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 [MoO2F4]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].H2O (1) and [Cu(C2H4N4)2][NbOF5].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] [NbOF5] (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.
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