Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi(12)B(8)

[Image: see text] Achieving kinetic control to synthesize metastable compounds is a challenging task, especially in solid-state reactions where the diffusion is slow. Another challenge is the unambiguous crystal structure determination for metastable compounds when high-quality single crystals suitable for single-crystal X-ray diffraction are inaccessible. In this work, we report an unconventional means of synthesis and an effective strategy to solve the crystal structure of an unprecedented metastable compound LiNi(12)B(8). This compound can only be produced upon heating a metastable layered boride, HT-Li(0.4)NiB (HT: high temperature), in a sealed niobium container. A conventional heating and annealing of elements do not yield the title compound, which is consistent with the metastable nature of LiNi(12)B(8). The process to crystallize this compound is sensitive to the annealing temperature and dwelling time, a testament to the complex kinetics involved in the formation of the product. The unavailability of crystals suitable for single-crystal X-ray diffraction experiments prompted solving the crystal structure from high-resolution synchrotron powder X-ray diffraction data. This compound crystallizes in a new structure type with space group I4/mmm (a = 10.55673(9) Å, c = 10.00982(8) Å, V = 1115.54(3) Å(3), Z = 6). The resulting complex crystal structure of LiNi(12)B(8) is confirmed by scanning transmission electron microscopy and solid-state (11)B and (7)Li NMR spectroscopy analyses. The extended Ni framework with Li/Ni disorder in its crystal structure resulted in the spin-glass or cluster glass type magnetic ordering below 24 K. This report illustrates a “contemporary twist” to traditional methodologies toward synthesizing a metastable compound and provides a recipe for solving structures by combining the complementary characterization techniques in the cases where the traditionally used single-crystal X-ray diffraction method is nonapplicable.