| Abstract: | Two Tetrachlorothiotantalates: Na‐15‐crown‐5]TaSCl4 · dioxane] and Na‐15‐crown‐5]2(TaSCl4)2dioxane] · S8 During the reaction of Na2S4, TaCl5 and 15‐crown‐5 in dichloromethane the crown ether partly suffers degradation to 1,4‐dioxane. Aside from sulfur, Na‐15‐crown‐5]TaSCl4 · dioxane] was the first product obtained. It crystallizes in the monoclinic space group P21/n with a = 1066.1, b = 1781.3, c = 1258.3 pm, β = 97.14°, Z = 4. In the TaSCl4 · dioxane]– ion a dioxane molecule is loosely bonded to a square‐pyramidal TaSCl4– unit; two chlorine atoms are in contact with an Na+ ion. Upon standing with the mother liquor Na‐15‐crown‐5]2(TaSCl4)2dioxane] · S8 was formed. It crystallizes in the monoclinic space group C2/m; a = 1768.5, b = 1084.0, c = 1517.3 pm, β = 118.46°, Z = 4. In this case a dioxane molecule is coordinated with two TaSCl4– units. The (TaSCl4)2 · dioxane]2– ions and S8 molecules alternate in the stacking direction b. |
