Zur kenntnis ‚Kationen-reicher’︁ Tantalate und Niobate Über Na5TaO5 und Na5NbO5

On Tantalates and Niobates ‘rich in Cations’. On Na₅TaO₅ and Na₅NbO₅ Colourless, transparent single crystals of Na₅TaO₅ [annealed mixtures of Na₂O, Li₂O, and Ta₂O₅, Na : Li : Ta = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] as well as Na₅NbO₅ [annealed mixtures of Na₂O, Li₂O, and Nb₂O₅, Na : Li : Nb = 6.6 : 1.1 : 1, Ni-cylinder, 1000°C, 75 d] have been prepared. Single crystal data show that both isotypic oxides represent a deformed variant of the NaCl-type of structure [Na₅TaO₅: 1154 from 1250 I₀ (hkl), four-cycle diffractometer Philips PW 1100, ω2-θ scan, Ag? Kα , R = 4.88%, space group c2/c with a = 629.3(1) pm, b = 1025.4(2) pm, c = 1004.6(2) pm, b? 106.80(2)°, z = 4 and Na₅NbO₅: 998 from 1247 I₀(hkl), four-cycle diffractometer Philips PW 1100, ω-2θ scan, Ag? Kα , R = 8.58% and R_w = 7.67%, space group C2/2 with a = 629.1(1) pm, b = 1024.4(2) pm, c = 1004.2(2) pm, b? = 106.80(2)°, Z = 4]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Fictive Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.     

Symmetrieverwandtschaften bei Varianten des ReO3‐Typs

Symmetry Relationships among Derivatives of the ReO₃ Type The relationships among the derivatives of the ReO₃ structure type have been rationalized with a genealogical tree of group‐subgroup relations between the corresponding space groups. The symmetry reductions from the space group Pm3¯m of the ReO₃ type result from tilting or distortions of the coordination octahedra, and also when there is an ordered substitution of the Re position by atoms of several elements. One branch of the genealogical tree contains different modifications of WO₃. Another branch contains skutterudite (CoAs₃) and several hydroxides like In(OH)₃ or CaSn(OH)₆; in these the octahedra tilting is such that square As or (OH^—)₄ units result. Somewhat different tiltings have been found among CuSn(OH)₆ and NaSb(OH)₆. A third branch comprehends cubic and rhombohedral structures like NaSbF₆, VF₃ and LiSbF₆ and their derivatives. The rhombohedral structures have octahedra that have been rotated about a threefold rotation axis; in addition, different distortions occur. The genealogical tree shows between which structure types second order phase transitions may be considered and what kinds of twinned crystals can possibly be expected.     

The crystal structures of two Mercury Perrhenates

The mercury perrhenates with the empirical formulas HgReO₄ and Hg₂ReO₅ were prepared by annealing powdered mixtures of mercury(II)oxide and mercury(II)metaperrhenate Hg(ReO₄)₂ in sealed silica tubes. Their crystal structures were determined from single-crystal X-ray data. HgReO₄ crystallizes dimeric with nearly linear O₃Re? O? Hg? Hg? O? ReO₃ molecular units and Hg₂ReO₅ has a solid state structure, where Hg(I) and Hg(II) together with oxygen atoms form 14-membered rings, which are condensed to two-dimensionally infinite polycationic nets of composition (Hg₂²⁺ · 2 HgO)_n. These nets are separated from each other by tetrahedral ReO₄^? anions.     

[{ReN(PMe2Ph)3}{ReO3N}]2 – Structural Evidence for the Nitridotrioxorhenate(VII) Anion, [ReO3N]2−

Air‐stable, orange‐red single crystals of [{ReN(PMe₂Ph)₃}{ReO₃N}]₂ are formed when mer‐[ReNCl₂(PMe₂Ph)₃] reacts with strong bases in MeOH. The resulting centrosymmetric tetranuclear complex contains each two {ReN(PMe₂Ph)₃}²⁺ and {ReO₃N}^2? building blocks. They are connected by two oxygen and two nitrogen atoms giving an almost planar {Re₄O₂N₂} ring. The Re–N–Re bridges are only slightly bent (175.2(2)°), while the Re–O–Re angles are 160.9(1)°. The coordination environment of the rhenium atom in the nitridotrioxorhenate(VII) anion is a slightly distorted tetrahedron with O–Re–O and O–Re–N angles between 108.7(1)° and 111.3(1)°.     

