Tetrafluoroaurate(III) der Lanthaniden MF[AuF4]2 (M = Tm,Yb, Lu)

Tetrafluoroaurates(III) of Lanthanides MF[AuF₄]₂ (M = Tm, Yb, Lu) . Tetrafluoroaurates(III) MF[AuF₄]₂ with M = Tm, Yb, Lu, all yellow, have been prepared for the first time. From single crystal data they crystallize orthorhombic, space group Pbcn-D (No. 60) with M = Tm: a = 1 102.92(8) pm, b = 904.38(8) pm, c = 2 164.46(23) pm; M = Yb: a = 1 100.98(12) pm, b = 902.23(8) pm, c = 2 157.36(23) pm; M = Lu: a = 1 099.28(18) pm, b = 900.70(15) pm, c = 2 151.50(46) pm.     

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.     

Synthese und Struktur neuer Tetrafluoroaurate(III), TlF2[AuF4], M2F[AuF4]5 (M = Bi,La, Y) und Sm[AuF4]3

Synthesis and Structure of Tetrafluoroaurates(III), TlF₂[AuF₄], M₂F[AuF₄]₅ (M = Y, La, Bi), Sm[AuF₄]₃ with an Appendix on Sm[AuF₄]₂ In the system MF₃/AuF₃ the structures of several yellow Tetrafluoroaurates(III) have been determinated. TlF₂[AuF₄] crystallizes tetragonal, space group P4₁2₁2 – D (Nr. 92) with a = 573.17(4) pm, c = 2780.4(3) pm, Z = 8; M₂F[AuF₄]₅ (M = Bi, La) tetragonal, space group P4₁2₁2 – D (Nr. 92) with a = 822.89(5) pm, c = 2557.1(3) pm, Z = 4 (Bi); with a = 836.80(3) pm, c = 2602.2(2) pm, Z = 4 (La); Y₂F[AuF₄]₅ monoclin, space group P2/n – C (Nr. 13) with a = 1188.9(3) pm, b = 797.4(2) pm, c = 895.7(3) pm, β = 89.18(3), Z = 4 and Sm[AuF₄]₃ trigonal, space group R3c – D (Nr. 167) with a = 1034.5(1) pm, c = 1614.1(3) pm, Z = 6. All these yellow crystals have been obtained by solid state reactions in autoclaves or sealed goldtubes.     

Fluoroplatinate(IV) der Lanthaniden LnF[PtF6]. (Ln = Pr,Sm, Gd,Tb, Dy,Ho, Er)

Fluoroplatinates(IV) of the Lanthanides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er) For the first time fluorides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er), all yellow have been obtained. From single crystal data they crystallize monoclinic, space group P2₁/n?C (No. 14), Z = 4, Pr: a = 1 125.77(19) pm, b = 559.04(7) pm, c = 910.27(17) pm, β = 107.29(1)°; Sm: a = 1 114.63(31) pm, b = 552.70(12) pm, c = 898.02(20) pm, β = 107.24(2)°; Gd: a = 1 112.12(15) pm, b = 551.22(7) pm, c = 891.99(11) pm, β = 107.09(1)°; Tb (Powder data): a = 1 108.88(20) pm, b = 552.71(9) pm, c = 889.56(16) pm, β = 107.30(1)°; Dy: a = 1 100.28(23) pm, b = 547.77(8) pm, c = 882.41(13) pm, β = 107.32(1); Ho: a = 1 099.11(16) pm, b = 546.16(7) pm, c = 879.45(15) pm, β = 107.34(1)°; Er: a = 1 095.10(16) pm, b = 544.82(10) pm, c = 874.85(14) pm, β = 107.37(1)°.     

Zur Kristallstruktur von La[AuF4]3, dem Anfangsglied der Reihe M[AuF4]3−xFx (x = 0, 0,5 und 1)

On the Crystal Structure of La[AuF₄]₃, the Final Link in the Series M[AuF₄]_3?xF_x (x = 0, 0.5 and 1) Yellow La(AuF₄)₃ was prepared for the first time in form of single crystals and investigated by X-ray methods. It crystallizes in space group R3 c-D (Nr. 167) with a = 1056.2(2) pm, c = 1633.7(8) pm, Z = 6.     

