Hydrothermal Crystal Growth and Crystal Structures of the Mercury(II) Chromates(VI) α-HgCrO4, β-HgCrO4, and HgCrO4·H2O

Abstract

Single crystals of α-HgCrO4, β -HgCrO4 and HgCrO4 ・ H2O were obtained by reacting yellow HgO in chromic acid of various concentrations under hydrothermal conditions at 200 °C (4 d). All crystal structures were solved and refined from single crystal diffractometer data sets [α-HgCrO4: P21/n, Z = 4, a = 5.5079(8), b = 8.5266(12), c = 7.3503(10) Å , β = 94.022(3)°, 955 structure factors, R[F2 > 2σ (F2)] = 0.0296; β -HgCrO4: Cmcm, Z = 4, a = 5.7187(9), b = 9.0169(14), c = 7.0114(11) Å, 361 structure factors, R[F2 > 2σ (F2)] = 0.0275; HgCrO4 ・ H2O: P1̅, Z = 2, a=5.6157(15), b =6.1115(16), c= 7.590(2) Å , α =108.850(5), β =91.666(5), γ =116.569(5)°, 1235 structure factors, R[F2 > 2σ (F2)] = 0.0316]. The previously reported structure of α-HgCrO4 has been re-determined. It contains distorted [HgO7] pentagonal bipyramids in which the short bonds are directed towards the apices. The new polymorph β -HgCrO4 adopts the CrVO4 (β -CrPO4) structure type and is composed of slightly distorted [HgO6] octahedra. The previously unknown monohydrate HgCrO4 ・ H2O crystallizes in an unique structure and is composed of one nearly regular [HgO4(H2O)2] octahedron and one considerably distorted [HgO6] octahedron. All three structures contain tetrahedral chromate anions CrO4 2− as the second building units with average Cr-O distances of ca. 1.65 Å