Synthese,Struktur und Thermolyse von NH4[Re3Br10]

Synthesis, Structure and Thermolysis of NH₄[Re₃Br₁₀] NH₄[Re₃Br₁₀] crystallizes as dark brown single crystals upon slow cooling of a hot, saturated hydrobromic-acid solution of [Re₃Br₉(H₂O)₂] after the addition of NH₄Br. The crystal structure (monoclinic, C2/m (Nr. 12); Z = 4; a = 1461.6(7), b = 1 085.6(4), c = 1030.3(7) pm, β = 92.63(4)°, V_m = 245.9(4)cm³/mol; R = 0.097, R_w = 0.043) contains [Re₃Br₁₂]^? units that share two common edges. These chains run along [010] and are held together by NH₄⁺ ions. Each NH₄⁺ is surrounded by eight Br^? from four different chains. The first step of the thermal decomposition at 290°C is the disproportionation to ReBr₃ (ReCl₃ type), rhenium metal and (NH₄)₂[ReBr₆]. Secondly, the internal reduction of (NH₄)₂[ReBr₆] at 390°C to rhenium metal takes place.     

Synthese und Kristallstruktur von Rb8[P4N6(NH)4](NH2)2 mit dem adamantanartigen Anion [P4N6(NH)4]6−

Synthesis and Crystal Structure of Rb₈[P₄N₆(NH)₄](NH₂)₂ with the Adamantane-like Anion [P₄N₆(NH)₄]^6? RbNH₂ reacts with P₃N₅ (molar ratio 6:1) at 400°C within 5 d to colourless Rb₈[P₄N₆(NH)₄](NH₂)₂. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P₄N₆(NH)₄]^6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly.     

Synthese und Struktur der ternären Ammoniumnitrate (NH4)2[M(NO3)5] (M = Tb?Lu,Y

Synthesis and Structure of the Ternary Ammonium Nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) Single crystals of the ternary ammonium nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) are obtained from the solution of the sesquioxides in a melt of NH₄NO₃ and sublimation of the excess NH₄NO₃. In the crystal structure of (NH₄)₂[Tm(NO₃)₅] (trigonal, P3₁, Z = 3; a = 1 123.76(8), c = 930.1(1) pm; R = 0.062; R_w = 0.034) Tm³⁺ is surrounded by five bidentate nitrate ligands. The isolated [Tm(NO₃)₅]^2? groups are held together by ammonium ions.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

AlCl3 · 3NH3 — eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-diammintetrachloroaluminats: [AlCl2(NH3)4]+[AlCl4(NH3)2]−

AlCl₃ · 3NH₃ — a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl₂(NH₃)₄]⁺[AlCl₄(NH₃)₂]^? . AlCl₃ · 3 NH₃ ? [AlCl₂(NH₃)₄]⁺ [AlCl₄(NH₃)₂]^? forms during the reaction of two mole NH₃ with AlCl₃(NH₃) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH₃. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: The compound contains elongated [AlCl₂(NH₃)₄]⁺ octahedra and compressed [AlCl₄(NH₃)₂]^? octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ? d(N—H … Cl) ? 3.589 Å stabilize the atomic arrangement.     

Synthese und Kristallstruktur von Na10[P4(NH)6N4](NH2)6(NH3)0,5 mit dem adamantanartig aufgebauten Anion [P4(NH)6N4]4−

