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

“…Each one of the bismuth sites is in a distorted octahedral configuration, with three short Bi−Cl bonds (2.5−2.6 Å) and three longer Bi−Cl bonds (2.8−3.0 Å); see Table and Figure . Other compounds with face and edge sharing BiCl 6 octahedra show similar distributions of bond lengths, with the terminal Bi−Cl bonds being shorter and the bridging Bi−Cl bonds being longer. − The ClBiCl angles in the octahedra range from 81−98°. Given the only slightly distorted geometry, this is not taken as evidence for stereoactive lone pairs on the bismuth ions.…”

“…The formation of these polynuclear anions is promoted by the presence of large cations; these salts are usually made from the reaction of BiCl 3 with an organic chloride. Polymeric [BiCl 4 ] − anions in the form of infinite zigzag chains formed from edge-sharing octahedra are the most common, being found in salts with the diethylammonium cation, the ferricinium cation, the bis(ethylenedithio)tetraselenafulvalene cation, and the 1-methylimidazolium cation . Edge-sharing octahedra are also observed in the isolated dimeric units [Bi 2 Cl 10 ] 4− , in a salt with piperazinium cations .…”

Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety

“…Wrsemann and co-workers [54] [X] (X = Cl or Br) indicated that ILs could be useful media for the stabilization of unusual metal coordination environments [55]. Attempted synthesis of the BiCl 3 adduct of 1-methyl-2-imidazolethione and 1,3-dimethyl-2-imidazoletellurone led to the formation of high temperature imidazolium melts with tetrachlorobismuthate(III) anion (47) [56]. Crystal structure showed that the polymeric network of BiCl À 4 caused a parallel stacking of the imidazolium cation.…”

“…BruceÕs and SeddonÕs groups reported the first liquid crystalline [C n -MIM][MCl 4 ] 55 and 56 (M = Co (55), Ni (56), C n = alkyl chain of C n H 2n+1 , n = 12-18) [61]. Thermal stability of these compounds was found to depend on the chain length; the longer the chain, the more stable the compound.…”

Crystallographic Insights into the Behavior of Highly Acidic Metal Cations in Ionic Liquids from Reactions of Titanium Tetrachloride with [1-Butyl-3-Methylimidazolium][X] Ionic Liquids (X = Chloride, Bromide, Tetrafluoroborate)

“…This is especially clear if one looks at the published crystal structures of 1,3-dialkylimidazolium chlorometallates, an especially well-investigated subset of halometallate ILs. Many such structures are reported for divalent metal ions including Cr, Cu, − Co, ,, Fe, , Ge, Hg, Mn, Ni, , Pb, Pd, ,− Pt, Sn, , and Zn. , In addition to the well-studied [AlCl 4 ] − systems, crystal structures are known for chlorometallates of trivalent Au, , Bi, Ce, , Dy, Er, , Eu, , Fe, − Gd, La, , Nd, Pr, Sb, Sc, Sm, , Y, and Yb . However, for tetravalent metal ions, the list is restricted to just Ge, Ir, Pt, Sn, Ti, − U, V, and Zr, ,,− for pentavalent ions only Np, and Nb, , and for hexavalent ions only U and Mo. , This may reflect how the weakly coordinating ions found in many commonly used ILs cannot dissolve salts of highly charged ions.…”