Preparation and crystal structures of ruthenium and osmium oxide tetrahalides

RuOF4 as the highest valence oxide fluoride exist as a molecular compound (a = 606.0(1), b = 836.1(1), c = 626.3(1) pm, beta = 91.637(3), Z = 4: P2(1)/n) as well as fluorine bridged polymer (a = 547.7(2), b = 928.5(3), c = 1252.4(3) pm, Z = 8, P2(1)2(1)2(1)). A reproducible method for pure. deep blue OsOF4 is given. Pure OsOF4-I is isostructural to the fluorine bridged polymeric RuOF4 (a = 554.6(1), b = 955.4(2), c = 1278.4(2), Z = 8, P2(1)2(1)2(1)). OsOF4-II is also a fluorine bridged polymer (a = 537.8(2), b = 1274.8(4), c = 555.2(2), beta = 117.716(6)degrees, Z = 4, P2(1)/c). OsOCl4 again is a molecular species (a = 938.9(2), b = 561.3(1), c = 1192.0(2), beta = 109.944(4)degrees, Z = 4, P2(1)/c).