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.     

Hexamincyclotriphosphazenhemiammoniakat,P3N3(NH2)6 · 0,5 NH3, ein Produkt der Hochdruckammonolyse von weißem Phosphor

Hexaminecyclotriphosphazenehemiammoniate, P₃N₃(NH₂)₆ · 0.5 NH₃, a Product of High Pressure Ammonolysis of White Phosphorus White phosphorus gives at NH₃-pressures ≥5 kbar and temperatures above 250°C in a disproportionation reaction P₃N₃(NH₂)₆ · 0.5 NH₃; besides these products red phosphorus is formed. The yield on P₃N₃(NH₂)₆ · 0.5 NH₃ increases with T and is about 70–80% at 400°C as to the disproportionation reaction of the amount of white phosphorus. X-ray structure determination was successful on single crystals of P₃N₃(NH₂)₆ · 0.5 NH₃. Pbca, N = 8 a = 11.395(3) Å, b = 12.935(4) Å, c = 12.834(4) Å R = 0.035, R_w = 0.041 with w = 1, N (F_o²) ≥ 3σ(F_o²) = 1371, N(Var.) = 166. The molecules are connected by N? H? N-bridgebonds with 3.04 Å ≤ d(N …? N) ≤ 3,19 Å and d (N? H) = 0.87 Å. The compound is furthermore characterized by IR-data and its thermical behaviour.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

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.     

Rubidium-decaamidodichromat(III), Rb4Cr2(NH2)10 – Synthese und Kristallstruktur

Rubidium Decaamidodichromate(III), Rb₄Cr₂(NH₂)₁₀ – Synthesis and Crystal Structure The reaction of chromium(III) with rubidium amide in a molar ratio of Cr(NH₂)₃/RbNH₂ = 1 : 1.75 at 140 °C and p(NH₃) = 3 kbar in a high-pressure autoclave results after 90 days in dark violet crystals of Rb₄Cr₂(NH₂)₁₀. Structure determination was done by single crystal X-ray methods:Pna2₁ (No. 33), Z = 4, a = 12.244(3) Å, b = 6.727(1) Å, c = 19.775(5) Å, N(F²_o > 3σ(F²_o)) = 1046, N(Var.) = 94, R/R_w = 0,051/0,059&#TAB;The structure of Rb₄Cr₂(NH₂)₁₀ contains isolated, face-sharing N-octahedra around two Cr³⁺-ions giving [Cr(NH₂)₃(NH₂)_3/2]₂^3–. These are arranged to oneanother following the motif of a hexagonal closest packing. They are connected via Rb⁺- and one further amide ion not bound to Cr³⁺. The compound is characterized by thermoanalytical and IR-/Raman-spectroscopic measurements.     

Synthese und Kristallstruktur von Na2Zn(OH)4

Synthesis and Crystal Structure of Na₂Zn(OH)₄ Crystallization from saturated sodium hydroxozincate solutions yields colourless platelets of crystals of Na₂Zn(OH)₄. The X‐ray structure determination on these crystals was successful including all hydrogen positions. P2₁/n, Z = 4, a = 7.959(3) Å, b = 6.534(1) Å, c = 8.501(3) Å, β = 93.97(3)°, N(F²_o ° 2σ F²_o) = 1668, N(Var.) = 81, R₁/wR₂ = 0.043/0.107. Na₂Zn(OH)₄ crystallizes in a layered structure. Alternate layers contain Na⁺ in octahedral and Zn²⁺ in tetrahedral coordination by OH^–.     

Synthese,Kristallstruktur und Eigenschaften von Tetranatrium‐bis(trimetaphosphimato)cuprat(II)‐Decahydrat,Na4{Cu[(PO2NH)3]2} · 10 H2O

Synthesis, Crystal Structure, and Properties of Tetrasodium Bis(trimetaphosphimato)cuprate(II) Decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O Tetrasodium bis(trimetaphosphimato)cuprate(II) decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O, was obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with Cu(NO₃)₂ · 3 H₂O (molar ratio 2 : 1). The structure of Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O ( 1 ) was solved by single‐crystal X‐ray methods (P 1, a = 912.51(6), b = 932.14(6), c = 966.10(6) pm, α = 94.840(5), β = 108.652(6), γ = 118.588(6)°, Z = 1). The P₃N₃ rings of the trimetaphosphimate ions exhibit a slightly distorted sofa conformation. The conformation of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The trimetaphosphimate ions act as bidentate ligands of Cu²⁺. With additionally coordinated water molecules, anionic complexes {Cu[(PO₂NH)₃]₂ · 2 H₂O}^4– are formed. In the crystal these complexes are interconnected by N–H…O und O–H…O hydrogen bonds and they coordinate the Na⁺. Thus, a three‐dimensional network is formed.     

