A family of coordination compounds: CoBr2(1,4-dioxane)2 (1), CoBr2(1,4-dioxane)2(H2O)2 (2), CoBr2(1,4-dioxane)3(H2O)4 (3) and CoBr2(1,4-dioxane)2(H2O)4 (4 (C 2/c) and 5 (I 41/a)) with different dimensions have been crystallized from a solution of CH3OH/1,4-dioxane. The solvent-mediated transformation was observed from the blue kinetically favored 2D compound 1 to the red metastable 1D compound 2, 0D compound 3, and finally to the thermodynamically stable 0D compounds 4 and 5. The hydrogen bonds played a key role in the formation of the different networks of 2–5 with the increasing of the coordinated water molecules. The magnetic measurements showed that 1 was a canted antiferromagnet, and 3–5 acted as antiferromagnets.
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