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Crystals of BaSi 4 O 9  synthesized at 4 GPa and 1000 ℃ were determined to be isostructural with barium tetragermanate [trigonal, space group P3, a =11.2469(11) and c = 4.4851(6) Å, V= 491.3(1) Å 3 ]. The structure (R = 2.4%) features a corner-linked framework of three-member silicate tetrahedral rings, which are cross-linked by isolated silicate octahedra. Ba cations oc­cupy tenfold-coordinated sites in channels defined by the silicate framework. This structure is 4.2% denser than the topologically similar benitoite form of high-pressure BaSi 4 O 9 , which was produced by grinding the barium tetragermanate-type crystals described in this report.

Crystal chemistry of high-pressure BaSi 4 O 9 in the trigonal (P3) barium tetragermanate structure