The Crystal Structures and Thermal Behaviour of the Mercury Arsenates Hg2(H2AsO4)2, Hg2As2O6 and HgAs2O6
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Matthias Weil
Abstract
Crystals of Hg2(H2AsO4 )2 , which are isotypic with the corresponding dihydrogenphosphate Hg2 (H2PO4)2 , were obtained from a concentrated arsenic acid solution. The crystal structure (P21/n, a = 6.1838(4), b = 15.0987(9), c = 4.7989(3) Å, β = 91.977(1)°, Z = 2, R = 0.045 for 1318 structure factors, 56 variables) contains a Hg22+ dumbbell with a distance d(Hg-Hg) = 2.5040( 10) Å and a symmetrical coordination of four oxygen atoms for each mercury atom. The oxygen atoms also belong to tetrahedral dihydrogenarsenate groups H2AsO4−, which stabilize the structure by hydrogen bonding. On heating Hg2(H2AsO4)2 condenses to give the mercury(I) metaarsenate Hg2As2O6. Crystals of that compound were obtained under hydrothermal conditions at 165 °C starting from elemental mercury in 60 wt% aqueous H3AsO4 . The crystal structure (P3̄1m, a = 4.8411(2), c = 7.5961(9) Å, Z = 1, R = 0.037 for 376 structure factors, 13 variables) may be represented by sheets of edge sharing [AsO6] octahedra and layers of Hg22+ dumbbells, which alternate along the c axis. The dumbbells show a distance d(Hg-Hg) = 2.5190(10) Å and are coordinated symmetrically by six oxygen atoms at a distance d(Hg-O) = 2.374(4) Å. They are positioned above and below the vacant sites of adjacent [As2O6]2− layers. On further heating Hg2As2O6 disproportionates into elemental mercury and mercury(II) metaarsenate, HgAs2O6. Single crystals of HgAs2O6 were grown via chemical vapor transport from microcrystalline HgAs2O6 with HgCl2 as transport agent, using a temperature gradient of 650 → 550 °C. HgAs2O6 (P3̄1m, a = 4.8482(2), c = 4.9789(10) Å, Z = 1, R = 0.031 for 367 structure factors, 12 variables) crystallizes in the PbSb2O6 structure type, where anionic [Sb2O6]2− layers have the same arrangement. The divalent mercury atomsohave a pseudooctahedral environment of oxygen atoms with a distance d(Hg-O) = 2.353(3) Å.
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