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Title: Tuning complexity by lithiation: A family of intergrowth structures using condensed hypho-icosahedra in the Li-doped Ca–Zn system

Abstract

Cluster chemistry of intermetallics with valence electron counts (VECs) in the range of 2.0–3.0 is intriguing. Lithiation of polar intermetallics in this VEC region is found to be an effective chemical route to produce new complex structures with different stability mechanisms. In this work, two new complex intermetallic structures have been discovered in the Ca–Li–Zn system: Ca12LixZn59–x and Ca15LixZn75–x. Ca12LixZn59–x, x ≈ 5.65(3)–14.95(3), forms in the trigonal space group R3m, with a = 9.074(1)–9.1699(2) Å, c = 53.353(1)–53.602(1) Å, and Z = 3. In comparison, Ca15LixZn75–x, x ≈ 19.07(2), crystallizes in the space group P63/mmc, with a ≈ 9.183(1) Å, c ≈ 45.191(5) Å), and Z = 2. Both structures are members of a large intergrowth family featuring slabs of dimers (D) and trimers (T) stacking along [001], with the sequences DTDDTDDTD for Ca12LixZn59–x and TDDDTDDD for Ca15LixZn75–x. Each dimer consists of two face-sharing Zn-centered hypho-icosahedra, and each trimer comprises a Li-centered icosahedron sandwiched by two hypho-icosahedra. Furthermore, this intergrowth family includes several known intermetallic structure types involving very electropositive metals, e.g., SrMg5.2, Ba2Li4.21Al4.79, and Sr9Li17.5Al25.5. Because of cluster defects and condensation, both Ca12LixZn59–x and Ca15LixZn75–x are electronically akin to close-packed metals, and their structural stabilities can be interpreted bymore » a Hume-Rothery mechanism rather than the Zintl–Klemm concept.« less

Authors:
 [1];  [2];  [3]
  1. Ames Lab., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1257373
Report Number(s):
IS-J-8958
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lin, Qisheng, Zhu, Ran, and Miller, Gordon J. Tuning complexity by lithiation: A family of intergrowth structures using condensed hypho-icosahedra in the Li-doped Ca–Zn system. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.inorgchem.6b00612.
Lin, Qisheng, Zhu, Ran, & Miller, Gordon J. Tuning complexity by lithiation: A family of intergrowth structures using condensed hypho-icosahedra in the Li-doped Ca–Zn system. United States. https://doi.org/10.1021/acs.inorgchem.6b00612
Lin, Qisheng, Zhu, Ran, and Miller, Gordon J. Tue . "Tuning complexity by lithiation: A family of intergrowth structures using condensed hypho-icosahedra in the Li-doped Ca–Zn system". United States. https://doi.org/10.1021/acs.inorgchem.6b00612. https://www.osti.gov/servlets/purl/1257373.
@article{osti_1257373,
title = {Tuning complexity by lithiation: A family of intergrowth structures using condensed hypho-icosahedra in the Li-doped Ca–Zn system},
author = {Lin, Qisheng and Zhu, Ran and Miller, Gordon J.},
abstractNote = {Cluster chemistry of intermetallics with valence electron counts (VECs) in the range of 2.0–3.0 is intriguing. Lithiation of polar intermetallics in this VEC region is found to be an effective chemical route to produce new complex structures with different stability mechanisms. In this work, two new complex intermetallic structures have been discovered in the Ca–Li–Zn system: Ca12LixZn59–x and Ca15LixZn75–x. Ca12LixZn59–x, x ≈ 5.65(3)–14.95(3), forms in the trigonal space group R3m, with a = 9.074(1)–9.1699(2) Å, c = 53.353(1)–53.602(1) Å, and Z = 3. In comparison, Ca15LixZn75–x, x ≈ 19.07(2), crystallizes in the space group P63/mmc, with a ≈ 9.183(1) Å, c ≈ 45.191(5) Å), and Z = 2. Both structures are members of a large intergrowth family featuring slabs of dimers (D) and trimers (T) stacking along [001], with the sequences DTDDTDDTD for Ca12LixZn59–x and TDDDTDDD for Ca15LixZn75–x. Each dimer consists of two face-sharing Zn-centered hypho-icosahedra, and each trimer comprises a Li-centered icosahedron sandwiched by two hypho-icosahedra. Furthermore, this intergrowth family includes several known intermetallic structure types involving very electropositive metals, e.g., SrMg5.2, Ba2Li4.21Al4.79, and Sr9Li17.5Al25.5. Because of cluster defects and condensation, both Ca12LixZn59–x and Ca15LixZn75–x are electronically akin to close-packed metals, and their structural stabilities can be interpreted by a Hume-Rothery mechanism rather than the Zintl–Klemm concept.},
doi = {10.1021/acs.inorgchem.6b00612},
journal = {Inorganic Chemistry},
number = 10,
volume = 55,
place = {United States},
year = {2016},
month = {4}
}

