Preparation and Crystal Structures of Ruthenium and Osmium Oxide Tetrahalides

RuOF 4 as the highest valence oxide fluoride exist as a molecular compound ( a = 606.0(1), b = 836.1(1), c = 626.3(1) pm, β = 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, P 2 1 2 1 2 1 ). A reproducible method for pure, deep blue OsOF 4 is given. Pure OsOF 4 ‐I is isostructural to the fluorine bridged polymeric RuOF 4 ( a = 554.6(1), b = 955.4(2), c = 1278.4(2), Z = 8, P 2 1 2 1 2 1 ). OsOF 4 ‐II is also a fluorine bridged polymer ( a = 537.8(2), b = 1274.8(4), c = 555.2(2), β = 117.716(6)°, Z = 4, P 2 1 /c). OsOCl 4 again is a molecular species ( a = 938.9(2), b = 561.3(1), c = 1192.0(2), β = 109.944(4)°, Z = 4, P 2 1 /c).