Coordination polymers with carborane anions: Silver dinitrile complexes

Crystalline materials have been isolated and characterized from mixing the silver carborane salts Ag(CB11H12) or Ag[Co(C2B9H11)(2)] with nitrile ligands, either terminal acetonitrile or potentially bridging alkanedinitriles. Most of the complexes showed B-(HAg)-Ag-... interactions between the silver center and carborane anion. [Ag(acetonitrile)(2)(CB11H12)] has a hexagonal network structure. [Ag(malonitrile)(2)(CB11H12)] is a discrete dimeric complex, while [Ag-4(succinonitrile)(5)(CB11H12)(4)], [Ag(glutaronitrile)(2)][Co(C2B9H12)(2)], and {Ag(glutaronitrile)[Co(C2B9H11)(2)]} all show coordination chain structures. The carborane anions in {Ag(adiponitrile)[Co(C2B9H11)(2)]} bridge between Ag centers to give a 3D CdSO4-related coordination polymer. The structure of [Ag(malonitrile)(2)](BF4) was also determined to have an unusual chiral diamondoid structure with a skewed 2-fold interpenetration.