Die Kristallstruktur des Natriumoxohydroxoaluminathydrates Na2[Al2O3(OH)2] · 1,5 H2O

The Crystal Structure of the Sodium Oxohydroxoaluminate Hydrate Na₂[Al₂O₃(OH)₂] · 1.5 H₂O The crystal structure of the sodium oxohydroxoaluminate hydrate Na₂[Al₂O₃(OH)₂] ·s 1.5 H₂O (up to now described as Na₂O · Al₂O₃ · 2.5 H₂O and Na₂O · Al₂O₃ · 3 H₂O, respectively) was solved. The X-ray single crystal diffraction analysis (tetragonal, space group P-42₁m, a = 10.522(1) Å, c = 5.330(1) Å, Z = 4) results in a polymeric layered structure, consisting of AlO_3/2(OH) tetrahedral groups. Between these layers the Na⁺ ions are situated, which form tetrameric groups of face-linked NaO₆ octahedra. The involved O^2? ions are due to Al? O? Al bridges, Al? OH groups and water of crystallization. ²⁷Al and ²³Na MAS NMR investigations confirm the crystal structure analysis. The relations between the crystallization behaviour of the compound and the constitution of the aluminate anions in the corresponding sodium aluminate solution and in the solid, respectively, are discussed.     

Darstellung,Strukturen und EPR-Spektren der Rhenium(II)-Nitrosylkomplexe [Re(NO)Cl2(PPh3)(OPPh3)(OReO3)], [Re(NO)Cl2(OPPh3)2(OReO3)] und [Re(NO)Cl2(OPPh3)3](ReO4)

Synthesis, Structures, and EPR-Spectra of the Rhenium(II) Nitrosyl Complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂(OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) The paramagnetic rhenium(II) nitrosyl complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂ · (OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) are formed during the reaction of [ReOCl₃(PPh₃)₂] with NO gas in CH₂Cl₂/EtOH. These and two other Re^II complexes with 5 d⁵ ”︁low-spin”︁”︁-configuration can be observed during the reaction EPR spectroscopically. Crystal structure analysis shows linear coordinated NO ligands (Re–N–O-angles between 171.9 and 177.3°). Three OPPh₃ ligands are meridionally coordinated in the final product of the reaction, [Re(NO)Cl₂(OPPh₃)₃][ReO₄] (monoclinic, P2₁/c, a = 13.47(1), b = 17.56(1), c = 24.69(2) Å, β = 95.12(4)°, Z = 4). [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)] (triclinic P 1, a = 10.561(6), b = 11.770(4), c = 18.483(8) Å, α = 77.29(3), β = 73.53(3), γ = 64.70(4)°, Z = 2) and [Re(NO)Cl₂ (OPPh₃)₂(OReO₃)] (monoclinic P2₁/c, a = 10.652(1), b = 31.638(4), c = 11.886(1) Å, β = 115.59(1)°), Z = 4) can be isolated at shorter reaction times besides the complexes [Re(NO)Cl₃(Ph₃P)₂], [Re(NO)Cl₃(Ph₃P) · (Ph₃PO)], and [ReCl₄(Ph₃P)₂].     

Nonanatrium-bis(hexahydroxoaluminat)-trihydroxid-hexahydrat (Na9[Al(OH)6]2(OH)3 · 6H2O) – Kristallstruktur,NMR-Spektroskopie und thermisches Verhalten

