixtures in LiCl–KCl eutectic melt were investigated by X-ray absorption fine structure (XAFS) technique. The first Bi–Cl correlation in molten pure BiCl 3 shows covalent nature, since the distance was almost the same as sum of the covalent radii of Bi and Cl and the coordination number was almost 3. The similar property was also observed in the mixture of 75% BiCl 3 with LiCl–KCl eutectic melt. Drastic change was detected in 25% BiCl 3 mixture melt. The first Bi–Cl distance was the sum of the ionic radii in molten 25% BiCl 3 melt. The results suggest that BiCl 3 changes from molecular liquid to ionic by mixing with alkali chlorides.

Preparation and Characterization of Novel Inorganic−Organic Hybrid Materials Containing Rare, Mixed-Halide Anions of Bismuth(III)

Three new hybrid inorganic-organic salts containing novel mixed haloanions of bismuth were synthesized by the solvothermal reaction of bismuth iodide with a haloacid, HX (X = Cl or Br), and the alkylamine 4,4'-trimethylenedipiperidine (TMDP). All three compounds were structurally characterized by single-crystal X-ray diffraction. Reaction of TMDP and BiI(3) with HCl yielded two crystalline products: [H(2)TMDP](2)[(Bi(2)I(9))(BiCl(2)I(2))] (1, major yield) and [H(2)TMDP](2)[Bi(2)Cl(10-x)I(x)] (2, x = 3.83, minor yield). Compound 1 crystallizes in the monoclinic space group Cc (a = 22.8586(11) A, b = 15.5878(7) A, c = 17.6793(9) A, beta = 118.7010(10) degrees , Z = 4) and contains the mononuclear mixed-halide anion BiCl(2)I(2)(-) in addition to a face-sharing bioctahedral Bi(2)I(9)(3)(-) anion and two independent H(2)TMDP(2+) cations. The BiCl(2)I(2)(-) anion has a sawhorse geometry (equatorially vacant trigonal bipyramidal geometry) that is not commonly observed in bismuth chemistry. Compound 2 crystallizes in the monoclinic space group P2(1)/c (a = 14.9471(7) A, b = 12.7622(6) A, c = 13.3381(7) A, beta = 116.1030(10) degrees , Z = 2) and contains an edge-sharing bioctahedral mixed-halide anion in which iodide occupies one and chloride occupies two of the five crystallographically independent halide sites. The remaining two sites have mixed-chloride and -iodide occupancy. Reaction of TMDP and BiI(3) with HBr yielded the crystalline product [H(2)TMDP][BiBr(5-x)I(x)] (3, x = 0.99), which contains, in addition to the organic cation, a polymeric, mixed-haloanion of bismuth(III). Compound 3 crystallizes in the chiral, orthorhombic space group P2(1)2(1)2(1) (a = 8.5189(5) A, b = 14.8988(9) A, c = 17.9984(11) A, Z = 4) and consists of an H(2)TMDP(2+) cation in addition to the anion, which is built up of corner-sharing BiX(6) octahedra. Of the five crystallographically independent halide sites in this anion, two are occupied solely by Br and the remaining three have mixed-bromide and -iodide occupancy. Other anion stoichiometries have been observed crystallographically for 3, as the specific stoichiometry is dependent on the relative concentration of the haloacid starting material used.

Syntheses, crystal structures and antimicrobial activities of monomeric 8-coordinate, and dimeric and monomeric 7-coordinate bismuth(III) complexes with tridentate and pentadentate thiosemicarbazones and pentadentate semicarbazone ligands

