(C2H10N2)[BPO4F2] — Structural Relations between [BPO4F2]2— and [Si2O6]4—

(C₂H₁₀N₂)[BPO₄F₂] — Strukturbeziehungen zwischen [BPO₄F₂]^2— und [Si₂O₆]^4— Colourless crystals of (C₂H₁₀N₂)[BPO₄F₂] were prepared from mixture of ethylendiamine, H₃BO₃, BF₃ · C₂H₅NH₂, H₃PO₄ and HCl under mild hydrothermal conditions (220 °C). The crystal structure was determined by single crystal methods (triclinic, P1¯ (no. 2), a = 451.85(5) pm, b = 710.20(8) pm, c = 1210.2(2) pm, α = 86.08(1)°, β = 88.52(2)°, γ = 71.74(1)°, Z = 2) and contains infinite tetrahedral zweier‐single‐chains {[BPO₄F₂]^2—} which are isoelectronic (48e^—) with the polyanions {[Si₂O₆]^4—} of the pyroxene family.     

Ba[CoN]: Ein niedervalentes Nitridocobaltat mit gewinkelten Ketten [CoN2/22−]

Ba[CoN]: A Low-Valency Nitridocobaltate with Angled Chains [CoN_2/2^2?] Ba[CoN] is prepared by reaction of barium and cobalt (molar ratio Ba : Co = 1 : 2.5) in tantalum crucibles at 870°C with flowing nitrogen (1 atm) within a period of 96 h. After cooling down to room temperature (24°C/h) black single crystals of the ternary phase with a platy habit are obtained (orthorhombic, Pnma; a = 959.9(2) pm, b = 2 351.0(3) pm, c = 547.6(2) pm; Z = 20). The crystal structure of Ba[CoN] contains angled (planar) chains [CoN_2/2^2?] which run along the [010]-direction (N? Co? N[°]: 178.5(5), 179.6(6), 180.0; Co? N? Co[°]: 82.9(6), 84.2(5), 177.1(8); Co? N[pm]: 174.6(12), 177.2(12), 181.9(13), 184.3(13), 187.1(12)). Nitrogen is in an octahedral coordination (N Ba₄Co₂) and is arranged in a distorted cubic close packing. Barium occupies one half of the tetrahedral holes (Ba? N[pm]: 274.8(16) ? 308.2(12)). The cis-positions of the Co-atoms at the nitrogen coordination-octahedra cause short Co? Co contacts within the chains [CoN_2/2^2?]. Through this, Co₂-units (Co? Co[pm]: 247.8(4); bridged by nitrogen) and linear Co₃-groups (Co? Co [pm]: 245.5(2); Co? Co? Co[°]: 180.0; bridged by nitrogen) alternate along the chains. The crystal structure of Ba[CoN] is closely related to the Ba[NiN] type structure.     

Einkristalle von CuPrS2 im A— und Pr2S3 im C—Typ bei Versuchen zur Synthese ternärer Kupfer(I)—Praseodym(III)—Sulfide

