The structures of some hexaammine metal(II) halides of 3d metals: [V(NH3)(6)]I-2, [Cr(NH3)(6)]I-2, [Mn(NH3)(6)]Cl-2, [Fe(NH3)(6)]Cl-2, Fe(NH3)(6)]Br-2, [Co(NH3)(6)]Br-2, and [Ni(NH3)(6)Cl-2

Crystals of yellow [V(NH3)(6)]I-2 and green [Cr(NH3)(6)]I-2 were obtained by the reaction of VI2 and CrI2 with liquid ammonia at room temperature. Colourless crystals of [Mn(NH3)(6)]Cl-2 were obtained from Mn and NH4Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH3)(6)]Cl-2 and [Fe(NH3)(6)]Br-2 were obtained by the reaction of FeCl2 and FeBr2 with supercritical ammonia at 400 degrees C. Under the same conditions orange crystals of [Co(NH3)(6)]Br-2 were obtained from [Co-2(NH2)(3)(NH3)(6)]Br-3. Purple crystals of [Ni(NH3)(6)]Cl-2 were obtained by the reaction of NiCl2 . 6H(2)O and NH4Cl with aqueous NH3 solution. The structures of the isotypic compounds (Fm3m, Z = 4) were determined from single crystal diffractometer data (see ''Inhaltsubersicht''). All compounds crystallize in the K-2[PtCl6] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.