Synthesis and Structural Characterization of [bpyr]₄[V₄O₄Cl₁₂] and [bpyr]₄[Bi₄Cl₁₆] grown in Ionic Liquid [bpyr][AlCl₄] (bpyr = 1-Butylpyridinium)

Abstract

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.

Cholesteryl-containing ionic liquid crystals composed of alkylimidazolium cations and different anions

“…The imidazolium tetrachloroaluminates were obtained via one step reaction among the imidazolium chloride salts and AlCl 3 in a 1:1 mol ratio. The purification of AlCl 3 and the preparation of the imidazolium tetrachloroaluminates were described earlier [38,39]. The chemical structure characterization of the synthesized materials is in good agreement with the prediction, which is performed by EA, FT-IR spectra, 1 H and 13 C NMR spectra.…”

A Series of Tetrathiafulvalene Bismuth Chlorides: Effects of Oxidation States of Cations on Structures and Electric Properties

“…The anion is based on two dimeric units [Bi 2 Cl 10 ] 3– connected by cis edges to the centrosymmetric tetramer (Figure b). Similar to the case for 1 , there are two sets of Bi–Cl bond lengths in 2 , short bonds (2.491–2.763 Å) and longer bonds (3.025–3.051 Å), in agreement with those reported . The nuclearities in 3 and 4 are further decreased to be [Bi 3 Cl 13 ] 4– and [Bi 2 Cl 10 ] 4– clusters, respectively.…”

Understanding distortions of inorganic substructures in chloridobismuthates(III)

“…Commercially available (BiO) 2 CO 3 , N,N-dimethylethane-1,2diamine, N,N,N 0 ,N 0 -tetramethylguanidine and hydrochloric acid (35-38%) were the starting materials for the syntheses of 1-4 and were used directly without further purification. Single (Mahjoor & Latturner, 2009) and (h) {[BiCl 4 ] À } n (Toma et al, 2013). crystals of all the compounds were obtained by crystallization from aqueous solutions of hydrochloric acid (ca 20%) containing (BiO) 2 CO 3 and (CH 3 ) 2 N(CH 2 ) 2 NH 2 or NHC{N-(CH 3 ) 2 } 2 .…”

“…Figure 1 Selected types of inorganic substructures of chloridobismuthates(III) with organic cations composed of basic [BiCl 6 ] 3À octahedra in a polyhedral representation (Macrae et al, 2020): (a) [BiCl 6 ] 3À (Li et al, 2020), (b) [Bi 2 Cl 11 ] 5À (Jakubas et al, 2005), (c) [Bi 2 Cl 10 ] 4À (Wang et al, 2020), (d) {[BiCl 5 ] 2À } n (Anyfantis et al, 2020), (e) [Bi 2 Cl 9 ] 3À (Wang et al, 2019), (f) {[Bi 2 Cl 9 ] 3À } n (Mencel et al, 2019), (g) [Bi 4 Cl 16 ] 4À(Mahjoor & Latturner, 2009) and (h) {[BiCl 4 ] À } n(Toma et al, 2013).…”