Ungewöhnliche Koordinationspolyeder um Sauerstoff in Li4Cl(OH)3

Unusual Coordination Polyhedra around Oxygen in Li₄Cl(OH)₃ The pseudobinary system LiOH/LiCl was investigated by X-ray methods. Two compounds, Li₄Cl(OH)₃ and Li₂Cl(OH), were obtained. The crystal structure of Li₄Cl(OH)₃ solved by single-crystal methods is delt with. For Li₂Cl(OH) powder diffraction data are given: Li₄Cl(OH)₃: P2₁/m, Z = 2, a = 5.4096(8) Å, b = 7.382(2) Å, c = 6.2076(8) Å, β = 94.40(1)°, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 483, Z (parameter) = 50, R/R_w = 0.022/0.025 Li₂Cl(OH): Pmma, Z = 2, a = 7.680(8) Å, b = 4.001(7) Å, c = 3.899(6) Å The hydroxide rich compound crystallizes in a new type of structure which contains puckered layers [Li₄(OH)₃⁺] connected via chloride ions.     

Li2Br(NH2): Das erste ternäre Alkalimetallamidhalogenid

Li₂Br(NH₂): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH₂/LiBr was investigated by X-ray methods. The crystal structure of the compound Li₂Br(NH₂) was solved by single crystal data: Li₂Br(NH₂): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 348, Z (parameter) = 51, R/R_w = 0.019/0.021 Li₂Br(NH₂) crystallizes in a new type of structure. To one another isolated chains of [Li₂Li_4/2(NH₂)₂²⁺] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement.     

Rb2I(OH): Ein Hydroxidiodid im System RbOH/RbI

Rb₂I(OH): A Hydroxide Iodide in the System RbOH/RbI The pseudobinary system RbOH/RbI was investigated by X-ray methods. The crystal structure of Rb₂I(OH) was solved by single crystal data: Rb₂I(OH): Pnma, Z = 4, a = 7.748(1) Å, b = 5.654(2) Å,c = 13.254(2) Å Z(F_o) with (F_o)² ? 3σ = (F_o)² = 449, Z (parameter) = 25, R/R_w = 0.021/0.023 Rb₂I(OH) crystallizes in a new type of structure, built up by a three dimensional network of [Rb₂(OH)⁺] containing the iodide ions.     

K2Br(OH) und Rb2Br(OH): Zwei neue ternäre Alkalimetallhalogenidhydroxide mit ausgeprägter Strukturverwandtschaft zu KOH bzw. RbOH

K₂Br(OH) and Rb₂Br(OH): Two New Ternary Alkali Metal Halide Hydroxides with a Pronounced Structural Relationship to KOH resp. RbOH Two isotypic compounds K₂Br(OH) and Rb₂Br(OH) were prepared in the systems KOH/KBr and RbOH/RbBr. Their structures were determined by single crystal X-ray methods: K₂Br(OH): P2₁/m, Z = 2, a = 6.724(1) Å, b = 4.272(4) Å, c = 8.442(2) Å, β = 108.14(2)°, Z(F_o) = 651 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.041/0.047 Rb₂Br(OH): P2₁/m, Z = 2, a = 6.918(3) Å, b = 4.483(2) Å, c = 8.850(5) Å, β = 108.08(6)°, Z(F_o) = 326 mit (F_o)² ≥ 3σ(F_o)², Z(parameter) = 27, R/R_w = 0.074/0.082. The compounds are built up by chains of [M₂(OH)⁺] connected via Br^?. The structure of the chains as well as their orientation to one another show a pronounced relationship to the structures of the room temperature modifications of the isotypic binary hydroxides KOH and RbOH.     

Synthese und Kristallstruktur von Sr2Zn(OH)6 und Ba2Zn(OH)6

Synthesis and Crystal Structure of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ Crystallization from supersaturated sodium hydroxozincate solutions by adding solutions of alkali earth metal hydroxides yields crystals of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆. The X-ray structure determination on these crystals was successful including all hydrogen positions: Sr₂Zn(OH)₆: P2₁/n, Z = 2, a = 5.794(1) Å, b = 6.160(1) Å, c = 8.141(1) Å, b = 91.23(1)°, N(F ³° 2σ F) = 1127, N(Var.) = 53, R₁/wR₂ = 0.047/0.081Ba₂Zn(OH)₆: P2₁/n, Z = 2, a = 6.043(1) Å, b = 6.336(1) Å, c = 8.451(2) Å, b = 91.23(2)°, N(F ° 2σ F) = 1669, N(Var.) = 54, R₁/wR₂ = 0.029/0.067. Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ crystallize isotypic in a distorted Li₂O structure type. Sr²⁺ resp. Ba²⁺ form a cubic primitive arrangement. Distorted octahedra of OH^– around Zn²⁺ fill therein alternating cubic gaps in an ordered way.     

Kristallstrukturen und Wasserstoffbrückenbindungen bei β-Be(OH)2 und ϵ-Zn(OH)2

Crystal Structures and Hydrogen Bonding for β-Be(OH)₂ and ϵ-Zn(OH)₂ Crystals of β-Be(OH)₂ sufficient for x-ray structure determination were grown from a saturated hot solution of freshly prepared Be(OH)₂ in NaOH by slowly cooling down and in the case of ϵ-Zn(OH)₂ by electrochemical oxidation of zinc in a NaOH/NH₃ solution. The structures of the isotypic compounds were determined including the H-positions: β-Be(OH)₂: P2₁2₁2₁, Z = 4, a = 4.530(2) Å, b = 4.621(2) Å, c = 7.048(2) Å N(F > 3σ F) = 432, N(parameters) = 36, R/R_w = 0.044/0.052 ϵ-Zn(OH)₂: P2₁2₁2₁, Z = 4, a = 4.905(3) Å, b = 5.143(4) Å, c = 8.473(2) Å N(F > 3σ F) = 1107, N(parameters) = 36, R/R_w = 0.025/0.027For neutron diffraction experiments microcrystalline β-Be(OD)₂ was prepared. With time-of-flight data the D positions were determined giving d(O–D) = 0.954(4) Å. The structures are closely related to that of β-cristobalite: As in SiO₂ a quarter of tetrahedral interstices in a distorted cubic close packed arrangement of O is regularily occupied by the metal atoms. The filled O tetrahedra are twisted against one another in such a way, that O–H…O–H hydrogen bonds are favoured which are surprisingly stronger in the zinc than in the beryllium compound.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Zur Kristallstruktur von SrZn(OH)4 · H2O

Crystal Structure of SrZn(OH)₄ · H₂O Colorless crystals of SrZn(OH)₄ · H₂O are obtained by electrochemical oxidation of Zn in a zinc/iron pair in an aqueous ammonia solution saturated with strontium hydroxide. The X-ray crystal structure determination was now successful including all hydrogen positions: P1 , Z = 2, a = 6.244(1) Å, b = 6.3000(8) Å, c = 7.701(1) Å, α = 90.59(1)°, β = 112.56(2)°, γ = 108.66(2)°, N(F ≥ 3σF) = 1967, N(Var.) = 84, R/R_w = 0.020/0.024. In SrZn(OH)₄ · H₂O Zn²⁺ is tetrahedrally coordinated by four OH^? -ions while Sr²⁺ has 6 OH^? and one H₂O as neighbours. The polyhedra around Sr²⁺ are connected to chains which are linked three-dimensionally by isolated tetrahedra [Zn(OH)₄]. Hydrogen bonds between H₂O as donor and OH^? are characterized by raman spectroscopy.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

Zur Kristallstruktur von CaZn2(OH)6 · 2 H2O

Crystal Structure of CaZn₂(OH)₆ · 2 H₂O The electrochemical oxidation of zinc in a zinc/iron-pair leads in an aqueous NH₃ solution of calciumhydroxide at room temperature to colourless crystals of CaZn₂(OH)₆ · 2 H₂O. The X-ray structure determination was now successful including all hydrogen positions. P2₁/c, Z = 2, a = 6.372(1) Å, b = 10.940(2) Å, c = 5.749(2) Å, β = 101.94(2)° N(F ≥ 3σF) = 809, N(Var.) = 69, R/R_W = 0.011/0.012 The compound CaZn₂(OH)₆ · 2H₂O contains Zn²⁺ in tetrahedral coordination by OH^? and Ca²⁺ in octahedral coordination by four OH^? and two H₂O. The tetrahedra around Zn²⁺ form corner sharing chains, three-dimensionally linked by isolated polyhedra around Ca²⁺. Weak hydrogen bridge bonds result between H₂O as donor and OH^?.     

Zur Kenntnis von Na4Br(NH2)3: Ein Amidbromid im System NaNH2/NaBr

Na₄Br(NH₂)₃: An Amide Bromide in the System NaNH₂/NaBr The pseudobinary system NaNH₂/NaBr was investigated by X-ray methods. The crystal structure of Na₄Br(NH₂)₃ was solved by single crystal data: Pnnm, Z = 4, a = 6.579(2) Å, b = 12.755(4) Å, c = 8.776(2) Å Z(F_o) with (F_o)² ≥ 3σ = (F_o)² = 503, Z(parameter) = 39, R/R_w = 0.082/0.106. It is a new type of structure, built up by a three-dimensional network of [Na₄(NH₂)₃⁺] containing the bromide ions.     

Na2Mn(NH2)4: Ein neuer Schichtenstrukturtyp

Na₂Mn(NH₂)₄: A New Type of Layered Structure The structure of Na₂Mn(NH₂)₄ was solved by X-ray single crystal data including H-positions: P2₁/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/R_W = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

Synthese und Struktur eines Caesium-tetraimidophosphat-diamids,Cs5[P(NH)4](NH2)2 = Cs3[P(NH)4] · 2 CsNH2

Synthesis and Crystal Structure of a Cesium-tetraimidophosphate-diamide, Cs₅[P(NH)₄](NH₂)₂ = Cs₃[P(NH)₄] · 2 CsNH₂ Well crystallized Cesium-tetraimidophosphate-diamide is obtained by the reaction of CsNH₂ with P₃N₅ in autoclaves at 673 K within three days. X-ray single crystal investigations led to the following data

• Ccca, Z = 4, a = 8.192(5) Å, b = 20.472(5) Å,
• c = 8.252(3) Å
• Z(F) ≥3σ(F) = 916, Z(Var.) = 32, R/R_w=1 = 0.017/0.021

The compound contains the hitherto unknown anion [P(NH)₄]^3?.     

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.     

Über Oxocobaltate der Alkalimetalle. Zur Kenntnis von Li8CoO6

Oxocobaltates of Alkali Metals. On Li₈CoO₆. Hitherto unknown Li₈CoO₆, rubin- red single crystals, cristallizes according to WEISSENBERG and precession photographs (MoK_α) hexagonal with a = 5.44 Å, c = 10.87 Å; c/a = 2.0; Z = 2, space group C? P6₃cm. Atomic parameters see text. The structure derives from a closest packing of O^2?, ABACA … (The tetrahedral, ?isolated”? groups [CoO₄] show remarkable short distances Co–O (1.66 Å), comparable with [CoO₄] in Li₄CoO₄, being isotypic with Li₄SiO₄. The MADELUNG Part of Lattice Energy is calculated and discussed.     

Verbindungen in den Systemen Kalium(Rubidium)/Gold/Antimon: K3Au3Sb2, Rb3Au3Sb2 und K1,74Rb0,26RbAu3Sb2

Compounds in the Systems Potassium(Rubidium)/Gold/Antimony: K₃Au₃Sb₂, Rb₃Au₃Sb₂, and K_1,74Rb_0,26RbAu₃Sb₂ Brittle, silver coloured single crystals of K₃Au₃Sb₂, Rb₃Au₃Sb₂ and K_1,74Rb_0,26RbAu₃Sb₂ were obtainded by reaction of the alkali metal azides (KN₃, RbN₃) with gold and antimon powder at 550°C. The structures of the isotypic compounds (R3 m, Z = 3) were determined by X-ray single-crystal diffractometer data: K₃Au₃Sb₂, a = 6,198(2) Å, c = 21,520(5) Å, R/R_w (w = 1) = 0,046/0,058, Z(F) ? 3σ(F) = 175, Z(Var.) = 14; Rb₃Au₃Sb₂, a = 6,443(3), c = 21,69(2), R/R_w (w = 1) = 0,059/0,082, Z(F) ? 3σ(F₀²) = 258, Z(Var.) = 14; K_1,74Rb_0,26RbAu₃Sb₂, a = 6,288(2) Å, c = 21,617(5) Å, R/R_w (w = 1) = 0,049/0,069, Z(F) ? 3σ(F) = 390, Z(Var) = 14. The compounds crystallize with the K₃Cu₃P₂-structure type. The Au? Sb partial structures consist of [AuSb_2/3] layers with linear Sb? Au? Sb dumb-bells and SbAu₃ pyramids. The layers are separated by two crystallographically independent alkali metal atoms along [001].     

Na7I2(OH)5: Ein Hydroxidiodid im System NaOH/NaI

Na₇I₂(OH)₅: A Hydroxide Iodide in the System NaOH/NaI The pseudobinary system NaOH/NaI is investigated by X-ray methods. The crystal structure of the compound Na₇I₂(OH)₅ was solved by single crystal data: Na₇I₂(OH)₅: P4/nmm, Z = 2, a = 7.748(2) Å, c = 10.260(3) Å, Z(F_o) = 443 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.044/0.059 Na₇I₂(OH)₅ crystallizes in a new type of structure which contains puckered layers of ∞²[Na₇(OH)₅²⁺] connected via iodide ions.