Introducing copper ions into zeolite Y by the thallous ion exchange method: single crystal structure of |Cu21.6Tl39.2|[Si121Al71O384]–FAU

The thallous ion exchange (TIE) method was used for the first time in an attempt to introduce copper ions into zeolite Y (FAU, Si/Al = 1.69). |Cu 10.9 + Cu 10.7 2+ Tl 39.2 + |[Si 121 Al 71 O 384 ]–FAU was prepared by reacting fully dehydrated and fully Tl + -exchanged zeolite Y (Tl 71 –Y) with CuCl 2 ( g ) and its decomposition products CuCl( g ) and Cl 2 ( g ) at 673 K under anhydrous conditions. Its structure was determined using single-crystal crystallography with synchrotron X-radiation and was refined in the space group F d 3 ¯ m ( a = 24.769(1) Å) with all 903 unique data; the final error index, R 1 = 0.075, was calculated using only the 858 reflections with F o > 4σ( F o ). About 45 % of the Tl + ions were replaced by 21.6 copper ions per unit cell at the following sites (distances to nearest framework oxygen atoms are given): 10.7 Cu 2+ at site I′ in the sodalite cavity opposite double 6-rings (Cu 2+ –O = 2.093(9) Å), 3.5 Cu + at site II opposite single 6-rings in the supercage (Cu + –O = 2.24(3) Å), and 7.4 Cu + at site III near 12-rings in the supercage (Cu + –O = 2.45(7) Å). All Cu + ions are in supercages where they are easily accessible to guest molecules. The remaining ca. 39 Tl + ions per unit cell occupy three distinct positions: 12 are at a second site I′ (Tl + –O = 2.571(9) Å), 23 are at a second site II (Tl + –O = 2.732(10) Å), and 4 are at site III′ (Tl + –O = 2.871(16) Å) near triple 4-rings in the supercages.