Molecular structure, spectroscopic properties, and Hirshfeld surface analysis of chlorobis(N-methyl-1,3-propanediamine)copper(II) tetrafluoroborate and azidobis(2,2-dimethyl-1,3-propanediamine) copper(II) azide

Two new copper (II) complexes, [Cu(N-Metn)(2)Cl]BF4 (1) and [Cu(Me(2)tn)(2)(N-3)]N-3 (2) (N-Metn = N-methyl-1,3-propanediamine; Me(2)tn = 2,2-dimethyl-1,3-propanediamine), have been prepared, fully characterized, and their structures established by X-ray single-crystal analysis from synchrotron diffraction data. For these complexes, the Cu(II) ions are five-coordinate in an axially elongated square pyramidal environment, with the four amine N atoms at the equatorial positions and the Cl atom (1) or N atom of one azide (2) at an apical site. The Cu N bond lengths for amine N atoms in the complex I (2.0198(13)-2.0735(12) A degrees) and complex 2 (2.0239(9)-2.0489(9) angstrom) are typical, but the axial ligands are coordinated with a Cu-Cl bond length of 2.5962 (7) angstrom for complex 1, and the Cu-N (azido) bond length is 2.1990 (10) A for complex 2, adopting square-planar geometry around the Cu(II) with four N atoms from two N-Metn or Me(2)tn ligands. The crystals are stabilized by a three-dimensional network of intermolecular hydrogen bonds that are formed between the primary and secondary amine groups of the N-Metn ligands, the Cl ligands, and the F atoms of BF4- anion in 1, and by the primary amine groups of the Me(2)tn ligands and the N atoms of the azido ligand and azide ion in 2. Hirshfeld surface analysis with 2D fingerprint plots revealed that the H center dot center dot center dot H, F center dot center dot center dot H, Cl center dot center dot center dot H contacts in 1 and the H center dot center dot center dot H and N center dot center dot center dot H contacts in 2 are the main intermolecular interactions. The electronic absorption and IR spectral properties are also discussed. (C) 2017 Elsevier B.V. All rights reserved.