Refinement of the crystal structures of Cu6O8InCl and Cu6O8Cu2Cl by neutron powder diffraction

Hiroshi Hayakawa, Etsuo Akiba, Shuitiro Ono, Hideo Ihara, Fujio Izumi, Hajime Asano

Research output: Contribution to journalArticle

Abstract

Two titled compounds which have different structures have been synthesized by heating mixtures of hydrates of copper(II) nitrate and copper(II) chloride, or indium nitrate. Their crystal structures have been refined by the Rietveld method using neutron powder diffraction data Cu6O8InCl is a stoichiometric compound and has a murdochite - like structure (E. Dubler, 1983). The obtained crystallographic data are: space group Fm3̄m, a = 9.1555(2)angstrom, d0 = 5.69g/cm3 and Z = 4. Final S(= Rwp/R3) was 1.04. A [Cu6O8] block, a 3-dimensional network of 26-sided polyhedra, is composed of [CuO4] planes sharing oxygen atoms (Cu-O: 1.908angstrom). Another block is a network of [InO8] cubes sharing corner oxygens with the 26-sided polyhedra (In-O: 2.257 angstrom). The centers of each block are occupied by Cl and In, respectively. Oxygen (32f) and chlorine sites (4b) were found to be fully occupied. This compound has been concluded to have a ordered structure with a chemical composition of Cu6O8InCl. In Cu6O8Cu2Cl, Cl sites were found to be partly substituted by NO3-. Its crystallographic data are: space group Fm3̄m, a = 9.381(1)angstrom, d0 = 4.95g/cm3 and Z = 4. S was 1.15. The crystal structure of Cu6O8Cu2Cl is essentially the same as that of Cu6O8InCl except Cu sites corresponding to the In sites. The Cu atoms are not located at the In site (2b) in the cube, but distributed among 6 equivalent sites (24e) around the center of the oxygen cube with an occupation factor of about 0.29. A Cu atom in the cube is coordinated to 4 oxygens to form a distorted [CuO4] plane with a Cu-O distance of 1.916angstrom, and [CuO4] planes form a 3-dimensional network. Therefore, this type of compounds can be expressed as Cu6-mO8 · Cu2-nCl0.7(NO 3)0.3 where m+n are 0.4. For the sample used in this work, m was 0.1. Cu6O8Cu2Cl has a larger unit cell than Cu6O8InCl, which is explained in terms of the fact that the former contains large NO3- instead of Cl-.

Original languageEnglish
Pages (from-to)726-732
Number of pages7
JournalJournal of the Ceramic Society of Japan. International ed.
Volume101
Issue number7
Publication statusPublished - Jul 1 1993

All Science Journal Classification (ASJC) codes

  • Engineering(all)

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