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.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

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.     

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.     

Beiträge zum thermischen Verhalten von Sulfaten. VIII. Zum chemischen Transport von FeSO4 mit NH4Cl und von von Fe2(SO4)3 mit Cl2 oder NH4Cl. Experimente und Modellrechnungen

Contributions on the Thermal Behaviour of Sulfates. VIII. The Chemical Vapour Transport of FeSO₄ with NH₄Cl and Fe₂(SO₄)₃ with Cl₂ or NH₄Cl. Experiments and Calculations Well shaped crystals of FeSO₄ and Fe₂(SO₄)₃ can be grown by CVT (T₁? 650°C). We investigated the dependence of the transport rate on the concentration of the transport agent (Fe₂(SO₄)₃/Cl₂ and Fe₂(SO₄)₃/NH₄Cl) as well as on the temperature (FeSO₄/NH₄Cl and Fe₂(SO₄)₃/Cl₂). Using Δ_fH(FeSO₄) = ?220 kcal/ mol, C^p(T) = 30.1 + 9.9 · 10^?3 ×T and Δ_fH(Fe₂(SO₄)₃) = ?615.4 kcal/mol a satisfying agreement between thermodynamical calculations and experimental results can be reached     

RbLi(NH2)2, a Rubidium Amido Lithiate Investigated by X‐Ray and Neutron Diffraction

RbLi(NH₂)₂ and the fully deuterated compound are obtained in autoclaves by the reaction of RbNH₂/RbND₂ and Li metal in supercritical NH₃/ND₃ (470 K, 220 Mpa, 41 d). X‐ray single crystal and neutron powder diffraction led to a new type of crystal structure closely related to the ThCr₂Si₂type. It is an orthorhombic distorted variant with an ordered half occupation by lithium on tetrahedral sites of puckered 4⁴ nets of amide ions to{[Li(NH₂)_1/1(NH₂)_3/3]} units and fully filled up sites of CN = 8 by Rb. The compound crystallizes in the space group Pnma with Z = 4 and a = 7.772 (2)Å, b = 3.843 (1)Å, c = 11.583 (2)Å. It contains an unexpected hydrogen bridge bonding system between crystallographic different amide ions.     

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.     

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.     

Neutral and Cationic Hexanuclear Rhenium Phosphine Clusters with μ3‐(Phosphido‐Chalcogenido), μ3‐(Arsenido‐Chalcogenido), and μ3‐(Imido or Oxo‐Chalcogenido) Hetero Ligand Shells

Reactions of dry THF/MeCN solutions of Ca[Re₆SCl(Cl^a)₆] with silylated derivatives E(SiMe₃)₂ (E = PhAs, PSiMe₃, HN, O, S) and addition of trialkylphosphine PPr₃ afford in high yields and at room temperature either the neutral clusters [Re₆SX(PPr₃)] ( 1 : X = As, 2 : X = P) or the ionic compounds [Re₆SX(PPr₃)]²⁺ · [Re₆S₆Cl₈]^2– ( 3 : X = NH, 4 : X = O, 5 : X = S). The compounds 1 – 5 were characterised by X‐ray crystal structure analysis. A di‐substitution reaction occurs on the {Re₆SCl}⁴⁺ cluster core, where the two inner μ₃‐chloro ligands Clⁱ are substituted by X (X = As, P, NH, O, S) and all six terminal chloro ligands Cl^a are exchanged by terminal PPr₃‐ligands.     

Maximum carbonyl‐coordination number of scandium Computational study of Sc(CO)n (n = 1–7), Sc(CO)7− and Sc(CO)63−

Understanding the maximum bonding ability is very important with the potential both to design new compounds and to broaden chemists' imagination. While the coordination ability of the late transition metals has been richly understood, that of scandium is very poor. In this work, a detailed computational study on the equilibrium geometries, stability and vibrational frequencies of a series of Sc(CO)_n (n = 1–7), Sc(CO) and Sc(CO) is reported using density functional theory functionals and the coupled cluster (single‐point) method with 6‐311+G(3df) basis set. It was shown that the obtained sequential and average CO binding energies of Sc(CO)_n (n = 4–7), Sc(CO) and Sc(CO) are comparable to those of the experimentally known species, i.e., smaller Sc‐carbonyls (n ≤3) and the analog Ti(CO)₇⁺. Thus, the studied high scandium carbonyls could all be experimentally accessible. In addition, the studied Sc(CO)_n generally favor the low‐spin ground state (doublet) structures except ScCO and Sc(CO)₃ that are in the quartet states. The previously uncertain spectrum bands were assigned to Sc(CO)₄ and Sc(CO)₅ in this work. In all, the appreciable stability suggested that the last 18‐electron first‐row transition metal carbonyls, that is, Sc(CO) and Sc(CO), could be accessible in experiment. © 2013 Wiley Periodicals, Inc.     

[ScCl2{N(SiMe3)2}(THF)2] als Vorläufer für die Synthese von Scandiumnitrid

[ScCl₂{N(SiMe₃)₂}(THF)₂] – a Precursor for the Synthesis of Scandium Nitride [ScCl₂{N(SiMe₃)₂}(THF)₂] ( 1 ) has been prepared by the reaction of [ScCl₃(THF)₃] with the trisamide Sc[N(SiMe₃)₂]₃ in tetrahydrofurane solution forming colourless moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P 1, Z = 2, lattice dimensions at –50 °C: a = 841.4(1), b = 924.2(1), c = 1550.0(1) pm, α = 90.046(7)°, β = 95.671(9)°, γ = 106.066(6)°, R₁ = 0.0329. In the molecular structure of 1 the scandium atom has a distorted trigonal‐bipyramidal coordination with the THF molecules in apical positions. At 400 °C 1 is converted into scandium nitride, ScN, by stepwise leaving of THF and ClSiMe₃.     