Nonasodium Bis(hexahydroxoaluminate) Trihydroxide Hexahydrate (Na₉[Al(OH)₆]₂(OH)₃ · 6H₂O) – Crystal Structure, NMR Spectroscopy and Thermal Behaviour The crystal structure of the nonasodium bis(hexahydroxoaluminate) trihydroxide hexahydrate Na₉[Al(OH)₆]₂(OH)₃ · 6H₂O (4.5 Na₂O Al₂O₃ · 13.5 H₂O) (up to now described as 3 Na₂O · Al₂O₃ · 6H₂O, 4Na₂O · Al₂O₃ · 13 H₂O and [3 Na₂O · Al₂O₃ · 6H₂O] [xNaOH · yH₂O], respectively) was solved. The X-ray single crystal diffraction analysis (triclinic, space group P1 , a = 8.694(1) Å, b = 11.344(2) Å, c = 11.636(3) Å, α = 74.29(2)°, β = 87.43(2)°, γ = 70.66(2)°, Z = 2) results in a structure, consisting of monomeric [Al(OH)₆]^3? aluminate anions, which are connected by NaO₆ octahedra groups. Furthermore the structure contains both, two hydroxide anions only surrounded by water of crystallization and OH groups of [Al(OH)₆]^3? aluminate anions and a hydroxide anion involved in three NaO₆ coordination octahedra directly and moreover connected with a water molecule by hydrogen bonding. The results of ²⁷Al and ²³Na-MAS-NMR investigations, the thermal behaviour of the compound and possible relations between the crystal structure and the conditions of coordination in the corresponding sodium aluminate solution are discussed as well.     

Rhenium Trichloride Dioxide,ReO2Cl3, Preparation and Reactions

A one step synthesis of ReO₂Cl₃ is reported. ReO₂Cl₃ reacts with [(C₂H₅)₄P]⁺Cl^?, forming [(C₂H₅)₄P]⁺[cis–ReO₂Cl₄]^?, a = 1257.0(2), b = 1026.8(2), c = 1277.9(2) pm, β = 106.659(3)°, P2₁/n. Also an unstable NO⁺[ReO₂Cl₄]^? can be obtained from NOCl and ReO₂Cl₃. With the Lewis acid GaCl₃ the zwitter ion [ReO₂Cl₂]⁺[GaCl₄]^? is formed. a = 1184.0(3), b = 829.2(2), c = 1100.8(2) pm, β = 112.98(1)°, P2₁/c.     

Über Oxotitanate der Alkalimetalle. Zur Kenntnis von Na4Ti5O12

On Oxotitanates of the Alkaline Metals: On Na₄Ti₅O₁₂ Colourless single crystals of the new titanate Na₄Ti₅O₁₂ (starting from mixtures Na₂O/TiO₂, 1000°C, 6 d, Au-crucible, open system) crystallize in the monoclinic system, space group C2/m, a = 26.544(9), b = 2.952(1), c = 6.322(3) Å, β = 95.79(3)°, Z = 2, d_rö = 3.45 and d_pyk = 3.38 g · cm^?3 (four-cycle-diffractometer data, PW 1100, 2?-scan, MoKα). R = 5.09% and R_w = 4.87% for 1178 independent I₀(hkl) with 3° ≤ 2? ≤ 34°. Corrugated layers of Ti₅O₁₂, held together by Na⁺, are stacked along [001]. Details about partially occupied positions of Na⁺, Effective Coordination Numbers (ECoN), the Madelung part of lattice energy (MAPLE), and the structural differences to Na₂Ti₃O₇ 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.     

3D Supramolecular structure of the coordination polymer [Ag(2-MePyz)ReO<Subscript>4</Subscript>]

The complex [Ag(2-MePyz)ReO₄] (I) is synthesized, and its structure is determined. The crystals are monoclinic, space group P 2₁/c, a = 7.234(1), b = 15.451(1), c = 8.036(3) Å, β = 92.56(1)°, V = 897.3(2) ų, ρ_calcd = 3.347 g/cm³, Z = 4. Structure I consists of cationic polymer chains [Ag(2-MePyz)] _∞ ⁺ . Anions ReO ₄ ^? are weakly bound to Ag⁺ (Ag...O_average 2.693 Å) and join the latter into a supramolecular framework. The Ag⁺ ion has a linear coordination (NAgN 177.9(2)°, distances Ag-N 2.223(5) and 2.242(5) Å).     

