Synthesis of Fully Dehydrated Partially Cs+-exchanged Zeolite Y (FAU, Si/Al = 1.56), |Cs45Na30|[Si117Al75O384]-FAU and Its Single-crystal Structure

Large single crystals of zeolite, |$Na_{75}$|[$Si_{117}Al_{75}O_{384}$]-FAU (Na-Y, Si/Al = 1.56), were synthesized from gels with composition of 3.58Si$O_2$ : 2.08NaAl$O_2$ : 7.59NaOH : 455$H_2$O : 5.06TEA : 2.23TCl. One of these, a colorless single-crystal was ion exchanged by allowing aqueous 0.02 M CsOH to flow past the crystal at 293 K for 3 days, followed by dehydration at 673 K and 1 ${\times}\;10^{-6}$ Torr for 2 days. The crystal structure of fully dehydrated partially $Cs^+$-exchanged zeolite Y, |$Cs_{45}Na_{30}$|[$Si_{117}Al_{75}O_{384}$]-FAU per unit cell (a = 24.9080(10) $\AA$) was determined by single-crystal X-ray diffraction technique in the cubic space group Fd $\overline{3}$ m at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 877 reflections with $F_o\;>\;4{\sigma}(F_o))\;R_1$ = 0.0966 (Based on F) and $R_2\;=\;0.2641\;(Based\;on\;F^2$). About forty-five $Cs^+$ ions per unit cell are found at six different crystallographic sites. The 2 $Cs^+$ ions occupied at site I, at the centers of double 6-ring (D6Rs, Cs-O = 2.774(10) $\AA$ and O-Cs-O = 88.9(3) and 91.1(3)$^o$). Two $Cs^+$ ions are found at site I’ in the sodalite cavity; the $Cs^+$ ions were recessed 2.05 $\AA$ into the sodalite cavity from their 3-oxygen plane (Cs-O = 3.05(3) $\AA$ and O-Cs-O = 77.4(13)$^o$). Site-II’ positions (opposite single 6-rings in the sodalite cage) are occupied by 7 $Cs^+$ ions, each of which extends 2.04 $\AA$ into the sodalite cage from its 3-oxygen plane (Cs-O = 3.067(11) $\AA$ and O-Cs-O = 80.1(3)$^o$). The 26 $Cs^+$ ions are nearly three-quarters filled at site II in the supercage, being recessed 2.34 $\AA$ into the supercage (Cs-O = 3.273(8) $\AA$ and O-Cs-O = 74.3(3)$^o$). The 4 $Cs^+$ ions are found at site III deep in the supercage (Cs-O = 3.321(19) and 3.08(3) $\AA$), and 4 $Cs^+$ ions at another site III’ (Cs-O = 2.87(4) and 3.38(4) $\AA$). About 30 $Na^+$ ions per unit cell are found at one crystallographic site; The $Na^+$ ions are located at site I’ in the sodalite cavity opposite double 6-rings (Na-O = 2.578(11) $\AA$ and O-Na-O = 97.8(4)$^o$).