A new naturally-occurring nanoporous copper sheet–silicate with 6482 cages related to synthetic “CuSH” phases

Abstract

The structure of a new naturally-occurring nanoporous copper silicate of formula Na{sub 2}CaCu{sub 2}Si{sub 8}O{sub 20}·H{sub 2}O (disodium calcium dicopper octasilicate monohydrate) is reported and its relations to synthetic nanoporous “CuSH” compounds are discussed. The new phase is monoclinic C2/m with unit cell parameters a=12.2439(6) A, b=15.7514(4) A, c=10.6008(3) A, β=125.623(2)°, and V=1661.87(10) A{sup 3} (Z=4). The structure has been refined to R{sub 1}(all)=0.033, wR{sub 2}(all)=0.071, and GoF=1.090. In the double-sheet of SiO{sub 4} tetrahedra, 6{sup 4}8{sup 2} cages connect to form a chequer-board motif within which Na atoms and H{sub 2}O groups occupy channels. Each cage is occupied by 7-coordinated Na atom lying in a mirror plane. An intra-sheet corridor between the 6{sup 4}8{sup 2} cages is occupied by Na in 8-fold cuboidal coordination. The silicate skeleton is highly porous, with obvious channels and pathways for ion migration. The interlayer between double-sheets is occupied by CaO{sub 8}, CuO{sub 5} and NaO{sub 5}(H{sub 2}O) polyhedra. CuO{sub 5} polyhedra occur as rows of edge-sharing Cu{sub 2}O{sub 9} pairs connected by NaO{sub 5}(H{sub 2}O) octahedra and CaO{sub 8} square antiprisms. Both CuO{sub 5} and NaO{sub 5}(H{sub 2}O) polyhedra are features shared with closely-related synthetic “CuSH” phases of interest to the solid-state chemistrymore » community as potential nanoporous catalysts. However, Na{sub 2}CaCu{sub 2}Si{sub 8}O{sub 20}·H{sub 2}O is the only natural representative of this group of structures, and the only one to contain essential Ca. The discovery of Na{sub 2}CaCu{sub 2}Si{sub 8}O{sub 20}·H{sub 2}O points to a new group of CuSH-type phases containing alkaline-earth elements. Its close natural association and structural affinity with wesselsite SrCuSi{sub 4}O{sub 10} suggest the possibility of transformation between CuSH and gillespite-type phases, and thereby a route to synthesising alkaline-earth CuSH derivatives, so widening their potential as nanoporous catalysts. - Graphical abstract: Projection onto (010) of the structure of the natural nanoporous sheet silicate Na{sub 2}CaCu{sub 2}Si{sub 8}O{sub 20}·H{sub 2}O showing the double sheet of corner-linked SiO{sub 4} tetrahedra, intralayer Na and interlayer Na, Ca Cu and H{sub 2}O. Small green sphere Cu, large blue spheres Ca, orange purple and yellow small spheres Na, large grey sphere H{sub 2}O molecules. Bonds from inter/intralayer species to sheets have been omitted for clarity. - Highlights: • A new naturally-occurring nanoporous Cu sheet–silicate containing 6{sup 4}8{sup 2} cages. • A bridge between synthetic nanoporous CuSH phases and gillespite-type.« less