Abstract: | ![]() The title compound, [Te8][NbOCl4]2, was obtained as translucent black crystals by reaction of elemental tellurium, niobium(V) chloride and niobium(V) oxychloride in the ionic liquid BMImCl (BMImCl is 1‐butyl‐3‐methylimidazolium chloride). The synthesis was performed in argon‐filled glass ampoules. According to X‐ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and consists of infinite {[Te8]2+}n cations associated with pyramidal [NbOCl4]− anions. The novel catena‐octatellurium(2+) cation is composed of Te5 rings that are linked via Te3 units [Te—Te = 2.6455 (18)–2.8164 (19) Å]. The composition and purity of [Te8][NbOCl4]2 were further confirmed by energy‐dispersive X‐ray diffraction (EDX) analysis. |