Structural, spectroscopic, and computational studies on Tl4Si5O12: a microporous thallium silicate.

Single crystals of the previously unknown thallium silicate Tl4Si5O12 have been prepared from hydrothermal crystallization of a glassy starting material at 500 °C and 1 kbar. Structure analysis resulted in the following basic crystallographic data: monoclinic symmetry, space group C2/c, a = 9.2059(5) Å, b = 11.5796(6) Å, c = 13.0963(7) Å, β = 94.534(5)°. From a structural point of view the compound can be classified as an interrupted framework silicate with Q(3)- and Q(4)-units in the ratio 2:1. Within the framework 4-, 6-, and 12-membered rings can be distinguished. The framework density of 14.4 T-atoms/1000 Å(3) is comparable with the values observed in zeolitic materials like Linde type A, for example. The thallium cations show a pronounced one-sided coordination each occupying the apex of a distorted trigonal TlO3 pyramid. Obviously, this reflects the presence of a stereochemically active 6s(2) lone pair electron. The porous structure contains channels running along [110] and [-1 1 0], respectively, where the Tl(+) cations are located for charge compensation. Structural investigations have been completed by Raman spectroscopy. The interpretation of the spectroscopic data and the allocation of the bands to certain vibrational species have been aided by DFT calculations, which were also employed to study the electronic structure of the compound.