Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Manganese(II) Complexes with Bridging Selenidoarsenate(III) Anions [AsSe2(Se2)]3− and [(AsSe2)2(μ‐Se2)]4−

Solvothermal reaction of [MnCl₂(terpy)] with elemental As and Se at a 1:1:2 molar ratio in H₂O/trien (10:1) at 150 °C affords the linear trimanganese(II) complex [{Mn(terpy)}₃(μ‐AsSe₄)₂] ( 1 ). The tridentate [AsSe₂(Se₂)]^3? anions of 1 chelate the terminal {Mn(terpy)}²⁺ fragments and bridge these through their remaining Se atom to the central {Mn(terpy)}²⁺ moiety. Weak interactions of Mn1···Se and Mn3···Se bonds with length 2.914(7) and 3.000(7) Å link the molecules of 1 into infinite chains. Treatment of [MnCl₂(cyclam)]Cl with As and Se at a 1:1:2 molar ratio in superheated H₂O/CH₃OH (1:1) at 150 °C yields the dinuclear complex [{Mn(cyclam)}₂ (μ‐As₂Se₆)] ( 2 ), whose novel [(AsSe₂)₂(μ‐Se₂)]^4? ligands bridge the Mn^II atoms in a μ‐1κ²Se¹, Se²: 2κ²Se⁵,Se⁶ manner.     

Synthesis and Thermal Behaviour of Compounds in the System [Ph4P]Cl/BiCl3 and the Crystal Structures of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]2[Bi2Cl8] · 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl₃ and Ph₄PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂, [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃, [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃, [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN, [Ph₄P]₄[Bi₆Cl₂₂], and [Ph₄P]₄[Bi₈Cl₂₈]. We report the crystal structure of [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) ų, Z = 2. The anion is formed from two face‐sharing BiCl₆‐octahedra. [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃ crystallises with monoclinic symmetry in the S. G. P2₁/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) ų, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) ų, Z = 2. Two Bi₂Cl₈ dimers in syn‐position form the cubic anion. Lattice parameters of [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ and [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state.     

Cs4BiAs3Se7: A Novel Bismuth‐Selenoarsenate with Infinite [BiAs3Se7]4– Chains Containing Two Different Anions, [AsSe3]3– and trans‐[As2Se4]4–

A new phase has been prepared by methanolothermal reaction of Cs₂CO₃, BiCl₃ and Li₃AsSe₃ at 130 °C for 36 hours. Cs₄BiAs₃Se₇ ( I ) reveals the first Bi‐selenoarsenate polyanionic chain [Bi(As₂Se₄)(AsSe₃)]^4–, consisting of Bi³⁺ ions in a distorted octahedral environment of [AsSe₃]^3– and trans‐[As₂Se₄]^4– units. The latter anion consists of a central “As₂⁴⁺” dumb‐bell whereby two Se atoms are attached to each of the As atoms. Structural Data: Space Group P2₁/n, a = 13.404(4) Å, b = 23.745(8) Å, c = 13.880(4) Å, β = 99.324(6)°, Z = 8.     

The Phase Diagram of the System [Ph4P]Br/BiBr3. Synthesis,Crystal Structure,Thermal Behaviour,and Vibrational Spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 and two Modifications of [Ph4P]4[Bi6Br22]

The phase diagram of the system [Ph₄P]Br/BiBr₃ was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr₃ and [Ph₄P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃, which crystallises with monoclinic symmetry in the S. G. P2₁/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) ų, Z = 4 and the crystal structures of two modifications of the compound [Ph₄P]₄[Bi₆Br₂₂]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) ų, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) ų, Z = 2. Lattice parameters of [Ph₄P]₄[Bi₈Br₂₈] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃ are presented and discussed.     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

Neue Kronenether‐stabilisierte Oxoniumhalogenochalkogenate: [H3O(Dibromo‐benzo‐18‐Krone‐6)]2[Se3Br10] und [H5O2(Bis‐dibromo‐dibenzo‐24‐Krone‐8]2[Se3Br8]

