Arizona porphyry copper/hydrothermal deposits II: crystal structure of ajoite, (K + Na)3Cu20Al3Si29O76(OH)16*~8H2O.

A crystal from the type locality Ajo, AZ, yielded just enough intensity from streaked diffractions using synchrotron x-rays at the Advanced Photon Source to solve the crystal structure with composition (K + Na)3Cu20Al3Si29O76(OH)16* approximately 8H2O; triclinic, P1, a = 13.634(5) A, b = 13.687(7), c = 14.522(7), alpha = 110.83(1) degrees, beta = 107.21(1), gamma = 105.68(1); refined to a final R = 12.5%. Electron microprobe analysis yielded a similar chemical composition that is slightly different from the combined chemical and electron microprobe analyses in the literature. The ajoite structure can be described as a zeolitic octahedral-tetrahedral framework that combines the alternate stacking of edge-sharing octahedral CuO6 layers and curved aluminosilicate layers and strings. Channels bounded by elliptical 12-rings and circular 8-rings of tetrahedra contain (K and Na) ions and water. The Al atoms occupy some of the Si tetrahedral sites. Each Cu atom has near-planar bonds to four oxygen atoms plus two longer distances that generate a distorted octahedron. Valence bond estimates indicate that 8 oxygen atoms of 46 are hydroxyl. Only one alkali atom was located in distorted octahedral coordination, and electron microprobe analyses indicate K and Na as major substituents. The water from chemical analysis presumably occurs as disordered molecules of zeolitic type not giving electron density from diffraction. The high R factor results from structural disorder and many weak intensities close to detection level. The crystal chemistry is compared with shattuckite, Cu5(SiO3)4(OH)2, and planchéite, Cu8Si8O22(OH)4.H2O, both found in oxidized copper deposits of Arizona but only the former directly with ajoite.