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. 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.     

Kristallstrukturuntersuchungen an Verbindungen des Typs A3(M,Nb)8O21 (A  Tl,Ba; M  Fe,Ni)

Crystal Structure Investigations of Compounds with the A₃(M, Nb)₈O₂₁-Type (A ? Tl, Ba; M ? Fe, Ni) Tl₃Fe_0,5Nb_7,5O₂₁ (A), a hitherto unknown phase of the A₃(M, Nb)₈O₂₁-type, and Ba₃Fe₂Nb₆O₂₁ (B), Ba₃Ni_1.33Nb_6,66O₂₁ (C) were prepared and investigated by single crystal X-ray technique. ((A): a = 9.145(1), c = 11.942(1) Å; (B): a = 9.118(2), c = 11.870(1) Å; (C) a = 9.173(3), c = 11.923(1) Å, space group D? P6₃/mcm, Z = 2). There is a statistic occupation of the M-positions by Nb⁵⁺ and Fe³⁺ or Nb⁵⁺ and Ni²⁺, respectively. An other compound Ba₃Fe₂Ta₆O₂₁ is partially ordered in respect to Ta⁵⁺ and Fe³⁺. Calculations of the Coulomb-part of lattice energy are 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.     

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).     

Uber Hexafluorotitanate (III). Cs2MTiF6 und Rb2MTiF6 (M  K bzw. Na); mit einer Bemerkung über Tl3TiF6

On Hexafluorotitantes (III). Cs₂MTIF₄ and Rb₂MTIF₄(M?K, Na); with a Remark on TI₃TIF₆ By heating the binary fluorides in a closed system we obtained Cs₂KTiF₆ (a = 9.12₄ Å), Rb₂KTiF₆ (a = 8.93₂ Å) and Rb₂NaTiF₆ (a = 8.53₃ Å), all cubic Elpasolithes of light blue colour as well as Cs₂NaTiF₆ (hexagonal a = 6.27₂, c = 30.91 Å, isotypic with Cs₂NaCrF₆) and Tl₃TiF₆ TiF₃ (3.1–295.5°K) and Cs₂KTiF₆ (74.9–297.7°K) have been measured magnetically. The spectra of reflection in the range of 10 000 to 30 000 cm^?1 of TiF₃ and the new quaternary fluorides are similar. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.     

Synthese von (C6F5)2SF+MF6− (M  As,Sb) und Kristallstruktur von (C6F5)2SF+SbF6− [1]

Preparation of (C₆F₅)₂SF⁺MF₆^? (M ? As, Sb) and Crystal Structure of (C₆F₅)₂SF⁺SbF₆^? XeF⁺MF₆^? (M ? As, Sb) reacts with (C₆F₅)₂S in HF to form (C₆F₅)₂SF⁺MF₆^?. The deeply violet sulfonium salts can be kept without decomposition up to 24 h at room temperature. The hexafluoroantimonate salt crystallizes in the monoclinic space group P2₁/n with a = 1056.4(7) pm, b = 1446.3(10) pm, c = 1102.9(8) pm, β = 91.29(6)° und Z = 4. The SF-bond distance with 158.4(3) pm is of unusual length. Cations and anions are connected via interionic fluorine contacts to an infinite chain, in which cations and anions form to ABAB sequence along the chain.     

Über die Ordnung von BIII und MV in Perowskiten vom Typ ABIIIMVO6 (AII  Ba,Sr; MV  Sb,Nb, Ta)

On the Ordering of B^III and M^V in Perovskites of Type A B^IIIM^VO₆ (A^II ? Ba, Sr; M^V ? Sb, Nb, Ta) The perovskites Ba₂B^IIISbO₆ crystallize monoclinic (B^III ? La, Pr, Nd) and cubic (B^III ? Sm, Eu, Gd, Tb, Dy, Yb, Lu, Y) respectively. The Sr compounds, Sr₂B^IIISbO₆, have a monoclinic (B^III ? Nd, Sm, Eu, Dy), orthorhombic (B^III ? Yb, Lu, Y, Sc) or cubic (B^III ? In, Ga) perovskite structure. By intensity calculations and vibrational spectroscopic investigations deviations from a complete order between B^III and Sb^V are detectable. For perovskites Ba₂B^IIIM^VO₆ with M^V ? Nb, Ta the incompleteness of cationic order can be demonstrated as well.     

