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

The complexes trans-[MI(2)(CNC6H4-CN-4)(2)], (M = Pd and Pt), trans-[FeI(2)L(4)] (L = CNC6H4-CN-4 and CNC6H2-Me(2)-2,6-CN-4), and [Mn(CNC6H4-CN-4)(6)][SO3CF3] were prepared. The compounds are thermally stable up to 230 degrees C or higher. The molecular structure of trans-[FeI2(CNC6H4-CN-4)(4)] was determined by X-ray crystallography: monoclinic, space group P2(1)/n, a = 11.570(2) Angstrom, b = 10.1052(8) Angstrom, c = 28.138(7) Angstrom, beta = 92.034(9)degrees, 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)], [FeI2(CNC6H4-CN-4)(4)] and AgSO3CF3, [FeI2(CNC6H2-Me(2)-2,6-CN-4)(4)] and [Rh-2(O2CCF3)(4)], and [Mn(CNC6H4-CN-4)(6)] [SO3CF3] and [Rh-2(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 P2(1)/c, a = 8.317(2) Angstrom, b = 13.541(1) Angstrom, c = 22.568(5) Angstrom, beta = 100.45(1)degrees, Z = 2, 3279 unique reflections, R = 0.037, R(w) = 0.047.