New Ternary Phosphides Ln25Ni49P33 (Ln = Ce,Pr, Nd,Sm, Gd,Tb, Dy,Ho, Er)

New ternary phosphides Ln₂₅Ni₄₉P₃₃ (Ln = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er) have been synthesized by arc melting of pure components. Crystal structure has been determined for Sm₂₅Ni₄₉P₃₃ using X‐ray powder diffraction data and the Rietvelt method: P6m2, a = 22.096(4), c = 3.8734(9) Å, R = 0.096. Crystal structure of Sm₂₅Ni₄₉P₃₃ is of a new type and belongs to large family of ternary compounds with trigonal‐prismatic coordination of the smallest size atoms and metal to nonmetal ratio equal or close to 2 : 1. It is a member of homologous subseries of the compounds with unit cell contents described by general chemical formula R M X . Lattice parameters of the isotypic compounds Ln₂₅Ni₄₉P₃₃ have been refined using X‐ray powder diffraction data.     

Neue Verbindungen zum BaNiNd2O5-Typ: BaNiLn 2O5 (Ln=Sm,Gd, Ho,Er, Tm)

Five new compounds of the BaNiNd₂O₅-type with the rare earth elements Sm, Gd, Ho, Er, Tm are prepared and examined by X-ray single crystal technique. The atomic parameters are refined by least-square methods. The crystal chemical differences in the surrounding of rare earth ions in BaMLn ₂O₅-compounds (M=Pt, Pd, Cu, Ni) are discussed.

     

Synthese und Struktur von Silber(II)-tetrafluoroaurat(III) Ag[AuF4]2

Synthesis and Structure of Silver(II) Tetrafluoroaurate(III) Ag[AuF₄]₂ Intensive green single crystals of Ag[AuF₄]₂ can be obtained by heating up micro crystalline Ag[AuF₄]₂ in autoclaves (p(F₂) ～ 200 bar, T ～ 400°C, t ～ 14 d). It crystallizes monoclinic, space group P2₁/n ? C; (No. 14) with a = 522.3(1), b = 1101.3(3), c = 550.5(2) pm, β = 94.98(3), Z = 2 and is isotypic with Pd[AuF₄]₂.     

Crystal Structure of the RE2PbS4 (RE = Y,Dy, Ho,Er, and Tm) Compounds and a Comparison with the Crystal Structures of other Rare Earth Lead Chalcogenides

The crystal structure of the RE₂PbS₄ (RE = Y, Dy, Ho, Er and Tm) compounds (space group Cmc2₁, Pearson symbol oC112, a = 0.79301(3) nm, b = 2.86966(9) nm, c = 1.20511(5) nm, R_Bragg = 0.0979 for Y₂PbS₄; a = 0.79484(8) nm, b = 2.8721(3) nm, c = 1.2039(1) nm, for Dy₂PbS₄; a = 0.79081(2) nm, b = 2.86222(7) nm, c = 1.20220(4) nm, R_Bragg = 0.0859 for Ho₂PbS₄; a = 0.7863(2) nm, b = 2.8525(5) nm, c = 1.1995(2) nm, R1 = 0.0482 for Er₂PbS₄ and a = 0.78419(3) nm, b = 2.84184(9) nm, c = 1.19655(4) nm, R_Bragg = 0.0893 for Tm₂PbS₄) was investigated by means of X‐ray single crystal and powder diffraction. Each RE atoms is octahedrally coordinated by six S atoms. Each Pb atoms is surrounded by seven S atoms to form a mono‐capped trigonal prism.     

Ternary rare earth metal boride carbides containing two-dimensional boron–carbon network: The crystal and electronic structure of R2B4C (R=Tb, Dy, Ho, Er)

The ternary rare earth boride carbides R₂B₄C (R=Tb, Dy, Ho, Er) have been synthesized by reacting the elements at temperatures between 1800 and 2000K. The crystal structure of Dy₂B₄C has been determined from single-crystal X-ray diffraction data. It crystallizes in a new structure type in the orthorhombic space group Immm (a=3.2772(6) Å, b=6.567(2) Å, c=7.542(1) Å, Z=2, R1=0.035 (wR₂=0.10) for 224 reflections with I_o>2σ(I_o)). Boron atoms form infinite chains of fused B₆ rings in [100] joined with carbon atoms into planar, two-dimensional networks which alternate with planar sheets of rare earth metal atoms. The electronic structure of Dy₂B₄C was also analyzed using the tight-binding extended Hückel method.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Selten‐Erd‐Metall‐Koordinationspolymere: Synthesen und Kristallstrukturen von sechs neuen Pimelinaten, [M(Pim)(PimH)(H2O)](H2O) (M = Ce,Pr) und [M2(Pim)3(H2O)4] (M = Tb,Ho, Er,Tm)

