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Evaporative co-crystallization of MCl (M = Na, K, Rb, Cs) with BiOCl in aqueous HCl produces double salts: MxBiyCl(x+3y)·zH2O. The sodium salt, Na2BiCl5·5H2O (monoclinic P21/c, a = 8.6983(7) Å, b = 21.7779(17) Å, c = 7.1831(6) Å, β = 103.0540(10)°, V = 1325.54(19) Å3, Z = 4) is composed of zigzag chains of μ2-Cl-cis-linked (BiCl5)n2n– chains. Edge-sharing chains of NaCln(OH2)6−n octahedra (n = 0,...
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