A simultaneous reduction, substitution, and self-assembly reaction under hydrothermal conditions afforded the first diiodopyridine copper(I) coordination polymer.

A simultaneous reduction of copper(II) to copper(I) by pyridinecarboxylate and the substitution of carboxylato groups by iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded a new iodine-inclusion coordination polymer [CuI(C5H3NI2)*1/2I2] 1. The synthetic studies of the substitution process produced a new supramolecular compound [IC5H3NCOOH] 2 and revealed that the catalytic properties of copper ions in redox and substitution reactions under hydrothermal conditions are attractive. Crystal data for [CuI(C5H3NI2)*1/2I2]: triclinic, space group P1; cell dimensions a = 4.216(1) A, b = 11.254(2) A, c = 12.196(2) A, alpha = 80.34(3) degrees, beta = 88.44(3) degrees, gamma = 83.10(3); V = 566.2(2) A(3), Z = 2. Crystal data for [IC(5)H(3)NCOOH]: monoclinic, space group P2(1)/c; cell dimensions a = 5.041(1) A, b = 17.313(2) A, c = 8.639(1) A, beta = 95.042(2) degrees; V = 751.02(13) A(3), Z = 4.