ChemInform Abstract: Structure of Inorganic Phosphorus‐Nitrogen Tetrahedral Compounds

The oxonitridophosphate SrP(3)N(5)O has been synthesized by heating a multicomponent reactant mixture that consisted of phosphoryl triamide OP(NH(2))(3), thiophosphoryl triamide SP(NH(2))(3), SrS, and NH(4)Cl enclosed in evacuated and sealed silica-glass ampoules up to 750 °C. The compound was obtained as nanocrystalline powder with needle-shaped crystallites. The crystal structure was solved ab initio on the basis of electron diffraction data by means of automated electron diffraction tomography (ADT) and verified by Rietveld refinement with X-ray powder diffraction data. SrP(3)N(5)O crystallizes in the orthorhombic space group Pnma (no. 62) with unit-cell data of a=18.331(2), b=8.086(1), c=13.851(1) Å and Z=16. The compound is a highly condensed layer phosphate with a degree of condensation κ=½. The corrugated layers (∞)(2){(P(3)N(5)O)(2-)} consist of linked, triangular columns built up from P(O,N)(4) tetrahedra with 3-rings and triply binding nitrogen atoms. The Sr(2+) ions are located between the layers and exhibit six-, eight-, and ninefold coordination. FTIR and solid-state NMR spectra of SrP(3)N(5)O are discussed as well.

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“…[38] HP 4 N 7 , [39] P 4 N 6 O, [40] Na 3 P 6 N 11 , [41] and K 3 P 6 N 11 . [42] According to the formula…”

Section: Resultsmentioning

confidence: 99%

SrP₃N₅O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

Sedlmaier

Mugnaioli

Kolb

et al. 2011

Chemistry A European J

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“…In nitridophosphates higher condensed frameworks intrigue with structural motifs like triply bridging N and edge-sharing tetrahedra. Currently, the alkali metal nitridophosphates MP 4 N 7 and M 3 P 6 N 11 (M = Na–Cs) are the only reported cases of such frameworks comprising metal ions. − Hence, closing the gap between κ = 1/2 and 3/5 in rare-earth nitridophosphates is likely to uncover unprecedented tetrahedra networks. Such compounds feature rigid frameworks of all-side vertex-sharing tetrahedra, making them, for example, promising candidates as host lattices for inorganic solid-state lighting …”

Section: Introductionmentioning

confidence: 99%

Puzzling Intergrowth in Cerium Nitridophosphate Unraveled by Joint Venture of Aberration-Corrected Scanning Transmission Electron Microscopy and Synchrotron Diffraction

et al. 2017

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Thorough investigation of nitridophosphates has rapidly accelerated through development of new synthesis strategies. Here we used the recently developed high-pressure metathesis to prepare the first rare-earth metal nitridophosphate, CeLiPN, with a high degree of condensation >1/2. CeLiPN consists of an unprecedented hexagonal framework of PN tetrahedra and exhibits blue luminescence peaking at 455 nm. Transmission electron microscopy (TEM) revealed two intergrown domains with slight structural and compositional variations. One domain type shows extremely weak superstructure phenomena revealed by atomic-resolution scanning TEM (STEM) and single-crystal diffraction using synchrotron radiation. The corresponding superstructure involves a modulated displacement of Ce atoms in channels of tetrahedra 6-rings. The displacement model was refined in a supercell as well as in an equivalent commensurate (3 + 2)-dimensional description in superspace group P6(α, β, 0)0(-α - β, α, 0)0. In the second domain type, STEM revealed disordered vacancies of the same Ce atoms that were modulated in the first domain type, leading to sum formula CeLiPNO (x ≈ 0.72) of the average structure. The examination of these structural intricacies may indicate the detection limit of synchrotron diffraction and TEM. We discuss the occurrence of either Ce displacements or Ce vacancies that induce the incorporation of O as necessary stabilization of the crystal structure.

