Amine‐Templated One‐Dimensional Metal Sulfates Including a Mixed‐Valent Fe Compound with a Half‐Kagome Structure

Abstract

Organically templated metal sulfates are relatively new. Six amine-templated transition-metal sulfates with different types of chain structures, including a novel iron sulfate with a chain structure corresponding to one half of the kagome structure, were synthesized by hydro/solvothermal methods. Amongst the one-dimensional metal sulfates, [C10N2H10][Zn(SO4)Cl2] (1) is the simplest, being formed by corner-linked ZnO2Cl2 and SO4 tetrahedra. [C6N2H18][Mn(SO4)2(H2O)2] (2) and [C2N2H10][Ni(SO4)2(H2O)2] (3) have ladder structures comprising four-membered rings formed by SO4 tetrahedra and metal-oxygen octahedra, just as in the mineral kröhnkite. [C4N2H12][V(III)(OH)(SO4)2]H2O (4) and [C4N2H12][VF3(SO4)] (5) exhibit chain topologies of the minerals tancoite and butlerite, respectively. The structure of [C4N2H12][H3O][Fe(III)Fe(II) F6(SO4)] (6) is noteworthy in that it corresponds to half of the hexagonal kagome structure. It exhibits ferrimagnetic properties at low temperatures and the absence of frustration, unlike the mixed-valent iron sulfate with the full kagome structure.

Open‐Framework Structures of Transition‐Metal Compounds

“…[ (Figure 14 a), [122,123] resemble the mineral butlerite, [M(TO 4 )f 3 ] (where f is any unspecified anion ligand). [ (Figure 14 a), [122,123] resemble the mineral butlerite, [M(TO 4 )f 3 ] (where f is any unspecified anion ligand).…”

“…Similar to the phosphate structures, the one-dimensional sulfate structures form in any one of the well established structure types described earlier. Thus, the compounds with the general formula, [C 4 N 2 H 12 ][MF 3 (SO 4 )], (M = V, Fe) (Figure 14 a), [122,123] resemble the mineral butlerite, [M(TO 4 )f 3 ] (where f is any unspecified anion ligand). [124] Magnetic susceptibility studies indicate weak antiferromagnetic behavior (Figure 14 b) [127] Magnetic susceptibility studies indicate a ferromagnetic behavior with hysteresis at 5 K.…”

A Slow Leak Synthetic Route to Organically Templated Gallium Sulfates

“…See Figure b. This compound is isostructural to both [H 3 N(CH 2 ) 2 NH 3 ][V III (OH)(SO 4 ) 2 ]·H 2 O and (C 2 H 10 N 2 ) 4 [GaV 3 (SO 4 ) 8 (OH) 4 ]·4H 2 O …”

catena-Poly[[[diaqua(tetramethylethylenediamine-κ2N,N′)nickel(II)]-μ-sulfato-κ2O:O′] monohydrate]

“…For crystal structures of oligo-and polymeric nickel(II) tmeda complexes, see: Anderson et al (2009); Erer et al (2010). For related literature on one-dimensional metal sulfates, see: Behera & Rao (2006).…”

“…Erer et al, 2010). A related chain structure consisting of corner-sharing NiO 4 (H 2 O) 2 octahedra and SO 4 tetrahedra has been observed in the compound[C 2 N 2 H 10 ][Ni(SO 4 ) 2 (H 2 O) 2 ](Behera & Rao, 2006). However, in contrast to compound (I) each NiO 4 (H 2 O) 2 octahedron of the chain is connected to four SO 4 tetrahedra.The crystal packing of the [Ni(H 2 O) 2 (tmeda)]SO 4 chains is supported by a network of hydrogen bridges(Figs.…”