Thiochloroanionen von Molybdän(IV). Die Kristallstruktur von (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl · CH2Cl2 Kristallstruktur,EPR-Spektrum und magnetische Eigenschaften von (NEt4)2[Mo2(μ-S2)(μ-Cl)2Cl6]

Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt₄)₃Mo₃(μ₃-S)(μ-S₂)₃Cl₆]Cl μ CH₂Cl₂. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt₄)₂ Mo₂(μ-S₂)(μ-Cl)₂Cl₆] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH₂Cl₂ an insoluble product of composition (NEt₄)₂Mo₂S₃Cl₉] was obtained along with a brown solution, from which (NEt₄)₂Mo₂(S₂)Cl₈] was crystallized. The insoluble product and NEt₄Cl react in CH₂Cl₂ to yield, among others, (NEt₄)₃Mo₃(S)(S₂)₃Cl₆]Cl · CH₂Cl₂. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the Mo₃(S)(S₂)₃Cl₆]^2? ion consists of an Mo₃ triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo₃ triangle; the single chloride ion is looseley associated to three S atoms. (NEt₄)₂Mo₂(S₂)Cl₈] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the Mo₂(S₂)Cl₈]^2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron.