The study described here builds on recent solution and solid-state NMR studies to establish their usefulness in MA'AT analysis. Solid-state C NMR (ssNMR) provides experimental J CC values in conformationally-defined C-labeled crystalline compounds that are devoid of effects from motional averaging in solution. Direct comparisons between these experimental values and DFT-calculated J CC values in corresponding in silico structures can be used to evaluate the accuracy of J CC values calculated by DFT. Using this approach, crystalline doubly C-labeled methyl aldohexopyranosides 1 1,2 , 2 1,2 , 1 , 2 , 3 1,2 , 4 , and 5 (superscripts denote the labeled carbons) (Scheme 1) were used to measure onebond C- C spin-coupling constants between the contiguously labeled carbons by solid-state C NMR. This group of monosaccharides was chosen due to their ease of synthesis and crystallization, their structural simplicity, and their structural diversity (different anomeric configurations, configurations at other ring carbons, and Scheme 1. Chemical structures of doubly C-labeled 1 1,2 , 2 1,2 , 1 , 2 , 3 1,2 , 4 1,2 and 5 . The one-bond C- C spin-coupling between the two labeled carbons was investigated in each compound. Superscripts on the compound numbers denote the labeled carbons.