Synthesis and structure of mixed chloride-tetrachloroaluminate salts

Two mixed chloride-tetrachloroaluminate salts of simple ammonium cations, [NH₃(CH₂Ph)]₄Cl[AlCl₄]₃ 1 and [NH₃(C₆H₁₁)]₂Cl[AlCl₄] 2 have been prepared, crystallized from hydrocarbon solution, and 2 has been characterized via single-crystal X-ray crystallography. The salts melt at 109-112 and 107-108 °C, respectively, however the structures are significant in the general context of interionic attractions in ambient-temperature chloroaluminate melts, particularly the basic variety, and are discussed in such a context. Salt 2 exhibits N-H ⋯ Cl^- hydrogen bonding [d_{N ⋯ Cl} range 3.134(10)-3.203(9) Å] leading to a cationic polymer. Comparisons are made between the structure of 2 and that of 1, which was communicated earlier.