Hydrothermal Synthesis and a Composite Crystal Structure of Na6Cu7BiO4(PO4)4[Cl,(OH)]3 as a Candidate for Quantum Spin Liquid

Abstract

A novel sodium bismuth oxo-cuprate phosphate chloride, Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], containing square-kagomé layers of Cu2+ has been synthesized by hydrothermal techniques. The compound crystallizes in the tetragonal space group P4/nmm, a = 10.0176(4), c = 10.8545(6), Z = 2, V = 1089.3(1) Å3, R1 = 0.021, wR = 0.053, S = 1.32. Its composite crystal structure includes [O4Cu6Bi]7+ layers, which are formed by the clusters of oxygen-centered tetrahedra [OCu3Bi]. These positively charged two periodic fragments are intercalated in a negatively charged [CuNa6Cl3(PO4)4]7- matrix built by Na-centered polyhedra, PO4 tetrahedra, and CuO4Cl pyramids. The composite character of the crystal structure of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], as well as the way of its self-assembly, are discussed in close connection with the sulfohalite Na6ClF(SO4)2 salt. It is shown that the "host-guest" model of the formation of the tetragonal Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] phase is due to the group-subgroup symmetry relation with the cubic crystal structure of mineral sulfohalite and is also supported by the crystallization condition in excess sodium chloride. The magnetic subsystem of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] is represented by a dense square-kagomé network of 2Cu1 and 4Cu2 ions, decorated with weakly bonded Cu3 ions. Measurements of magnetization and heat capacity indicate the absence of long-range order up to 2 K, which makes this compound a candidate for a highly demanded spin liquid.