CsAl(H2AsO4)2(HAsO4): a new monoclinic protonated arsenate with decorated kröhnkite‐like chains

The crystal structure of hydro­thermally synthesized caesium aluminium bis­[dihydrogen arsenate(V)] hydrogen arsen­ate(V), CsAl(H₂AsO₄)₂(HAsO₄), was determined from single‐crystal X‐ray diffraction data collected at room temperature. The compound represents a new structure type that is characterized by decorated kröhnkite‐like [100] chains of corner‐sharing AlO₆ octa­hedra and AsO₄ tetra­hedra. Ten‐coordinated Cs atoms are situated between the chains, which are inter­connected by five different hydrogen bonds [O⋯O = 2.569 (4)–2.978 (4) Å]. All atoms are in general positions. CsAl(H₂AsO₄)₂(HAsO₄) is very closely related to CsGa(H_1.5AsO₄)₂(H₂AsO₄) and isotypic CsCr(H_1.5AsO₄)₂(H₂AsO₄).     

CsGa(H1.5AsO4)2(H2AsO4) and isotypic CsCr(H1.5AsO4)2(H2AsO4): decorated kröhnkite‐like chains in two unusual hydrogen arsenates

Hydro­thermally synthesized caesium gallium(III) hydrogen arsenate(V), CsGa(H_1.5AsO₄)₂(H₂AsO₄), (I), and isotypic caesium chromium(III) hydrogen arsenate(V), CsCr(H_1.5AsO₄)₂(H₂AsO₄), (II), represent a new structure type and stoichiometry among M^I–M^III hydrogen arsenates. The crystal structure, determined from single‐crystal X‐ray diffraction data, is based on an infinite octa­hedral–tetra­hedral chain and can be described as a decorated kröhnkite‐like chain. The chains extend parallel to [100] and are separated by ten‐coordinated Cs atoms. The hydrogen‐bonding scheme comprises one very short symmetry‐restricted hydrogen bond, with O⋯O distances of 2.519 (4) and 2.508 (4) Å in (I) and (II), respectively, and two further medium–strong hydrogen bonds, all of which reinforce the connections between adjacent chains. The average Ga—O and Cr—O bond lengths are 1.973 (15) and 1.980 (13) Å, respectively, and the average As—O bond lengths in the two protonated arsenate groups lie within a very narrow range [1.690 (18)–1.69 (3) Å]. The Cs atom is located on a centre of inversion, while the M^III and As2 atoms lie on twofold axes. Relationships to CaBa₂(HPO₄)₂(H₂PO₄)₂ and other compounds containing decorated kröhnkite‐type or kröhnkite‐like chains are discussed.     

Neue Hexafluoromanganate(III): (NH4)2NaMnF6, (NH4)2KMnF6 und (NH4)3MnF6

New Hexafluoromanganates(III): (NH₄)₂NaMnF₆, (NH₄)₂KMnF₆, and (NH₄)₃MnF₆ (NH₄)₂NaMnF₆ and (NH₄)₂KMnF₆ were prepared by solid state reaction in sealed platinum tubes under pressure. From solution pure (NH₄)₃MnF₆ has been obtained at first time. The compounds crystallize in three different variants of the elpasolite structure: (NH₄)₂NaMnF₆ tetragonally, (NH₄)₃KMnF₆ monoclinic, (NH₄)₃MnF₆ monoclinic, perhaps with triclinic symmetry. Relations between decreasing symmetry in structure and the JAHN -TELLER effect of Mn(III) as well as the influence of ionic radii are discussed. The reflectance spectra were measured, the magnetic properties of the title compounds as well as (NH₄)₂MnF₅ were investigated.     

