Kristallstruktur von Na5P3O10 · 6 H2O

Crystal Structure of Na₅P₃O₁₀ · 6 H₂O Na₅P₃O₁₀ · 6 H₂O crystallizes triclinic in P1 with a = 1 037.0(2), b = 984.8(4), c = 761.5(3) pm; α = 92.24(7)°, β = 94.55(9), γ = 90.87(6)°; Z = 2. The structure has been determined from fourcycle diffractometer data (2 089 independent reflections, R = 0.053). All hydrogen positions have been taken from a weighted difference-fourier-syntheses. Na₅P₃O₁₀ · 6 H₂O forms colorless, plate-like crystals, which are twinned systematically parallel (001) and can be divided mechanically into single-crystalline portions.     

Phase equilibrium in the system Na5P3O10-Na8La2(PO3)8O3

The phase diagram Na₈La₂(PO₃)₈O₃-Na₅P₃O₁₀, which comprises part of the ternary system La₂O₃-Na₂O-P₂O₅, was constructed in the laboratory. The oxyphosphate Na₈La₂(PO₃)₈O₃ crystallizes in the orthorombic system; the lattice parameters are as follows a=8.96(4)Å, b=9.35(8)Å, c=12.29(7)Å.

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Zusammenfassung Es wurde das Phasendiagramm Na₈La₂(PO₃)₈O₃ - Na₅P₃O₁₀, welches einen Teil des ternären Systemes La₂O₃ - Na₂O - P₂O₅ enthält, konstruiert. Das Oxyphosphat Na₈La₂(PO₃)₈O₃ kristallisiert rhombisch mit folgenden Gitterkonstanten: a=8.96(4)Å, b=9.35(8)Å, c=12.29(7)Å.

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The author thanks Mrs. E. Dlugoszewska for technical assistance.     

Na7Y2(P2O7)2 (P3O10) – A New Layer and Tunnel Structure

A new layered phosphate, Na₇Y₂(P₂O₇) ₂(P₃O₁₀), containing both [P₂O₇]^4? and [P₃O₁₀]^5? groups, has been prepared. It crystallizes in the monoclinic space group P2/c with a = 16.205(4), b = 5.3746(9), c = 12.309(4) Å, β = 97.96(2)°, V = 1061.7(5) ų and Z = 2. The structure was solved and refined to R₁ = 0.0298 and wR₂ = 0.0698 for 1844 independent reflections with I > 2σ(I). It consists of layers of corner and edge-sharing YO₇ polyhedra, P₂O₇ and P₃O₁₀ groups. Each layer is built up from two parallel [YP₂O₇] slabs, held together by the P₃O₁₀ groups. This arrangement gives rise to intersecting tunnels within the layer. The Na⁺ cations are located in the tunnels and between the layers. Both P₂O₇ and P₃O₁₀ groups contain unshared oxygen atoms directed toward the interlayer space and toward the tunnels. The P₂O₇ groups show a staggered configuration. In addition to this original layered framework, the title compound provides the third example of a compound containing a mixed anion of [P₂O₇]^4? and [P₃O₁₀]^5?. The structure was compared with the two previously reported ones, containing such a mixed anion: NH₄Cd₆(P₂O₇) ₂(P₃O₁₀) [6] and Cs₂Mo₅O₂(P₂O₇)₃ · (P₃O₁₀) [7].     

Preparation and crystal data for two trimetaphosphate tellurates: Te(OH)6 · 2Na3P3O9 · 6H2O and Te(OH)6 · K3P3O9 · 2H2O

Te(OH)₆ · 2Na₃P₃O₉ · 6H₂O, is hexagonal (P6₃/m) with a = 11,67(1), c = 12,12(1) Å, Z = 2 and D_x = 2,225 g/cm³. Te(OH)₆ · K₃P₃O₉ · 2H₂O, is monoklin (P2₁/c) with a = 19,61(5), b = 7,456(1), c = 14,84(6) Å, = 108,01(4), Z = 4 and D_x = 2,506 g/cm³. Both compounds are the first examples of phosphate tellurates in which the anion phosphate is condensed to the ring anion P₃O₉. As in phosphate tellurates already described the phosphate groups are independent of the TeO₆ octahedra.     

