Using CuCl vapor to ion exchange copper into zeolite Na-Y. Single crystal structure of |Cu30Na30Cl9|[Si121Al71O384]-FAU containing Cu16Cl721+, Cu4Cl7+, Cu3Cl2+, and Cu2+

A single crystal of zeolite Na-Y (FAU, Si/Al = 1.69) was treated with 1.6 Pa of anhydrous CuCl vapor at 623 K to yield Cu30Na30Cl9-Y, in more detail vertical bar Na30+Cu22+(Cu16Cl721+)(0 44)(Cu4Cl7+)(3.2)(Cu3Cl2+)(2.8)vertical bar[Si121Al71O384]-FAU. Its structure was determined crystallographically with synchrotron X-radiation and was refined in the space group Fd (3) over barm (a = 24.644(1) angstrom) with all 1159 unique data; the final error index, R-1 = 0.064, was calculated using only the 1028 reflections with F-o > 4 sigma(F-o). About 58% of the Na+ ions in the zeolite were replaced by Cu2+, Cu3Cl2+, Cu4Cl7+, and Cu16Cl721+center dot Cu4Cl7+ clusters center 41% of the sodalite cavities. Each is a centered tetrahedron with Cu-Cl = 2.931(3) angstrom; each terminal Cu2+ ion bonds to three framework oxygen atoms of one ring of a double 6-ring with Cu-O = 2.222(4) angstrom and O-Cu-O = 110.8(5)degrees. Cu16Cl721+ clusters center 5.5% of the supercages. Four Cu+ ions coordinate tetrahedrally to the chloride ion at its center (Cu-Cl = 2.66(11) angstrom). Each pair of these Cu+ ions is bridged by a Cl- ion (Cu-Cl= 3.03(7) angstrom) along each tetrahedral edge. Each of these Cl- ions then coordinates to two Cu2+ ions (Cu-Cl = 2.58(7) angstrom), each of which bonds to two 12-ring oxygen atoms (Cu-O = 2.35(3) and 2.41(4) angstrom with O-Cu-O = 67.8(8)degrees). About 17.5% of the 12-rings are centered by near trigonal planar Cu3Cl2+ clusters (Cl- at the center, Cu-Cl-Cu = 117.2(3)degrees, and Cu-O = 2.52(4) angstrom). The single 6-rings are fully occupied by the remaining 2.0(5) Cu2+ ions (Cu-O = 2.158(7) angstrom) and the 30.0(5) Na+ ions (Na-O = 2.297(4) angstrom) per unit cell. Most of the Cu+ and Cu2+ ions in this material are accessible to guest molecules via the 12-ring channel system. (C) 2013 Elsevier Inc. All rights reserved.