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Tetragonal Mg 2.12 Fe 3.17 Ge 2.56 O 12  is a new germanate forming at 1 atm pressure in the MgO-Fe 2 O 3-  GeO 2  system. It is an analogue of the high-pressure silicate mineral TAPP occurring as inclusions in diamonds of lower-mantle origin. Its crystal structure was determined by X-ray diffraction using single-crystals grown from a potassium molybdate flux. It crystallizes in the I4̄2d space group with a = 6.8153(4) Å, c = 18.669(2) Å, Z = 4. The refinement of its cation distribution,  VIII (Mg 0.52 Fe 0.33 ) VI (Mg 1.60 Fe 2.40 ) IV (Ge 2.56 Fe 0.44 )O 12 , shows the presence of a partially filled (85%) dodecahedral site characterized by an unusual geometry with two very different bond lengths [2.169 Å (×4) and 2.609 Å (×4)]. The structure determinations of the Ca 2+ - and Y 3+ -substituted phases show that the larger cations are completely partitioned in the dodecahedral site, increasing its occupancy slightly (up to 92% in the case of Ca 2+ ). Cubic Mg 2.35 Y 2.00 Fe 0.97 Ge 2.59 O 12  is a new garnet phase forming at 1 atm pressure in the MgO-Y 2 O 3 -Fe 2 O 3 -GeO 2  system. Its crystal structure and cation distribution were also determined by singlecrystal X-ray diffraction:  VIII (MgY 2 ) VI (Mg 1.35 Fe 0.56 ) IV (Ge 2.59 Fe 0.41 )O 12 , Ia3̄d space group, a = 12.232(1) Å, Z = 8. In spite of similarities in their chemical compositions, the tetragonal and garnet phases are structurally distinct, with different ratios of dodecahedral to octahedral sites, viz.,  VIII A VI B 4  IV T 3 O 12  and  VIII A 3  VI B 2  IV T 3 O 12  respectively. As a consequence, the tetragonal phase forms in systems containing smaller cations, such as Mg 2+ , Fe 3+ , Ni 2+ , Co 2+ , whereas larger cations, such as Y 3+ , show a strong preference for the garnet phase.

VIII (Mg,Fe) 0.85 VI (Mg,Fe) 4 IV (Fe,Ge) 3 O 12 : A new tetragonal phase and its comparison with garnet