Doppelkettenstruktur von (pipzH2)[MnF2(HPO4)(H2O)](H2PO4)

By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH₂)[MnF₂(HPO₄)(H₂O)](H₂PO₄) can be crystallized. Its structure is built by piperazinium(2+) cations, (H₂PO₄)^? anions, and an anionic double‐chain of [HPO₄] tetrahedra and [MnO₃F₂(H₂O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with [MnO₃F₂(H₂O)] octahedra strongly elongated along the F–Mn–OH₂ axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds.     

Optical,thermal, and magnetic properties of a microporous fluorinated iron phosphate: (H3O)2[Fe4(H2O)2F4(PO4)2(HPO4)2](H2O)

The non-centrosymmetric microporous fluorinated iron phosphate, (H₃O)₂[Fe₄(H₂O)₂F₄(PO₄)₂(HPO₄)₂](H₂O), is endowed with properties. In fact, the thermogravimetric analysis study shows a mass loss evolution as a temperature function. The optical study was also examined by UV–vis absorption. The magnetic results reveal the appearance of a ferromagnetic behavior at low temperature (Tc = 11.64 K).     

Hydrothermal synthesis and structural determination of a three-dimensional microporous iron(III)phosphate: [H3N(CH2)4NH3]3[Fe8(HPO4)12(PO4)2(H2O)6]

A new microporous iron (III) phosphate, [H₃N(CH₂)₄NH₃]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆], has been prepared using low temperature hydrothermal methods and characterized by single-crystal X-ray diffraction, EDAX, infrared spectroscopy, thermogravimetric analysis and bond valence sums. The title compound crystallizes as light pink hexagonal-shaped tabs in the centrosymmetric hexagonal space group 3¯ (No.147) with a = b = 13.495(2) Å, c = 9.396(2) Å, V = 1481.9(4) ų and Z = 4 with R/R_w = 0.044/0.048. The compound exhibits a complicated three-dimensional microporous structure with quaternary ammonium ions acting as a template for the framework. It is similar to previously reported [HN(CH₂CH₂)₃NH]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆].     

Two caesium vanadium hydrogenphosphates with tunnelled structures: Cs2V2O3(PO4)(HPO4) and Cs2[(VO)3(HPO4)4(H2O)]·H2O

Dicaesium divanadium trioxide phosphate hydrogenphosphate, Cs₂V₂O₃(PO₄)(HPO₄), (I), and dicaesium tris[oxidovanadate(IV)] hydrogenphosphate dihydrate, Cs₂[(VO)₃(HPO₄)₄(H₂O)]·H₂O, (II), crystallize in the monoclinic system with all atoms in general positions. The structures of the two compounds are built up from VO₆ octahedra and PO₄ tetrahedra. In (I), infinite chains of corner‐sharing VO₆ octahedra are connected to V₂O₁₀ dimers by phosphate and hydrogenphosphate groups, while in (II) three vanadium octahedra share vertices leading to V₃O₁₅(H₂O) trimers separated by hydrogenphosphate groups. Both structures show three‐dimensional frameworks with tunnels in which Cs⁺ cations are located.     

Preparation and Crystal Structure of Potassium Iron Hydrogen Phosphate,KFe3(HPO4)2(H2PO4)6 · 4 H2O

Single crystals of potassium iron hydrogen phosphate, KFe₃(HPO₄)₂(H₂PO₄)₆ · 4 H₂O, were prepared hydrothermally by heating a mixture of Fe₂O₃, H₃PO₄ and K₂CO₃ with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F₀ > 4σ(F₀) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO₄-tetrahedra around the FeO₆-octahedra parallel to (001). K⁺ and H₂O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations.     

Synthesis and crystal structure of two fluorophosphated compounds with different infinite sheets: Sr2Ga(HPO4)(PO4)F2 and Sr2Fe2(HPO4)(PO4)2F2

New compounds, Sr₂Ga(HPO₄)(PO₄)F₂ and Sr₂Fe₂(HPO₄)(PO₄)₂F₂, have been prepared by hydrothermal synthesis (700°C, 180 MPa, 24 h) and characterized by single-crystal X-ray diffraction. Sr₂Ga(HPO₄)(PO₄)F₂ crystallizes in the monoclinic space group P2₁/n with a = 8.257(1) Å, b = 7.205(1) Å, c = 13.596(2) Å, β = 108.02(1)°, V = 769.2(2) ų and Z = 4 and Sr₂Fe₂(HPO₄)(PO₄)₂F₂ in the triclinic space group P2₁/n with a = 8.072(1) Å, b = 8.794(1) Å, c = 8.885(1) Å, α = 102.46(1)°, β = 115.95(1)°, γ = 89.95(1)°, V = 550.6(1) ų and Z = 2. Structures are both based on different sheets involving corner-linkage between octahedra and tetrahedra. The sheets are linked by Sr²⁺ cations. Structural relationships exist between the descloizite mineral and the title compounds.     

