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pp.28-34
The structure of a carbon monoxide sorption complex of dehydrated fully Ca2+-exchanged zeolite X, |Ca46(CO)27|[Si100Al92O384]-FAU, has been determined in the cubic space group Fd 3 at 21℃ (a = 24.970(4) ) by single-crystal X-ray diffraction techniques. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Ca(NO3)2 for three days, followed by dehydration at 400℃ and 2×10-6 Torr for two days, and exposure to 100 Torr of zeolitically dry carbon monoxide gas at 21℃. The structure was determined in this atmosphere and was refined, using the 356 reflections for which Fo 〉 4Σ(Fo), to the final error indices R1 = 0.059 and wR2 = 0.087. In this structure, Ca2+ ions occupy three crystallographic sites. Sixteen Ca2+ ions fill the octahedral site I at the centers of hexagonal prisms (Ca-O = 2.415(7) a). The remaining 30 Ca2+ ions are found at two nonequivalent sites II (in the supercages) with occupancies of 3 and 27 ions. Each of these Ca2+ ions coordinates to three framework oxygens, either at 2.276(10) or 2.298(8) a, respectively. Twenty-seven carbon monoxide molecules have been sorbed per unit cell, three per supercage. Each coordinates to one of the latter 16 site-II Ca2+ ions: C-Ca = 2.72(8) a. The imprecisely determined N-C bond length, 1.26(14) a, differs insignificantly from that in carbon monoxide(g), 1.13 a.