Novel bismuth(III) complexes 1– 4 with the tridentate thiosemicarbazone ligand of 2N1S donor atoms [Hmtsc ( L1); 2-acetylpyridine ( 4 N-morpholyl thiosemicarbazone)], the pentadentate double-armed thiosemicarbazone ligand of 3N2S donor atoms [H 2dmtsc ( L3); 2,6-diacetylpyridine bis( 4 N-morpholyl thiosemicarbazone)] and the pentadentate double-armed semicarbazone ligand of 3N2O donor atoms [H 2dasc ( L4b); 2,6-diacetylpyridine bis(semicarbazone)], were prepared by reactions of bismuth(III) nitrate or bismuth(III) chloride and characterized by elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), FTIR and NMR ( 1H and 13C) spectroscopy. The crystal and molecular structures of complexes 1, 2a, 2b and 4b, and the “free” ligand L1 were determined by single-crystal X-ray structure analysis. The dimeric 7-coordinate bismuth(III) complex [Bi(dmtsc)(NO 3)] 2, 1, and the monomeric 7-coordinate complexes [Bi(Hdasc)(H 2O)](NO 3) 2 · H 2O (major product), 2a, and [Bi(dasc)(H 2O)]NO 3 · H 2O (minor product), 2b, all with pentagonal bipyramidal bismuth(III) centers, are depicted with one electron pair (6s 2) of the bismuth(III) atom, deprotonated forms of multidentate thiosemicarbazone or semicarbazone ligands, and monodentate NO 3 or H 2O ligands, respectively. These complexes are related to the positional isomers of one electron pair of the bismuth(III) atom; 1 has an electron pair positioned in the pentagonal plane (basal position), while 2a and 2b have an electron pair in the apical position. The monomeric 8-coordinate complex [Bi(mtsc) 2(NO 3)], 4b, which was obtained by slow evaporation in MeOH of the 1.5 hydrates 4a, was depicted with one electron pair of the bismuth(III) atom, two deprotonated mtsc − ligand and one nitrate ion. On the other hand, crystals of the complex “[Bi(mtsc)Cl 2]”, 3, prepared by a reaction of BiCl 3 with L1 showed several polymorphs ( 3a, 3b, 3c and 3d) due to coordination and/or solvation of dimethyl sulfoxide (DMSO) used in the crystallization. Bismuth(III) complexes 1 and 4a showed selective and effective antibacterial activities against Gram-positive bacteria. The structure–activity relationship was discussed.

Antifungal activity of organobismuth compounds against the yeast Saccharomyces cerevisiae: structure–activity relationship

Antifungal activity of organobismuth(III) and (V) compounds 1– 9 was examined against the yeast, Saccharomyces cerevisiae. A clear structure–activity relationship was observed in these compounds. Thus, triarylbismuth dichlorides 2 {(4-YC 6H 4) 3BiCl 2: Y=MeO, F, Cl, CF 3, CN, NO 2} and halobismuthanes 6 {2- tBuSO 2C 6H 4(4-YC 6H 4)BiX: Y=MeO, Me, H, Cl; X=Cl, Br, I}, 7 {Bi(X)(C 6H 4-2- SO 2C 6H 4-1 ′-): X=Cl, Br, I}, 8 {2-Me 2NCH 2C 6H 4(Ph)BiX: X=Cl, Br} and 9 {4-MeC 6H 4(8-Me 2NC 10H 6-1-)BiCl} showed the growth inhibition effect, while triarylbismuth difluorides 3 {(4-YC 6H 4) 3BiF 2} and triarylbismuthanes 1 {(4-YC 6H 4) 3Bi}, 4 {2- tBuSO 2C 6H 4(4-YC 6H 4) 2Bi} and 5 {4-YC 6H 4Bi(C 6H 4-2-SO 2C 6H 4-1 ′-)} were not active at all irrespective of the nature of the substituents. Generation of the inhibition effect is governed by the facility of nucleophilic reaction at the bismuth center and the Lewis acidic bismuth center is an active site. Of all the bismuth compounds attempted, halobismuthanes 7 derived from diphenyl sulfone exhibited the highest activities. An X-ray crystallographic study of 7a {Bi(Cl)(C 6H 4-2-SO 2C 6H 4-1 ′-)} revealed that the bismuth center adopts a seven-coordinated geometry, which is unusual in organobismuth(III) compounds, through the intramolecular and intermolecular coordination between the bismuth and oxygen atoms. The marked inhibition effect of 7 may be attributed to such a highly coordinated geometry, which allows the bismuth center to bind tightly with some biomolecules playing important roles in the growth of S. cerevisiae.