Synthesis,Crystal Structure and Magnetic Properties of Na3OsO5

Na₃OsO₅ has been synthesized by solid state reaction of Na₂O₂ and osmium powder under a flow of oxygen. Na₃OsO₅ crystallizes trigonal in space group P3₁21 with a = 5.5529(2) Å, c = 13.4726(8) Å, V = 359.77(3) ų, Z = 3, 958 independent reflections, R₁ = 1,97 %, wR₂ = 4.27 %. The crystal structure consists of OsO₅ trigonal bipyramids separated by sodium cations, and is isostructural to Na₃ReO₅. The osmium atoms adopt a packing analogous to ccp, where Na occupies the octahedral and tetrahedral vacancies, so the cation structure is derived from the Li₃Bi structure type. Features of the synthesis of Na₃OsO₅ and related osmates are discussed. Na₃OsO₅ shows paramagnetic behaviour down to 25 K where it orders antiferromagnetically. Below 7 K a weak ferromagnetic contribution is detected. The paramagnetic region of the 5d¹ system has been successfully described in the temperature range 50 – 330 K accounting for strong spin‐orbit coupling, ligand‐field potential of D_3h symmetry (corresponding to the trigonal bipyramidal unit), and cooperative magnetic effects (molecular field parameter λ_MF).     

Neuartige Mäander mit Co3+ und Au3+: Na4[AuCoO5] = Na8 [(O2/2(CoO)O2AuO2/2)2]

Novel meander with Co³⁺ und Au³⁺: Na₄[AuCoO₅] = Na₈ ¹∞ [(O_2/2 (CoO)O₂AuO_2/2)₂] By “reaction with the wall” we obtained for the first time transparent brown single crystals of Na₄[AuCoO₅] while heating intimate mixtures of Co₃O₄, Na₂O₂, and K₂O₂ (Co: Na: K = 1.00:4.91:2.20; 650°C/44d) in a sealed gold-tube: monoclinic, P2₁/m, with a = 555.69(4) pm, b = 1042.11 (8) pm, c = 555.69(4) pm, β = 117.387(5)°, Z = 2. Characteristic features of Na₄[AuCoO₅] are meandric chains [(O_2/2 (CoO)O₂AuO_2/2)₂]. The structure has been determined by four-circle diffractometer data (Siemens AED 2; Mo? Kα , graphite, 881 I₀(hkl), R = 0.0366, R_w = 0.0316), parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, these via Mean Fictive Ionic Radii, and Charge-distribution, CHARDI, are calculated and discussed.     

(PPh4)[(ReO2S2)CuI] und (NEt4)2[(ReOS3)Cu3Cl4]: Fixierung der bisher nicht isolierten Ionen [ReO2S2]− und [ReOS3]− durch Ausnutzung der Stabilität der CuS2(Re)- und Cu3S3(Re)-Fragmente

(PPh₄)[(ReO₂S₂)CuI] and (NEt₄)₂[ReOS₃)Cu₃Cl₄]: Fixation of the up to now not Isolated Ions [ReO₂S₂]^? and [ReOS₃]^? Utilizing the Stability of the CuS₂(Re) and Cu₃S₃(Re) Fragments (PPh₄)[(ReO₂S₂)CuI] ( 1 ) and (NEt₄)₂[ReOS₃)Cu₃Cl₄] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO₂S₂]^? and [ReOS₃]^? as ligands, have been prepared by the reaction of (NEt₄)[ReS₄] with PPh₃ and CuI in acetone in the presence of (PPh₄)I (( 1 )) or with CuCl in CH₂Cl₂ in the presence of (NEt₄)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

Zur Kenntnis ternärer Oxide des Bleis: Über Na2PbO2

On Ternary Oxides of Lead. The Na₆PbO₅ Na₆PbO₅ (pale yellow) crystallizes orthorhombic in Cmcm with a=10.6₈, b=5.70₉, c=10.9₉, å; Z=1. Parameters were refined by least-squares (479 hkO–hk7, MO–K_α) R=0.112₄, R′=0.116, (parameters see text). Isolated PbO₅ groups of pseudotetragonal pyramids lend Pb⁴⁺ Coordination Number (CN) 5. Along [100] and [010] the pyramids are equivalent orientated, but along [001] alternately twisted by 180°. Na+ occupies holes between O^2?, leading to CN 6 (Na″+) and Na″′⁺ and CN 4 (Na′⁺). The MADELUNG part of lattice energy (MAPLE) is calculated and discussed.     

