Synthese und Kristallstruktur der Ternären Selten-Erd-Chloride Na2MCl5 (M = Sm,Eu, Gd)

Synthesis and Crystal Structure of the Ternary Rare Earth Chlorides Na₂MCl₅ (M = Sm, Eu, Gd) Single crystals of Na₂EuCl₅ were obtained from the melt of NaCl and EuCl₃ in a 2:1.2 molar ratio by slow cooling. It crystallizes in the orthorhombic crystal system (space group Pnma) with the structure of K₂PrCl₅ with a = 1 204.0(3) pm, b = 833.9(3) pm, c = 768.2(3) pm, Z = 4. Pure powder samples of the compounds Na₂MCl₅ (M = Sm? Gd) are available by heating mixtures of the binary components below the melting point.     

Synthesis and Structure of the Ordered Modification of Ba6EuF12Cl2

Crystals of ordered Ba₆EuF₁₂Cl₂ were found to form during high temperature flux growth. The structure was refined in the hexagonal space group P 6 to R^F(R ) = 0.024(0.024) for 326 reflections and 46 parameters. Lattice parameters are a = b = 1059.27(8) pm and c = 416.36(2) pm; Z = 1. The structure is isotypic to Ba₇F₁₂Cl₂. No solid solution of Ba/Eu was observed, the Eu²⁺ ions are located in the channels formed by 3 + 6 fluorine ions, occupying only one of the three metal sites of the Ba₇F₁₂Cl₂ structure.     

Zwei neue Silicat-Chloride mit zweiwertigem Europium: LiEu3[SiO4]Cl3 und Li7Eu8[SiO4]4Cl7

Two New Silicate-Chlorides with Divalent Europium: LiEu₃[SiO₄]Cl₃ and Li₇Eu₈[SiO₄]₄Cl₇ LiEu₃[SiO₄]Cl₃ was prepared by reaction of LiCl with Eu₂SiO₄ and Li₇Eu₈[SiO₄]₄Cl₇ from Li with Eu₂O₃, SiO₂ and LiCl. The crystal structures of LiEu₃[SiO₄]Cl₃ (Pmna, a = 946.95(13); b = 699.52(8); c = 1 368.0(2) pm; Z = 4; R1 = 0.0325, R2_w = 0.0642) and Li₇Eu₈[SiO₄]₄Cl₇ (P2₁/c; a = 851.85(5); b = 948.62(7); c = 1 679.0(2) pm; β = 96.221(8)°; Z = 2; R1 = 0.0352, R2_w = 0.0744) were determined from four-circle diffractometer data. LiEu₃[SiO₄]Cl₃ contains [Li(SiO₄)₂] units and LiCl₆ octahedra while in Li₇Eu₈[SiO₄]₄Cl₇ larger ?lithosilicate”? groups are found. In both structures, the Eu²⁺ ions are coordinated mostly eightfold by O^2? and Cl^? ligands.     

Synthesis,structures and luminescence of two new Europium(II) Silicate-Chlorides,Eu2SiO3Cl2 and Eu5SiO4Cl6

Eu₂SiO₃Cl₂ and Eu₅SiO₄Cl₆ were prepared by reaction of EuCl₂ with EuSiO₃ and Eu₂SiO₄, respectively, Sr₂SiO₃Cl₂: Eu²⁺ from mixtures of SrCO₃, Eu₂O₃, SrCl₂ · 6H₂O and SiO₂ under reducing conditions. The crystal structures of Eu₂SiO₃Cl₂ [a = 1118.7(5), c = 952.6(1) pm, tetragonal, I4/m, Z = 8, R = 3.3, R_w = 3.0%] and Eu₅SiO₄Cl₆ [a = 900.4(1), b = 1401.7(2), c = 1112.3(2) pm, β = 103.51(1)°, monoclinic, C2/c, Z = 4, R = 3.6, R_w = 2.6%] were determined from four-circle diffractometer data and compared with related compounds. The luminescence properties were investigated at 300 K and at 4.2 K; all compounds show intense bluish-green photoluminescence. Sr₂SiO₃Cl₂:Eu²⁺ shows thermoluminescence.     

Eu3+ und Eu2+ in Oxometallaten der Zusammensetzung MBeLn2O5: SrBeEu2O5 und EuBeNd2O5

Eu³⁺ and Eu²⁺ in Oxides of the Composition MBeLn₂O₅: SrBeEu₂O₅ and EuBeNd₂O₅ Single crystals of (I): SrBeEu₂O₅ and (II): EuBeNd₂O₅ were prepared by CO₂-LASER (I) in air and plasma torch (II) technique in H₂ atmosphere. X-ray investigations led to orthorhombic symmetry, space group D-Pnma; (I): a = 9.488, b = 7.156, c = 6.495 Å; (II): a = 9.534, b = 7.225, c = 6.544 Å, Z = 4. Sr²⁺ and Eu³⁺ as well as Eu²⁺ and Nd³⁺ are in statistical distribution within a Kagomé framework. Both compounds are discussed with respect to the monoclinic form of MBeLn₂O₅.     

