Transition metal complexes of cyanoisocyanoarenes as building blocks for one-, two-, and three-dimensional molecular solids

Article abstract of DOI:10.1021/ic950580e

The complexes trans-[MI₂(CNC₆H₄-CN-4)₂]< (M = Pd and Ft), trans-[FeI₂L₄] (L = CNC₆H₄-CN-4 and CNC₆H₂-Me_2-2.6-CN-4), and [Mn(CNC₆H₄-CN-4)₆][SO₃CF ₃] 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) A?, b = 10.1052(8) A?, c = 28.138(7) A?, β= 92.034(9)°, Z = 4, 3464 unique reflections, R = 0.074, R_w = 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], [FeI₂CNC₆H₄-CN-4₄)] and AgSO₃CF₃, [FeI₂(CNC₆H₂-Me₂-2,6-CN-4) ₄] and [Rh₂(O₂CCF₃)₄], and [Mn(CNC₆H₄-CN-4)₆][SO₃CF ₃] 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) A?, b = 13.541(1) A?, c = 22.568(5) A? β= 100.45(1)°, Z = 2, 3279 unique reflections, R = 0.037, R_w = 0.047.