Zur Kenntnis des RbNiCrF6-Typs. V. Neue Fluoride CsBMF6 mit B = MnII bzw. NiII und M = Ga,Fe, Rh bzw. Sc,In, Tl,Rh

On the RbNiCrF₆ Type. V. New Fluorides of the Type CsBMF₆ with B = Mn^II or Ni^II and M = Ga, Fe, Rh or Sc, In, Tl, Rh New prepared are the cubic compounds CsNiScF₆ (light yellow, a = 10.60 Å); CsNiInF₆ (lightyellow, a = 10.64 Å); CsNiTlF₆ (light yellow, a = 10.60 Å); CsNiRhF₆ (light redbrown, a = 10.37 Å); CsMnGaF₆ (pink, a = 10.42 Å); CsMnFeF₆ (light green, a = 10.55 Å) and CsMnRhF₆ (redbrown, a = 10.58 Å), all RbNiCrF₆ type of structure. The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Zur Kenntnis des RbNiCrF6-Typs,IV. Neue Fluoride des Typs CsPdMF6 mit M = Al,Ga, In und Sc,Fe, Mo,Rh

On the RbNiCrF₆ Type. IV. New Fluorides of the Type CsPdMF₆ (M = Al, Ga, Sc, In, Fe, Rh, Mo) New prepared are the cubic compounds CsPdScF₆ (brown violet, a = 10.82 Å); CsPdInF₆ (brown violet, a = 10.89); CsPdFeF₆ (redbrown, a = 10.64 Å); CsPdRhF₆ (redbrown, a = 10.65 Å), all of RbNiCrF₆-Type of structure. In addition prepared are CsPdAlF₆ (light violet, non cubic) CsPdGaF₆ (violet, non cubic) and CaPdMoF₅ (redbrown, non cubic). The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Zur Kenntnis des RbNiCrF6-Typs: über CsCuMF6 (M  NiIII,TiIII), CsMgMF6 (M  Co,Fe, Ga) und CsZnMF6 (M  NiIII,CoIII, FeIII)

On the RbNiCrF₆ Type(¹): On CsCuMF₆ (M?Ni^III, Ti^III), CsMgMF₆ (M ?Co, Fe, Ga), and CsZnMF₆ (M?Ni^III, Co^III, Fe^III) New prepared are the cubic compounds CsCuNi^IIIF₆ (dark brown, a = 10.14 Å); CsZnNi^IIIF₆ (dark brown, a = 10.17 Å); CsCuTi^IIIF₆ (light grey, a = 10.39 Å); CsMgGaF₆ (colourless, a = 10.23 Å); CsMgFeF₆ (colourless, a = 10.53 Å); CsZnFeF₆ (colourless, a = 10.42 Å); CsMgCo^IIIF₅ (light blue, a = 10.27 Å) and CsZnCo^IIIF₆ (light blue, a = 10.34 Å), all RbNiCrF₆-type of structure. The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Die Struktur des RbNiCrF6-Typs und ihre Beziehung zur Pyrochlorstruktur

The results of X-ray single crystal work on RbNiCrF₆ (a = 10.21 Å) and of powder work on KNiCrF₆ (a = 10.24 Å) and KNiCrF₆ · H₂O (a = 10.45 Å) are reported. All three compounds crystallize cubically in the space group Fd3m. They contain a network M₂X₆ of octahedra, analogous to that of the pyrochlores and with distances Ni–F = Cr–F = = 1.93 ± 0.02 Å which are equal within the error of determination. The structural relations between the three compounds, and compared with the pyrochlore structure are discussed, as well as the relations to the tetragonal bronze-type structure occuring as a high pressure phase of KNiCrF₆.     

Über Hexafluoroferrate(III): Cs2TlFeF6, Cs2KFeF6, Rb2KFeF6, Rb2NaFeF6 und Cs2NaFeF6

On Hexafluoroferrates(III): Cs₂TlFeF₆, Cs₂KFeF₆, Rb₂KFeF₆, Rb₂NaFeF₆, and Cs₂NaFeF₆ New prepared are the compounds Cs₂TlFeF₆ (a = 9.21₁ Å), Cs₂KFeF₆ (a = 9.04₁ Å), Rb₂KFeF₆ (a = 8.86₈ Å) and Rb₂NaFeF₆ (a = 8.46 ₄Å) all cubic Elpasolithes as well as Cs₂NaFeF₆ (Cs₂NaCrF₆?type, hexagonal with a = 6.28₁, c = 30.53₂ Å), all colourless. Cs₂KFeF₆ was measured magnetically (70–297,2 K). The spectra of reflection were measured (9000–36000 cm^?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

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.     

