2-1/4 x 3-1/4 is the American size, and 6.5x9cm is the European size. The filmholders fit the same cameras, but the film size is different. Presumably the guide with the deeper curve is for the larger, European size.
I'm not sure about 2-1/2 x 3-1/2, but it could be pack film, which is a slightly different size from cut film. I've experimented with old film packs of this format, but I've always just processed the film in trays.
I'm not sure all 4x5" films would hold up to agitation without falling out of the grooves and sticking together with a tank of this design.
I have two of the other type of Nikor sheet film tank, which can be adjusted for all sizes from 2-1/4 x 3-1/4 to 4x5".