Novel Oxonium Halogenochalcogenates Stabilized by Crown Ethers: [H₃O(Dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] and [H₅O₂(Bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] Two novel complex oxonium bromoselenates(II,IV) and –(II) are reported containing [H₃O]⁺ and [H₅O₂]⁺ cations coordinated by crown ether ligands. [H₃O(dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] ( 1 ) and [H₅O₂(bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] ( 2 ) were prepared as dark red crystals from dichloromethane or acetonitrile solutions of selenium tetrabromide, the corresponding unsubstituted crown ethers, and aqueous hydrogen bromide. The products were characterized by their crystal structures and by vibrational spectra. 1 is triclinic, space group (Nr. 2) with a = 8.609(2) Å, b = 13.391(3) Å, c = 13.928(3) Å, α = 64.60(2)°, β = 76.18(2)°, γ = 87.78(2)°, V = 1404.7(5) ų, Z = 1. 2 is also triclinic, space group with a = 10.499(2) Å, b = 13.033(3) Å, c = 14.756(3) Å, α = 113.77(3)°, β = 98.17(3)°, γ = 93.55(3)°. V = 1813.2(7) ų, Z = 1. In the reaction mixture complex redox reactions take place, resulting in (partial) reduction of selenium and bromination of the crown ether molecules. In 1 the centrosymmetric trinuclear [Se₃Br₁₀]^2? consists of a central Se^IVBr₆ octahedron sharing trans edges with two square planar Se^IIBr₄ groups. The novel [Se₃Br₈]^2? in 2 is composed of three planar trans‐edge sharing Se^IIBr₄ squares in a linear arrangement. The internal structure of the oxonium‐crown ether complexes is largely determined by the steric restrictions imposed by the aromatic rings in the crown ether molecules, as compared to complexes with more flexible unsubstituted crown ether ligands.     

Reaction of Selenium with Bromine in the Presence of Methyltriphenylphosphonium Bromide: Syntheses and Crystal Structures of [PMePh3]2[Se2Br6] and [PMePh3]2[SeBr6(SeBr2)2]

The brown crystals of [PMePh₃]₂[Se₂Br₆] ( 1 ) and red crystals of [PMePh₃]₂[SeBr₆(SeBr₂)₂] ( 2 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of methyltriphenylphosphonium bromide. The crystal structures of 1 and 2 has been determined by the X‐ray methods and refined to R = 0.0373 for 2397 reflections and 0.0397 for 3417 reflections, respectively. The salt 1 crystallizes in the monoclinic space group P2₁/n with the cell dimensions a = 13.202(5) Å, b = 11.954(4) Å, c = 13.418(6) Å, β = 93.08(4)° (193(2)). The crystals of 2 are triclinic, space group with the cell dimensions a = 10.266(3) Å, b = 11.311(3) Å, c = 11.619(2) Å, α = 108.87(2)°, β = 105.72(2)°, γ = 99.40(2)° (193(2) K). In the solid state structure of 1 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square planar SeBr₄ units sharing a common edge through two μ‐bridging Br atoms. The terminal Se^II–Br bonds are 2.3984(11) and 2.4273(11) Å, whereas the bridging μBr–Se^II bonds are 2.7817(11) and 2.9081(12) Å. In the solid state the trinuclear [SeBr₆(SeBr₂)₂]^2? anion of 2 is centrosymmetric too and contains a nearly regular [SeBr₆] octahedron where the four equatorial bromo ligands each have developed bonds to the Se^II atoms of the SeBr₂ molecules. The contacts between the bridging bromo and the Se^II atoms of the SeBr₂ molecules are 3.0603(15) and 3.1043(12) Å, and can be interpreted as bonds of the donor‐acceptor type with the bridging bromo ligands as donors and the SeBr₂ molecules as acceptors. The Se^IV–Br distances are in the range 2.5570(9)–2.5773(11) Å and the Se^II–Br bond lengths in coordinated SeBr₂ molecules – 2.3411(12) and 2.3421(10) Å.     

Darstellung,Schwingungsspektren und Normalkoordinatenanalyse von mer-[OsCl3I(NCS)]2− sowie Kristallstrukturanalyse von zwei Modifikationen des mer-(Ph4As)2[OsCl3I(NCS)2c]