Rare‐Earth‐Metal Coordination Polymers: Syntheses and Crystal Structures of Six New Pimelinates, [M(Pim)(PimH)(H₂O)](H₂O) (M = Ce, Pr) and [M₂(Pim)₃(H₂O)₄] (M = Tb, Ho, Er, Tm) The new rare‐earth metal carboxylates [M(Pim)(PimH)(H₂O)](H₂O) (M = Ce ( 1 ), Pr ( 2 )) and [M₂(Pim)₃(H₂O)₄] (M = Tb ( 3 ), Ho ( 4 ), Er ( 5 ), Tm ( 6 )) were prepared from the reaction of pimelinic acid with CeO₂, Pr₆O₁₁, Tb₄O₇, HoCl₃, ErCl₃ and Tm(NO₃)₃, respectively. Their crystal structures were determined by single‐crystal X‐ray diffraction. [M(Pim)(PimH)(H₂O)](H₂O) crystallize in the monoclinic space group P2₁/n (no. 14) with a = 909.6(1), b = 870.6(1), c = 2240.5(2) pm, β = 92.30(1)°, Z = 4 (crystal data for M = Ce). The isostructural pimelinate‐hydrates [M₂(Pim)₃(H₂O)₄] crystallize with orthorhombic symmetry, Pbcn (no. 60), with a = 1392.5(1), b = 902.3(1), c = 2408.8(2) pm, Z = 4 (crystal data for M = Tb). The rare‐earth cations have coordination numbers of 10 ( 1 , 2 ) and 9 ( 3 , 4 , 5 and 6 ), respectively. In the crystal structure of [M(Pim)(PimH)(H₂O)](H₂O) bidentate and tridentate‐bridging carboxylate groups form rather dense structures in which chains are bridged to layers and further to networks. Pimelinic acid molecules fill the channels. In [M₂(Pim)₃(H₂O)₄] tridentate‐bridging carboxylate groups coordinating to two rare‐earth ions lead to dimers that are linked with other dimers to strands. The channels thus formed between the strands are rather small in diameter. They do not contain any non‐coordinated water molecules.     

Sm2As4O9: Ein ungewöhnliches Samarium(III)‐Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]

Sm₂As₄O₉: An Unusual Samarium(III) Oxoarsenate(III) According to Sm₄[As₂O₅]₂[As₄O₈] Pale yellow single crystals of the new samarium(III) oxoarsenate(III) with the composition Sm₄As₈O₁₈ were obtained by a typical solid‐state reaction between Sm₂O₃ and As₂O₃ using CsCl and SmCl₃ as fluxing agents. The compound crystallizes in the triclinic crystal system with the space group (No. 2, Z = 2; a = 681.12(5), b = 757.59(6), c = 953.97(8) pm, α = 96.623(7), β = 103.751(7), γ = 104.400(7)°). The crystal structure of samarium(III) oxoarsenate(III) with the formula type Sm₄[As₂O₅]₂[As₄O₈] (≡ 2 × Sm₂As₄O₉) contains two crystallographically different Sm³⁺ cations, where (Sm1)³⁺ is coordinated by eight, but (Sm2)³⁺ by nine oxygen atoms. Two different discrete oxoarsenate(III) anions are present in the crystal structure, namely [As₂O₅]^4? and [As₄O₈]^4?. The [As₂O₅]^4? anion is built up of two Ψ¹‐tetrahedra [AsO₃]^3? with a common corner, whereas the [As₄O₈]^4? anion consists of four Ψ¹‐tetrahedra with ring‐shaped vertex‐connected [AsO₃]^3? pyramids. Thus at all four crystallographically different As³⁺ cations stereochemically active non‐binding electron pairs (“lone pairs”) are observed. These “lone pairs” direct towards the center of empty channels running parallel to [010] in the overall structure, where these “empty channels” being formed by the linkage of layers with the ecliptically conformed [As₂O₅]^4? anions and the stair‐like shaped [As₄O₈]^4? rings via common oxygen atoms (O1 – O6, O8 and O9). The oxygen‐atom type O7, however, belongs only to the cyclo‐[As₄O₈]^4? unit as one of the two different corner‐sharing oxygen atoms.     

