RbLi2Ga2(BO3)3

The structure of rubidium dilithium digallium tris­(borate), RbLi₂Ga₂(BO₃)₃, contains two‐dimensional sheets of open‐branched rings of GaO₄ tetrahedra and planar BO₃ triangles that are joined by LiO₄ tetrahedra to form a three‐dimensional framework. Ten‐coordinate Rb atoms lie on twofold axes and occupy channels within the framework that extend along the b axis.     

The solid solution (Fe0.81Al0.19)(H2PO4)3 with a strong hydrogen bond

Single crystals of the solid solution iron aluminium tris(dihydrogenphosphate), (Fe_0.81Al_0.19)(H₂PO₄)₃, have been prepared under hydrothermal conditions. The compound is a new monoclinic variety (γ‐form) of iron aluminium phosphate (Fe,Al)(H₂PO₄)₃. The structure is based on a two‐dimensional framework of distorted corner‐sharing MO₆ (M = Fe, Al) polyhedra sharing corners with PO₄ tetrahedra. Strong hydrogen bonds between the OH groups of the H₂PO₄ tetrahedra and the O atoms help to consolidate the crystal structure.     

The iron phosphate NaZnFe2(PO4)3

Crystals of sodium zinc diiron(III) triphosphate, NaZnFe₂(PO₄)₃, have been synthesized and structurally characterized by single‐crystal X‐ray diffraction. The compound features a new structural type built up from ZnO₆ octahedra, FeO₆ octahedra and FeO₄ tetrahedra, linked together via the corners and edges of PO₄ tetrahedra to form a three‐dimensional framework, with tunnels running along [100]. Within these tunnels, Na⁺ cations occupy a highly distorted cubic site.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

The rich crystal chemistry of the AMM′(PO4)2 morphotropic series: NaZnAl(PO4)2, the first Na representative with a new structure type

A novel phosphate, sodium zinc aluminium bis(phosphate), NaZnAl(PO₄)₂, was obtained under mild‐temperature hydrothermal conditions at 553 K. The crystal structure has been studied using single‐crystal X‐ray experimental data. The pseudo‐hexagonal phase NaZnAl(PO₄)₂ crystallizes in the monoclinic space group P2₁/c. Its unique crystal structure is based on a three‐dimensional (3D) framework built by Zn‐, Al‐ and P‐centred tetrahedra sharing vertices. Channels parallel to the [101] and [01] directions are limited by six‐ and eight‐membered windows, and incorporate Na atoms. The new compound is discussed as a member of the morphotropic series AMM′PO₄, where A = Na, K, Rb or NH₄, M = Cu, Ni, Co, Fe, Zn or Mg and M′ = Fe, Al or Ga. The title compound is the first Na representative within the series and is characterized by a 3D architecture of tetrahedra populated in an ordered manner by Zn²⁺, Al³⁺ and P⁵⁺ ions.     

AgCo3PO4(HPO4)2

The structure of the hydro­thermally synthesized compound AgCo₃PO₄(HPO₄)₂, silver tricobalt phosphate bis­(hydrogen phosphate), consists of edge‐sharing CoO₆ chains linked together by the phosphate groups and hydrogen bonds. The three‐dimensional framework delimits two types of tunnels which accommodate Ag⁺ cations and OH groups. The title compound is isostructural with the compounds AM₃H₂(XO₄)₃ (A = Na or Ag, M = Co or Mn, and X = P or As) of the alluaudite structure type.     

[Zn3(PO4)2(H2O)0.8(NH3)1.2]

The structure of the title compound, ammineaquadi‐μ₅‐phosphato‐trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], consists of two parts: (i) PO₄ and ZnO₄ vertex‐sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO₂(N/O)₂ tetrahedra located between the layers. Elemental analysis establishes the ammine‐to‐water ratio as 3:2. ZnO₂(N/O)₂ tetrahedra are located at special position 4e (site symmetry 2) in C2/c. The two O atoms of ZnO₂(N/O)₂ are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO₂(N/O)₂ tetrahedra with two adjacent bc plane layers. A noteworthy feature of the structure is the presence of NH₃ and H₂O at the same crystallographic position and, consequently, qualitative changes in the pattern of hydrogen bonding and weaker N/O—H...O electrostatic interactions, as compared to two closely related structures.     

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.     

RbGa3(P3O10)2: a new gallium phosphate isotypic with RbAl3(P3O10)2

Rubidium trigallium bis(triphosphate), RbGa₃(P₃O₁₀)₂ has been synthesized by solid‐state reaction and studied by single‐crystal X‐ray diffraction at room temperature. This compound is the first anhydrous gallium phosphate containing both GaO₄ tetra­hedra (Ga1) and GaO₆ octa­hedra (Ga2 and Ga3). The three independent Ga atoms are located on sites with imposed symmetry 2 (Wickoff positions 4a for Ga1 and 4b for Ga2 and Ga3). The GaO₄ and GaO₆ polyhedra are connected through the apices to triphosphate groups and form a three‐dimensionnal host lattice. This framework presents inter­secting tunnels running along the [001] and <110> directions, where the Rb²⁺ cations are located on sites with imposed symmetry 2 (Wickoff position 4a). The structure also exhibits remarkable features, such as infinite helical columns created by the junction of GaO₄ and PO₄ tetra­hedra.     