Etude EXAFS de la structure pyrochlore type RbNiCrF6

EXAFS studies of modified pyrochlore RbNiCrF₆-like structure have been performed to obtain independent informations about the local environment of M^II and M^III ions. MF distances (for example, ZnF = 2.01 Å and GaF = 1.89 Å in CsZnGaF₆) were found to be consistent with mean distances observed in well-known fluoride compounds and their significant difference establishes that the Fd3m space group does not apply at the local scale. With a near-constant MM distance, locally different MF distances lead to variable MFM angles and can explain the large thermal parameter values found in X-ray determinations.     

Über Neue Hexafluororhodate(IV): AIIRhIVF6 (AII = Ba,Sr, Ca,Mg, Zn,Cd, Hg,Ni sowie Cu)

On Novel Hexafluoro Rhodates(IV): A^IIRh^IVF₆. (A^II = Ba, Sr, Ca, Mg, Zn, Cd, Hg, Ni, Cu) We obtained hithertoo unknown BaRhF₆ and SrRhF₆ (both lemon yellow) of (hexag.) BaSiF₆?Type [a = 7.37₉, c = 7.21₁Å bzw. a = 7.15₇, c = 6.94₈ Å] as well as CaRhF₆ (light yellow) [a = 5.26₇, c = 14.61₂ Å], MgRhF₆ (light yellow) [a = 5.02₇, c 13.51₁Å], ZnRhF₅ (light yellow) [a = 4.99₆, c = 13.68₃ Å], CdRhF₆ (light yellow) [a = 5.,12₈ c = 14.44₇ Å], HgRhF₆ (orange) [a = 5.13₃, c = 14.67₆ Å], NiRhF₆ (light brown) [a = 4.96₀, c = 13.51₄ Å] all of (hexag.) LiSbF₆?type. The strukture of CuRhF₆ (light brown) is yet unknown.     

Über Verbindungen des Typs Ba3SE2TeO9

Compounds of the Type Ba₃RE₂TeO₉ In the BaO? RE₂O₃? TeO₃ system homogeneous perovskite compounds of formula Ba₃RE₂TeO₉ with RE = Nd, Sm–Gd, Dy–Lu, and Y are formed under special preparation conditions. With RE = ND and Sm A monoclinic lattice is observed whereas for the other RE a primitive cubic (a = 4.30₃ Å (Eu) to a = 4.21₄ Å (Lu)) lattice is found.     

Neue ternäre Oxide der Seltenen Erden: Über RbSEO 2 (SE = La,Nd, Sm,Eu, Gd) sowie CsNdO2 [1,2]

On Ternary Oxides of the Rare Earths: RbLaO₂, RbNdO₂, RbSmO₂, RbEuO₂, RbGdO₂ and CsNdO₂ New prepared are the compounds RbLaO ₂ (a = 3.73 ₉ Å, c = 19.6 ₄ Å), colourless, RbNdO ₂ (a = 3.63 ₈ Å, c = 19.5 ₈ Å), light greyblue, RbSmO ₂ (a = 3.59 ₅ Å, c = 19.5 ₅ Å), RbEuO ₂ (a = 3.57 ₂ Å, c = 19.5 ₃ Å) as well as RbGdO ₂ (a = 3.54 ₈ Å, c = 19.5 ₈ Å), all colourless, all show-ing the α-NaFeO ₂ type of structure. CsNdO ₂ (a = 3.67 ₂ Å, c = 13.7 ₂ Å), yellow-green, corresponds to the hexagonal β-RbScO ₂ type of structure (Z = 2). The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Über Alkalihexafluorobismutate(V)

The compounds LiBiF₆ (a = 5.18, c = 13.9₉ Å), NaBiF₆ (a = 5.47, c = 15.1₆ Å), RbBiF₆ (a = 7.71, c = 7.89 Å) and CsBiF₆ (a = 7.93, c = 8.27 Å, hexagonal lattice constants) are rhombohedral. The hexagonal unit cell contains three formula weights. LiBiF₆ and NaBiF₆ are isotypic with LiSbF₆, RbBiF₆ and CsBiF₆ are KOsF₆-isotypes. All compounds are colourless and very moisture sensitive.     

Neue Heteropolyanionen des M2X2W20‐Typs mit Antimon(III) als Heteroatom

New Heteropolyanions of the M₂X₂W₂₀ Structure Type with Antimony(III) as a Heteroatom The syntheses of two new heteropolyanions of the M₂X₂W₂₀ structure type are presented. They are characterized by X‐ray structure analysis and vibrational spectra. Na₆(NH₄)₄[Zn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·36H₂O (1) is monoclinic (P2₁/n) with a = 12.873(3)Å, b = 25.303(4)Å, c = 15.975(4)Å and β = 91.99(3)°. Na₁₀[Mn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·40H₂O (2) also crystallizes in the space group P2₁/n with a = 12.892(3)Å, b = 25.219(5)Å, c = 16.166(3)Å and β = 94.41(3)°. Both polyanions are isostructural to anions of this structure type containing other heteroatoms. They are built up by two β‐B‐SbW₉ fragments, which are derived from defect structures of the Keggin anion. These subÍunits are connected by two formal WO₂ groups with further stabilization by addition of two M(H₂O)₃ groups (M = Zn^II, Mn^II, Fe^III, Co^II) leading to the M₂X₂W₂₀‐type heteropolytungstates.     

