Über Fluoride mit vierwertigem Kupfer: Cs2[CuF6]

Chlorides Ag₃MCl₆ have been obtained with M = Dy? Lu, Y, Sc from AgCl/MCl₃ mixtures (sealed Pyrex ampoule, 380°C, 8 d). They crystallize like Na₃GdCl₆-I with a “stuffed” LiSbF₆-type structure (R3 , Z = 3). Thermal expansion was followed for Ag₃HoCl₆ and Ag₃YCl₆ and is remarkably different from that of Na₃GdCl₆-I.     

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.     

The chlorides Na3MCl6 (M  Eu?Lu,Y, Sc): Synthesis,crystal structures,and thermal behaviour

Single crystals of Na₃ErCl₆ were obtained via the metallothermic reduction of ErCl₃ with Na. The crystal structure is that of the mineral cryolite with a = 684.54(4), b = 725.18(4), c = 1012.39(6) pm, β = 90.768(5)°, Z = 2, space group P2₁/n. Two applicable synthetic routes to pure powder samples of the chlorides Na₃MCl₆ (M ? Eu? Lu, Y, Sc) are described. With M ? Dy? Lu, Y, Sc, these are isotypic with Na₃ErCl₆ while those with M ? Eu, Gd, Tb adopt a ?stuffed”? LiSbF₆-type structure. The dimorphism of Na₃GdCl₆ and dependence of the lattice constants and the molar volume upon temperature has been investigated: At 205°C, a first-order phase transition from the stuffed LiSbF₆-type Na₃GdCl₆-I to the cryolite-type Na₃GdCl₆-II occurs exhibiting a 3.71% negative molar volume discontinuity.     

Na2ZrS3: Ein ternäres Sulfid des Zirconiums mit aufgefüllter AlCl3‐Struktur

Na₂ZrS₃: A Ternary Zirconium Sulfide with Stuffed AlCl₃‐type Structure Dark green, plate‐like single crystals of Na₂ZrS₃ (monoclinic, C2/m; a = 664.69(6), b = 1152.5(1), c = 695.48(7) pm, β = 108.78(1)°; Z = 4) are obtained along with pale yellow platelets of NaZr₂N₂SCl (trigonal, R3m; a = 363.56(3), c = 2951.2(4) pm; Z = 3) upon oxidation of zirconium metal with sulfur and sodium azide (NaN₃) in the presence of fluxing NaCl (molar ratio 7:6:2:3) in evacuated silica tubes at 850°C within three weeks. The crystal structure is best described as stuffed AlCl₃ type with all cations (Na⁺ and Zr⁴⁺) in octahedral coordination of the S^2– anions, which build up a cubic closest packed host lattice. The internuclear metal sulfur distances range from 276 to 296 pm for all three crystallographically different Na⁺ cations, and from 258 to 260 pm for Zr⁴⁺.     

Na3GdCl6: Einkristalle der Tieftemperaturform bei der metallothermischen Reduktion von GdCl3 mit Na

Na₃GdCl₆: Single Crystals of the Low Temperature Form by Metallothermic Reduction of GdCl₃ with Na Single crystals of Na₃GdCl₆-I (low-temperature form, transition to form II at 205°C) are obtained by reaction of GdCl₃ with Na (tantalum tube, 700°C, 9 d). The crystal structure [a = 700.72(8), c = 1879.1(3) pm, c/a = 2,682, V_m = 160.40(3) cm³ mol^?1, trigonal, R3 (No. 148), Z = 3] may be derived from the LiSbF₆ type: Na2 ? Li Gd ? Sb, Cl: ¨AB¨ or h₆, with two Na 1 statistically distributed over four “octahedral” in terstices.     

Neues über Oxouranate: Über α-Li6UO6. Mit einer Bemerkung über β-Li6UO6

New Investigations about Oxo Uranates: On α-Li₆UO₆. With a Remark about β-Li₆UO₆ The crystal structure of transparent, bright yellow single crystals of α-Li₆UO₆ has been determined. [a = 838.07(5), c = 738.34(7) pm; d_pyk = 4.02, d_x = 4.17 g · cm^?3; space group R3 ; Z = 3; R = 3.17%, R_w = 3.06%; 408 symmetry independent I₀(hkl); AgKα fourcircle diffractometer Philips PW 1100]. The structure is dominated by a threedimensional framwork of “hollow spaces”, built up by 12 O^2? (and 12 Li⁺). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Ternäre Halogenide vom Typ A3MX6. I A3YCl6 (A = K,NH4, Rb,Cs): Synthese,Strukturen, Thermisches Verhalten. Über einige analoge Chloride der Lanthanide

