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.     

Cd2Cu(PO4)2

During an investigation of the insufficiently known system M1O–M2O–X₂O₅–H₂O (M1 = Cd²⁺, Sr²⁺ and Ba²⁺; M2 = Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺ and Mg²⁺; X = P⁵⁺, As⁵⁺ and V⁵⁺), single crystals of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd₂Cu(PO₄)₂, were obtained. This compound belongs to a small group of compounds adopting a Cu₃(PO₄)₂‐type structure and having the general formula M1₂M2(XO₄)₂ (M1/M2 = Cd²⁺, Cu²⁺, Mg²⁺ and Zn²⁺; X = As⁵⁺, P⁵⁺ and V⁵⁺). The crystal structure is characterized by the interconnection of infinite [Cu(PO₄)₂]_n chains and [Cd₂O₁₀]_n double chains, both extending along the a axis. Exceptional characteristics of this structure are its novel chemical composition and the occurrence of double chains of CdO₆ polyhedra that were not found in related structures. In contrast to the isomorphous compounds, where the M1 cations are coordinated by five O atoms, the Cd atom is coordinated by six. The dissimilarity in the geometry of M1 coordination between Cd₂Cu(PO₄)₂ and the isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with the Cu, Mg and Zn cations. Sharing a common edge, two CdO₆ polyhedra form Cd₂O₁₀ dimers. Each such dimer is bonded to another dimer sharing common vertices, forming [Cd₂O₁₀]_n double chains in the [100] direction. The Cu atoms, located on an inversion centre (site symmetry ), form isolated CuO₄ squares interconnected by PO₄ tetrahedra, forming [Cu(PO₄)₂]_n chains similar to those found in related structures. Conversely, the [Cd₂O₁₀]_n double chains, which were not found in related structures, are an exclusive feature of this structure.     

A New Type of Anionic Framework in Microporous Potassium Iron(II) Phosphate K[Fe(PO4)]

A new iron(II) orthophosphate K[Fe(PO₄)] has been obtained by hydrothermal synthesis and its crystal structure was determined by single‐crystal X‐ray diffraction: space group P2₁/n, Z = 8, a = 9.6199(10), b = 8.6756(8), c = 10.8996(13) Å, β = 115.577(8)° at 193 K, R = 0.023. Fe^II shows coordination numbers (CN) 4 (distorted tetrahedral) and CN 5 (distorted trigonal bipyramidal). The [FeO₄] and [FeO₅] units form together with the [PO₄] tetrahedra a microporous 3D para‐framework with open channels along the a and b directions. The potassium ions positioned in the channels show CN 7 and 8. The structural relations within the morphotropic row of non‐isotypic K[M(PO₄)] structures (M = Zn, Ni, Mn, Fe) are discussed on the basis of common basic structural units.     

Novel K/Mn phosphate hydrates,K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X‐ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit‐cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al‐topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.     

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.     

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.     

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.     

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.     

ASb2(SO4)2(PO4) (A = H3O+, K,Rb): Layered Structure Containing Ordered Sulfate and Phosphate Anions

Three compounds ASb₂(SO₄)₂(PO₄) (A = H₃O⁺, K, Rb) were obtained from the reactions of Sb₂O₃, A₂CO₃ (A = Li, Rb) or K₂SO₄ and NH₄H₂PO₄ in H₂SO₄ (98 %) at 220–250 °C. Their structures were determined by single‐crystal X‐ray diffraction. All compounds crystallize in the triclinic space group P$\bar{1}$ (no.2) and are isostructural. The crystal structures consist of two‐dimensional ²_∞[Sb₂(SO₄)₂(PO₄)]^– anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO₄] ψ‐trigonal bipyramids, [SbO₅] ψ octahedra, [SO₄] tetrahedra, and [PO₄] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT‐IR spectroscopy, and Raman spectroscopy.     

