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Single crystals of the compounds Ca 4 OCl 6 , Sr 4 OBr 6 , Ba 4 OBr 6 , and Ba 2 OI 2  were obtained by solid-state reactions. The crystals of Ba 2 OI 2  are transparent and colorless and isopointal to K 2 ZnO 2  adopting the orthorhombic space group Ibam (no. 72, Z = 4) with the cell parameters a = 747.20(9), b = 1392.02(18), and c = 678.12(9) pm. Sr 4 OBr 6  and Ba 4 OBr 6  are isotypic to Ba 4 OCl 6  (or isopointal to K 6 ZnO 4 ) and crystallize in the hexagonal space group P6 3 mc (no. 186, Z = 2) exhibiting the cell parameters a = 982.20(4) and c = 750.41(7) pm for Sr 4 OBr 6  and a = 1030.10(2) and c = 785.92(4) pm for Ba 4 OBr 6 . In the ternary systems Ca-O-X (X = Cl, Br or I) the only compound found other than the starting materials was the already known Ca 4 OCl 6  which is also isotypic to Ba 4 OCl 6  crystallizing in the hexagonal space group P6 3 mc (no. 186, Z = 2) with the cell parameters a = 903.30(6) and c = 683.27(8) pm.

Alkaline Earth Metal Oxyhalides Revisited – Syntheses and Crystal Structures of Sr 4 OBr 6 , Ba 4 OBr 6 and Ba 2 OI 2