Three organically templated magnesium sulfates: Chemical preparation, hydrogen-bonded structures and thermal behavior
Graphical abstract
Highlights
► 3 Organically templated magnesium sulfates were synthesized by the slow evaporation method. ► Compound (I) crystallizes in P −1 space group while the two other crystallize in C2/c. ► The thermal decomposition depends on the crystal structure type and the used amine.
Introduction
Organic–inorganic hybrid materials are the subject of major interest, allowing to combine some properties of an inorganic material (or a molecule), and these of an organic molecule (or a polymer). This symbiosis between two worlds of chemistry too long regarded as opposites can also lead to completely new properties, and opens a wide field of investigations for the chemist. The applications of these “new” materials cover diverse areas as the properties of strength, optics, ferroelectricity and ferroelasticity, electronics and ionic solid… Indeed, the crystal engineering of supramolecular compounds is known to favor electric and magnetic properties (see, for example [1], and refs therein). On the other hand, the compounds with hydrogen-bonded structures can leads to interesting ONL properties [2], [3], [4], [5]. Recently, we reported some new organic–inorganic hybrid solids composed of 3d transition metal, sulfate groups and protonated diamine [6], [7], [8], [9], [10], [11], [12], [13], [14], [15]. In this work, we change the transition metals by an alkaline earth metal, Mg, in order to find new structure type and interesting properties due to the difference between the electronic configurations. In the field of our investigations in the organic–inorganic hybrid materials, we report here the chemical preparation, the thermal behavior and the crystallographic characterization of three magnesium sulfates templated by ethylenediamine (I), piperazine (II) and 1,4-diazabicyclo[2.2.2]octane (III).
Section snippets
Chemical preparation
Single crystals of the three compounds were grown as follows: 1 mmol of the magnesium sulfate heptahydrate MgSO4·7H2O, 1 mmol of the amine, ethylenediamine (C2H8N2), piperazine hexahydrate (C4H10N2)·6H2O and 1.4-diazabicyclo[2.2.2]octane (abbreviated dabco) (C6H12N2) for compounds (I), (II) and (III) respectively, and 1 mmol of sulfuric acid H2SO4 were mixed together in a minimum amount of distilled water. The clear solutions were stirred for 15 min and allowed to stand at room temperature.
Crystal structures
The crystal structure of ethylenediammonium tetraaquadisulfatomagnesate(II), [NH3(CH2)2NH3][Mg(SO4)2(H2O)4], (I), consists of [Mg(SO4)2(H2O)4]2− anions, that are built from octahedral Mg(H2O)4O2 and SO4 tetrahedral units linked by corner sharing, and of ethylenediammonium cations linked to the anions via N–H⋯O hydrogen bonds. The asymmetric unit contains only one half of the compound being the other half related to the first one by the inversion center. The crystal structure presents alternate
Concluding remarks
In summary, the synthesis, structure and thermal behavior of three inorganic–organic hybrid magnesium sulfates has been accomplished. The present studies show that the change of the amine, which plays the role of directing agent in this family of hybrid materials, leads to different structure types and influences the thermal decomposition of precursors. Indeed, the use of aliphatic diamine, ethylenediamine, gives a centrosymmetric compound crystallizing in P −1 space group. While the two other
Acknowledgments
Grateful thanks are expressed to Dr. T. Roisnel (Centre de Diffractométrie X, Université de Rennes I) for the assistance in single-crystal X-ray diffraction data collection.
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