Über Komplexe Fluoride des zweiwertigen Palladiums

On Complex Fluorides of Divalent Palladium For the first time single crystals of the new compounds RbPdPdF₅, KPdPdF₅, and K₂CsPdF₅ have been obtained. Orange brown RbPdPdF₅ crystallizes orthorhombic, space group Imma–D_2h²⁸ (No. 74) with a = 633.6(1) pm, b = 765.5.(1) pm, c = 1067.5(1) pm and Z = 4 and is isotypic with CsPdPdF₅ [1]. Structure related KPdPdF₅ (also orange brown) crystallizes orthorhombic too, but in space group Pnma–D_2h¹⁶ (No. 62) with a 614.12(9) pm, b = 748.7(1) pm, c = 1065.0(2) pm and Z = 4. K₂CsPdF₅, light yellow, crystallizes tetragonal with a = 736.3(1) pm, c = 628.0(1) pm, Z = 2, and is isotypic with Rb₂CsPdF₅ (space group P4/mbm? D_4h⁵ Nr. 127), an ordered structure variant of the Rb₃PdF₅-Type [1].     

Darstellung und Kristallstruktur von K6[Al2O6] und Rb6[Al2O6]

Preparation of Crystal Structure of K₆[Al₂O₆] and Rb₆[Al₂O₆] Colourless single crystals of K₆[Al₂O₆] have been prepared from intimate mixtures of KAlO₂ and K₂O (550°C, 90 d). The structure determination from four-circle diffractometer data (MoKα , 742 I_o(hkl), R = 2.2%, R_w = 2.1%) confirms the space group C2/m with Z = 2; a = 698.25 pm, b = 1 103.54 pm, c = 646.49 pm, β = 102.49°. Colourless single crystals of hitherto unknown Rb₆[Al₂O₆] have been prepared from intimate mixtures of RbAlO₂ and Rb₂O (520°C, 120 d). The structure determination from four-circle diffractometer data (MoKα , 1 240 I_o(hkl)) results in the residual values R = 7.2%, R_w = 4.9%; space group C2/m; a = 725.92 pm, b = 1 143.33 pm, c = 678.06 pm, β = 104.05°; Z = 2. K₆[Al₂O₆] and Rb₆[Al₂O₆] are isostructural with K₆[Fe₂O₆]. A characteristic structure unit is the anion [Al₂O₆]^6? consisting of two edge-sharing [AlO₄] tetrahedra. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.     

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.     

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 Oxide mit dem “Butterfly-Motiv”: Rb6[Fe2O5] und K6[Fe2O5]

New Oxides with the “Butterfly-Motive”: Rb₆[Fe₂O₅] and K₆[Fe₂O₅] Rb₆[Fe₂O₅] and K₆[Fe₂O₅] were obtained for the first time by annealing intimate mixtures of “Rb₆CdO₄” with CdO (molar ratio 1 : 1.1) and KO_0.48 with CdO (molar ratio 5.9 : 1) respectively in closed Fe-cylinders. Determination and refinement of the crystalstructure confirms the space group C2/m (four-circle-diffractometer data). Rb₆[Fe₂O₅]: Ag Kα , 720 out of 1220 Io(hkl), R = 9.68%, R_w = 6.09%; a = 718.9pm, b = 1183.1 pm, c = 695.4pm, β = 95.05°, Z = 2; K₆[Fe₂O₅]: MoKα , 1214 Out of 12141_o(hkl), R = 3.20070, R_w = 2.48%, a = 691.21 pm, b = 1142.78pm, c = 665.50pm, β = 93.82°, Z = 2. The binuclear unit [O₂FeOFeO₂]^6? already known to be planar with oxoferrates(II) now was observed to be angular here and closely related to Na₆[Be₂O₅].     