Ternary Halides of the A₃MX₆ Type I. A₃YCI₆ (A = K, NH₄, Rb, Cs): Synthesis, Structures, Thermal Behaviour. Some Analogous Chlorides of the Lanthanides Reaction of the trichlorides MCl₃ (M = Y, Tb? Lu) with alkali chlorides AC1 (A = K, Rb, Cs) in evacuated silica ampoules at 850?900°C yields A₃MCl₆-type chlorides. (NH₄)₃YCl₆ is obtained via the ammonium-chloride route. The crystal structure of Rb₃YCl₆ (monoclinic, C2/c (no. 15), Z = 8, a = 2583(1)pm, b = 788.9(4)pm, c = 1283.9(7)pm, p = 99.63(4)°, R = 0.062, R_w = 0.050) is that of Cs₃BiCl₆. The Rb₃YCl₆/Cs₃BiCl₆ structure and the closely related structures of K₃MoCl₆ and In₂CI₃ are derived from the elpasolite-type of structure (K₂NaAlF₆) making use of the model of closest-packed layer structures. Cell parameters for the chlorides Rb₃MCl₆ (M = Y, Tb? Lu) and Cs₃YCl₆ and Cs₃ErCl₆ as well, which are all isostructural with Rb₃YCl₆, are given. The “system” (K, NH₄, Rb, Cs)YCl₆ has been investigated by DTA and high-temperature X-ray powder diffractometry.     

Über Na2PrO3 und Na2TbO3

On Na₂PrO₃ and Na₂TbO₃ Using an exchange reaction of Na₂O with Li₈TbO₆ (Na : Tb = 2.1 : 1; au-tube; 750°C, 30 d) yellow-orange colored single crystals of Na₂TbO₃ could be prepared for the first time. Na₂TbO₃ crystallizes monoclinic in C2/c (Z = 8; a = 576.92(6), b = 1001.27(9), c = 1117.91(14) pm, β = 99.98(1)°). According to four-circle data the Li₂SnO₃-type of structure is adopted (PW 1100, MoKα , 1935 I₀ (hkl), R = 4.86%, R_w = 3.63% for all 928 unique reflexions). By a similar exchange reaction of Na₂O with Li₈PrO₆ for the first time single crystals of Na₂PrO₃ could be prepared, too (Na : Pr = 2.2 : 1; au-tube; 700°C; 23 d). The structure determination reveils that there is a variant of the NaCl-type of structure, which ressembles to the Li₂SnO₃-type of structure (PW 1100, MoKα , 2199 I₀ (hkl)), R = 8.88%, R_w = 5.21% for all 947 unique reflexions; C2/c, Z = 8, a = 678.78(5), b = 977.47(7), c = 1080.38(9) pm, β = 108,4(1)°. In contrast to Na₂TbO₃ there are no layers according to NaO(Na_1/3Tb_2/3)O. All octahedral intersticies are occupied systematically with Pr⁴⁺ and Na⁺ : (Na_2/3Pr_1/3)O(Na_2/3Pr_1/3)O.     

Über Alkali-hexachlorochromate(III): Na3CrCl6

Alkali-hexachlorochromates(III): Na₃CrCl₆ X-ray investigations on single crystals yielded for Na₃CrCl₆ a trigonal structure: space group P3 1c; a = 682.0(3) pm; c = 1203.4(5) pm; Z = 2. In a hexagonal-close arrangement of Cl^? ions, 2/3 of the octahedral holes are occupied orderly by Na⁺ and Cr³⁺ ions. The Na compounds of V³⁺ and Mo³⁺ are isotypic. The chlorochromates with K and Rb are crystallizing with the K₃MoCl₆ structure according to X-ray photos of powders. The alkali metal ions habe the C.N. 8 or 11 related to the chloride ions. These compounds and elpasolithes A₂BCrCl₆ (A = Cs? K; B = Rb? Na) can be treated in the same way with the concept of tolerance factors as it is known for the chloro-perovskites AMCl₃. For all compounds the temperatures of phase transitions were determined by DTA. Some structures could be solved from high-temperature-Guinier-patterns, by comparing them with patterns of substances with known structures.     