Single Crystals of A—type CuPrS₂ and C—type Pr₂S₃ from Attempts to Synthesize Ternary Copper(I) Praseodymium(III) Sulfides Coarse, yellowish‐green single crystals of the ternary copper(I) praseodymium(III) sulfide CuPrS₂ form within seven days at 800°C by oxidation of elemental copper and praseodymium with sulfur (molar ratio: 1:1:2) in evacuated silica tubes when equimolar quantitites of CsCl are present as flux. Attempts to synthesize CuPr₃S₅ or CuPr₅S₈ under analogous conditions always yield two‐component mixtures of CuPrS₂ and Pr₂S₃ (C type) instead of the desired target compounds. The crystal structure of CuPrS₂ (monoclinic, P2₁/c; a = 655.72(6), b = 722.49(6), c = 686.81(6)pm, β = 98.686(7)°; Z = 4) exhibits undulated layers {[Cu(S1)_3/3(S2)_1/1]^3—} parallel (100) which consist of vertex‐linked pairs of two [CuS₄]^7— tetrahedra ([Cu₂S₆]^10—) sharing a common edge. Their three‐dimensional cross‐linkage is achieved by Pr³⁺ cations in monocapped trigonal prismatic coordination of seven S^2— anions each. The metal sulfur distances in the [CuS₄] units cover with 233 (Cu—S2) and 236 (Cu—S1) as well as 247 (Cu—S1′) and 248pm (Cu—S1″) a rather broad interval, whereas those (Pr—S: 284—304 pm) within the [PrS₇] polyhedra lie relatively closer together. According to Pr_2.677□_0.333S₄ (with Z = 4), C—Pr₂S₃ crystallizes in a cation‐deficient Th₃P₄‐type structure (cubic, I4¯3d; a = 857.68(7) pm; Z = 5.333 for Pr₂S₃). In conformity with the Niggli formula {PrS_8/5.333} Pr³⁺ is surrounded trigon‐dodecahedrally by eight S^2— at distances of 287 (4×) and 307pm (4×). Neither the X‐ray single‐crystal structure refinement nor electron‐beam microprobe analyses leave any evidence for the incorporation of Cu⁺ cations into this crystal structure.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Thiosilicate der Selten‐Erd‐Elemente: I. Die isotypen Verbindungen KCe[SiS4] und Eu2[SiS4]

Thiosili‐Thiosilicates of the Rare‐Earth Elements: I. The Isotypic Compounds KCe[SiS₄] and Eu₂[SiS₄] Both isotypic thiosilicates KCe[SiS₄] (a = 649.15(6), b = 656.18(6), c = 863.96(8) pm, β = 107.531(9)°) and Eu₂[SiS₄] (a = 651.71(6), b = 659.54(6), c = 821.93(8) pm, β = 108.437(9)°) crystallize monoclinically in the space group P2₁/m and Z = 2. By the reaction of KCl, Ce₂S₃ and SiS₂ in the ratio 1 : 1 : 1 using a sixfold molar amount of KCl as flux in evacuated silica tubes (7 d, 850°C) brownish yellow, plate‐shaped single crystals, resistant both to air and water are obtained. The conversion of Eu, S and SiS₂ in molar ratios of 2 : 2 : 1 with an excess of CsCl as flux in evacuated silica tubes (7 d, 850°C) leads to deep red, plate‐shaped single crystals, which remain air‐ and water‐stable for a few days. The crystal structure contains isolated ortho‐thiosilicate units, that together with the Ce³⁺ or (Eu2)²⁺ cations build corrugated anionic layers parallel (001) according to {(Ce[SiS₄])^—} and {(Eu2[SiS₄])^2—}, respectively. These layers are alternatingly piled with cationic layers consisting solely of K⁺ or (Eu1)²⁺ cations. The latter show coordination numbers of eight in the shape of a bicapped trigonal prism, whereas the cations of the position Ce³⁺ and (Eu2)²⁺ have a (2+1)‐fold capped trigonal prismatic environment with a coordination number of 8+1. The comparison of both compounds KCe[SiS₄] and Eu₂[SiS₄] (≡ EuEu[SiS₄]) demonstrates, that Eu²⁺ is able to substitute both K⁺ and Ce³⁺ isomorphically.     

Preparation and Crystal Structure of Li4[TaN3]

The new lithium nitridotantalate(V), Li₄[TaN₃], was prepared by reaction of Li₁₅[CrN₄]₂N with the wall of a welded Ta ampoule in the presence of metallic Li at 1470 K. Li₄[TaN₃] forms colourless single crystals (platelets, space group Ibca, No. 73, a = 491.85(4) pm, b = 973.59(6) pm, c = 1415.0(1) pm, Z = 8, R1 = 0.0288). The crystal structure is described as Li₂O superstructure with ordered occupation of the tetrahedral sites by Li and Ta. The resulting arrangement leads to infinite chains [TaN₂N_2/2^4—] running along [100].     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

Die Schichtstruktur von Tl[CuAsO4] und Tl[CuPO4] mit Zwischenschichten aus Thallium(I) mit stereoaktivem Elektronenpaar