[La2Cl3(OAc)2(H2O)7]Cl: Das erste Lanthanid-Acetat-Halogenid-Hydrat mit Chlorid in innerer Koordinationssphäre

[La₂Cl₃(OAc)₂(H₂O)₇]Cl: The First Lanthanide-Acetate-Halide-Hydrate with Chloride in Inner-Sphere Coordination [La₂Cl₃(OAc)₂(H₂O)₇]Cl has been obtained as single crystals through the reaction of LaCl₃ · 7H₂O with diluted acetic acid or from La₂O₃ with acetyl chloride. In the crystal structure (triclinic, Z = 2, P1 (no. 2), a = 919.6(2), b = 950.7(2), c = 1178.9(2) pm, α = 82.52(1), β = 84.14(1), γ = 64.69(1)°, R = 0.021, R_w = 0.020), La³⁺ is surrounded by nine ligands (O, Cl). La1 has two chloride and seven oxygen ligands whereas La2 has one chloride and eight oxygen atoms as nearest neighbours. Four of the oxygen ligands of each lanthanum cation originate from a ?tetradentate”? acetate anion, the others from crystal water molecules. The ?tetradentate”? acetate groups are coordinated not only to one central La³⁺ as chelate ligands, but also to the ?left”? and ?right”? La³⁺ neighbours. Thereby, a one-dimensional infinite cationic chain, [La₂Cl₃(OAc)₂(H₂O)₇]⁺, is formed that runs in the [011] direction. These chains are held together by ?lonesome”? chloride ions which are surrounded by (4 + 1) water molecules and connected to the chains via hydrogen bonds.     

Die Chloride Na3xM2–xCl6 (M = La?Sm) und NaM2Cl6 (M = Nd,Sm): Derivate des UCl3-Typs. Synthese,Kristallstruktur und Röntgenabsorptionsspektroskopie (XANES)

The Chlorides Na_3xM_2–xCl₆ (M = La? Sm) and NaM₂Cl₆ (M = Nd, Sm): Derivatives of the UCl₃-Type of Structure. Synthesis, Crystal Structure and X-Ray Absorption Spectroscopy (XANES) Single crystals of the derivatives of the UCl₃-type structure Na_3xM_2–xCl₆ (M = La/x = 0.364(4); Ce/0.349(5); Pr/0.318(8); Nd/0.305(5); Sm/0.246(4)) and NaSm₂Cl₆ were grown by different methods generally under reducing conditions. They are addition [Na(Sm₂)Cl₆] and addition/substitution variants [Na_2x(Na_xM_2–x)Cl₆] of the UCl₃ structure type [□(U₂)Cl₆]. X-Ray Absorption Spectroscopy (XANES) at the L_III edge characterizes NaSm₂Cl₆ and NaNd₂Cl₆ as mixed-valence compounds with valences of +2 and +3 in statistical distribution (approximately 1:1) for Sm and Nd, respectively.     

Ternäre Halogenide vom Typ A3MX6. III [1, 2]. Synthese,Strukturen und Ionenleitfähigkeit der Halogenide Na3MX6 (X = Cl,Br)

Ternary Halides of the A₃MX₆ Type. III [1, 2]. Synthesis, Structures, and Ionic Conductivity of the Halides Na₃MX₆ (X = Cl, Br) The bromides Na₃MBr₆ crystallize with the stuffed LiSbF₆-type structure (type I; M = Sm? Gd) or with the structure of the mineral cryolite (type II; M = Gd? Lu). The structure types were refined from single crystal X-ray data (Na₃SmBr₆: trigonal, space group R3 , a = 740.8(2) pm, c = 1 998.9(8) pm, Z = 3; Na₃YBr₆: monoclinic, space group P2₁/n, a = 721.3(4) pm, b = 769.9(2) pm, c = 1 074.8(4) pm, β = 90.60(4)°, Z = 2). Reversible phase transitions from one structure to the other occur. The phase transition temperatures were determined for the bromides as well as for the chlorides Na₃MCl₆ (M = Eu? Lu). The refinement of both structures for one compound was possible for Na₃GdBr₆ (I: trigonal, space group R3 , a = 737.1(5) pm, c = 1 887(2) pm, Z = 3; II: monoclinic, space group P2₁/n, a = 725.2(1) pm, b = 774.1(3) pm, c = 1 080.1(3) pm, β = 90.76(3)°, Z = 2). All compounds exhibit ionic conductivity of the sodium ions which decreases with the change from type I to type II. The conductivity of the bromides is always higher when compared with the respective chlorides.     

