Synthesis, structure and the Hirshfeld surface analysis of three novel metal-tiron coordination complexes

• Published in: RSC advances Vol. 11; no. 18; pp. 1767 - 1776
• Main Authors: Tiwari, Ranjay K, Shruti, Ipsha, Behera, J. N
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 12.03.2021; The Royal Society of Chemistry
• Subjects: Angles (geometry); Antiferromagnetism; Chemistry; Coordination compounds; Coordination polymers; Crystal structure; Crystallography; Crystals; Fourier transforms; Infrared analysis; Ligands; Single crystals; Surface analysis (chemical); Thermogravimetric analysis; X ray powder diffraction; X-ray diffraction
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/d1ra00207d

Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4′-bipyridyl)-centered coordination polymers of the formulae [Cd(tiron)(bpy) 2 (H 2 O) 2 ]·0.5(H 2 O), 1 , [Co 3 (tiron-bpy) 2 (bpy)(H 2 O) 8 ]·(H 2 O) 2 , 2 , and [Ba 2 (tiron-bpy) 2 (H 2 O) 4 ][solvent], 3 , were successfully synthesized under hydrothermal conditions. The as-synthesized materials were well characterized by complimentary techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy and thermogravimetric analysis techniques. The as-synthesized coordination polymers of 1 and 2 featured 1D chains, while 3 shows a layered structure. Co-based 2 shows linear trinuclear Co( ii ) ions and these Co( ii ) ions have antiferromagnetic interactions among themselves. The structure of 1 features a zig-zag chain formed by the linkage between monodentate tiron ligands and octahedral Cd( ii ) ions, interconnected by a twisted bpy ligand, 2 shows a linear chain constructed from corner-sharing trinuclear octahedral Co( ii ) ions and coordinated with a tridentate tiron-bpy adduct ligand, whereas 3 shows nona-coordinated Ba( ii ) ions sharing edges with other Ba( ii ) ions and connected by hexadentate tiron-bridged structures resulting in a layered structure. In 2 and 3 , the bpy nitrogen attacks at the ortho position of the tiron ligand and forms an in situ ligand adduct. The central metal ions show an octahedral geometry in 1 (Cd( ii ) ions) and 2 (Co( ii ) ions), but nona-coordination of Ba( ii ) ions in 3 . The short interatomic interactions in the crystal structures were evaluated by mapping the Hirshfeld surface process using pseudo-mirrored 2D fingerprint plots. The major short interatomic interactions H H, O H and C H cover the Hirshfeld surfaces. Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4-bipyridyl) centered coordination polymers were successfully synthesized and characterized.