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The tite compound, lithium penta­sodium nona­molybdate, LiNa5Mo9O30, was synthesized by solid-state reaction. The three-dimensional [Mo9O30]6- framework is built up from MoO6 octa­hedra and MoO5 bipyramids, linked together by edges and corners. The framework delimits two types of inter­secting tunnels running along [100] and [010] in which the Na+ and Li+ ions are located. The asymmetric unit contains one Mo, one Na and one Li site located on a twofold rotation axis. The crystal studied was a racemic twin with site a twin ratio of 0.51 (10):0.49 (10). Relationships between the structures of K2Mo3O10, K2Mo4O13, Cs2Mo7O22, Na6Mo10O33 and Na6Mo11O36 compounds are discussed.
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