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 der RbNiCrF6Typs. III. Neue Fluoride des Typs CsZnMF6 mit M = Al,Ga, In,Tl, Sc,Ti, V,Mn, Cu,Rh

On the RbNiCrF₆ Type. III. New Fluorides of the Type CsZnMF₆ (M = Al, Ga, In, Tl, Sc, Ti, V, Mn, Cu, Rh) Cubic compounds are CsZnGaF₆ [3] (colourless, a = 10.29 Å); CsZnInF₆ (colourless, a = 10.58 Å); CsZnTlF₆ (colourless, a = 10.62 Å); CsZnScF₆ (colourless, a = 10.58 Å); CsZnTiF₆ (lightblue, a = 10.50 Å); CsZnVF₆ (lightgreen, a = 10.43 Å); CsZnMnF₆ (redbrown, a = 10.40 Å); CsZnCuF₆ (light brown, a = 10.24 Å); CsZnRhF₆ (redbrown, a = 10.41 Å), all RbNiCrF₆ type of structure, in addition non cubic: CsZnAlF₆ (colourless). 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.     

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.     

Ternäre Fluoride mit vierwertigem Chrom: M″CrF6mit M″ = Ba,Sr, Ca,Mg, Zn,Cd, Hg,Ni

Ternary fluorides with tetravalent chromium: M^IICrF₆ with M^II = Ba, Sr, Ca, Mg, Zn, Cd, Hg, Ni. We obtained hithertoo unknown BaCrF₆ (light yellow) and SrCrF₆ (yellow), both of (hexag.) BaSiF_B-type [a = 7.32₈, c = 7.13₇ Å; and a = 7.10₉ c = 6.86₃ Å, respectively] as well as CaCrF₆ (pink) [a = 5.33₆, c = 14.15₃ Å], MgCrF₆ (pink) [a = 5.09₁ c = 13.14₃ Å], CdCrF₆ (pink) [a = 5.14₆, c = 14.07₅ Å] and HgCrF₆ (orange-yellow) [a = 5.12₈, c = 14.26₅ A], all of (hexag.) LiSbF₆-type. NiCrF₆ (brown) [a = 4.97₅, c = 13.26₂ Å] and ZnCrF₆ (orange-yellow) [a = 5.02₆, c = 13.33₇ Å] crystallize in the hexag. VF₃-type.     

Zur Kenntnis der Fluoride zweiwertiger Lanthanoide. III. Neue Fluoroperowskite vom Typ CsLn1−xLn′xF3 und RbLn1−xLn′xF3 mit Ln = Eu2+ bzw. Sm2+ und Ln′ = Yb2+

On Fluorides of Divalent Lanthanoids. III. New Fluoroperovskites of the MLn_1?xLn′_xF₃ Type with M = Cs, Rb; Ln = Eu²⁺, Sm²⁺; Ln′ Yb²⁺ New fluoroperovskites with divalent lanthanoids have been prepared. They are: CsEu_1?xYb_xF₃, yellow, with x = 0.25, a = 4.737(1) Å; x = 0.50, a = 4.696(1) Å; x = 0.75, a = 4.653(1) Å; CsSm_xYb_1?xF₃, violet, with x = 0.25, a = 4.656(1) Å; x = 0.18, a = 4.645(1) Å, the latter mixed with Sm_0.68Yb_0.32F₃, a = 5.781(1) Å; RbEu_xYb_1?xF₃, orange, with x = 0.25, a = 4.573(1) Å; x = 0.23, a = 4.568(1) Å, the latter mixed with Eu_0.94Yb_0.06F₂, a = 5.827(1) Å; RbSm_0.13Yb_0.87F₃, brown, a = 4.555(1) Å.     

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.     

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.     

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3– und trans‐[Rh(CN)2(SeCN)4]3–, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

Synthesis and Spectroscopic Characterization of [Rh(SeCN)₆]^3– and trans ‐[Rh(CN)₂(SeCN)₄]^3–, Crystal Structure of (Me₄N)₃[Rh(SeCN)₆] Treatment of RhCl₃ with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)₆]^3– and trans‐[Rh(CN)₂(SeCN)₄]^3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me₄N)₃[Rh(SeCN)₆] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me₄N)₃[Ir(SCN)₆]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu₄N)₃[Rh(SeCN)₆] ( 1 ) and trans‐(n‐Bu₄N)₃[Rh(CN)₂(SeCN)₄] ( 2 ) are in the range of 170–250 cm^–1. In 2 ν_as(CRhC) is observed at 479 cm^–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and f_d(RhC) = 3.14 mdyn/Å ( 2 ). f_d(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)₆]^3–, which has not been calculated so far. The ¹⁰³Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the ⁷⁷Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the ¹³C NMR spectrum at 136.3 ppm.     

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.     

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.     

