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Author Wang, Yi ♦ Suen, Nian-Tzu ♦ Kunene, Thabiso ♦ Stoyko, Stanislav ♦ Bobev, Svilen
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ALUMINIUM COMPOUNDS ♦ ANTIMONY COMPOUNDS ♦ ARSENIC COMPOUNDS ♦ CALCIUM IONS ♦ CATIONS ♦ EUROPIUM IONS ♦ EXPERIMENTAL DATA ♦ GALLIUM COMPOUNDS ♦ HEXAGONAL LATTICES ♦ INDIUM COMPOUNDS ♦ PHOSPHORUS COMPOUNDS ♦ SODIUM IONS ♦ SPACE GROUPS ♦ STRONTIUM IONS ♦ SYNTHESIS ♦ X-RAY DIFFRACTION
Abstract 15 new quaternary Zintl phases have been synthesized by solid-state reactions from the respective elements, and their structures have been determined by single-crystal X-ray diffraction. Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) crystallize in the hexagonal crystal system with the non-centrosymmetric space group P6{sub 3}mc (No. 186). The structure represents a variant of the K{sub 6}HgS{sub 4} structure type (Pearson index hP22) and features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. The nominal formula rationalization [Na{sup +}]{sub 3}[E{sup 2+}]{sub 3}[TrPn{sub 4}]{sup 9–} follows the octet rule, suggesting closed-shell configurations for all atoms and intrinsic semiconducting behavior. However, structure refinements for several members hint at disorder and mixing of cations that potentially counteract the optimal valence electron count. - Graphical abstract: The hexagonal, non-centrosymmetric structure of Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. - Highlights: • 15 quaternary phosphides, arsenides, and antimonides are synthesized and structurally characterized. • The structure is a variant of the hexagonal K{sub 6}HgS{sub 4}-type, with distinctive pattern for the cations. • Occupational and/or positional disorder of yet unknown origin exists for some members of the series.
ISSN 00224596
Educational Use Research
Learning Resource Type Article
Publisher Date 2017-05-15
Publisher Place United States
Journal Journal of Solid State Chemistry
Volume Number 249


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