Crystal structure and thermal study of the new hydrated cadmium-cerium(III) chloride CeCd4Cl11·13H2O

The new double-salt CeCd₄Cl₁₁·13H₂O in the ternary system CeCl₃-CdCl₂-H₂O has been prepared from aqueous solution upon evaporation at 5°C and characterized based on elemental analysis, spectroscopic data, thermal studies and X-ray powder and single-crystal diffraction. CeCd₄Cl₁₁·13H₂O crystallizes in the monoclinic space group P2₁ with a=7.667(2), b=17.351(3), c=11.970(2)Å, β=101.61(3)° and Z=2. After refinement of the structure the reliability factor R in the final cycle is 0.064. The structure can be regarded as consisting of endless double chains of CdCl₆ and CdOCl₅ octahedra and isolated tricapped triangular prisms surrounding the cerium cations. Differential scanning calorimetry showed that the title compound exhibits five endothermic anomalies interpreted from thermogravimetry. A comparison with the structure of SrCd₂Cl₆·8H₂O is proposed.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Complexes of ytterbium(III) nitrate and triflate with homoazacalix[n]arenes (n=3, 4)

The synthesis and crystal structures of three ytterbium(III) complexes of homoazacalixarenes are reported. In all cases, the complexes are obtained without addition of a base, the protons of the complexing phenolic moieties being transferred to the amine groups upon complexation. The 1:1 complex between p-chloro-N-benzylhexahomotriazacalix[3]arene (1) and Yb(NO₃)₃ is analogous to the neodymium(III) complex reported previously, with the metal ion bound to three phenoxide groups and three nitrate ions. A second 1:1 complex is obtained with Yb(NO₃)₃ and p-methyl-N-benzyltetrahomodiazacalix[4]arene (2), in which the metal ion is bound to two phenoxide groups only. The replacement of nitrate by triflate counter-ions results in the formation of a 1:2 ‘sandwich’ complex with 1, in which two divergent calixarene molecules are bridged by the metal ion, the counter-ions being non-bonding.     

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.     

Th2F7[AuF4] – das erste „fluorobasische”︁ Tetrafluoroaurat(III) im System ThF4/AuF3

Th₂F₇[AuF₄] – the First Fluoroaurate in the System MF₄/AuF₃ We observed for the first time single crystals of Th₂F₇[AuF₄] [1] in attempts to synthesize ternary fluoroaurates with tetravalent cations. Concerning to X‐Ray‐data (Mo–Kα), the light‐yellow compound crystallizes tetragonal in the space group I4/mcm (No. 140) with a = 1130.6(1) pm, c = 631.34(7) pm and Z = 4.     

Crystal and Electronic Structures of the New Carbomolybdates(III), RE2[Mo2C3] with RE = Ce,Sm, Tb,and Dy

Four new ternary carbometalates of the general formula RE₂[Mo₂C₃] with RE = Ce, Sm, Tb and Dy have been prepared by a high temperature synthesis route. The Ce, Tb and Dy compounds crystallize isotypic to Er₂[Mo₂C₃], Sm₂[Mo₂C₃], however, is an isotype of Ho₂[Cr₂C₃]. The crystal structures comprise polyanionic layers [(Mo₂C₃)^6?] with the rare‐earth metal ions in between. The layers are constructed by edge and vertex connected MoC₄ tetrahedra, which display strong covalent Mo–C bonds. The compounds show metallic behaviour close to the classical limit of 100 μΩ cm for metallic conductors. The magnetic properties are quite different, however they are consistent with the presence of trivalent RE³⁺ ions with the exception of Ce₂[Mo₂C₃], which contains nonmagnetic Ce species. Electronic structure calculations reveal that the additional electron mainly populates the Ce partial structure. The title compounds extend the series of known carbomolybdates RE₂[Mo₂C₃]. The late lanthanides Gd, Tb, Dy, Ho, Er, Tm, and Lu with comparatively small RE³⁺ ions and Ce as Ce⁴⁺ adopt the Er₂[Mo₂C₃] structure type, whereas the early lanthanides Sm and Pr with larger RE³⁺ ions crystallize in the structure types of Ho₂[Cr₂C₃] and Pr₂[Mo₂C₃], respectively.     

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.