Mercury Cyanamide / Carbodiimide Networks: Synthesis and Crystal Structures of Hg2(NCN)Cl2 and Hg3(NCN)2Cl2
2014
Liu, Xiaohui | Dronskowski, Richard
We report about the synthesis and crystal structure determination of Hg₂(NCN)Cl₂ (P2₁/c (No. 14), Z = 4, a = 806.7(1), b = 907.1(2), c = 788.0(1) pm, β = 106.446(3)°, 1374 independent reflections, 67 variables, R₁ = 0.0463) and Hg₃(NCN)₂Cl₂ (Pca2₁ (No. 29), Z = 4, a = 702.0(2), b = 1078.5(2), c = 1050.3(2) pm, 1977 independent reflections, 71 variables, R₁ = 0.0380). Both compounds contain infinite -Hg-NCN-Hg- zigzag chains which are linked by additional Hg atoms to result in two-dimensional frameworks characterized by 20-membered rings sharing edges. The remarkably flexible structural backbone [Hg₃(NCN)₂]²⁺ hosts additional Cl! anions and HgCl₂ molecules in Hg₂(NCN)Cl2 but only Cl⁻ anions in Hg₃(NCN)₂Cl₂, by that reaching a high packing efficiency in both cases.While Hg₂(NCN)Cl₂ exclusively contains carbodiimide N=C=N²⁻ species, Hg₃(NCN)₂Cl₂ is the first structural example of an inorganic network built up from both carbodiimide N=C=N²⁻ and cyanamide N-C≡N²⁻ groups.
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