New Microporous Copper Diphosphate Chloride in a Series of Homeotypic Compounds: Hydrothermal Synthesis, Crystal Structure, and Crystal Chemistry

Single crystals of the new zeolite-like copper diphosphate chloride |(NH 4 ) 5 (H 2 O) 9 CaVCl 3 (OH)| [(Cu 6 (P 2 O 7 ) 4 Cl 3 ] were prepared by the hydrothermal synthesis route. The crystal structure of the new compound was studied by X-ray diffraction using synchrotron radiation (λ = 0.64066 Å) at T = 100 К ( R = 0.052): a = 17.9357(5) Å, c = 13.5377(4) Å, sp. gr. I 4/ mcm , Z = 4, ρ calc = 2.541 g/cm 3 . A copper tetramer is the main structural unit, which is formed by four CuO 4 Cl pyramids sharing a vertex occupied by a Cl atom. The clusters of the composition Cu 4 O 12 Cl are connected through diphosphate groups and additional Cu-centered polyhedra to form a mixed-type open framework. Large channels in the framework are occupied by , V 4+ , and Ca 2+ cations, (OH) – and Cl – anions, and H 2 O molecules. Similar complex ionic inclusions are characteristic of a series of homeotypic copper diphosphate chlorides exhibiting ion-exchange properties.