The Layer Structure of Tl[CuAsO₄] and Tl[CuPO₄] with Layers of Thallium(I) with Stereoactive Lone Pair Single crystals of Tl[CuAsO₄] and Tl[CuPO₄] were prepared by reaction of oxygen with Tl/Cu/As and Tl/Cu/P alloys, respectively. The new isotypic compounds crystallize in spacegroup C2/c with Z = 8 and lattice constants a = 684.70(7) pm, b = 712.64(5) pm, c = 1822.4(2) pm, β = 92.76(1)° for Tl[CuAsO₄] and a = 671.57(8) pm, b = 697.09(6) pm, c = 1789.1(2) pm, β = 93.12(1)° for Tl[CuPO₄]. Square planar [CuO₄]-units are connected by common corners to form undulated [CuO₃]₂-chains running along [010]. Interconnection of the chains by arsenate or phosphate groups results in the formation of anionic cuprate-arsenate- and cuprate-phosphate-slabs, respectively. Along [001] these slabs are alternating with double layers of thallium(I) ions in which the stereochemical activity of the Tl⁺ lone pair is apparent from an hemispheric coordination of thallium by oxygen. The structure is related to that of the orthorhombic form of KCuPO₄.     

Ho2O[SiO4] und Ho2S[SiO4]: Zwei Chalkogenid‐Derivate von Holmium(III)‐ortho‐ Oxosilicat

Ho₂O[SiO₄] and Ho₂S[SiO₄]: Two Chalcogenide Derivatives of Holmium(III) ortho‐Oxosilicate Ho₂O[SiO₄] crystallizes monoclinically with the space group P2₁/c (a = 904.15(9), b = 688.93(7), c = 667.62(7) pm, β = 106.384(8)°, Z = 4) in the A‐type structure of rare‐earth(III) oxide oxosilicates. Yellow platelet‐shaped single crystals were obtained as by‐product during an experiment to synthesize Ho₃Cl[SiO₄]₂ by reacting Ho₂O₃ and SiO₂ in the ratio 4 : 6 with an excess of HoCl₃ as flux at 1000 °C for seven days in evacuated silica ampoules. Both crystallographically different Ho³⁺ cations show coordination numbers of 8+1 and 7 with coordination figures of 2+1‐fold capped trigonal prisms and octahedra, in which one of the vertices changes to an edge by two instead of one coordinating atoms, respectively. The O^2— anion not linked to silicon is surrounded tetrahedrally by four Ho³⁺ cations which built a layer parallel (100) by vertex‐ and edge‐sharing of the [OHo₄]¹⁰⁺ units according to {[(O5)(Ho1)_1/1(Ho2)_3/3]⁴⁺}. Within rhombic meshes of these layers the isolated oxosilicate tetrahedra [SiO₄]^4— come to lie. Ho₂S[SiO₄] crystallizes orthorhombically in the space group Pbcm (a = 605.87(5), b = 690.41(6), c = 1064.95(9) pm, Z = 4). It also emerged as a single‐crystalline by‐product obtained during the synthesis of Ho₂OS₂ by reaction of a mixture of Ho₂O₃, Ho and S with the wall of the evacuated silica tube used as container with an excess of CsCl as flux at 800 °C. The structure of the yellow platelet‐shaped, air and water resistant crystals also distinguishes two Ho³⁺ cations with bicapped trigonal prisms and trigondodecahedra as coordination polyhedra for CN = 8. The S^2— anions are almost square planar surrounded by four Ho³⁺ cations, but situated completely outside this plane. The [SHo₄]¹⁰⁺ squares form strongly corrugated layers perpendicular to [100] by corner‐sharing according to {[(S)(Ho1)_2/2(Ho2)_2/2]⁴⁺}. Contrary to the oxide oxosilicates the isolated oxosilicate tetrahedra [SiO₄]^4— do not lie within the rhombic meshes of these layers, but above and below the (Ho2)³⁺ cations while viewing along [100].     

