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Reaction of Dehydrated Ag$_2$Ca$_5$-A with Cesium. Crystal Structures of Fully Dehydrated Ag$_2$Ca$_5$-A and Ag$_2$Cs$_{10}$-A

  • Kim, Yang (Department of Chemistry, Pusan National University) ;
  • Song, Seong-Hwan (Department of Chemistry, Pusan National University) ;
  • Park, Jong-Yul (Department of Chemistry, Pusan National University) ;
  • Kim, Un-Sik (Department of Chemistry, Pusan National University)
  • Published : 1989.06.20

Abstract

Two crystal structures of dehydrated $Ag^+\;and\;Ca^{2+}$ exchanged zeolite A, $Ag_2Ca_$5-A, reacting with 0.01 Torr of Cs vapor at $200^{\circ}C$ for 2 hours and 0.1 Torr of Cs vapor at $250^{\circ}C$ for 48 hours, respectively, have been determined by single crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at $21(1)^{\circ}C$. The stoichiometry of first crystal was $Ag_2Ca_5$-A (a = 12.294(1)${\AA}$), indicating that Cs vapor did not react with cations in zeolite A and that of second crystal was $Ag_2Cs_{10}$-A (a = 12.166(1)${\AA}$), indicating that all $Ca^{2+}$ ions were reduced by Cs vapor and replaced by $Cs^+$ ions. Full-matrix least-squares refinements of $Ag_2Ca_5-A\;and\;Ag_2Cs_{10}$-A has converged to the final error indices, $R_1\;=\;0.041\;and\;R_2$ = 0.048 with 227 reflections, and $R_1\;=\;0.117\;an\;n\;fdd\;R_2$ = 0.120 with 167 reflections, respectively, for which I > $3{\sigma}$(I). In the structure of $Ag_2Ca_5$-A, both $Ag^+$ ions and $Ca^{2+}$ ions lie on two crystal symmetrically independent threefold axis sites on the 6-rings; $2\;Ag^+$ ions are recessed 0.33 ${\;AA}$ from the (111) planes of three O(3) oxygens and 5 $Ca^{2+}$ ions lie on the nearly center of each 6-oxygen planes. In the structure of $Ag_2Cs_{10}-A,\;Cs^+$ ions lie on the 5 different crystallographic sites. 3 $Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry. 6 $Cs^+$ ions lie on the threefold axes of unit cell: $4\;Cs^+$ ions are found deep in the large cavity and 2 $Cs^+$ ions are found in the sodalite cavity. One $Cs^+$ ion is found in the large cavity near a 4-ring.

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References

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