Cyanide bridged 2-D homometallic mixed-valence copper coordination polymer: synthesis, crystal architecture, Hirshfeld surface analysis and magnetic behavior

Abstract

A 2-D homometallic mixed-valence copper coordination polymer, catena-poly[[tetrakis(μ-cyanido)-{(1-(N-acetopyridinine)-2-aminoethane)}-tri-copper] methanol monosolvate], {[Cu₃(L)(CN)₄]·CH₃OH}_n (1) [L = 1-(N-acetopyridinine)-2-aminoethane], has been isolated using a one-pot reaction of the building components and was characterized. The crystal structure consists of [Cu^IIL]²⁺ units and copper(I) ions bridged by μ-CN anions. The copper(II) center of the CuN₅ chromophore displays a square pyramidal coordination geometry provided by three N atoms of the tridentate Schiff base and two N atoms of μ-NC ions, while the copper(I) centers adopt a trigonal-planar geometry. Three copper centers are interconnected through μ-CN/μ-NC via {-Cu¹(L)(μ-NC)₂Cu²(μ-CN)Cu³(μ-NC)-} units to form 2-D polymeric ribbons parallel to the b-axis. These 2-D polymeric ribbons in the crystalline state are further stabilized through π···π stacking interactions. Hirshfeld surface analysis was performed to gain additional insight into the interactions responsible for the packing of 1. Variable-temperature magnetic susceptibility studies showed a weak ferromagnetic interaction among the copper centers in 1 through cyanide bridges with J = 1.28 cm⁻¹.

Graphical abstract

Keywords:

• 2-D homometallic CP of mixed valence copper
• terminal and bridging cyanides
• X-ray structure
• Hirshfeld surface analysis
• ferromagnetism

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

The work is financially supported by the Department of Science and Technology, Government of India, by a grant (SR/S1/IC-0013/2010) (to CA).