Synthesis and Structure Determination of the Quaternary Zinc Nitride Halides Zn2NX1−yX′y (X, X′ = Cl, Br, I; 0 < y < 1)
The quaternary series Zn2NCl1−yBry and Zn2NBr1−yIy were synthesized from solid-liquid reactions between zinc nitride and the respective zinc halides in closed ampoules, and the evolution of their crystal structures was investigated by single-crystal and powder X-ray diffraction. Zn2NX1−yX′y (X, X′ = Cl, Br, I) adopts the anti-β-NaFeO2 motif in which each nitride ion is tetrahedrally coordinated by four zinc cations, and the halide anions are located in the voids of the skeleton formed by corner-sharing [NZn4] tetrahedra. While Zn2NCl1−yBry crystallizes in the acentric orthorhombic space group Pna21 (No. 33), isotypic to Zn2NX (X = Cl, Br), the structure of Zn2NBr1−yIy is a function of the iodide concentration, namely, Zn2NBr (Pna21) for low iodine content and Zn2NI (Pnma) for higher (y ≥ 0.38).
A new yttrium sesquichloride nitride, .beta.-Y2Cl3N, that is isostructural with the binary yttrium sesquichloride
Reactions of YCl{sub 3}, YN, and Y metal in sealed Nb containers over a range of temperatures and compositions afford {beta}-Y{sub 2}Co{sub 3}N, whereas only {alpha}-Y{sub 2}Cl{sub 3}N in the ({alpha}-)Gd{sub 2}Cl{sub 3}N structure is obtained in the absence of metal. {beta}-Gd{sub 2}Cl{sub 3}N is synthesized similarly. The {beta}-Y{sub 2}Cl{sub 3}N ({beta}-Gd{sub 2}Cl{sub 3}N) gives a powder pattern that is indistinguishable from that of the infinite cluster chain phase Y{sub 2}Cl{sub 3} (Gd{sub 2}Cl{sub 3}) except from small increases in lattice parameters corresponding to a 2% (1%) increase in cell volume. Crystal structures of both the {alpha}- and {beta}- compounds are reported. A single-crystal x-ray study of {beta}-Y{sub 2}Cl{sub 3}N (R = 3.9%, R{sub w} = 4.8%) demonstrates that the nitrogen atoms are positioned in tetrahedral metal sites above and below the shared metal edges of the infinite chain of octahedra found in Y{sub 2}Cl{sub 3}. The need for metal in the syntheses, the black color of the fibrous crystals, and the refined occupancy of nitrogen (81 (2)%) in the yttrium phase all suggest a small nitrogen deficiency in {beta}-(Y,Gd){sub 2}Cl{sub 3}N. The close correspondence of distances in the binary vs the ternary ({beta}) sesquichlorides, particularly the small (0.024 {angstrom})more » increase in the shared Y-Y edge, is discussed. 22 refs., 1 fig., 3 tabs.« less
Über das System Li3N/LiCl
Durch Umsetzung von Li3N mit LiCl bei hoheren Temperaturen wurden in dem System Li3N/LiCl die Phasen Li11N3Cl2 und Li9N2Cl3 festgestellt. 
 
Li9N2Cl3 kristallisiert im Anti-CaF2-Typ, wobei die Nichtmetallagen vollstandig mit Stickstoff- und Chlorionen in statistischer Verteilung, die Metallagen entsprechend der Zusammensetzung der Phase unvollstandig mit Lithiumionen besetzt sind. Die Struktur der Li11N3Cl2-Phase konnte infolge der Kompliziertheit ihres Rontgendiagramms nicht aufgeklart werden.