From RCSB PDB Statistics: The cumulative number of structures and NMR structures deposited every year.  The number of NMR structures deposited each year is not increasing. 
Using the advanced search option: there are 227 solution NMR structures of proteins with more than 200 residues.  Thus, 2% of the 10,282 solution NMR structures are of protein with more than 200 residues. Furthermore, 0.3% of the 70,795 structures if proteins with more than 200 residues are determined by solution NMR.
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