Synthesis,Structure, and Decomposition of (NH4)2[Mo6Cl14] · H2O

(NH₄)₂[Mo₆Cl₁₄] · H₂O ( 1 ) was prepared from reactions of MoCl₂ in ethanol with aqueous NH₄Cl solution. It crystallizes in the monoclinic space group I2/a (no. 15), Z = 4 with a = 912.3(1), b = 1491.2(2), c = 1724.8(2) pm, β = 92.25(1)°; R1 = 0.023 (based on F values) and wR2 = 0.059 (based on F² values), for all measured X‐ray reflections. The structure of the cluster anion can be given as [(Mo₆Cl)Cl]^2– (i = inner, a = outer ligands). Thermal stability studies show that 1 loses crystal water followed by the loss of NH₄Cl above 350 °C to yield MoCl₂. The water‐free compound (NH₄)₂[Mo₆Cl₁₄] ( 2 ) was synthesized by solid state reaction of MoCl₂ and NH₄Cl in a sealed quartz ampoule at 270 °C. No single‐crystals could be obtained. Decompositions of 1 and 2 under nitrogen and argon exhibited the loss of NH₄Cl at about 350 °C. Decomposition under NH₃ resulted in the formation of MoN and Mo₂N at 540 °C and 720 °C, respectively.     

Protonenlagen bei Kaliumtetraamidozinkat,K2Zn(NH2)4

Positions of the Protons in Potassium Tetraamidozincate, K₂Zn(NH₂)₄ X-ray single crystal data for K₂Zn(NH₂)₄ allowed the determination of the so far unknown positions of the protons: P1 , Z = 2, a = 6.730(1) Å, b = 7.438(1) Å, c = 8.019(2) Å, α = 72.03(2)°, β = 84.45(2)°, γ = 63.82(1)°, Z(F₀) with (F₀)² ≥ 3σ(F₀)² = 2166, Z(parameters) = 96, R/R_W = 0.032/0.039. In the structure of K₂Zn(NH₂)₂ the amide ions are nearly hexagonal close packed. One layer of octahedral holes parallel to (010) is fully occupied by potassium atoms and zinc is in an ordered way in a quarter of the tetrahedral holes of the next layer. The orientation of the protons of the amide ions is characteristic for this type of structure (filled up CdI₂ type).     

Kaliumamidotrioxogermanate(IV) – Wasserstoff-Brückenbindungen in K3GeO3NH2 und K3GeO3NH2 · KNH2

Potassium Amido Trioxo Germanates(IV) – Hydrogen Bridge Bonds in K₃GeO₃NH₂ and K₃GeO₃NH₂ · KNH₂ Colorless crystals of K₃GeO₃NH₂ and of K₃GeO₃NH₂ · KNH₂ were obtained by the reaction of KNH₂ with GeO₂ in supercritical ammonia at 450°C and p = 6 kbar in high-pressure autoclaves within 15 resp. 5 days. The crystal structures of both compounds were solved by X-ray single crystal methods. K₃GeO₃NH₂: P1 , a = 6.390(1) Å, b = 6.684(1) Å, c = 7.206(1) Å, α = 96.47(1)°, β = 101.66(1)°, γ = 91.66(1)°, Z = 2, R/R_w = 0.020/0.022, N(I) ≥ 2σ(I) = 3023, N(Var.) = 82 K₃GeO₃NH₂ · KNH₂: P2₁/c, a = 10.982(6) Å, b = 6.429(1) Å, c = 12.256(8) Å, β = 106.12(1)°, Z = 4, R/R_w = 0.022/0.029, N(F) ≥ 3σ(F) = 1745, N(Var.) = 107. In K₃GeO₃NH₂ tetrahedral ions GeO₃NH₂^3? are connected to chains by N? H …? O bridge bonds with 2.18 Å ≤ d(H …? O) ≤ 2.40 Å for d(N? H) ? 1.0 Å and by potassium ions while in K₃GeO₃NH₂ · KNH₂ bridge bonds between NH₂ groups of GeO₃NH₂^3? and NH₂^? ions as acceptors occur with 2.41 Å ≤ d((N? )H …? NH₂^?) ≤ 2.61 Å for d(N? H) ? 1.0 Å.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

