Crystal structure interconnections in a family of hydrated phosphate-sulfates

The phosphate-sulfate family incorporates several water-containing hypergene minerals with various structures. We determined the crystal structure of lately discovered [1] fibrous mineral arangasite, [Al2F(H2O)6(PO4)(SO4)]·3(H2O) using single-crystal synchrotron diffraction at 100 K (a =7.073(1), b=9.634(2), c=10.827(2) Å, β=79.60(1)0, P2/a, Z=2). Its crystal chemical interpretation has allowed us to reveal some interesting features in a title group of compounds. The arangasite crystal structure is dominated by chains extending in the [100] direction and built of pairs of corner-shared Al octahedra joined through bridging F atoms and P tetrahedra. They alternate in the [001] with S tetrahedra forming layers parallel to the ac plane through a system of hydrogen bonds. Along [010] the complex layers are separated by layers of H2O molecules. Hydrogen bonding serves here as the only mechanism providing linkage between the main structural fragments. The Al/ P chains are topologically identical to the chains built from Fe octahedra and P tetrahedra in the triclinic structure of destinezite, Fe2(OH)(PO4)(SO4)(H2O)6[2]. The repeating subunit of both chains consists of two octahedra and one tetrahedron sharing vertices. A main difference among the chains arises from their chemistry; Al octahedra in arangasite form pairs by sharing the F vertex of neighboring polyhedra, whereas pairs of Fe octahedra in destinezite are linked together through the oxygen vertex of an OH group. As a result, the larger size of the Fe octahedra compared to Al octahedra causes a larger c = 7.31 Å along the chain in destinezite. Additional SO4tetrahedra here are attached to these chains along their periphery through an oxygen vertex bridge with Fe octahedra. The monoclinic sanjuanite, Al2(PO4)(SO4)(OH)(H2O)9structure [3] is composed of Al/P chains, parallel to a = 6.11 Å. These chains are also built from three-member units that include corner-sharing pairs of octahedra connected by PO4tetrahedron, but they are not topologically equivalent to the chains in the arangasite and destinezite structures. Similar to arangasite, sulfate groups and H2O molecules reside between chains in the sanjuanite structure with hydrogen bonding. Thus, similar the crystal chemical formulae of sanjuanite and arangasite differ with respect to the (OH) → F substitution, which results in contrasting unit cell parameters. Note, that the unit cell volume of sanjuanite, is twice as large as arangasite.

A re-examination of churchite

In the course of a study of certain cerium minerals, a spectrogram of churchite was taken and it was noticed that the cerium lines were barely visible, whereas the yttrium lines were very strong. We therefore decided to re-investigate this species.Churchite was originally described by A. H. Church in 1865, and named by C. G. Williams in the same year. The specimens were collected by R. Talling from an unnamed locality in Cornwall. It has only been analysed once, by Church, who showed it to be a hydrated phosphate of rare-earths and lime; his quantitative data have been recalculated and included in table I. Church obtained qualitative reactions for the cerium group of rare-earths, and for cerium itself, but made no attempt to determine the ratio of cerium to yttrium earths; he assumed a mean molecular weight for the rare-earths which would correspond to R2O3 324, essentially a mixture of cerium earths with but little yttria, but did not adduce any evidence for this assumption.

Florencite, a new hydrated Phosphate of Aluminium and the Cerium Earths, from Brazil

Florencite was first discovered as a rare constituent of the cinnabar-bearing sands of Tripuhy, near Ouro Preto, Minas Geraes, Brazil. Here it occurred in well-developed crystals (up to ½ cm. in, length), in association with monazite, xenotime and the titano-anti. monates (lewisite and derbylite) previously described. Blowpipe experiments made hy Dr. W. Florence showed that the mineral was a phosphate of the cerium earths, while angular measurements of the crystals and observations of the optical characters suggested its close relationship with hamlinite, the new hydrated phosphate of aluminium, barium and strontium, recently described by Hidden and Penfield.