Synthesis and Crystal Structure of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 with an Adamantane-like Anion [P₄(NH)₆N₄]^4? Crystals of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 were obtained by the reaction of P₃N₅ with NaNH₂ (molar ratio 1:20) within 5 d at 600°C in autoclaves. The following data characterize X-ray investigations: Fm3 m, Z = 8, a = 15.423(2) Å, Z(F) = 261 with F ≥ 3 σ(F) Z(Variables) = 27, R/R_w = 0.086/0.089 The compound contains the hitherto unknown anion [P₄(NH)₆N₄]^4?, which resembles adamantane. The total structure can be described as follows: The centers of gravity of units of [Na₈(NH₂)₆(NH₃)]²⁺ – 8Na⁺ on the corners of a cube, 6NH₂^? on the ones of an inscribed octahedron with NH₃ in the center – follow the motif of a cubic-closest packed arrangement. Units of [Na₁₂(NH₂)₆]⁶⁺ – 12Na⁺ on the corners of a cuboctahedron and 6NH₂^? on the ones of an inscribed octahedron – occupy all octahedral and those of [P₄(NH)₆N₄]^4? all tetrahedral sites.     

Synthese und Struktur von Hydrogensulfaten des Typs M(HSO4)(H2SO4) (M = Rb,Cs und NH4)

Synthesis and Structure of Hydrogen Sulfates of the Type M(HSO₄)(H₂SO₄) (M = Rb, Cs and NH₄) From the binary systems M₂SO₄/H₂SO₄ (M = Rb, Cs, NH₄), three new hydrogen sulfates of the type M(HSO₄)(H₂SO₄) could be synthesized and structural characterized. The rubidium and caesium compounds are isotypic whereas NH₄(HSO₄)(H₂SO₄) is topologically very similar to both. All three compounds crystallize with nearly identical cell parameters [Rb: a = 7.382(1), b = 12.440(2), c = 7.861(2), β = 93.03(3); Cs: a = 7.604(1), b = 12.689(2), c = 8.092(2), β = 92.44(3); NH₄: a = 7.521(3), b = 12.541(5), c = 7.749(3), β = 92.74(3)], in the monoclinic space group P2₁/c, There exist two kinds of SO₄-tetrahedra: HSO₄^? anions (S1) and H₂SO₄-molecules (S2). The HSO₄^? anions form hydrogen bridged zigzag chains. In the case of the Rb and Cs compounds, the H₂SO₄ molecules connect these chains forming double layers. The metal atoms are coordinated by 9 O-atoms with M? O-distances of 2.97 – 3.39 Å (Rb) and 3.13 – 3.51 Å (Cs). In the ammonium compound additional hydrogen bonds are formed originating from the NH₄⁺ cation. This finally leads to the formation of S2? NH₄⁺ chains (parallel to the S1 chains) as well as to a three-dimensional connection of both kinds of chains.     

Synthese und Kristallstrukturen von NH4[Si(NH3)F5] und [Si(NH3)2F4]

Synthesis and Crystal Structures of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] Single crystals of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] are obtained by reaction of silicon powder with NH₄HF₂ in sealed Monel ampoules at 400°C. NH₄[Si(NH₃)F₅] crystallizes with the tetragonal space group P4/n (no. 85) with a = 614.91(7) pm, c = 721.01(8) pm, Z = 2. Characteristic for the structure is the anionic octahedron [Si(NH₃)F₅]^?. Si(NH₃)₂F₄ crystallizes with the monoclinic space group P2₁/c (no. 14) with a = 506.9(1) pm, b = 728.0(1) pm, c = 675.9(1), β = 93,21(2)°, Z = 2. Trans-[Si(NH₃)₂F₄] molecules are characteristic for this structure.     

Darstellung und Kristallstruktur von Cs8P8O24 · 8H2O

Synthesis and Crystal Structure of Cs₈P₈O₂₄ · 8H₂O Cs₈P₈O₂₄ · 8H₂O was obtained from Na₈P₈O₂₄ · 6H₂O by cation exchange. Crystal growth was achieved by applying gel techniques (agar agar). The crystal structure (P1 ; a = 766.6(8); b = 1 156.9(9); c = 1 163.4(9) pm; α = 100,2(1)°; β = 106.5(2)°; γ = 92.2(1)°; Z = 1; 4 099 unique diffractometer data; R = 0.051; R(w) = 0.037) contains cyclo-octaphosphate anions with point symmetry C_2h. The cesium atoms are coordinated irregularily by eight and ten oxygen atoms, respectively. The threedimensional linkage of the P₈O₂₄^8?-rings is established via bonds to cesium atoms and hydrogen bonds Provided by H₂O molecules.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Das wasserfreie Lanthanacetat,La(CH3COO)3, und sein Precursor,NH4)3[La(CH3COO)6] · 1/2 H2O: Synthese,Strukturen, thermisches Verhalten