Hypervalent 5–Bi–12 derivatives containing dichalcogenoimidodiphosphinato ligands. Crystal structure and solution behaviour of [2-(Me2NCH2)C6H4]BiCl[(XPR2)(YPR′2)N] (X, Y = O, S, Se; R, R′ = Me, Ph)

The reaction between [2-(Me2NCH2)C6H4]BiCl2 and M[(XPR2)(YPR′2)N] in 1 ∶ 1 molar ratio affords the new functionalised [2-(Me2NCH2)C6H4]BiCl[(XPR2)(YPR′2)N] derivatives [R = Me, R′ = Ph, X = O, Y = S (1); R = R′ = Ph, X = Y = S (2), Se (3)]. Variable-temperature NMR studies suggest a fluxional behaviour in solution. The investigation of the molecular structures of 1–3 by single-crystal X-ray diffraction revealed that the N atoms of the pendant CH2NMe2 arm are strongly coordinated to the Bi atom and the organophosphorus ligands act as a bidentate moiety through both chalcogens, thus resulting in a square pyramidal coordination geometry around the metal atoms. The analysis of the crystal packing of 2 and 3 reveals the presence of pairs of enantiomers (the metal center is chiral) associated through weak intermolecular Bi⋯Cl interactions. The crystal of 1 contains only the trans-O–Bi–Cl isomer as a 1 ∶ 1 mixture of the two enantiomers, in a unique square pyramidal (C,N)BiCl(O,S) coordination geometry with five different atoms attached to the metal atom.

Heavy-Metal π Complexes. 13. Trichloro(1,2,3-trimethylbenzene)bismuth(III)

The title compound, [BiCl3(1,2,3-Me3C6H3)], contains quasi-dimeric units of arene-coordinated BiCl3 fragments that are further associated via additional Bi—Cl contacts to form coordination-polymeric layers. The resulting coordination number of Bi is 3 + 3 + 1 (primary + secondary Cl contacts + arene). The Bi—arene bonding is characterized by Bi—C distances in the range 3.168 (7)–3.751 (8) Å.

Bismuth(III) coordination compounds. Synthesis, characterization, and X-ray structures of [Bi(Cl)(μ-Cl) 2(THF) 2] ∞, Bi(O 2CMe) 3(Solv) x (Solv = py, x = 2 or MeIm, x = 4) [1], and [Bi(μ-OCH 2CMe 3)(OCH 2CMe 3) 2(Solv)] 2 (Solv = HOCH 2CMe 3 or py)

We have isolated and structurally characterized several novel bismuth coordination compounds. Dissolution of Bi(NO 3) 3 · 5H 2O in concentrated HCl, followed by crystallization from THF lead to the isolation of [Bi(Cl)(μ-Cl) 2(THF 2] ∞ 1. Each bismuth metal center of 1 adopts a 7-coordinated pentagonal bipyramidal geometry. One THF solvent molecule and one terminal chloride ligand are located in each of the axial positions. A terminal THF solvent molecule and four bridging chlorides reside in the equatorial positions. Dissolution of Bi(O 2CMe) 3 in pyridine (py) or N-methylimidazole (MeIm) results in the isolation of the appropriate amine adduct, either Bi(O 2CMe) 3(py) 2, 2 or Bi(O 2CMe) 3(MeIm) 3 · (MeIm), 3. Compound 2 uses two py molecules to adopt an unusual (for bismuth acetate species) 8-coordinated triangular dodecahedral geometry. In contrast, 3 incorporates three MeIm molecules to adopt the 9-coordinated tricapped trigonal prismatic geometry typically observed for bismuth acetate compounds (a “free” MeIm molecule is located in the lattice). The reaction of Bi[N(SiMe 3) 2] 3 with HOCH 2CMe 3 (HONp) yields [Bi(μ-ONp)(ONp) 2(HONp)] 2, 4. An alternative synthetic route to 4 is the metathical exchange between BiCl 3 and 3 equivalents of NaONp in the presence of HONp. The bismuth atoms of 4 are 5-coordinated and adopt an apical-shared, square base pyramidal (SP) arrangement. Recrystallization of 4 from py yields the dinuclear complex [Bi(μ-ONp)(ONp) 2(py)] 2, 5. The Bi atoms of 5 also adopt a 5-coordinated SP geometry; however, the two metal centers are linked through a basal-shared arrangement. The apical ONp ligands are in an up-down relationship to each other.

