RuS4Cl12 and Ru2S6Cl16, two new ruthenium(II) complexes with SCl2 ligands

Ru powder was reacted with SCl2 in closed silika ampoules at 140 degrees C. From the black solution three compounds RuS4Cl12 1, Ru2S6Cl16 2, and Ru2S4 Cl13 3 could be crystallized and characterized by x ray analysis. Black cry stals of 1 (monoclinic, a = 9.853(1) Angstrom, b = 11.63(1) Angstrom, c = 1 5.495(1) Angstrom, beta = 105.23(1)degrees, space group P2(1)/c, z = 4) are identified as Trichlorsulfonium-tris(dichlorsulfan)trichlororuthenat(II) S Cl3[RuCl3(SCl2)(3)]. In the structure the complex anions fac-[RuCl3(SCl2)(3 )](-) and the cations [SCl3](+) are connected to ion pairs by three chlorin e bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Angstrom, b = 7 .997(2) Angstrom, c = 10.708(2) Angstrom, alpha = 103.74(3)degrees, beta = 98.44(3)degrees, gamma = 108.58(3)degrees, space group P-1, z = 1) contain the binuclear complex Bis-mu-chloro-dichloro-hexakis(dichlorsulfan)-diruthe nium(II), (SCl2)(3)ClRu(mu-Cl)(2)RuCl(SCl2)(3) with two fac-RuCl3(SCl2)(3)- units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl-2(SCl2)Ru(mu-Cl)(3)Ru(SCl2)(3)]. T he vibrational spectra and the thermal behaviour of the compounds are discu ssed.