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.     

Synthesis,structure and NMR characterization of a new monomeric aluminophosphate [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4 containing four different types of monophosphates

A new zero-dimensional (0D) aluminophosphate monomer [dl-Co(en)₃]₂[Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂](H₃PO₄)₄ (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en)₃Cl₃ as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂]^6? monomer. Notably, there exists intramolecular symmetrical O?H?O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by ³¹P NMR and ¹H NMR spectra. The crystal data are as follows: AlPO-CJ38, [dl-Co(en)₃]₂[Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂](H₃PO₄)₄, M = 1476.33, monoclinic, C2/c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å³_, Z = 4, R₁ = 0.0509 (I > 2σ(I)) and wR₂ = 0.1074 (all data). CCDC number 689491.     

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).     

Hydrothermal synthesis and structure determination of [VF(PO4), N2C2H9] and [Ti(OH)(PO4), N2C2H9], two M(III) phosphates with the ULM-11 bidimensional topology

[V^IIIF(PO₄), en] and [Ti^III(OH)(PO₄), en] (en = ethylenediamine) are two new layered compounds isostructural with ULM-11. Both were synthesized hydrothermally (453 K, 3 days for ULM-11 (V^III) and 453 K, 28 days for ULM-11 (Ti^III)). Structures were determined by single-crystal X-ray diffraction (V^III sample) or powder X-ray diffraction (Ti^III sample). Both compounds crystallize in the monoclinic system (space group P2₁/ c) with cell parameters at 293 K: a = 9.2272 (3) A, b = 7.3532 (2) A, c = 9.8496 (2) A, β = 101.315 (1) °, V = 655.30 A³, Z = 4 for the vanadium phase and a = 9.265 (1) Å, b = 7.329 (1) A, c = 9.911 (1) A, β = 100.89 (1) °, V = 660.90 ų, Z = 4 for the titanium compound. In both lamellar structures, layers consist of chains of MO₃X₂N octahedra (M = V, Ti and X = F, OH) related together via PO₄ tetrahedra. One amino group of the diamine is directly bound to the metallic center (via the N atom) while the protonated second amino group points at the interlayer space interacting with terminal P-O groups by strong hydrogen bonds.     

Hydrothermal Synthesis and Crystal Structure of CaIn2(PO4)2(HPO4): An octahedral-tetrahedral framework ternary calcium indium(III) phosphate

The new ternary calcium indium(III) phosphate CaIn₂(PO₄)₂(HPO₄) with mixed octahedral-tetrahedral framework was synthesized through hydrothermal reaction of stoichiometric amounts of CaO and InCl₃ with excess of H₃PO₄ and H₂O at pH = 1. Single crystal x-ray diffraction studies show the compound to crystallize in monoclinic symmetry, space group P2₁/n (#14) with a = 657.08(6), b = 2023.7(2), c = 665.72(7) pm, β = 91.20(1)°, Z = 4 and R = 0.043. The framework is built up of dimers of edge-sharing InO₆ octahedra forming In₂O₁₀ units sharing all their OXO ligands with PO₄ tetrahedra, and HPO₄ groups.     

Ein Fluoridphosphat von Mangan(III) mit ungewöhnlicher Schichtstruktur: Na7[Mn5F13(PO4)3(H2O)3]

A Fluoride Phosphate of Manganese(III) with Unusual Layer Structure: Na₇[Mn₅F₁₃(PO₄)₃(H₂O)₃] The title compound was crystallized from a solution of MnF₃ · 3 H₂O in aqueous HF by addition of NaH₂PO₄ · H₂O in 2 M phosphoric acid. The crystal structure has been determined at 295 and 150 K on a trigonal crystal twinned by merohedry: Space group P3c1, Z = 4, a = 1055,0(1), c = 2314,0(1) pm (a = 1052,5(1), c = 2304,2(1) pm at 150 K), wR₂ = 0.0651 (0.0651). The structure contains anionic layers formed by triangular moieties of three [MnF₃O₂(H₂O)] octahedra sharing one common μ₃-F atom and bridged by three phosphate groups. Three of those groups, respectively, are interconnected by two [MnF₃O₃] octahedra over six phosphate O-atoms to form a trigonal layer in the a,b plane. Stacking of these layers gives channels along the c axis in which most of the Na⁺ ions are located. The [MnF₃O₂(H₂O)] octahedra show strong elongation along the μ₃-F–Mn–OH₂ axis mainly due to the Jahn-Teller effect whereas in the [MnF₃O₃] octahedra with C₃ symmetry weak signs only of a dynamical Jahn-Teller-effect can be observed. The magnetic properties (μ_eff = 4.61 μ_B, 3-D ordering point T_N = 3.3 K) were determined on powders and possible magnetic exchange pathways are discussed.     

