The first characterization of dimeric lanthanide complex anion: synthesis and crystal structure of [NH(Et)3]2[Lu(L)4]2·6CH3OH

Two lanthanide complexes with acrylic acid ligand: [Ho(L)3(CH3OH)2]2·CH3OH·H2O (1) and [NH(Et)3]2[Lu(L)4]2·6CH3OH (2) (L=(E)-3-(2-hydroxyl-phenyl)-acrylic acid) are studied. The crystal structure data for 1: C59H60Ho2O24, orthorhombic, Pbcn, a=15.4289(12) Å, b=7.9585(6) Å, c=23.041(2) Å, β=99.657(2)°, Z=4, R1=0.0637, wR2=0.0919; for 2: C27H30.50LaO13.75, triclinic, P−1, a=13.3034(4) Å, b=13.3087(4) Å, c=14.5461(6) Å, α=85.932(2)°, β=64.611(2)°, γ=81.595(2)°, Z=2, R1=0.0394, wR2=0.0446. Two structure data were collected using graphite monochromated molybdenum Kα radiation and refined using full-matrix least square techniques on F2. Complex 2 is the first dimeric lanthanide complex anion. Two structures show dinuclear complexes with bis-monodentate and bidentate chelate bridge modes of carboxylato ligand. Bidentate chelate coordination mode were also included in these two complexes. The smallest bridge angle of bidentate chelate carboxylato bridge (η3-O, 104.70(9)°) has been found for the first time. Complexes 1 and 2 act as supramolecular synthons assembled by 2D and 3D hydrogen bonding in the crystal lattices.