From Zintl to Wade: Ba3LiGa5 – A Structure Pattern with Pyramidal Cluster Chains –[Ga5]n

Investigation of the correlation between the crystal structure, electronegativity difference and valence electron concentration in intermetallic gallides lead to the discovery of the new compound Ba3LiGa5 (space group Immm, a = 6.2720(2) Å, b = 6.5872(2) Å, c = 12.6878(8) Å). A combination of quantu...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2020-08, Vol.2020 (29), p.2842-2849
Main Authors: Kotsch, Matthias, Prots, Yurii, Ormeci, Alim, Bobnar, Matej, Wagner, Frank R., Senyshyn, Anatoliy, Grin, Yuri
Format: Article
Language:English
Subjects:
Chains
Chemical bonds
Cluster analysis
Clusters compounds
Crystal structure
Crystallography
Electronegativity
Gallium
Inorganic chemistry
Intermetallic phases
Lithium
Neutron diffraction
NMR
NMR spectroscopy
Nuclear magnetic resonance
Quantum chemistry
Substructures
Transition metals
Zintl phases
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Summary:Investigation of the correlation between the crystal structure, electronegativity difference and valence electron concentration in intermetallic gallides lead to the discovery of the new compound Ba3LiGa5 (space group Immm, a = 6.2720(2) Å, b = 6.5872(2) Å, c = 12.6878(8) Å). A combination of quantum chemical bonding analysis with NMR study revealed the gallium substructure to be formed of chains built of the interconnected pyramidal [Ga5] clusters. Analysis of chemical bonding by means of the electron localizability approach confirmed the presence nido‐[Ga5] Wade clusters. Lithium species are not only required for the purpose of charge compensation, but also – analogous to a transition metal – occupies partially the same crystallographic position as gallium. The new compound Ba3LiGa5 is the first known one in the ternary Ba–Li–Ga system. It can be best described by means of the nido–[Ga5] cluster poly‐anion with Ba and Li cationic counterparts. Their interaction within the gallium poly‐anion is multi–atomic and strongly polar. Lithium plays a dual role in Ba3LiGa5: on the one hand, it bodies for the charge compensation, and on the other one, it substitutes gallium at the same crystallographic position, thus behaving rather as a transition metal.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202000413