Strukturen aus AlB2- und CeMg2Si2-analogen Einheiten. Die Verbindungen Eu3Pd4As4, Ca4Pd5P5 und Ca5Pd6P6

Structures with AlB₂- and CeMg₂Si₂-Type Units. The Compounds Eu₃Pd₄As₄, Ca₄Pd₅P₅, and Ca₅Pd₆P₆ The new compounds Eu₃Pd₄As₄, Ca₄Pd₅P₅, and Ca₅Pd₆P₆ (space groups and lattice constants see ?Inhaltsübersicht”?) have been prepared by heating mixtures of the elements. Their structures were determined by means of single-crystal X-ray methods and contain exclusively units, which are characteristic for the AlB₂- and CeMg₂Si₂-type. The non-metal atoms are isolated from each other or connected to pairs; the ratio between these two kinds can be interpreted by ionic splittings of the formulas.     

AM2X2-Verbindungen mit CaAl2Si2-Struktur. XI. Struktur und Eigenschaften der Verbindungen ACd2X2 (A: Eu,Yb; X: P,As, Sb)

AM₂X₂ Compounds with the CaAl₂Si₂-Type Structure. XI. Structure and Properties of ACd₂X₂ (A: Eu, Yb; X: P, As, Sb) EuCd₂P₂, EuCd₂As₂, EuCd₂Sb₂, YbCd₂As₂, and YbCd₂Sb₂ were prepared by heating mixtures of the elements and investigated by means of single-crystal X-ray methods. The compounds are isotypic (lattice constants see “Inhaltsübersicht”) and crystallize in the CaAl₂Si₂-type structure (P3 m1; Z = 1). Magnetic measurements showed, that Eu is divalent and that the compounds order magnetically at low temperatures.     

Quaternäre Chloride des zweiwertigen Europiums mit dreiwertigen Übergangsmetallen: Synthese und Kristallstruktur von Na6Eu3M4Cl24 (M = Ti,V, Cr)

Quaternary Chlorides of Divalent Europium and Trivalent Transition Metal Ions: Synthesis and Crystal Structure of Na₆Eu₃M₄Cl₂₄ (M = Ti, V, Cr) The reaction of EuCl₂, NaCl and MCl₃ (M = Ti, V, Cr) yields the chlorides Na₆Eu₃M₄Cl₂₄. According to X‐ray single crystal investigations, their crystal structure is a variant of the monoclinic cryolite‐type structure. One crystallographic site is occupied by Na1 and Eu simultaneously. For charge compensation the Na2 site is not fully occupied. In Na₆Eu₃Ti₄Cl₂₄ (P2₁/n, Z = 1/2, a = 663.8(1) pm, b = 718.3(1) pm, c = 953.3(2) pm, β = 91.55(2)°, R_all = 0.0314), Na₆Eu₃V₄Cl₂₄ (P2₁/n, Z = 1/2, a = 660.4(1) pm, b = 715.8(1) pm, c = 946.5(2) pm, β = 91.41(2)°, R_all = 0.0313) and Na₆Eu₃Cr₄Cl₂₄ (P2₁/n, Z = 1/2, a = 654.8(1) pm, b = 706.5(1) pm, c = 945.4(2) pm, β = 91.07(2)°, R_all = 0.0368) the ratio of Na1 : Eu amounts to 5 : 3. The colours of the compounds, orange yellow for M = Ti, orange red for M = V and dark red for M = Cr, indicate electronic interactions between Eu²⁺ and M³⁺.     

Synthese und Kristallstrukturen von Chlororhenaten(III) mit den zweiwertigen Kationen Ethylendiammonium und Piperazinium:(EnH2)2(Pipzh2)[Re3Cl12]2· 6H2O,und (PipzH2) [Re3Cl12]CI·H2O und (Pipzh2) [Re3Cl11(H2O)]·3H2O

