[C₅H₁₄N₂][(MoO₃)₃(SO₄)]·H₂O:  Sulfated α-Molybdena Chains

Abstract

Recent work in the preparation of organically templated metal sulfates under hydrothermal conditions has been extended to include the sulfation of alpha-molybdena through the synthesis of [C(5)H(14)N(2)][(MoO(3))(3)(SO(4))].H(2)O. Single crystals were grown under hydrothermal conditions from molybdenum oxide, water, sulfuric acid, and an enantiomerically pure (R)-2-methylpiperazine source and characterized using both single-crystal X-ray diffraction and infrared spectroscopy. One-dimensional [(MoO(3))(3)(SO(4))](n)(2n-) chains, based on a neutral alpha-molybdena backbone, are connected through an extensive hydrogen-bonding network containing [C(5)H(14)N(2)](2+) cations and occluded water molecules. The direction of the hydrogen bonding is primarily dictated by the nucleophilicity of the respective oxide ligands, as determined using bond valence sums.

Three-dimensional porous framework formed by [Fe4Mo6O26]4− anions belts in brick-wall mode

“…Compared to the 145.8°tilts angle in previous reports [11], the tilts angles of the M(Mo, Fe)O 6 -M(Mo, Fe)O 6 (152.05°) and FeO 6 -MoO 4 (156.40°) lead to the structural expansion in 1 due to the pliability of the units. These hybrid iron a-molybdena species are self-aggregated to each other via l 2 -oxygen to an infinite onedimensional belt.…”

“…As reported by Prof. Zubieta et.al., some organic ligands such as 2,2 0 -bipyridine, which acted as the ''passivation'', might preclude the further formation of metal-oxo bond, to lead to two-dimensional iron molybdates [10]. Recent work in the organically templated metal has been extended to the decoration of a-molybdena chains by sulfates [11]. Despite the breadth of incorporation of phosphate and sulfate structure direction agents into metal oxides [11,12], there is still no report involving the a-molybdena chain and hybrid iron a-molybdena chain aggregating into multi-dimensional compound so far.…”

“…Recent work in the organically templated metal has been extended to the decoration of a-molybdena chains by sulfates [11]. Despite the breadth of incorporation of phosphate and sulfate structure direction agents into metal oxides [11,12], there is still no report involving the a-molybdena chain and hybrid iron a-molybdena chain aggregating into multi-dimensional compound so far. Herein, we report the synthesis, structure and magnetic property of {(H 3 O) 2 [Fe 2 Mo 3 O 13 ]} n , which shows, to the best of our knowledge, the first positive result of attempting to self-aggregate of hybrid iron a-molybdena chains into a novel three-dimensional porous structure in brick-wall mode.…”

Noncentrosymmetric Inorganic Oxide Materials: Synthetic Strategies and Characterisation Techniques

“…[51][52][53] As stated previously, the first challenge in synthesising NCS materials is to use inherently asymmetric NCS polyhedra. In using the SOJT-distorted Mo 6þ , Norquist et al synthesised materials where the d 0 cation is substantially displaced from the centre of its oxide octahedra.…”

“…The lone-pair cation coordination environment may be considered as pre-distorted, [38] as these cations are almost always found in local NCS environments. Halasyamani et al, [38][39][40][41][42][43][44][45][46][47][48][49][50] Norquist et al, [51][52][53] and others [54][55][56][57][58][59][60][61][62][63] have used SOJT-distorted cations in the design and synthesis of new NCS materials.…”