The structure of a single crystal of tetraammindioxoosmium(VI) sulfate [OsO2(NH3)4]SO4 • H 2O, which is synthesized by the reaction of K2[OsO 2(OH)4] with (NH4)2SO4 in an aqueous solution, is investigated using X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system, space group P2 1/c, a = 13.102(2) Å, b = 6.158(3) Å, c = 11.866(2) Å, β = 98.13(2)°, and Z = 4. The [OsO2(NH 3)4]SO4 • H2O compound has an island structure. Two crystallographically independent osmium atoms are situated at the centers of symmetry, and their octahedral coordination includes two oxygen atoms and four nitrogen atoms of the ammonia molecules. In both octahedra, the osmyl group is linear. The Os-O distances in the octahedra are identical within the standard deviations [Os(1)-O, 1.762(2) Å; Os(2)-O, 1.769(2) Å]. The Os-N bond lengths vary from 2.082(3) to 2.101(3) Å. The cationic complexes, SO4 groups, and water molecules are linked via the system of hydrogen bonds. The assignment of the absorption bands in the IR spectrum of the compound synthesized is performed, and its thermal behavior in air is studied. © Nauka/Interperiodica 2007.