Structural Investigations and Thermal Behaviour of Mercury(II) Sulfito Complexes

The crystal structures of (NH4)[HgSO3Cl] (1) and of (NH4)2[Hg(SO3)2] (2) were determined from single crystal diffractometer data sets. 1: 22 °C, Pnma, Z = 4, a = 15.430(3), b = 5.525(1), c = 6.679(1) A, R(F) = 0.0256, Rw(F2) = 0.0642 (all 1056 unique reflections). 2: −108 °C, P212121, Z = 4, a = 6.2240(4), b = 9.3908(6), c = 13.6110(8) A, R(F) = 0.0179, Rw(F2) = 0.0493 (all 2699 unique reflections). The structure of 1 contains bent Cl-Hg-SO3 entities (site symmetry m; d(Hg-Cl) = 2.3403(13) A, d(Hg-S) = 2.3636(12) A, ∠(Cl-Hg-S) = 164.51(5)°, d(S-O) 2×1.458(3) A, 1.468(4) A, = 1.461A) linked to undulated ribbons parallel to the b-axis by intermolecular secondary bonds SO···Hg (d(O···Hg) = 2×2.595(3) A). These ribbons in turn aggregate to layers around the bc-plane. The layers are stacked along the a-axis with interlayer distances of a/2. The structure of 2 is made up of O3S-Hg-SO3 moieties (d(Hg-S) = 2.3935(7), 2.3935(8) A; ∠(Hg-S-Hg) = 174.41(3)°; = 1.474A), that are linked to ribbons parallel to the a axis by coordination of Hg to three remote O atoms (2.801(4) < d(Hg-O) < 2.844(3) A). Adjacent ribbons are joined together by an additional Hg-O contact of 2.733(3) A, leading to a three-dimensional anionic framework. Both crystal structures are stabilised by disordered NH4+ cations, placed between the anionic layers or in the vacancies of the framework, via moderate hydrogen bonding interactions N-H···O with donor-acceptor distances ranging from 2.8 to 3.2A. 1 and 2 were further characterised by thermal analysis (TG, DSC). They start to decompose at temperatures above 130 °C.

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