Neue Hexafluoromolybdate(III). Cs2MMoF6, Rb2MMoF6, TI2MMoF6 (M = K,Na) und Cs2TIMof6. Mit einer Notiz über MoF3

Novel Hexafluoromolybdates(III): Cs₂MMoF₆, Rb₂MMoF₆, TI₂MMoF₆ (M = K, Na), and Cs₂TIMoF₆. With a Notice on MoF₃ MoF3, light yellow, hexag., a = b = 5.21, c = 14.41 Å, pure prepared by a new method, forms at higher temperatures with the corresponding Fluorides AF the hitherto unknown compounds Cs₂KMoF₆ (a = 9.2₀ Å), Cs₂TlMoF₆ (a = 9.39₂ Å). Rb₂KMoF₆ (a = 8.91₁ Å), Rb₂NaMoF₆ (a = 8.63₂ Å), Tl₂KMoF₆ (a = 8,97₇ Å), Tl₂NaMoF₆ (a = 8.64₉ Å) and K₂NaMoF₆ (a = 8.50₁ Å), all cubic Elpasolithes and all light yellow. The magnetic properties of MoF₃ (100.4–295.2 K) and Tl₂NaMoF₆ (81.4–251.3 K) are investigated. The spectra of reflection were measured (15000–36000 cm^?1). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

K4Au8Ga: eine Auffüllungsvariante des MgCu2‐Typs

K₄Au₈Ga: a Filling Variant of the MgCu₂ Type Black, brittle single crystals of K₄Au₈Ga were obtained as the main product of the reaction of potassium azide with gold sponge and gallium at T = 770 K. The structure of the compound (space group C2/m, Z = 4, a = 20.850(4) Å, b = 5.630(1) Å, c = 10.912(2) Å, β = 97,45(2)°) was determined from X‐ray single‐crystal diffractometry data. K₄Au₈Ga crystallizes in a filling variant of the MgCu₂ type. The gold atoms form a [Au_4/2]‐framework. One quarter of the tetrahedra is filled by gallium. The potassium atoms are placed in channel‐like cavities of the Au–Ga partial structure.     

Über Ordnungsvarianten des NaCl-Typs. Neue kubische Formen von NaMO2 (M=Sc,Y, Dy,Tm, Yb,Lu), K2MO3 Rb2MO3, (M = Ce,Pr, Th) und Cs2ThO3

On Ordered Variants of the NaCl Type of Structure: New Cubic Forms of NaMO₂ (M = Sc, Y, Dy, Tm, Yb, Lu), K₂MO₃, Rb₂MO₃ (M = Ce, Pr, Th), and Cs₂ThO₃ We obtained hithertoo unknown cubic forms of NaScO₂ (a = 4.52₅ Å), NaYO₂ (a = 4.79₁ Å), NaDyO₂ (a = 4.80₀ Å), NaTmO₂ (a = 4.74₃Å), NaYbO₂ (a = 4.73₀ Å), NaLuO₂ (a = 4.71₅ Å) [all colourless], K₂CeO₃ (a = 5.20₃ Å), K₂PrO₃ (a = 5.18₅ Å), K₂ThO₃ (a = 5.30₈ Å), Rb₂CeO₃ (a = 5.39₇ Å), Rb₂PrO₃ (a = 5.36₇ Å), Rb₂ThO₃ (a = 5.47₅ Å), and Cs₂ThO₃ (a = 5.70₄ Å) [colour see ins.] by heating mixtures of the binary oxides AO_x (A = Na, K, Rb, Cs) with active forms of M₂O₃, respectively. It is discussed MO₂, how one may understand the existence of the cubic forms, which according to powder data show a statistical distribution of cations (with different charge and ionic radius).     

Über neue Verbindungen Cs2NaMF6 und K2NaMF6 sowie über Cs2KMnF6

Newly prepared are the cubic derivatives of the perovskite type of structure: K₂NaInF₆ (a = 8.56₀ Å), K₂NaTlF₆ (8.66₈), K₂NaScF₆ (8.48₂), K₂NaYF₆ (8.71₁), Cs₂NaInF₆ (8.90₅), Cs₂NaTiF₆ (8.99₅), Cs₂NaScF₆ (8.85₃), all colourless, as well as K₂NaCuF₆ (8.20₃ Å, green) and Cs₂KMnF₆ (tetragonal, a = 8.93₃; c = 9.26₅ Å, violett). K₂NaCuF₆ [μ = 2.8₇ μ_B, θ = ?17°] and Cs₂KMnF₆ [;μ = 4.8₈ μ_B, θ = ?5°] obey the Curie-Weiss law. The volume chemistry of the compounds is discussed in detail.     

