Electronic interaction in an outer-sphere mixed-valence double salt:: A polarized neutron diffraction study of K3(MnO4)2

The mixed-valence double salt K-3(MnO4)(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O4](-), and "manganate", [(MnO4)-O-VI](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T= 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75+/-1% of one unpaired electron with an upper limit of 2.5%.