skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Undistorted linear Bi chains with hypervalent bonding in La 3 TiBi 5 from single-crystal X-ray diffraction

Abstract

The crystal structure of the lanthanum titanium bismuthide La 3TiBi 5(Pearson codehP18, Wyckoff sequenceb 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 TiBi 6octahedra 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.

Authors:
ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1541445
DOE Contract Number:  
SC0008885
Resource Type:
Journal Article
Journal Name:
Acta Crystallographica. Section C, Structural Chemistry (Online)
Additional Journal Information:
Journal Volume: 74; Journal Issue: 5; Journal ID: ISSN 2053-2296
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Crystallography

Citation Formats

Ovchinnikov, Alexander, and Bobev, Svilen. Undistorted linear Bi chains with hypervalent bonding in La 3 TiBi 5 from single-crystal X-ray diffraction. United States: N. p., 2018. Web. doi:10.1107/s205322961800565x.
Ovchinnikov, Alexander, & Bobev, Svilen. Undistorted linear Bi chains with hypervalent bonding in La 3 TiBi 5 from single-crystal X-ray diffraction. United States. doi:10.1107/s205322961800565x.
Ovchinnikov, Alexander, and Bobev, Svilen. Fri . "Undistorted linear Bi chains with hypervalent bonding in La 3 TiBi 5 from single-crystal X-ray diffraction". United States. doi:10.1107/s205322961800565x.
@article{osti_1541445,
title = {Undistorted linear Bi chains with hypervalent bonding in La 3 TiBi 5 from single-crystal X-ray diffraction},
author = {Ovchinnikov, Alexander and Bobev, Svilen},
abstractNote = {The crystal structure of the lanthanum titanium bismuthide La3TiBi5(Pearson codehP18, Wyckoff sequenceb 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 TiBi6octahedra 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.},
doi = {10.1107/s205322961800565x},
journal = {Acta Crystallographica. Section C, Structural Chemistry (Online)},
issn = {2053-2296},
number = 5,
volume = 74,
place = {United States},
year = {2018},
month = {4}
}

Works referenced in this record:

A local exchange-correlation potential for the spin polarized case. i
journal, July 1972


New Ternary Rare-Earth Transition-Metal Antimonides RE3MSb5 (RE = La, Ce, Pr, Nd, Sm; M = Ti, Zr, Hf, Nb)
journal, December 1995

  • Bollore, Gwenael; Ferguson, Michael J.; Hushagen, Ryan W.
  • Chemistry of Materials, Vol. 7, Issue 12
  • DOI: 10.1021/cm00060a005

Yb 14 MnSb 11 :  New High Efficiency Thermoelectric Material for Power Generation
journal, April 2006

  • Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck
  • Chemistry of Materials, Vol. 18, Issue 7
  • DOI: 10.1021/cm060261t

Optimization of the thermopower of the antimonide Mo3Sb7 by a partial Sb/Te substitution
journal, January 2002

  • Dashjav, Enkhtsetseg; Szczepenowska, Aleksandra; Kleinke, Holger
  • Journal of Materials Chemistry, Vol. 12, Issue 2
  • DOI: 10.1039/b107468g

Crystal structures of La3ZrSb5, La3HfSb5, and LaCrSb3· Structural relationships in ternary rare-earth antimonides
journal, March 1997


STRUCTURE TIDY – a computer program to standardize crystal structure data
journal, April 1987


Calcium gallium arsenide, Ca14GaAs11: A new compound containing discrete GaAs4 tetrahedra and a hypervalent As3 polyatomic unit
journal, September 1991

  • Kauzlarich, Susan M.; Thomas, Michele M.; Odink, Debra A.
  • Journal of the American Chemical Society, Vol. 113, Issue 19
  • DOI: 10.1021/ja00019a017

Structure and properties of the transition-metal zintl compounds: A14MnBi11 (A = Ca, Sr, Ba)
journal, March 1992

  • Kuromoto, Traci Y.; Kauzlarich, Susan M.; Webb, David J.
  • Chemistry of Materials, Vol. 4, Issue 2
  • DOI: 10.1021/cm00020a036

