@muelgrub - the one thing you *can* do is move the location of your entire library. That is the question you were asked when you first installed calibre, and via the Library dropdown menu on the toolbar it is possible to move your library to a different location if inside your users folder is not where you want it.
Moving your library to a different drive for reasons of space, or backup purposes etc is a perfectly reasonable thing to do. However as theducks pointed out, if it is just because you intend to navigate into the library folders and start "fiddling" with the files in there, dragging them around etc that is a major no-no as per the sticky.
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