Anion control over interpenetration and framework topology in coordination networks based on homoleptic six-connected scandium nodes

Reaction of ScX3 (X = NO3-, CF3SO3-, ClO4-) with 4,4'-bipyridine-N,N'-dioxide (L) affords topologically distinct six-connected three-dimensional coordination frameworks, {[Sc(L)(3)](NO3)(3)}(infinity) (1), {[Sc(L)(3)](CF3SO3)(3)(CH3OH)(2.7)(H2O)(3)}(infinity) (2), {[Sc(L)(3)](ClO4)(3)}(infinity) (3) and {[Sc(L)(4)(H2O)(2)](ClO4)(3)}(infinity) (4). Compounds 1, 2 and 3 are networks based on octahedrally co-ordinated ScO6 centres bound through six oxygen atoms from six separate N-oxide ligands L. Compounds 1 and 3 are doubly interpenetrated and have alpha-polonium-type structures of 4(12)6(3) topology based upon three intersecting (4,4) nets. The structure of 2 is unusual and shows parallel, co-planar layers of (4,4) nets connected in a criss-crossed fashion to afford a new 4(8)6(6)8 topology. In 4 only four ligands L bind to each Sc-III centre with two additional water molecules bridging metal nodes. Significantly, the bridges formed by L do not sit in a plane and if connections through L are considered alone the resultant structure is a diamondoid array typically based upon a tetrahedral connecting node at Sc. Five interpenetrating diamondoid networks are observed that are cross-bridged by water molecules to form a single three-dimensional array of 4(8)6(7) topology. Compound 4 can also be viewed as incorporating two intersecting (4,4) grids based upon two ligands L and two bridging waters. Thus, variation of anion, solvent and conditions critically affects the structures of products formed, and the series of polymers reported herein illustrates how tectons based upon (4,4) grids can be combined and distorted to form non-NaCl topologies and even cross-bridged, multiply interpenetrated diamondoid materials. Both compounds 2 and 4 represent unusual examples of self-penetrated coordination frameworks.