AgNi3(PO4)(HPO4)2: an alluaudite‐like structure

The new title phosphate, silver trinickel phosphate bis(hydrogenphosphate), has been synthesized by the hydro­thermal method. It has an alluaudite‐like structure but shows some differences owing to the presence of the H atoms. The structure is isomorphous with the compounds of general formula AM₃(XO₄)(HXO₄)₂ (A is Na or Ag, M is Co, Zn or Mn, and X is As or P), with the Ag atom, one Ni atom and one P atom lying on twofold axes.     

Ca3GeO4Cl2 with a norbergite‐like structure

The title compound, tricalcium monogermanate dichloride, is orthorhombic and consists of one distinct Ge site on special position 4c, site symmetry m, and two different Ca sites, Ca1 and Ca2, one on general position 8d, site symmetry 1, and the other on special position 4c. Two of the O atoms occupy the 4c position (symmetry m); the third O atom is situated on the general 8d position, symmetry 1, as is the one distinct Cl position. By sharing common edges, the distorted Ca1 octahedra form infinite crankshaft‐like chains parallel to the b direction. Along a and c, these chains are connected to one another via common corners, thereby forming a three‐dimensional framework of edge‐ and corner‐sharing Ca1O₄Cl₂ octahedra. Triangular prisms of Ca2O₄Cl₂ polyhedra and GeO₄ tetrahedra fill the interstitial space within the Ca1 polyhedral framework. Relationships between the structures of the title compound and the humite‐type materials norbergite (Mg₃SiO₄F₂) and Mn₃SiO₄F₂ are discussed.     

Das Mischkristallsystem (NH4)2ReCl6-;(NH4)2SnCl6

The Mixed Crystal System (NH₄)₂ReCl₆? (NH₄)₂SnCl₆ Homogeneous mixed crystals between (NH₄)₂ReCl₆ and (NH₄)₂SnCl₆ have been prepared in any composition ratio by precipitation from concentrated solutions with concentrated hydrochloric acid. The lattice constants follow VEGARD 'S rule.     

Magnetic properties of a new cobalt hydrogen vanadate with a dumortierite‐like structure: Co13.5(OH)6(H0.5VO3.5)2(VO4)6

The magnetic properties of a novel cobalt‐based hydrogen vanadate, Co_13.5(OH)₆(H_0.5VO_3.5)₂(VO₄)₆, are reported. This new magnetic material was synthesized in single‐crystal form using a conventional hydrothermal method. Its crystal structure was determined from single‐crystal X‐ray diffraction data and was also characterized by scanning electron microscopy. Its crystal framework has a dumortierite‐like structure consisting of large hexagonal and trigonal channels; the large hexagonal channels contain one‐dimensional chains of face‐sharing CoO₆ octahedra linked to the framework by rings of VO₄ tetrahedra, while the trigonal channels are occupied by chains of disordered V₂O₄ pyramidal groups. The magnetic properties of this material were investigated by DC magnetic measurements, which indicate the occurrence of antiferromagnetic interactions.     

First characterization of the ammine-ammonium complex [(NH4(NH3)4)2(mu-NH3)2]2+ in the crystal structure of [NH4(NH3)4][B(C6H5)4].NH3 and the [NH4(NH3)4]+ complex in [NH4(NH3)4][Ca(NH3)7]As3S6.2NH3 and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3

The compound [NH4(NH3)4][B(C6H5)4].NH3 (1) was prepared by the reaction of NaB(C(6)H(5))(4) with a proton-charged ion-exchange resin in liquid ammonia. [NH(4)(NH(3))(4)][Ca(NH(3))(7)]As(3)S(6).2NH(3) (2) and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3 (3) were synthesized by reduction of As(4)S(4) with Ca and Ba in liquid ammonia. All ammoniates were characterized by low-temperature single-crystal X-ray structure analysis. They were found to contain the ammine-ammonium complex with the maximal possible number of coordinating ammonia molecules, the [NH4(NH3)4]+ ion. 1 contains a special dimer, the [(NH4(NH3)4)2(mu-NH3)2]2+ ion, which is formed by two[NH4(NH3)4]+ ions linked by two ammonia molecules. The H(3)N-H...N hydrogen bonds in all three compounds range from 1.82 to 2.20 A (DHA = Donor-H...Acceptor angles: 156-178 degrees). In 2 and 3, additional H(2)N-H...S bonds to the thioanions are observed, ranging between 2.49 and 3.00 A (DHA angles: 120-175 degrees). Two parallel phenyl rings of the [B(C(6)H(5))(4)](-) anion in 1 form a pi...pi hydrogen bond (C...C distance, 3.38 A; DHA angles, 82 degrees), leading to a dimeric [B(C6H5)4]2(2-) ion.     