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“…Synthesis : Diverse synthetic approaches have been reported in the literature for the synthesis of PON 3. 32–34 Some of these methods are rather specific and thus difficult to perform, some yield quite humid samples, and many of them are rather susceptible to contamination. The most defined procedure for obtaining PON, however, is the thermal decomposition of water‐sensitive phosphoryl triamide (PO(NH 2 ) 3 ) 35.…”

Section: Resultsmentioning

confidence: 99%

High‐Pressure Synthesis and Structural Investigation of H₃P₈O₈N₉: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure

Sedlmaier

Celinski

Günne

et al. 2012

Chemistry A European J

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The first crystalline phosphorus oxonitride imide H(3)P(8)O(8)N(9) (=P(8)O(8)N(6)(NH)(3)) has been synthesized under high-pressure and high-temperature conditions. To this end, a new, highly reactive phosphorus oxonitride imide precursor compound was prepared and treated at 12 GPa and 750 °C by using a multianvil assembly. H(3)P(8)O(8)N(9) was obtained as a colorless, microcrystalline solid. The crystal structure of H(3)P(8)O(8)N(9) was solved ab initio by powder X-ray diffraction analysis, applying the charge-flipping algorithm, and refined by the Rietveld method (C2/c (no. 15), a=1352.11(7), b=479.83(3), c=1820.42(9) pm, β=96.955(4)°, Z=4). H(3)P(8)O(8)N(9) exhibits a highly condensed (κ=0.47), 3D, but interrupted network that is composed of all-side vertex-sharing (Q(4)) and only threefold-linking (Q(3)) P(O,N)(4) tetrahedra in a Q(4)/Q(3) ratio of 3:1. The structure, which includes 4-ring assemblies as the smallest ring size, can be subdivided into alternating open-branched zweier double layers {oB,2(2)(∞)}[(2)P(3)(O,N)(7)] and layers containing pairwise-linked Q(3) tetrahedra parallel (001). Information on the hydrogen atoms in H(3)P(8)O(8)N(9) was obtained by 1D (1)H MAS, 2D homo- and heteronuclear (together with (31)P) correlation NMR spectroscopy, and a (1)H spin-diffusion experiment with a hard-pulse sequence designed for selective excitation of a single peak. Two hydrogen sites with a multiplicity ratio of 2:1 were identified and thus the formula of H(3)P(8)O(8)N(9) was unambiguously determined. The protons were assigned to Wyckoff positions 8f and 4e, the latter located within the Q(3) tetrahedra layers.

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ChemInform Abstract: Structure of Inorganic Phosphorus‐Nitrogen Tetrahedral Compounds

Abstract: Structure of Inorganic Phosphorus-Nitrogen Tetrahedral Compounds-(39 refs.). -(VITOLA, A.; RONIS, J.; AVOTINS, V.; MILLERS, T.; Latv.

Cited by 6 publications

References 0 publications

SrP₃N₅O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

SrP₃N₅O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

Puzzling Intergrowth in Cerium Nitridophosphate Unraveled by Joint Venture of Aberration-Corrected Scanning Transmission Electron Microscopy and Synchrotron Diffraction

High‐Pressure Synthesis and Structural Investigation of H₃P₈O₈N₉: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure

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ChemInform Abstract: Structure of Inorganic Phosphorus‐Nitrogen Tetrahedral Compounds

Abstract: Structure of Inorganic Phosphorus-Nitrogen Tetrahedral Compounds-(39 refs.). -(VITOLA, A.; RONIS, J.; AVOTINS, V.; MILLERS, T.; Latv.

Cited by 6 publications

References 0 publications

SrP3N5O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

SrP3N5O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

Puzzling Intergrowth in Cerium Nitridophosphate Unraveled by Joint Venture of Aberration-Corrected Scanning Transmission Electron Microscopy and Synchrotron Diffraction

High‐Pressure Synthesis and Structural Investigation of H3P8O8N9: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure

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SrP₃N₅O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

SrP₃N₅O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

High‐Pressure Synthesis and Structural Investigation of H₃P₈O₈N₉: A New Phosphorus(V) Oxonitride Imide with an Interrupted Framework Structure