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Four new hexanuclear niobium cluster compounds of the general formula [Nb 6 Cl 12 (HIm) 6 ]( A ) n  ⋅  x (solvent molecule) (HIm=1 H ‐imidazole,  A =mineral acid anion, Cl −  ( n =2) ( 1 ), (SO 4 ) 2−  ( n =1) ( 2 ), (CrO 4 ) 2−  ( n =1) ( 3 ),  and  (HAsO 4 ) 2−  ( n =1) ( 4 )) were prepared. Their synthesis can be done in basic ionic liquids, which form on the addition of a mineral acid, which also delivers the counter anion for the final cluster compound, to an excess of the 1 H ‐imidazole. Some addition of an auxiliary solvent, like methanol, improves the speed of crystallisation. The cluster unit comprises a hexanuclear Nb 6  unit of octahedral shape with the edges bridged by Cl atoms and the exo sites being occupied by N‐bonded 1 H ‐imidazole ligands. The cluster cation carries sixteen cluster‐based electrons. Between the NH groups of the ligands of the cluster unit, the anions and the co‐crystallised water ( 1 ), or 1 H ‐imidazole and methanol molecules ( 2 ,  3 , and  4 ) a network of hydrogen bonds exists.

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Cluster Salts [Nb 6 Cl 12 (HIm) 6 ] A n   (with HIm=1 H ‐imidazole and  A =Mineral Acid Anion,  n =1 or 2) Made in and with Brønsted‐basic Ionic Liquids and Liquid Mixtures