Whiteite-(MnMnMn), a new jahnsite-group mineral species from the Foote mine, North Carolina, USA, and chemical pressure effects in jahnsite-group minerals.

Whiteite-(MnMnMn), Mn2+Mn2+Mn22+Al2(PO4)(4)(OH)(2).8H(2)O, is a new whiteite-subgroup member of the jahnsite group from the Foote Lithium Company mine, Kings Mountain district, Cleveland County, North Carolina, USA. It was found in small vugs of partially oxidised pegmatite minerals on the East dump of the mine, in association with eosphorite, hureaulite, fairfieldite, mangangordonite, whiteite-(CaMnMn) and jasonsmithite. It occurs as sugary aggregates of blade-like crystals up to 0.1 mm long and as epitaxial overgrowths on whiteite-(CaMnMn). The crystals are colourless to very pale brown, with a vitreous lustre and a white streak. The blades are flattened on {001} and elongated along [010], with poor cleavage on {001}. The calculated density is 2.82 g.cm(-3). Optically it is biaxial (-) with alpha = 1.599(2), beta = 1.605(2), gamma = 1.609(2) (white light); 2V (calc.) = 78.2 degrees, having no observable dispersion or pleochroism, and with orientation X = b. Electron microprobe analyses and structure refinement gave the empirical formula (Mn0.592+Ca0.38Na0.03)(Sigma 1.00)Mn-1.00(Mn1.042+Fe0.583+Fe0.232+Zn0.16Mg0.08)(Sigma 2.09)Al-2.04(PO4)(3.89)(OH)(3.18)(H2O)(7.26). Whiteite-(MnMnMn) is monoclinic, P2/a, a = 15.024(3) angstrom, b = 6.9470(14) angstrom, c = 9.999(2) angstrom, beta = 110.71(3)degrees, V = 976.2(4) angstrom (3) and Z = 2. The crystal structure was refined using synchrotron single-crystal data to wR(obs) = 0.057 for 2014 reflections with I > 3 sigma (I). Site occupancy refinements confirm the ordering of dominant Mn in the X, M1 and M2 sites of the general jahnsite-group formula XM1(M2)(2)(M3)(2)(H2O)(8)(OH)(2)(PO4)(4). A review of published crystallochemical data for jahnsite-group minerals shows a consistent chemical pressure effect in these minerals, manifested as a contraction of the unit-cell parameter, a, as the mean size of the X and M1 site cations increases. This is analogous to negative thermal expansion, but with increasing cation size, rather than heating, inducing octahedral rotations that result in an anisotropic contraction of the unit cell.