Crystal structures of two heterotrimetallic dysprosium–manganese–sodium 12-metallacrown-4 complexes with the bridging ligands 3-hydroxybenzoate and 4-hydroxybenzoate

Abstract

<jats:p>The syntheses and crystal structures for the compounds tetra-μ-aqua-tetrakis{2-[azanidylene(oxido)methyl]phenolato}tetrakis(μ<jats:sub>2</jats:sub>-3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>-dimethylacetamide decasolvate, [DyMn<jats:sub>4</jats:sub>Na(C<jats:sub>7</jats:sub>H<jats:sub>5</jats:sub>O<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>(C<jats:sub>7</jats:sub>H<jats:sub>4</jats:sub>NO<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub>]·10C<jats:sub>4</jats:sub>H<jats:sub>9</jats:sub>NO or [Dy<jats:sup>III</jats:sup>Na(4-OHben)<jats:sub>4</jats:sub>{12-MC<jats:sub>Mn(III)N(shi)</jats:sub>-4}(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub>]·10DMA, <jats:bold>1</jats:bold>, and tetra-μ-aqua-tetrakis{2-[azanidylene(oxido)methyl]phenolato}tetrakis(μ<jats:sub>2</jats:sub>-3-hydroxybenzoato)dysprosium(III)tetramanganese(III)sodium(I) <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>-dimethylformamide tetrasolvate, [DyMn<jats:sub>4</jats:sub>Na(C<jats:sub>7</jats:sub>H<jats:sub>5</jats:sub>O<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>(C<jats:sub>7</jats:sub>H<jats:sub>4</jats:sub>NO<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub>]·4C<jats:sub>3</jats:sub>H<jats:sub>7</jats:sub>NO or [Dy<jats:sup>III</jats:sup>Na(3-OHben)<jats:sub>4</jats:sub>{12-MC<jats:sub>Mn(III)N(shi)</jats:sub>-4}(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub>]·4DMF, <jats:bold>2</jats:bold>, and where MC is metallacrown, shi<jats:sup>3−</jats:sup> is salicylhydroximate, 3-OHben is 3-hydroxybenzoate, DMA is <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>-dimethylacetamide, 4-OHben is 4-hydroxybenzoate, and DMF is <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>-dimethylformamide, are reported. For both <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold>, the macrocyclic metallacrown consists of an [Mn<jats:sup>III</jats:sup>—N—O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a Dy<jats:sup>III</jats:sup> ion on the convex side of the metallacrown and an Na<jats:sup>+</jats:sup> ion the concave side. The Mn<jats:sup>III</jats:sup> ions are six-coordinate with an elongated tetragonally distorted octahedral geometry. Both the Dy<jats:sup>III</jats:sup> and Na<jats:sup>+</jats:sup> ions are eight-coordinate. The Dy<jats:sup>III</jats:sup> ions possess a square-antiprismatic geometry, while the Na<jats:sup>+</jats:sup> ions have a distorted biaugmented trigonal–prismatic geometry. Four 3-hydroxybenzoate or 4-hydroxybenzoate ligands bridge each Mn<jats:sup>III</jats:sup> ion to the central Dy<jats:sup>III</jats:sup> ion. For <jats:bold>1</jats:bold>, whole-molecule disorder is observed for the main molecule, excluding only the Dy<jats:sup>III</jats:sup> and Na<jats:sup>+</jats:sup> ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14). Three DMA molecules were refined as disordered with two in general positions by an approximate 180° rotation and the third disordered twice by general disorder as well as by an exact 180° rotation about a twofold axis that bisects it. The occupancy ratios refined to 0.496 (8):0.504 (8), 0.608 (9):0.392 (9), and 2×0.275 (7):2×0.225 (7), respectively. For <jats:bold>2</jats:bold>, segments of the metallacrown are disordered including the Dy<jats:sup>III</jats:sup> ion, one of the Mn ions, two of the Mn-bound 4-hydroxybenzoate ligands, the Mn-bridging salicylhydroximate ligand, and portions of the remaining three shi<jats:sup>3−</jats:sup> ligands. The occupancy ratio for the metallacrown disorder refined to 0.849 (9):0.151 (9). Two DMF solvent molecules are also disordered, each over two orientations. The disorder ratios refined to 0.64 (3):0.36 (3) and to 0.51 (2):0.49 (2), respectively. For <jats:bold>2</jats:bold>, the crystal under investigation was refined as a non-merohedric twin by a 90° rotation around the real <jats:italic>a</jats:italic> axis [twin ratio 0.9182 (8):0.0818 (8)].</jats:p>

