Organic-inorganic hybrid chains and layers constructed from copper-amine cations and early transition metal (Nb, Mo) oxyfluoride anions

Under hydrothermal conditions in HF-containing media, the combination of early (Nb5+, Mo6+) and late (Cu2+) transition metals with four different organic amine ligands yields eight novel hybrid compounds with chain and layer structures. The eight new compounds were synthesised from a systematic series of reactions and can be subdivided into four pairs, the topologies of which are essentially unique to each ligand, containing in each case a Cu-based cationic species, but alternately either [MoOF4](2-) or [NbOF5](2-), in an isomorphous manner, as the anionic moiety. The overall structures of theses materials reflect the influences of the organo amine ligands. [Cu(C2H4N4)(2)][MoO2F4]center dot H2O (1) and [Cu(C2H4N4)(2)][NbOF5]center dot H2O (2) exhibit an infinite copper fluoride amine chain, while the anionic moieties act as 'decoration' to the chain. [Cu(C3H4N2)(4)][MoO2F4] (3) and [Cu(C3H4N2)(4)][NbOF5] (4) form infinite 1D chains with alternating cationic and anionic units. [Cu2F2(C10H9N3)(2)][MoO2F4] (5) and [Cu2F2(C10H9N3)(2)] [NbOF4] (6) contain a dimeric copper fluoride complex, bridged through anions to form a 1D infinite chain. [Cu(C10H8N2)(2)(H2O)(2)][MoO2F4] (7) and [Cu(C10H8N2)(2)(H2O)(2)][NbOF5] (8) contain a 2D interpenetrated network formed from the copper-4,4'-bipy complex, with open channels which accommodate the oxyfluoride anions via hydrogen bond interactions.