Sequence of Structural and Magnetic Phase Transitions in (NO)Mn₆(NO₃)₁₃

Abstract

New nitrosonium manganese(II) nitrate, (NO)Mn6(NO3)13, has been synthesized and structurally characterized. In the temperature range of 45–298 K, the crystal is hexagonal (centrosymmetric sp. gr. P63/m). Mn2+ ions are assembled into tubes along axis c with both NO3 – filling and coating. The nitrosonium cation is located in the framework cavity and is disordered by a 3-fold axis. At the temperature T S1 = 190 K, a structural phase transition related to the libration of the intertube NO3 group and a small variation of Mn polyhedron is observed. Moreover, the anomalies in physical properties of (NO)Mn6(NO3)13 allow suggesting that ordering of NO+ units occurs at low temperatures. The antiferromagnetic ordering in this compound is preceded by the formation of a short-range correlation regime at about 25 K and takes place in two steps at T N1 = 12.0 K and T N2 = 8.4 K.