A Nitridic Clathrate: P₄N₄(NH)₄(NH₃)

Abstract

In molecular and solid-state chemistry, some phosphorus-and nitrogen-containing compounds exhibit specific similarities and analogies to silicon-oxygen compounds. This resemblance is explained by the isolobal relation between PÀN and SiÀO bonds. [1, 2] Simple examples are phosphorus nitride imide, PN(NH), [3,4] and phosphorus oxide nitride, PON, [5] which are both isoelectronic with silica, SiO 2 . Accordingly, both compounds crystallize in b-cristobalite-analogous network structures and are made up of corner-sharing PX 4 tetrahedra (X = O, N). The ternary nitridophosphates NaPN 2 and LiPN 2 [6][7][8][9] have filled isoelectronic [PN 2 ] À network structures and are structurally related to PON and PN(NH), as they adopt the chalcopyrite structure type. More complex silica analogues are represented by the class of nitridosodalites [10][11][12][13] and related oxonitridosodalites. [14] Recently, we synthesized and identified the first oxonitridic zeolite, [15] namely, Li x H 12ÀxÀy+z [P 12 O y N 24Ày ]X z with X = Cl, Br.[16] The [P 12 O y N 24Ày ] framework of this new framework type (NPO [17] ) contains large 12-ring channels and is solely made up of 3-rings (i.e., rings composed of 12 or 3 corner-sharing tetrahedra, respectively) as fundamental building units (FBUs). [16] The specific topology of the framework type NPO has been identified previously as a possible candidate structure for microporous SiO 2 , [18] but this prediction has not been proven by experiment so far.Besides the diverse and manifold substance class of zeolites [19] and zeosils, [20] another group of microporous solids is formed by clathrasils and clathralites [20,21] (generic term: clathrate). Usually these compounds contain uncharged SiO 2 framework structures of corner-sharing SiO 4 tetrahedra with neutral molecules (or nothing) in their cagelike pores. Herein we report on the first nitridic clathrate [P 4 N 4 (NH) 4 ]-(NH 3 ) (1), which is based on a novel PN(NH) framework structure.[P 4 N 4 (NH) 4 ](NH 3 ) (1) was obtained by a high-pressure high-temperature reaction [22][23][24][25] at 600 8C and 11 GPa in a Walker-type multianvil assembly starting from a mixture of ammonium azide NH 4 N 3 [26] we have employed the multianvil technique for the synthesis and investigation of the high-pressure behavior of silicaanalogous phosphorus nitrides [9,22,25] and recently we synthesized the high-pressure polymorph g-P 3 N 5 .[28] We have frequently used high N 2 partial pressures, generated in situ by thermolysis of azides, in our synthetic approaches to metalcontaining nitridophosphates starting from the respective metal azide and P 3 N 5 . Thereby, phosphorus nitride P 3 N 5 (thermal decomposition > 850 8C at normal pressure [22] ) is prevented from dissociation into the elements [Eq. (2)] at thehigh reaction temperatures [22] above 1000 8C that are usually necessary for the crystallization of the desired metal nitridophosphates.In the current work we utilized the thermolysis of ammonium azide NH 4 N 3 under high pressure and high temperature ...

Li+ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li10P4N10 and Li13P4N10X3 with X=Cl, Br

“…[7][8][9][10][11] Synthetic approaches to nitridophosphates are somewhat challenging due to the limited thermal stability of the starting materials (e.g.,P 3 N 5 decomposes above 850 8C). [12] To prevent thermald issociation at higher temperatures, the multi-anvil technique has emerged as apowerful tool, and has led to nitridophosphates with unprecedented topologies and properties. [9,[12][13][14] To date, an umber of lithium nitridophosphates have been obtained at reactiont emperatures below 850 8C.…”

“…[12] To prevent thermald issociation at higher temperatures, the multi-anvil technique has emerged as apowerful tool, and has led to nitridophosphates with unprecedented topologies and properties. [9,[12][13][14] To date, an umber of lithium nitridophosphates have been obtained at reactiont emperatures below 850 8C. [6,[15][16][17][18][19] Reactiono ft he binary nitrides P 3 N 5 and Li 3 Nb etween 620 and 800 8Cl ed to four lithium nitridophosphates with different complex P/N anions in am atrix of Li + ions.…”

Ba3P5N10Br:Eu2+: A Natural‐White‐Light Single Emitter with a Zeolite Structure Type

“…[7,8] Conventional oxidic zeolite structures are typically composed of a three-dimensional network of vertex-sharing [SiO 4 ] and [AlO 4 ] tetrahedra, in which a negative charge is associated with each [AlO 4 ] tetrahedron. [12,13] Its network structure has been predicted for silica but to date has only been found in this particular nitride compound. The formal substitution of O atoms by N atoms in a tetrahedral network implies significant new structural possibilities.…”

An Unprecedented AB2 Tetrahedra Network Structure Type in a High‐Pressure Phase of Phosphorus Oxonitride (PON)

“…[1] However, the importance of dense AB 2 networks should not be underestimated. The few known compounds in this system include the first nitridic zeolites NPO [6] and Ba 19 P 36 O 6+x N 66Àx Cl 8+x (x % 4.54) [7] as well as the nitridic clathrate P 4 N 4 (NH) 4 (NH 3 ) [8] and the polymorphs of PON exhibiting cristobalite-, [9] quartz-, [10] and moganite-type [11] structures. [3,4] Owing to the variety of applications, widespread research into novel AB 2 -type structures was conducted, including the prediction of more than two million unique prospective crystal structures for zeolites.…”