Ionic solids with large inorganic cluster anions have been synthesized from the reaction of oxides with a chloroaluminate ionic liquid, [bpyr][AlCl4] (bpyr = 1-butylpyridinium cation). The reaction of the AlCl4 − anion with vanadium and bismuth oxides in the presence of metal reducing agents has resulted in two new salts with anionic cluster complexes of vanadium(IV) ([bpyr]4[V4O4Cl12]) and bismuth(III) ([bpyr]4[Bi4Cl16]). The compound [bpyr]4[V4O4Cl12] crystallizes in the monoclinic space group C2/c (a = 32.771(2) Å, b = 9.4505(6) Å, c = 17.5068(11) Å, β = 106.474(1)°) and compound [bpyr]4[Bi4Cl16] crystallizes in the triclinic space group P1̅ (a = 10.9179(1) Å, b = 11.2495(2) Å, c = 13.3045(2) Å, α = 109.460(3)°, β = 94.883(3)°, γ = 101.055(3)°). These materials consist of inorganic clusters of [VOCl3]4 4−and [BiCl4]4 4−, respectively, which are separated by discrete butylpyridinium cations. The crystal structure of the neat frozen ionic liquid has also been determined, confirming the presence of AlCl4 − tetrahedral units in the compound.

Single crystals of a new reduced vanadate phase, Cs(5)FeV(5)O(13)Cl(6), have been grown from the reaction of metal oxides V(2)O(5) and Fe(2)O(3) in the presence of a metal reducing agent in a eutectic CsCl/NaCl flux. This compound adopts a tetragonal structure (P4/nmm, a = 10.943(3) A, c = 10.535(4) A, Z = 2) that consists of reduced vanadate layers separated by ionic layers comprised of [FeCl(6)](3-) anions and Cs(+) cations. There are two distinct vanadium sites in the structure of this compound; V(4+) is in square pyramidal configuration, and V(5+) has a tetrahedral coordination environment. The (51)V NMR Knight shift and the magnetic susceptibility data indicate the delocalization of the unpaired electron of vanadium. Ferrimagnetic ordering is observed at 5 K.

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Vanadium Bronze Cs5FeV5O13Cl6. -Single crystals of the title compound are prepared by reaction of V2O5 and Fe2O3 in the presence of V powder in a eutectic CsCl/ NaCl flux (silica tube, 600°C, 48 h). Cs5FeV5O13Cl6 crystallizes in the tetragonal space group P4/nmm with Z = 2 (single crystal XRD). The structure consists of reduced vanadate layers separated by ionic layers comprised of [FeCl 6 ] 3-anions and Cs + cations.