Abstract

We report the crystal structures of four synthetic members of the variscite group (space group type Pbca) and of bonacinaite, the first naturally occurring scandium arsenate member of the metavariscite group. All structures were determined using single-crystal X-ray intensity data. The following members were all synthesised under either mild hydrothermal conditions or by wet-chemical methods (<90°C). CrAsO4⋅2H2O (deep green): a = 8.894(2), b = 9.946(2), c = 10.206(2) Å and V = 902.8(3) Å3; R1 = 2.14%. Tl3+PO4⋅2H2O (colourless): a = 10.2848(7), b = 8.8578(6), c = 10.3637(7) Å and V = 944.14(11) Å3 (data at –173°C); R1 = 2.56%. MnSeO4⋅2H2O (pale pink): a = 10.441(2), b = 9.2410(18), c = 10.552(2) Å and V = 1018.1(3) Å3; R1 = 2.19%. A different method of preparation of MnSeO4⋅2H2O yielded crystals with very similar unit-cell parameters, a = 10.4353(5), b = 9.2420(5) and c = 10.5349(6) Å; R1 = 2.25%. CdSeO4⋅2H2O (colourless) has a = 10.481(1), b = 9.416(1), c = 10.755(1) Å and V = 1061.4(2) Å3; R1 = 1.53%. The thermal behaviour of the two selenate members was studied by a combination of DSC and TG, supplemented by PXRD. Bonacinaite (IMA2018-056), metavariscite-type natural (Sc,Al)(As,P)O4⋅2H2O (ideally ScAsO4⋅2H2O), crystallises in the space group P21/n, with a = 5.533(1), b = 10.409(2), c = 9.036(2) Å, β = 91.94(3)° and V = 520.11(18) Å3; R1 = 3.66%. The structural formula, supported by chemical analysis, is (Sc0.807(1)Al0.193)(As0.767(7)P0.233)O4⋅2H2O. All structures are based on frameworks built by corner-sharing of TO4 tetrahedra (T = P5+, As5+ or Se6+) with MO4(H2O)2 (M = Mn2+, Cd2+, Cr3+, Sc3+ or Tl3+) octahedra. The flexible frameworks are reinforced by partly bifurcated, strong to weak hydrogen bonds.

The crystal chemistry of all known synthetic and natural members of the variscite and metavariscite groups is discussed and compared, and the relative stabilities are evaluated. With the aid of the COMPSTRU program (Bilbao Crystallographic Server), a quantitative comparison of the crystal structures in both groups is given. Calculations of the structural and topological complexity reveal that the metavariscite structure type is structurally and topologically simpler than that of variscite. It is suggested that metavariscite and phosphosiderite are metastable kinetically stabilised phases, in contrast to thermodynamically stable variscite and strengite, respectively. The 3D frameworks of the members of both groups have been shown to be potential electrode materials for rechargeable Li ion batteries.

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