Anisotropic Transport and Magnetic Properties of Ternary Uranium Antimonides U 3 ScSb 5 and U 3 TiSb 5
journal, September 2006

  • Mar, Arthur; Tougait, Olivier; Potel, Michel
  • Chemistry of Materials, Vol. 18, Issue 18
  • DOI: 10.1021/cm061281y

Physical Properties and Bonding in RE 3 TiSb 5 ( RE = La, Ce, Pr, Nd, Sm)
journal, November 2002

  • Moore, S. H. Devon; Deakin, Laura; Ferguson, Michael J.
  • Chemistry of Materials, Vol. 14, Issue 11
  • DOI: 10.1021/cm020731t

Hypervalent Bismuthides La 3 MBi 5 (M = Ti, Zr, Hf) and Related Antimonides: Absence of Superconductivity
journal, April 2017


On the effect of Ga and In substitutions in the Ca 11 Bi 10 and Yb 11 Bi 10 bismuthides crystallizing in the tetragonal Ho 11 Ge 10 structure type
journal, February 2018

  • Ovchinnikov, Alexander; Bobev, Svilen
  • Acta Crystallographica Section C Structural Chemistry, Vol. 74, Issue 3
  • DOI: 10.1107/S2053229618001596

The Ternary Alkaline-Earth Metal Manganese Bismuthides Sr 2 MnBi 2 and Ba 2 Mn 1– x Bi 2 ( x ≈ 0.15)
journal, October 2017


Synthesis and crystal structures of La3MgBi5 and LaLiBi2
journal, April 2006

  • Pan, Da-Chun; Sun, Zhong-Ming; Mao, Jiang-Gao
  • Journal of Solid State Chemistry, Vol. 179, Issue 4
  • DOI: 10.1016/j.jssc.2005.12.030

Building up Complexity from Strips and Sheets: The Electronic Structure of the La12Mn2Sb30Alloy
journal, August 1998

  • Papoian, Garegin; Hoffmann, Roald
  • Journal of Solid State Chemistry, Vol. 139, Issue 1
  • DOI: 10.1006/jssc.1998.7773

Electron-Rich Rods as Building Blocks for Sb Strips and Te Sheets
journal, July 2001

  • Papoian, Garegin; Hoffmann, Roald
  • Journal of the American Chemical Society, Vol. 123, Issue 27
  • DOI: 10.1021/ja003420x

Preparation and Crystal Structure of the Titanium and Hafnium Bismuthides Ti8Bi9and Hf8Bi9
journal, November 1997

  • Richter, Carolin G.; Jeitschko, Wolfgang
  • Journal of Solid State Chemistry, Vol. 134, Issue 1
  • DOI: 10.1006/jssc.1997.7525

Phasen mit oktaedrischen Bauelementen des �bergangsmetalls
journal, January 1965

  • Rieger, W.; Nowotny, H.; Benesovsky, F.
  • Monatshefte f�r Chemie, Vol. 96, Issue 1
  • DOI: 10.1007/BF00912313

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Various Arsenic Network Structures in 112-Type Ca 1– x La x Fe 1– y Pd y As 2 Revealed by Synchrotron X-ray Diffraction Experiments
journal, February 2017


Structure and physical properties of ternary uranium transition-metal antimonides U3MSb5 (M=Zr, Hf, Nb)
journal, July 2006


Crystal structure of TiBi 2
journal, August 2016

  • Watanabe, Kei; Yamane, Hisanori
  • Acta Crystallographica Section E Crystallographic Communications, Vol. 72, Issue 9
  • DOI: 10.1107/S2056989016012391

publCIF : software for editing, validating and formatting crystallographic information files
journal, June 2010


Ternary Rare-Earth Manganese Bismuthides:  Structures and Physical Properties of RE 3 MnBi 5 (RE = La−Nd) and Sm 2 Mn 3 Bi 6
journal, January 2008

  • Zelinska, Oksana Ya.; Mar, Arthur
  • Inorganic Chemistry, Vol. 47, Issue 1
  • DOI: 10.1021/ic701428p