Ternäre Halogenide vom Typ A3MX6. VI [1]. Ternäre Chloride der Selten-Erd-Elemente mit Lithium,Li3MCl6 (M  Tb?Lu,Y, Sc): Synthese,Kristallstrukturen und Ionenbewegung

Ternary Halides of the A₃MX₆ Type. VI. Ternary Chlorides of the Rare-Earth Elements with Lithium, Li₃MCl₆ (M ? Tb? Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion Single crystal X-ray studies on the ternary chlorides Li₃ErCl₆, Li₃YbCl₆ and Li₃ScCl₆ show that they crystallize in three different structure types. Li₃ErCl₆ (trigonal, P3 ml, Z = 3, a = 1117.7(2); c = 603.6(2) pm; the chlorides with M ? Tb? Tm, Y are isotypic) and Li₃YbCl₆ (orthorhombic, Pnma, Z = 4, a = 1286.6(1); b = 1113.2(1); c = 602.95(8) pm; Li₃LuCl₆ is isotypic) have very similar structures that may be derived from hexagonal closest packings of chloride ions with the cations occupying octahedral holes in part statistically. Li₃ScCl₆ (monoclinic, C2/m, Z = 2, a = 639.8(1); b = 1104.0(2); c = 639,1(1) pm; β = 109.89(1)°) crystallizes isotypic with Na₃GdI₆ and Li₃ErBr₆, structures that may be derived from a cubic closes packings of anions. The ionic movement in Li₃YCl₆ and Li₃YbCl₆ has been investigated by impedance and ⁷Li-NMR spectroscopy.     

Die Zinn-Rhodiumboride SnRh3B1−x,Sn4Rh6B und Sn5Rh6B2

The Tin Rhodium Borides SnRh₃B_1–x, Sn₄Rh₆B, and Sn₅Rh₆B₂ The new compounds SnRh₃B_1–x (x ～ 0.2, tetragonal, P4/mbm, a = 570.31(2) pm, c = 835.99(8) pm, Z = 4, 514 reflexions, 26 parameters, R = 0.026), Sn₄Rh₆B (hexagonal, P6₃/mmc, a = 560.01(3) pm, c = 1367.5(1) pm, Z = 2, 746 reflexions, 17 parameters, R = 0.035), and Sn₅Rh₆B₂ (hexagonal, P6 2m, a = 654.80(7) pm, c = 557.32(9) pm, Z = 1, 361 reflexions, 16 parameters, R = 0.039) were prepared by reaction of the elements. SnRh₃B_1–x crystallizes with the filled U₃Si type of structure, a distortion variant of the cubic perovskite; the structure of Sn₄Rh₆B may be derived from the hexagonal perovskite BaNiO₃. Both compounds contain nearly regular Rh₆B-octahedra. Sn₅Rh₆B₂ with the Sn₅Ir₆B₂ type of structure contains isolated colums composed of trigonal Rh₆B-prisms.     

Einkristalluntersuchungen an LiMF6 (M = Rh,Ir), Li2RhF6 und K2IrF6

Single Crystal Investigations on LiMF₆ (M = Rh, Ir), Li₂RhF₆, and K₂IrF₆ LiRhF₆, LiIrF₆, Li₂RhF₆, and K₂IrF₆ were obtained again, but for the first time investigated by single crystal X‐ray methods. Rubyred LiRhF₆ and yellow LiIrF₆ crystallize isostructural in the trigonal space group R3 – C²_3i (Nr. 148) with the lattice parameters LiRhF₆: a = 502.018(7) pm, c = 1355.88(3) pm, Z = 3 and d(Rh–F) = 185.5(1) pm; LiIrF₆: a = 506.148(4) pm, c = 1362.60(2) pm, Z = 3, d(Ir–F) = 187.5(3) pm (LiSbF₆‐Typ). Yellow Li₂RhF₆ crystallizes tetragonal in the space group P4₂/mnm – D¹⁴_4h (Nr. 136) with a = 463.880(8) pm, c = 905.57(2) pm, Z = 2 and d(Rh–F) = 190.3(4)–191.4(3) pm (Trirutil‐Typ). Yellow K₂IrF₆ crystallizes trigonal in the space group P3m1 – D³_3d (Nr. 164) with a = 578.88(7) pm, c = 465.06(5) pm, Z = 1 and d(Ir–F) = 194.0(6) pm, isotypic with K₂GeF₆.     