The structure of [C12H14N2]3[BiCl6]2 · 2H2O at room temperature

Abstract At room temperature, tris(1,1′-dimethyl-4,4′-bipyridinium) bishexachlorobismuthat(3-) dihydrate, [C12H14N2]3[BiCl6]2 · 2H2O, crystallizes in the triclinic space group C i 1; P[unk]; (No. 2) with a = 797.0(2) pm, b = 1215.8(2) pm, c = 1303.9(3) pm, α = 88.76(1)°, β = 83.01(1)°, γ = 73.86(1)°, Z = 1, D x = 1.977 g/cm3. The cell contains three [C12H14N2]2+ cations (methyl viologen), two slightly distorted BiCl6 octahedra ([unk]Bi–Cl = 269.4(2) pm) and two water molecules.

Tellurium Polycations Stabilized by Halogenobismutates – Syntheses and Crystal Structure of te4[bi6Cl20] and te4[bi2br8

AbstractThe reaction of Te, TeX4 and BiX3 [X = Cl, Br] in sealed, evacuated glass ampoules in the temperature range 170° 100°C yields a variety of compounds composed of tellurium polycations and halobismutate anions. Two of these have been identified by crystal structure analyses as Te4[Bi6Cl20] (triclinic, P., a = 738.8(2), b = 875.1(2), c = 1389.1(6) pm, α = 87.89(2), β = 82.87(4), γ = 87.89(2) ·, Z = 1) and Te4[Bi2Nr8 (triclinic, P., a = 726.0(4), b = 773.7(4), c = 901.8(5) pm, α = 92.95(2), β = 102.23(2), γ = 92.87(2)., Z = 1). Both compounds were obtained as black crystals with a violet lustre and contain square‐planar Te42+ cations. Te4[Bi6Cl20] contains a two‐dimensional polymeric anion [Bi6Cl20]2− made up of corner‐ and edge‐sharing BiCl6 octahedra with attached BiCl3 groups. The Bi–Cl distances vary over a very wide range from 245 to 334 pm. Te4[Bi2Br8] consists of a onedimensional chain [BiBr2Br4/2−[n of cis‐edge‐connected BiBr6 octahedra with Bi–Br distances ranging from 264 to 318 pm.

Pt 2(PPh 3) 4(μ-S) 2] as a metalloligand toward main-group Lewis acids. Crystal structures and bonding analysis of two low-coordinate BiCl 3 adducts—[Pt 2(PPh 3) 4( μ3-S) 2BiCl 3] and [Pt 2(PPh 3) 4( μ3-S) 2BiCl 2]PF 6

Addition of BiCl 3 to [Pt 2(PPh 3) 4(μ-S) 2] gives [Pt 2(PPh 3) 4( μ 3-S) 2BiCl 3], which undergoes dissociation and metathesis with NH 4PF 6 to give [Pt 2(PPh 3) 4( μ 3-S) 2BiCl 2]PF 6. An X-ray single-crystal diffraction analysis established two highly distorted square-pyramidal and tetrahedral structures, respectively. The four- and five-coordination numbers are unusually low among the known Bi III halide adducts. Fenske-Hall MO analysis offers an explanation to the structural characteristics with reference to the stereochemically active lone pairs, coordination numbers, uneven BiCl and BiS lengths and the butterfly geometry of the {Pt 2S 2} core. These parameters are compared with those of the other intermetallics previously reported.

