Transition Metal Complexes of Cyanoisocyanoarenes as Building Blocks for One-, Two-, and Three-Dimensional Molecular Solids

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Abstract
The complexes trans-[MI2(CNC6H4-CN-4)2], (M = Pd and Pt), trans-[FeI2L4] (L = CNC6H4-CN-4 and CNC6H2-Me2-2,6-CN-4), and [Mn(CNC6H4-CN-4)6][SO3CF3] were prepared. The compounds are thermally stable up to 230 °C or higher. The molecular structure of trans-[FeI2(CNC6H4-CN-4)4] was determined by X-ray crystallography: monoclinic, space group P21/n, a = 11.570(2) Å, b = 10.1052(8) Å, c = 28.138(7) Å, β = 92.034(9)°, Z = 4, 3464 unique reflections, R = 0.074, Rw = 0.089. The complexes contain the peripheral cyano groups in linear, planar, and octahedral dispositions, respectively. Solids were obtained by combining solutions of [PdI2(CNC6H4-CN-4)2] and [Cu(hfacac)2], [FeI2(CNC6H4-CN-4)4] and AgSO3CF3, [FeI2(CNC6H2-Me2-2,6-CN-4)4] and [Rh2(O2CCF3)4], and [Mn(CNC6H4-CN-4)6][SO3CF3] and [Rh2(O2CCF3)4]. [PdI2(CNC6H4-CN-4)2] and [Cu(hfacac)2] in a ratio of 1:2 form a crystalline, one-dimensional solid: monoclinic, space group P21/c, a = 8.317(2) Å, b = 13.541(1) Å, c = 22.568(5) Å, β = 100.45(1)°, Z = 2, 3279 unique reflections, R = 0.037, Rw = 0.047.