Hi
From a strength standpoint, the 4x4 is plenty for corners. The plans you've seen that double up 2x4's are generally designed to enable them to be screwed together, with a direct load, rather than just as a doubled 2x4. If you look at those plans, one 2x4 is directly between the top and bottom rails, where weight pushes them together. The 2nd 2x4 runs above and below the horizontal rails, allowing you a surface to screw into, without trying to screw through a 3.5" tall beam, on edge.
4x4 and 2x6 is going to be plenty strong... provided you're not trying to run the entire 72" span without support. I probably wouldn't recommend that, regardless of the lumber dimension.
Before you get too far into this, you might consider a steel stand. 220 gallons of water is a lot of weight, and if something fails, it's enough water to be a real nightmare. When I was planning my 140g stand, I called a small local steel fab shop, sent them a drawing, and they built me a welded steel stand, 11 gauge, 1.5" square steel tube, for less than what I was going to have to spend on lumber to build it myself. A local powder coating company sand blasted and powder coated it for less than I'd have spent on paint. Steel is strong, stable, and allows for a much more open design than wood does. On bigger tanks, it can end up being the same, or even less, from a cost standpoint, than a nice wood stand. Once you've got a strong, stable stand, skinning it to look however you might want, since it's not structural, is fairly simple.