The crystal structure of bannisterite, a modulated, mica-like mineral species, of general composition Ca0.5(K,Na)0.5(Mn,Fe,Mg,Zn)10(Si,Al)16O38(OH)8·nH2O, has been solved and refined for specimens from Franklin Furnace, New Jersey (FF), and Broken Hill, Australia (BH). The crystals are mono-clinic in space group A2/a, with (for FF) a = 22.265(1) Å, b = 16.368(1) Å, c = 24.668(2) Å, β = 94.285(5)°; and (for BH) a = 22.286(1) Å, b = 16.386(1) Å, c = 24.575(2) Å, β = 94.355(7)°; Z = 8. Refinement with anisotropic thermal factors reached Rw = 0.034 (FF) and 0.039 (BH). Like stilpnomelane and ganophyllite, bannisterite has a modified 2:1 trioctahedral layer structure in which some of the tetrahedra are inverted towards the interlayer region and linked to inverted tetrahedra in the opposite layer. The octahedral sheet is strongly corrugated along b. The tetrahedral sheet consists of 5-, 6-, and 7-fold rings, and bond distance calculations indicate that Al is concentrated into two of the four inverted tetrahedra. The interlayer Ca, K, and H2O species are highly disordered, as indicated by anomalously large temperature factors and partial occupancies. Localized differences in the Al/Si arrangements in the inverted tetrahedra induce disorder among the interlayer cations.

Bannisterite is a modulated 2:1-type phyllosilicate having ten octahedral sites with hydroxyl groups in trans, cis and combined trans-cis configurations. Each octahedral site, depending on its proximity to the layer modulation, is exposed to a different degree of distortion. The electric field gradient at the Fe site and the site distortion are used to propose a model for the site assignment and oxidation mechanism in bannisterite. The results show that two models are compatible with the experimental results of fitting the spectrum of bannisterite. However, the model which allows for site distortion accounts better for the observed line overlap of the [6]Fe2+ sites. Accordingly, the octahedral sites with a greater degree of distortion are assigned to the [6]Fe2+ with lower electric quadrupole splitting, and the octahedral sites with lower site distortion are assigned to the [6]Fe2+ with higher electric quadrupole splitting. Moreover, the ease of oxidation decreases in the order trans > trans-cis > cis.

Chemical analyses of bannisterite from the Kamo mine, Toba City, Mie Prefecture, Japan, give Ba : Ca = 69:31–55:45, yielding the ideal formula with Ba > Ca, i.e. (Ba,Ca)(K,H3O)(Mn2+ · Mg,Fe2+)21 (Si,Al)32(O,OH)92 · nH2O, where Ba > Ca, Mn2+ > Mg, Fe2+,Si ≫ Al, and O > OH. The unit cell parameters calculated after the indexing of the X-ray powder pattern are: a = 22.95, b = 16.52, c = 25.66 Å, β = 94.2°. It occurs as dark brown veinlets cutting massive caryopilite-rhodochrosite ore, which is also cut by veinlets of manganoan chlorite (Mn/(Mg + Mn + Fe) = c. 0.30–0.39) with minor barian orthoclase (Ba/(K+ Ba) = 0.05 ∼ 0.06).