Preparation and structure of [RuII/III2(O2CMe)4]2[Fe(CN)5NO] and magnetically ordered Hx[RuII/III2(O2CMe)4]3−x[Cr(CN)5NO] possessing interpenetrating lattices

Reaction of [Ru2(O2CMe)4]Cl with K3[Cr(CN)5NO] in water forms Hx[RuII/III2(O2CMe)4]3−x-[Cr(CN)5NO]·zH2O (x = 0.2) that magnetically orders at 4.0 K and possesses an interpenetrating body centered cubic [a = 13.2509(2) Å] structure with random locations of the bridging nitrosyl ligands, and x/3 vacant cation sites. Similarly, the aqueous reaction of [Ru2(O2CMe)4]Cl with Na2[Fe(CN)5NO] forms paramagnetic [Ru2(O2CMe)4]2[Fe(CN)5NO]·H2O, which has a similar tetragonal interpenetrating structure [a = 13.0186(1) Å, c = 13.0699(2) Å] where the NO ligands are presumably nonbridging and 1/3 of the expected cation sites are unoccupied. The presence of uncoordinated NO sites in addition to missing neighboring [Ru2(O2CMe)4]+ units, results in significant vacancies (or holes) in the lattice.

Graphical abstractThe reaction of [Ru2(O2CMe)4]+ with [Cr(CN)5NO]3− forms body center cubic and magnetically ordered Hx[Ru2(O2CMe)4]3−x[Cr(CN)5NO] with random NOs, and x/3 vacant cation sites. In contrast, the reaction of [Ru2(O2CMe)4]+ with [Fe(CN)5NO]2− forms Ru2(O2CMe)4]2[Fe(CN)5NO] that has a interpenetrating tetragonal structure where the NO ligands are presumably nonbridging and 1/3 of the cation sites are vacant.Figure optionsDownload full-size imageDownload as PowerPoint slide