Preparation, Vibrational Spectra, and Normal Cooordinate Analysis of mer-[OsCl₃I(NCS)₂^c]^2? and Crystal Structures of two Modifications of mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] By treatment of cis-/trans-[OsCl₄I₂]^2? or fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane mixtures of different linkage isomers are formed, from which mer-[OsCl₃I(NCS)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. With tetraphenylarsonium ions mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] crystallizes in two different modifications. From acetone solution the high-temperature form α precipitates above ?10°C, the low-temperature form β below, ?65°C. The X-Ray structure determinations on single crystals of α-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.245(5), b = 11.690(5), c = 22.027(5) Å, α = 83.650(5)°, β = 85.734(5)°, γ = 72.566(5)°, Z = 2) and β-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.959(5), b = 11.122(5), c = 21.745(5) Å, α = 97.677(5)°, β = 92.339(5)°, γ = 104.712(5)°, Z = 2) reveal the ordering of the complex anions, which significantly differ in their geometry. The via N coordinated thiocyanate groups exhibit Os? N? C angles of 172.7° and 173.3° (α) and of 164.4° and 175.4° (β). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the complex anion are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.66 and 1.64 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Synthesis and Crystal Structure of Bis(tetraphenylphosphonium) Hexabromo‐diselenate(II)‐bis{dibromodiselenate(I)}, [PPh4]2[Se2Br6(Se2Br2)2], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The Red crystals of [PPh₄]₂[Se₂Br₆(Se₂Br₂)₂] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraphenylphosphonium bromide. The crystal structure of 1 has been determined by X‐ray diffraction and refined to R = 0.0201 for 4024 reflections. The crystals are triclinic, space group with Z = 2 and a = 11.2757(4) Å, b = 12.3347(5) Å, c = 12.4948(5) Å, α = 113.152(4)°, β = 114.745(4)°, γ = 91.208(3)° (120(2) K). In the solid state the anion of 1 is built up of the Se₂Br₆ core and two Se₂Br₂ molecules each of which is linked to one of the trans‐positioned terminal Br_t atoms of the Se₂Br₆ core. The central Se₂Br₆ part consists of a nearly planar arrangement of two planar SeBr₄ units sharing a common edge through two μ₂‐bridging Br atoms. The contact between the Br_t and the Se^I atom of the Se₂Br₂ molecule is 3.0872(5) Å and can be interpreted as a bond of the donor‐acceptor type with the Br_t as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II–Br and μ₂Br–Se^II bond lengths are 2.3654(4), 2.6699(5) Å and 2.5482(5), 3.0265(5) Å, respectively. The bond lengths in the coordinated Se₂Br₂ molecule are: Se^I–Se^I = 2.2686(5) Å, Se^I–Br = 2.3779(5) and 2.3810(5) Å.     

One‐Dimensional Zinc Selenophosphates: A2ZnP2Se6 (A = K,Rb, Cs)

The new compounds A₂ZnP₂Se₆ (A = K, Rb, Cs) were synthesized via molten salt flux syntheses. The crystals feature one‐dimensional ¹/_∞[ZnP₂Se₆]^2– chains charge balanced by alkali metal ions between the chains. K₂ZnP₂Se₆ crystallizes in the monoclinic space group P2₁/c; cell parameters a = 12.537(3) Å, b = 7.2742(14) Å, c = 14.164(3) Å, β = 109.63(3)°, Z = 4, and V = 1216.7(4) ų. Rb₂ZnP₂Se₆ and Cs₂ZnP₂Se₆ are isotypic, crystallizing in the triclinic space group P$\bar{1}$ . Rb₂ZnP₂Se₆ has cell parameters of a = 7.4944(15) Å, b = 7.6013(15) Å, c = 12.729(3) Å, α = 96.57(3)°, β = 105.52(3)°, γ = 110.54(3)°, Z = 2, and V = 636.6(2) ų. Cs₂ZnP₂Se₆ has cell parameters of a = 7.6543(6) Å, b = 7.7006(6) Å, c = 12.7373(11) Å, α = 97.007(7)°, β = 104.335(7)°, γ = 109.241(6)°, Z = 2, and V = 669.54(10) ų.     

Synthesis and Crystal Structure of CpFe(CO)l(η1-Ph2PCH2P(O)Ph2)

CpFe(CO)I(η¹-Ph₂PCH₂P(O)Ph₂) 2 was obtained in small yield from reaction of [CpFe(CO)]₂[μ-(Ph₂P)₂CH₂] with diiodine in benzene, or prepared in 82% yield on treating CpFe(CO)I(η¹-Ph₂PCH₂PPh₂) 1 with H₂O₂. Compound 2 crystallizes in the space group P2₁/n, with a = 8.441(2) Å, b = 10.054(2) Å, c = 33.343(8) Å, β = 92.33(2)°, Z = 4, V = 2827(1) ų, R_F = 0.057, and R_w = 0.056.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Die Kristallstrukturen der Polyselenide [Cs(18-Krone-6)]2Se5 · DMF, [Rb(222-Crypt)]2Se6, [Ba(15-Krone-5)2]Se6 · DMF und [Na(12-Krone-4)2]2Se7