Crystal structures of CrH2P3O10 and InH2P3O10

The crystal structures of chromium and indium dihydrogen triphosphates, CrH₂P₃O₁₀ and InH₂P₃O₁₀, in modification II are refined by the Rietveld method using X-ray powder diffraction data. The compounds crystallize in the monoclinic crystal system, space group P21/n. Z = 4, a = 7.3225(4)Å, b = 8.6835(6)Å, c = 11.6599(7) Å, and b = 102.388(3)° for CrH₂P₃O₁₀, and a = 7.5332(1)Å, b = 9.0841(1)Å, c = 11.8600(1) Å, and b = 103.9596(7)° for InH₂P₃O₁₀. The structures are refined in the isotropic approximation (pseudo-Voigt profile function): R_p = 4.8%, R_wp = 6.9%, R_Bragg = 7.5%, R_F = 9.9% for CrH₂P₃O₁₀; R_p = 6.3%, R_wp = 8.3%, R_Bragg = 6.2%, R_F = 4.1% for InH₂P₃O₁₀. The crystal structures of compounds in the isostructural series M^IIIH₂P₃O₁₀-II, where M^III = Al, Ga, Cr, V, Fe, and In, are examined and compared.     

Phase equilibria in the P2O5-rich part of the system Y2O3−Na2O−P2O5

In the ternary system Y₂O₃?Na₂O?P₂O₅, the partial system Y(PO₃)₃?NaPO₃?P₂O₅ was examined by means of differential thermal analysis and X-ray powder diffraction; its phase diagram is given.     

Ein neues Oxophosphat (IV/III)-Anion – Darstellung und Kristallstruktur von Na6P4O10 · 2 H2O

A New Oxophosphate (IV/III) Anion – Preparation and Crystal Structure of Na₆P₄O₁₀ · 2 H₂O A new oxophosphate anion, P₄O₁₀^6?, was obtained by cleavage and simultaneous oxidation of the cyclo-hexaphosphate(III) anion in a solution of aqueous ammonia and ethanol. With sodium it forms a salt with the composition Na₆P₄O₁₀ · 2 H₂O. The crystal structure has been determined by single crystal X-ray diffraction (3 745 diffractometer data), the cell constants were obtained from X-ray powder data, space group P1 ; a = 6.004(1), b = 6.173(2), c = 11.496(2) Å, α = 99.26(2)°, β = 95.92(2)°, γ = 117.63(2)°, Z = 1, R = 0.044. The backbone of the anion is formed by phosphorus atoms directly bonded to each other. The coordination of each phosphorus atom is completed to four by oxygene. The resulting oxidation numbers are +III for the inner phosphorus atoms and +IV for the terminal phosphorus atoms. The site symmetry of the anion is approximately C_2h. Based on a ³¹P-NMR spectra of a solution the coupling constants of the AA ‘BB’ system were determined.     

Zur Kenntnis von Na5HI2O10 · 14 H2O

On Na₅HI₂O₁₀ · 14 H₂O Single crystals of Na₅HI₂O₁₀ · 14 H₂O were obtained for the first time. According to the results of an X-ray crystal structure determination (P1 , a = 8.450(7), b = 8.533(6), c = 9.066(6) Å, α = 76.96(6), β = 62.94(5), γ = 86.98(6°, Z = 1, 4970 diffractometer data) iodine is in a distorted octahedral coordination. Two IO₆ polyhedra are connected by a common edge forming dimeric anions H₂I₂O₁₀^4?, the site symmetry is 1 . Sodium exhibits C.N. 6 (mainly hydrate). A 3-d network is formed largely by H-bonds.     

The system Mg2P2O7−Na8Mg6(P2O7)5−NaPO3−Mg(PO3)2

Phase equilibria in the partial system Mg₂P₂O₇?Na₈Mg₆(P₂O₇)₅?NaPO₃?Mg(PO₃)₂ were examined by differential thermal analysis and powder X-ray diffraction. It was found that there are six sections in the composition range under investigation.     

Complexation of the [Rh(NH3)5H2O]3+ ion in aqueous solutions of H3PO4 based on 31P NMR data

The kinetics of the reaction between the [Rh(NH₃)₅H₂O]³⁺ ion and H₃PO₄ was studied by ³¹P NMR at 323?C343 K (E _a = 100.9 ± 0.3 kJ/mol, lnA = 35.7 ± 0.1). An empirical dependence of the ³¹P chemical shift on the equilibrium pH was found. The acid dissociation constants of the coordinated H₂PO ₄ ^? (3.9) and H PO ₄ ^2? ions (9.1) were estimated. The chemical shifts of the [Rh(NH₃)₅H₂PO₄]²⁺, [Rh(NH₃)₅HPO₄]⁺, and [Rh(NH₃)₅PO₄]⁰ complex ions were 8.38 ± 0.03, 10.76 ± 0.05, and 13.63 ± 0.05 ppm, respectively.     

