A new form of NaMnAsO4.

A new form of NaMnAsO4, sodium manganese(II) orthoarsenate, has been obtained under hydro-thermal conditions, and is referred to as the β-polymorph. In contrast to the previously reported ortho-rhom-bic α-polymorph that crystallizes in the olivine-type of structure and has one manganese(II) cation in a distorted octa-hedral coordination, the current β-polymorph contains two manganese(II) cations in [5]-coordination, inter-mediate between a square-pyramid and a trigonal bipyramid. In the crystal structure of β-NaMnAsO4, four [MnO5] polyhedra are linked through vertex- and edge-sharing into finite {Mn4O16} units strung into rows parallel to [100]. These units are linked through two distinct orthoarsenate groups into a framework structure with channels propagating parallel to the manganese oxide rows. Both unique sodium cations are situated inside the channels and exhibit coordination numbers of six and seven. β-NaMnAsO4 is isotypic with one form of NaCoPO4 and with NaCuAsO4.