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You can't move the actual Administrator's folders. You are going to screw up the installation by trying.
I'm using the operating system to move them, Location tab and move to different partition, (and I've always done much the same thing in XP.)
I tend to 'explode' my OS installs on a fairly regular basis and I've found that keeping as little as possible on the OS partition, and keeping regular Ghosts makes recovery easier.
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This is a bit confusing ... why are you trying to use 32
and 64bit OS's on one computer?

Because I'm testing things out, never had a 64bit OS before so comparing it to the 32bit version (spent 20 years trying to break software as a career, it's a hard habit to break).