Hydrothermal synthesis and characterization of the first 1-D indiumphosphate chain In2(HPO4)2(H2PO4)2F2·C4N2H12, a precursor for high dimensional structures

The first one-dimensional (1-D) indiumphosphate chain, In₂(HPO₄)₂(H₂PO₄)₂F₂·C₄N₂H₁₂ (1), has been hydrothermally prepared using piperazine (PIP) as a template. The structure consists of infinite chains of trans,trans-corners-sharing InO₄F₂ octahedra with the adjacent octahedra being bridged by tetrahedral PO₃(OH) and PO₂(OH)₂ units, which are H-bonded with amine groups of the organic cations. Interestingly, this macroanionic chain InP₂O₈H₃F⁻ is similar to that found in the mineral tancoite-like chains and has potential to further set up higher-dimensional networks. On heating 1 in the presence of additional phosphoric acid at 180 °C under hydrothermal condition, compound 2, In₂(OH)(H₂O)(PO₄)₂·H₃O·H₂O, possessed a 3-D structure building from the repetition of a secondary building unit is obtained. When 1 is heated with additional PIP, an unknown phase, compound 3 is formed. Finally, on treatment with another amine, such as diethylenetriamine or 1,4-diaminobutane, at 180 °C, 1, as a precursor, can convert into a previously known 3-D framework structure with 16-membered ring compound 4. Compounds 1 and 2 are determined by single-crystal X-ray diffraction. Furthermore, 1 is characterized by X-ray powder diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis and differential thermal analysis.     

Synthesis and Structure of a Molecular Zinc Phosphate [(C12H8N2Zn)2(HPO4)(H2PO4)2]

A hydrothermal reaction of a mixture of ZnCO₃, phosphoric acid, 1, 10‐phenanthroline in H₂O gave rise to large plates of a new zinc phosphate, [(C₁₂H₈N₂Zn)₂(HPO₄)(H₂PO₄)₂], I . The structure consists of ZnO₃N₂ distorted trigonal‐bipyramidal and PO₄ tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)ų, Z = 8.     

A novel chain-like molybdenum phosphate: hydrothermal synthesis,crystal structure and characterization of [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]-Na5[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O

A novel organic/inorganic hybrid molybdenum phosphate, [NH₃(CH₂CH₂)₂NH₃]₃[NH₃(CH₂CH₂)₂NH₂]Na₅-[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂·4H₂O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃] units bonded together with NaO₆ octahedra, forming dimers. Further, these dimers connect with each other through four Na⁺ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.     

Phase formation in the ZrO(NO3)2-H3PO4-CsF(HF)-H2O system

The phase formation in the system ZrO(NO₃)₂-H₃PO₄-CsF(HF)-H₂O was studied at the molar ratio CsF/Zr = 1 along the sections PO ₄ ^3? /Zr = 0.5 and 1.5 at a ZrO₂ concentration in the initial solution of 2?C14 wt %. The following compounds were isolated: Cs₅Zr₄F₂₁ · 3H₂O, CsZr₂(PO₄)₃ · 2HF · 2H₂O, CsZrF₂PO₄ · H₂O, CsZr₂F₆PO₄ · 4H₂O (for the first time), CsHZrF₃PO₄ (for the first time), Cs_0.70ZrF(PO₄)_1.23 · nH₂O, and CsHZr₂F₂(P_O4)_2.66 · nH₂O. The compositions of CsZrF₂PO₄ · H₂O, Cs_0.70ZrF(PO₄)_1.23 · nH₂O, and CsHZr₂F₂(PO₄)_2.66 · nH₂O are conditional. All the compounds were characterized by crystal-optical, X-ray powder diffraction, thermal analyses, and IR spectroscopy. The formula CsHZrF₃PO₄ was established by energy-dispersive analysis with a LEO-1450 scanning electron microscope and an MS-46 CAMECA X-ray microanalyzer.     

