The compound Na2B6Si2 was synthesized
under high-pressure, high-temperature conditions at pressures ranging
from 6 to 9.5 GPa and temperatures from 1070 to 1270 K before quenching
to room temperature followed by slow decompression. The crystal structure
was determined from microcrystals using precession-assisted electron
diffraction tomography, validated by dynamical refinement and full-profile
refinements using optimized coordinates from quantum chemical calculations
(space group R3̅m, Pearson
symbol hR30, a = 5.0735(1) Å
and c = 16.0004(7) Å). The atomic arrangement
consists of a unique framework formed by electron-precise octahedral
closo (B6)2– clusters connected via ethane-like
(Si2)0 dumbbells. The Na+ cations
occupy cavities in the hierarchical variation of a Heusler-type framework.
The balance (Na+)2([B6]2–)(Si0)2 reveals an electron precise Zintl-Wade
phase, which is in line with electronic band structure calculations
predicting semiconducting behavior.