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Abstract ▼ AI-Helper

The crystal structures of $Sr_{31}K_{30}-X\;(Sr_{31}K_{30}Si_{100}A1_{92}O_{384};\;a=25.169(5) {\AA}$) and $Sr_{8.5}Tl_{75}-X (Sr_{8.5}Tl_{75}Si_{100}A1_{92}O_{384};\;a=25.041(5) {\AA}$) have been determined by single-crystal X-ray diffraction techniques in the cubic space grou...

The crystal structures of $Sr_{31}K_{30}-X\;(Sr_{31}K_{30}Si_{100}A1_{92}O_{384};\;a=25.169(5) {\AA}$) and $Sr_{8.5}Tl_{75}-X (Sr_{8.5}Tl_{75}Si_{100}A1_{92}O_{384};\;a=25.041(5) {\AA}$) have been determined by single-crystal X-ray diffraction techniques in the cubic space group $\=F{d3}\;at\;21(1)^{\circ}C$. Each crystal was prepared by ion exchange in a flowing stream of aqueous $Sr(ClO_4)_2\;and\;(K\;or\;T1)NO_3$ whose mole ratio was 1 : 5 for five days. Vacuum dehydration was done at $360^{\circ}C$ for 2d. Their structures were refined to the final error indices $R_1=0.072\;and\;R_w=0.057$ with 293 reflections, and $R_1= 0.058\;and\;R_w=0.044$ with 351 reflections, for which $I>2{\sigma}(I)$, respectively. In dehydrated $Sr_{31}K_{30}-X,\;all\;Sr^{2+}$ ions and $K^+$ ions are located at five different crystallographic sites. Six-teen $Sr^{2+}$ ions per unit cell are at the centers of the double six-rings (site I), filling that position. The remaining 15 $Sr^{2+}$ ions and 17 $K^+$ ions fill site II in the supercage. These $Sr^{2+}$ and $K^+$ ions are recessed ca $0.45{\AA}\;and\;1.06{\AA}$ into the supercage, respectively, from the plane of three oxygens to which each is bound. ($Sr-O=2.45(1){\AA}\;and\;K-O=2.64(1){\AA}$) Eight $K^+$ ons occupy site III'($K-O=3.09(7){\AA}\;and\;3.11(10){\AA}$) and the remaining five $K^+$ ions occupy another site III'($K-O=2.88(7){\AA}\;and\;2.76(7){\AA}$). In $Sr_{8.5}Tl_{75}-X,\;Sr^{2+}\;and\;Tl^+$ ions also occupy five different crystallographic sites. About 8.5 $Sr^{2+}$ ions are at site I. Fifteen $Tl^+$ ions are at site I' in the sodalite cavities on threefold axes opposite double six-rings: each is $1.68{\AA}$ from the plane of its three oxygens ($T1-O=2.70(2){\AA}$). Together these fill the double six-rings. Another 32 $Tl^+$ ions fill site II opposite single six-rings in the supercage, each being $1.48{\AA}$ from the plane of three oxygens ($T1-O=2.70(1){\AA}$). About 18 $Tl^+$ ions occupy site III in the supercage ($T1-O=2.86(2){\AA}$), and the remaining 10 are found at site III' in the supercage ($T1-O=2.96(4){\AA}$).