Assembled structures of tetrakis(biimidazole)dirhodium complexes hydrogen‐bonded with common inorganic anions

Eight new structures of dirhodium complexes, each with four biimidazole (H 2 bim) ligands, were obtained: [Rh 2 (H 2 bim) 4 (H 2 O) 2 ](NO 3 ) 4 ·4H 2 O (I), [Rh 2 (H 2 bim) 4 (H 2 O) 2 ](ClO 4 ) 4 ·5H 2 O (II), [Rh 2 (H 2 bim) 4 (MeOH) 2 ](ClO 4 ) 4 (III), [Rh 2 (H 2 bim) 4 (DMF) 2 ](BF 4 ) 4 (IV), [Rh 2 (H 2 bim) 4 (Mepy) 2 ](SiF 6 ) 2 ·8H 2 O (V), [{Rh 2 (H 2 bim) 4 (pz)} 2 (μ‐pz)](SiF 6 )(ClO 4 ) 6 ·12.7H 2 O (VI), [{Rh 2 (H 2 bim) 4 (pz)} 2 (μ‐pz)](ClO 4 ) 8 ·11.4H 2 O (VII) and [Rh 2 (H 2 bim) 4 (μ‐pz)](SiF 6 ) 2 ·6H 2 O (VIII). The unbridged Rh—Rh bond distances range between 2.6313 (8) and 2.7052 (5) Å. The dirhodium units adopt a staggered conformation with torsion angles N—Rh—Rh—N of 37.6 (4)–48.98 (8)°. Various assembled structures were constructed by hydrogen bonding between the complexes and the anions: a discrete structure in (IV), one‐dimensional structure in (II), two‐dimensional structures in (I), (III), (VI), (VII) and (VIII) and a three‐dimensional structure in (V).