Control of Ionic Conductivity by Lithium Distribution in Cubic Oxide Argyrodites LiPSiOCl.

Argyrodite is a key structure type for ion-transporting materials. Oxide argyrodites are largely unexplored despite sulfide argyrodites being a leading family of solid-state lithium-ion conductors, in which the control of lithium distribution over a wide range of available sites strongly influences the conductivity. We present a new cubic Li-rich (>6 Li per formula unit) oxide argyrodite LiSiOCl that crystallizes with an ordered cubic (23) structure at room temperature, undergoing a transition at 473 K to a Li site disordered 4̅3 structure, consistent with the symmetry adopted by superionic sulfide argyrodites.

Element selection for crystalline inorganic solid discovery guided by unsupervised machine learning of experimentally explored chemistry.

The selection of the elements to combine delimits the possible outcomes of synthetic chemistry because it determines the range of compositions and structures, and thus properties, that can arise. For example, in the solid state, the elemental components of a phase field will determine the likelihood of finding a new crystalline material. Researchers make these choices based on their understanding of chemical structure and bonding.

LiSiOCl: A Hexagonal Argyrodite Based on Antiperovskite Layer Stacking.

A hexagonal analogue, LiSiOCl, of the cubic lithium argyrodite family of solid electrolytes is isolated by a computation-experiment approach. We show that the argyrodite structure is equivalent to the cubic antiperovskite solid electrolyte structure through anion site and vacancy ordering within a cubic stacking of two close-packed layers. Construction of models that assemble these layers with the combination of hexagonal and cubic stacking motifs, both well known in the large family of perovskite structural variants, followed by energy minimization identifies LiSiOCl as a stable candidate composition.

Expected and unexpected products of reactions of 2-hydrazinylbenzo-thia-zole with 3-nitro-benzene-sulfonyl chloride in different solvents.

The syntheses and crystal structures of 2-[2-(propan-2-yl-idene)hydrazin-yl]-1,3-benzo-thia-zol-3-ium 3-nitro-benzene-sulfonate (CHNS·CHNOS), (I), 2-[2-(3-nitro-benzene-sulfon-yl)hydrazin-yl]-1,3-benzo-thia-zole (CHNOS), (II) and 2-[2-(3-nitro-benzene-sulfon-yl)hydrazin-yl]-1,3-benzo-thia-zol-3-ium 3-nitro-benzene-sulfonate (CHNOS·CHNOS), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo-thia-zole with the acetone solvent in the presence of 3-nitro-benzene-sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N-H⋯O (s = sulfonate) hydrogen bonds; adjacent cations inter-act by way of short π-π stacking inter-actions between the thia-zole rings [centroid-centroid separation = 3.