Abstract
Several oxidoborates, self-assembled from B(OH)3 and templated by cationic Ni(II) coordination compounds, were synthesized by crystallization from aqueous solution. These include the ionic compounds trans-[Ni(NH3)4(H2O)2][B4O5(OH)4].H2O (1), s-[Ni(dien)2][B5O6(OH)4]2 (dien = N-(2-aminoethyl)-1,2-ethanediamine (2), trans-[Ni(dmen)2(H2O)2] [B5O6(OH)4]2.2H2O (dmen = N,N-dimethyl-1,2-diaminoethane) (3), [Ni(HEen)2][B5O6(OH)4]2 (HEen = N-(2-hydroxyethyl)-1,2-diaminoethane) (4), [Ni(AEN)][B5O6(OH)4].H2O (AEN = 1-(3-azapropyl) -2,4-dimethyl-1,5,8-triazaocta-2,4-dienato(1-)) (5), trans-[Ni(dach)2(H2O)2][Ni(dach)2] [B7O9(OH)5]2.4H2O (dach = 1,2-diaminocyclohexane) (6), and the neutral species trans-[Ni(en)(H2O)2{B6O7(OH)6}].H2O (7) (en = 1,2-diaminoethane), and [Ni(dmen)(H2O){B6O7(OH)6}].5H2O (8). Compounds 1–8 were characterized by single-crystal XRD studies and by IR spectroscopy and 2, 4–7 were also characterized by thermal (TGA/DSC) methods and powder XDR studies. The solid-state structures of all compounds show extensive stabilizing H-bond interactions, important for their formation, and also display a range of gross structural features: 1 has an insular tetraborate(2-) anion, 2–5 have insular pentaborate(1-) anions, 6 has an insular heptaborate(2-) anion (‘O+’ isomer), whilst 7 and 8 have hexaborate(2-) anions directly coordinated to their Ni(II) centers, as bidentate or tridentate ligands, respectively. The Ni(II) centers are either octahedral (1–4, 7, 8) or square-planar (5), and compound 6 has both octahedral and square-planar metal geometries present within the structure as a double salt. Magnetic susceptibility measurements were undertaken on all compounds.