Crystal supramolecular motifs for [Ph4P]+ salts of [M(mnt)2]2−, [M(mnt)2]−, [{M(mnt)2}2]2−, [M(mnt)3]3− and [M(mnt)3]2− (mnt2− = maleonitriledithiolate)

摘要: The crystal structures of [Ph4P]2[M(mnt)2] (M = Zn 1, Cu 2 or Ni 3), [Ph4P][M(mnt)2] (M = Cu 4 5), [Ph4P]2[{M(mnt)2}2] (M = Co 6 Fe 7), [Ph4P]2[M(mnt)3] (M = Fe 8 Cr 10) and [Ph4P]3[Cr(mnt)3] 9 {mnt = maleonitriledithiolate, [S2C2(CN)2]2−} have been determined to investigate the packing supramolecular motifs in crystals containing [Ph4P]+ cations [M(mnt)n]z− anions. Seven different packings are described. Crystals isomorphous with 3, as 5, 7, two dimorphs were identified (orthorhombic α-8 monoclinic β-8). lattices all compounds planar (2, 4, 5) approximately (6, 7) anions contain segregated parallel stacks (canted stack axis) columns embracing cations. 3 linear sequences alternating sixfold phenyl embraces (6PE) offset-face-to-face (OFF) between cations, while 7 chains engaged translational fourfold (4PE). Where not (tetrahedral 1 octahedral 8–10), OFF interactions subsections (i.e. mnt ligands) rings) occur, a concerted motif involving four ions (1), new sandwich (α-8, This motif, Ph⋯mnt⋯Ph, occurs for one ligand per anion α-8, ligands β-8. Calculated energies reported. Weak C–H⋯S C–H⋯N hydrogen bonds occur structures, appear control details commensurability Edge-to-face (EF) rings do occur. All except (9) devoid solvent, implying an absence shape awkwardness this type. related compound [MePh3P][Ni(mnt)2] contains stacked