Na10(Na,Mn)7Mn43(PO4)36: a new synthetic fillowite‐type phosphate

Na₁₀(Na,Mn)₇Mn₄₃(PO₄)₃₆ (sodium manganese phosphate) was synthesized hydrothermally at 873 K and 0.35 GPa. The complex crystal structure is almost identical to that of natural fillowite‐type phosphates and can be described as a hexagonal packing of three types of rods parallel to the c axis. The rods are constituted by an alternation of five‐ to seven‐coordinated Mn sites [average Mn—O = 2.243 (3) Å], of six‐ to nine‐coordinated Na sites [average Na—O = 2.590 (3) Å], of PO₄ tetrahedra [average P—O = 1.548 (3) Å] and of cation vacancies.     

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.     

K3Ga2(PO4)3 and Na3Ga(PO4)2

The structures of tripotassium digallium tris(phosphate), K₃Ga₂(PO₄)₃, and trisodium gallium bis(phosphate), Na₃Ga(PO₄)₂, have different irregular one‐dimensional alkali ion‐containing channels along the a axis of the orthorhombic and triclinic unit cells, respectively. The anionic subsystems consist of vortex‐linked PO₄ tetrahedra and GaO₄ tetrahedra or GaO₅ trigonal bipyramids in the first and second structure, respectively.     

Synthesis and Crystal Structure of Lithium Tetrametaphosphimate Tetrahydrate Li4(PO2NH)4 · 4 H2O

Single crystals of Li₄(PO₂NH)₄ · 4 H₂O were obtained by dissolving LiOH and H₄(PO₂NH)₄ · 2 H₂O in water and subsequent precipitation with acetone and ethanol followed by slow evaporation of the solvents. The structure of Li₄(PO₂NH)₄ · 4 H₂O was solved by single‐crystal X‐ray methods ( (No. 2), a = 489.2(2), b = 853.2(2), c = 880.5(2) pm, α = 101.71(3), β = 102.39(3), γ = 94.88(3)°, Z = 1). The structure is composed of LiO₄ tetrahedra and (PO₂NH)₄^4? ions. The P₄N₄ rings of the anions exhibit a slightly distorted chair–1 conformation, which is supported by IR data and has been described by torsion angles, displacement asymmetry parameters and puckering parameters. Via Li⁺ ions and hydrogen bonds, the tetrametaphosphimate anions are connected forming a three‐dimensional network.     

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.     

Darstellung,Kristallstruktur und Eigenschaften des Kupfer(II)‐Indium(III)‐Orthophosphats Cu3In2[PO4]4

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXIV. Preparation, Crystal Structure, and Properties of Copper(II) Indium(III) Orthophosphate Cu₃In₂[PO₄]₄ Crystals of Cu₃In₂[PO₄]₄ were grown by chemical vapour transport (temperature gradient 1273 K → 1173 K) using chlorine as transport agent. The mixed metal phosphate forms a new structure type (P2₁/c, Z = 2, a = 8.9067(6), b = 8.8271(5), c = 7.8815(5) Å, β = 108.393(5)°, 13 atoms in asymmetric unit, 2549 unique reflections with F_o > 4σ, 116 variables, R(F²) = 0.065). The crystal structure shows a hexagonal closest packing of [PO₄]^3– tetrahedra. Close‐packed layers parallel (1 0 –1) are stacked according to the sequence A, B, A′, B′, A. The octahedral interstices in this packing are completely occupied by two In³⁺, one (Cu1)²⁺ and a “dumb bell” (Cu2)₂⁴⁺. In the latter case four of the six phosphate groups that belong to this octahedral void act as bi‐dentate ligands, thus forming dimers [(Cu2)₂O₁₀] with d_Cu–Cu = 3.032 Å. Cu₃In₂[PO₄]₄ is paramagnetic (μ_eff = 1.89 μ_B, θ_P = –16.9 K). The infrared and UV/Vis reflectance spectra are reported. The observed d‐electron levels of the Cu²⁺ cations agree well with those obtained from angular overlap calculations.     

