Abstract
Sodium manganese(II) phosphate bis(hydrogenphosphate), NaMn 3(PO 4)(HPO 4) 2, has been prepared hydrothermally and its structure has been determined from single-crystal diffraction data. It crystallizes in space group C 2/ c of the monoclinic system with Z = 4 in a cell of dimensions a = 12.179(2) Å, b = 12.405(1) Å, c = 6.6602(8) Å, and β = 114.616(7)°. The structure consists of a complex network of edge-sharing Mn(II)O 6 octahedral chains that are linked together by both corner-sharing PO 4 tetrahedra and O-H···O bonds, forming channels along which Na atoms reside. The structure thus represents an unoxidized variant of the alluaudite structure type, containing Mn atoms in only the single oxidation state of + II. The structure is embellished by the presence of hydrogen bonds, evidence for which was obtained from bond-valence calculations, infrared spectroscopy, and thermal measurements which suggest the loss of one H 2O molecule per formula unit. Magnetic susceptibility measurements confirm the assignment of high-spin Mn 2+ in the title compound, as well as in its dehydrated form.
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