Undistorted linear Bi chains with hypervalent bonding in La3TiBi5 from single-crystal X-ray diffraction

Ovchinnikov, Alexander; Bobev, Svilen

doi:10.1107/S205322961800565X

Undistorted linear Bi chains with hypervalent bonding in La₃TiBi₅ from single-crystal X-ray diffraction

Journal Article · Fri Apr 20 00:00:00 EDT 2018 · Acta Crystallographica. Section C, Structural Chemistry (Online)

DOI:https://doi.org/10.1107/S205322961800565X· OSTI ID:1595736

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

The crystal structure of the lanthanum titanium bismuthide La₃TiBi₅ (Pearson code hP18, Wyckoff sequence b d g2) has been established from single-crystal X-ray diffraction data and analyzed in detail using first-principles calculations. There are no anomalies pertaining to the atomic displacement parameter of the Ti site, previously reported based on a powder X-ray diffraction analysis of this compound. The anionic substructure contains columns of face-sharing TiBi₆ octahedra and linear Bi chains. Due to a significant La(5d) and Bi(6p) orbital mixing, a perfectly one-dimensional character of the Bi chains is not realised, while a three-dimensional electronic structure is established instead. The latter fact explains the stability of the polyanionic pnictide units against Peierls distortions. The hypervalent bonding in the Bi chains is reflected in a rather long Bi—Bi distance of 3.2264 (4) Å and a typical pattern of bonding and antibonding interactions, as revealed by electronic structure calculations.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

DOE Contract Number:: SC0008885

OSTI ID:: 1595736

Journal Information:: Acta Crystallographica. Section C, Structural Chemistry (Online), Journal Name: Acta Crystallographica. Section C, Structural Chemistry (Online) Journal Issue: 5 Vol. 74; ISSN 2053-2296; ISSN ACSCGG

Publisher:: International Union of Crystallography

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Bi chains
DFT
bismuthide
crystal structure
electronic structure
hypervalent bonding
rare-earth metals

Undistorted linear Bi chains with hypervalent bonding in La3TiBi5 from single-crystal X-ray diffraction

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Undistorted linear Bi chains with hypervalent bonding in La₃TiBi₅ from single-crystal X-ray diffraction