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Free keywords:
dicyanamide; mercury; thallium; crystal structure; volume chemistry; IR spectrum; metathesis
Abstract:
Crystals of Hg2[N(CN)2]2 were grown by a slow diffusion-reaction between aqueous Hg2(NO3)2·2H2O and Na[N(CN)2]. Hg2[N(CN)2]2 adopts the triclinic space group P 1¯ (no. 2) with a = 3.7089(5), b = 6.4098(6), c = 8.150(6) Å, α = 81.575(6)°, β = 80.379(7)°, γ = 80.195(7)°, and Z = 1. Crystals of Tl[N(CN)2] were obtained from the reaction of TlBr with Ag[N(CN)2] in water. Single-crystal structure analyses evidence that Tl[N(CN)2] is isotypic to α-K[N(CN)2] and adopts the orthorhombic space group Pbcm (no. 57) with a = 8.5770(17), b = 6.4756(13), c = 7.2306(14) Å, and Z = 4. Regarding volume chemistry, the dicyanamide anion occupies ca. 44 cm3·mol−1, and so it corresponds to a large pseudohalide. The IR spectra of both compounds exhibit vibrational modes that are characteristic of the dicyanamide anion.
