Formation of supramolecular hydrogen-bonding chains and networks from copper (II) halogenobenzoates with N-methylnicotinamide: Supramolecular isomerism

The self-assembly of supramolecular structures from copper (11) halogenobenzoate complexes containing N-methylnicotinamide ligand have been explored. The following compound and polymorph structures were determined by single-crystal X-ray structural analysis-the compounds [Cu(4-Fbz)(2)(mna)(2)(H2O)], [Cu(4-Clbz)(2)(mna)(2)(H2O)], [Cu(4-Brbz)(2)(mna)(2)(H2O)], two polymorphs of [Cu(2,6-Cl(2)bz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, [Cu(3,5-Cl(2)bz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, [Cu(3-Fbz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, and [Cu(3-Clbz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, two polymorphs of [Cu(3-Brbz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, [Cu(3-Ibz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, [Cu(2,5-Cl(2)bz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O, [Cu(2,3-Cl(2)bz)(2)(mna)(2)(H2O)(2)]center dot H2O, [Cu (2,6-Cl(2)bz)(2)(mna)(2)(H2O)]center dot 2H(2)O, [Cu(3,4-Cl(2)bz)(2)(mna)(2)(H2O)]center dot 2H(2)O, [Cu(3-Brbz)(2)(mna)(2)(H2O)] and [Cu (2-Fbz)(2)(mna)(2)(mu-H2O)](n), (mna = N-methylnicotinamide, 4-Fbz = 4-fluorobenzoate, 4-Clbz = 4-chlorobenzoate, 4-Brbz = 4-bromobenzoate, 3-Fbz = 3-fluorobenzoate, 3-Clbz = 3-chlorobenzoate, 3-Brbz = 3-bromobenzoate, 3-lbz = 3-iodobenzoate, 2-lbz = 2-iodobenzoate, 2,3-Cl(2)bz = 2,3-dichlorobenzoate, 2,5-Cl(2)bz = 2,5-dichlorobenzoate, 2,6-Cl(2)bz = 2,6-dichlorobenzoate, 3,4-Cl(2)bz = 3,4-dichlorobenzoate and 3,5-Cl(2)bz = 3,5-dichlorobenzoate). The compounds are monomeric complexes with a distorted octahedral or square-pyramidal coordination sphere around Cu2+ ion. The two polymorph sets of [Cu(2,6-Cl(2)bz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O and [Cu(3-Brbz)(2)(mna)(2)(H2O)(2)]center dot 2H(2)O are two examples of coordination compounds which are conformation and supramolecular isomers. The crystal structure of complex [Cu(4-Fbz)(2)(mna)(2)(H2O)] shows the phase transition in two temperatures. The compound [Cu (2-Fbz)(2)(mna)(2)(mu-H2O)In is a coordination polymer with bridging aqua ligand. The molecules of all compounds are connected by N-H center dot center dot center dot 0 and O-H center dot center dot center dot O hydrogen bonds from NHCH3 groups of N-methylnicotinamide and water molecules which create supramolecular hydrogen-bonding-coordination chains and networks. The intermolecular interactions were studied by Hirshfeld surface analysis. (C) 2019 Elsevier Ltd. All rights reserved.