In some of the monochrome Commodore motherboards, pin 5 was used for "NOROM": they had an expansion board that plugged into the 6502 socket to run the machine on a different CPU and/or with extra memory, and to keep the ROMs from being selected, NOROM could be activated so the RAM and/or ROM on the expansion board could be mapped to memory locations that were normally used for ROM. And remember, Commodore (MOS Technology) made the 6502.
I think the Apple 1 did something similar: it was compatible with the 6800 if you soldered some extra hardware on it to generate some extra clock signals and stuff. On the 6800 the extra signals were connected to some of the 6502 NC pins. I don't know the details about this.
Bottom line: for the original 6502 there's probably not much risk if you use the pins for something else (e.g. to plug something else in the socket). For the 65C02, it might be a different story and the WDC 65C02S is not totally pin compatible with the other 6502's. So the general rule is probably: NC means don't connect anything, but if you know what you're doing: have at it
===Jac