Kalium-Lanthanoid-Carbonate,KM(CO3)2 (M  Nd,Gd, Dy,Ho, Yb)

Potassium Lanthanoid Carbonates, KM(CO₃)₂ (M ? Nd, Gd, Dy, Ho, Yb) The ternary potassium lanthanoid carbonates KM(CO₃)₂ (M ? Nd, Gd, Dy, Ho, Yb) are obtained as single crystals by high-pressure synthesis in steel autoclaves with carbon dioxide (starting pressure approximately 50 bar at ambient temperature) in the presence of water from a mixture of K₂CO₃ and MCl₃ · x H₂O (x = 7 and 6, respectively) at 450°C within 4 weeks. In KNd(CO₃)₂ (orthorhombic, Pmn2₁, Z = 4, a = 973.1(2), b = 645.69(8), c = 855.58(14) pm, R₁ = 0.0763 for all data) [Nd-μ₁-(CO₃)₃-μ₂-(CO₃)₃] polyhedra are connected three-dimensionally to [Nd(CO₃)] layers as similarly in UO₂(CO₃); these layers are connected via the second half of the carbonate ligands and K⁺ ions. In KDy(CO₃)₂ (monoclinic, C2/c, Z = 4, a = 853.8(2), b = 949.1(1), c = 694.5(1) pm, β = 111.1(2)°, R₁ = 0.0266 for all data) and in the isotypic carbonates KM(CO₃)₂ (M = Gd, Ho, Yb) the polyhedra [Dy-μ₁-(CO₃)₄-μ₂-(CO₃)₂] and [K-μ₁-(CO₃)₆] are connected to “syndiotactic” zig-zag chains and by further O-ligator atoms of the carbonate ligands such that each zig-zag chain is surrounded by four unlike chains and vice versa.     

Über die Diphosphate M4(P2O7)3 mit M = V,Cr und die Elektronenspektren von Vanadium (III)- und Chrom(III)-Phosphaten

On the Diphosphates M₄(P₂O₇)₃ with M = V, Cr and the Electronic Spectra of Vanadium(III) and Chromium(III) Phosphates Single crystals of ochre colored or dark brown V₄(P₂O₇)₃ ( I ) can be obtained by thermal transformation of an amorphous intermediate synthesized from V₂O₅ and aqueous H₃PO₃ and H₃PO₄; brown crystals of Cr₄(P₂O₇)₃ ( II ) are formed during thermal decomposition of Cr(PO₃)₃, C. I and II are isostructural, crystallizing in orthorhombic space group Pbn2₁ or Pbnm with Z = 4 and lattice constants a = 9.601(2), b = 21.425(5), c = 7.470(4) Å and a = 9.38(1), b = 21.00(4), c = 7.26(2) Å, respectively. Probably due to slight substitution of vanadium(V) for phosphorus atoms (P:V^v ～ 40:1) nonstoichiometic phase composition is found for I prepared at T ～ 1400°C. I and II are characterized by IR and electronic spectroscopy; their electronic spectra are discussed in comparison with those of fourteen other V^III and Cr^III phosphates. This includes a discussion of optical properties of CsCrP₂O₇ changing color from brown to green on change from daylight to artificial light. Some conclusions on the structural arrangement of I and II are drawn.     

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.     

Wasserstoffbrückenbindungen in o- und m-Phenylendiammonium-aquapentafluorometallaten(III) (MIII = Al,Cr, Fe)

Hydrogen Bonds in o- and m-Phenylenediammonium Aquapentafluoro Metallates(III) (M^III = Al, Cr, Fe) m- and o-Phenylenediammonium-[M^IIIF₅(H₂O)] compounds of Al, Cr and Fe were synthesized and characterized by X-ray single crystal structure analysis. All structures are described in the space group P2₁2₁2₁ (Z = 4). m-Ph(NH₃)₂²⁺ (Ph(NH₃)₂²⁺ = phenylenediammonium) compounds: Al : a = 6.489(2), b = 7.943(2), c = 18.204(2) Å, R/wR = 0.084/0.050 for 1 533 reflections; Cr : a = 6.571(2), b = 8.006(2), c = 18.456(3) Å, R/wR = 0.050/0.040 for 1 571 reflections; Fe : a = 6.608(2), b = 8.052(2), c = 18.424(4) Å, R/wR = 0.042/0.034 for 1 947 reflections. o-Ph(NH₃)₂²⁺ compounds: Al : a = 6.580(2), b = 7.891(2), c = 18.319(5) Å, R/wR = 0.050/0.045 for 2 370 reflections; Cr : a = 6.642(2), b = 7.954(2), c = 18.484(4) Å, R/wR = 0.065/0.043 for 2 041 reflections; Fe : a = 6.693(2), b = 7.995(4), c = 18.529(7) Å, R/wR = 0.035/0.033 for 2 651 reflections. Isolated distorted octahedral [M^IIIF₅(H₂O)]^2? anions are connected by double O? H ?F hydrogen bonds of alternating strength to form chains in the b direction. Those chains, packed in a pseudohexagonal way, are further linked by the ammonium functions of the phenylenediammonium cations to a 3 D hydrogen bond network.     