Sur les carbonates basiques de fer (III): II. Préparation,radiocristallographie et spectres IR. du (NH4)2Fe2(OH)4(CO3)2 · H2O

The obtention of the crystalline basic carbonate of iron (III) and ammonium, (NH₄)₂Fe₂(OH)₄(CO₃)₂ · H₂O, is described and its formula is established by chemical analysis and infrared spectroscopy. The powder X-ray diagram could be indexed tetragonally leading to a body centred elementary cell with a = 12,04 ± 0,02 Å and c = 6,62 ± 0,01 Å. The infrared spectra show that in the CO groups either one oxygen atom is linked to one iron atom or, rather, two oxygen atoms are linked to two iron atoms. The symmetry of the NH groups is lower than C_3v. The OH-groups are linked by hydrogen bonds of 2,75 Å. Two sorts of OH-groups can be distinguished, with a radius of approximately 1,34 Å and 1, 48 Å, respectively. The iron atoms are octahedrally coordinated by oxygen atoms, but either the octahedra are deformed or the iron atoms are in part coordinated tetrahedrally.     

Synthese und Struktur von (NH4)2[(AuI4)(AuI2(μ2-I4))], einem Iodoaurat(III) mit I-Ionen als Liganden

Synthesis and Structure of (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))], a Iodoaurate(III) with I₄^2? Anions as Ligands (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))] is obtained in a sealed glass ampoule by slow cooling of a mixture of NH₄I, Au, and I₂ beforehand heated to 500°C. The compound forms black crystals decomposing slowly under loss of I₂. It crystallizes in the orthorhombic space group Pnma with a = 1357.7(1), b = 2169.9(2), c = 755.6(3) pm, and Z = 4. The crystal structure is built up by NH cations and square-planar [AuI₄]^? anions as well as [AuI₂(μ₂-I₄)]^? groups being linked together by the I ligands to form chains. The distances Au? I are in the range of 258.7(2) to 262.4(2) pm. The nearly linear I anions are characterized by a short central I? I distance of 270.9(3) pm and two longer outer distances of 338.7(2) pm.     

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.     

Schichtenweise Substitution von Kationen im Lithiumamid: Kaliumtrilithiumamid,KLi3(NH2)4 und Kaliumheptalithiumamid,KLi7(NH2)8

Substitution in Layers of Cations in Lithium Amide: Potassium Trilithium Amide, KLi₃(NH₂)₄, and Potassium Heptalithium Amide, KLi₇(NH₂)₈ Four ternary amides were characterized in the system KNH₂/LiNH₂ by x-ray techniques: K₂Li(NH₂)₃ (dimorphous), KLi(NH₂)₂, KLi₃(NH₂)₄, and KLi₇(NH₂)₈. The compounds were prepared by the reaction of ammonia with the metals in high-pressure autoclaves. The atomic arrangements of the potassium-poor amides, KLi₃(NH₂)₄, and KLi₇(NH₂)₈ which have been investigated by x-ray single crystal analysis are discussed: Layers of edge sharing aniontetrahedra occupied to three quarters by lithium are the dominating structural feature. These layers ? [Li₃(NH₂)₄^?] — are primitively stacked in such a manner that potassium occupies quadratic prismatic sites. In KLi₇(NH₂)₈ the layers are connected alternatively by lithium in tetrahedral sites and potassium in an eightfold coordination. The ordered distribution of the cations is controlled by the orientation of amide ions. KLi₃(NH₂)₄ can structure-geometricly be considered as a further example of an “ordered defect structure” of the ThCr₂Si₂ type structure.     

L'action de l'ammoniac sur l'oxyde cuivrique. et les hydroxo-complexes de cuivre (II)

Using a new mathematical treatment, the nature and stability constants of the simple and mixed complex-species of copper(II) with hydroxyde and ammonia as ligands have been determined. The solubility curves of CuO in heterogeneous equilibrium have been identified in function of pH only and in function of pH and pNH_3tot at 25° and unit ionic strength (NaClO₄). The predominent species in the relatively dilute system limited by the ionic strength are [Cu²⁺], [Cu(OH)₂], [Cu(OH)], [Cu(OH)], [Cu(NH₃)], [Cu(NH₃)], [Cu(NH₃)], [Cu(NH₃) (OH)⁺], [Cu(NH₃)₃(OH)⁺] and [Cu(NH₃)₂(OH)₂].     

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?.     

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.     

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.     

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ were prepared by the reaction of Ni(NH₃)₂X₂ with NiX₂ at 350 °C in a steel autoclave. The crystal structures were determined by X‐ray powder diffraction using synchrotron radiation and refined by Rietveld methods. Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ are isotypic and crystallize in the space group I2/m with Z = 8 and for Ni(NH₃)Cl₂: a = 14.8976(3) Å, b = 3.56251(6) Å, c = 13.9229(3) Å, β = 106.301(1)°; Ni(NH₃)Br₂: a = 15.5764(1) Å, b = 3.74346(3) Å, c = 14.4224(1) Å, β = 105.894(1)°. The crystal structures are built up by two crystallographically distinct but chemically mostly equivalent polymeric octahedra double chains [NiX_3/3X_2/2(NH₃)] (X = Cl, Br) running along the short b‐axis. The octahedra NiX₅NH₃ share common edges therein. The crystal structures of the ammines Ni(NH₃)_mX₂ with m = 1, 2, 6 can be derived from that of the halides NiX₂ (X = Cl, Br) by successive fragmentation of its CdCl₂ like layers by NH₃.