Crystal structure refnements of borate dimorphs inderite and kurnakovite using ¹¹B and ²⁵Mg nuclear magnetic resonance and DFT calculations

Borate minerals composed of [BΦ₃] triangles and/or [BΦ₄] tetrahedra (Φ = O or OH) commonly exhibit complex polymerizations to form diverse polyanion groups. High-resolution solid-state magic angle spinning (MAS) ¹¹B and ²⁵Mg NMR spectroscopy at moderate to ultrahigh magnetic fields (9.4, 14.1, and 21.1 T) allows for very accurate NMR parameters to be obtained for the borate dimorphs, inderite, and kurnakovite, [MgB₃O₃(OH)₅·5H ₂O]. Improved agreement between experimental results and ab initio density functional theory (DFT) calculations using Full Potential Linear Augmented Plane Wave (FP LAPW) with WIEN2k validates the geometry optimization procedures for these minerals and permits refinements of the hydrogen positions relative to previous X-ray diffraction crystal structures. In particular, the optimized structures lead to significant improvements in the positions of the H atoms, suggesting that H atoms have significant effects on the ¹¹B and ²⁵Mg NMR parameters in inderite and kurnakovite. This study shows that combined high-resolution NMR spectroscopy and ab initio theoretical modeling provides an alternative method for the refinement of crystal structures, especially H positions.