Crystal Structures of the Polyselenides [Cs(18-Crown-6)]₂Se₅ · DMF, [Rb(222-Crypt)]₂Se₆, [Ba(15-Crown-5)₂]Se₆ · DMF, and [Na(12-Crown-4)₂]Se₇ . The title compounds have been prepared by reactions of the corresponding diselenides with excess selenium in the presence of crown ethers in dimethylformamide solutions, forming black crystals. [Cs(18-Crown-6)]₂Se₅ · DMF: Space group P2₁/m, Z = 2, 2 194 observed unique reflections, R = 0.119. Lattice dimensions at 20°C: a = 1 041.2; b = 1 496.3; c = 1 459.7 pm; β = 100.39°. The compound forms an ionic triple with Cs…Se-contacts between 374 and 381 pm. [Rb(222-Crypt)]₂Se₆: Space group P1 , Z = 2, 7 405 observed unique reflections, R = 0.056. Lattice dimensions at – 70°C: a = 1 106.8; b = 1 460.8; c = 1 718.8 pm; α = 89.22°; β = 86.65°; γ = 71.53°. The compound contains Se₆^2? chains without direct contact with each other. [Ba(15-Crown-5)₂]Se₆ · DMF: Space group P2₁/n, Z = 4, 2 680 observed unique reflections, R = 0.055. Lattice dimensions at – 80°C: a = 1 051.9; b = 1 322.4; c = 2 729.9 pm; β = 100.93°. The compound contains Se₆^2? chains, which are isolated from each other by the cations and the included DMF molecules. [Na(12-Crown-4)₂]₂Se₇: Space group P1 , Z = 2, 7 313 observed unique reflections, R = 0.042. Lattice dimensions at – 70°C: a = 1 260.9; b = 1 433.6; c = 1 462.9 pm; α = 80.27°; β = 78.60°; γ = 69.34°. The compound contains Se₇^2? chains without direct contacts with each other.     

(CuBr)3P4Se4: A Low Symmetric Variant of the (CuI)3P4Se4 Structure Type

Bright orange (CuBr)₃P₄Se₄ is obtained from the reaction of CuBr, P, and Se in stoichiometric amounts (CuBr : P : Se = 3 : 4 : 4). The composition and the crystal structure of the compound were determined from single crystal X‐ray diffraction data. Lattice constants are a = 33.627(2) Å, b = 6.402(1) Å, c = 19.059(1) Å, β = 90.19(3) °, V = 4103.2(3) ų, and Z = 12. The compound crystallizes in a structure that is related to (CuI)₃P₄Se₄. Cages of β‐P₄Se₄ are stacked along the b‐axis and are separated by columns of copper(I) bromide. However, the coordination of the β‐P₄Se₄ cage molecules to the copper atoms in the CuBr columns in (CuBr)₃P₄Se₄ is quite different from (CuI)₃P₄Se₄. The monoclinic compound (space group: P2₁, no. 4) has an almost orthorhombic metric in combination with a threefold superstructure in [100]. Structural aspects of (CuBr)₃P₄Se₄ are discussed with respect to the heavier homologue (CuI)₃P₄Se₄.     

Li6+2x[B10Se18]Sex (x ≈ 2), ein ionenleitendes Doppelsalz

Li_6+2x[B₁₀Se₁₈]Se_x (x ≈ 2), an Ion‐conducting Double Salt Li_6+2x[B₁₀Se₁₈]Se_x (x ≈ 2) was prepared in a solid state reaction from lithium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 800 °C. Subsequent cooling from 600 °C to 300 °C gave amber colored crystals with the following lattice parameters: space group I2/a (at 173 K); a = 17.411(1) Å, b = 21.900(1) Å, c = 17.820(1) Å, β = 101.6(1)°. The crystal structure contains a well‐defined polymeric selenoborate network of composition ([B₁₀Se₁₆Se_4/2]^6?)_n consisting of a system of edge‐sharing [B₁₀Se₁₆Se_4/2] adamantanoid macro‐tetrahedra forming large channels in which a strongly disorderd system of partial occupied Li⁺ cations and additional disordered Se^2? anions is observed. The crystal structure of the novel selenoborate is isotypic to Li_6+2x[B₁₀S₁₈]S_x (x ≈ 2) [1]. X‐ray and ⁷Li magic‐angle spinning NMR data suggest that the site occupancies of the three crystallographically distinct lithium ions exhibit a significant temperature dependence. The lithium ion mobility has been characterized by detailed temperature dependent NMR lineshape and spin‐lattice relaxation measurements.     

