Room temperature stirring of H2Ru(P(OE)(3))(4) (E = Me and Et) and elemental sulfur in benzene afforded the optically active compounds Ru(P(OMe)(3))(3)S-5 (1) and Ru(P(OEt)(3))(3)S-5 (2). Compounds I-and 2 are crystallized in the trigonal space group P3(1) with a = 14.231(10) Angstrom, c = 10.24(1) Angstrom, V = 1794(2) Angstrom(3), and Z = 3, and orthorhombic space group P2(1)2(1)2(1) With a 15.393(5) Angstrom, b = 18.126(6) Angstrom, c = 12.421(4) Angstrom, V = 3465(1) Angstrom(3), and Z = 4, respectively. Solutions of 1 and 2 did not show any optical activity since the bulk materials are racemic mixtures. The X-ray analyses also reveal that in both compounds polysulfide S-5(2-) ion acts as a novel tridentate ligand, resulting in an asymmetric bicyclic RuS5 unit having three- and five-membered rings around the ruthenium atom. Fragmentation of the S-5(2-) ring to S2- ion was observed in the presence of sulfur-abstracting reagents such as PR3 (R = Ph, OMe, and Oft) and also to S-2(2-) ion when the compounds were reacted with RuCl2(P(OE)(3))(4) (E = Me and Et).