Die Kristallstruktur des Bleimonohydrogentriphosphats,Pb2HP3O10

Crystal Structure of Lead Monohydrogentriphosphate, Pb₂HP₃O₁₀ By heating of Pb₂P₄O₁₂ · 2 H₂O at 150°C crystalline Pb₂HP₃O₁₀ is formed topotactically. In these crystals amorphous H₃PO₄ is included. The monoclinic crystals are fourfold twinned. Space group: Cm; unit cell: a = 6.93 ± 0.01, b = 14.34 ± 0.01, c = 5.97 ± 0.01 Å, β = 135.1 ± 0.1°. The crystal structure was determined by heavy-atom method and refined by least-squares calculations. The P₃O₁₀^5? anion consists of three PO₄ tetrahedra connected by common oxygen atoms. The chain has mirror symmetry across a plane passing the middle P atom. Lead is coordinated by eight oxygen atoms. The polyhedra of Pb are connected parallel y and z by common edges. Six P₃O₁₀^5? chains are joined by one lead ion.     

Complexation of the [Rh(H2O)6]3+ ion with phosphoric acid as probed by 31P NMR

The kinetics of the reaction [Rh(H₂O)₆]³⁺ + H₃PO₄ ? [Rh(H₂O)₅H₂PO₄]²⁺ + H₃O⁺ has been studied by ³¹P NMR; E _a = 142 ± 12 kJ/mol, logA = 17 ± 2. An empirical dependence of the ³¹P NMR chemical shift on the equilibrium pH value has been found. The acid dissociation constant of the coordinated ion has been evaluated: pK = 1.5. The ³¹P NMR chemical shifts of individual [Rh(H₂O)₅H₂PO₄]²⁺ and [Rh(H₂O)₅HPO₄]⁺ complex ions are, respectively, 14.5 and 15.8 ppm at 323 K.     

Synthese,Kristallstruktur und Eigenschaften von Tetranatrium‐bis(trimetaphosphimato)cuprat(II)‐Decahydrat,Na4{Cu[(PO2NH)3]2} · 10 H2O

Synthesis, Crystal Structure, and Properties of Tetrasodium Bis(trimetaphosphimato)cuprate(II) Decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O Tetrasodium bis(trimetaphosphimato)cuprate(II) decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O, was obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with Cu(NO₃)₂ · 3 H₂O (molar ratio 2 : 1). The structure of Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O ( 1 ) was solved by single‐crystal X‐ray methods (P 1, a = 912.51(6), b = 932.14(6), c = 966.10(6) pm, α = 94.840(5), β = 108.652(6), γ = 118.588(6)°, Z = 1). The P₃N₃ rings of the trimetaphosphimate ions exhibit a slightly distorted sofa conformation. The conformation of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The trimetaphosphimate ions act as bidentate ligands of Cu²⁺. With additionally coordinated water molecules, anionic complexes {Cu[(PO₂NH)₃]₂ · 2 H₂O}^4– are formed. In the crystal these complexes are interconnected by N–H…O und O–H…O hydrogen bonds and they coordinate the Na⁺. Thus, a three‐dimensional network is formed.     

Layered metal(IV) phosphonate materials: Solid‐state 1H, 13C, 31P NMR spectra and NMR relaxation

Multinuclear solid‐state NMR and powder X‐ray diffraction data collected for phosphonate materials Zr(O₃PC₆H₄PO₃) · 3.6H₂O and Sn(O₃PC₆H₄PO₃)_0.85(O₃POH)_0.30 · 3.09H₂O have resulted in the layered structure, where the phosphonic acids cross‐link the layers. The main structural motif (the 111 connectivity in the PO₃ group) has been established by determination of chemical shift anisotropy parameters for phosphorus nuclei in the phosphonate groups. An analysis of the variable‐temperature ³¹P T₁ measurements and the shapes of the phosphorus resonances in the ³¹P static NMR spectra have resulted in the dipolar mechanism of the phosphorus spin‐lattice relaxation, where the rotating phenylene rings reorient dipolar vectors P^…H as a driving force of the relaxation process. It has been found that water protons do not affect the ³¹P T₁ times. The activation energy of the phenylene rotation in both compounds has been determined as low as 12.5 kJ/mol. The interpretation of the phosphorus relaxation data has been independently confirmed by the measurements of ¹H T₁ times for protons of the phenylene rings.     

