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Synthesis, Crystal Structure, and Bonding Analysis of the Hypoelectronic Cubic Phase Ca5Pd6Ge6.

Doverbratt, Isa LU ; Ponou, Simeon LU ; Wang, Fei LU and Lidin, Sven LU (2015) In Inorganic Chemistry 54(18). p.9098-9104
Abstract
The title compound, Ca5Pd6Ge6, was obtained during a systematic investigation of the Ca-Pd-Ge ternary phase diagram. The crystal structure was determined and refined from single-crystal X-ray diffraction data. It crystallizes in a new structure variant of the Y4PdGa12-type structure (Im3̅m, a = 8.7764(4) Å) that features an arrangement of vertex-sharing body-centered cubes of calcium, Ca@Ca8, with a hierarchical bcc network, interpenetrating a second (Pd6Ge6) network consisting of Ge2 dumbbells surrounded by Pd in a strongly flattened octahedron with Pd(μ(2)-η(2),η(4)-Ge2)-like motifs. These octahedra are condensed through the Pd to form a 3D open fcc network. Theoretical band structure calculations suggested that the compound is... (More)
The title compound, Ca5Pd6Ge6, was obtained during a systematic investigation of the Ca-Pd-Ge ternary phase diagram. The crystal structure was determined and refined from single-crystal X-ray diffraction data. It crystallizes in a new structure variant of the Y4PdGa12-type structure (Im3̅m, a = 8.7764(4) Å) that features an arrangement of vertex-sharing body-centered cubes of calcium, Ca@Ca8, with a hierarchical bcc network, interpenetrating a second (Pd6Ge6) network consisting of Ge2 dumbbells surrounded by Pd in a strongly flattened octahedron with Pd(μ(2)-η(2),η(4)-Ge2)-like motifs. These octahedra are condensed through the Pd to form a 3D open fcc network. Theoretical band structure calculations suggested that the compound is hypoelectronic with predominantly multicenter-type interatomic interactions involving all three elements and essentially a Hume-Rothery-like regime of electronic stabilization. The similar electronegativity between germanium and palladium atoms has a decisive impact on the bonding picture of the system. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
54
issue
18
pages
9098 - 9104
publisher
The American Chemical Society
external identifiers
  • pmid:26325237
  • wos:000361865600034
  • scopus:84942098897
ISSN
1520-510X
DOI
10.1021/acs.inorgchem.5b01528
language
English
LU publication?
yes
id
d20c540b-2edc-480e-b44e-45cb0710b7a6 (old id 8043570)
date added to LUP
2015-10-30 13:06:05
date last changed
2017-01-01 03:51:35
@article{d20c540b-2edc-480e-b44e-45cb0710b7a6,
  abstract     = {The title compound, Ca5Pd6Ge6, was obtained during a systematic investigation of the Ca-Pd-Ge ternary phase diagram. The crystal structure was determined and refined from single-crystal X-ray diffraction data. It crystallizes in a new structure variant of the Y4PdGa12-type structure (Im3̅m, a = 8.7764(4) Å) that features an arrangement of vertex-sharing body-centered cubes of calcium, Ca@Ca8, with a hierarchical bcc network, interpenetrating a second (Pd6Ge6) network consisting of Ge2 dumbbells surrounded by Pd in a strongly flattened octahedron with Pd(μ(2)-η(2),η(4)-Ge2)-like motifs. These octahedra are condensed through the Pd to form a 3D open fcc network. Theoretical band structure calculations suggested that the compound is hypoelectronic with predominantly multicenter-type interatomic interactions involving all three elements and essentially a Hume-Rothery-like regime of electronic stabilization. The similar electronegativity between germanium and palladium atoms has a decisive impact on the bonding picture of the system.},
  author       = {Doverbratt, Isa and Ponou, Simeon and Wang, Fei and Lidin, Sven},
  issn         = {1520-510X},
  language     = {eng},
  number       = {18},
  pages        = {9098--9104},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {Synthesis, Crystal Structure, and Bonding Analysis of the Hypoelectronic Cubic Phase Ca5Pd6Ge6.},
  url          = {http://dx.doi.org/10.1021/acs.inorgchem.5b01528},
  volume       = {54},
  year         = {2015},
}