Synthese,Kristallstruktur und thermischer Abbau von Fluoroaluminaten der Zusammensetzung (NH4)[M(H2O)6][AlF6] (M = Zn,Ni), [Zn(H2O)6][AlF5(H2O)] und (PyH)4[Al2F10] · 4 H2O

Synthesis, Crystal Structure and Thermal Behaviour of Fluoroaluminates of the Composition (NH₄)[M(H₂O)₆](AlF₆) (M = Zn, Ni), [Zn(H₂O)₆][AlF₅(H₂O)], and (PyH)₄[Al₂F₁₀] · 4 H₂O Four new fluoroaluminates were obtained from fluoroacidic solutions of respective metal salts. The compounds of zinc ( I a : P2₁/c, a = 12.688(3), b = 6.554(1), c = 12.697(3) Å, β = 95.21(3)°, V = 1051.5(4) ų, Z = 4) and nickel ( I b : P2₁/c, a = 12.685(3), b = 6.517(1), c = 12.664(2)Å, β = 94.55(2)°, V = 1043.6(4) ų, Z = 4) are isotypic and represent a new structure type consisting of two different cations, NH₄⁺ and [M(H₂O)₆]²⁺ and [AlF₆]^3–‐anions. [Zn(H₂O)₆][AlF₅(H₂O)] ( II : C2/m, a = 10.769(2), b = 13.747(3), c = 6.487(1)Å, β = 100.02(3)°, V = 945.7(3) ų, Z = 4) is characterized by a H₂O/F‐disorder in the [AlF₅(H₂O)]‐octahedra in two trans positions. In (PyH)₄[Al₂F₁₀] · 4 H₂O ( III : Cmc2₁, a = 15.035(3), b = 20.098(4), c = 12.750(4) Å, V = 5364(2) ų, Z = 8), bioctahedral [Al₂F₁₀]^4– anions have been found for the first time. The structures are described and discussed in comparison. The new compounds were used as precursors in order to obtain new AlF₃‐phases. However, the thermal decomposition did not result in the formation of any new metastable AlF₃‐phase. Instead, phase mixtures of either α‐AlF₃ and β‐AlF₃ or AlF₃ and MF₂ were obtained.     

(NH4)3[M2NCl10] (M = Nb,Ta): Synthese,Kristallstruktur und Phasenumwandlung

(NH₄)₃[M₂NCl₁₀] (M = Nb, Ta): Synthesis, Crystal Structure, and Phase Transition The nitrido complexes (NH₄)₃[Nb₂NCl₁₀], and (NH₄)₃[Ta₂NCl₁₀] are obtained in form of moisture-sensitive, tetragonal crystals by the reaction of the corresponding pentachlorides with NH₄Cl at 400 °C in sealed glass ampoules. Both compounds crystallize isotypically in two modifications, a low temperature form with the space group P4/mnc and a high temperature form with space group I4/mmm. In case of (NH₄)₃[Ta₂NCl₁₀] a continuous phase transition occurs between –70 °C and +60 °C. For the niobium compound this phase transition is not yet fully completed at 90 °C. The structure of (NH₄)₃[Nb₂NCl₁₀] was determined at several temperatures between –65 °C und +90 °C to carefully follow the continuous phase transition. For (NH₄)₃[Ta₂NCl₁₀] the structure of the low temperature form was determined at –70 °C, and of the high temperature form at +60 °C. The closely related crystal structures of the two modifications contain NH₄⁺ cations and [M₂NCl₁₀]^3– anions. The anions with the symmetry D_4h are characterized by a symmetrical nitrido bridge M=N=M with distances Nb–N = 184.5(1) pm at –65 °C or 183.8(2) pm at 90 °C, and Ta–N = 184.86(5) pm at –70 °C or 184.57(5) pm at 60 °C.     

Cs2Ba(O3)4 · 2 NH3, das erste ionische Erdalkaliozonid

Cs₂Ba(O₃)₄ · 2 NH₃, the First Ionic Alkaline Earth Metal Ozonide Cs₂Ba(O₃)₄ · 2 NH₃ is the first ionic ozonide containing an alkaline earth metal cation. Its synthesis has been achieved via partial cation exchange of CsO₃ dissolved in liquid ammonia. According to a single crystal X‐ray structure determination (Pnnm; a = 6.312(2) Å, b = 12.975(3) Å, c = 8.045(2) Å; Z = 2; R₁ = 4.6%; 848 independent reflections) ozonide anions, cesium cations and ammonia molecules form a CsCl‐type arrangement, where Cs⁺ and NH₃ occupy one half of the cation sites, each. Ba²⁺ is coordinated by four ozonide groups and two ammonia molecules. Because of a short hydrogen bond to one of the terminal oxygen atoms, the respective O–O‐distance in the ozonide ion is longer than the other. The shortest intermolecular O–O‐distance ever observed in ionic ozonides has been found in this compound, which can be taken as a first clue for the radical ozonide anion to dimerize like the isoelectronic SO₂^– does.     