Quaternäre Caesium‐Kupfer(I)‐Lanthanoid(III)‐Selenide vom Typ CsCu3M2Se5 (M = Sm,Gd — Lu)

Quaternary Cesium Copper(I) Lanthanoid(III) Selenides of the Type CsCu₃M₂Se₅ (M = Sm, Gd — Lu) By oxidation of mixtures of copper and lanthanoid metal with elemental selenium in molar ratios of 1 : 1 : 2 and in addition of CsCl quaternary cesium copper(I) lanthanoid(III) selenides with the formula CsCu₃M₂Se₅ (M = Sm, Gd — Lu) were obtained at 750 °C within a week from torch‐sealed evacuated silica tubes. An excess of CsCl as flux helps to crystallize golden yellow or red, needle‐shaped, water‐resistant single crystals. The crystal structure of CsCu₃M₂Se₅ (M = Sm, Gd — Lu) (orthorhombic, Cmcm, Z = 4; e. g. CsCu₃Sm₂Se₅: a = 417.84(3), b = 1470.91(8), c = 1764.78(9) pm and CsCu₃Lu₂Se₅: a = 407.63(3), b = 1464.86(8), c = 1707.21(9) pm, respectively) contains [MSe₆]^9— octahedra which share edges to form double chains running along [100]. Those are further connected by vertices to generate a two‐dimensional layer parallel to (010). By edge‐ and vertex‐linking of [CuSe₄]^7— tetrahedra two crystallographically different Cu⁺ cations build up two‐dimensional puckered layers parallel to (010) as well. These sheet‐like structure interconnects the equation/tex2gif-stack-3.gif{[M₂Se₅]^4—} layers to create a three‐dimensional network according to equation/tex2gif-stack-4.gif{[Cu₃M₂Se₅]^—}. Thus empty channels along [100] form, apt to take up the Cs⁺ cations. These are surrounded by eight plus one Se^2— anions in the shape of (2+1)‐fold capped trigonal prisms with Cs—Se distances between 348 and 368 pm (8×) and 437 (for M = Sm) or 440 pm (for M = Lu), respectively, for the ninth ligand.     

Synthese und Struktur von MII[AuF4]2 (MII  Cd,Hg)

Synthesis and Structure of M^II[AuF₄]₂ (M^II ? Cd, Hg) Cd[AuF₄]₂ and the isotypic compound Hg[AuF₄]₂, both are yellow, crystallize tetragonal in the space-group P4/mcc-D (No. 124) with a = 575.0/575.6 pm, c = 1034.8/1042.3 pm and Z = 2. The single-crystals were obtained by solid-state reactions in goldtubes.     

Darstellung und Struktur der Tetrafluoroaurate(III) MI[AuF4] mit MI = Li,Rb

Synthesis and Structure of Tetrafluoroaurates(III) M^I[AuF₄] with M^I = Li, Rb Single crystal investigations on Rb[AuF₄], light yellow, confirm the tetragonal unit cell (K[BrF₄]-type) with a = 618.2(1) and c = 1191(1) pm, Z = 4, space group I 4/mcm-D (No. 140). Li[AuF₄], light yellow too, crystallizes monoclinic with a = 485.32(7), b = 634.29(8), c = 1004.43(13) pm, β = 92.759(12), Z = 4; space group P 2/c-C (No. 13). The structure of Li[AuF₄] is related to the Rb[AuF₄]-type of structure.     

Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 — zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]XX

Cs₄[Sc₆C]Cl₁₃ and Cs₄[Pr₆(C₂)]I₁₃ — Two Examples for the Missing Link in the Connectivity of [M₆Z]X X Building Units Cs₄[Sc₆C]Cl₁₃ (tetragonal, I4₁/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, R_w = 0.026) and Cs₄[Pr₆(C₂)]I₁₃ (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, R_w = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl₃ and PrI₃, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc₆C] and [Pr₆(C₂)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xⁱ and 6 X^a; X = Cl or I). The connection is carried out via the motif [M₆Z]XXXX (M = Sc and Pr; Z = C and C₂, respectively) and is thereby the missing link of the motifs of connection for the composition A_x[M₆Z]X₁₃. Analogous interconnection of [TiO₆] octahedra is found in the anatase-type of structure of TiO₂.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