Synthesis and Crystal Structures of Chlororhenates(III) with the Divalent Cations Ethylenediammonium and Piperazinium: (EnH₂)₂(PipzH₂) [Re₃Cl₁₂]₂·6H₂O, (EnH₂) (PipzH₂) [Re₃Cl₁₂]Cl· H₂O, and (PipzH₂) [Re₃Cl₁₁(H₂O)] · 3H₂O The deep red salt (EnH₂)₂(PipzH₂)[Re₃CI₁₂] · 6 H₂O ( 1 ), (EnH₂)(PipzH₂)[Re₃Cl₁₂]CI · H₂O ( 2 ), and (PipzH₂)[Re₃Cl₁₁(H₂O)] · 3H₂O ( 3 ) crystallize upon evaporation from hydrochloride acid solutions of ReCl₃ on addition of ethylenediammonium chloride (EnH₂Cl₂) and/or piperazinium chloride (PipzH₂Cl₂). The crystal structures have been determined from four-circle diffractometer data. 1: monoclinic; a = 1889.63(11), b = 1615.82(8), c = 790.28(4)pm; β = 101.354(5)°; Z = 2; P2₁/n; R = 0.119, R_w = 0.070. 2: triclinic; a = 1330.35(4), b = 1051.14(5), c = 1165.32(6)pm; α = 122.308(4), β = 102.412(3), γ = 92.226(4)°; Z = 2, P1 ; R = 0.092, R_w = 0.059. 3: orthorhombic; a = 971.43(4), b = 1619.51(7), c = 1478.87(6)pm; Z = 4; Pbcm; R = 0.034, R_w = 0.032.     

Synthese und Kristallstruktur von BaEu(Ba0,5Eu0,5)YbSi6N11

Synthesis and Crystal Structure of BaEu(Ba_0.5Eu_0.5)YbSi₆N₁₁ Pure BaEu(Ba_0.5Eu_0.5)YbSi₆N₁₁ was obtained by stoichiometric reaction of silicon diimide with metallic barium, europium, and ytterbium. The reaction was carried out under nitrogen atmosphere in a high-frequency furnace at 1650 °C. BaEu(Ba_0.5Eu_0.5)YbSi₆N₁₁ is cubic (space group P2₁3, a = 1043.64(5) pm, Z = 4, R1 = 0.0406, wR2 = 0.0988). The compound contains alkaline earth and rare earth ions in a three-dimensional network structure of corner-sharing SiN₄ tetrahedra.     

RuS4Cl12 und Ru2S6Cl16, zwei neue Ruthenium(II)‐Komplexe mit SCl2‐Liganden

RuS₄Cl₁₂ and Ru₂S₆Cl₁₆, Two New Ruthenium(II) Complexes with SCl₂ Ligands Ru powder was reacted with SCl₂ in closed silika ampoules at 140 °C. From the black solution three compounds RuS₄Cl₁₂ 1 , Ru₂S₆Cl₁₆ 2 , and Ru₂S₄Cl₁₃ 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P2₁/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl₃[RuCl₃(SCl₂)₃]. In the structure the complex anions fac‐[RuCl₃(SCl₂)₃]^– and the cations [SCl₃]⁺ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl₂)₃ClRu(μ‐Cl)₂RuCl(SCl₂)₃ with two fac‐RuCl₃(SCl₂)₃‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl₂(SCl₂)Ru(μ‐Cl)₃Ru(SCl₂)₃]. The vibrational spectra and the thermal behaviour of the compounds are discussed.     

Hochdrucksynthese und Struktur von Rb2PtH6 und Cs2PtH6, ternären Hydriden mit K2PtCl6-Struktur

High-pressure Synthesis and Structure of Rb₂PtH₆ and Cs₂PtH₆, Ternary Hydrides with K₂PtCl₆-Structure The ternary platinum hydrides Rb₂PtH₆ and Cs₂PtH₆ were synthesized by the reaction of rubidium hydride and cesium hydride, respectively, with platinum sponge under a hydrogen pressure above 1 500 bar at 500°C. X-ray investigations on powdered samples and elastic neutron diffraction experiments on the deuterated compounds at the time-of-flight spectrometer POLARIS led to their complete structure determination. Their atomic arrangements are isotypic with that of K₂PtCl₆ containing isolated [PtH₆]^2?-octahedra (space group: Fm3 m, Z = 4).     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

NaAuIn2, ein ternäres Aurid mit ethananalogen In2Au6-Baueinheiten und [In2/2]-Ketten

NaAuIn₂, a Ternary Auride with Ethane Analogous In₂Au₆ Building Units and [In_2/2] Chains Silver coloured, brittle single crystals of NaAuIn₂ were synthesized by the reaction of NaN₃, gold-sponge and indium at 500°C. The structure was determined from X-ray single-crystal diffractometry data: space group Cmcm, Z = 4, a = 4.482(1) Å, b = 10.366(2) Å, c = 7.869(2) Å, R/R_w(w = 1) = 0.017/0.020, Z(F) ≥ 3σ(F) = 547 and N(var.) = 16. NaAuIn₂ crystallizes in the MgCuAl₂-structure type. Gold and indium form a framework structure. [AuIn_6/3] layers with trigonal prismatically coordinated gold are connected via In—In contacts along [010] which consist of ethane analogous In₂Au₆-building units. The In-partial structure consists of saw tooth like [In_2/2] chains along [001]. The sodium atoms occupy channel-like cavities within the Au—In framework structure.