[CrBr2(NH3)4][CrBr4(NH3)2], a new chromium(III) complex

Green single crystals of trans‐tetraamminedibromidochromium(III) trans‐diamminetetrabromidochromate(III), [CrBr₂(NH₃)₄][CrBr₄(NH₃)₂], are found to contain two symmetry‐independent sixfold coordinated Cr^III cations on centres of inversion. The structure is composed of octahedral trans‐[CrBr₂(NH₃)₄]⁺ cations and octahedral trans‐[CrBr₄(NH₃)₂]⁻ anions, and adopts a distorted CsCl‐type lattice. The cations and anions are linked by N—H...Br interactions. This is the first example in which both ions are mixed ammine–bromide Cr^III complexes.     

Zwei Mercuri‐Ammin‐Komplexe: [Hg(NH3)2][HgCl3]2 und [Hg(NH3)4](ClO4)2

Two Mercuric Ammoniates: [Hg(NH₃)₂][HgCl₃]₂ and [Hg(NH₃)₄](ClO₄)₂ [Hg(NH₃)₂][HgCl₃]₂ ( 1 ) is obtained by saturating an equimolar solution of HgCl₂ and NH₄Cl with Hg(NH₂)Cl at 75 °C. 1 crystallizes in the orthorhombic space group Pmna with a = 591.9(1) pm, b = 800.3(1) pm, c = 1243.3(4) pm, Z = 2. The structure consists of linear cations [Hg(NH₃)₂]²⁺ and T‐shaped anions [HgCl₃]^—. The coordination sphere of mercury is ?effectively”? completed to compressed hexagonal bipyramids and distorted octahedra, respectively. Single crystals of [Hg(NH₃)₄](ClO₄)₂ ( 2 ) are obtained by passing gaseous ammonia through a solution of mercuric perchlorate, while the solution was cooled to temperatures below 10 °C. 2 crystallizes in the monoclinic space group P2₁/c with a = 791.52(9) pm, b = 1084.3(2) pm, c = 1566.4(2) pm, β = 120.352(1)°, Z = 4. The structure consists of compressed [Hg(NH₃)₄]²⁺ tetrahedra and perchlorate anions. The packing of the heavy atoms Hg and Cl is analogous to the baddeleyite (α‐ZrO₂) type of structure.     

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).     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

(m‐CH3C6H4NH3)6P6O18

In hexakis(m‐toluidinium) cyclo­hexaphosphate, 6C₇H₁₀N⁺·­P₆O₁₈^6?, the atomic arrangement is typical of a layer structure. Layers including the centrosymmetric P₆O₁₈ ring anions develop around the (100) planes at x = . The hydrogen‐bond distribution is described.     

Darstellung und Strukturaufklärung von Ammonium‐tetraamminlithium‐amidotrithiophosphat‐Ammoniak(1/1) (NH4) [Li(NH3)4] [P(NH2)S3] · NH3

Synthesis and Crystal Structure of Ammonium Tetraamminelithium Amidotrithiophosphate‐Ammonia(1/1)(NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ Colourless crystals of (NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ were prepared by the reduction of P₄S₁₀ with a solution of lithium in liquid ammonia. The X‐ray structure determination shows them to contain the pseudo‐tetrahedral amidotrithiophosphate anion [P(NH₂)S₃]²⁻ (point group C_S), which is the hitherto unknown final member of a series of previously characterized amidothiophosphates. The ammonium ion and the ammonia molecule of solvation form an diamminehydrogen(1+)‐ion N₂H₇⁺ with a short, nearly linear hydrogen bond of 2.864(3) Å.     

