Pressure-induced crystallization and characterization of the tin borate β-SnB4O7

In the last years, several investigations were performed in the ternary system Sn-B-O as a simplified variant of the tin-based amorphous composite oxide (TCO), a material in use as negative electrode of lithium-ion rechargeable batteries. All compounds in this system are glasses, so the synthesis of crystalline approximands for a more detailed structural investigation would be favorable. The use of high-pressure/high-temperature conditions (7.5 GPa and 1100 degrees C; Walker-type multianvil apparatus) led to the synthesis of the first crystalline tin borate beta-SnB4O7. The single-crystal structure determination of beta-SnB4O7 showed Pmn2(1), a = 1086.4(2) pm, b = 444.80(9) pm, c = 423.96(8) pm, Z = 2, R-1 = 0.0155, and wR(2) = 0.0324 (all data). In contrast to the isotypic phases MB4O7 (M = Sr, Pb, Eu, beta-Ca, and beta-Hg), the position of the tin atom in beta-SnB4O7 is influenced by the existence of a stereochemically active lone pair. Furthermore, we report on thermoanalytical aspects (DTA-TG and temperature-resolved in situ powder diffraction), DFT calculations, IR spectroscopy, Mossbauer spectroscopic results, and solid-state NMR investigations on beta-SnB4O7. The latter method allows us to make a general differentiation of Sn2+ and Sn4+ in Sn-O systems on the basis of well-separated Sn-117/119 chemical shifts.