The crystal structure of stilpnomelane. Part II. The full cell

Abstract

Summary The structural formula of stilpnomelane averaged from 37 representative literature analyses and based on the determined structure is (Ca,Na,K)4(Ti0·1Al2·3Fe35·5Mn0·8Mg9·3)[Si63Al9](O,OH)216·nH2O. Ferrostilpnomelanes have up to 12 R3+ cations in the octahedral sheet, ferristilpnomelanes commonly have between 24 and 30 R3+ cations, rarely up to 37. The two groups can be distinguished by accurate X-ray powder diffraction, ferrostilpnomelanes having d001 less and a greater than have ferristilpnomelanes. The unit cell is triclinic, a = b∼21·8 Å, γ = 120°, d001∼12·2 Å, P. Hexagonal groups or ‘islands’ of 24 silicon-oxygen tetrahedra co-ordinate to the octahedral sheet, the centres of the ‘islands’ are displaced by 5a/12, 8b/12 on either side of the octahedral sheet as a result of warping of this sheet to permit articulation with the smaller tetrahedral sheet. The 24-tetrahedra ‘islands’ are linked laterally by 6-member rings of inverted tetrahedra, which in turn link at their apices to like rings connecting the next sheet of ‘islands’. Thus a single tetrahedral layer is 4 tetrahedra thick and has symmetry 6/m. The 6-member rings of tetrahedra act as hinges permitting up to 0·5 Å extension or contraction of the tetrahedral sheet to accommodate variations in the octahedral sheet dimensions with varying R2+/R3+ ratio.