Network Motifs and Thermal Properties of Copper(I) Halide and Pseudohalide Coordination Polymers with 1, 7‐ and 4, 7‐Phenanthroline

The coordination polymers [CuBr(1, 7‐phen‐κN7)] (1a), [CuI(1, 7‐phen)] (2a) and [(CuI)2(1, 7‐phen‐κN7)] (2b) may be prepared by treatment of the appropriate copper(I) halide with 1, 7‐phenanthroline (1, 7‐phen) in acetonitrile. 1a exhibits staircase CuBr double chains, 2a novel quadruple CuI chains. Their thermal properties were investigated by DTA‐TG and temperature resolved powder X‐ray diffraction. On heating, both 1:1 compounds decompose to 2:1 polymers and then finally to CuBr or CuI. With 4, 7‐phenanthroline (4, 7‐phen), CuBr affords both 1:1 and 2:1 complexes (5a, 5b), CuI 1:1 , 2:1 and 3:1 complexes(6a, 6b, 6c) in acetonitrile at 20 °C. 5a and 6a display lamellar coordination networks, with the former containing zigzag CuBr single chains, the latter 4‐membered (CuI)2 rings. A second 2:1 complex [(CuI)2(4, 7‐phen‐μ‐N4, N7)] (6b′) with staircase CuI double chains can be obtained by reacting CuI with 4, 7‐phen in a sealed glass tube at 110 °C. Both 5a and 6a exhibit thermal decomposition pathways of the general type 1:1 → 2:1 → 3:1 → CuX, and novel CuX triple chains are proposed for the isostructural 3:1 polymers 5c and 6c. X‐ray structures are reported for complexes 1a, 2b, [(CuCN)3(CH3CN)(1, 7‐phen‐μ‐N1, N7)] (3c·CH3CN), [CuSCN(1, 7‐phen‐κN7)] (4a), 5a, 6a and [CuCN(4, 7‐phen‐μ‐N4, N7)] (7a).