Redetermination and new description of the crystal structure of vanthoffite, Na6Mg(SO4)4

Acta Crystallogr E Crystallogr Commun. 2020 May 1;76(Pt 6):785-789. doi: 10.1107/S2056989020005873. eCollection 2020 Jun 1.

Abstract

The crystal structure of vanthoffite {hexa-sodium magnesium tetra-kis[sulfate-(VI)]}, Na6Mg(SO4)4, was solved in the year 1964 on a synthetic sample [Fischer & Hellner (1964 ▸). Acta Cryst. 17, 1613]. Here we report a redetermination of its crystal structure on a mineral sample with improved precision. It was refined in the space group P21/c from a crystal originating from Surtsey, Iceland. The unique Mg (site symmetry ) and the two S atoms are in usual, only slightly distorted octa-hedral and tetra-hedral coordinations, respectively. The three independent Na atoms are in a distorted octa-hedral coordination (1×) and distorted 7-coordinations inter-mediate between a 'split octa-hedron' and a penta-gonal bipyramid (2×). [MgO6] coordination polyhedra inter-change with one half of the sulfate tetra-hedra in <011> chains forming a (100) meshed layer, with dimers formed by edge-sharing [NaO7] polyhedra filling the inter-chain spaces. The other [NaO7] polyhedra are organized in a parallel layer formed by [010] and [001] chains united through edge sharing and bonds to the remaining half of sulfate groups and to [NaO6] octa-hedra. The two types of layers inter-connect through tight bonding, which explains the lack of morphological characteristics typical of layered structures.

Keywords: Na-Mg sulfate; atomic coordinations; crystal structure; redetermination; vanthoffite.