LaCl(BO2)2 und Er2Cl2[B2O5]: Zwei Chlorid‐Oxoborate dreiwertiger Lanthanide

LaCl(BO₂)₂ and Er₂Cl₂[B₂O₅]: Two Chloride Oxoborates of Trivalent Lanthanides Er₂Cl₂[B₂O₅] is obtained as single crystals by the reaction of ErCl₃, Er₂O₃ and B₂O₃ with an excess of ErCl₃ as flux in evacuated silica tubes after two weeks at 850 °C. The compound crystallizes as long, pale pink needles and appears to be air‐ and water‐resistant. Single‐crystalline LaCl(BO₂)₂ emerges from the reaction of La₂O₃, LaCl₃, and B₂O₃ with an excess of B₂O₃ as flux in evacuated silica tubes after four weeks at 900 °C. LaCl(BO₂)₂ crystallizes as thin, colourless, air‐ and water‐resistant needles which tend to severe twinning due to their fibrous habit. The crystal structure of Er₂Cl₂[B₂O₅] (orthorhombic, Pbam; a = 1489.65(9), b = 1004.80(6), c = 524.86(3) pm; Z = 4) contains two crystallographically different erbium cations. (Er1)³⁺ resides in pentagonal‐bipyramidal coordination of seven anions while (Er2)³⁺ is surrounded by only six anions with the shape of an octahedron. The planar oxodiborate units [B₂O₅]^4— consisting of two vertex‐shared [BO₃]^3— triangles are isolated according to {([BOO]₂)^4—}. LaCl(BO₂)₂ crystallizes isostructurally with PrCl(BO₂)₂ in the triclinic space group P1¯ (a = 423.52(4), b = 662.16(7), c = 819.33(8) pm; α = 82.081(8), β = 89.238(9), γ = 72.109(7)°; Z = 2). The characteristic unit consists of endless chains built up by corner‐linked [BO₃]^3— triangles. These quasi‐planar zigzag chains of the composition {[(B1)OO(B2)OO]^2—} (≡ {[BO₂]^—} run parallel [100]. The La³⁺ cations exhibit coordination numbers of ten and are coordinated by three Cl^— and seven O^2— anions.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Cs[Er10(C2)2]I18 und [Er10(C2)2]Br18: zwei neue Beispiele für „reduzierte”︁ Halogenide der Lanthanide mit isolierten [M10(C2)2]-Clustern

Cs[Er₁₀(C₂)₂]I₁₈ and [Er₁₀(C₂)₂]Br₁₈: Two New Examples for Reduced Halides of the Lanthanides with Isolated [M₁₀(C₂)₂] Clusters Cs[Er₁₀(C₂)₂]I₁₈ is obtained from the reaction of ErI₃ with caesium and carbon in sealed tantalum containers at 700°C and [Er₁₀(C₂)₂]Br₁₈ through the metallothermic reduction of ErBr₃ with rubidium in the presence of carbon at 750°C in sealed niobium containers. The crystal structures {Cs[Er₁₀(C₂)₂]I₁₈: triclinic, P1 ; a = 1 105.2(8) pm, b = 1 112.0(7) pm; c = 1 122.9(8) pm; α = 66.91(3)°, β = 87.14(3)°; γ = 60.80(3)°; Z = 1; R = 0.049, R_w = 0.043; [Er₁₀(C₂)₂]Br₁₈: monoclinic, P2₁/n, a = 971.8(6) pm, b = 1 623.4(9) pm, c = 1 163.8(6) pm, β = 104.00(6)°; Z = 2; R = 0.077, R_w = 0.057} contain isolated dimeric [Er₁₀(C₂)₂] clusters. Due to the inclusion of C₂ units, the octahedra are elongated in the direction of the pseudo C₄ axis. The connecting edges of the two octahedra are exceptionally short (316.7 pm and 314.8 pm respectively). The dimeric units are connected via X^i?a and X^a?i (X = Br, I) bridges according to [Er₁₀(C₂)₂XX]X. Cs⁺ is surrounded by a cuboctahedron of iodide ions in Cs[Er₁₀(C₂)₂]I₁₈.     