Synthesis and Characterization of a New Layered Zinc Phosphite (NH4)[{Zn(H2O)4}0.5Zn2(HPO3)3]

A new layered zinc phosphite with the formula (NH₄)[{Zn(H₂O)₄}_0.5Zn₂(HPO₃)₃] has been synthesized under hydrothermal conditions. Its structure was determined by single‐crystal X‐ray diffraction. The compound crystallizes in the triclinic system, space group (No. 2), a = 7.2507(4), b = 9.7982(6), c = 10.2642(6) Å, α = 63.425(2), β = 87.165(2), γ = 72.999(3)°, V = 620.84(6) ų, Z = 2. The connectivity of ZnO₄ tetrahedra, HPO₃ pseudo pyramids and ZnO₂(H₂O)₄ octahedra results in macroanionic layers with 4.8 net.     

A new refinement of the crystal structure of the inverse weberite Fe2F5(H2O)2

Fe₂F₅(H₂O)₂ is related to the weberite structure, whose space group is not clearly defined. A careful reexamination of the structure confirms and refines the previous results: Fe₂F₅(H₂O)₂ belongs to the space group Imma with cell parameters a = 7.477(1) Å, b = 10.862(2) Å, c = 6.652(1) Å (Z = 4). The structure has been refined from 379 reflections to R = 0.029 (R_w = 0.034). Fe₂F₅(H₂O)₂ must be considered as an antiweberite structure since M²⁺ and M³⁺ positions are inverse of those of the weberite structure.     

Fe6.67(PO4)5.35(HPO4)0.65 and Fe6.23(PO4)4.45(HPO4)1.55: two new mixed‐valence iron phosphates

Two new mixed‐valence iron phosphates, namely heptairon pentaphosphate hydrogen phosphate, Fe_6.67(PO₄)_5.35(HPO₄)_0.65, and heptairon tetraphosphate bis(hydrogen phosphate), Fe_6.23(PO₄)_4.45(HPO₄)_1.55, have been synthesized hydrothermally at 973 K and 0.1 GPa. The structures are similar to that of Fe^II₃Fe^III₄(PO₄)₆ and are characterized by infinite chains of Fe polyhedra parallel to the [101] direction. These chains are formed by the Fe1O₆ and Fe2O₆ octahedra, alternating with the Fe4O₅ distorted pentagonal bipyramids, according to the stacking sequence ...Fe1–Fe1–Fe4–Fe2–Fe2.... The Fe3O₆ octahedra and PO₄ tetrahedra connect the chains together. Fe^II is localized on the Fe3 and Fe4 sites, whereas Fe^III is found in the Fe1 and Fe2 sites, according to bond‐valence calculations. Refined site occupancies indicate the presence of vacancies on the Fe4 site, explained by the substitution mechanism Fe^II + 2(PO₄³⁻) = vacancies + 2(HPO₄²⁻).     

The dimeric unit [La(H2O)4(m-PO3C6H4COOH)(m-PO2(OH)C6H4COOH)(m-PO(OH)2C6H4COOH)]2 as building block of layered hybrid material

A new hybrid organic–inorganic material with the structural formula unit [La(H₂O)₄(m-PO₃C₆H₄COOH)(m-PO₂(OH)C₆H₄COOH)(m-PO(OH)₂C₆H₄COOH)]₂ (or [La(H₂O)₄C₂₁H₁₈O₁₅P₃]₂) has been synthesized under hydrothermal condition from La(NO₃)₃·6H₂O and 3-phosphonobenzoic acid (m-PO(OH)₂–C₆H₄–COOH) which is a rigid organic precursor possessing two types of functional groups: phosphonic acid and carboxylic acid. The two units of the produced hybrid are linked together by hydrogen bonds leading to a layered framework composing of by a repetition of inorganic and organic slices. The organic layers consist of dimeric units made of two meta-phosphono-benzoic acid linked together by hydrogen bonds involving their COOH groups. Two kinds of dimeric units are observed: PO₃C₆H₄COOH?HOOCC₆H₄PO(OH)₂, present 2 times in the structure, and PO₂(OH)C6H4COOH?HOOCC₆H₄PO₂(OH). The material crystallises in a monoclinic cell (C2/c (15) space group) with the following parameters: a = 42.515(4) Å, b = 7.4378(6) Å, c = 20.307(2) Å, β = 118.031(6)°, V = 5668.2(9) Å³, Z = 4, density = 1.908 g/cm³.