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The high-pressure behaviour of the oxonitridosilicate chlorides Ce 4 [Si 4 O 3+x N 7–x ]Cl 1–x O x ,  x  = 0.12 and 0.18, is investigated by  in situ  powder synchrotron X-ray diffraction. Pressures up to 28 GPa are generated using the diamond-anvil cell technique. A reversible phase transition of first order occurs at pressures between 8 and 10 GPa. Within this pressure range the high- and the low-pressure phases are observed concomitantly. At the phase transition the unit cell volume is reduced by about 5%, and the cubic symmetry (space group  P 2 1 3) is reduced to orthorhombic (space group  P 2 1 2 1 2 1 ) following a  translationengleiche  group-subgroup relationship of index 3. A fit of a third-order Birch-Murnaghan equation of state to the  p – V  data results in a bulk modulus  B  0  = 124(5) GPa with its pressure derivative  B ′ = 5(1) at  V  0  = 1134.3(4) Å 3  for the low-pressure phase and in  B  0  = 153(10) GPa with  B ′ = 3.0(6) at  V  0  = 1071(3) Å 3  for the high-pressure phase. The orthorhombic phase shows an anisotropic axial compression with the  a  axis (which is the shortest axis) being more compressible ( k(a)  = 0.0143(4) 1/GPa) than the  b  and  c  axes ( k(b)  = 0.0045(2),  k(c)  = 0.0058(2) 1/GPa). The experimental results confirm an earlier prediction of the pressure-induced instability of isotypic Ce 4 [Si 4 O 4 N 6 ]O, and also show that the bulk modulus was predicted reasonably well.

High-pressure phase transition of the oxonitridosilicate chloride Ce 4 [Si 4 O 3+x N 7–x ]Cl 1–x O x with x = 0.12 and 0.18