LiFe(MoO4)2, LiGa(MoO4)2 and Li3Ga(MoO4)3

The structures of lithium iron dimolybdate, LiFe(MoO₄)₂, and lithium gallium dimolybdate, LiGa(MoO₄)₂, are shown to be isomorphous with each other. Their structures consist of segregated layers of LiO₆ bicapped trigonal bipyramids and Fe(Ga)O₆ octahedra separated and linked by layers of isolated MoO₄ tetrahedra. The redetermined structure of trilithium gallium trimolybdate, Li₃Ga(MoO₄)₃, shows substitional disorder on the Li/Ga site and consists of perpendicular chains of LiO₆ trigonal prisms and two types of differently linked Li/GaO₆ octahedra.     

The high‐temperature modification of zinc catena‐polyphosphate, β‐Zn(PO3)2

Single crystals of the high‐temperature modification of zinc catena‐polyphosphate, β‐Zn(PO₃)₂, were grown from a melt and quenched from 1093 K to room temperature. The structure was solved from single‐crystal X‐ray diffraction data and is built of corrugated (PO₃)_∞ polyphosphate chains, which extend along the c direction with an eight‐tetrahedra repeat. Slightly distorted [ZnO₄] tetrahedra link the polyphos­phate chains into a three‐dimensional network.     

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.     

A new type of mixed anionic framework in microporous rubidium copper vanadyl(V) phosphate,Rb2Cu(VO2)2(PO4)2

In dirubidium copper bis[vanadyl(V)] bis(phosphate), Rb₂Cu(VO₂)₂(PO₄)₂, three different oxo complexes form an anionic framework. VO₅ polyhedra in a trigonal bipyramidal configuration and PO₄ tetrahedra share vertices to form eight‐membered rings, which lie in layers perpendicular to the a axis of the monoclinic unit cell. Cu atoms at centres of symmetry have square‐planar coordination and link these layers along [100] to form a three‐dimensional anionic framework, viz. [Cu(VO₂)₂(PO₄)₂]_∞²⁻. Intersecting channels in the [100], [001] and [011] directions contain Rb⁺ cations. Topological relations between this new structure type and the crystal structures of A(VO₂)(PO₄) (A = Ba, Sr or Pb) and BaCrF₂LiF₄ are discussed.     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Hydrothermal synthesis and crystal structure of a new ammonium gallium hydroxyphosphate (NH4)Ga(OH)PO4

A new ammonium gallium hydroxyphosphate (NH₄)Ga(OH)PO₄ was synthesized under mild hydrothermal conditions (200°C, τ = 168 h). The equimolar content of Ga and P was determined by chemical analysis and electron probe X-ray microanalysis. The presence of NH₄ and OH groups was demonstrated by IR and Raman spectroscopy. An ab initio model of the crystal structure was refined by the Rietveld method (space group P2₁/m, Z = 2): a = 4.4832(1) Å, b = 6.0430(1) Å, c = 8.5674(1) Å, β = 98.019(1)°, R _p = 0.0552, R _wp = 0.0723. A zero SHG signal (T = 300 K) confirmed a centrosymmetric structure of the compound. The structure contains layers composed of GaO₄(OH)₂ octahedra and PO₄ tetrahedra. The interlayer space accommodates ammonium cations. The layer is based on linear chains of edge-sharing GaO₄(OH)₂ octahedra with a zigzag trans-arranged-Ga-(OH)-Ga-(OH)-backbone. The construction of the layer in (NH₄)Ga(OH)PO₄ was found to be topologically related to that in (En)_0.5Fe(OH)PO₄. The effect of the gradual F^? → OH^? substitution in the quasi-morphotropic series (NH₄)GaF_1-δ(OH)_δPO₄ (δ = 0, 0.5, 1.0) on the degree of polarization of the mixed anionic radical was considered. (NH₄)Ga(OH)PO₄ is thermally unstable: removal of NH₃ and H₂O molecules in the range 170–450°C is accompanied by the formation of two polymorphs of GaPO₄.     

Potassium gadolinium polyphosphate,KGd(PO3)4

Potassium gadolinium polyphosphate, KGd(PO₃)₄, was synthesized using the flux method. The atomic arrangement consists of an infinite long‐chain polyphosphate organization. Two types of chains, with a period of eight PO₄ tetrahedra, run along the [101] direction. The Gd atoms have an eightfold coordination, while the K atoms have nine O‐atom neighbours.     

