A New Phase of the Octahedral Tellurium-Iodine Cluster Complex of Rhenium

cluster complex of the composition [Re 6 Te 8 (TeI 2 ) 6 ]I 2 ·[Re 6 Te 8 (TeI 2 ) 4 (TeI 3 ) 2 ]·I 2 is obtained by a reaction between [Re 6 Te 8 Te 7 ] and I 2 in a sealed quartz ampoule at 400 °C. More than three times increase in the volume of the ampoule in which the reaction is performed with maintaining the other conditions is shown to lead to the formation of the previously described cluster complex [Re 6 Te 8 (TeI 2 ) 6 ]I 2 . An increase in the synthesis temperature to 450 °C leads to the formation of X-ray amorphous products of the unknown composition. The [Re 6 Te 8 (TeI 2 ) 6 ]I 2 ·[Re 6 Te 8 (TeI 2 ) 4 (TeI 3 ) 2 ]·I 2 compound obtained at 400 °C crystallizes in the triclinic crystal system, space group P1̅ , and unit cell parameters a = 11.0859(3) Å, b = 11.9021(4) Å, c = 21.1308(7) Å, α = 79.259(2)°, β = 85.533(2)°, γ = 66.220(2)°, V = 2506.55(14) Å 3 , Z = 1. The crystal structure consists of four layers of two types that alternate along the c parameter: 1 ) the layer formed by iodine anions and [Re 6 Te 8 (TeI 2 ) 6 ] 2+ cluster cations and 2 ) the layer formed by neutral cluster complexes [Re 6 Te 8 (TeI 2 ) 4 (TeI 3 ) 2 ] and crystallization I 2 molecules. Weak interactions between the adjacent cluster complexes are observed in both layers along with I⋯I halogen bonds. The layers are linked with each other via I⋯I and Te⋯I interactions.