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Azide/nitrate route; Magnetic properties; Manganese; Polyanions; Mixed valent manganese
Abstract:
Cs23Mn16O23 was synthesized via the azide/nitrate route from mixtures of Mn2O3, CsNO3, and CsN3. This manganese(II/III) mixed-valent oxide, which contains only one Mn3+ besides 15 Mn2+ cations, was studied by single-crystal X-ray diffraction and magnetic susceptibility measurements. Its crystal structure [P (1) over bar, Z = 1, a = 1114.26(2), b = 1185.53(2), c = 1205.39(2) pm, a = 70.596(1), beta = 80.377(2), gamma = 83.072(2)degrees, R-1 = 0.033] is based on a honeycomb-like arrangement of cesium atoms, providing the space for two different types of one-dimensional polyoxomanganate anions, illustrated by the syntax Cs-23[MnO2](4)[Mn3O5](4). Magnetic susceptibility measurements indicate dominant antiferromagnetic intra-chain interactions present already at ambient temperature and long range inter-chain magnetic ordering at 11 K.