[Ga(en)3][Ga3Se7(en)] · H2O: Ein Galliumchalkogenid mit Ketten aus [Ga3Se6Se2/2(en)]3–-Bicyclen

[Ga(en)₃][Ga₃Se₇(en)] · H₂O: A Gallium Chalcogenide with Chains of [Ga₃Se₆Se_2/2(en)]^3– Bicycles The new selenidogallate [Ga(en)₃][Ga₃Se₇(en)] · H₂O ( I ) was produced from a ethylendiamine suspension of Ga and Se at 130 °C. I crystallizes in the orthorhombic space group Pna2₁ with unit constants a = 1347.9(3) pm, b = 961.6(1) pm, c = 1967.6(4) pm and Z = 4. The crystal structure contains an anion so far not observed in gallium chalcogenides. It is built from [Ga₃Se₆Se_2/2(en)]^3– bicycles of three Ga^IIIL₄ tetrahedra (L = en, Se) connected via selenium corners to linear chains. The cations, Ga^III ions coordinated by three ethylendiamine in a distorted octahedral geometry are positioned in the holes of the hexagonal rod packing of these chains.     

Metall-Schwefelstickstoff-Verbindungen. 22. S4N3Cl als Ausgangsprodukt zur Herstellung von Komplexen mit dem S3N−-Liganden Die Komplexe [Ph6P2N][Cu3(S3N)2(CN)2]und [Ph4As][(CuS3N)2(CN)]

The reaction of S₄N₃Cl with metal salts leads to complexes containing the S₃N^?chelating ligand, a reaction which proceeds smoothly especially in an alkaline medium. Thus we were able to prepare, by the reaction of CuCN with S₄N₃Cl and [Ph₆P₂N]OH (Ph = phenyl), the salt [Ph₆P₂N][Cu₃(S₃N)₂(CN)₂], a compound in which the anions build a bidimensional network through supplementary Cu - S contact interactions. The salt is monoclinic, space group C2/c, a = 18.960, b = 14.651 and c = 15.400 Å, β = 101.03° and Z = 4. Metal Sulfur Nitrogen Compounds. 22. S₄N₃Cl as a Starting Compound for the Preparation of Complexes Containing the S₃N^? Ligand. Complexes [Ph₆P₂N] [Cu₃(S₃N)₂ (CN)₂] and [Ph₄As] [(CuS₃N)₂ (CN)] In contrast, the reaction of CuN with S₄N₃Cl and [Ph₄As]OH led to the compound [Ph₄As][(CuS₃N)₂(CN)], monoclinic, space group C2/c, a = 18.478, b = 6.405, c = 27.051 Å, β = 119.50°, Z = 4. In the centrosymmetric anion the two Cu(S₃N) groups are linked together by disordered CN^? groups. An additional linkage results from Cu - Cu contact interactions, with d = 2.84 Å.     

Three Crystal Structures,One Chemical Formula – Barium Dihydrogen‐hypodiphosphate(IV)‐dihydrate,BaH2P2O6·2H2O

Three polymorphs of barium dihydrogen‐hypodiphosphate(IV)‐dihydrate, BaH₂P₂O₆ · 2H₂O ( A , B and C ), were obtained and structurally characterized by single‐crystal X‐ray diffraction. A crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 7.459(1) Å, b = 8.066(1) Å, c = 12.460(2) Å, β = 91.27(1) ° and Z = 4. B crystallizes in the monoclinic space group C2/c (no. 15) with a = 11.049(8) Å, b = 6.486(3) Å, c = 10.956(6) Å, β = 106.89(5) ° and Z = 4. C crystallizes in the orthorhombic space group C222₁ (no. 20) with a = 9.193(3) Å, b = 6.199(2) Å, c = 12.888(4) Å and Z = 4. Discrete [H₂P₂O₆]^2– units, barium cations and water molecules, held together by intermolecular hydrogen bonds of the type O–H ··· O, build up the structures of the three polymorphs. The phase purity of A and C was verified by powder diffraction measurements.