Multinuclear (11B, 31P) MAS NMR spectroscopy of borophosphates

¹¹B and ³¹P MAS NMR spectroscopy of three borophosphates was used to monitor their phase composition via the isotropic chemical shifts. CaBPO₅ and BPO₄ represent nearly pure samples, SrBPO₅ contains β-Sr₂P₂O₇ as well as BPO₄ as impurities. The anisotropic chemical shift data provide additional information on the geometry and connectivity of the BO₄ and PO₄ building units. Received: 25 July 1996 / Revised: 19 August 1996 / Accepted: 23 August 1996     

Multinuclear (11B, 31P) MAS NMR spectroscopy of borophosphates

¹¹B and ³¹P MAS NMR spectroscopy of three borophosphates was used to monitor their phase composition via the isotropic chemical shifts. CaBPO₅ and BPO₄ represent nearly pure samples, SrBPO₅ contains β-Sr₂P₂O₇ as well as BPO₄ as impurities. The anisotropic chemical shift data provide additional information on the geometry and connectivity of the BO₄ and PO₄ building units. Received: 25 July 1996 / Revised: 19 August 1996 / Accepted: 23 August 1996     

17O solid-state NMR and first-principles calculations of sodium trimetaphosphate (Na3P3O9), tripolyphosphate (Na5P3O10), and pyrophosphate (Na4P2O7)

The assignment of high-field (18.8 T) (17)O MAS and 3QMAS spectra has been completed by use of first-principles calculations for three crystalline sodium phosphates, Na 3P 3O 9, Na 5P 3O 10, and Na 4P 2O 7. In Na 3P 3O 9, the calculated parameters, quadrupolar constant ( C Q), quadrupolar asymmetry (eta Q), and the isotropic chemical shift (delta cs) correspond to those deduced experimentally, and the calculation is mandatory to achieve a complete assignment. For the sodium tripolyphosphate Na 5P 3O 10, the situation is more complex because of the free rotation of the end-chain phosphate groups. The assignment obtained with ab initio calculations can however be confirmed by the (17)O{ (31)P} MAS-J-HMQC spectrum. Na 4P 2O 7 (17)O MAS and 3QMAS spectra show a complex pattern in agreement with the computed NMR parameters, which indicate that all of the oxygens exhibit very similar values. These results are related to structural data to better understand the influence of the oxygen environment on the NMR parameters. The findings are used to interpret those results observed on a binary sodium phosphate glass.     

The system Y2O3−CaO−P2O5

The ternary system Y₂O₃?CaO?P₂O₅ has been examined by DTA, X-ray diffraction, IR and microscopic methods. Its phase diagram has been provided within the composition range YPO₄?Ca₃(PO₄)₂?P₂O₅. The occurrence of four mixed phosphates: Ca₃Y(PO₄)₃, CaYP₃O₁₀, CaY(PO₃)₅, Ca₂Y(PO₃)₇ has been discovered in the system. Basic X-ray data have been determined for these newly discovered compounds and several methods of their synthesis developed.     

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ5,5λ5-[1,4,2,5]-dioxadiphosphinan-2,5-diyl)-bis-phosphonsäure

P,P′-(2,5-Dihydroxy-3,6-dimethyl-2,5-dioxo-2λ⁵,5λ⁵-[1,4,2,5]dioxadiphosphinane-2,5-diyl)-bis-phosphonic Acid The tetrahydrate 1 of the title compound crystallizes in the monoclinic space group P2₁/c with a = 845.8, b = 1 098, c = 981.7 pm, β = 113.02° and Z = 2. The anions of the oxonium compound (H₃O⁺ · H₂O)₂(C₄H₁₀O₁₂P₄^2?) are layered by hydrogen bridges. The ¹H, ¹³C and ³¹P NMR spectra (4 and 5 spin systems) are discussed.     

Neue Cyclosilicate der Alkalimetalle: Cs5AgSi3O9 und Cs6Na6Si6O18

New Alkali Cyclosilicates: Cs₅AgSi₃O₉ and Cs₆Na₆Si₆O₁₈ The new cyclosilicates were obtained from reactions of the binary oxides at 450–500 °C under inert gas atmosphere. Cs₅AgSi₃O₉ crystallizes in the space group P2₁/m with the lattice constants a = 968,2(2) pm, b = 652,7(1) pm, c = 1162,6(3) pm, β = 93,84(2)° and Cs₆Na₆Si₆O₁₈ in R‐3m with a = 1208,0(1) pm, c = 1458,9(2) pm (IPDS data sets). The characteristic features are isolated rings, [Si₃O₉]^6– and [Si₆O₁₈]^12–, respectively. In Cs₅AgSi₃O₉ these are connected via Ag⁺ to chains. Layers of [NaO₄]‐tetrahedra separate the hexameric rings in Cs₆Na₆Si₆O₁₈. Coordination numbers of caesium are observed between C.N. 3 and C.N. 9 in these alkali rich cyclosilicates. MAPLE calculations of both cyclosilicates as well as the absorption and IR spectrum of Cs₅AgSi₃O₉ are presented. Preparative and thermoanalytical techniques have been used to investigate the reactivity of Cs₅AgSi₃O₉ in the presence of cobalt and nickel metal.