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

The complexes trans-[MI(2)(CNC(6)H(4)-CN-4)(2)], (M = Pd and Pt), trans-[FeI(2)L(4)] (L = CNC(6)H(4)-CN-4 and CNC(6)H(2)-Me(2)-2,6-CN-4), and [Mn(CNC(6)H(4)-CN-4)(6)][SO(3)CF(3)] were prepared. The compounds are thermally stable up to 230 degrees C or higher. The molecular structure of trans-[FeI(2)(CNC(6)H(4)-CN-4)(4)] was determined by X-ray crystallography: monoclinic, space group P2(1)/n, a = 11.570(2) Å, b = 10.1052(8) Å, c = 28.138(7) Å, 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 [PdI(2)(CNC(6)H(4)-CN-4)(2)] and [Cu(hfacac)(2)], [FeI(2)(CNC(6)H(4)-CN-4)(4)] and AgSO(3)CF(3), [FeI(2)(CNC(6)H(2)-Me(2)-2,6-CN-4)(4)] and [Rh(2)(O(2)CCF(3))(4)], and [Mn(CNC(6)H(4)-CN-4)(6)][SO(3)CF(3)] and [Rh(2)(O(2)CCF(3))(4)]. [PdI(2)(CNC(6)H(4)-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) Å, b = 13.541(1) Å, c = 22.568(5) Å, beta = 100.45(1) degrees, Z = 2, 3279 unique reflections, R = 0.037, R(w) = 0.047.