Structural studies of [Pt(CNMe)4][M(mnt)2]n {M = Pd or Pt, mnt = [S2C2(CN)2]2-, n = 1 or 2}:: structure-dependent paramagnetism of three crystal forms of [Pt(CNMe)4][Pt(mnt)2]2

The reaction of [NEt4](2)[Pt(mnt)(2)] {mnt = [S2C2(CN)(2)](2-)} with [Pt(CNMe)(4)][PF6](2) gave the diamagnetic 'stacked' salt [Pt(CNMe)(4)][Pt(mnt)(2)]. In acetonitrile, nitromethane and nitropropane solution respectively, treatment of [NEt4][Pt(mnt)(2)] with [Pt(CNMe)(4)][PF6](2) yielded three different crystal forms of the salt of 1 :2 stoichiometry: [py(NMe)(4)][pt(mnt)(2)](2) . 2MeCN, [Pt(CNMe)(4)][Pt(mnt)(2)](2) . MeNO2 and [Pt(CNMe)(4)][Pt(mnt)(2)](2). These show structure-dependent antiferromagnetism, reflecting differing arrangements of the formally platinate(III) anions [Pt(mnt)(2)](-) within the crystal lattice. The palladium salts [Pt(CNMe)(4)][Pd(mnt)(2)] and [Pt(CNMe)(4)][Pd(mnt)(2)](2) . 2MeCN are isomorphous with their platinum analogues.