New thallium iodates—Synthesis, characterization, and calculations of Tl(IO 3) 3 and Tl 4(IO 3) 6, [Tl +3Tl 3+(IO 3) 6

Abstract

Two new thallium iodates have been synthesized, Tl(IO 3) 3 and Tl 4(IO 3) 6 [Tl + 3Tl 3+(IO 3) 6], and characterized by single-crystal X-ray diffraction. Both materials were synthesized as phase-pure compounds through hydrothermal techniques using Tl 2CO 3 and HIO 3 as reagents. The materials crystallize in space groups R-3 (Tl(IO 3) 3) and P-1 (Tl 4(IO 3) 6). Although lone-pairs are observed for both I 5+ and Tl +, electronic structure calculations indicate the lone-pair on I 5+ is stereo-active, whereas the lone-pair on Tl + is inert.