Preparation and Crystal Structure of Rare Earth Rhenates: the Series Ln5Re2O12 with Ln = Y,Gd–Lu,and the Praseodymium Rhenates Pr3ReO8, Pr3Re2O10, and Pr4Re2O11

The crystal structure of the known compounds Ln₅Re₂O₁₂ (Ln = Y, Gd, Dy–Lu) and the new isotypic terbium rhenate Tb₅Re₂O₁₂ was determined from X‐ray data of a twinned crystal of Ho₅Re₂O₁₂: B2/m, a = 1236.5(4) pm, b = 748.2(2) pm, c = 563.8(1) pm, γ = 107.73(3)°, Z = 2, R = 0.034 for 379 structure factors and 37 variable parameters. The rhenium atoms (oxidation number +4.5) have octahedral oxygen coordination. These ReO₆ octahedra share edges, thus forming infinite strings with alternating short and long Re–Re distances: 243.6(2) and 320.1(2) pm. Of the three holmium positions two are surrounded by seven oxygen atoms and the third one has octahedral oxygen coordination. The crystal structure of Pr₃ReO₈ was refined from single‐crystal X‐ray data: P2₁/a, a = 1498.0(2) pm, b = 749.09(8) pm, c = 610.48(9) pm, γ = 110.39(1)°, R = 0.017 for 2082 F values and 110 variable parameters. It is isotypic with a structure first determined for Sm₃ReO₈. The new compounds Pr₃Re₂O₁₀ and Pr₄Re₂O₁₁ were prepared by reaction of elemental praseodymium with the metaperrhenate Pr(ReO₄)₃. They were characterized through their X‐ray powder diagrams. Pr₃Re₂O₁₀ was found to be monoclinic: a = 778.47(9) pm, b = 773.62(9) pm, c = 706.10(8) pm, β = 114.77(1)°. It is isotypic with La₃Os₂O₁₀ and La₃Re₂O₁₀. Pr₄Re₂O₁₁ crystallizes with Nd₄Re₂O₁₁ type structure with the tetragonal lattice constants a = 1272.49(3) pm, c = 562.29(2) pm. The compounds Nd₄Re₂O₁₁ and Sm₄Re₂O₁₁ are confirmed. The magnetic properties of Ho₅Re₂O₁₂, Tb₅Re₂O₁₂, Pr₃Re₂O₁₀, Pr₄Re₂O₁₁, Nd₄Re₂O₁₁, and Sm₄Re₂O₁₁ were investigated with a Faraday balance. None of these compounds shows magnetic order above 200 K.     

ReV‐Phthalocyaninate und ReV‐Tetraphenylporphyrinate mit Oxo‐Liganden: Synthese,Eigenschaften und Kristallstruktur