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Works referenced in this record:

Revisiting the Zintl–Klemm Concept: Alkali Metal Trielides
journal, August 2011

  • Wang, Fei; Miller, Gordon J.
  • Inorganic Chemistry, Vol. 50, Issue 16
  • DOI: 10.1021/ic200643f

The Zintl-Klemm Concept - A Historical Survey: The Zintl-Klemm Concept - A Historical Survey
journal, November 2014

  • Nesper, Reinhard
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 14
  • DOI: 10.1002/zaac.201400403

New refinements of the γ brass type structures Cu5Zn8, Cu5Cd8 and Fe3Zn10
journal, June 1974

  • Brandon, J. K.; Brizard, R. Y.; Chieh, P. C.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 6
  • DOI: 10.1107/S0567740874004997

CaZn 3 : a structure with mixed BaLi 4 - and CeCu 2 -like ordering
journal, August 1980

  • Fornasini, M. L.; Merlo, F.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 36, Issue 8
  • DOI: 10.1107/S0567740880007133

Die Kristallstruktur von CaZn2
journal, January 1961


Kristallstruktur von CaZn5 und CaCu5
journal, May 1940


Polar binary Zn/Cd-rich intermetallics: Synthesis, crystal and electronic structure of A(Zn/Cd)13 (A = alkali/alkaline earth) and Cs1.34Zn16
journal, September 2006


Explicit, First-Principles Tight-Binding Theory
journal, December 1984


Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

  • Dronskowski, Richard; Bloechl, Peter E.
  • The Journal of Physical Chemistry, Vol. 97, Issue 33
  • DOI: 10.1021/j100135a014

Preparation and crystal structure of SrMg5.2
journal, February 1988


Ca 6 Li x Al 23- x , Sr 9 Li 7+ x Al 36- x , and Ba 2 Li 3+ x Al 6- x :  New Ternary Intermetallic Compounds Linking Close-Packed Metal Structures and Zintl Phases
journal, January 1996

  • Häussermann, Ulrich; Wörle, Michael; Nesper, Reinhard
  • Journal of the American Chemical Society, Vol. 118, Issue 47
  • DOI: 10.1021/ja961127k

Sr9Mg38: structural redetermination of 'SrMg4'
journal, June 1982

  • Merlo, F.; Fornasini, M. L.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 6
  • DOI: 10.1107/S0567740882007213

The crystal structures of Sr 6 Mg 23 , SrMg 4 , Ba 6 Mg 23 and BaLi 4
journal, January 1965


Polyhedral skeletal electron pair approach. A generalised principle for condensed polyhedra
journal, January 1983

  • Mingos, D. Michael P.
  • Journal of the Chemical Society, Chemical Communications, Issue 12
  • DOI: 10.1039/c39830000706

A Unifying Electron-Counting Rule for Macropolyhedral Boranes, Metallaboranes, and Metallocenes
journal, May 2001

  • Jemmis, Eluvathingal D.; Balakrishnarajan, Musiri M.; Pancharatna, Pattath D.
  • Journal of the American Chemical Society, Vol. 123, Issue 18
  • DOI: 10.1021/ja003233z

Intermetallische Verbindungen
journal, January 1939


Zintl Phases: Transitions between Metallic and Ionic Bonding
journal, September 1973

  • Schäfer, Herbert; Eisenmann, Brigitte; Müller, Wiking
  • Angewandte Chemie International Edition in English, Vol. 12, Issue 9
  • DOI: 10.1002/anie.197306941

Rhombohedrally Distorted γ-Au 5– x Zn 8+ y Phases in the Au–Zn System
journal, January 2013

  • Thimmaiah, Srinivasa; Miller, Gordon J.
  • Inorganic Chemistry, Vol. 52, Issue 3
  • DOI: 10.1021/ic301933a

    Works referencing / citing this record: