Spin-Canted Antiferromagnetic Ordering in Transition Metal–Organic Frameworks Based on Tetranuclear Clusters with Mixed V- and Y‑Shaped Ligands

Four transition metal–organic frameworks were solvothermally synthesized with V-shaped 1,3-bis­(1-imidazolyl)­benzene (bib) and two Y-shaped carboxylate ligands (1,3,5-benzenetricarboxylic acid (H3btc) and 3,5-pyridinedicarboxylic acid (H2pydc)), namely, {[M2(μ3-OH)­(bib)­(btc)]­·H2O} n (M = Co (1) and Fe (2)) and {[M′2(μ3-OH)­(μ2-NO3)­(bib)­(pydc)]­·solvents} n (M′ = Co (3) and Ni (4)). All of them are characterized by single-crystal X-ray diffraction, infrared spectrosopy, and powder X-ray diffraction. Both complexes 1 and 2 present two-dimensional (3,8)-connected layer structures, and the point symbol is (3.42)2(34.46.­56.68.73.8), but Fe2 in 2 is weakly coordinated to O5 as a trigonal bipyramidal geometry compared with the tetrahedral Co2 in 1, while complexes 3 and 4 exhibit three-dimensional “pillar-layer” structures with (3,8)-connected tfz-d net. Interestingly, nitrate anions with a rare μ2-η2 coordination mode take part in coordination, and rectangular channels along the c axis exist in 3 and 4. Magnetic studies indicate that 1 and 2 present antiferromagnetic behaviors, while 3 and 4 show the coexistence of spin-canting and long-range magnetic ordering.