Ionothermal Synthesis, Structure, and Bonding of the Catena -Heteropolycation 1 ∞ [Sb 2 Se 2 ] +
AuthorsGroh, Matthias F.
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AbstractThe reaction of antimony and selenium in the Lewis-acidic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoaluminate, [BMIm]Cl•4.7AlCl3, yielded dark-red crystals of [Sb2Se2]AlCl4. The formation starts above 160 ° C; at about 190 ° C, irreversible decomposition takes place. The compound crystallizes in the triclinic space group P 1¯ with a = 919.39(2) pm, b = 1137.92(3) pm, c = 1152.30(3) pm, α = 68.047(1)° , β = 78.115(1)° , γ = 72.530(1)° , and Z = 4. The structure is similar to that of [Sb2Te2]AlCl4 but has only half the number of crystallographically independent atoms. Polycationic chains 1∞ [Sb2Se2]+ form a pseudo-hexagonal arrangement along [011¯] ], which is interlaced by tetrahedral AlCl4 - groups. The catena-heteropolycation 1∞ [Sb2Se2]+ is a sequence of three different four-membered [Sb2Se2 ] rings. The chemical bonding scheme, established from the topological analysis of the real-space bonding indicator ELI-D, includes significantly polar covalent bonding in four-member rings withinthepolycation.Theringsareconnectedintoaninfinitechainbyhomonuclear non-polar Sb-Sb bonds and highly polar Sb-Se bonds. Half of the selenium atoms are three-bonded.
CitationGroh MF, Breternitz J, Ahmed E, Isaeva A, Efimova A, et al. (2015) Ionothermal Synthesis, Structure, and Bonding of the Catena -Heteropolycation 1 ∞ [Sb 2 Se 2 ] + . Z anorg allg Chem 641: 388–393. Available: http://dx.doi.org/10.1002/zaac.201400543.
SponsorsWe thank Dr. A. I. Baranov for helpful discussions. This work was supported by the Deutsche Forschungsgemeinschaft (DFG).