Synthese und Strukturuntersuchungen von Iodocupraten(I). XV Iodocuprate(I) mit solvatisierten Kationen: [Li(CH3CN)4][Cu2I3] und [Mg{(CH3)2CO}6][Cu2I4]

Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH₃CN)₄] [Cu₂I₃] and [Mg{(CH₃)₂CO}₆][Cu₂I₄] [Li(CH₃CN)₄][Cu₂I₃] 1 and [Mg((CH₃)₂CO)₆][Cu₂I₄] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI₂ in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH₃CN)₄]⁺ cations are located between rod packings of CuI₄ tetrahedra double chains [(CuI_2/2I_2/4)₂]^? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P2₁/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH₃)₂CO)₆]²⁺ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu₂I₄]^2? occupy holes in the trigonal prismatic channels formed by the cations.     

Zur Insertion in die Lanthanoid–Kohlenstoffbindung Synthese und Struktur von [CpSm(C6H5CH2NNO)]2 und [K(18-Krone-6)CpYb(NCS)2]∞

On the Insertion into the Lanthanide–Carbon Bond. Synthesis and Structure of [Cp Sm(C₆H₅CH₂NNO)]₂ and [K(18-crown-6)Cp Yb(NCS)₂]_∞ The compound [CpSm(CH₂C₆H₅)(thf)] was investigated, regarding its reactions with small molecules. The main subject was to detect an insertion into the Ln–C bond. With N₂O an insertion reaction is observed, yielding the dimer [CpSm(C₆H₅CH₂NNO)]₂ ( 1 ). The structural data of 1 was collected by a single crystal X-Ray diffraction analysis. (Space group P 1, Z = 1, a = 982.8(2) pm, b = 1052.2(2) pm, c = 1383.8(3) pm, α = 89.29(3)°, β = 73.64(3)°, γ = 66.41(3)°). In the dimer, the two Samarium ions are linked via an (η¹ : η²) bridge by two benzyl diazotato ligands. A nearly planar six-membered central Sm₂N₂O₂-ring is formend. Two pentamethylcyclopentadienyl ligands complete the coordination sphere of each Samarium ion, which are thus surrounded by four ligands each and have a distorted tetrahedral coordination geometry. An insertion of a SCN^– fragment in the Ln–C bond could not be observed. The substitution of the benzyl ligand leads to a polymeric chain structure. The new compound [K(18-crown-6)CpYb(NCS)₂]_∞ 2 contains a tetrahedrally coordinated Yb(III)-ion. (Space group P2₁/n}, Z = 4, a = 1640.6(3) pm, b = 1482.2(3) pm, c = 1674.5(3) pm, β = 102.82(1)°).     

K2NdP2S7: A Mixed‐Valent Neodymium(III) Thiophosphate According to K4Nd2[PS4]2[P2S6] with Discrete [PS4]3– and [S3P–PS3]4– Anions

Pale blue, lath‐shaped single crystals of K₂NdP₂S₇ (≡ K₄Nd₂[PS₄]₂[P₂S₆]; monoclinic, P2₁/n, a = 904.76(8), b = 677.38(6), c = 1988.7(2) pm, β = 97.295(5)°, Z = 2) are obtained by the reaction of Nd, S and P₂S₅ with an excess of KCl as a flux in evacuated silica tubes at 750 °C (7 d) which should produce Nd[PS₄] instead. Beside isolated [PS₄]^3– tetrahedra, the crystal structure contains discrete ethane‐analogous [P₂S₆]^4– (≡ [S₃P–PS₃]^4–) units in staggered conformation with tetravalent phosphorus cations and a P–P distance of 219 pm. The two crystallographically different potassium cations show coordination numbers of nine and ten in the shape of distorted mono‐ and bicapped square antiprisms. Finally, the Nd³⁺ cations are surrounded by eight sulfur atoms arranged as (uncapped) square antiprisms. The entire structure is dominated by (K1)⁺ containing {(Nd₂[PS₄]₂[P₂S₆])^4–} layers parallel (101) which are three‐dimensionally interconnected by (K2)⁺ cations.