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

Abstract

Under hydrothermal conditions in HF-containing media, the combination of early (Nb(5+), Mo(6+)) and late (Cu(2+)) 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 [MoO(2)F(4)](2-) or [NbOF(5)](2-), in an isomorphous manner, as the anionic moiety. The overall structures of theses materials reflect the influences of the organo amine ligands. [Cu(C(2)H(4)N(4))(2)][MoO(2)F(4)].H(2)O () and [Cu(C(2)H(4)N(4))(2)][NbOF(5)].H(2)O () exhibit an infinite copper fluoride amine chain, while the anionic moieties act as 'decoration' to the chain. [Cu(C(3)H(4)N(2))(4)][MoO(2)F(4)] () and [Cu(C(3)H(4)N(2))(4)][NbOF(5)] () form infinite 1D chains with alternating cationic and anionic units. [Cu(2)F(2)(C(10)H(9)N(3))(2)][MoO(2)F(4)] () and [Cu(2)F(2)(C(10)H(9)N(3))(2)] [NbOF(5)] () contain a dimeric copper fluoride complex, bridged through anions to form a 1D infinite chain. [Cu(C(10)H(8)N(2))(2)(H(2)O)(2)][MoO(2)F(4)] () and [Cu(C(10)H(8)N(2))(2)(H(2)O)(2)][NbOF(5)] () 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.