Anhydrous Lanthanum Acetate, La(CH₃COO)₃, and its Precursor, ·NH₄)₃[La(CH₃COO)₆] · 1/2 H₂O: Synthesis, Structures, Thermal Behaviour Single crystals of (NH₄)₃[La(CH₃COO)₆] · ½ H₂O are obtained by refluxing La₂O₃in (CH₃COO)₃ · 1.5 H₂O with an excess of NH₄CH₃COO in methanol. The crystal structure (trigonal, R3 , Z = 6, a = 1 365.0(3) pm, c = 2 360(1) pm, R = 0.088, R_w = 0.061 exhibits the coordination number of nine for La³⁺, which is surrounded by three chelating-type bidentate and three unidentate acetate groups. Characteristic are monomeric units of [La(CH₃COO)₆]^3? which are connected to a three-dimensional network by hydrogen bonds with the NH ions. Thermal decomposition consists of four steps with La(CH₃COO)₃, La₂(CO₃)₃ and La₂O₂CO₃ as intermediates and La₂O₃ as the final Product. Single crystals of La(CH₃COO)₃ are obtained from La₂O₃ in a melt of NH₄CH₃COO (molar ratio 1:12) in a sealed glass ampoule. The crystal structure (trigonal, R3 , Z = 18, a = 2 203.0(5) pm; c = 987.1(3) pm, R = 0.027, R_w = 0.023) shows the coordination number of ten for La³⁺. These are three-dimensionally connected by oxygen atoms of the acetate groups with two tetradentate double-bridging and one Z,Z-type-bridging bidentate acetate group.     

[Na(12-Krone-4)2]2[Ni(Se4)2] · DMF; Synthese,Kristallstruktur und magnetisches Verhalten

[Na(12-Crown-4)₂]₂[Ni(Se₄)₂] · DMF; Synthesis, Crystal Structure, and Magnetic Behaviour The title compound has been prepared from NiCl₂ and sodium polyselenide in dimethylformamide solution in the presence of 12-crown-4, forming black crystal needles. They were characterized by an X-ray structure determination, by FIR spectroscopy as well as by the magnetic behaviour. [Na(12-crown-4)₂]₂[Ni(Se₄)₂] · DMF crystallizes monoclinically in the space group P2₁, 3650 observed unique reflections, R = 0.046. Lattice dimensions at ?80°C: a = 1020.3(2); b = 1889.5(2); c = 1498.7(3) pm; β = 108.29(1)°. The compound has an ionic structure, in which the sodium atoms of the [Na(12-crown-4)₂]⁺ cations are coordinated by the oxygen atoms of the crown ether molecules in an antiprismatic fashion. The nickel atom of the anion [Ni(Se₄)₂]^2? is surrounded by four selenium atoms of the tetraselenide chelates in an almost planar environment. The DMF molecules are inserted in the lattice without a bonding interaction. The magnetic susceptibility observed in the temperature interval 4.2 to 330K can be interpreted by means of a ³E ground term and D₂ as local symmetry, which was established by X-ray crystallography.     

