Darstellung, Kristallstruktur und IR‐spektroskopische Untersuchung von Phosphor(V)‐nitrid‐imid, HPN₂

Abstract

Reines und feinkristallines Phosphor(V)‐nitrid‐imid (HPN2) wurde durch heterogene Ammonolyse von P3N5 mit gasförmigem NH3 (T = 580°C, p = 30 bar, 6d) dargestellt. Die Kristallstruktur von HPN2 wurde auf der Basis von Röntgen‐Pulverdiffraktometerdaten mit Hilfe der Rietveld‐Methode verfeinert (I42d, a = 461,82(2) pm, c = 702,04(3) pm; Z = 4; 41 beobachtete Reflexe, 17° < 2Θ < 125°; CuKα1, Germanium‐Monochromator; R(wp) = 0,072; R(I,hkl) = 0,048). Im Festkörper ist HPN2 aus einem dreidimensionalen Netz allseitig eckenverknüpfter PN4‐Tetraeder (PN: 159,9(4) pm; PNP: 130,1(4)°) aufgebaut. Die H‐Atome sind kovalent an die Hälfte der N‐Atome gebunden. Im IR‐Spektrum werden sechs Schwingungsbanden (v(NH): 3224; vas(PNP): 1330, 1223; vas(PNHP): 971, 901; δ(PNP): 531 cm−1) beobachtet.

The Stuffed Framework Structure of SrP2N4: Challenges to Synthesis and Crystal Structure Determination

“…Usually these values range between 1.55-1.70 (e.g. HPN 2 : 1.599(4) , [5] LiPN 2 : 1.645(7) , [7] BaP 2 N 4 : 1.630(6)-1.661(7) [2] ). However, a distance-least-squares (DLS) refinement [51] led to a smaller distribution of the PÀN bond length and the resulting structural model exhibits a significantly worse agreement with the measured diffraction data.…”

“…5 We define the "diameter" of a void in this structure as the largest circle that can be inscribed in an equilateral triangle built up of three N atoms.…”

“…A series of nitridophosphate network structures [PN 2 ] À are known [2][3][4] that are formally isoelectronic with SiO 2 . However, structural similarities with known oxosilicates have scarcely been identified: Phosphorus nitride imide PN(NH) [5,6] at ambient pressure adopts a structure homeotypic with the cristobalite structure type and both LiPN 2 [7,8] and NaPN 2 [9,10] crystallize analogously adopting the chalcopyrite structure type. Furthermore, a series of nitridosodalites [11][12][13][14][15] and oxonitridosodalites [16] have been found.…”

Li14(PON3)2O – A Non‐Condensed Oxonitridophosphate Oxide

“…However, owing to intrinsic difficulties in crystal growth, comprehensive structural descriptions were not possible until the advent of modern powder diffraction techniques. [4][5][6] Due to the fact that both PON and PN(NH) are isoelectronic to SiO 2 , [7] (oxo)nitridophosphates and silicates often display similar structural features. Many of the well-studied structures of SiO 2 have also been found in PON, such as the cristobalite, [8] quartz, [9] and coesite structure types.…”

Hochdruck-Synthese, Kristallstruktur und Eigenschaften von NaPN2

“…Vor einiger Zeit wurde bereits u È ber das Phosphornitrid-imid HPN 2 sowie die deuterierte Verbindung DPN 2 berichtet [7,8]. Beide kristallisieren in einem verzerrten, aufgefu È llten b-Cristobalit-Typ.…”