Re^V‐Phthalocyaninates and Re^V‐Tetraphenylporphyrinates: Synthesis, Properties, and Crystal Structure Hexa‐coordinated Re^V phthalocyaninates (pc) and Re^V tetraphenylporphyrinates (tpp) of the type [Re(O)(X)p] (p: pc, tpp) with X = OCH₃, ReO₄, Cl/pc, F/pc, OH/tpp, [{Re(O)p}₂(μ‐O)] and (cat)^trans[Re(O)₂p] (cat: ⁿBu₄N, Et₄N/tpp) have been isolated and characterised by their UV‐Vis‐NIR, IR and resonance Raman (RR) spectra. In the RR spectra, the intensity of the (Re=O) and (Re–X) stretching vibrations (ν(Re=O/–X)) in [Re(O)(X)p] and [{Re(O)p}₂(μ‐O)] is selectively enhanced with excitation in coincidence with O → Re–CT between ca 19000 and 22000 cm^–1. In accordance to selection rules, data of ν(Re=O/–X) compare well with those of the complementary IR spectra. Because of the trans influence ν(Re=O) depends on the axial ligand X, ranging from 940 to 1010 cm^–1. The crystallographic characterization of [Re(O)(ReO₄)tpp] · CHCl₃ ( 1 ), [{Re(O)tpp}₂(μ‐O)] · py ( 2 ), (ⁿBu₄N)^trans[Re(O)₂tpp] ( 3 ), and (Et₄N)^trans[Re(O)₂tpp] · 2 H₂O ( 4 ) is described. The tpp centered Re atom is in a distorted octahedron of four N atoms of the porphyrinate and two axial O atoms in a mutual trans position. Average Re–N distances are 2.062 Å in 1 , 2.086 Å in 2 , 2.089 Å in 3 , and 2.082/2.086 Å in 4 . The Re–O distance of the terminal rhenyl group varies from 1.64(1) Å ( 1 ), 1.73(1)/1.70(1) Å ( 2 ) to 1.80(1) Å ( 4 ), that of the monodentate rhenate(VII) from 1.70(1) to 1.75(1) Å. The Re–O distances in the bridge of the linear O=Re–O–Re=O skeleton in 2 are 1.95(1)/1.89(1) Å. In 1 , with a bent O=Re–O^ ReO₃ moiety (∢(Re–O^ReO₃) = 143(1)°) and a mostly ionic coordinated rhenate(VII), these distances differ significantly (2.20(1) Å vs 1.75(1) Å). The porphyrinate in 1 is saucer‐shaped with a distal rhenate(VII), and the tpp centered Re atom is displaced by 0.31 Å out of the (N)₄ plane towards the rhenyl‐O atom. The distorted porphyrinates in 2 are rotated by 30.4(4)°, and the Re atoms are 0.1 Å out of their (N)₄ planes towards the terminal O atoms. In 3 and 4 the porphyrinates are almost planar with the Re atom in their centre.     

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.     

X-ray diffraction and vibrational data for a series of triphosphates type MIINa3P3O10.12H2O (MII = Cu,Ni and Mg) and their anhydrous forms MIINa3P3O10

Chemical preparation methods, X-ray diffraction and vibrational data are reported for six triphosphates type M^IINa₃P₃O₁₀.12H₂O (M^II = Cu, Ni and Mg) and their anhydrous forms M^IINa₃P₃O₁₀. These condensed phosphates are respectively, CuNa₃P₃O₁₀.12H₂O, MgNa₃P₃O₁₀.12H₂O, NiNa₃P₃O₁₀.12H₂O, CuNa₃P₃O₁₀, NiNa₃P₃O₁₀ and MgNa₃P₃O₁₀. The hydrate triphosphates were prepared by the method of ion-exchange resin, where as their anhydrous forms were prepared by total thermal dehydration of M^IINa₃P₃O₁₀.12H₂O (M^II = Cu, Ni and Mg).CuNa₃P₃O₁₀.12H₂O, MgNa₃P₃O₁₀.12H₂O and NiNa₃P₃O₁₀.12H₂O are isotypic, and crystallize in the monoclinic system, space group is P2₁/n, Z = 4, the unit-cell parameters are: CuNa3P3O10.12H2O, a = 15.052(8) Å, b = 9.234(3) Å,c = 14.767(8) Å and β = 90.03(5)°. MgNa3P3O10.12H2O: a = 15.049(1) (1) Å, b = 9.245(4) Å, c = 14 0.722(3) (2) Å and β = 90.00(5)°.NiNa₃P₃O₁₀.12H₂O: a = 15.010(1) Å, b = 9.208(4) Å, c = 14.710(2) Å and β = 90.00(5)°.The anhydrous forms CuNa₃P₃O₁₀, MgNa₃P₃O₁₀ and NiNa₃P₃O₁₀ crystallize in the monoclinic system, space group is P2₁/n, Z = 4, the unit-cell parameters are: CuNa₃P₃O₁₀, a = 12.464(0) Å, b = 8.437(7) Å, c = 12.083(1) Å and β = 109.77(8) °; MgNa₃P₃O₁₀: a = 11.931(4) (1) Å, b = 12.912(2) Å, c = 10.057(0) Å and β = 113.83(2)° and NiNa₃P₃O₁₀: a = 12.686(8)Å, b = 9.271(2) (4) Å, c = 11.440(3) Å and β = 102,95(5)°.