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The hydrothermal reactions of α-K4SiW12O40 with NiCl2·6H2O yielded two unprecedented silicotungstates containing a triangular inorganic Ni6 core. Furthermore, Na2[Ni6(μ3-OH)3(H2O)9SiW9O34]2·17H2O (1) presents a rare dimer, in which two SiW9 units sandwich double Ni6 cores by W–O–Ni linking instead of conventional Ni–O–Ni.
![Graphical abstract: Combination between [B-α-SiW9O34] unit and triangular inorganic Ni6 core under hydrothermal conditions: from monomer to rare dimer with malposed dodeca-nickel centers](http://hg.y866.cn/compound/lib/scimg/usr/1/C2DT32122J.jpg)
