Abstract
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).
Highlights
IntroductionThere is a growing interest in mixed-anions solids such as metal nitride halides
The N3− ion is coordinated by four zinc atoms (2 × Zn1 and 2 × Zn2), with an average (X = Cl, Br) in Pna21, the anti-β-NaFeO2 type
Zn2 NBr0.62 I0.38 adopts the orthorhombic space group Pnma in which the N3− ion is coordinated by four zinc atoms, whereas the halide anions occupy the tetrahedral voids in the framework
Summary
There is a growing interest in mixed-anions solids such as metal nitride halides. It has been suggested that the ternary alkaline-earth metal nitride halides M2 NX (X = F, Cl, Br and I), and the quaternary variants M2 NX1−y X0 y (X, X0 = Cl, Br and I) are more complicated in terms of crystal structure. The variation of the mixed halides may change both structure and other properties [7]. After the successful synthesis of Zn2 NX (X = Cl, Br and I) [30], we became interested in such quaternary nitride halides because of a potential change in crystallographic symmetry. This paper presents the synthesis and structure determination of the mixed zinc nitride halides Zn2 NX1−y X0 y (X, X0 = Cl, Br, I).
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