A validated experimental NMR parameter dataset of organic molecules to assist benchmarking of 3D structure determination methods.

Over 1000 accurately defined and validated experimental long-range proton-carbon (nJCH) and proton-proton (nJHH) scalar coupling constants, with assigned 1H/13C chemical shifts and their corresponding 3D structures are reported for fourteen relatively complex organic molecules. The experimental dataset comprises 775 nJCH, 300 nJHH, 332 1H chemical shifts and 336 13C chemical shifts, all validated against DFT-calculated values to identify misassignments. A subset of 565 nJCH, 205 nJHH, 172 1H chemical shifts and 202 13C chemical shifts from rigid portions of these molecules have been identified which could be particularly valuable for benchmarking computational methods for predicting NMR parameters. An exemplar application of this dataset is presented through benchmarking of the DFT mPW1PW91/6-311g(dp) level of theory for computation of chemical shifts and scalar coupling constants and for testing scaling approaches for generating experimentally-relevant chemical shifts from DFT-computed magnetic shielding tensors.