So apperantly block-0 exists, but it has no special behaviours or abilities. Also there are blocks past block-638 (a SMB3 beach slope) up to 700 - they too have no special behaviours or abilities, and will appear blank in SMBX since there's no graphic files for them to display in the graphics folder. So if you want to use these blocks, include your own custom graphics for them so that they will be visible.
If you go past 700, and use, let's say, block-701, SMBX crashes.
So yeah, that's a total of 62 'unused' but usable blocks!