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The successful attempt to solve the crystal structure of Co(CO3)0.5(OH) 0.11H2O (denoted CCH), based on synchrotron powder diffraction data, leads to a drastic revision of the chemical formula to Co6(CO3)2(OH)8 H2O [hexacobalt(II) bis(carbonate) octahydroxide monohydrate] and to a hexagonal cell instead of the orthorhombic cell suggested previously [Porta et al. (1992). J. Chem. Soc. Faraday Trans. 88, 311–319]. This results in a new structure-type related to malachite involving infinite chains of [CoO6] octahedra sharing edges along a short c axis, delimiting tunnels having a three-branched star section. All reports discussing cobalt hydroxycarbonates (CCH) without any structural knowledge and especially its topotactic decomposition into Co3O4 have, as a result, to be reconsidered.

A quarter of a century after its synthesis and with 200 papers based on its use, `Co(CO3)0.5(OH)0.11H2O proves to be Co6(CO3)2(OH)8H2O from synchrotron powder diffraction data