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We discovered a new CaGe 2 O 5  polymorph in high-pressure experiments (above 8 GPa). The phase is orthorhombic, space group P bam , with a = 7.306(2), b = 8.268(2), c = 5.714(1) Å, V = 345.2(1) Å 3 , and Z = 4. The new phase, which we call post-titanite CaGe 2 O 5 , is the high-pressure polymorph of titanite CaGe 2 O 5 . The structure of this new polymorph is based on a network of 5- and 6-coordinated Ge polyhedra and 8-coordinated Ca atoms. Following the germanate analog to silicate, post-titanite CaSi 2 O 5  could be expected to form at high-pressure conditions and thus might exist in Earthʼs mantle.

Letter. A new high-pressure CaGe 2 O 5 polymorph with 5- and 6-coordinated germanium