Tetraammonium Diglycinyl‐octamolybdate(VI) Dihydrate, (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O

The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH₄)₄[(NH₃CH₂CO)₂(Mo₈O₂₈)] · 2 H₂O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 ų, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH₃CH₂CO)₂(Mo₈O₂₈)]^4–, with two zwitterionic glycine molecules as ligands.     

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.     

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 der Übergangsmetalltrimetaphosphimate Zn3[(PO2NH)3]2 · 14 H2O und Co3[(PO2NH)3]2 · 14 H2O

Synthesis and Crystal Structure of the Transition Metal Trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O The transition metal trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O were obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with the respective metal nitrate or halide (molar ratio 1 : 4). The structure of Zn₃[(PO₂NH)₃]₂ · 14 H₂O was solved by single crystal X‐ray methods. The structure of isotypic Co₃[(PO₂NH)₃]₂ · 14 H₂O was refined from X‐ray powder diffraction data using the Rietveld method (Zn₃[(PO₂NH)₃]₂ · 14 H₂O ( 1 ): P 1, a = 743.7(2), b = 955.9(2), c = 980.1(2) pm, α = 102.70(3), β = 90.46(3), and γ = 100.12(3)°, Z = 1; Co₃[(PO₂NH)₃]₂ · 14 H₂O ( 2 ): P 1, a = 746.05(1), b = 957.06(2), c = 988.51(2) pm, α = 102.162(1), β = 90.044(1), and γ = 99.258(1)°, Z = 1). In 1 and 2 the P₃N₃ rings of the trimetaphosphimate ions attain a conformation which can be described as a combination of an ideal boat and an ideal twist conformation. The trimetaphosphimate ions act as bridging ligands. Thus chains of alternating M²⁺ and (PO₂NH)₃^3– ions are formed which are interconnected by additional M²⁺ ions forming electro‐neutral double chains. In the solid these double chains are connected by hydrogen bonds.     

Zinkiodate – Schwingungsspektren (IR,Raman) und Kristallstruktur von Zn(IO3)2 · 2 H2O

Zinc Iodates – Infrared and Raman Spectra, Crystal Structure of Zn(IO₃)₂ · 2 H₂O The zinc iodates Zn(IO₃)₂ · 2 H₂O and Zn(IO₃)₂ as well as α‐Co(IO₃)₂ · 2 H₂O were studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure of the dihydrate, which is isostructural with the respective cobalt compound, was determined by X‐ray single‐crystal studies (space group P1, Z = 2, a = 490,60(4), b = 667,31(5), c = 1088,85(9) pm, α = 98,855(6), β = 91,119(7), and γ = 92,841(6)°, R1 = 2,55%, 2639 unique reflections I > 2σ(I)). Transconfigurated Zn(IO₃)₄(H₂O)₂ octahedra are threedimensionally connected via common IO₃^– ions parallel to [001] and hydrogen bonds parallel to [100] and [010], respectively. Anhydrous Zn(IO₃)₂ crystallizes in space group P2₁ (Z = 2) with a = 548,9(2), b = 512,4(1), c = 941,8(2) pm, and β = 90,5(3)°. The structure of Zn(IO₃)₂ is a monoclinically distorted variant of the structures of β‐Ni(IO₃)₂ (space group P6₃) and Co(IO₃)₂ (P3). The O–H … O–IO₂ hydrogen bonds of the crystallographically different H₂O molecules of the dihydrates (ν_OD (OD stretching modes of isotopically dilute samples) 2430, 2415, 2333 and 2300 cm^–1, Zn(IO₃)₂ · 2 H₂O, 90 K) are examples to the matter of fact that O … O distances are only a bad measure for the strength of hydrogen bonds. The infrared and Raman spectra as well as a group theoretical treatment are presented and discussed with respect to mutual exclusion principle (possible space groups), the strength of the hydrogen bonds and the distortion of the IO₃^– ions at the C₁ lattice sites.