Die Antimonid–Triantimonidometallate(III) Cs6K3Sb[AlSb3] und Cs6K3Sb[GaSb3]

The Antimonide Triantimonidometallates(III) Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] The novel compounds Cs₆K₃Sb[AlSb₃] and Cs₆K₃Sb[GaSb₃] are formed from stoichiometric mixtures of Cs, AlSb (GaSb) and KSb in sealed niobium ampoules at 950 K. The hexagonal structures are especially characterized by one-dimensional rod packings ¹∞[Cs₆K₃Sb] which are formed from columns of condensed (Cs₆K_6/2) icosahedra. The icosahedra are centered by Sb^3-? anions. The trigonal planar anions [AlSb₃]^6-? and [GaSb₃]^6-? are embedded between the icosahedra columns, and they are coordinated by alkali metal atoms. The FIR spectra were assigned to the vibrations of the [MSb₃]^6-? anions, with respect to the 6 m2-D_3h symmetry. (P6₃/mmc, No. 194; a = 1101.7 and 1097.2 pm; c = 1158.9 and 1150.1 pm; Z = 2; Single crystal data: 574 and 546 reflections; R = 0.073 and 0.029. Distances:d(Al? Sb) = 265.4 pm; d(Ga? Sb) = 265.1 pm; d(Sb? Cs) = 401.6–423.0 pm; d(Sb? K) = 358.6–367.3 pm).     

Die Kristallstruktur des gemischtvalenten Eisenfluoridhydrates Fe3F8 · 2 H2O

Crystal Structure of the Mixed-Valence Iron Fluorid Hydrate Fe₃F₈ · 2 H₂O Newly prepared was the red, monoclinic compound Fe₃F₈ · 2 H₂O, single crystals of which could be obtained under hydrothermal high pressure conditions (space group C2/m with a = 761.2(3), b = 750.0(1), c = 746.9(3) pm, β = 118.38(2)° and Z = 2). The X-ray structure determination (R_G = 0.0192 and 635 reflexions) yielded a framework structure, in which layers of octahedra 2[Fe^IIIF_6/2] are connected via corners of [Fe^IIF_4/2(H₂O)₂]-octahedra. The average distances in the nearly ideal octahedra are Fe^III? F = 193.0, Fe^II? F = 208.1 and Fe^II? OH₂ = 211.5 pm.     

New Pd(II) fluorides

Single crystals of CsPd₂F₅ (orange-brown, ImmaD²⁸_2h, No. 74; Z = 2; a = 6.53₃, b = 7.86₂, c = 10.79 ā)have been obtained (instead of ‘CsPdF₃’) by heating mixtures of CsF and PdF₂ (ratio 1:1) in sealed gold tubes (under dry Ar) up to t ≈ 600°C (20–3O d). The structure is related closely to the CsAgFeF₆-type of structure [1], but, because of the ‘absence’ of one F^?, one half of the Pd²⁺-ions is coordinated planar quadratically, the other half octehedrally. From Guinier data are isotypic Me^IPd₂F₅ (Me^I  K, Rb, Tl), brown and CsMe^IIPdF₅ (Me^II  Zn, Cd, Ni, Co, Mg), brown or yellow.Under similar conditions single crystals of Rb₃PdF₅ (yellow, P4/mbm-D⁵_4h, No. 127; Z = 2, a = 7.46₇, c = 6.49₇ ā) have been obtained (instead of ‘Rb₂PdF₄’) by heating mixtures of RbF and PdF₂ (ratio 2:1) in sealed gold tubes (under dry Ar) up to t ≈ 560°C (20–30 d). The coordinationnumber of Pd²⁺ is C.N. = 4 (planar quadratic). Isotypic are (single crystal data) Cs₃PdF₅, Rb₂CsPdF₅ (with ordered distribution of Rb, Cs) and K₃PdF₅, all yellow.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

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.     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

