Synthesis and structural refinement of fully dehydrated fully Zn²⁺-exchanged zeolite Y (FAU), |Zn_35.5|[Si₁₂₁Al₇₁O₃₈₄]-FAU

Abstract

The single-crystal structure of |Zn_35.5|[Si₁₂₁Al₇₁O₃₈₄]-FAU per unit cell, a = 24.794(1), dehydrated at 673 K and 1 × 10⁻⁶ Torr, has been determined by single-crystal X-ray diffraction techniques in the space group $Fd\bar{3}m$ at 294(1) K. The structure was refined using all intensities to the final error indices (using the 930 reflections for which F _o > 4σ(F _o)) R ₁ = 0.0448 (based on F) and wR ₂ = 0.1545 (based on F ²). About 35.5 Zn²⁺ ions per unit cell are found at an unusually large number of crystallographic distinct positions, six. The 0.5 Zn²⁺ ion per unit cell is located at the center of double 6-ring (D6R, site I; Zn(I)-O(3) = 2.642(3) Å and O(3)-Zn(I)-O(3) = 81.23(12) and 98.77(12)°). Two different site-I′ positions (in the sodalite cavities opposite D6Rs) are occupied by 14 and 3 Zn²⁺ ions per unit cell, respectively; these Zn²⁺ ions are recessed 0.67 Å and 1.02 Å, respectively, into the sodalite cavities from their 3-oxygens plane (Zn(I′a)-O(3) = 2.094(3) Å, Zn(I′b)-O(3) = 2.23(5) Å, O(3)-Zn(I′a)-O(3) = 110.32(12)°, and O(3)-Zn(I′b)-O(3) = 100.9(30)°). Site-II′ positions (in the sodalite cavities opposite S6Rs) are occupied by 6 Zn²⁺ ions, each of which extends 0.63 Å into the sodalite cavities from their 3-oxygens plane (Zn(II′)-O(2) = 2.164(3) Å and O(2)-Zn(II′)-O(2) = 112.00(12)°). Twelve Zn²⁺ ions are found at two nonequivalent sites II (in the supercage) with occupancies of 7 and 5 ions, respectively; these Zn²⁺ ions are recessed 0.52 Å and 0.96 Å, respectively, into the supercage from their 3-oxygens plane (Zn(IIa)-O(2) = 2.138(12) Å, Zn(IIb)-O(2) = 2.28(4) Å, O(2)-Zn(IIa)-O(2) = 114.2(10)°, and O(2)-Zn(IIb)-O(2) = 103.7(25)°).