Isolation of a Bismuth Chloride-Iron Carbonyl Adduct: Synthesis and Structural Characterization of [PhCH(2)NMe(3)](2)[Bi(2)Cl(4)(&mgr;-Cl)(2){&mgr;-Fe(CO)(4)}

The reaction of bismuth(III) chloride with [PhCH(2)NMe(3)](2)[Fe(CO)(4)] at a ratio of 2:1 in acetonitrile yields the iron carbonyl-bismuth chloride adduct [PhCH(2)NMe(3)](2)[Bi(2)Cl(4)(&mgr;-Cl)(2){&mgr;-Fe(CO)(4)}] cleanly in high yield. The complex consists of two BiCl(3) groups bridged by an [Fe(CO)(4)](2)(-) unit. Two chloride ligands are shared between the Bi atoms, producing square-pyramidal coordination at bismuth and octahedral coordination at the iron center. The production of this complex represents the synthesis of a stable adduct of a highly nucleophilic metal carbonyl anion with a strongly Lewis acidic main group halide. The compound C(24)H(32)N(2)O(4)Bi(2)Cl(6)Fe crystallizes in the orthorhombic space group Pba2 (No. 32) with cell parameters a = 14.624(3) Å, b = 17.010(3) Å, c = 7.1990(10) Å, V = 1790.8(5) Å(3), and Z = 2.

Phosphorus donor complexes of bismuth(III). Structural characterisation of [Bi2Cl6(Ph2PCH2PPh2)2], [Bi2Cl6(Ph2PCH2CH2PPh2)2] and [Bi2Cl6(Ph2PCH2CH2PPh2)3

The reactions of the diphosphines dppm [bis(diphenylphosphino)methane] and dppe [1,2-bis(diphenylphosphino)ethane] with bismuth(III) chloride in acetonitrile solution have been studied. The resulting complexes [Bi2Cl6(dppm)2]1 and [Bi4Cl12(dppe)5]2 respectively, have been structurally identified by X-ray diffraction studies. The centrosymmetric structure 1·2MeCN consists of coplanar halide-bridged Bi2Cl6 units with each of the two dppm ligand molecules in a bidentate bridging mode between the two metal sites. The overall co-ordination geometry at each bismuth atom is approximately octahedral with four (equatorial) chlorine atoms and two (axial) phosphorus atoms: Bi–Cl (terminal) 2.475(3), 2.530(4), Bi–Cl (bridging) 2.808(4), 2.820(3), Bi–P 2.872(3), 3.090(3)A. In 2 there are two separate and independent molecules in the asymmetric unit cell identified as [Bi2Cl6(dppe)2]2a and [Bi2Cl6(dppe)3]2b respectively. For 2a the centrosymmetric structure is made up of halide-bridged Bi2Cl6 units with bidentate chelate attachment of a dppe ligand molecule to each bismuth atom giving rise to an overall edge-shared bioctahedral geometry: Bi–Cl (terminal) 2.409(9), 2.470(11), Bi–Cl (bridging) 2.619(9), 2.945(9), Bi–P 2.699(8), 2.956(10)A. In the case of 2b the centrosymmetric dimer contains two BiCl3(dppe) moieties connected by a bridging dppe ligand; thus both bidentate chelate and bidentate bridging bonding modes are observed. Each bismuth atom is surrounded by three terminal chlorine atoms, Bi–Cl 2.514(8), 2.521(9), 2.555(9)A, and three phosphorus atoms, two from the chelating ligand, Bi–P 2.654(8), 2.916(9)A, and one from the bridging ligand, Bi–P 2.973(9)A, in an approximately mer-octahedral arrangement.

Redox Potentials of Bromo- and Chloro(phthalocyaninato)bismuth(III) Complexes

Abstract The redox potentials of the titled complexes, [Bi(pc)X] (pc2− = phthalocyaninate, C32H16N82−, and X = Cl− and Br−), in N,N-dimethylformamide solutions have been determined by cyclic voltammetry for the first time as phthalocyanine complexes of group-15 elements. The voltammograms of [Bi(pc)Cl] consisted of one oxidation (E1/2 = 0.36 V vs. ferrocene/ferricinium+) and two reduction couples (ca. −1.2 and ca. −1.0 V), each of which was a quasi-reversible one-electron process. The voltammograms of [Bi(pc)Br] were quite similar to those obtained with [Bi(pc)Cl], with the exception of the appearance of an additional irreversible anodic peak at 0.30 V, which could be attributable to the oxidation of non-ligand bromide, suggesting the dissociation of [Bi(pc)Br] into [Bi(pc)]+ and Br− in DMF. This is the first case in which [M(pc)X]-type (M = trivalent metal) complex dissociated into [M(pc)]+ and X− in solution.