Zur Kenntnis Neuer Hexafluoroplatinate(IV)

On New Hexafluoroplatinates(IV) New prepared are PbPtF₆ (light yellow), hex. BaGeF₆-Type, [a = 7.22₇, c = 7.07₁ Å]; CaPtF₆ (light yellow) [a = 5.24₅, c = 14.78₄ Å]; ZnPtF₆ (light yellow) [a = 4.98₀, c = 13.82₈ Å]; CdPtF₆ (light yellow) [a = 5.11₈, c = 14.62₃ Å]; HgPtF₆ (light yellow) [5.13₂, c = 14.81₄ Å]; MnPtF₆ (ocker) [a = 5.09₄, c = 14.23₁ Å], CoPtF₆ (light brown) [a = 5.00₂, c = 13.81₅ Å]; NiPtF₆ (egg yellow) [a = 4,93₇, c = 13.68₇Å], all these of hex. LiSbF₆-structure. The structure of CuPtF₆ (light yellow) is yet unknown.     

Synthesis and X-ray diffraction study of LaM 1.5 II MnFeO6 manganitoferrites (MII = Mg,Ca, Sr,Ba)

LaM _1.5 ^II MnFeO₆ manganitoferrites (M^II = Mg, Ca, Sr, Ba) have been synthesized by ceramic technology from lanthanum oxide, manganese(III) oxide, iron(III) oxide, and alkali-earth carbonates. X-ray powder diffraction shows that these compounds crystallize in cubic crystal system with the following unit cell parameters: for LaMg_1.5MnFeO₆: a = 20.232 ± 0.032 Å, V ⁰ = 8281.642 ± 0.096 ų, Z = 10, ρ_X = 7.38 g/cm³, ρ_pycn = 7.29 ± 0.06 g/cm³; for LaCa_1.5MnFeO₆: a = 20.056 ± 0.017 Å, V ₀ = 8067.388 ± 0.051 ų, Z = 8, ρ_X = 5.89 g/cm³, ρ_pycn = 5.78 ± 0.06 g/cm³; for LaSr_1.5MnFeO₆: a = 20.117 ± 0.021 Å, V ₀ = 8141.223 ± 0.063 ų, Z = 8, V _u.c. ⁰ = 1017.653 ± 0.008 ų, ρ_X = 6.64 g/cm³, ρ_pycn = 6.56 Å 0.08 g/cm³; for LaBa_1.5MnFeO₆: a = 20.361 ± 0.025 Å, V ₀ = 8441.066 ± 0.075 ų, Z = 8, ρ_X = 7.31 g/cm³, ρ_pycn = 7.25 ± 0.07 g/cm³.     

The structure of R-NiF3, and synthesis,and magnetism of new R3 MIINiIVF6 (M = Fe,Co, Cu,Zn), and MIINiIIF4 (M = Co,Cu)

Neutron diffraction, at 2 K, of R-NiF₃ indicates the formulation approaches Ni^IINi^IVF₆, with Ni^II − F = 1.959(3) and Ni^IV − F = 1.811(3) Å, but 295 K data allow for only a slight increase in any Ni^III. Relatives have been precipitated from liquid anhydrous HF, at ≤ 20 °C, by adding K₂NiF₆ to M(SbF₆)₂ (M = Co, Cu, Zn) or M(AsF₆)₂ (M = Fe). CuNiF₆ like NiNiF₆ is metastable and loses F₂ easily, above 40 °C. CuNiF₆ is reduced by Xe or C₃F₆ at −20 °C; CoNiF₆ by H₂ at 350 °C, each giving pseudo-rutile MNiF₄. Magnetic data indicate the dominant formulation is M^IINi^IVF₆ (Ni(IV) low spin d⁶) with field dependence in CoNiF₆ (≤ 220 K) and FeNiF₆ (≤ 295 K).     

Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

X-ray diffraction characteristics of new chromitomanganites LaM 3 I CrMnO6 and LaM 3 II CrMnO7.5 (MI = Li, Na; MII = Mg, Ca)

