A novel pillared-layer framework with a (52.6)(53.63.73.8) Schlaifli symbol, [Mn(H2O)(Htrc)(Hbtc)]n (1), was prepared by the reaction of 1,2,4-triazole (Htrz), 1,3,5-benzene- tricarboxylic acid (H3btc), and MnII salt and structurally and magnetically characterized. It crystallizes in the orthorhombic system, space group P212121 with a = 7.1618(5), b = 9.0356(6), c = 10.9740(13) A, V = 1292.54(15) A3, Dc = 1.799 g/cm3, Mr = 350.15, Z = 4, F(000) = 708, p = 1.064 mm-1, and the final R = 0.0177 and wR = 0.0462 for 2273 observed reflections with I〉 2σ(I). The unique octahedral Mnn ion in 1 is periodically linked into a two-dimensional (2D) magnetic layer by p2-N1, N4-Htrz and syn, anti-COO of doubly deprotonated Hbtc2- anion, which is further supported by the phenyl backbone of Hbtc2- ligand to generate a 3D pillared-layer framework. Magnetically, complex 1 displays an antiferromagnetic ordering below 5.0 K due to the cooperative antiferromagnetic couplings mediated by the mixed heterobridges within the magnetic layer.
A new 2-naphthate(NA-)-based coordination complex,[Cu3(μ3-OH)4(NA)2]n(1),was hydrothermally prepared and structurally and magnetically characterized.1 crystallizes in the monoclinic P21/c space group with a = 19.990(7),b = 5.616(2),c = 9.179(3) A,β = 96.536(6)°,V = 1023.8(7) A^3,Dc = 1.950 g/cm^3,Mr = 300.49,Z = 4,F(000) = 602,μ = 3.138 mm^-1,the final R = 0.0317 and w R = 0.0818 for 4944 observed reflections with I 〉 2σ(I).Complex 1 exhibits an extended corner-sharing {Cu3(μ3-OH)}^5+ triangle-based layered structure with the NA^-ligands located on both sides.The interplay of the typical anti-and ferromagnetic interactions mediated by μ3-OH^-and μ-syn,syn-carboxylate heterobridges leads to the overall intralayer ferromagnetic couplings of 1.
A new magnetic MOF with cyclic triazolate and linear azido mediators, [Co2(trz)3fN3)], 1 (trz- = 1,2,4-triazolate), was hydrothermally synthesized and structurally and magnetically characterized. 1 crystallizes in the rhombohedral P63/mmc space group with a = b = 10.0716(17), c = 7.5860(14) A, V = 666.4(2) A3, Dc = 1.814 g/cm3, Mr = 364.09, Z = 2, F(000) = 360,μ = 2.499 mm-1, the final R = 0.0676 and wR = 0.1952 for 229 observed reflections with 1 〉 20(/). Complex 1 consists of linear {Co(trz)3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral Con ion by μ3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.
Two 4,5-dichlorophthalate-based metal complexes, {[Cu(bipy)(dcpa)].H2O}n, (1) and {[Cu2Coipy)2(Hdcpa)3]·H2O·C2H5OH.Hdcpa} (2, H2dcpa = 4,5-dichlorophthalic acid and bipy = 2,2'-bipyridine), were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a = 20.5821(8), b = 20.9013(12), c = 17.0270(7) A, V= 7324.9(6) A3, Dc = 1.707 g/cm3, Mr = 470.74, Z = 16, F(000) = 3792, p = 1.519 mm^-1, the final R = 0.0223 and wR = 0.0549 for 9239 observed reflections with I〉 2σ(I). Complex 2 crystallizes in triclinic, space group P1 with a = 14.1439(12), b = 14.2981(12), c = 15.1054(14) A, a = 72.121(2), β = 77.703(2),γ = 81.829(2)°, V= 2830.9(4) A3, Dc = 1.689 g/cm3, M,. = 1439.55, Z = 2, F(000) = 1452,μ = 1.207 mm^-1, the final R = 0.0536 and wR = 0.0981 for 16422 observed reflections with 1 〉 2σ(I). Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.