Ein neues Bleistrontiumferrat(III): Die Kristallstruktur der Phase Pb4Sr2Fe6O15

A New Lead Strontium Ferrate(III): The Crystal Structure of the Phase Pb₄Sr₂Fe₆O₁₅ At orthorhombic single crystals of Pb₄Sr₂Fe₆O₁₅ (a = 568.73(8), b = 392.03(4), c = 2107.5(3) pm; Z = 4/3, space group Pnma) a X-ray structure determination has been performed (R₁ = 0,036 for 488 ?observed”? resp. wR₂ = 0,073 for all 643 independent reflexions). It revealed a framework of polyhedra related to perovskite, in which chains of edgesharing pyramids [FeO₅] (average Fe1? O: 197 pm; Fe1? Fe1: 305.5 pm) are linked via apices with corner-sharing [FeO₆] octahedra (Fe2? O: 201 pm). 12–fold, strongly distorted cuboctahedrally coordinated ?perovskite positions”? show mixed occupancy by 2/3 Sr + 1/3 Pb (= Sr2; Sr2? O: 287 pm). More spacy channels, running parallel to the chains of pyramids along [010] of the structure, contain lead atoms only. The double occupancy of the corresponding cages results in short distances Pb1? Pb1 (355.9 pm) and Pb1? Fe2 (314.4 pm), as well as in a very asymmetric [PbO₆] coordination (Pb1? O: 253 pm), in the opposite hemisphere of which the lone electron pair s² is supposed to be located. Details are communicated and structural relations discussed.     

Discrete Pr6Pd Octahedra in Pr6Pd13Cd4 – An Intermetallic Analogon to the Subnitride Na16Ba6N

The new intermetallic compound Pr₆Pd₁₃Cd₄ was synthesized from the elements in a sealed tantalum ampoule in an induction furnace. Pr₆Pd₁₃Cd₄ was investigated by X‐ray powder and single crystal diffraction: Na₁₆Ba₆N type, , a = 975.6(1) pm, wR2 = 0.0192, 162 F² values and 12 variables. The striking motif of the Pr₆Pd₁₃Cd₄ structure are discrete palladium centred Pr₆ octahedra (296 pm Pr–Pd1) in bcc packing. The octahedra are embedded by a three‐dimensional [Pd₃Cd] network with short Pd–Pd (282 pm) and Pd–Cd (274 pm) distances. The structural similarities with the subnitrides Na₁₆Ba₆N and Ag₁₆Ca₆N are discussed.     

Darstellung und Kristallstrukturen der ersten Alkalimetall‐hexacarbonatooxotetraberyllate: K6[Be4O(CO3)6] · 7 H2O und K6[Be4O(CO3)6]

Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K₆[Be₄O(CO₃)₆] · 7 H₂O and K₆[Be₄O(CO₃)₆] K₆[Be₄O(CO₃)₆] · 7 H₂O has been prepared by dissolving freshly precipitated Be(OH)₂ in an aqueous KHCO₃ solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, V_EZ = 1290, 6(3)·10⁶ pm³, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, V_EZ = 2961, 4(3)·10⁶ pm³, Z = 6).     

Ein neues Oxotantalat(V): Über KLi6[TaO6] [1]

A New Oxotantalate(V): On KLi₆[TaO₆] [1] For the first time hitherto unknown KLi₆[TaO₆] was obtained by intimately pulverized mixtures of K₂O, Li₂O and Ta₂O₅ (molar ratio K:Li:Ta = 1.1:6.6:1) in a closed Ni-cylinder (800°C, 30 d) in form of colourless single crystals; trigonal-rhomboedral (space group R3 m) with a = 822.6(1) pm, c = 721.2(1) pm (Guinier-Simonpowder data), Z = 3. The determination of the crystal structure (four cycle diffractometer data, 224 out of 224 I₀ (hkl), R = 1.80%, R_w = 1.79%, absorption not considered) proves that KLi₆[TaO₆] is isotypic with KLi₆[IrO₆], a stuffed derivative of the α-Li₆[UO₆] structure type. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Ionic Radii, MEFIR, as well as the Charge Distribution, CHARDI, are calculated and discussed.     

