The Crystal Structure of Manganotychite, Na₆Mn₂(CO₃)₄(SO₄), and Structural Relations in the Northupite Group

The crystal structure of manganotychite has been refined using the holotype specimen from the Alluaiv Mountain, Lovozero massif, Kola peninsula, Russia. The mineral is cubic, Fd$\overline{3}$, a = 14.0015(3) Å, V = 2744.88(18) ų, Z = 8, R₁ = 0.020 for 388 independently observed reflections. Manganotychite is isotypic to tychite and ferrotychite. Its crystal structure is based upon a three-dimensional infinite framework formed by condensation of MnO₆ octahedra and CO₃ groups by sharing common O atoms. The sulfate groups and Na⁺ cations reside in the cavities of the octahedral-triangular metal-carbonate framework. In terms of symmetry and basic construction of the octahedral-triangular framework, the crystal structure of manganotychite is identical to that of northupite, Na₃Mg(CO₃)₂Cl. The transition northupite → tychite can be described as a result of the multiatomic 2Cl⁻ → (SO₄)²⁻ substitution, where both chlorine and sulfate ions are the extra-framework constituents. However, the positions occupied by sulfate groups and chlorine ions correspond to different octahedral cavities within the skeletons of Na atoms. The crystal structure of northupite can be considered as an interpenetration of two frameworks: anionic [Mg(CO₃)₂]²⁻ octahedral-triangular framework and cationic [ClNa₃]²⁻ framework with the antipyrochlore topology. Both manganotychite and northupite structure types can be described as a modification of the crystal structure of diamond (or the dia net) via the following steps: (i) replacement of a vertex of the dia net by an M₄ tetrahedron (no symmetry reduction); (ii) attachment of (CO₃) triangles to the triangular faces of the M₄ tetrahedra (accompanied by the Fd$\overline{3}$m → Fd$\overline{3}$ symmetry reduction); (iii) filling voids of the resulting framework by Na⁺ cations (no symmetry reduction); and (iv) filling voids of the Na skeleton by either sulfate groups (in tychite-type structures) or chlorine atoms (in northupite). As a result, the information-based structural complexity of manganotychite and northupite exceeds that of the dia net.