Fourier-transform Raman and infrared spectra and normal coordinate analysis of (C6H5)2BiCl and [N(CH3)4]+[(C6H5)2BiCl2

Abstract The vibrational properties of the diphenylbismuth(III) chloride compounds (C 6 H 5 ) 2 BiCl and [N(CH 3 ) 4 ] + [(C 6 H 5 ) 2 BiCl 2 ] − have been investigated. A comprehensive assignment of the fundamental modes in the measured Fourier-transform Raman and infrared spectra has been carried out. Normal coordinate calculations of these compounds based on new X-ray crystal structure data have been performed to identify the BiCl stretching and bending vibrations of both compounds. For [N(CH 3 ) 4 ] + [(C 6 H 5 ) 2 BiCl 2 ] − in the solid state, the ν s (BiCl 2 ) and ν as (BiCl 2 ) occur at 215 cm − (Raman) and 237 cm − (Raman), respectively, in good agreement with the calculated wavenumbers. The force constant calculation yields a BiCl stretching force constant of 0.89 × 10 2 N m −1 .

Syntheses and Characterization of Bromo- and Chloro(phthalocyaninato)bismuth(III) Complexes

Abstract By the reactions of BiX3 (X = Cl−, Br−, I−, and NO3−) with Li2(pc) (pc = phthalocyaninate dianion, C32H16N82−) in dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, and acetone, [Bi(pc)X] complexes have been produced. These complexes were also produced by heating a mixture of BiX3 and phthalonitrile. Among them, [Bi(pc)Cl] and [Bi(pc)Br] were isolated for the first time as a phthalocyanine complex of group-15 elements and successfully characterized by elemental analyses, solution chemistry, electronic and IR spectroscopy. The latter two complexes were soluble in polar solvents, but were insoluble in nonpolar solvents. In solutions, bismuth(III) in [Bi(pc)X] was labile and was readily expelled from a pc ring by a trace amount of water, acids, and bases, and it was replaced by a divalent transition metal upon the addition of MSO4 (M = cobalt(II), nickel(II), copper(II), and zinc(II)) forming [M(pc)]. The electronic and IR spectra of the [Bi(pc)X]s were characteristic of the usual metallophthalocyanines, except that a hyper metal-to-ligand charge-transfer band appeared in their electronic spectra.

Bismuth(III) complexes with sulfur and selenium donor ligands: synthesis and crystal structures of BiCl3·Prn2P(S)P(S)Prn2and [(Me2N)3PSeSeP(NMe2)3]2+[(BiCl4)2]n2n–

Direct addition of bismuth(III) chloride and tetra-n-propyldiphosphane disulfide gave bright yellow crystals of the 1 : 1 adduct BiCl3·Prn2P(S)P(S)Prn2. An X-ray crystallographic investigation reveals a halide-bridged dimeric structure in which each bismuth atom is surrounded by an essentially octahedral arrangement of four chlorine [two terminal. Bi–Cl 2.500(5), 2.516(5), and two bridging, Bi–Cl 2.653(4). 3.015(5)Å] and two sulfur atoms [Bi–S 2.857(4), 2.973(4)Å]. Each of the two ligand molecules is involved in bidentate (S,S′) chelation to a bismuth atom to form a five-membered ring. Crystals are monoclinic, space group P21n, with a= 10.127(6), b= 16.057(6), c= 13.843(6)Å, β= 93.3(1)°, Z= 4. The reaction of BiCl3and tris(dimethylamino)phosphane selenide in acetonitrile gave the yellow crystalline salt [(Me2N)3PSeSeP(NMe2)3]2+[(BiCl4)2]n2n– as identified by a crystal structure determination. Formation of the unusual cation follows from air oxidation of the organophosphine selenide in the presence of BiCl3. The Se–Se bond distance is 2.309(5)Å and the torsion angle P–Se–Se–P is –112.4(4)°. For the anion, linkage of dimeric (BiCl4)2 units via further halide bridging results in an infinite chain structure of edge-shared octahedra. Crystals are triclinic, space group P with a= 7.386(6), b= 12.813(8), c = 18.919(8)Å, α= 76.0(1 ), β= 78.9(1 ), γ= 73.2(1)° and Z= 2.

