Crystal Chemistry of Zemannite-Type Structures: III. Keystoneite, the Ni2+-Analogue of Zemannite, and Ferrotellurite Discredited

Abstract

Keystoneite (IMA87–049) is a tellurite mineral from the Keystone mine, Magnolia District, Boulder County, Colorado, USA. In this paper the first full description of keystoneite is presented. Keystoneite is the Ni2+ analogue of zemannite and has the ideal zemannite-like formula of Mg0.5Ni2+Fe3+(Te4+O3)3·4H2O. The chemical composition via electron-probe micro-analysis (in wt.%; standard deviations in brackets) is Na2O 0.3 (0.2), K2O 0.1 (0.0), MgO 4.3 (0.3), Mn2O3 1.1 (0.7), Fe2O3 5.1 (1.2), NiO 12.7 (1.7), and TeO2 65.5 (0.7). H2O was determined by TGA analysis, giving 15(3) wt.% H2O, however, H2O from the structural determination gave 10.0 wt.%, the latter giving an analytical total of 99.1 wt.%. Keystoneite crystallizes in the non-centrosymmetric space group P63. The six strongest observed powder-diffraction lines [d,Å(I)(hkl)] are 8.12(90)(100), 4.05(80)(200), 2.952(50)(112), 2.838(50)(121,211), 2.774(100)(202), and 1.720(60)(204). The unit-cell parameters determined from single-crystal X-ray diffraction are a = 9.3667(5) Å, c = 7.6173(3) Å, V = 578.77(6) Å3, and Z = 2. Keystoneite was first identified from a specimen of “ferrotellurite”, a mineral with the reported formula Fe2+Te6+O4. The discreditation of “ferrotellurite” has been accepted by the IMA-CNMNC, Proposal 19-G, as no material corresponding to a phase remotely similar to Fe2+Te6+O4 was found on any historical samples labelled as containing “ferrotellurite”.