Ein neues Doppelsalz, (NH4)2SiF6 · NH4NO3

A New Double Salt, (NH₄)₂SiF₆ · NH₄NO₃. From a aqueous solutions of (NH₄)₂SiF₆ and NH₄NO₃ crystallizes by cooling to room-temperature a new double-salt of the composition (NH₄)₂SiF₆ · NH₄NO₃. Its hexagonal unit containing two molecules has the dimensions: a₀ = 5.868, c₀ = 14.799 Å.     

Synthesis and Structure of the First Three‐legged Low‐dimensional Iron Phosphate, [H3N(CH2)3NH2(CH2)2NH2(CH2)3NH3][Fe3F6(HPO4)2(PO4)]·3H2O

A hydrothermal reaction of iron acetylacetonate, phosphoric acid, HF, N, N′‐bis(3‐aminopropyl)ethylenediamine and water at 150 °C gave rise to a new iron phosphate, [H₃N(CH₂)₃NH₂(CH₂)₂NH₂(CH₂)₃NH₃][Fe₃F₆(HPO₄)₂(PO₄)] · 3H₂O ( I ). The structure consists of Fe(1)O₄F₂, Fe(2)O₃F₃ octahedral and P(1)O₃(OH) and P(2)O₄ tetrahedral building units connected through their vertices to form fragments of tancoite‐type units. The tancoite‐type units are linked through the phosphate tetrahedra forming an unusual iron phosphate with a hitherto unknown low‐dimensional structure with three‐iron center.Magnetic studies indicate a complex behavior at low temperature and the high‐temperature data (150 — 300 K) has a Curie‐Weiss behavior. The calculated room temperature magnetic moment is 6 μ_B per Fe atom, and the Neel temperature, T_N = 46K. Crystal data: orthorhombic, space group = I2₁2₁2₁ (no. 24), a = 9.9042(11), b = 12.8865(14), c = 19.783(2)Å, U = 2524.9(5), Z = 4.     

(NH4)2ZrGe3O9: a new microporous zirconogermanate

A new microporous zirconogermanate, di­ammonium zirconium trigermanate, (NH₄)₂ZrGe₃O₉ (FDZG‐2), analogous to wadeite (K₂ZrSi₃O₉), was hydro­thermally synthesized using ZrO(NO₃)₂·2H₂O as the source of zirconium and 1,4‐di­amino­butane as a structure‐directing agent. Single‐crystal X‐ray diffraction analysis reveals that the framework structure is built up of cyclic trigermanate units crosslinked by ZrO₆ octahedra. The Zr atom lies at a site with symmetry and the unique N atom of the ammonium ion lies at a site with threefold symmetry. Large cages are observed, with two NH₄⁺ cations in each. The structure contains intersecting six‐ and three‐membered ring (6MR and 3MR) channels, but only the 6MR channels can accommodate the NH₄⁺ ions.     

Darstellung,Röntgen-Pulverdaten und Gitterkonstanten von K2Cd(N3)4 und Tl2Cd(N3)4

Preparation, X-Ray Powder Data, and Lattice Parameters of K₂Cd(N₃)₄ and Tl₂Cd(N₃)₄ Two monoclinic complex azides of cadmium have been crystallized from aqueous solutions containing HN₃: Dipotassium-cadmium-tetraazide, K₂Cd(N₃)₄: a = 1425.4 b = 378.5 c = 888.3 pm. β = 92.9° and dithallium-cadmium-tetraazide, Tl₂Cd(N₃)₄: a = 1066.9 b = 735.9 c = 656.3 pm, β = 104.4°.