Antiperovskite Nitridophosphate Oxide Ho₃[PN₄]O by High‐Pressure Metathesis

Abstract

Rare-earth nitridophosphates are a recently discovered class of materials, which are accessible by high-pressure metathesis. Antiperovskite-type Ho 3 [PN 4 ]O was synthesized from HoF 3 , LiPN 2 , Li 3 N, and Li 2 O at 5 GPa and ca. 1025°C by this method and the multianvil technique. Ho 3 [PN 4 ]O contains rarely observed isolated PN 4 tetrahedra and can be derived by the hierarchical substitution of the ABX 3 perovskite, in which Ho occupies the X positions, O occupies the B position, and the PN 4 tetrahedra occupy the A position. The structure was refined on the basis of powder diffraction data [I4/mcm, a = 6.36112(3), c = 10.5571(1) Å, Z = 4, R wp = 0.04, R Bragg = 0.01, 2 = 2.275] starting from the structural model of isotypic Gd 3 [SiN 3 O]O. To characterize Ho 3 [PN 4 ]O, elemental analyses were performed [a]

Open‐Shell 3d Transition Metal Nitridophosphates MIIP8N14 (MII=Fe, Co, Ni) by High‐Pressure Metathesis

“…The formed lithium halide is the thermodynamic driving force of the exothermic reaction and flux medium enhancing the growth of single crystals . By addition of nitrides or oxides like Li 3 N, P 3 N 5 , Li 2 O, PON, or P 2 O 5 to this route, a systematic access to rare‐earth nitridophosphates has been established resulting in compounds with structural motifs ranging from highly condensed frameworks (e.g., Ce 4 Li 3 P 18 N 35 ) down to non‐condensed tetrahedra (e.g., Ho 3 [PN 4 ]O) …”

Nitridophosphate – eine Erfolgsgeschichte der Nitridsynthese

“…(8)] zwei neue Zeolith-Typen synthetisiert werden, die von der International Zeolite Association (IZA) als "Nitridophosphate One" (NPO,L i x H 12ÀxÀy+z [P 12 O y N 24Ày ]X z mit X = Cl, Br;A bbildung 6) und "Nitridophosphate Tw o" (NPT,Ba 19 P 36 O 6+x N 66Àx Cl 8+x , x % 4.54) benannt wurden. (8)] zwei neue Zeolith-Typen synthetisiert werden, die von der International Zeolite Association (IZA) als "Nitridophosphate One" (NPO,L i x H 12ÀxÀy+z [P 12 O y N 24Ày ]X z mit X = Cl, Br;A bbildung 6) und "Nitridophosphate Tw o" (NPT,Ba 19 P 36 O 6+x N 66Àx Cl 8+x , x % 4.54) benannt wurden.…”

“…[27] . [8,79] Diese Reihe von Verbindungen zeigt, dass die Hochdruckmetathese einen großen Bereich von k zugänglich macht. [5] hochkondensierte Ce 4 Li 3 P 18 N 35 mit dreifach-verbrückenden N [3] -Atomen mit zusätzlichem P 3 N 5 hergestellt werden konnte.…”

Ammonothermal Synthesis of Ba2PO3N – An Oxonitridophosphate with Non‐Condensed PO3N Tetrahedra

“…However, there is no ammonothermally synthesized ortho ‐(oxo)nitridophosphate showing non‐condensed [PO 4– x N x ] (3+ x )– tetrahedra, up to now. Such structural features were only observed in Li 7 PN 4 , Li 14 [PON 3 ] 2 O, EA 2 PO 3 N ( EA = Ca, Sr) and Ho 3 [PN 4 ]O, which were synthesized in ampoules or via high‐pressure synthesis, respectively . Especially, the EA 2 PO 3 N compounds are of special interest, as they crystallize isotypically to β‐K 2 SO 4 .…”

“…[21] However, there is no ammonothermally synthesized ortho- 4 ]O, which were synthesized in ampoules or via highpressure synthesis, respectively. [23][24][25][26] Especially, the EA 2 PO 3 N compounds are of special interest, as they crystallize isotypically to -K 2 SO 4 . Accompanied with a plethora of compounds crystallizing in this structure type, a great diversity of materials properties is observed.…”