Crystal structure of cronstedtite-6T 2, a non-MDO polytype

Abstract

The crystal structure of cronstedtite-6 T 2 was refined using a crystal from the new occurrence in Pohled, Czech Republic. The space group is P 3 1 , lattice parameters a = 5.4976(3), c = 42.601(1) A, Z = 6, composition (Fe 2+ 2.515 Fe 3+ 0.485 ) (Si 1.515 Fe 3+ 0.485 ) O 5 (OH) 4 , R obs = 4.13% for 3244 independent reflections. The separate R obs values 2.50% and 6.96% were obtained for 1033 subfamily and 2196 characteristic reflections, respectively. The structure is built of edge-sharing octahedral ( Oc ), and corner-sharing tetrahedra l ( Tet ) sheets forming the 1:1 layers by sharing apical corners of Tet sheet. There are two independent 1:1 layers, where the odd one is shifted with respect of the even one by −( a 1 + a 2 )/3 and raised by c /6 of the hexagonal cell. The sextuple multiplicity is achieved by mapping this pair of layers by 3 1 axis repeatedly to two other equivalent positions raised by c /3, 2 c /3. The polytype belongs to the subfamily (Bailey’s group) A. There are two tetrahedral and three octahedral sites per 1:1 layer ( T 1, T 2, M 1, M 2, M 3 in even layers, T 11, T 12, M 11, M 12, M 13 in odd layers), all in general positions. The M 3, M 13 octahedra are smaller than M 1, M 2, M 11, M 12, thus Oc sheets in both layers are meso-octahedral . In even layers, however, the M 2 octahedron is somewhat smaller than M 1, so the Oc sheet is “transitional” to a hetero-octahedral character. The occupancies of Si:Fe in T positions were refined to: T 1, 0.96:0.04(1); T 2, 0.63:0.37(1); T 11, 0.55:0.45(1); T 12, 0.89:0.11(1). Both rings of tetrahedra are strongly ditrigonalized, α values are +11.4(5)°, and +10.9(5)°, in even and odd layers, respectively. The Franzini type is A. Four hydrogen positions were localized in each layer (eight altogether). Three of them per layer (six altogether) are involved in hydrogen bonds linking the OH groups (donors) of the Oc sheet with basal oxygen atoms of the Tet sheet of the adjacent 1:1 layer. The structure is an example of OD structure of more than one kind of layers with a very low degree of desymmetrization. Cronstedtite-6 T 2 is a non-MDO polytype, because it contains more than one kind of layer triplets. Comparison of stacking sequences with other polytypes of the A subfamily is presented.