Zur Kenntnis komplexer Fluoride mit Cu2+ und Pd2+: MPtF6 (M  Pd,Cu) und RbCuPdF5

On Complex Fluorides with Cu²⁺ and Pd²⁺: MPtF₆ (M ? Pd, Cu) and RbCuPdF₅ For the first time single crystals of PdPtF₆ (green), trigonal-rhomboedric, a = 503.8, c = 1431.6 pm, spcgr. R3 ? C (No. 148), Z = 3, CuPtF₆ (orange), triclinic, a = 495.2, b = 498.5, c = 962.4 pm, α = 89.98, β = 104.23, γ = 120.35°, spcgr. P1 ? C (No. 2), Z = 2 and RbCuPdF₅ (orange brown, in connection with investigations on M^IPd₂F₅ [1]), orthorhombic, a = 626.9, b = 719.9, c = 1076.3 pm, spcgr. Pnma? D (No. 62), Z = 4, four circle diffractometer data, have been obtained.     

Über Geordnete Perowskite mit Kationenfehlstellen. IX. Verbindungen vom Typ Sr2Sr1/4B□1/4WO6≙Sr8SrB□W4O24 (BIII  La,Pr, Nd,Sm – Tm,Y)

On Ordered Perovskites with Cationic Vacancies. IX. Compounds of the Type Sr₂Sr_1/4B □_1/4WO₆?Sr₈SrB ?W₄O₂₄ (B^III ? La, Pr, Nd, Sm–Tm, Y) The compounds Sr₂Sr_1/4B□_1/4WO₆?Sr₈SrB?W₄O₂₄ belong to the group of perovskites with octahedral cationic vacancies (cation/vacancy ratio (CN 6) ?:1). For the larger B^III ions (La, Pr, Nd, Sm–Dy) different ordering effects are observed. The perovskites with B^III ? Sm, Eu, Gd are polymorphic too (HT modification: higher ordered cubic perovskite (B^III ? Gd: a = 2X8.23₄ Å); LT modification: hexagonal perovskite stacking polytype (B^III ? Gd: a = 9.95₄ Å; c = 19.0₄ Å)). With the smaller B^III ions (Ho, Er, Tm and Y) a cubic, 1:1 ordered perovskite type is observed.     

Magnetic Anisotropy in a Family of Experimentally Synthesized and Theoretically Modeled M′6M8(CN24) Systems

A theoretical density functional study of the magnetic coupling interactions and magnetic anisotropy in a family of experimentally synthesized and theoretically modeled M′₆M₈(CN₂₄) (M′=Cu^II, Ni^II or Co^II; M=Fe^III or Cr^III) systems is presented. The calculations show that the interactions in the selected M′₆M₈(CN₂₄) are all ferromagnetic and the near cubic symmetry of Cu₆Fe₈ is the origin of its negative magnetic anisotropy parameter D.     

Crystal Structure of Tetrakis (phenacetin) Dihydrogentetraiodide Dihydrate {[H5C2OC6H4N (H)C(CH3)O]4·H2I4·2H2O}

(Phenacetin)₄·₂I₄·2H₂O is triclinic, a = 13.641 (7), b = 12.807 (6), c = 7.201 (3) Å, α = 99.8 (4), b? = 86.5 (4), γ = 104.0 (5)°, P1 , Z = 1. The ordered crystal structure has been refined to R_F = 0.050, using 4173 independent reflections measured on a four-circle diffractometer with MoKa (graphite monochromator) radiation. The crystals are composed of alternating positively and negatively charged slices; each positive slice contains a double layer of stacks of hemi-protonated phenacetin molecules which are H-bonded through their carbonyl groups (d(O - - - O) = 2.432 (4) Å) while each negative slice contains a single layer of I^2?₄-ions linked in chains along [100] through H-bonds to pairs of water molecules. The axes of the phenacetin stacks are parallel to the planes of the (I^2?₄·2H₂O)-layers. The I^2?₄-ion is centro-symmetric and can be approximately represented as I^?- - - I–I- - - I^? (d(I^? - - - I) = 3.404 (1) Å; d(I–I) = 2.774 (1) Å). The compound is a pseudo-type A basic salt.     

