Double Salts and Mixed Crystals of Tellurium Clusters Te 4 2+ /Te 8 2+ and TeCl 3 + Ions with Anions based on Molybdenum and Zirconium (Oxy)chlorides

The reaction of elemental tellurium, tellurium tetrachloride, zirconium tetrachloride, and molybdenum oxytetrachloride yields black plate‐like crystals of Te 4 [MoZr 2 O 2 Cl 11 ] ( 1 ) and yellow crystals of (TeCl 3 ) 2 [Mo 2 O 2 Cl 8 ] x [Zr 2 Cl 10 ] 1– x ( 2 ). Using molybdenum oxytrichloride instead of the oxytetrachloride, black crystals of (Te 4 ) 2 [Mo 2 O 2 Cl 8 ][ZrCl 6 ] ( 3 ), Te 8 [ZrCl 6 ] ( 4 ), and bronze‐colored crystals of Te 4 [ZrCl 6 ] ( 5 ) are obtained. All obtained crystals are air‐sensitive and were characterized by single‐crystal X‐ray diffraction and energy‐dispersive X‐ray fluorescence spectroscopy. 1 contains a layered polymeric anion of unprecedented structural features with zirconium atoms coordinated in a pentagonal bipyramidal ZrO 3 Cl 4 and ZrOCl 6 environment. Magnetic susceptibility data of 1 and 2 show nearly ideal paramagnetic behavior according to the Curie law with magnetic moments of 1.55(7) μ B for 1 and 1.66(6) μ B for 2 indicating the presence of magnetically isolated d 1 configured Mo V . The double salt 3 adopts the structure type of the selenium containing congener (Se 4 ) 2 [Mo 2 O 2 Cl 8 ][ZrCl 6 ], 4 and 5 are isotypic to the respective hafnium containing representatives Te 4 [HfCl 6 ] and Te 8 [HfCl 6 ].