Five new ternary indium-arsenides discovered. Synthesis and structural characterization of the Zintl phases Sr3In2As4, Ba3In2As4, Eu3In2As4, Sr5In2As6 and Eu5In2As6

Childs, Amanda B.; Baranets, Sviatoslav; Bobev, Svilen

doi:10.1016/j.jssc.2019.07.050

Five new ternary indium-arsenides discovered. Synthesis and structural characterization of the Zintl phases Sr₃In₂As₄, Ba₃In₂As₄, Eu₃In₂As₄, Sr₅In₂As₆ and Eu₅In₂As₆

Journal Article · Tue Oct 01 00:00:00 EDT 2019 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2019.07.050· OSTI ID:1595067

Childs, Amanda B. ^[1]; Baranets, Sviatoslav ^[2]; Bobev, Svilen ^[2]

Univ. of Delaware, Newark, DE (United States); University of Delaware
Univ. of Delaware, Newark, DE (United States)

Five new ternary indium aresenides, AE₃In₂As₄ (AE=Sr, Ba, Eu), and AE₅In₂As₆ (AE=Sr, Eu), have been synthesized using molten metal In, Pb, and Sn fluxes. Structure elucidation was aided by powder X-ray and single crystal X-ray diffraction. This demonstrated Sr₃In₂As₄ and Eu₃In₂As₄ are orthorhombic and isostructural to Sr₃In₂P₄ (space group Pnnm, Z=2), while Ba₃In₂As₄ is monoclinic and isostructural to Ca₃Al₂As₄ (space group C2/c, Z=4). In addition, Sr₅In₂As₆ and Eu₅In₂As₆ crystallize orthorhombically and adopt the Ca₅Ga₂As₆ structure type (space group Pbam, Z=2). The valence electron count for all structures conform to the Zintl-Klemm concept, and as such can be rationalized as divalent Sr, Ba, Eu cations and polyanionic In–As fragments of different dimensionality. In Sr₃In₂As₄ and Eu₃In₂As₄, one-dimensional chains [In₂As₄]^6– running along the crystallographic c-axis exist, and they are made up of edge- and corner-shared tetrahedra InAs₄. The [In₂As₄]^6– two-dimensional sheets in the structure of Ba₃In₂As₄ are composed of a pair of edge-shared InAs₄ tetrahedra, that are further connected by corner-sharing. In Sr₅In₂As₆ and Eu₅In₂As₆, the InAs₄ tetrahedra are only corner-shared to make infinite [InAs₂As_2/2]^6– chains running along the a-axis, which are dimerized via As–As bonds into [In₂As₆]^10- ribbons. Furthermore, electronic structure calculations affirm these assignments and suggest intrinsic, narrow-gap seminconducting behavior.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0008885

OSTI ID:: 1595067

Alternate ID(s):: OSTI ID: 1556189

Journal Information:: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: C Vol. 278; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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On the divalent character of the Eu atoms in the ternary Zintl phases Eu ₅ In ₂ Pn ₆ and Eu ₃ MAs ₃ (Pn = As–Bi; M = Al, Ga) Radzieowski, Mathis; Stegemann, Frank; Klenner, Steffen Materials Chemistry Frontiers, Vol. 4, Issue 4 https://doi.org/10.1039/c9qm00703b	journal	January 2020
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Zintl phases
arsenides
crystal structure
electronic structure
single-crystal X-ray diffraction

CSD 1936704: Experimental Crystal Structure Determination B., Childs, Amanda; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc2309bs The current record is supplemented by this dataset	dataset	January 2019
CSD 1936705: Experimental Crystal Structure Determination B., Childs, Amanda; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc2309ct The current record is supplemented by this dataset	dataset	January 2019
CSD 1936706: Experimental Crystal Structure Determination B., Childs, Amanda; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc2309dv The current record is supplemented by this dataset	dataset	January 2019
CSD 1936707: Experimental Crystal Structure Determination B., Childs, Amanda; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc2309fw The current record is supplemented by this dataset	dataset	January 2019
CSD 1936708: Experimental Crystal Structure Determination B., Childs, Amanda; Sviatoslav, Baranets,; Svilen, Bobev, https://doi.org/10.25505/fiz.icsd.cc2309gx The current record is supplemented by this dataset	dataset	January 2019