Preparation,Single Crystal Structure Analysis,and Thermal Behaviour of the Acidic Mercury(I) Phosphate (Hg2)2(H2PO4)(PO4)

Yellowish single crystals of acidic mercury(I) phosphate (Hg₂)₂(H₂PO₄)(PO₄) were obtained at 200 °C under hydrothermal conditions in 32% HF from a starting complex of microcrystalline (Hg₂)₂P₂O₇. Refinement of single crystal data converged at a conventional residual R[F² > 2σ(F²)] = 3.8% (C2/c, Z = 8, a = 9.597(2) Å, b = 12.673(2) Å, c = 7.976(1) Å, β = 110.91(1)°, V = 906.2(2) ų, 1426 independent reflections > 2σ out of 4147 reflections, 66 variables). The crystal structure consists of Hg₂²⁺‐dumbbells and discrete phosphate groups H₂PO₄^– and PO₄^3–. The Hg₂²⁺ pairs are built of two crystallographically independent Hg atoms with a distance d(Hg1–Hg2) = 2.5240(6) Å. The oxygen coordination sphere around the mercury atoms is asymmetric with three O atoms for Hg1 and four O atoms for Hg2. The oxygen atoms belong to the different PO₄ tetrahedra, which in case of H₂PO₄‐groups are connected by hydrogen bonding. Upon heating over 230 °C, (Hg₂)₂(H₂PO₄)(PO₄) condenses to (Hg₂)₂P₂O₇, which in turn disproportionates at higher temperatures into Hg₂P₂O₇ and elemental mercury.     

Synthese und Kristallstruktur von Te3O3(PO4)2, einer Verbindung mit fünffach koordiniertem Tellur(IV)

Synthesis and Crystal Structure of Te₃O₃(PO₄)₂, a Compound with 5‐fold Coordinate Tellurium(IV) Polycrystalline Te₃O₃(PO₄)₂ is formed during controlled dehydration of (Te₂O₃)(HPO₄) with (Te₈O₁₀)(PO₄)₄ as an intermediate product. Colourless single crystals were prepared by heating stoichiometric amounts of the binary oxides P₂O₅ und TeO₂ in closed silica glass ampoules at 590 °C for 8 hours. The crystal structure (P2₁/c, Z = 4, α = 12.375(2), b = 7.317(1), c = 9.834(1)Å, β = 98.04(1)°, 1939 structure factors, 146 parameters, R[F² > 2σ(F²)] = 0.0187, wR2(F² all) = 0.0367) was determined from four‐circle diffractometer data and consists of [TeO₅] polyhedra und PO₄ tetrahedra as the main building units. The framework structure is made up of cationic zigzag‐chains of composition [Te₂O₃]²⁺ which extend parallel to [001] and anionic [Te(PO₄)₂]^2— units linked laterally to these chains. This leads to the formation of [Te₂O₃][Te(PO₄)₂] layers parallel to the bc plane which are interconnected via weak Te‐O bonds.     

A layered fluorinated gallium phosphate organically templated by propane‐1,3‐diaminium,an analog of the aluminophosphate MIL‐12: Ga2(PO4)F5·C3H12N2

Crystals of the oxyfluorinated gallium phosphate MIL‐12 (digallium phosphate penta­fluoride propane‐1,3‐diaminium), (C₃H₁₂N₂)[Ga₂(PO₄)F₅], were synthesized hydro­thermally at 453 K under autogenous pressure using propane‐1,3‐diamine as the structure‐directing agent. The title compound is isomorphous with the aluminium phosphate having the MIL‐12 structural type. The structure is built up from a two‐dimensional anionic network inter­calated by the diamine species. The inorganic layer is composed of corner‐linked GaO₂F₄ octa­hedra and PO₄ tetra­hedra. The diprotonated diamine group is located on a mirror plane, between the inorganic sheets, and inter­acts preferentially via hydrogen bonding through the ammonium groups and the terminal F and bridging O atoms of the inorganic layer. One of the Ga atoms lies on an inversion centre and the other lies on a mirror plane, as does the P atom, two of the phosphate O atoms and one of the F atoms.     

Darstellung und Kristallstruktur von Cs2Mn(PO3)4

Synthesis and Crystal Structure of Cs₂Mn(PO₃)₄ On heating mixtures of Cs₂CO₃, MnO and H₃PO₄ with Cs:Mn:P = 3:1:5 at 500°C Cs₂Mn(PO₃)₄ is formed. The by-product (CsPO₃)_n may be removed by leaching with water. The x-ray structure determination (P2₁/n; a = 797.62(3), b = 1324.91(6), c = 1154.62(8) pm; β = 101.97(1)°; Z = 4) proves the title compound to contain an infinite chain of corner sharing tetrahedra.