The Crystal Structure of Malhmoodite from Custer, South Dakota, USA

An occurrence of malhmoodite, Fe2+Zr(PO4)2·4H2O, from the Scott's Rose Quartz mine, Custer County, South Dakota, USA, has been identified. It occurs as divergent groups of yellowish, flat-lying platy crystals on football-size masses of altered löllingite with scorodite, parasymplesite, karibibite, schneiderhöhnite, kahlerite, and zircon. An electron probe microanalysis of malhmoodite yielded an empirical formula (based on 12 O apfu) of Fe1.06(Zr1.10Hf0.03)Σ1.13[(P0.93As0.01)Σ0.94O4]2·4H2O. Single-crystal X-ray structure analysis shows that malhmoodite is the Fe-analogue of zigrasite, MgZr(PO4)2·4H2O. Malhmoodite is triclinic with space group P and unit-cell parameters a = 5.31200(10), b = 9.3419(3), c = 9.7062(3) Å, α = 97.6111(13), β = 91.9796(11), γ = 90.3628(12)°, V = 477.10(2) Å3, Z = 2, in contrast to the previously reported monoclinic symmetry with space group P21/c and unit-cell parameters a = 9.12(2), b = 5.42(1), c = 19.17(2) Å, β = 94.8(1)°, V = 944.26 Å3, Z = 4. The crystal structure of malhmoodite is characterized by sheets composed of ZrO6 octahedra sharing all vertices with PO4 tetrahedra. These sheets are parallel to (001) and are joined together by the FeO2(H2O)4 octahedra. The structure determination of malhmoodite, along with that of zigrasite, warrants a re-investigation of synthetic compounds M2+Zr(PO4)2·4H2O (M = Mn, Ni, Co, Cu, or Zn) that have been assumed previously to be monoclinic.