(Me2NH2)10[H2-Dodecatungstate] polymorphs: dodecatungstate cages embedded in a variable dimethylammonium cation + water of crystallization matrix

Abstract

Two polymorphs and a solvatomorph of a new dimethylammonium polytungstate—decakis(dimethylammonium) dihydrogendodecatungstate, (Me₂NH₂)₁₀(W₁₂O₄₂)·nH₂O (n = 10 or 11)—have been synthesized. Their structures were characterized by single-crystal X-ray diffraction and solid-phase NMR methods. The shape of the dodecatungstate anions is essentially the same in all three structures, their interaction with the cations and water of crystallization, however, is remarkably variable, because the latter forms different hydrogen-bonded networks, and provides a highly versatile matrix. Accordingly, the N–H⋯O and C–H⋯O hydrogen bonds are positioned in each crystal lattice in a variety of environments, characteristic to the structure, which can be distinguished by solid-state ¹H-CRAMPS, ¹³C, ¹⁵N CP MAS and ¹H–¹³C heteronuclear correlation NMR. Thermogravimetry of the solvatomorphs also reflect the difference and multiformity of the environment of the water molecules in the different crystal lattices. The major factors behind the variability of the matrix are the ability of ammonium cations to form two hydrogen bonds and the rigidity of the polyoxometalate anion cage. The positions of the oxygen atoms in the latter are favourable for the formation of bifurcated and trifurcated cation–anion hydrogen bonds, some which are so durable that they persist after the crystals are dissolved in water, forming ion associates even in dilute solutions. The H atom involved in furcated hydrogen bonds cannot be exchanged by deuterium when the compound is dissolved in D₂O. An obvious consequence of the versatility of the matrix is the propensity of these compounds to form multiple polymorphs.