The crystal and molecular structure of 5,5-diphenyloctafluorogermanthrene, (C6H5)2GeC12F8

F---F steric interaction between the two 6,6′-fluorines of the C₆F₄ rings in C₁₂F₈Ge(C₆H₅)₂ cause quite distortions in the molecule as these two fluorine atoms are forced to within 2.419 Å of each other (Van der Waals distance ⋍ 2.7 Å). Crystal data: C₁₂F₈Ge(C₆H₅)₂, M_r 522.89, C2/c, a 29.065(2), b 8.066(2), c 23.000(3) Å, β 129.85°, U 4139.63 ų, Z = 8, D_x 1.678 Mg m⁻³, Mo-K_α, λ 0.7107 Å, μ 15.58 cm⁻¹, F(000) = 2064, T 293 K, R = 0.044 for 2264 reflections with I > 3σ(I); Δϱ ± 0.5 e⁻     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von [(Mo6Br)Y]2−; Ya  CN,NCS

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of [(Mo₆Br )Y ]^2?; Y^a ? CN, NCS By treatment of [(Mo₆Br)Br^a₆]^2? with AgNO₃ in acetone and addition of KCN or KNCS the hexacyano and hexaisothiocyanato derivates [(Mo₆Br)Y]^2?, Y^a ? CN, NCS are formed. X-ray structure determinations of (Ph₄P)₂ [(Mo₆Br)(CN)^a₆]·4H₂ O ( 1 ) (triclinic, spacegroup P1, a = 11.63(3), b = 11.85(1), c = 14.23(5) Å, α = 71.8(1)°, β = 67.6(3)°, γ = 62.8(1)°, Z= 1) and (n-Bu₄N)₂[(Mo₆Br ⁱ₈)(NCS)^a₆] · 2Et₂O ( 2 ) (monoclinic, spacegroup P2₁/n, a = 11.483(3), b = 16.348(5), c = 20.059(6) Å, β= 95.44(3)°, Z = 2) have been performed. The via C coordinated cyano ligands of ( 1 ) reveal facial groups with (MoCN) angles of 168.0–171,5° and 174.1°–175.7°. In ( 2 ) the via N coordinated isothiocyanato groups at the apical positions show MoNC-angles of 164.4°, the equatorial angles are 172.7–173.5°. Using the molecular parameters of the X-ray determinations the 10 K IR and Raman spectra of the (n-Bu₄N) cluster salts are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(MoMo) = 1.41 (CN^a), 1.43 (NCS^a), f_d (MoBrⁱ) = 0.97 (CN^a), 0.96 (NCS^a), f_d(MoC) = 1.62, f_d(Mo-N) = 2.09 mdyne/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.     

Über Hexafluorovanadate(III). Cs2MVF6 und Rb2MVF6 (MTl,K und Na); mit einer Bemerkung über Na3VF6

On Hexafluorovanadates(III). Cs₂MVF₆ and Rb₂MVF₆ (M?Tl, K. and Na); with a Remark on Na₃VF₆ By heating the binary fluorides in a closed system we obtained Cs₂TlVF₆ (a = 9.23₄ Å), Cs₂KVF₆ (a = 9.04₇ Å), Rb₂KVF₆ (a = 8.85₅ Å) and Rb₂NaVF₆ (a = 8.46₈ Å), all cubic Elpasolithes of soft green colour as well as Cs₂NaVF₆ (hexagonal a = 6.24 Å, c = 30.58 Å, isotypic with Cs₂NaCrF₆) and Na₃VF₆ (monoclinic a = 5.51₃ Å, b = 5.72₁ Å, c = 7.96₃ Å, β = 90.4₇°, isotypic with Na₃AlF₆). VF₃ (3.0–296.2°K), Cs₂TlVF₆, Cs₂KVF₆ and Rb₂KVF₆ (all from 70–299°K) have been measured magnetically. The spectra of reflection in the range of 9 000 to 33 000 cm^?1 of VF₃ and the new quaternary fluorides are measured and discussed. The Madelung Part of Lattice Energy (MAPLE) is calculated and discussed.