A family of mono-, di-, and tetranuclear DyIIIcomplexes bearing the ligand 2,6-diacetylpyridine bis(picolinoylhydrazone) and exhibiting slow relaxation of magnetization

“…5 and Table S7†). The biaugmented trigonal prismatic geometry (Dy1 and Dy1′) is a trigonal prism capped on two of the three rectangular faces; 45 the latter faces consist of the atoms O5/O8/O3/O1, O8/O3/N6/N7, and O5/O1/N6/N7, while the capping atoms are the O2 and O1′. In the muffin-like geometry of Dy2 (and Dy2′), the basal trigonal plane is formed by O2, O4, and N2 atoms, the equatorial pentagonal plane is made of O6, O1, O3, N4, and N3, and the O9′ atom occupies the vertex of the muffin; the Dy2–O9′ distance of 2.370(5) Å is the shortest one within the muffin polyhedron.…”

“…5 and Table S7 †). The biaugmented trigonal prismatic geometry (Dy1 and Dy1′) is a trigonal prism capped on two of the three rectangular faces; 45 the latter faces consist of the atoms O5/O8/O3/O1, O8/O3/N6/N7, and O5/O1/ N6/N7, while the capping atoms are the O2 and O1′. In the muffin-like geometry of Dy2 (and Dy2′), the basal trigonal plane is formed by O2, O4, and N2 atoms, the equatorial pentagonal plane is made of O6, O1, O3, N4, and N3, and the O9′ Although there are many tetranuclear {Dy 4 } clusters reported in the literature, possessing the {Dy 4 (μ 3 -OH) 2 (μ-OR) 4 } 6+ 'butterfly'-like core, 46 complex 4 is structurally more reminiscent to the complex [Dy 4 (μ 3 -OH) 2 ( php) 2 (O 2 CMe) 6 (H 2 O) 2 ], featuring the dianion of 2,6-( picolinoylhydrazone)pyridine (H 2 php).…”

Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propylvalerate anion bridges

“…Therefore, 2-hydroxybenzoate is the most electron-withdrawing in the series, and this may affect the magnetic coupling between the Dy III and Mn III ions. We have also extended the types of DyNaY 4 [12-MC Mn III Nshi -4] structures by synthesizing complexes with 3-hydroxy-and 4-hydroxybenzoate (Manickas et al, 2020) and with halogenated benzoate anions (2-fluoro-, 3-fluoro-, 4-fluoro-, 2-chloro-, 3-chloro-, 3-bromo-, and 2-iodobenzoate; (Michael et al, 2021). These carboxylates have a range of pK a values that spans from 2.86 to 4.57 (Haynes, 2010), although at this time we have not investigated the SMM properties of these compounds.…”

“…A range of bridging carboxylate anions (Y) have been used including acetate (OAc), trimethylacetate (TMA), benzoate (ben), 2-hydroxybenzoate (2-OHben), 3-hydroxybenzoate (3- OHben), 4-hydroxylbenzoate (4-OHben), 2-fluorobenzoate (2-Fben), 3-fluorobenzoate (3-Fben), 4-fluorobenzoate (4-Fben), 2-chlorobenzoate (2-Clben), 4-chlorobenzoate (4-Clben), 3-bromobenzoate (3-Brben), and 2-iodobenzoate (2-Iben). Of the forty structures, thirteen contain both Dy III and Na + as in 1 (Azar et al, 2014;Boron et al, 2016;Manickas et al, 2020;Michael et al, 2021). The structural comparison of 1 will be limited to the MCs that contain Dy III and Na + ions captured in the central MC cavity (Table 5).…”

“…A survey of the Cambridge Structural Database (CSD version 5.43, update September 2022, Groom et al, 2016) reveals forty LnXY 4 [12-MC Mn III N(shi) -4] structures, where X is a countercation with a 1+ charge and Y is a carboxylate anion (Azar et al, 2014;Travis et al, 2015Travis et al, , 2016Boron et al, 2016;Cao et al, 2016;Qin et al, 2017;Anthanasopoulou et al, 2018;Manickas et al, 2020;Michael et al, 2021). The central Ln III metal ions include the lanthanide ions from Pr to Yb (except Pm) and yttrium.…”