Low pH constructed Co(ii) and Ni(ii) 1D coordination polymers based on Cα-substituted analogues of zoledronic acid: structural characterization, and spectroscopic and magnetic properties

Abstract

Three novel coordination compounds based on α,α-disubstituted analogues of zoledronic acid with a cyclopropane (cpp) or cyclobutane (cbt) ring on the C_α carbon, isomorphous [Co(H₂cppZol)(H₂O)]·H₂O (1a), [Ni(H₂cppZol)(H₂O)]·H₂O (1b) and [Co(H₂cbtZol)(H₂O)]·H₂O (2a), were synthesized under hydrothermal conditions at low pH. Single-crystal X-ray diffraction analysis revealed that all the compounds had a 1D double zig–zag chain architecture with an 8 + 8 ring motif formed by alternately arranged symmetrical (–O–P–O–)₂ bridges linking equivalent octahedral metal centres. Both the ligand coordination mode and chain architecture displayed by 1a, 1b and 2a are unique among 1D [M(H₂L)(H₂O)_x]·yH₂O coordination polymers based on nitrogen-containing bisphosphonates reported so far. All the compounds exhibit similar decomposition pathways upon heating with thermal stabilities decreasing in the order 1b > 1a > 2a. The IR spectra revealed that lattice water release above 227, 178 and 97 °C, respectively, does not change the chain architecture leaving them intact up to ca. 320, 280 and 240 °C. Magnetic behaviour investigations indicated that 1a, 2a and 1b exhibit weak alternating antiferromagnetic–ferromagnetic exchange interactions propagated between the magnetic centres through double (–O–P–O–)₂ bridges. The boundary between antiferro- and ferromagnetic couplings for the Co–O⋯O–Co angle in 1a and 2a was estimated to be ca. 80°. This value is also applicable for recently reported [M₃(HL)₂(H₂O)₆]·6H₂O (M = Co, Ni) complexes based on α,α-disubstituted analogues of zoledronic acid and can be used to the explain magnetic behaviour of 1b.