Die KristallStrukturen von K6[Ge2Te6] und K6[Sn2Te6] und ihre kristall-chemische Beziehung zum K6[Si2Te6]-Typ

Crystal Structures of K₆[Ge₂Te₆] and K₆[Sn₂Te₆] and their Relations to the K₆[Si₂Te₆] Type K₆[Ge₂Te₆] and K₆[Sn₂Te₆], the first members of the families of telluro-digermanates and telluro-distannates have been prepared and their structures determined. The space group is C 2/c with cell constants a = 16.010(8), b = 13.619(8), c = 9.713(5) Å, β = 95.19(5)° and Z = 4 for the Ge compound. The Sn compound has space group P 2₁/c, a = 9.590(5), b = 13.654(8), c = 9.606(5) Å, β = 116.84(5) and Z = 2. The structures were established by direct methods, using four-circle diffractometer data. The final R value for 828 (1677) independent reflexions is 0.068 (0.047) for the Ge (Sn) compound. Both structures have discrete X₂Te₆ groups (X = Ge, Sn) in staggered conformation connected by K atoms in distorted octahedral or trigonal prismatic environments and bear direct subgroup relationships to that of K₆[Si₂Te₆]. The average X? Te distance is 2.579 (2.724) Å and the X? X distance 2.492 (2.814) Å.     

Über Sauerstoffperowskite des fünfwertigen Rutheniums ABIIIRuVO6 mit AII = Ba,Sr

On Oxygen Perovskites with Pentavalent Ruthenium A B^IIIRu^VO₆ with A^II = Ba, Sr The perovskites Ba₂B^IIIRu^VO₆ with B^III = La, Nd, Sm, Eu, Gd, Dy, Y, are cubic (B^III = La: a = 8,54₄ Å; Y: a = 8,33₇ Å); with a partial order for B^III and Ru^V. The Sc compound, Ba₂ScRuO₆, has a hexagonal 6 L structure (a = 5.79₅ Å; c = 14.22₉ Å; sequence (hcc)₂)₂. The lattice of the Sr perovskites, Sr₂B^IIIRu^VO₆, with B^III = Eu, Gd, Dy, Y is rhombic distorted. The IR and FRI spectra are discussed.     

Neue Elpasolithvertreter mit CoIII: Cs2KCoF6, Rb2KCoF6, Rb2NaCoF6 (mit einer Notiz über Cs2NaCoF6)

New Elpasolithes with Co^III: Cs₂KCoF₆, Rb₂KCoF₆, Rb₂NaCoF₆ (with a Notice on Cs₂NaCoF₆) New prepared are the compounds Cs₂KCoF₆ (a = 8.97₉ Å), Rb₂KCoF₆ (a = 8.80₉ Å), Rb₂NaCoF₆ (a = 8.42₁ Å), all cubic Elpasolithes, as well as Cs₂NaCoF₆ (Cs₂NaCrF₆?type, hexagonal with a = 6.23, c = 30.32 Å) all of light blue colour. Cs₂KCoF₆ (72.7–299.7 K) and Rb₂KCoF₆ (71.4–298.0 K) have been measured magnetically. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Die Kristallstruktur von Cs2PrO3, sowie über Cs2CeO3, Cs2TbO3, Rb2CeO3 und Rb2TbO3

Crystal Structure of Cs₂PrO₃ and also about Cs₂CeO₃, Cs₂TbO₃, Rb₂CeO₃, and Rb₂TbO₃ New prepared Cs₂PrO₃ (dark brown) is orthorhombic due to single crystal data, K₂PbO₃ type of structure (Cmc2₁) with a = 11.4₇, b = 7.72₂, c = 6.42₇ Å and Z = (4). Cs₂CeO₃ (colourless, a = 11.49₅, b = 7.75₃, c = 6.43₇ Å), Cs₂TbO₃ (red-brown, a = 11.3₇, b = 7.72₆, c = 6.14₂ Å), and the low-temperature form of (LT-) Rb₂TbO₃ (red-brown, a = 10.9₁, b = 7.39₀, c = 6.09₉ Å) are isotypic. Hitherto unknown HT-Rb₂CeO₃ (high-temperature form, colourless, a = 3.83₇, c = 18.4₇ Å, Z = 2, hexagonal) and “HT-Rb₂TbO₃” (red-brown, a = 3.77₃, c = 18.0₀ Å) correspond according to powder-data to the α-NaFeO₂ type of structure. Cs₂PrO₃ has been measured magnetically (100–300 K). The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.