Two polymorphs of (anilinium)(18-crown-6)[Ni(dmit)2]:: Structure and magnetic properties

Two polymorphs of monovalent [Ni(dmit)(2)](-) (dmit(2-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dMit)(2)], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)(2)](-) molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dMit)(2)], whose magnetism had been well fitted by spin ladder equation with the spin gap of Delta = 190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dMit)(2)](-) dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dMit)(2)]-arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K. (C) 2002 Elsevier Science (USA).