Three-dimensional Copper(I) Halide Based Coordination Networks with Asymmetrically Substituted Bridging N-Donor Ligands

Abstract

The discrete complex [(Cul)2 (pyzCN)4] (1) and the coordination polymers ^ [CuI(pyzCN)] (2) and 3 [(CuX)3 (pyzCN)2] (3, 4; X = Br, Cl) may be prepared from the respective copper(I) halide CuX and 2-cyanopyrazine (pyzCN) by self-assembly in acetonitrile solution at 100-120°C. Whereas 2 exhibits 1 [Cul] staircase double chains as its characteristic substructure, the three-dimensional netwo'rks of 3 and 4 contain single zigzag CuX strings. The influence of the copper(I) halide on both the connectivity pattern and the dimensionality of a resulting coordination network is particularly apparent for the 1:1 complexes ^ [CuI(pymMe)] (5), 3 [(CuBr)3(pymMe)_3] (6) and ^ [CuCl(pymMe)] (7), which were generated by reaction of öaX with 4-methylpyrimidine (pymMe) under reaction conditions similar to those above.

Di-μ-iodo-bis[(3-cyanopyridine-κN)copper(I)]

“…This centrosymmetric compound has a structure similar to that of the 3-cyanopyrazine adduct, with the Cu I atom in a tetrahedral N 2 I 2 Cu geometry. The structure of the 3-cyanopyrazine adduct has been described in detail (Rossenbeck & Sheldrick, 1999).…”

Deliberate combination of coordination polymers and hydrogen bonds in a supramolecular design strategy for inorganic/organic hybrid networks

“…7 Copper(I) complexes with monodentate ligands, (CuXL) ∞ (where L is a pyridine derivative and X is a halide), are known to form robust halogen-bridged 1-D step, stair or chain structures, 8 and several 2-D coordination polymers based on 'pre-formed' 1-D copper(I) iodide chains and cross-linking bidentate ligands have recently been reported. [9][10][11] In order to change network strength and flexibility without making significant changes to the topology of the structure, we have replaced the bidentate bridging ligand (e.g. pyrazine or 4,4A-bipyridine) with a supramolecular linker capable of simultaneous metal coordination and self-complementary hydrogen bonding.…”

Non-centrosymmetric CuSCN Based Coordination Polymers with Substituted Pyrazine and Pyrimidine Ligands

“…1. The Einer Coordination of the sterically more accessible nitrogen atom N4 has also been reported for [(CuI) 2 (2 NCpyz) 4 ] and 1 I [(CuI) 2 (2 NCpyz) 2 ] [10]. It is interesting to note that individual (CuI) 2 rings of the 1 I [(CuI) 2 ] stairlike double chains in the latter polymer contain crystallographic centres of symmetry leading, thereby, to opposite orientations of the 2-cyano substituents in the flanking 2 NCpyz ligands.…”