Neue schnelle Ionenleiter vom Typ MMIIICl6 (MI = Li,Na, Ag; MIII = In,Y)

Novel Fast Ion Conductors of the Type M M^IIICl₆ (M^I = Li, Na, Ag; M^III = In, Y) The ternary chlorides Li₃InCl₆, Na₃InCl₆, Ag₃InCl₆, and Li₃YCl₆ have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na₃InCl₆ < Li₃YCl₆ < Ag₃InCl₆ < Li₃InCl₆. In the range of 300°C, Li₃InCl₆ is the best lithium ion conductor known so far (σ = 0,2 Ω^?1 cm^?1 at 300°C). With the exception of Na₃InCl₆, the chlorides exhibit complicated order-disorder phase transitions.     

Zur Kristallstruktur von Li8PbO6 [1]

On the Structure of Li₈PbO₆ For the first time single crystals of Li₈PbO₆ have been prepared by heating of mixtures of Na₂PbO₃ and Li₂O [Ag-cylinders, 650°C, 150 d]. The structure [382 I₀(hkl), four circle diffractometer PW 1100, ω/2Θ-scan, MoKα, R = 3.07%, R_w = 3.00%, space group R3 ; a = 555.09(4), c = 1564.13(17) pm, D_x = 4.28 g · cm^?3, D_pyk = 4.24 g · cm^?3, Z = 3] is characterized by the motive of a hexagonal-closed O^2? packing. Half of the octahedral sites are occupied by Pb⁴⁺ and Li⁺ and half of the tetrahedral sites only by Li⁺. The Madelung Part of Lattice Energy, MAPLE, and the Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Die Kristallstrukturen von SeCl3 +SbCl6−, SeBr3+GaBr4−, PCl4+SeCl5− und (PPh4+)2SeCl42− · 2 CH3CN

Crystal Structures of SeCl₃⁺SbCl₆^?, SeBr₃⁺GaBr₄^?, PCl₄⁺SeCl₅^?, and (PPh₄⁺)₂SeCl₄^2? · 2 CH₃CN The crystal structures of the title compounds were determined by X-ray diffraction. SeCl₃⁺SbCl₆^?: Space group P2₁/m, Z = 4, structure determination with 1795 observed unique reflections, R = 0.022. Lattice dimensions at ?80°C: a = 940.9, b = 1066.3, c = 1234.9 pm, β = 102.79°. The compound forms ion pairs with the structure of a double octahedron with linked surfaces. SeBr₃⁺GaBr₄^?: Space group Pc, Z = 2, structure determination with 1461 observed unique reflections, R = 0.058. Lattice dimensions at ?60°C: a = 660.1, b = 655.3, c = 1431.3 pm, β = 101.177°. The compound crystallizes in the SCl₃[AlCl₄] lattice type. Between the ions there are two relatively short Se … Br? Ga contacts. PCl₄⁺SeCl₅^?: Space group Ima2, Z = 8, structure determination with 1757 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1651.6, b = 1201.2, c = 1166.4 pm. The SeCl₅^? ions are associated to chains via interionic Se? Cl … Se contacts along the crystallographic c-axis. (PPh₄⁺)₂SeCl₄^2? · 2CH₃CN: Space group P2₁/n, Z = 2, structure determination with 2578 observed unique reflections, R = 0.050. Lattice dimensions at ?80°C: a = 1288.5, b = 726.0, c = 2585.8 pm, β = 101.65°. The compound includes planar-tetragonal SeCl₄^2? ions, which almost meet D_4h symmetry.     

[Sb(NPPh3)4]+SbF6−: Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum

[Sb(NPPh₃)₄]⁺SbF₆^?: Synthesis, Crystal Structure, and ¹²¹Sb Mössbauer Spectrum The title compound as well as the hexachloro antimonate [Sb(NPPh₃)₄]⁺SbCl₆^? have been prepared by the reaction of Me₃SiNPPh₃ with SbF₅ and SbCl₅, respectively, in acetonitrile solutions. The compounds form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy, by ¹²¹Sb Mössbauer spectroscopy, and by crystal structure analyses. A complete crystal structure analysis, however, could be carried out with [Sb(NPPh₃)₄]⁺SbF₆^? only. The compound crystallizes orthorhombically in the space group Pccn with four formula units per unit cell. The structure determination was done with 3 972 observed unique reflections, R = 0.053. Lattice dimensions at 19°C: a = 1 658,6; b = 1 698.9, c = 2 361.9 pm. In the cation [Sb(NPPh₃)₄]⁺ the antimony atom is tetrahedrally coordinated by the four nitrogen atoms of the phosphoraneiminato ligands with extremely short Sb? N bond lengths of 193 pm.     

