While TiCl4 and Na2S4 react in in the presence of PPh4Cl in dichloromethane to yield (PPh4)2[TiSCl4]·2CH2Cl2, we obtained [Ti4O6(OSMe2)12]Cl4·5Me2SO · 1/2H2O (1) from the same reactants in dimethylsulfoxide. Compound 1 is only stable in the presence of dimethylsulfoxide. The crystal structure determination at 153 K shows the presence of cations having an adamantane-like Ti4O64+ skeleton with three Me2SO molecules coordinated to each Ti atom via their O atoms. Crystal data: monoclinic, P 21/n, Z = 4, a = 1096.9, b = 3097, c = 2342.7 pm, β = 93.90° (at -120 °C; R = 0.087 % for 4098 reflections). In an attempt to produce the same compound only from TiCl4 and Me2SO, [TiO(OSMe2)5]Cl2 was obtained. Its cation has a rather short Ti=O bond (164.8 pm) and a distorted octahedral coordination of the titanium atom. The crystals are triclinic, P1̄, Z = 2, R = 0.050 for 2063 reflections measured at 153 K.
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