A hypersilicic Cl-bearing mica was synthesized at 4 GPa and 1200–1250 °C, close to the solidus of the join diopside-jadeite-KCl, in association with diopside-jadeite pyroxene, K-rich aluminosilicate glass and/or sanidine and (K,Na)Cl. The mica shows a negative correlation between tetrahedral Si and octahedral (Al + Mg), suggesting an Al-celadonitic substitution (Si + VIAl + VI□ = IVAl + VIMg) and a chemical formula: 1.01(Mg2.45Al0.19□0.35)Σ=3(Si3.52Al0.48) Σ=4O10[(OH,O)1.66Cl0.34)] Σ=2. The presence of hydroxyl was confirmed by OH stretching modes at 3734 and 3606 cm−1 in the Raman spectra. Single-crystal X-ray diffraction data provide the unit-cell parameters (space group C2/m, 1M polytype): a = 5.299(4), b = 9.167(3), c = 10.226(3) Å, β =100.06(4)°, V = 489.1(4) Å3. The structure refinement shows the presence of vacancies on the octahedral sites (15% for M1 and 6.5% for M2). Chlorine occupies a position about 0.5 Å from O4 with partial occupancy (0.39 apfu). Crystal-chemical mechanisms seem to govern chlorine incorporation in mica, since a large A site is necessary to locate the anion in the structure. A large A site results when the six-tetrahedra ring is hexagonal and the tetrahedral rotation angle α is 0°. Such a geometry is achieved either by increasing the annite component in biotite or by increasing the hypersilicic character of phlogopite through the Al-celadonite substitution. The present Si-rich mica shows a partial dioctahedral character due to the Al-celadonite substitution, which lowers the α angle and expands its stability field at high pressure.
High aK2O conditions, like in potassium-rich brine or potassic carbonatitic melts, increase the Al-celadonite component in the phlogopite solid solution, explaining the association of Si-rich micas with inclusions of potassic liquids in kimberlitic diamonds.