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The folder layout is correct. It was changed in calibre 3.x
The cantopenerror literally means that sqlite issued an open() system call for the metadata.db file and it failed. That can happen only because:
1) The library path points to a non-existing directory/drive/etc.
2) Something is blocking access
3) permissions on the file/directory are screwed up
I suggest you start with a new library, run calibre from a command prompt as
calibre --with-library c:\library
making sure that the folder c:\library exists and is writable by your user account.
If that works you know it is something wrong with the old library folder, if it doesn't you know it is something blocking calibre.
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