Pure, stoichiometric, hydrogen-free, and crystalline phosphorus nitride P 3 N 5 has been obtained for the first time by reaction of (PNCl 2 ) 3 and NH 4 Cl between 770 and 1050 K. The compound has been characterized by elemental analyses, 31 P and 15 N MAS NMR, EXAFS, IR spectroscopy, X-ray powder diffraction, and electron microscopy. In the solid a threedimensional cross-linked network structure of corner sharing PN 4 tetrahedra has been identified with 2 / 5 of the nitrogen atoms bonded to three P atoms and 3 / 5 of the nitrogen atoms bonded to two P atoms. By electron diffraction (ED) and high-resolution transmission electron microscopy (HRTEM) two distinguishable modifications R-P 3 N 5 and β-P 3 N 5 have been identified which differentiate only by the stacking order of identical sheets similar to the polytypes of SiC.
Reines Lithium‐phosphor(V)‐nitrid (LiPN2) wurde durch Festkörperreaktion der binären Nitride Li3N und P3N5 erhalten. Die Kristallstruktur von LiPN2 wurde auf der Basis von Röntgen‐Pulverdiffraktometerdaten mit Hilfe der Rietveld‐Methode verfeinert (I42d; a = 457,5(2) pm; c = 711,8(3) pm; 31 beob. Reflexe 20° < 2Θ < 105°; Germanium‐Monochromator, CuKα1; R(wp) = 0,059; R(I, hkl) = 0,061). Die Kristallstruktur von LiPN2 leitet sich vom Chalcopyrit‐Typ ab. Phosphor und Stickstoff bilden ein dreidimensionales Netz eckenverknüpfter PN4‐Tetraeder (PN 164,5(7) pm; PNP 123,6(8)°). Die Lithium‐Kationen besetzen die verbleibenden Lücken. Sie sind verzerrt tetraedrisch von jeweils vier Stickstoff‐Atomen koordiniert (LiN 209,3(10) pm).
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°; CuKα1, Germanium‐Monochromator; R(wp) = 0,072; R(I,hkl) = 0,048). Im Festkörper ist HPN2 aus einem dreidimensionalen Netz allseitig eckenverknüpfter PN4‐Tetraeder (PN: 159,9(4) pm; PNP: 130,1(4)°) aufgebaut. Die H‐Atome sind kovalent an die Hälfte der N‐Atome gebunden. Im IR‐Spektrum werden sechs Schwingungsbanden (v(NH): 3224; vas(PNP): 1330, 1223; vas(PNHP): 971, 901; δ(PNP): 531 cm−1) beobachtet.
The novel compound SiPN3 has been prepared by reacting hexachloro-N-silylphosphinimine Cl3Si-N=PC13 with liquid ammonia a t -78 "C followed by subsequent removal of the ammonium chloride byproduct and annealing of the resulting polymeric imide at 800 "C for 12 h. The compound has been characterized by elemental analysis and 29Si and 31P MAS-NMR, as well as X-ray powder diffraction methods. The powder data suggest a defect Wurtzite type structure which is closely related to the structures of SizNzO and SiZNzNH. (Rietveld analysis data: space group CmcB1, 2 = 4, a = 902.4(4) pm, b = 527.5(2) pm, c = 469.8(2) pm; 44 reflections observed; scan range 10" < 279 < 81"; germanium monochromator, Cu Kal, R(wp) = 0.047, R(l,h,k,l) = 0.071.) At 920 "C SiPN3 decomposes into Si3N4, P4, and Nz. The Si3N4 obtained on pyrolysis of SiPN3 consists of a pure a-phase and has an extremely low oxygen content.
A three‐dimensional network of corner‐sharing PN4 tetrahedrons is found in the sodalite‐like [P12N24] framework of the title compound, synthesized simply from NH4C1, (PNC12)3, and ZnCl2. A Cl− ion surrounded tetrahedrally by Zn2+ ions occupies the center of the β cages, as is shown on the right. The modification of the sodalite framework by exchanging O atoms for N atoms opens new horizons in zeolite research. • P; o N.
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