Oxometallate neuen Typs: Über Ba3NaNbO6 und Ba3NaTaO6

Oxometallates of a new Type: On Ba₃NaNbO₆ and Ba₃NaTaO₆ For the first time in form of colourless, transparent single crystals of Ba₃NaNbO₆ [annealed mixtures of BaO, Na₂O and Nb₂O₅, Ba : Na : Nb = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] as well as Ba₃NaTaO₆ [annealed mixtures of BaO, Na₂O and Ta₂O₅, Ba : Na : Ta = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] have been prepared. The crystal structure was solved by fourcycle-diffractometer data [Ba₃NaNbO₆: Mo? Kα , 356 out 356 I₀ (hkl), space group R3 c with a = 1026.6(1)pm, c = 1195.3(2)pm (Guinier-Simon powder data), Z = 6, R = 2.4%, R_w = 2.0% and Ba₃NaTaO₆: Ag? Kα , 498 out of 498 I₀ (hkl), space group R3 c with a = 1027.6(1)pm, c = 1196.0(2)pm (Guinier-Simon powder data), Z = 6, R = 4.9%, R_w = 4.4%], parameters see text. The Ba₃M part of structure (M = Nb, Ta) corresponds to a slightly (hexagonal) deformed Nb₃Al arrangement with Na inserted along [001] between adjacent M^v, which are nearly perfectly octahedrally surrounded by 6 O. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.     

La6(BN3)O6, ein Nitridoborat‐Oxid des Lanthans

La₆(BN₃)O₆, a Nitridoborate Oxide of Lanthanum Single‐crystals of La₆(BN₃)O₆ were formed in reactions of Li₃BN₂, Li₃N, and LaOCl at 950 °C. The structure was solved by single‐crystal X‐ray diffraction. La₆(BN₃)O₆crystallizes with the space group Cmcm (no. 63) containing Z = 4 formula units in the unit cell, with lattice parameters of a = 366.88(3) pm, b = 2509.2(3) pm, and c = 1101.1(1) pm (R1 = 0.054, wR2 = 0.065 for all collected symmetry independant reflections). The crystal structure reflects typical patterns obtained in structures of nitridoborates. Tri‐nitridoborate ions are coordinated by La³⁺ ions in a tricapped trigonal prismatic arrangement, being stacked via shared trigonal faces to form columns. The arrangement of the columns in the structure provides space for O^2— ions with CN = 4, 5, and 6.     

Ein neues Oxomanganat(II): Na3Li5Mn5O9

A New Oxomanganate(II): Na₃Li₅Mn₅O₉ Na₃Li₅Mn₅O₉ (orange-coloured, transparent single crystals) has been prepared for the first time, it crystallizes trigonal (R3 m) with a = 335.6 pm, c = 2612.0 pm, Z = 1, R = 4.4%, R_w = 3.6% for 159 I₀(hkl) of 162 I₀(hkl). The structure refinement led to a statistically distribution of 5 Mn²⁺ and 5 Li⁺ each in a sixfold position, according to Na₃(Li₅□)(Mn₅□)O₉. The structure can be described by closest packings of spheres. Several models for the calculation of the Madelung Part of Lattice Energy, MAPLE, are discussed.     

Neue Beryllate der Alkalimetalle: Na6Be8O11

Novel Beryllates of the Alkali Metals: Na₆Be₈O₁₁ For the first time transparent, colourless single crystals of Na₆Be₈O₁₁ have been prepared (Na₂O/BeO; Na:Be = 6:8, Ni-tube; 650°, 14 d). The compound crystallizes triclinic (P1 ) with a = 532.1(1) pm, b = 642.4(2) pm, c = 839.1(2) pm, α = 101.7°, γ = 105.8°, Z = 2, d_x = 2.42 g/cm³, d_pyk=2.51 g/cm³. The crystal structure was solved by four-circle diffractometer data [Siemens AED 2, MoKα , R = 7.9%, R_w = 6.2%, 1429 I₀(hkl)]. Effektive Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.