LaM ₃ ^I CrMnO₆ (M^I = Li, Na) and LaM ₃ ^II CrMnO_7.5 (M^II = Mg, Ca) chromitomanganites were synthesized by ceramic technology from lanthanum oxide, chromium(III) oxide, manganese(III) oxide, lithium carbonate, sodium carbonate, magnesium carbonate, and calcium carbonate. X-ray powder diffraction shows that these compounds crystallize in cubic or tetragonal systems with the following unit cell parameters: for LaLi₃CrMnO₆ (cubic): a = 10.98 Å, V ^○ = 1323.75 ų, Z = 8, V _u.c ^○ = 165.47ų, ρ_X = 3.64, ρ_pycn= 3.60 ± 0.04 g/cm³; for LaNa₃CrMnO₆ (tetragonal): a = 10.96 Å, c = 15.73 Å, V ^○ = 1889.51 ų, Z = 16, V _u.c ^○ = 118.09 ų, ρ_X = 5.77 g/cm³, ρ_pycn = 5.70 ± 0.07 g/cm³; LaMg₃CrMnO_7.5 (cubic), a = 10.98 Å, V ^○ = 1322.31 ų, Z = 8, V _u.c ^○ = 165.29 ų, ρ_X = 4.41 g/cm³, ρ_pycn = 4.35 ± 0.07 g/cm³; and for LaCa₃CrMnO_7.5 (cubic): a = 10.97 Å, V ^○ = 1319.78 ų, Z = 8, V _u.c ^pO = 164.97 ų, ρ_X = 4.89 g/cm³, ρ_pycn = 4.85 ± 0.05 g/cm³.     

Synthesis of [M(NH3)5Cl](ReO4)2 (M = Cr, Co, Ru, Rh, Ir) and investigation of thermolysis products. Crystal structure of [Rh(NH3)5Cl](ReO4)2

Complex salts [M(NH₃)₅Cl](ReO₄)₂, where M = Cr, Co, Ru, Rh, Ir, have been prepared. The crystal structure of [Rh(NH₃)₅Cl](ReO₄)₂ was determined by single crystal X-ray diffraction. Crystal data: a = 17.369(4) Å, b = 7.7990(16) Å, c = 11.218(2) Å, V = 1430.5(5) ų, space group C2/m, Z = 4, d _calc = 3.19 g/cm³, R = 0.0447. Complex salts from the above series are shown to be isostructural; they were defined by X-ray crystallography. Thermal decomposition of the compounds in an inert atmosphere and under hydrogen has been studied. According to X-ray phase analysis (XRPA) data, the M_0.33Re_0.67 (M = Co, Ru, Rh, Ir) monophase solid solutions are the products of reduction of the salts under hydrogen.     

Synthesis and x-ray diffraction study of new nanostructured manganite ferrites NdM 1.5 II MnFeO6 (MII = Mg, Ca, Sr, Ba)

Manganite ferrites NdM _1.5 ^II MnFeO₆ (M^II = Mg, Ca, Sr, Ba) were synthesized from neodymium(III), manganese(III), and iron(III) oxides and alkaline-earth metal carbonates by a ceramic technology. By grinding the obtained compounds in a ball mill, their nanostructured particles were produced, the sizes of which were determined with an electron microscope. X-ray diffraction study established that the nanostructured compounds crystallize in the cubic and tetragonal systems with the following lattice parameters: NdMg_1.5MnFeO₆ (tetragonal): a = 10.955 Å, c = 17.848 Å, V ⁰ = 2141.975 ų, Z = 16, V _e1.cel1 ⁰ = 133.873 ų, ρ_X-ray = 4.80 g/cm³, and ρ_pycn = 4.76 ± 0.05 g/cm³; NdCa_1.5MnFeO₆ (cubic): a= 10.809 Å, V ⁰ = 1262.864 ų, Z = 8, V _e1.cel1 ⁰ = 157.858 ų, ρ_X-ray = 4.32 g/cm³, and ρ_pycn = 4.27 ± 0.03 g/cm³; NdSr_1.5MnFeO₆ (cubic): a = 10.911 Å, V ⁰ = 1298.953 ų, Z = 8, V _e1.cel1 ⁰ = 162.369 ų, ρ_X-ray = 4.93 g/cm³, and ρ_pycn= 4.88 ± 0.05 g/cm³; and NdBa_1.5MnFeO₆ (tetragonal): a = 11.011 Å, c = 18.001 Å, V ₀ = 2182.479 ų, Z = 16, V _e1.cel1 ⁰ = 136.405 ų, ρ_X-ray = 6.78 g/cm³, and ρ_pycn= 6.75 ± 0.07 g/cm³.     

Duroquinonerhodium(I) complexes. Crystal structure of [Rh(DQ)(C6H5Me)]PF6

The preparation of cationic arenerhodiiim(I) complexes of the type [Rh(DQ)-(arene)]PF₆ (DQ = duroquinone; arene = C₆H_6-nMe_n, n duroquinone complexes with Group VB donor ligands are described. The crystal structure of [Rh(DQ)(C₆H₅Me)]PF₆ has been determined by X-ray diffraction. The compound crystallizes in the P2₁/n space group, in a unit cell of dimensions a 15.9866(5), b 11.8438(3), c 9.9968(3) Å, β 98.473(4)Å. The structure was solved by Patterson and Fourier methods and refined to R and R_w values of 0.062 and 0.076, respectively. The Rh atom is coordinated to a toluene group (η⁶) and a duroquinone ligand (η⁴), which eclipse each other. Both ligands are distorted to adopt boat-like conformations.     

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.