Synthese,Struktur und Phasenumwandlung von Te4[AsF6]2·SO2

Synthesis, Crystal Structure, and Solid State Phase Transition of Te₄[AsF₆]₂·SO₂ The oxidation of tellurium with AsF₅ in liquid SO₂ yields Te₄²⁺[AsF₆^—]₂ which can be crystallized from the solution in form of dark red crystals as the SO₂ solvate. The crystals are very sensitive against air and easily lose SO₂, so handling under SO₂ atmosphere or cooling is required. The crystal structure was determined at ambient temperature, at 153 K, and at 98 K. Above 127 K Te₄[AsF₆]₂·SO₂ crystallizes orthorhombic (Pnma, a = 899.2(1), b = 978.79(6), c = 1871.61(1) pm, V = 1647.13(2)·10⁶pm³ at 297 K, Z = 4). The structure consists of square‐planar Te₄²⁺ ions (Te‐Te 266 pm), octahedral [AsF₆]^— ions and of SO₂ molecules which coordinate the Te₄ rings with their O atoms in bridging positions over the edges of the square. At room temperature one of the two crystallographically independent [AsF₆]^— ions shows rotational disorder which on cooling to 153 K is not completely resolved. At 127 K Te₄[AsF₆]₂·SO₂ undergoes a solid state phase transition into a monoclinic structure (P112₁/a, a = 866.17(8), b = 983.93(5), c = 1869.10(6) pm, γ = 96.36(2)°, V = 1554, 2(2)·10⁶ pm³ at 98 K, Z = 4). All [AsF₆]^— ions are ordered in the low temperature form. Despite a direct supergroup‐subgroup relationship exists between the space groups, the phase transition is of first order with discontinuous changes in the lattice parameters. The phase transition is accompanied by crystal twinning. The main difference between the two structures lies in the different coordination of the Te₄²⁺ ion by O and F atoms of neighbored SO₂ and [AsF₆]^— molecules.     

Synthese und Kristallstrukturen von Chlororhenaten(III) mit den zweiwertigen Kationen Ethylendiammonium und Piperazinium:(EnH2)2(Pipzh2)[Re3Cl12]2· 6H2O,und (PipzH2) [Re3Cl12]CI·H2O und (Pipzh2) [Re3Cl11(H2O)]·3H2O

Synthesis and Crystal Structures of Chlororhenates(III) with the Divalent Cations Ethylenediammonium and Piperazinium: (EnH₂)₂(PipzH₂) [Re₃Cl₁₂]₂·6H₂O, (EnH₂) (PipzH₂) [Re₃Cl₁₂]Cl· H₂O, and (PipzH₂) [Re₃Cl₁₁(H₂O)] · 3H₂O The deep red salt (EnH₂)₂(PipzH₂)[Re₃CI₁₂] · 6 H₂O ( 1 ), (EnH₂)(PipzH₂)[Re₃Cl₁₂]CI · H₂O ( 2 ), and (PipzH₂)[Re₃Cl₁₁(H₂O)] · 3H₂O ( 3 ) crystallize upon evaporation from hydrochloride acid solutions of ReCl₃ on addition of ethylenediammonium chloride (EnH₂Cl₂) and/or piperazinium chloride (PipzH₂Cl₂). The crystal structures have been determined from four-circle diffractometer data. 1: monoclinic; a = 1889.63(11), b = 1615.82(8), c = 790.28(4)pm; β = 101.354(5)°; Z = 2; P2₁/n; R = 0.119, R_w = 0.070. 2: triclinic; a = 1330.35(4), b = 1051.14(5), c = 1165.32(6)pm; α = 122.308(4), β = 102.412(3), γ = 92.226(4)°; Z = 2, P1 ; R = 0.092, R_w = 0.059. 3: orthorhombic; a = 971.43(4), b = 1619.51(7), c = 1478.87(6)pm; Z = 4; Pbcm; R = 0.034, R_w = 0.032.     