Die Kristallstruktur von KPdMIVF7 (MIV = Zr,Hf)

The Crystal Structure of KPdM^IVF₇ (M^IV = Zr, Hf) Blue single crystals of KPdZrF₇ are obtained by heating the binary fluorides in sealed Pt-tubes under dry argon (solid state reaction, T ≈? 720°C, t ≈? 14 d). The compound crystallizes orthorhombically in the space group Pnna-D (Nr. 52); lattice parameters are a = 1 132.3(5) pm, b = 797.5(2) pm, c = 639.8(1) pm; Z = 4 (Four cycle diffractometer data, AED2). According to [F₄PdF_2/1ZrF₅] distortet [PdF₆]-octaedra are connected with pentagonal-bipyramidal [ZrF₇]-polyhedra via two bridging F^?, resulting in [PdZrF₁₁]-groups. These [PdZrF₁₁]-groups built up a threedimensional-network with K⁺ in its spacings. KPdHfF₇ crystallizes isotypically (a = 1 136.1(3) pm, b = 796.4(2) pm und c = 638.8(1) pm; four cycle diffractometer data, AED2).     

Ein- und zweikernige Fluorokomplexe des Titan(III), Chrom(III) und Eisen(III) Darstellung und Struktur von (NMe4)(Ti(H2O)4F2)TiF6 · H2O, (NMe4)3Cr2F9 und (NMe4)3Fe2F9

Mono- and Dinuclear Fluoro Complexes of Titanium (III), Chromium (III), and Iron(III). Syntheses and Structures of (NMe₄) (Ti(H₂O)₄F₂)TiF₆ · H₂O, (NMe₄)₃Cr₂F₉, and (NMe₄)₃Fe₂F₉ The title compounds have been prepared by reaction of MCl₃ (M = Ti, Cr, Fe) with NMe₄F in dimethylformamide. (NMe₄)₃Cr₂F₉ and (NMe₄)₃Fe₂F₉ contain the face-sharing biocathedral M₂F₉^3? unit. The M…M distances are 277.1(1) and 289.8(3) pm in (NMe₄)₃Cr₂F₉ and (NMe₄)Fe₂F₉, respectively. (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O contains trans-Ti^III(H₂O)₄F₂⁺ cations and Ti^IVF₆^2? anions. Crystal data: (NMe₄)₃Cr₂F₉: hexagonal, space group P6₃/m, a = 804.1(3), c = 1857.5(4) pm, Z = 2, 529 reflections, R = 0.049; (NMe₄)₃Fe₂F₉: hexagonal, space group P6₃/m, a = 804.7(5), c = 1 861.6(5) pm, Z = 2, 635 reflections, R = 0,046; (NMe₄)(Ti(H₂O)₄F₂)TiF₆ · H₂O: orthorhombic, space group Pbca, a = 776.9(2), b = 1 616.3(3), c = 2 428.6(7) pm, Z = 8, 2 784 reflections, R = 0,056.     

Kristallstruktur des „supramolekularen”︁ Komplexes [Cs2(18-Krone-6)][HgI4] mit ungewöhnlich koordinierten Cs-Ionen

Crystal Structure of the “Supramolecular” Complex [Cs₂(18-crown-6)][HgI₄] with Unusually Coordinated Cs Ions The reaction of 18-crown-6, 1,4,7,10,13,16-hexaoxacyclooctadecane, with HgI₂/CsI in methanol yields crystals of [Cs₂(C₁₂H₂₄O₆)][HgI₄]. The compound crystallizes monoclinically, space group P2₁/c, Z = 4, a = 1574.8(3), b = 1067.0(3), c = 1693.2(6) pm, and β = 98.29(3)º. The structure consists of a network made up of two different types of [Cs-(18-crown-6)-Cs]²⁺ cations, interconnected by [HgI₄]^2? anions. The cations form an “anti-sandwich” structure with relatively short Cs ? Cs distances of 382 pm in the first type of cations and a longer distance of 480 pm in the second type of cations.     

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.