Abstract

Abstract The binary Zintl phase Ba ₁₆ Sb ₁₁ has been synthesized and structurally characterized. Detailed studies via single‐crystal X‐ray diffraction methods indicate that although Ba ₁₆ Sb ₁₁ appears to crystallize in the tetragonal Ca ₁₆ Sb ₁₁ structure type (space group P 2 ₁ m with a =13.5647(9) Å, c =12.4124(12) Å, Z =2, R ₁ =3.14 %; wR ₂ =4.77 %), there exists an extensive structural disorder. Some Ba ₁₆ Sb ₁₁ crystals were found to be monoclinic and the structure was solved and refined in space group P 2 ₁ ( a =18.3929(12) Å, b =13.5233(8) Å, c =18.3978(12) Å, β =94.6600(10)°; Z =4, R ₁ =5.84 %; wR ₂ =9.58 %). The latter corresponds to a 2‐fold superstructure of the tetragonal one, which provides a disorder‐free structural model. In both descriptions, the disordered tetragonal and the ordered monoclinic superstructure, the basic building units that make up the structure of this Ba‐rich compound are pairs of face‐shared square antiprisms of Ba atoms, which are centered by Sb atoms. The dimerized antiprisms are linked into parallel chains via square prisms of Ba atoms, which are also centered by Sb atoms. The Zintl concept can be applied in a straightforward manner andmore » as result, the structure of Ba ₃₂ Sb ₂₂ (=2×Ba ₁₆ Sb ₁₁ ) can be rationalized as (Ba ²⁺ ) ₃₂ (Sb ³⁻ ) ₂₀ [Sb ₂ ] ⁴⁻ . The partitioning of the valence electrons is done taking into an account the homoatomic Sb−Sb contacts ( d =3.01 Å), which can be clearly distinguished in the lower symmetry space group. Electronic structure calculations of Ba ₁₆ Sb ₁₁ are in good accordance with the Zintl rationalization and predict a semiconductor with a band gap of 0.77 eV.« less

Authors:

Baranets, Sviatoslav  ^[1];

• Search DOE PAGES for author "Baranets, Sviatoslav"
• Search DOE PAGES for ORCID "0000-0003-3449-3344"

Ovchinnikov, Alexander  ^[2];

• Search DOE PAGES for author "Ovchinnikov, Alexander"
• Search DOE PAGES for ORCID "0000-0002-0537-4234"

Samarakoon, S. M. Gayomi K. ^[3]; Bobev, Svilen  ^[4]

• Search DOE PAGES for author "Bobev, Svilen"
• Search DOE PAGES for ORCID "0000-0002-0780-4787"

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+ Show Author Affiliations

1. Department of Chemistry Louisiana State University Baton Rouge Louisiana 70803 United States, Department of Chemistry and Biochemistry University of Delaware Newark Delaware 19716 United States
2. Department of Chemistry and Food Chemistry Technische Universität Dresden 01062 Dresden Germany, Department of Chemistry and Biochemistry University of Delaware Newark Delaware 19716 United States
3. Department of Chemistry Louisiana State University Baton Rouge Louisiana 70803 United States
4. Department of Chemistry and Biochemistry University of Delaware Newark Delaware 19716 United States

Publication Date:

Mon Aug 07 00:00:00 EDT 2023

Sponsoring Org.:

USDOE

OSTI Identifier:

1993995

Resource Type:

Publisher's Accepted Manuscript

Journal Name:

Zeitschrift fuer Anorganische und Allgemeine Chemie

Additional Journal Information:

Journal Name: Zeitschrift fuer Anorganische und Allgemeine Chemie Journal Volume: 649 Journal Issue: 18; Journal ID: ISSN 0044-2313

Publisher:

Wiley Blackwell (John Wiley & Sons)

Country of Publication:

Germany

Language:

English