CsNb3Br7S: Synthese,Struktur und Bindungsverhältnisse

CsNb₃Br₇S: Synthesis, Structure, and Bonding States The reaction of NbBr₅ with Nb, Cs and S in a sealed Nb container affords CsNb₃Br₇S at 800°C (3 days). Further on isotypic compounds of the general formula ANb₃X₇Ch with A = Rb, Cs; X = Cl, Br and Ch = S, Se are obtained. CsNb₃Br₇S crystallizes monoclinic (space group P2₁/a, Z = 2), with the lattice parameters a = 707.4(2), b = 1 888.4(4), c = 994.1(2) pm and β = 98.59(2)°. The crystal structure contains Nb₃ clusters being linked by two additional Nb? Nb bonds to form infinite chains. Adjacent chains are bridged by Cs atoms in a cubeoctahedral coordination sphere of Br atoms. Similar with Nb₃Br₈ seven electrons occupy metal—metal bonding states.     

Ternäre Hydroxide. I. Synthese,Struktur und Eigenschaften von Li2[Sn(OH)6] · 2 H2O

Ternary Hydroxides. I. Synthesis, Structure, and Properties of Li₂[Sn(OH)₆] · 2 H₂O Colourless crystals of Li₂[Sn(OH)₆] · 2 H₂O were synthesized by reaction of SnCl₄ with LiOH in aqueous solution. The crystal structure was determined from single crystal data. Li₂[Sn(OH)₆] · 2 H₂O: monoclinic, P2₁/n (Nr. 14), a = 502.3(1), b = 692.3(1), c = 1020.2(3) pm, β = 99.78(1)°, V = 349.6(2) · 10⁶ pm³, Z = 2, R/Rw = 0.0192/0.0472, N(I) > 2σ(I) = 1527, N(Par.) = 54. Within the crystal structure only slightly distorted octahedrally [Sn(OH)₆]^2? ions are bonded via hydrogen bonds with water molecules forming layers, which themselve are linked by tetrahedrally coordinated Li ions; the structure is in accordance with the IR-data and the results of the ¹¹⁹Sn solid state NMR-spectroscopy; the hydrat water is eliminated at 117.1°C, the condensation reaction – forming the ternary oxide – takes place at 257.7°C.     

Hydrogensulfate mit fehlgeordneten Wasserstoffatomen – Synthese und Struktur von Li[H(HSO4)2](H2SO4)2 sowie Verfeinerung der Struktur von α-NaHSO4

Hydrogen Sulfates with Disordered Hydrogen Atoms – Synthesis and Structure of Li[H(HSO₄)₂](H₂SO₄)₂ and Refinement of the Structure of α-NaHSO₄ The structure of Li[H(HSO₄)₂](H₂SO₄)₂ has been determined for the first time whereas the structure of α-NaHSO₄ has been refined, so that direct determination of the hydrogen positions was possible. Both compounds crystallize triclinic in the space group P1 with the lattice constants a = 6.708(2), b = 6.995(1), c = 7.114(1) Å, α = 75.53(1), β = 84.09(2) and γ = 87.57(2)° (Z = 4) for α-NaHSO₄ and a = 4.915(1), b = 7.313(1), c = 8.346(2) Å, α = 82.42(3), β = 86.10(3) and γ = 80.93(3)° (Z = 1) for Li[H(HSO₄)₂](H₂SO₄)₂. In both compounds there are disordered hydrogen positions. In the structure of α-NaHSO₄ there are two crystallographically different HSO₄^? tetrahedra and two different coordinated Na atoms. The system of hydrogen bonds can be described by chains in [0–11] direction. The disordering of the H atoms reduces the differences between the S? O and S? OH distances (1.45 and 1.50 Å) while in the ordered HSO₄ unit “regular” bond lengths are observed (1.45 und 1,57 Å). In the structure of Li[H(HSO₄)₂](H₂SO₄)₂ there are two crystallographically different SO₄-tetrahedra. The first one belongs to the [H(HSO₄)₂]^? unit while the second one represents H₂SO₄ molecules. The H atom which is located nearby the symmetry centre and connects two HSO₄ units by a short O…?O distance of 2.44 Å. Li is located on a symmetry centre and is slightly distorted octahedrally coordinated by oxygen atoms of six different SO₄ tetrahedra. The system of hydrogen bonds can be regarded as consisting of double layers parallel to the xy-plane.