Synthesis and single-crystal structure determination of the zinc nitride halides Zn{sub 2}NX (X=Cl, Br, I)

• Published in: Journal of solid state chemistry 2013-07, Vol.203
• Main Authors: Liu, Xiaohui, Wessel, Claudia, Pan, Fangfang, Dronskowski, Richard
• Format: Article
• Language: English
• Subjects: ANIONS; DENSITY FUNCTIONAL METHOD; DIFFERENTIAL THERMAL ANALYSIS; ELECTRONIC STRUCTURE; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; LIQUIDS; MONOCRYSTALS; ORTHORHOMBIC LATTICES; SOLIDS; SPACE GROUPS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS; VACANCIES; X-RAY DIFFRACTION; ZINC; ZINC HALIDES
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/J.JSSC.2013.03.046

A series of zinc nitride halides, Zn{sub 2}NX (X=Cl, Br, I), has been synthesized from solid–liquid reactions of zinc nitride with the respective zinc halides under vacuum, and their crystal structures were determined using single-crystal and powder X-ray diffraction. While Zn{sub 2}NCl and Zn{sub 2}NBr crystallize in the acentric orthorhombic space group Pna2{sub 1}, Zn{sub 2}NI adopts the centrosymmetric space group Pnma; Zn{sub 2}NCl and Zn{sub 2}NBr can be considered to belong to the anti-β-NaFeO{sub 2} type, and Zn{sub 2}NI is closely related. Each N{sup 3−} is tetrahedrally coordinated by zinc atoms, and the X{sup −} anions are located in the vacancies of the framework formed by corner-sharing [NZn{sub 4}] tetrahedra. According to TGA/DTA analyses, the Zn{sub 2}NX compounds exhibit good thermal stability. The electronic structure has been analyzed by employing density-functional theory and the HSE06 hybrid functional. - Graphical abstract: Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been synthesized, and their crystal structures (Cl and Br phases: Pna2{sub 1}; I phase: Pnma) have been determined from XRD; the direct band gap of Zn{sub 2}NCl is theoretically (HSE06 hybrid functional) predicted as 3.7 eV. - Highlights: • Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been synthesized from solid–liquid reactions. • The crystal structures of Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been determined from single-crystal X-ray diffraction. • Zn{sub 2}NCl and Zn{sub 2}NBr crystallize in the acentric space group Pna2{sub 1} whereas Zn{sub 2}NI adopts the centrosymmetric space group Pnma. • Zn{sub 2}NCl and Zn{sub 2}NBr are stable up to 750 °C whereas Zn{sub 2}NI decays at 600 °C already. • The direct band gap of Zn{sub 2}NCl is theoretically predicted as 3.7 eV using the HSE06 hybrid functional.