K3Eu5(PO4)6: hydrothermal synthesis,crystal structure and photoluminescence properties

An anhydrous orthophosphate, K₃Eu₅(PO₄)₆ (tripotassium pentaeuropium hexaphosphate), has been prepared by a high‐temperature solid‐state reaction combined with hydrothermal synthesis, and its crystal structure was determined by single‐crystal X‐ray diffraction analysis (SC‐XRD). The results show that the compound crystallizes in the monoclinic space group C2/c and the structure features a three‐dimensional framework of [Eu₅(PO₄)₆]_∞, with the tunnel filled by K⁺ ions. The IR spectrum, UV–Vis spectrum and luminescence properties of polycrystalline samples of K₃Eu₅(PO₄)₆, annealed at temperatures of 650, 700, 750, 800 and 850 °C, were investigated. Although with a full Eu³⁺ concentration (9.96 × 10²¹ ions cm^?3), the self‐activated phosphor K₃Eu₅(PO₄)₆ shows s strong luminescence emission intensity with a quantum yield of 37%. Under near‐UV light excitation (393 nm), the series of samples shows the characteristic emissions of Eu³⁺ ions in the visible region from 575 to 715 nm. The sample sintered at 800 °C gives the strongest emission and its lifetime sintered at 800 °C (1.88 ms) is also the longest of all.     

Synthesis and Crystal Structure Determination by X‐Ray Powder Diffraction of Nickel Tetrametaphosphimate Octahydrate Ni2(PO2NH)4 · 8 H2O

Ni₂(PO₂NH)₄ · 8 H₂O is isotypic with M₂(PO₂NH)₄ · 8 H₂O (M = Mg, Mn, Co, Zn) and crystallizes in the space group P2₁/c, Z = 2, with a = 641.25(1), b = 1041.42(1), c = 1278.18(2) pm and β = 104.243(1)°. The structure is composed of Ni²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair–2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

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.     

Crystal Chemistry of the M11+,2+–M22+,3+–(H)‐Arsenites: the First Cadmium(II) Arsenite,Na4Cd7(AsO3)6

The crystal structures among M1–M2–(H)‐arsenites (M1 = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cd²⁺, Pb²⁺; M2 = Mg²⁺, Mn^2+,3+, Fe^2+,3+, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) are less investigated. Up to now, only the structure of Pb₃Mn(AsO₃)₂(AsO₂OH) was described. The crystal structure of hydrothermally synthesized Na₄Cd₇(AsO₃)₆ was solved from the single‐crystal X‐ray diffraction data. Its trigonal crystal structure [space group R$\bar{3}$ , a = 9.5229(13), c = 19.258(4) Å, γ = 120°, V = 1512.5(5) ų, Z = 3] represents a new structure type. The As atoms are arranged in monomeric (AsO₃)^3– units. The surroundings of the two crystallographically unique sodium atoms show trigonal antiprismatic coordination, and two mixed Cd/Na sites are remarkably unequal showing tetrahedral and octahedral coordinations. Despite the 3D connection of the AsO₃ pyramids, (Cd,Na)O_x polyhedra and NaO₆ antiprisms, a layer‐like arrangement of the Na atoms positioned in the hexagonal channels formed by CdO₄ deformed tetrahedra and AsO₃ pyramids in z = 0, 1/3, 2/3 is to be mentioned. These pseudo layers are interconnected to the 3D network by (Cd,Na)O₆ octahedra. Raman spectra confirmed the presence of isolated AsO₃ pyramids.     

Das erste Vanadium(III)‐Borophosphat: Darstellung und Kristallstruktur von CsV3(H2O)2[B2P4O16(OH)4]

The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH_(aq), VCl₃, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP₂O₈(OH)₂]^5–, which are built up by a central BO₂(OH)₂ tetrahedron and two PO₄ tetrahedra sharing common corners. V^III is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H₂O molecules, respectively (coordination octahedra VO₄(OH)₂ and VO₄(H₂O)₂). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via V^III‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO₄(OH)₂ and VO₄(H₂O)₂ octahedra as well as BO₂(OH)₂ and PO₄ tetrahedra results. The structure contains channels running along [001], which are occupied by Cs⁺ in a distorted octahedral coordination (CsO₄(H₂O)₂).