Five novel two-dimensional frameworks containing formate-bridged metal-centered octahedra are synthesized ionothermally from two ionic liquids previously unused as solvents in hybrid synthesis, 2-hydroxyethylammonium (HEA) formate, and 1-hydroxy-3-proplyammonium (HPA) formate. Templating effects of the cation from each ionic liquid drive the formation of different structures. [NH3C2H4OH]2[M(CHO2)4] (1: M = Co, 2: M = Ni) exhibit the same stoichiometry and connectivity as their manganese analogue (3: M = Mn), but the manganese form exhibits a different topology from 1 and 2. [NH3C3H6OH][M(CHO2)3(H2O)] (4: M = Co, 5: M = Mn) were synthesized using the HPA formate ionic liquid with a metal−formate connectivity related to those of 1−3. Canted antiferromagnetic ordering occurs at low temperatures (1: TN = 7.0 K, 2: TN = 4.6 K, 3: TN = 8.0 K, 4: TN = 7.0 K, 5: TN = 9.2 K), similar to the magnetic properties previously reported for other metal−formate hybrid materials.

A synthetic aluminogermanate and a gallogermanate with the Cancrinite group (CAN) framework topology have been synthesized under hydrothermal conditions and characterized by single crystal synchrotron X-ray diffraction. AlGe-CAN, Na6Cs2Al6Ge6O24 · Ge(OH)6, is hexagonal, with the space group P63 and a=12.968(1),c=5.132(1) Å, V=747.4(1) Å3. The T-sites exhibit complete ordering of Al and Ge atoms, similar to the framework models of aluminosilicate analogues. GaGe-CAN, Na6Cs2Ga6Ge6O24 · Ge(OH)6, is hexagonal, apparently with the space group P63mc and a=12.950(2),c=5.117(1) Å, V=743.2(2) Å3. Although the observed data are consistent with the presence of the c-glide and consequent disordering of Ga and Ge atoms at the T-sites, calculation using a DLS-optimized framework in the space group P63 reveals that the intensities of the reflections with l=2n+1 are less than 0.07% of the strongest (0 0 0 2) reflection, suggesting that P63 is probably the true space group. Resonant diffraction studies performed in the vicinity of the Ga K-edge confirmed the presence of the reflections with l=2n+1 and thus confirmed the ordering of the framework Ga/Ge atoms in GaGe-CAN. Inspection of the framework T–O–T bond angles demonstrates greater relative cell contraction for GaGe-CAN compared to AlGe-CAN and aluminosilicate counterparts. In both the structural models, Ge(OH)6 octahedra are occluded in the 12-ring channels running along the 63-axes. The sodium cations fully occupy the sites above the 6-ring windows in the 12-ring channels. The cesium cations fully occupy the sites in the middle of the cancrinite cages. Subtle differences in the coordination geometries of the extra-framework species are found, perhaps due to the pseudo-symmetry of GaGe-CAN. Thermogravimetry results indicate net weight losses of 3.5% and 3.0% for AlGe-CAN and GaGe-CAN, respectively, which are explainable by the dehydration of the Ge(OH)6 octahedra. In situ synchrotron X-ray powder diffraction demonstrated the formation of GaGe analogue of the nepheline hydrate I type structure at the temperature of complete dehydration.

The new composition Li4B4Si8O24 has been synthesized as single crystals employing a hydrothermal recrystallization technique and studied using single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21 with Z=2 and cell parameters a=5.0448(2), b=13.1688(4), c=13.3933(2) Å, β=90.069(2)°. The structure is composed of (20) layers of corner connected B- and Si-centered tetrahedra forming four-, five- and six-membered rings. These units are then joined via Si–O–Si linkages to form a unique 3-D framework structure. The lithium atoms can be considered as forming part of a lithoborosilicate framework or to be well ordered within the pores formed by the borosilicate structure.