Neue metallorganisch substituierte Bismut-Chalkogen-Verbindungen mit Mo2BiE-Gerüst (E = S, Se) / New Organometallic Bismuth Chalcogen Compounds with Mo2BiE Framework (E = S, Se)

[{Cp(CO)3Mo}2BiCl] 1 reacts with silylated chalcogens E(SiMe3)2 (E = S, Se) to give the compounds [{Cp(CO)2Mo}2EBiCl] (E = Se 2, S 3). The structures of 2 and 3 were determined by X-ray crystallography. In the solid state two [{Cp(CO)2Mo}2EBiCl] units are linked by two Bi—Cl—Bi bridges to form the dimer [{Cp(CO)2Mo}2EBiCl]2 with a planar Bi2Cl2 ring. The [{Cp(CO)2Mo}2EBiCl] units contain distorted Mo2BiE tetrahedra.

Synthesis and crystallographic studies of crown thioether complexes of bismuth(III)

The pale yellow bismuth(III)–crown thioether complexes BiCl3·[12]aneS41 and BiCl3·[15]aneS5·0.5MeCN 2 have been prepared and characterised. An X-ray crystal structure determination of 1 shows the central bismuth atom bonded to three chlorine atoms, Bi–Cl mean 2.571 A, Cl–Bi–Cl 90.9(1)–94.3(1)°, and all four sulfur atoms of the [12]aneS4 macrocycle, Bi–S 2.987(3)–3.206(3)A, in an approximate half-sandwich structure. The four sulfur atoms are exactly coplanar and the bismuth atom sits in a central location over the ring at a distance of 1.87 A from this plane. This is the first genuine example of endo complexation for [12]aneS4 involving a p-block element. Compound 1 crystallises in the monoclinic space group P21/n with a= 7.985(4), b= 12.956(7), c= 15.278(9)A, β= 101.47(4)° and Z= 4. 2099 Observed reflections [I/σ(I) 2.0] gave in the final refinement R= 0.037. The structure of BiCl3·[15]aneS5·0.5MeCN 2 shows full co-ordination of the [15]aneS5 macrocycle to the BiCl3 unit in a half-sandwich arrangement, with two independent identical molecules, Bi–Cl mean 2.565(7)A, Bi–S 3.057(7)–3.433(7)A, Cl–Bi–Cl 86.5(2)–93.0(2)° acetonitrile is trapped as lattice solvate. The ligand undergoes a conformational change (exo- to endo-dentate) on complex formation. Compound 2 crystallises in the orthorhombic space group Pbca with a= 16.972(9), b= 15.418(8), c= 30.60(2)A, and Z= 16. 2951 Observed reflections [I/σ(I) 2.0] gave in the final refinement R= 0.0545. The resulting conformations of the macrocyclic ligands are discussed in terms of gauche/anti preferences and structural comparisons are drawn between 1 and 2 and their oxocrown counterparts.

Synthesis and molecular structure of the adduct trichlorobismuth–1,4,7,10,13,16-hexathiacyclooctadecane (1/1)

The reaction (1:1) of BiCl3 and [18]aneS6 in acetonitrile provides colourless crystals of the adduct BiCl3·[18]aneS6. An X-ray crystal structure determination has revealed a BiCl3 pyramidal unit bonded to all six sulfur atoms of the macrocyclic ring which adopts an unusual S-shaped conformation. The bismuth atom sits on a crystallographically imposed three-fold axis in a nine-co-ordinate [3:3:3] geometrical arrangement involving two sets of three sulfur atoms and the three chlorine atoms respectively. Crystals are cubic, space group Pa3 with Z= 8 and a= 16.381(5)A 1312 independent reflections were measured of which 825 with [I/σ(I) 2.0] were used in the final refinement, R= 0.044 (R′= 0.067), Bi–S 3.146(4) and 3.225(4)A, Bi–Cl 2.607(4)A and Cl–Bi–Cl 89.0(1)°.